Application of the Hiyama reaction to the synthesis of bioactive compounds. A bibliographic review
Authorship
O.S.F.
Bachelor of Chemistry
O.S.F.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The bibliographic review highlights the relevance and advancements of the Hiyama reaction in the field of cross-coupling. It covers the early pioneering publications by Hiyama, just three decades ago, and traces the evolution of organosilanes. This trajectory allows us to understand how the reaction has evolved with the use of different organosilanes, consolidating itself as an essential methodology in organic synthesis, especially with the introduction of the advantageous safety-catch silanols. Numerous examples of the synthesis of biologically active compounds using this methodology are presented, highlighting its application in the creation of long-chain and unstable polyenes, such as retinoids and carotenoids. The review includes an extensive search in scientific databases, selecting the most prominent studies on the Hiyama reaction. The results indicate a broad interest and continuous development in this field, underscoring its significant potential for future research.
The bibliographic review highlights the relevance and advancements of the Hiyama reaction in the field of cross-coupling. It covers the early pioneering publications by Hiyama, just three decades ago, and traces the evolution of organosilanes. This trajectory allows us to understand how the reaction has evolved with the use of different organosilanes, consolidating itself as an essential methodology in organic synthesis, especially with the introduction of the advantageous safety-catch silanols. Numerous examples of the synthesis of biologically active compounds using this methodology are presented, highlighting its application in the creation of long-chain and unstable polyenes, such as retinoids and carotenoids. The review includes an extensive search in scientific databases, selecting the most prominent studies on the Hiyama reaction. The results indicate a broad interest and continuous development in this field, underscoring its significant potential for future research.
Direction
LOPEZ ESTEVEZ, SUSANA (Tutorships)
LOPEZ ESTEVEZ, SUSANA (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
New applications of gas diffusion microextraction (GDME) followed by analysis using chromatography and mass spectrometry.
Authorship
A.G.F.
Bachelor of Chemistry
A.G.F.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Cosmetic products are part of daily life for most people, whether in the form of personal hygiene products (shampoos, deodorants...), personal care products (sunscreens, moisturizers...), or beauty and/or makeup products (eyeshadows, hair stylers...). These products contain fragrances that give them a pleasant and attractive scent for consumers. In this work, a method for the simultaneous determination of allergenic fragrances was developed and validated, based on gas diffusion microextraction (GDME) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Once the experimental conditions of the extraction method were optimized through an experimental design, the method was validated in terms of precision (repeatability and reproducibility), linearity, and accuracy. Finally, GDME-GC-MS/MS was applied to real samples of various cosmetic products.
Cosmetic products are part of daily life for most people, whether in the form of personal hygiene products (shampoos, deodorants...), personal care products (sunscreens, moisturizers...), or beauty and/or makeup products (eyeshadows, hair stylers...). These products contain fragrances that give them a pleasant and attractive scent for consumers. In this work, a method for the simultaneous determination of allergenic fragrances was developed and validated, based on gas diffusion microextraction (GDME) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Once the experimental conditions of the extraction method were optimized through an experimental design, the method was validated in terms of precision (repeatability and reproducibility), linearity, and accuracy. Finally, GDME-GC-MS/MS was applied to real samples of various cosmetic products.
Direction
Carro Díaz, Antonia María (Tutorships)
LLOMPART VIZOSO, MARIA PILAR (Co-tutorships)
Carro Díaz, Antonia María (Tutorships)
LLOMPART VIZOSO, MARIA PILAR (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Arine generation under benign environmental conditions.
Authorship
A.V.G.
Bachelor of Chemistry
A.V.G.
Bachelor of Chemistry
Defense date
02.19.2024 10:00
02.19.2024 10:00
Summary
Arynes are reaction intermediates with high reactivity and a short lifetime, due to the presence of a triple bond in their structure. They are generated by the formal loss of two hydrogens through the homolytic cleavage of their bonds. They are characterised by functioning as intermediates in the synthesis of a large number of natural products. They also participate in the Diels-Alder reactions, forming benzocyclohexenes which are an important synthetic tool in chemistry. The COMMO group (Guitián / Pérez / Peña) is very active in the search for new synthetic routes for the synthesis of arynes. One of their notable advances in arynes chemistry is the development of metal-catalysed [2+2+2] arynes cycloaddition reactions, specifically palladium. In this end-of-degree project, the generation of aryne using ultrasound will be studied for the first time. Aryl dihalides will be used as starting materials that will react with different metals (Mg, Zn, Li) and furan to obtain the endoxide or 1,4-dihydro-1,4-epoxynaphthalene.
Arynes are reaction intermediates with high reactivity and a short lifetime, due to the presence of a triple bond in their structure. They are generated by the formal loss of two hydrogens through the homolytic cleavage of their bonds. They are characterised by functioning as intermediates in the synthesis of a large number of natural products. They also participate in the Diels-Alder reactions, forming benzocyclohexenes which are an important synthetic tool in chemistry. The COMMO group (Guitián / Pérez / Peña) is very active in the search for new synthetic routes for the synthesis of arynes. One of their notable advances in arynes chemistry is the development of metal-catalysed [2+2+2] arynes cycloaddition reactions, specifically palladium. In this end-of-degree project, the generation of aryne using ultrasound will be studied for the first time. Aryl dihalides will be used as starting materials that will react with different metals (Mg, Zn, Li) and furan to obtain the endoxide or 1,4-dihydro-1,4-epoxynaphthalene.
Direction
GUITIAN RIVERA, ENRIQUE (Tutorships)
PEREZ MEIRAS, MARIA DOLORES (Co-tutorships)
GUITIAN RIVERA, ENRIQUE (Tutorships)
PEREZ MEIRAS, MARIA DOLORES (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Synthesis and study of photo-dynamic self-assembly of a cyclopeptide precursor of peptide nanotubes with antimicrobial properties
Authorship
M.V.R.
Bachelor of Chemistry
M.V.R.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Despite the important progress carried out in medicine in the past decades, this advance has slowed down due to the increase of antimicrobial resistance through which pathogenic agents become insensitive to different treatments. This resistance has an important impact both on health and economic point of view, so nowadays new strategies are underdeveloped to find effective treatment of these diseases. One of these strategies is the use of cyclic peptide nanotubes, structures which through different mechanisms can induce bacterial cell death. In this work were carried out the synthesis and characterization of three cyclic peptides with different hydrophobic character, and therefore, with different membrane affinity, which potentially can form supramolecular nanotubes through self-assembly process. The presence of a double bond in the cyclopeptides structure allows to regulate its conformation by light irradiation, leading to an additional control of the self-assembly process and on the formation of supramolecular nanotubes.
Despite the important progress carried out in medicine in the past decades, this advance has slowed down due to the increase of antimicrobial resistance through which pathogenic agents become insensitive to different treatments. This resistance has an important impact both on health and economic point of view, so nowadays new strategies are underdeveloped to find effective treatment of these diseases. One of these strategies is the use of cyclic peptide nanotubes, structures which through different mechanisms can induce bacterial cell death. In this work were carried out the synthesis and characterization of three cyclic peptides with different hydrophobic character, and therefore, with different membrane affinity, which potentially can form supramolecular nanotubes through self-assembly process. The presence of a double bond in the cyclopeptides structure allows to regulate its conformation by light irradiation, leading to an additional control of the self-assembly process and on the formation of supramolecular nanotubes.
Direction
AMORIN LOPEZ, MANUEL (Tutorships)
Granja Guillán, Juan Ramón (Co-tutorships)
AMORIN LOPEZ, MANUEL (Tutorships)
Granja Guillán, Juan Ramón (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
New sources of bioctive compounds of natural origin
Authorship
S.O.O.
Bachelor of Chemistry
S.O.O.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
A drawback associated with the wine industry is the generation of waste. Grape marc is a biowaste from the must extraction process in winemaking, which is generated in large quantities. The reuse of this by-product makes it possible to reduce its storage; its characteristics also make it a matter of great interest in other fields. Grape marc contains a large amount of polyphenols, bioactive compounds with antioxidant, antimicrobial and anti-inflammatory properties used in the pharmaceutical, cosmetic and food industries, which will be studied in this work. In order to obtain extracts rich in bioactive compounds from the grape marc of the white grape variety Albariño, originally from Galicia, an extraction is performed with three solvents recognized as safe. In this work, carried out in the laboratories of the LIDSA research group (Ci-2085-USC) and the company iGrape Laboratory, a stability study of the different grape marc extracts is performed, in which the effect of factors such as temperature and storage conditions is evaluated against response variables such as pH, antioxidant activity (AA), total polyphenol index (IPT), solids content and color. The analytical monitoring of these parameters was carried out on 36 study samples every two weeks for 3 and a half months.
A drawback associated with the wine industry is the generation of waste. Grape marc is a biowaste from the must extraction process in winemaking, which is generated in large quantities. The reuse of this by-product makes it possible to reduce its storage; its characteristics also make it a matter of great interest in other fields. Grape marc contains a large amount of polyphenols, bioactive compounds with antioxidant, antimicrobial and anti-inflammatory properties used in the pharmaceutical, cosmetic and food industries, which will be studied in this work. In order to obtain extracts rich in bioactive compounds from the grape marc of the white grape variety Albariño, originally from Galicia, an extraction is performed with three solvents recognized as safe. In this work, carried out in the laboratories of the LIDSA research group (Ci-2085-USC) and the company iGrape Laboratory, a stability study of the different grape marc extracts is performed, in which the effect of factors such as temperature and storage conditions is evaluated against response variables such as pH, antioxidant activity (AA), total polyphenol index (IPT), solids content and color. The analytical monitoring of these parameters was carried out on 36 study samples every two weeks for 3 and a half months.
Direction
LORES AGUIN, MARTA (Tutorships)
LORES AGUIN, MARTA (Tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Recycling of battery black mass. A literature review
Authorship
J.P.D.S.J.
Bachelor of Chemistry
J.P.D.S.J.
Bachelor of Chemistry
Defense date
02.19.2024 10:00
02.19.2024 10:00
Summary
Lithium batteries have been one of the biggest revolutions in the world of electronics, as the 2019 Nobel Prize in Chemistry can confirm. However, the world is moving in the direction of electric vehicles, and this creates several environmental challenges. The raw materials for our future batteries powering these new vehicles are neither abundant nor easy to extract from the earth's crust, furthermore, the amount of waste from spent batteries that we will have to deal with in the future. Behind these challenges lies the recycling of lithium ion batteries (LIBs), an industry that is growing quickly and becoming increasingly sustainable, which will help us recover the valuable metals that make up LIBs and eliminate potentially environmentally hazardous waste. While pyrometallurgical and hydrometallurgical processes are already being applied at an industrial level, alternatives within the methods themselves and even new processes such as direct recycling are being investigated in the laboratory. During this review we will see the existing methods, both within the laboratory and on a large scale, to recycle LIBs waste and take a look into the future of the industry.
Lithium batteries have been one of the biggest revolutions in the world of electronics, as the 2019 Nobel Prize in Chemistry can confirm. However, the world is moving in the direction of electric vehicles, and this creates several environmental challenges. The raw materials for our future batteries powering these new vehicles are neither abundant nor easy to extract from the earth's crust, furthermore, the amount of waste from spent batteries that we will have to deal with in the future. Behind these challenges lies the recycling of lithium ion batteries (LIBs), an industry that is growing quickly and becoming increasingly sustainable, which will help us recover the valuable metals that make up LIBs and eliminate potentially environmentally hazardous waste. While pyrometallurgical and hydrometallurgical processes are already being applied at an industrial level, alternatives within the methods themselves and even new processes such as direct recycling are being investigated in the laboratory. During this review we will see the existing methods, both within the laboratory and on a large scale, to recycle LIBs waste and take a look into the future of the industry.
Direction
Sanmartin Matalobos, Jesus (Tutorships)
GARCIA DEIBE, ANA MARIA (Co-tutorships)
Sanmartin Matalobos, Jesus (Tutorships)
GARCIA DEIBE, ANA MARIA (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Electrochemical Synthesis and Characterization of Sub-Nanometer Clusters of Transition Metals
Authorship
S.F.G.
Bachelor of Chemistry
S.F.G.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
Nanotechnology has become a revolutionary field, with applications ranging from biomedicine to catalysis and optics. Its importance increases exponentially each year due to the ability to manipulate materials at atomic and molecular scales, allowing for the development of devices and materials with novel, unique, and enhanced properties. In this context, clusters are also included, exhibiting exceptional physicochemical properties due to their small size, losing their metallic behavior and approaching molecular behavior. Until now, studies have mainly focused on the use of noble metal clusters such as silver, gold, or copper. However, these materials are more expensive, and therefore, the feasibility of using more economical transition metals has been considered. For this reason, this project has focused on the electrochemical synthesis and characterization of low atomicity iron clusters, as there is not much research on this metal under such low atomicity conditions and with little or no stabilization. By detailed study of the synthesis parameters, the goal is to control and optimize the synthesis of these clusters in order to evaluate their suitability for replacing noble metal clusters.
Nanotechnology has become a revolutionary field, with applications ranging from biomedicine to catalysis and optics. Its importance increases exponentially each year due to the ability to manipulate materials at atomic and molecular scales, allowing for the development of devices and materials with novel, unique, and enhanced properties. In this context, clusters are also included, exhibiting exceptional physicochemical properties due to their small size, losing their metallic behavior and approaching molecular behavior. Until now, studies have mainly focused on the use of noble metal clusters such as silver, gold, or copper. However, these materials are more expensive, and therefore, the feasibility of using more economical transition metals has been considered. For this reason, this project has focused on the electrochemical synthesis and characterization of low atomicity iron clusters, as there is not much research on this metal under such low atomicity conditions and with little or no stabilization. By detailed study of the synthesis parameters, the goal is to control and optimize the synthesis of these clusters in order to evaluate their suitability for replacing noble metal clusters.
Direction
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
BLANCO TRILLO, JOSE MANUEL (Co-tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
BLANCO TRILLO, JOSE MANUEL (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Polymetallic clusters from phosphine-thiosemicarbazone ligands.
Authorship
C.D.F.
Bachelor of Chemistry
C.D.F.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This Final Degree Thesis deals with the synthesis of Ag(I) and Cu(I) complexes from a series of phosphine-thiosemicarbazone HLPR (R= H, Me Et, Ph) ligands using two different synthetic methodologies; electrochemical synthesis and traditional chemical synthesis, in order to see the differences between the two methodologies and which of them allows me to obtain cluster-type species. The complexes obtained were characterized both in solid state; using techniques such as melting point determination, elemental analysis and infrared spectroscopy; as in solution, by mass spectrometry and 1H and 31P NMR. The results obtained show that both methodologies allow to obtain tetranuclear clusters in the case of Ag(I) for all the ligands tested. In the case of Cu(I) the electrochemical methodology affords (CuLPR)n polymers, whereas the chemical synthesis gives rise to [Cu(HLPR)Cl] monomeric species.
This Final Degree Thesis deals with the synthesis of Ag(I) and Cu(I) complexes from a series of phosphine-thiosemicarbazone HLPR (R= H, Me Et, Ph) ligands using two different synthetic methodologies; electrochemical synthesis and traditional chemical synthesis, in order to see the differences between the two methodologies and which of them allows me to obtain cluster-type species. The complexes obtained were characterized both in solid state; using techniques such as melting point determination, elemental analysis and infrared spectroscopy; as in solution, by mass spectrometry and 1H and 31P NMR. The results obtained show that both methodologies allow to obtain tetranuclear clusters in the case of Ag(I) for all the ligands tested. In the case of Cu(I) the electrochemical methodology affords (CuLPR)n polymers, whereas the chemical synthesis gives rise to [Cu(HLPR)Cl] monomeric species.
Direction
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
Fernández Fariña, Sandra (Co-tutorships)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
Fernández Fariña, Sandra (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Unravelling the formation of guanine in the ISM
Authorship
D.P.L.
Bachelor of Chemistry
D.P.L.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The chemical processes within the Interstellar Medium (ISM) are intricate and involve a diverse array of organic molecules, composed of carbon, nitrogen, and oxygen among other elements. These molecules are believed to play a crucial role in the formation of bio-molecules, such as guanine. Understanding the genesis of such prebiotic molecules in the ISM has been a subject of significant interest for over half a century. Here, we present an extensive computational investigation to elucidate the possible chemical pathways leading to the formation of guanine in the cold regions of the ISM. With this purpose, the AutoMeKin software was used in combination with MOPAC and Gaussian16, along with the semi-empirical PM7 method and Density Functional Theory (DFT) [MO8HX/6-31+G(d,p)], respectively. Our findings reveal that guanine can be synthesized via different barrierless free radical pathways. Moreover, we established a correlation between guanine and structural isomers of cytosine, indicating a common potential pathway for the formation of other substantial nucleobases. This study also highlights the effectiveness of AutoMeKin software in generating tautomers of molecules, showing a strong alignment with both experimental and theoretical data obtained in recent years.
The chemical processes within the Interstellar Medium (ISM) are intricate and involve a diverse array of organic molecules, composed of carbon, nitrogen, and oxygen among other elements. These molecules are believed to play a crucial role in the formation of bio-molecules, such as guanine. Understanding the genesis of such prebiotic molecules in the ISM has been a subject of significant interest for over half a century. Here, we present an extensive computational investigation to elucidate the possible chemical pathways leading to the formation of guanine in the cold regions of the ISM. With this purpose, the AutoMeKin software was used in combination with MOPAC and Gaussian16, along with the semi-empirical PM7 method and Density Functional Theory (DFT) [MO8HX/6-31+G(d,p)], respectively. Our findings reveal that guanine can be synthesized via different barrierless free radical pathways. Moreover, we established a correlation between guanine and structural isomers of cytosine, indicating a common potential pathway for the formation of other substantial nucleobases. This study also highlights the effectiveness of AutoMeKin software in generating tautomers of molecules, showing a strong alignment with both experimental and theoretical data obtained in recent years.
Direction
FERNANDEZ RAMOS, ANTONIO (Tutorships)
CASTIÑEIRA REIS, MARTA (Co-tutorships)
FERNANDEZ RAMOS, ANTONIO (Tutorships)
CASTIÑEIRA REIS, MARTA (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Study of a potential optical sensor for metallic nanomateriall
Authorship
M.R.Q.
Bachelor of Chemistry
M.R.Q.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Nanomaterials (NMs) are small materials, from 1 to 100 nm, that can be synthesized naturally, artificially or in a mixture of both types. Quantum Dots (QDs) are a class of semiconductor NMs, with optical and electronic properties wich are given by the quantum confinement thanks to the reducement of the particle size to the nanometric scale. In recent years, nanotechnology has undergone a great change, with NMs in general and QDs in particular appearing in many areas such as biomedicine, the pharmaceutical and textil industry, cosmetics, telecommunications, electronics, information technology and the environment. To detect the presence of these NMs, the objective is to design a sensor carrying a fluorophore that binds to metal ions of the NMs, modifying their optical properties linearly according to their concentration. This will allow them to evaluate their presence in different media, such as aqueous media or solid media. The study addresses the interaction of this fluorescent species with CuO NPs, ZnO and CdSe-Cys QDs. The preliminary results obtained suggest that the proposed sensor is viable through fluorescence methods, both for dissolution and for cellulose paper, since the binding of QDs to this decreases its intensity depending on the NM concentration we present. However, other study pathways are also proposed such as UV-Vis methods for dissolution or diffuse reflectance for paper.
Nanomaterials (NMs) are small materials, from 1 to 100 nm, that can be synthesized naturally, artificially or in a mixture of both types. Quantum Dots (QDs) are a class of semiconductor NMs, with optical and electronic properties wich are given by the quantum confinement thanks to the reducement of the particle size to the nanometric scale. In recent years, nanotechnology has undergone a great change, with NMs in general and QDs in particular appearing in many areas such as biomedicine, the pharmaceutical and textil industry, cosmetics, telecommunications, electronics, information technology and the environment. To detect the presence of these NMs, the objective is to design a sensor carrying a fluorophore that binds to metal ions of the NMs, modifying their optical properties linearly according to their concentration. This will allow them to evaluate their presence in different media, such as aqueous media or solid media. The study addresses the interaction of this fluorescent species with CuO NPs, ZnO and CdSe-Cys QDs. The preliminary results obtained suggest that the proposed sensor is viable through fluorescence methods, both for dissolution and for cellulose paper, since the binding of QDs to this decreases its intensity depending on the NM concentration we present. However, other study pathways are also proposed such as UV-Vis methods for dissolution or diffuse reflectance for paper.
Direction
Sanmartin Matalobos, Jesus (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
Sanmartin Matalobos, Jesus (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Synthesis of an iminophosphorane-thiosemicarbazone ligand derived from ortho-carborane
Authorship
V.F.F.
Bachelor of Chemistry
V.F.F.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This project is focused on the synthesis, characterisation and study of the coordination capacity of an iminophosphorane-thiosemicarbazone ligand derived from o-carborane. To obtain it, the precursors 3-amine-o-carborane and 2-(diphenylphosphanyl)-benzaldehyde, along with the iminophosphorane-thiosemicarbazone intermediate, were successfully synthesized and isolated by means of different experimental techniques. This type of thiosemicarbazone ligands functionalised with an iminophosphorane group has not been studied before, nor any thiosemicarbazone ligand functionalised with a carborane moiety, despite the interesting potential pharmacological applications. The ability of this new compound to behave as a ligand towards metal atoms has been studied through the synthesis of two metal complexes, one with nickel (II) and another one with palladium (II). Although this ligand is potentially tridentate due to the presence of three donor atoms (S, N, N), X-ray analysis of both complexes showed that the iminophosphorane nitrogen atom has less tendency to coordinate the metal, as the ligands behave as (S, N) chelating ligands forming square-planar complexes in both cases. However, the ligand shows an interesting coordinative versatility, giving a different coordination mode in both structures: the more common (S, N) five-membered chelate coordination for the nickel complex and the rare (S, N) four-membered chelate coordination for the palladium complex.
This project is focused on the synthesis, characterisation and study of the coordination capacity of an iminophosphorane-thiosemicarbazone ligand derived from o-carborane. To obtain it, the precursors 3-amine-o-carborane and 2-(diphenylphosphanyl)-benzaldehyde, along with the iminophosphorane-thiosemicarbazone intermediate, were successfully synthesized and isolated by means of different experimental techniques. This type of thiosemicarbazone ligands functionalised with an iminophosphorane group has not been studied before, nor any thiosemicarbazone ligand functionalised with a carborane moiety, despite the interesting potential pharmacological applications. The ability of this new compound to behave as a ligand towards metal atoms has been studied through the synthesis of two metal complexes, one with nickel (II) and another one with palladium (II). Although this ligand is potentially tridentate due to the presence of three donor atoms (S, N, N), X-ray analysis of both complexes showed that the iminophosphorane nitrogen atom has less tendency to coordinate the metal, as the ligands behave as (S, N) chelating ligands forming square-planar complexes in both cases. However, the ligand shows an interesting coordinative versatility, giving a different coordination mode in both structures: the more common (S, N) five-membered chelate coordination for the nickel complex and the rare (S, N) four-membered chelate coordination for the palladium complex.
Direction
SOUSA PEDRARES, ANTONIO (Tutorships)
SOUSA PEDRARES, ANTONIO (Tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Regioselectivity control of allyl-allyl borilative cross-coupling by synergistic Cu/Pd catalysis
Authorship
M.A.A.V.
Bachelor of Chemistry
M.A.A.V.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
1,5-dienes are a very abundant compound in nature and a versatile one synthetically. For this reason, the development of brand-new synthetic methodologies to access this structure is high regarded. In recent years, Fañanás Mastral’s investigation group developed a brand-new synthetic path via Cu/Pd cooperative catalysis to selectively obtain two of the four possible regioisomers in a borylative allyl-allyl cross coupling. Basing on those previous works, we have developed a different transformation which allows us to obtain an effective and selective way to synthesize a different regioisomer giving us a new route to develop borylative 1,5-dienes.
1,5-dienes are a very abundant compound in nature and a versatile one synthetically. For this reason, the development of brand-new synthetic methodologies to access this structure is high regarded. In recent years, Fañanás Mastral’s investigation group developed a brand-new synthetic path via Cu/Pd cooperative catalysis to selectively obtain two of the four possible regioisomers in a borylative allyl-allyl cross coupling. Basing on those previous works, we have developed a different transformation which allows us to obtain an effective and selective way to synthesize a different regioisomer giving us a new route to develop borylative 1,5-dienes.
Direction
FAÑANAS MASTRAL, MARTIN (Tutorships)
FAÑANAS MASTRAL, MARTIN (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Control of the nuclease activity of a peptide helicate through light
Authorship
F.C.M.
Bachelor of Chemistry
F.C.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The selective recognition of certain non-canonical forms of DNA is a challenge that can be addressed from a chemical biology point of view. In particular, the recognition of three-way DNA is especially interesting, since these are structures that are formed transiently during DNA replication, repair and recombination processes, with the therapeutic interest that this entails. In this Final Degree Project, two peptide helicates have been designed and synthesised whose affinity to three-way DNA can be modulated by means of light. For this purpose, a ligand has been synthesised using solid-phase peptide synthesis (SPPS) methodology, and subsequently coordinated to Fe(II) and Cu(II) metal ions to give the resulting metallopeptides. These have three distinct sections. Firstly, at their N-terminal end they possess 6 bipyridines, which coordinate the metal ions to form the helicates, whose selectivities towards three-way DNA have been previously demonstrated. In addition, at their C-terminus they are equipped with a chain of twelve glutamic acids whose function is to inhibit by charge repulsion this binding to DNA. Finally, a photolabile spacer linker has been incorporated between these two domains, so that when the metallopeptide is irradiated with light, the polyglutamic chain is detached from the system, allowing the helicates to recover their affinity towards the three-way DNA. Once the Cu(II) and Fe(II) peptide helicates have been characterised, their affinities to the three-way DNA have been studied by fluorescence spectroscopy.
The selective recognition of certain non-canonical forms of DNA is a challenge that can be addressed from a chemical biology point of view. In particular, the recognition of three-way DNA is especially interesting, since these are structures that are formed transiently during DNA replication, repair and recombination processes, with the therapeutic interest that this entails. In this Final Degree Project, two peptide helicates have been designed and synthesised whose affinity to three-way DNA can be modulated by means of light. For this purpose, a ligand has been synthesised using solid-phase peptide synthesis (SPPS) methodology, and subsequently coordinated to Fe(II) and Cu(II) metal ions to give the resulting metallopeptides. These have three distinct sections. Firstly, at their N-terminal end they possess 6 bipyridines, which coordinate the metal ions to form the helicates, whose selectivities towards three-way DNA have been previously demonstrated. In addition, at their C-terminus they are equipped with a chain of twelve glutamic acids whose function is to inhibit by charge repulsion this binding to DNA. Finally, a photolabile spacer linker has been incorporated between these two domains, so that when the metallopeptide is irradiated with light, the polyglutamic chain is detached from the system, allowing the helicates to recover their affinity towards the three-way DNA. Once the Cu(II) and Fe(II) peptide helicates have been characterised, their affinities to the three-way DNA have been studied by fluorescence spectroscopy.
Direction
VAZQUEZ LOPEZ, MIGUEL (Tutorships)
VAZQUEZ LOPEZ, MIGUEL (Tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Determination of duloxetine in plasma by Gas chromatography - Mass spectrometry
Authorship
M.G.B.
Bachelor of Chemistry
M.G.B.
Bachelor of Chemistry
Defense date
02.19.2024 09:00
02.19.2024 09:00
Summary
Duloxetine is an antidepressant drug that belongs to the class of serotonin and norepinephrine reuptake inhibitors (SNRIs). It is mainly used to treat depression, major anxiety disorder, chronic neuropathic pain and fibromyalgia. This drug can be toxic if taken in large amounts or in combination with other medications or substances that affect the central nervous system. In this work, a method for the determination and quantification of duloxetine in plasma was validated using gas chromatography-mass spectrometry (GC-MS). The extraction procedure carried out was the dispersive liquid-liquid microextraction (DLLME) technique and the reagents employed were acetonitrile as dispersant, and dichloromethane as extractant solvent. For analyte determination, codeine-D3 was used as an internal standard. Validation of the proposed method was carried out following the guidelines of Food and Drug Administration (FDA) and results showed linearity for the analyte in the concentration range of 0.1 to 0.3 ug/mL. The determined limit of detection (LOD) was 0.045 ug/mL and the lower limit of quantification (LLOQ) was set at 0.1 ug/mL for the compound. Regarding the extraction performance, values higher than 80% were obtained in all assays performed.
Duloxetine is an antidepressant drug that belongs to the class of serotonin and norepinephrine reuptake inhibitors (SNRIs). It is mainly used to treat depression, major anxiety disorder, chronic neuropathic pain and fibromyalgia. This drug can be toxic if taken in large amounts or in combination with other medications or substances that affect the central nervous system. In this work, a method for the determination and quantification of duloxetine in plasma was validated using gas chromatography-mass spectrometry (GC-MS). The extraction procedure carried out was the dispersive liquid-liquid microextraction (DLLME) technique and the reagents employed were acetonitrile as dispersant, and dichloromethane as extractant solvent. For analyte determination, codeine-D3 was used as an internal standard. Validation of the proposed method was carried out following the guidelines of Food and Drug Administration (FDA) and results showed linearity for the analyte in the concentration range of 0.1 to 0.3 ug/mL. The determined limit of detection (LOD) was 0.045 ug/mL and the lower limit of quantification (LLOQ) was set at 0.1 ug/mL for the compound. Regarding the extraction performance, values higher than 80% were obtained in all assays performed.
Direction
BARCIELA ALONSO, Ma CARMEN (Tutorships)
Álvarez Freire, Iván (Co-tutorships)
BARCIELA ALONSO, Ma CARMEN (Tutorships)
Álvarez Freire, Iván (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Characterization of 2-Naphthol as a Fluorescent Probe
Authorship
L.O.R.
Bachelor of Chemistry
L.O.R.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Proton transfer processes are of great importance as they are present in numerous reactions that occur in both chemical and biological media. Among proton transfer reactions, those that occur in the excited electronic state deserve special attention. A very useful strategy for investigating these types of processes is the use of fluorescent probes, which are highly sensitive to the environment. In this work, the fluorescent probe 2-naphthol, which is an aromatic alcohol, was characterized. Acid-base equilibria of 2-naphthol in its ground state in aqueous solution were studied using UV-Vis absorption techniques, and its behavior in the excited electronic state in different solvents and acidity conditions was studied using fluorescence spectroscopy. Additionally, characteristic properties of this molecule, such as its fluorescence quantum yield, fluorescence lifetimes, and its radiative and non-radiative deactivation constants, were also determined. From these studies, it can be stated that 2-naphthol tends to deprotonate in the excited state to give the naphtholate ion, thus making it a photoacid. A significant difference in the behavior of the probe in the solvents used was observed, with proton transfer reaction occurring only in aqueous medium and in ethanol/water mixtures at high mole fractions of water. Moreover, this proton transfer process was favored by using a buffer solution containing a phosphate group, due to its activity as a basic catalyst, and disfavored by increasing the acidity of the medium, since, in sufficiently acidic media, the reprotonation of the naphtholate ion occurs in the excited state.
Proton transfer processes are of great importance as they are present in numerous reactions that occur in both chemical and biological media. Among proton transfer reactions, those that occur in the excited electronic state deserve special attention. A very useful strategy for investigating these types of processes is the use of fluorescent probes, which are highly sensitive to the environment. In this work, the fluorescent probe 2-naphthol, which is an aromatic alcohol, was characterized. Acid-base equilibria of 2-naphthol in its ground state in aqueous solution were studied using UV-Vis absorption techniques, and its behavior in the excited electronic state in different solvents and acidity conditions was studied using fluorescence spectroscopy. Additionally, characteristic properties of this molecule, such as its fluorescence quantum yield, fluorescence lifetimes, and its radiative and non-radiative deactivation constants, were also determined. From these studies, it can be stated that 2-naphthol tends to deprotonate in the excited state to give the naphtholate ion, thus making it a photoacid. A significant difference in the behavior of the probe in the solvents used was observed, with proton transfer reaction occurring only in aqueous medium and in ethanol/water mixtures at high mole fractions of water. Moreover, this proton transfer process was favored by using a buffer solution containing a phosphate group, due to its activity as a basic catalyst, and disfavored by increasing the acidity of the medium, since, in sufficiently acidic media, the reprotonation of the naphtholate ion occurs in the excited state.
Direction
RIOS RODRIGUEZ, MARIA DEL CARMEN (Tutorships)
Rodríguez Prieto, María de la Flor (Co-tutorships)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Tutorships)
Rodríguez Prieto, María de la Flor (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Conformational study of terpenic alcohols
Authorship
I.A.M.
Bachelor of Chemistry
I.A.M.
Bachelor of Chemistry
Defense date
02.19.2024 09:00
02.19.2024 09:00
Summary
In this study, a conformational analysis of odorant molecules was conducted, specifically focusing on the terpenic alcohols geraniol, nerol, linalool, and farnesol. The conformational search for each odorant was performed using TorsiFlex, a program that combines both preconditioned and stochastic conformational search strategies. A low computational level was used during this search, and subsequently, the conformers found were reoptimized to a higher computational level. Partition function and Gibbs free energy were calculated for each system, and the relative contribution of each conformer was estimated. The preconditioned search strategy proved to be more efficient than the stochastic one. Its main advantage lies in the fact that the test geometries are based on torsional angles chosen through chemical intuition, the optimisation of which usually results in a conformer. However, the results obtained via stochastic search are relevant as well. This strategy creates structures with random torsional angles, which often do not correspond to any known conformer. However, it has proven to be effective when identifying conformers with unexpected torsional angles. These conformers are often the product of intramolecular forces and would have been impossible to locate via preconditioned search. In all four systems, it was established that the most stable conformer on the potential energy surface (PES) did not correspond to the most stable conformer in terms of Gibbs free energy. While the most stable conformer on the PES adopted a semi-extended conformation, the most stable one in terms of Gibbs free energy had a more extended configuration. This is because extended conformations exhibit lower vibrational frequencies, increasing the associated entropy. This research represents the first step toward the study of the interactions between these types of odorants and various olfactory receptors (OR), which depends on the specific conformation of each particular odorant.
In this study, a conformational analysis of odorant molecules was conducted, specifically focusing on the terpenic alcohols geraniol, nerol, linalool, and farnesol. The conformational search for each odorant was performed using TorsiFlex, a program that combines both preconditioned and stochastic conformational search strategies. A low computational level was used during this search, and subsequently, the conformers found were reoptimized to a higher computational level. Partition function and Gibbs free energy were calculated for each system, and the relative contribution of each conformer was estimated. The preconditioned search strategy proved to be more efficient than the stochastic one. Its main advantage lies in the fact that the test geometries are based on torsional angles chosen through chemical intuition, the optimisation of which usually results in a conformer. However, the results obtained via stochastic search are relevant as well. This strategy creates structures with random torsional angles, which often do not correspond to any known conformer. However, it has proven to be effective when identifying conformers with unexpected torsional angles. These conformers are often the product of intramolecular forces and would have been impossible to locate via preconditioned search. In all four systems, it was established that the most stable conformer on the potential energy surface (PES) did not correspond to the most stable conformer in terms of Gibbs free energy. While the most stable conformer on the PES adopted a semi-extended conformation, the most stable one in terms of Gibbs free energy had a more extended configuration. This is because extended conformations exhibit lower vibrational frequencies, increasing the associated entropy. This research represents the first step toward the study of the interactions between these types of odorants and various olfactory receptors (OR), which depends on the specific conformation of each particular odorant.
Direction
FERNANDEZ RAMOS, ANTONIO (Tutorships)
FERRO COSTAS, DAVID (Co-tutorships)
FERNANDEZ RAMOS, ANTONIO (Tutorships)
FERRO COSTAS, DAVID (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Asymmetric synthesis of helicenes and chiral nanographenes through cycloaddition reactions of arynes
Authorship
M.B.L.
Bachelor of Chemistry
M.B.L.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The asymmetric synthesis of helicenes and other chiral nanographenes constitutes a scientific challenge of high interest due to the unique optoelectronic properties of this type of compounds and their potential application in the development of chiroptical materials. In this context, the present work was aimed at the study of the synthesis of a chiral heptahelicene in an enantioselective manner, by [2+2+2] cycloaddition of an aryne derived from phenanthrene (3,4-didehydrophenanthrene, 3-phenanthryne) with an electron-deficient alkyne, employing a palladium catalyst provided with a chiral ligand. The hereby described study involved the optimization of the synthesis of 3-(trimethylsilyl)-4-phenanthrenyl triflate, the confirmation of the effectiveness of this compound as a precursor of 3-phenanthryne through a trapping reaction with furan, the synthesis of a stable alkyne-Pd(0) complex with the chiral bisphosphine (R)-BINAP and, finally, the preliminary study of the cocycloaddition of 3-phenanthryne with DMAD in the presence of this chiral complex as catalyst. Although the reaction did not give the expected result, since the formation of the heptahelicene was not detected, a detailed analysis of the reaction mixtures allowed us to extract valuable information about the reactivity of this aryne under the conditions designed to carry out the asymmetric catalysis.
The asymmetric synthesis of helicenes and other chiral nanographenes constitutes a scientific challenge of high interest due to the unique optoelectronic properties of this type of compounds and their potential application in the development of chiroptical materials. In this context, the present work was aimed at the study of the synthesis of a chiral heptahelicene in an enantioselective manner, by [2+2+2] cycloaddition of an aryne derived from phenanthrene (3,4-didehydrophenanthrene, 3-phenanthryne) with an electron-deficient alkyne, employing a palladium catalyst provided with a chiral ligand. The hereby described study involved the optimization of the synthesis of 3-(trimethylsilyl)-4-phenanthrenyl triflate, the confirmation of the effectiveness of this compound as a precursor of 3-phenanthryne through a trapping reaction with furan, the synthesis of a stable alkyne-Pd(0) complex with the chiral bisphosphine (R)-BINAP and, finally, the preliminary study of the cocycloaddition of 3-phenanthryne with DMAD in the presence of this chiral complex as catalyst. Although the reaction did not give the expected result, since the formation of the heptahelicene was not detected, a detailed analysis of the reaction mixtures allowed us to extract valuable information about the reactivity of this aryne under the conditions designed to carry out the asymmetric catalysis.
Direction
PEREZ MEIRAS, MARIA DOLORES (Tutorships)
PEREZ MEIRAS, MARIA DOLORES (Tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Inventing new chiral ligands for asymmetric catalysis with Rh or Ir metal complexes
Authorship
S.M.R.
Bachelor of Chemistry
S.M.R.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Cyclopentadienyl (Cp) ligands are highly relevant in the field of organometallic catalysis, such as in the development of C-H functionalization reactions. These reactions transform inert C-H bonds directly into specific functional groups using Group IX metals (Co, Rh, Ir) as catalysts. Unfortunately, the technologies for the synthetic preparation of these chiral Cp ligands are complex and not very versatile. As a result, the development of enantioselective C-H functionalization reactions with chiral CpM catalysts has been very limited. Recently, we have discovered a cobalt-catalyzed cycloaddition that allows for the construction of cyclopentadienyl ligands in a single step, with a wide variety of substituents that modulate their steric and electronic properties. Additionally, we have found that the derived Cp-rhodium complexes are highly catalytically active. Based on this, our goal will be to prepare a completely new chiral Cp ligand and test its respective metal complex in relevant asymmetric C-H functionalization reactions.
Cyclopentadienyl (Cp) ligands are highly relevant in the field of organometallic catalysis, such as in the development of C-H functionalization reactions. These reactions transform inert C-H bonds directly into specific functional groups using Group IX metals (Co, Rh, Ir) as catalysts. Unfortunately, the technologies for the synthetic preparation of these chiral Cp ligands are complex and not very versatile. As a result, the development of enantioselective C-H functionalization reactions with chiral CpM catalysts has been very limited. Recently, we have discovered a cobalt-catalyzed cycloaddition that allows for the construction of cyclopentadienyl ligands in a single step, with a wide variety of substituents that modulate their steric and electronic properties. Additionally, we have found that the derived Cp-rhodium complexes are highly catalytically active. Based on this, our goal will be to prepare a completely new chiral Cp ligand and test its respective metal complex in relevant asymmetric C-H functionalization reactions.
Direction
Mascareñas Cid, Jose Luis (Tutorships)
Mascareñas Cid, Jose Luis (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Ruthenium catalysis in Bioorthogonal Chemistry: Viability of new methods based on vinylidenic intermediates
Authorship
L.P.P.
Bachelor of Chemistry
L.P.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The development of new bioorthogonal and biocompatible reactions has meant a revolution in Synthetic Chemistry and Biological Chemistry, due to the potential they offer in areas such as biomedicine. In this sense, the use of transition metal complexes (such as Ru, Cu and Au) as catalysts in these reactions can constitute a powerful tool, given the mechanistic versatility they offer. Specifically, the introduction of reactive species such as metallic vinylidenes in Bioorthogonal Chemistry is of great interest for advances in this field. In this Degree Final Project, we present the optimization of the isomerization of ortho-alkynyl anilines to indoles for its transfer to biological media. This reaction takes place through ruthenium vinylidenes, and it allows the formation of highly biologically interesting molecules. Moreover, we have synthesized a ruthenium complex containing an azaryphos ligand, which is highly efficient in reactions whose mechanism involves ruthenium vinylidenes. This complex has been used to catalyse the formation of indoles, and it has allowed us to adapt it to aqueous media. Lastly, we have prepared a ruthenium complex which catalyses the formation of furans through ruthenium vinylidenes and allenylidenes. It has been possible to perform this reaction in aqueous media and at low temperatures (40 ºC), which opens a door for future investigations for its transfer to biological media.
The development of new bioorthogonal and biocompatible reactions has meant a revolution in Synthetic Chemistry and Biological Chemistry, due to the potential they offer in areas such as biomedicine. In this sense, the use of transition metal complexes (such as Ru, Cu and Au) as catalysts in these reactions can constitute a powerful tool, given the mechanistic versatility they offer. Specifically, the introduction of reactive species such as metallic vinylidenes in Bioorthogonal Chemistry is of great interest for advances in this field. In this Degree Final Project, we present the optimization of the isomerization of ortho-alkynyl anilines to indoles for its transfer to biological media. This reaction takes place through ruthenium vinylidenes, and it allows the formation of highly biologically interesting molecules. Moreover, we have synthesized a ruthenium complex containing an azaryphos ligand, which is highly efficient in reactions whose mechanism involves ruthenium vinylidenes. This complex has been used to catalyse the formation of indoles, and it has allowed us to adapt it to aqueous media. Lastly, we have prepared a ruthenium complex which catalyses the formation of furans through ruthenium vinylidenes and allenylidenes. It has been possible to perform this reaction in aqueous media and at low temperatures (40 ºC), which opens a door for future investigations for its transfer to biological media.
Direction
Mascareñas Cid, Jose Luis (Tutorships)
Mascareñas Cid, Jose Luis (Tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Study of the reactivity of an aryne derived from anthracene
Authorship
R.F.D.
Bachelor of Chemistry
R.F.D.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Graphene-based materials join a unique combination of physical and chemical properties which makes them suitable for being used as molecular materials. During the last years, a great work has been made on the field of synthetic chemistry, in order to prepare, starting from small molecular units, a great variety of those materials. The COMMO group (Guitián/Pérez/Peña) is known by the development of synthetic methodologies based on aryne chemistry, to prepare nanographenes through solution chemistry. On the present undergraduate project, it has been developed a synthetic route to prepare an aryne precursor derived from anthracene; and it has been studied its reactivity in [4+2] and [2+2+2] cycloaddition processes, which have led to the obtention, in a single step, of various nanographenes with complex structure and interesting properties.
Graphene-based materials join a unique combination of physical and chemical properties which makes them suitable for being used as molecular materials. During the last years, a great work has been made on the field of synthetic chemistry, in order to prepare, starting from small molecular units, a great variety of those materials. The COMMO group (Guitián/Pérez/Peña) is known by the development of synthetic methodologies based on aryne chemistry, to prepare nanographenes through solution chemistry. On the present undergraduate project, it has been developed a synthetic route to prepare an aryne precursor derived from anthracene; and it has been studied its reactivity in [4+2] and [2+2+2] cycloaddition processes, which have led to the obtention, in a single step, of various nanographenes with complex structure and interesting properties.
Direction
PEÑA GIL, DIEGO (Tutorships)
PEÑA GIL, DIEGO (Tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Study on the reactivity and applications of cyclometalated derivatives of iminophosphoranes
Authorship
L.C.M.
Bachelor of Chemistry
L.C.M.
Bachelor of Chemistry
Defense date
02.19.2024 10:00
02.19.2024 10:00
Summary
In recent years, the study of metallacycles has experienced a remarkable increase. Within the framework of these compounds, the iminophosphorane derivates, although not being the most studied, show a great margin of study and development mainly due to the wide variety of substituents that can present phosphazenes and the modify both their properties and those of the resulting complex. In this work, a bibliographic study of metalacycles derived from iminophosphoranes was carried out with emphasis mainly on the synthesis of the phosphazene ligand and the corresponding metalacycles, their properties such as luminescence, their applications in the field of medicine due to their anticancer properties, and their use as catalysts.
In recent years, the study of metallacycles has experienced a remarkable increase. Within the framework of these compounds, the iminophosphorane derivates, although not being the most studied, show a great margin of study and development mainly due to the wide variety of substituents that can present phosphazenes and the modify both their properties and those of the resulting complex. In this work, a bibliographic study of metalacycles derived from iminophosphoranes was carried out with emphasis mainly on the synthesis of the phosphazene ligand and the corresponding metalacycles, their properties such as luminescence, their applications in the field of medicine due to their anticancer properties, and their use as catalysts.
Direction
ORTIGUEIRA AMOR, JUAN MANUEL (Tutorships)
ORTIGUEIRA AMOR, JUAN MANUEL (Tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Optimization of work with static bars in a chipwood press company through the study of electrical conductivity
Authorship
P.G.P.
Bachelor of Chemistry
P.G.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The wooden board, due to its properties and versatility, is a solution for structural, technical and ornamental areas. To optimize its production and finishing touches, it is necessary to know the operating ranges of the static generators/bars for each group of supports and decorative papers. Therefore, a set of tests has been designed with different commonly used boards, varying their thickness, as well as different decorative designs, varying humidity load conditions, resins, weight and type of impregnation. Analyzing the pH, Gurley porosity and the ash test of the raw paper. And also the humidity, fluidity and B state of the impregnated paper. The objective is to define the working conditions for each group of raw materials and to know the limits to work with, using the equipment that provides the necessary voltage for a proper implementation in the production chain.
The wooden board, due to its properties and versatility, is a solution for structural, technical and ornamental areas. To optimize its production and finishing touches, it is necessary to know the operating ranges of the static generators/bars for each group of supports and decorative papers. Therefore, a set of tests has been designed with different commonly used boards, varying their thickness, as well as different decorative designs, varying humidity load conditions, resins, weight and type of impregnation. Analyzing the pH, Gurley porosity and the ash test of the raw paper. And also the humidity, fluidity and B state of the impregnated paper. The objective is to define the working conditions for each group of raw materials and to know the limits to work with, using the equipment that provides the necessary voltage for a proper implementation in the production chain.
Direction
LEIS FIDALGO, JOSE RAMON (Tutorships)
LEIS FIDALGO, JOSE RAMON (Tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Levels of additives from plastic material in bivalve mollusk samples collected from the Galician estuaries
Authorship
I.G.A.
Bachelor of Chemistry
I.G.A.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
The particles generated from tire wear (Tire Wear Particles, TWPs) due to friction between the tire and road surfaces, as well as particles produced from subsequent use of recycled rubber, contain a variety of additives used in tire rubber manufacturing. Numerous studies have linked the presence of some of these additives to health effects in humans, including endocrine disruption, and to adverse effects on various aquatic species, sometimes leading to mortality. Given this context, it is clear that there is a need to develop analytical methods for the identification and quantification of these additives, as well as their determination in different environments. The objective of this undergraduate thesis is to develop a method for determining five additives present in rubber particles within mussel samples. A preliminary literature review was conducted, and the MSPD (Matrix Solid Phase Dispersion) extraction technique was selected, followed by analysis using gas chromatography-mass spectrometry (GC-MS). Subsequently, an experimental design was carried out, and once the method was optimized and validated, it was applied to several mussel samples from the Galician estuaries, demonstrating its validity. This study is highly novel as it is the first time MSPD has been applied to the selected compounds. Furthermore, it is the first work to identify these additives in mollusks.
The particles generated from tire wear (Tire Wear Particles, TWPs) due to friction between the tire and road surfaces, as well as particles produced from subsequent use of recycled rubber, contain a variety of additives used in tire rubber manufacturing. Numerous studies have linked the presence of some of these additives to health effects in humans, including endocrine disruption, and to adverse effects on various aquatic species, sometimes leading to mortality. Given this context, it is clear that there is a need to develop analytical methods for the identification and quantification of these additives, as well as their determination in different environments. The objective of this undergraduate thesis is to develop a method for determining five additives present in rubber particles within mussel samples. A preliminary literature review was conducted, and the MSPD (Matrix Solid Phase Dispersion) extraction technique was selected, followed by analysis using gas chromatography-mass spectrometry (GC-MS). Subsequently, an experimental design was carried out, and once the method was optimized and validated, it was applied to several mussel samples from the Galician estuaries, demonstrating its validity. This study is highly novel as it is the first time MSPD has been applied to the selected compounds. Furthermore, it is the first work to identify these additives in mollusks.
Direction
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Analysis of the Effect of Denaturing Agents on Fluorescence for the Study of Protein Denaturation
Authorship
A.M.T.
Bachelor of Chemistry
A.M.T.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Guanidinium chloride (GdmCl), urea, and sodium dodecyl sulfate (SDS) are the most commonly used denaturing agents for monitoring protein denaturation using spectroscopic methods. However, there is no information on the fluorescence of these denaturing agents or how this might affect the monitoring of the loss of native protein structure. A study was therefore carried out to determine how the emission of GdmCl affects the monitoring of the denaturation of bovine serum albumin (BSA), one of the model proteins used in biochemical studies. In an initial test, the effect of GdmCl fluorescence was analyzed at a concentration of 7.52 uM BSA in PBS pH 7.4. However, the results showed no evidence that GdmCl influenced the observed fluorescence. Thus, it was decided to investigate its effect at a lower concentration of BSA (1.50 uM) in order to obtain a more significant difference. In addition, alternative guanidinium salts to GdmCl, urea, and SDS were proposed. The fluorescence of the Gdm+ ion was studied with the following counterions: bromide (GdmBr), acetate (GdmAcetate), iodide (GdmI), carbonate (GdmCarbonate), and bisguanidinium chloride (BiGdmCl), with GdmBr being identified as the most attractive alternative.
Guanidinium chloride (GdmCl), urea, and sodium dodecyl sulfate (SDS) are the most commonly used denaturing agents for monitoring protein denaturation using spectroscopic methods. However, there is no information on the fluorescence of these denaturing agents or how this might affect the monitoring of the loss of native protein structure. A study was therefore carried out to determine how the emission of GdmCl affects the monitoring of the denaturation of bovine serum albumin (BSA), one of the model proteins used in biochemical studies. In an initial test, the effect of GdmCl fluorescence was analyzed at a concentration of 7.52 uM BSA in PBS pH 7.4. However, the results showed no evidence that GdmCl influenced the observed fluorescence. Thus, it was decided to investigate its effect at a lower concentration of BSA (1.50 uM) in order to obtain a more significant difference. In addition, alternative guanidinium salts to GdmCl, urea, and SDS were proposed. The fluorescence of the Gdm+ ion was studied with the following counterions: bromide (GdmBr), acetate (GdmAcetate), iodide (GdmI), carbonate (GdmCarbonate), and bisguanidinium chloride (BiGdmCl), with GdmBr being identified as the most attractive alternative.
Direction
VAZQUEZ SENTIS, MARCO EUGENIO (Tutorships)
LOPEZ BLANCO, ROI (Co-tutorships)
VAZQUEZ SENTIS, MARCO EUGENIO (Tutorships)
LOPEZ BLANCO, ROI (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Synthesis and characterization of quantum dot-polymer imprinted composites for the fluorimetric screening of citrulline
Authorship
N.G.B.
Bachelor of Chemistry
N.G.B.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
Currently, it is of interest to develop a method that allows for the rapid and simple determination of citrulline levels in blood so that patients suffering from citrullinemias, who are treated with this amino acid, can adjust their administration doses. This thesis, presented as a Final Degree Project for the Degree in Chemistry at the USC, is based on the preparation of sensor phases that combine the fluorescent sensitivity of quantum dots with the high selectivity of molecularly imprinted polymers. So that Mn doped ZnS quantum dots are synthesized and subsequently functionalized with molecularly imprinted polymers selective for the analyte of interest: citrulline. For the synthesis of the quantum dots, the ultrasound-assisted method was used, while for the functionalization with the molecularly imprinted polymers, two alternatives were used: one using the ultrasound-assisted method and the other using incubation in a thermoregulated chamber. Once the synthesis was finished, the structure of the composites was characterized and the decrease in the fluorescence emission intensity (quenching) of the functionalized quantum dots due to the presence of citrulline or other amino acids was evaluated. Quenching was observed when working with methionine as an amino acid, which indicates that this may represent an interference for the prepared material.
Currently, it is of interest to develop a method that allows for the rapid and simple determination of citrulline levels in blood so that patients suffering from citrullinemias, who are treated with this amino acid, can adjust their administration doses. This thesis, presented as a Final Degree Project for the Degree in Chemistry at the USC, is based on the preparation of sensor phases that combine the fluorescent sensitivity of quantum dots with the high selectivity of molecularly imprinted polymers. So that Mn doped ZnS quantum dots are synthesized and subsequently functionalized with molecularly imprinted polymers selective for the analyte of interest: citrulline. For the synthesis of the quantum dots, the ultrasound-assisted method was used, while for the functionalization with the molecularly imprinted polymers, two alternatives were used: one using the ultrasound-assisted method and the other using incubation in a thermoregulated chamber. Once the synthesis was finished, the structure of the composites was characterized and the decrease in the fluorescence emission intensity (quenching) of the functionalized quantum dots due to the presence of citrulline or other amino acids was evaluated. Quenching was observed when working with methionine as an amino acid, which indicates that this may represent an interference for the prepared material.
Direction
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Impact of Calcium on Cancer Immune Evasion at the Cellular Membrane Level: Insights from Computational Chemistry
Authorship
M.V.F.
Bachelor of Chemistry
M.V.F.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This work investigates the interaction of antimicrobial peptides (AMPs) FK-16 with cell membranes under different calcium ion (Ca2+) concentrations, using molecular dynamics (MD) simulations. AMPs, known for their therapeutic potential as both antimicrobial and anticancer agents, interact with different cell membranes in ways that depend on the ionic environment. Under low Ca2+ concentration conditions, FK-16 peptides dispersed in solution show a strong interaction with all types of membranes, suggesting possible toxicity towards healthy cells. In contrast, at high Ca2+ concentrations, the peptides tend to form compact aggregates, reducing their interaction, particularly with healthy membranes and, therefore, their toxicity. This differential behavior highlights the importance of the ionic environment in the therapeutic activity of AMPs and indicates that high Ca2+ concentration in certain types of cancer might contribute to immune system evasion by cancer cells. The study suggests that manipulating ionic conditions could improve the selectivity and efficacy of AMPs, minimizing undesirable side effects. These results provide a basis for designing new peptide-based therapeutic strategies, optimizing their effectiveness and specificity in treating cancer and other diseases. The research was conducted using the GROMACS software and the CESGA supercomputing center to perform simulations of up to 10 microseconds, with qualitative and quantitative analyses using VMD and Python scripts.
This work investigates the interaction of antimicrobial peptides (AMPs) FK-16 with cell membranes under different calcium ion (Ca2+) concentrations, using molecular dynamics (MD) simulations. AMPs, known for their therapeutic potential as both antimicrobial and anticancer agents, interact with different cell membranes in ways that depend on the ionic environment. Under low Ca2+ concentration conditions, FK-16 peptides dispersed in solution show a strong interaction with all types of membranes, suggesting possible toxicity towards healthy cells. In contrast, at high Ca2+ concentrations, the peptides tend to form compact aggregates, reducing their interaction, particularly with healthy membranes and, therefore, their toxicity. This differential behavior highlights the importance of the ionic environment in the therapeutic activity of AMPs and indicates that high Ca2+ concentration in certain types of cancer might contribute to immune system evasion by cancer cells. The study suggests that manipulating ionic conditions could improve the selectivity and efficacy of AMPs, minimizing undesirable side effects. These results provide a basis for designing new peptide-based therapeutic strategies, optimizing their effectiveness and specificity in treating cancer and other diseases. The research was conducted using the GROMACS software and the CESGA supercomputing center to perform simulations of up to 10 microseconds, with qualitative and quantitative analyses using VMD and Python scripts.
Direction
GARCIA FANDIÑO, REBECA (Tutorships)
CONDE TORRES, DANIEL (Co-tutorships)
GARCIA FANDIÑO, REBECA (Tutorships)
CONDE TORRES, DANIEL (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
New sources of bioactive compounds from natural origin
Authorship
F.J.M.V.
Bachelor of Chemistry
F.J.M.V.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This work focuses on the extraction, characterization, and analysis of extracts rich in bioactive compounds from acorns (Quercus robur) and provides an insight into the total polyphenolic content throughout their maturation process. This study was carried out using a fast, simple, economically viable and environmentally friendly extraction technique matrix solid phase dispersion (MSPD) which combines mild process conditions with generally recognized as safe solvents (GRAS): water, ethanol, propylene glycol, ethyl lactate and acetone. This work consists of two parts. In a first approach, the individual bioactive profile of the different parts of the acorn is evaluated throughout the maturation process by quantifying the total polyphenolic index (TPI). In the second phase, a solvent study was carried out and the complete bioactive profile of the green acorn extracts was obtained, quantifying the IPT, the antioxidant activity by two different methods (DPPH and ABTS), as well as the determination of the mean inhibitory concentration (IC50) for the different extracts. In this way, the global response for ethyl lactate and acetone was better than for propylene glycol and ethanol in both assays, IPT and AA. In the individual characterization of the polyphenols by liquid chromatography coupled to tandem mass spectrometry (LCMS/MS), 15 compounds were detected, with ellagic acid, 1,2,3,6teragalloylglucose, catechin, gallic acid and 1,3,6trigalloylglucose being the main phenolic compounds identified.
This work focuses on the extraction, characterization, and analysis of extracts rich in bioactive compounds from acorns (Quercus robur) and provides an insight into the total polyphenolic content throughout their maturation process. This study was carried out using a fast, simple, economically viable and environmentally friendly extraction technique matrix solid phase dispersion (MSPD) which combines mild process conditions with generally recognized as safe solvents (GRAS): water, ethanol, propylene glycol, ethyl lactate and acetone. This work consists of two parts. In a first approach, the individual bioactive profile of the different parts of the acorn is evaluated throughout the maturation process by quantifying the total polyphenolic index (TPI). In the second phase, a solvent study was carried out and the complete bioactive profile of the green acorn extracts was obtained, quantifying the IPT, the antioxidant activity by two different methods (DPPH and ABTS), as well as the determination of the mean inhibitory concentration (IC50) for the different extracts. In this way, the global response for ethyl lactate and acetone was better than for propylene glycol and ethanol in both assays, IPT and AA. In the individual characterization of the polyphenols by liquid chromatography coupled to tandem mass spectrometry (LCMS/MS), 15 compounds were detected, with ellagic acid, 1,2,3,6teragalloylglucose, catechin, gallic acid and 1,3,6trigalloylglucose being the main phenolic compounds identified.
Direction
LORES AGUIN, MARTA (Tutorships)
VERDES GOMEZ, JUAN JOSE (Co-tutorships)
LORES AGUIN, MARTA (Tutorships)
VERDES GOMEZ, JUAN JOSE (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Topotactic Transformations in Transition Metal Oxides through Reversible Oxygen Insertion using Solid Electrolytes
Authorship
A.G.A.C.
Bachelor of Chemistry
A.G.A.C.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The study of the electrochemical modification of the structure of a ceramic material, such as the transition metal oxides investigated in this work, generates changes in the system's properties. In this work, we have fabricated thin films of (Ca,Sr)FeOx oxides where x takes values between 2.5-3.0, using the PLD technique. The films have been deposited under PO2 conditions such that the obtained phase has an oxygen content close to 2.5 and a brownmillerite-type structure. By depositing the films on a substrate that is an O2- ion conductor, the application of an electric field between the film and the substrate at a sufficiently high temperature to allow ionic mobility can direct a flow of O2- ions that are inserted into the film, causing its oxidation to x=3.0 and a structural change to a perovskite-type structure (MFeO3). This implies changes in the electrical conductivity of the system, transitioning from a state with greater insulating character (Brownmillerite) to a state with greater conductive character (Perovskite). Additionally, a noticeable color change occurs to the naked eye, as the conductive film is dark and shiny, while the insulating one is transparent with a slight yellowish tint. These color changes reflect variations in the band-gap associated with changes in the oxidation state. Furthermore, the study of changes in thermal properties was conducted using FDTR, observing a variation in thermal conductivity between the involved phases.
The study of the electrochemical modification of the structure of a ceramic material, such as the transition metal oxides investigated in this work, generates changes in the system's properties. In this work, we have fabricated thin films of (Ca,Sr)FeOx oxides where x takes values between 2.5-3.0, using the PLD technique. The films have been deposited under PO2 conditions such that the obtained phase has an oxygen content close to 2.5 and a brownmillerite-type structure. By depositing the films on a substrate that is an O2- ion conductor, the application of an electric field between the film and the substrate at a sufficiently high temperature to allow ionic mobility can direct a flow of O2- ions that are inserted into the film, causing its oxidation to x=3.0 and a structural change to a perovskite-type structure (MFeO3). This implies changes in the electrical conductivity of the system, transitioning from a state with greater insulating character (Brownmillerite) to a state with greater conductive character (Perovskite). Additionally, a noticeable color change occurs to the naked eye, as the conductive film is dark and shiny, while the insulating one is transparent with a slight yellowish tint. These color changes reflect variations in the band-gap associated with changes in the oxidation state. Furthermore, the study of changes in thermal properties was conducted using FDTR, observing a variation in thermal conductivity between the involved phases.
Direction
RIVADULLA FERNANDEZ, JOSE FRANCISCO (Tutorships)
RIVADULLA FERNANDEZ, JOSE FRANCISCO (Tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Photodegradation studies of new emerging pollutants from tyre microplastics.
Authorship
N.M.R.
Bachelor of Chemistry
N.M.R.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Tire rubber contains numerous chemical agents that give it the optimal properties for proper functioning. These agents are released into the environment through wear particles generated during traffic, as well as rubber granules used in artificial grass fields and playgrounds. Currently, the transformation product of 6PPD (6PPDq) has been linked to the death of various aquatic species, when it reaches aquatic ecosystems through road runoff. In this final degree project (TFG), the UV light-induced photodegradation of six chemical agents present in rubber is investigated, including compounds from the paraphenylenediamine family (6PPD, 6PPDq, IPPD, DPPD), a cross-linking agent (HMMM) and a vulcanizing agent (MBTZ). The behavior of these compounds exposed to UV light in water and in solid medium (microextraction fiber) is analyzed. The extraction of the compounds from water, prior to chromatographic analysis (GC-MS/MS), is carried out by solid phase microextraction, which is also investigated as a solid support to study the photodegradation of chemical agents. Kinetic studies show that photodegradation occurs in both media, at different rates depending on the analyte. The kinetic curves are plotted and the kinetic parameters are calculated. Subsequently, different real matrices doped with the analytes are irradiated, checking how photodegradation occurs in real samples and thus, being a process that can occur in the environment, as well as a viable alternative for water purification treatment.
Tire rubber contains numerous chemical agents that give it the optimal properties for proper functioning. These agents are released into the environment through wear particles generated during traffic, as well as rubber granules used in artificial grass fields and playgrounds. Currently, the transformation product of 6PPD (6PPDq) has been linked to the death of various aquatic species, when it reaches aquatic ecosystems through road runoff. In this final degree project (TFG), the UV light-induced photodegradation of six chemical agents present in rubber is investigated, including compounds from the paraphenylenediamine family (6PPD, 6PPDq, IPPD, DPPD), a cross-linking agent (HMMM) and a vulcanizing agent (MBTZ). The behavior of these compounds exposed to UV light in water and in solid medium (microextraction fiber) is analyzed. The extraction of the compounds from water, prior to chromatographic analysis (GC-MS/MS), is carried out by solid phase microextraction, which is also investigated as a solid support to study the photodegradation of chemical agents. Kinetic studies show that photodegradation occurs in both media, at different rates depending on the analyte. The kinetic curves are plotted and the kinetic parameters are calculated. Subsequently, different real matrices doped with the analytes are irradiated, checking how photodegradation occurs in real samples and thus, being a process that can occur in the environment, as well as a viable alternative for water purification treatment.
Direction
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Formulation of a CeO2 “ink” for 3D printing of high surface-volume ratio structures.
Authorship
C.C.P.
Bachelor of Chemistry
C.C.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Nowadays, photocatalysis is becoming increasingly important due to the current need of controlling environmental pollution and obtaining renewable energy sources as green hydrogen. This control can be achieved by using a semiconductor acting as a catalyst. Therefore, the design and synthesis of catalytic structures are gaining more relevance, for their subsequent applications as solutions to these environmental problems. The following work focuses on the formulation of a CeO2 “ink” for catalytic applications. 3D printing is used as a material processing method to this end, because it allows the designing of structures difficult to achieve with other methodologies. Additionally, high surface-volume ratio structures are obtained. Interest in high surface-volume ratio structures lies in the need for having the largest number of catalytic activity points on the materials surface. The results corroborate the possibility of producing CeO2 “inks” to generate porous structures though 3D printing.
Nowadays, photocatalysis is becoming increasingly important due to the current need of controlling environmental pollution and obtaining renewable energy sources as green hydrogen. This control can be achieved by using a semiconductor acting as a catalyst. Therefore, the design and synthesis of catalytic structures are gaining more relevance, for their subsequent applications as solutions to these environmental problems. The following work focuses on the formulation of a CeO2 “ink” for catalytic applications. 3D printing is used as a material processing method to this end, because it allows the designing of structures difficult to achieve with other methodologies. Additionally, high surface-volume ratio structures are obtained. Interest in high surface-volume ratio structures lies in the need for having the largest number of catalytic activity points on the materials surface. The results corroborate the possibility of producing CeO2 “inks” to generate porous structures though 3D printing.
Direction
GIL GONZALEZ, ALVARO (Tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Co-tutorships)
GIL GONZALEZ, ALVARO (Tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
wet: superhydrophobic surfaces
Authorship
J.M.G.
Bachelor of Chemistry
J.M.G.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
The study of physicochemical parameters related to surface phenomena dates back to the 1805s, when the scientist Thomas Young proposed what is now known as Young's equation, which will open the door to the concept of superhydrophobicity of surfaces. It will also be the starting point for later thermodynamic models such as the Wenzel model or the Cassie-Baxter model, which are still outstanding for their experimental efficiency today. On the other hand, microscopic observation and developments in the field of nanotechnology led to the discovery in nature of living organisms with superhydrophobic, i.e. water-repellent and self-cleaning surfaces. The best known natural structure with these properties is the lotus leaf. It was from the study of the particularities of this natural system that the scientist Wilhelm A. Barthlott enunciated what is known today as the Lotus Effect. Currently, scientific research is focused on trying to replicate this effect in order to synthesise what are known as ideal superhydrophobic surfaces and obtain materials (coatings, paints, fabrics, etc.) that are immune to the action of water. In the present work, a bibliographic study on the wettability properties of superhydrophobic surfaces was carried out, focusing mainly on the most relevant thermodynamic models that study them. We will also discuss some of the most common methods used in their synthesis as well as some of their applications in different fields.
The study of physicochemical parameters related to surface phenomena dates back to the 1805s, when the scientist Thomas Young proposed what is now known as Young's equation, which will open the door to the concept of superhydrophobicity of surfaces. It will also be the starting point for later thermodynamic models such as the Wenzel model or the Cassie-Baxter model, which are still outstanding for their experimental efficiency today. On the other hand, microscopic observation and developments in the field of nanotechnology led to the discovery in nature of living organisms with superhydrophobic, i.e. water-repellent and self-cleaning surfaces. The best known natural structure with these properties is the lotus leaf. It was from the study of the particularities of this natural system that the scientist Wilhelm A. Barthlott enunciated what is known today as the Lotus Effect. Currently, scientific research is focused on trying to replicate this effect in order to synthesise what are known as ideal superhydrophobic surfaces and obtain materials (coatings, paints, fabrics, etc.) that are immune to the action of water. In the present work, a bibliographic study on the wettability properties of superhydrophobic surfaces was carried out, focusing mainly on the most relevant thermodynamic models that study them. We will also discuss some of the most common methods used in their synthesis as well as some of their applications in different fields.
Direction
BUJAN NUÑEZ, MARIA CARMEN (Tutorships)
BUJAN NUÑEZ, MARIA CARMEN (Tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Study of interatomic potentials in Kr-He, Ne, Ar, Kr complexes. Analysis of results using Python programming
Authorship
M.R.I.
Bachelor of Chemistry
M.R.I.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
From an interatomic potential energy curve, numerous system properties can be determined, such as vibrational energy levels or bond force constants, making it highly desirable to obtain a representation of this curve using “ab initio” methos. Therefore, there is great interest in obtaining a representation of this curve, either throw experimental procedures or correlated “ab initio” methods. Focusing on the latter, it is necessary to conduct a study to determine the combination of method and basis set for these calculations, as they will determine the exactness of the model. Once selected, a potential curve will be obtained for the van der Waals dimers Kr-He, Kr-Ne, Kr-Ar and Kr-Kr, from interaction energy values at a certain distance, Using these values, the van der Waals radius or the minimum interaction energy can be calculated. It is concluded that the CCSD(T) method with the aug-cc-pV5Z basis set, including midbond functions, shows good agreement with the bibliographic data.
From an interatomic potential energy curve, numerous system properties can be determined, such as vibrational energy levels or bond force constants, making it highly desirable to obtain a representation of this curve using “ab initio” methos. Therefore, there is great interest in obtaining a representation of this curve, either throw experimental procedures or correlated “ab initio” methods. Focusing on the latter, it is necessary to conduct a study to determine the combination of method and basis set for these calculations, as they will determine the exactness of the model. Once selected, a potential curve will be obtained for the van der Waals dimers Kr-He, Kr-Ne, Kr-Ar and Kr-Kr, from interaction energy values at a certain distance, Using these values, the van der Waals radius or the minimum interaction energy can be calculated. It is concluded that the CCSD(T) method with the aug-cc-pV5Z basis set, including midbond functions, shows good agreement with the bibliographic data.
Direction
FERNANDEZ RODRIGUEZ, BERTA (Tutorships)
FERNANDEZ RODRIGUEZ, BERTA (Tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Kinetic and computational study of the decarboxylation reaction of N-Chloro-Alanine
Authorship
I.D.V.
Bachelor of Chemistry
I.D.V.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
An experimental and computational kinetic study of the N-Cl-alanine decarboxylation reaction has been carried out. Experimentally it has been proven that the reaction is first order with respect to the concentration of N-Cl-alanine and is independent of the pH in the range 9-11. According to the values of activation parameters and the reaction products, it has been concluded that a concerted decarboxylation mechanism follows, in which it’s produced an elimination of the chloride ion and CO2 and the formation of an imine. This imine is hydrolyzed an aqueous medium to give the corresponding carbonyl compound, in this case an acetaldehyde, and ammonia. In the computational study, the reactant structure and transition state are optimized for this reaction and the activation parameters for the reaction have been calculated.
An experimental and computational kinetic study of the N-Cl-alanine decarboxylation reaction has been carried out. Experimentally it has been proven that the reaction is first order with respect to the concentration of N-Cl-alanine and is independent of the pH in the range 9-11. According to the values of activation parameters and the reaction products, it has been concluded that a concerted decarboxylation mechanism follows, in which it’s produced an elimination of the chloride ion and CO2 and the formation of an imine. This imine is hydrolyzed an aqueous medium to give the corresponding carbonyl compound, in this case an acetaldehyde, and ammonia. In the computational study, the reactant structure and transition state are optimized for this reaction and the activation parameters for the reaction have been calculated.
Direction
RIOS RODRIGUEZ, ANA MARIA (Tutorships)
CRUGEIRAS MARTINEZ, JUAN (Co-tutorships)
RIOS RODRIGUEZ, ANA MARIA (Tutorships)
CRUGEIRAS MARTINEZ, JUAN (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Characterisation of Galician calcareous peatlands, habitats of priority interest of the European Union: Part A - Analysis of their edaphic properties.
Authorship
R.V.S.
Double bachelor degree in Chemistry and Biology
R.V.S.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 11:00
07.18.2024 11:00
Summary
The calcareous peatland habitats of Cladium mariscus and Carex davalliana (7210) have been recognised as a priority and are essential in the fight against climate change. For this reason, a correct characterisation of these peatlands is essential, which is why their characterisation has been carried out in three locations in Galicia (Begonte, Pantín and Eo). Calcareous peatlands are defined by an organic carbon content higher than 15% in thicknesses greater than 30 cm under hydromorphic conditions. In this work, the physicochemical properties and the total contents of the elements present in these soils were analysed, the analysis of the concentration of these elements was carried out by X-ray fluorescence analysis (XFR). The results obtained reflect distributions and patterns between properties and elements. A positive correlation was observed between pH value (determinant for peatland classification) and elements such as calcium or magnesium. Furthermore, significant differences were shown between the three locations. After analysing and taking into account the existing classification for the determination of peatlands, it could be concluded that only the one present in Pantín could be classified as habitat 7210.
The calcareous peatland habitats of Cladium mariscus and Carex davalliana (7210) have been recognised as a priority and are essential in the fight against climate change. For this reason, a correct characterisation of these peatlands is essential, which is why their characterisation has been carried out in three locations in Galicia (Begonte, Pantín and Eo). Calcareous peatlands are defined by an organic carbon content higher than 15% in thicknesses greater than 30 cm under hydromorphic conditions. In this work, the physicochemical properties and the total contents of the elements present in these soils were analysed, the analysis of the concentration of these elements was carried out by X-ray fluorescence analysis (XFR). The results obtained reflect distributions and patterns between properties and elements. A positive correlation was observed between pH value (determinant for peatland classification) and elements such as calcium or magnesium. Furthermore, significant differences were shown between the three locations. After analysing and taking into account the existing classification for the determination of peatlands, it could be concluded that only the one present in Pantín could be classified as habitat 7210.
Direction
PONTEVEDRA POMBAL, FRANCISCO XABIER (Tutorships)
GARCIA-RODEJA GAYOSO, EDUARDO (Co-tutorships)
PONTEVEDRA POMBAL, FRANCISCO XABIER (Tutorships)
GARCIA-RODEJA GAYOSO, EDUARDO (Co-tutorships)
Court
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Characterisation of the calcareous peatlands of Galicia, habitats of priority interest of the European Union: Study of elemental content in Galician peatland waters
Authorship
R.V.S.
Double bachelor degree in Chemistry and Biology
R.V.S.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The characterisation of calcareous peatlands is currently important as they have been recognised as essential habitats for climate change mitigation. Therefore, a correct characterisation of these habitats is of primary importance. The present work studies the elemental content (Al, As, Ba, Ca, Cd, Cr, Cs, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Rb, S, Sc, Se, Sr, Th, Ti, U, V, W, Zn and Zr) of calcareous peatland waters in Galicia in three areas within this habitat: Begonte, Pantín and the Eo river. The analysis of the concentration of these elements was carried out by ICP-MS and ICP-OES after pre-treating the sample. In addition, the analytical characteristics of the methods used were studied; therefore precision, accuracy and repeatability were evaluated. The results obtained showed a clear dependence of the pH value on the elements Ca, K, Mg and Na; these elements being higher with higher pH levels. Significant differences in the concentration of the elements were demonstrated between the zones.
The characterisation of calcareous peatlands is currently important as they have been recognised as essential habitats for climate change mitigation. Therefore, a correct characterisation of these habitats is of primary importance. The present work studies the elemental content (Al, As, Ba, Ca, Cd, Cr, Cs, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Rb, S, Sc, Se, Sr, Th, Ti, U, V, W, Zn and Zr) of calcareous peatland waters in Galicia in three areas within this habitat: Begonte, Pantín and the Eo river. The analysis of the concentration of these elements was carried out by ICP-MS and ICP-OES after pre-treating the sample. In addition, the analytical characteristics of the methods used were studied; therefore precision, accuracy and repeatability were evaluated. The results obtained showed a clear dependence of the pH value on the elements Ca, K, Mg and Na; these elements being higher with higher pH levels. Significant differences in the concentration of the elements were demonstrated between the zones.
Direction
BARCIELA ALONSO, Ma CARMEN (Tutorships)
PEÑA VAZQUEZ, ELENA MARIA (Co-tutorships)
BARCIELA ALONSO, Ma CARMEN (Tutorships)
PEÑA VAZQUEZ, ELENA MARIA (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
In-vitro metabolism study of rubber production-related substances. Part B
Authorship
B.A.L.
Double bachelor degree in Chemistry and Biology
B.A.L.
Double bachelor degree in Chemistry and Biology
Defense date
07.17.2024 10:00
07.17.2024 10:00
Summary
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone is an oxidation product of the tire anti-degradant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and it is of great concern due to its presence in the vast majority of environmental matrix and having been recently detected in human samples. Although this compound has shown to be lethal to coho salmon, little is known about its effect on human health. The exposure level and its potential risk can be evaluated through biomonitoring, using urine as an appropriate matrix. This requires previous knowledge on the compounds that are excreted after exposure to this substance. In this study, Phase I and Phase II in-vitro metabolism assays are carried out to identify the potential metabolites, employing human liver microsomes for Phase I and glucuronidation reactions, and human liver cytosolic fractions in sulfation experiments, with the corresponding coenzyme in each case. Subsequently, potential metabolites are identified through Suspect Screening using Liquid Chromatography coupled to Tandem Mass Spectrometry. This workflow allows for the identification of 4 metabolites of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone and, after the study of their incubation trends, a possible biotransformation pathway is proposed. The generated metabolites could be suitable biomarkers in future human biomonitoring studies.
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone is an oxidation product of the tire anti-degradant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and it is of great concern due to its presence in the vast majority of environmental matrix and having been recently detected in human samples. Although this compound has shown to be lethal to coho salmon, little is known about its effect on human health. The exposure level and its potential risk can be evaluated through biomonitoring, using urine as an appropriate matrix. This requires previous knowledge on the compounds that are excreted after exposure to this substance. In this study, Phase I and Phase II in-vitro metabolism assays are carried out to identify the potential metabolites, employing human liver microsomes for Phase I and glucuronidation reactions, and human liver cytosolic fractions in sulfation experiments, with the corresponding coenzyme in each case. Subsequently, potential metabolites are identified through Suspect Screening using Liquid Chromatography coupled to Tandem Mass Spectrometry. This workflow allows for the identification of 4 metabolites of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone and, after the study of their incubation trends, a possible biotransformation pathway is proposed. The generated metabolites could be suitable biomarkers in future human biomonitoring studies.
Direction
MONTES GOYANES, ROSA MARIA (Tutorships)
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Co-tutorships)
MONTES GOYANES, ROSA MARIA (Tutorships)
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Co-tutorships)
Court
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
In-vitro metabolism study of rubber production-related substances. Part A
Authorship
B.A.L.
Double bachelor degree in Chemistry and Biology
B.A.L.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The tire anti-degradant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and its oxidation product N-(1,3-dimethylbutyl)-N'-phenyl-p-phenyl-enediamine-quinone (6PPDQ) are of great concern since they are present in the vast majority of environmental matrices and have also been recently detected in human samples. Even though 6PPDQ has shown to cause lethality in coho salmon, little is known about the effect of these compounds on human health. The level of exposure and their potential risk can be evaluated through human biomonitoring (HBM), being urine an appropriate matrix. This requires previous knowledge on the compounds that are excreted after the exposition to 6PPD and 6PPDQ. In this study, in-vitro Phase I and Phase II metabolism assays are carried out to identify their metabolites. Human liver microsomes (HLMs) are employed for Phase I and glucuronidation reactions, using the corresponding coenzyme. Human liver cytosolic fractions (HLCYTs) are employed in sulfation experiments. Potential metabolites of both substances are obtained and analysed, owing to previously created suspect lists, through screening by Liquid Chromatography Tandem Mass Spectrometry (LC-MS/MS). Both positive and negative ionization are applied in Data-dependent acquisition mode (DDA). The interpretation of the MS/MS spectra of these substances allows for the elucidation of seven compounds derived from 6PPD and four 6PPDQ metabolites. The analysis is completed by the study of their incubation trends. Biotransformation pathways starting from their parent compounds are proposed in both cases. These generated metabolites could be suitable biomarkers in future HBM studies.
The tire anti-degradant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and its oxidation product N-(1,3-dimethylbutyl)-N'-phenyl-p-phenyl-enediamine-quinone (6PPDQ) are of great concern since they are present in the vast majority of environmental matrices and have also been recently detected in human samples. Even though 6PPDQ has shown to cause lethality in coho salmon, little is known about the effect of these compounds on human health. The level of exposure and their potential risk can be evaluated through human biomonitoring (HBM), being urine an appropriate matrix. This requires previous knowledge on the compounds that are excreted after the exposition to 6PPD and 6PPDQ. In this study, in-vitro Phase I and Phase II metabolism assays are carried out to identify their metabolites. Human liver microsomes (HLMs) are employed for Phase I and glucuronidation reactions, using the corresponding coenzyme. Human liver cytosolic fractions (HLCYTs) are employed in sulfation experiments. Potential metabolites of both substances are obtained and analysed, owing to previously created suspect lists, through screening by Liquid Chromatography Tandem Mass Spectrometry (LC-MS/MS). Both positive and negative ionization are applied in Data-dependent acquisition mode (DDA). The interpretation of the MS/MS spectra of these substances allows for the elucidation of seven compounds derived from 6PPD and four 6PPDQ metabolites. The analysis is completed by the study of their incubation trends. Biotransformation pathways starting from their parent compounds are proposed in both cases. These generated metabolites could be suitable biomarkers in future HBM studies.
Direction
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Tutorships)
MONTES GOYANES, ROSA MARIA (Co-tutorships)
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Tutorships)
MONTES GOYANES, ROSA MARIA (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
COTynes in Synthesis of Three-Dimensional Polycyclic Hydrocarbons
Authorship
A.C.A.H.
Bachelor of Chemistry
A.C.A.H.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
As a result of their improved electronic properties, non-planar PAHs have attracted huge attention lately. By the introduction of non-planar eight-membered rings into the planar framework, desired curvature in these systems will be achieved. Just as the metal-catalyzed cyclotrimerization of arynes is developed and widely used methodology in the synthesis of planar PAHs, the cyclotrimerizarion of non-planar eight membered rings has scarcely been studied. This TFG proyect addresses the study of cyclotrimerization of symmetrical benzo-fused COTynes in order to obtain three-dimensional PAHs with the incorporation of eight-membered rings. The influence of aromatic and non-aromatic nuclei on the physical properties of new PAHs will be analyzed. In addition, preliminary studies of functionalization, halogenation and coordination with metal ions, will be also carried out.
As a result of their improved electronic properties, non-planar PAHs have attracted huge attention lately. By the introduction of non-planar eight-membered rings into the planar framework, desired curvature in these systems will be achieved. Just as the metal-catalyzed cyclotrimerization of arynes is developed and widely used methodology in the synthesis of planar PAHs, the cyclotrimerizarion of non-planar eight membered rings has scarcely been studied. This TFG proyect addresses the study of cyclotrimerization of symmetrical benzo-fused COTynes in order to obtain three-dimensional PAHs with the incorporation of eight-membered rings. The influence of aromatic and non-aromatic nuclei on the physical properties of new PAHs will be analyzed. In addition, preliminary studies of functionalization, halogenation and coordination with metal ions, will be also carried out.
Direction
SAA RODRIGUEZ, CARLOS EUGENIO (Tutorships)
VARELA CARRETE, JESUS ANGEL (Co-tutorships)
SAA RODRIGUEZ, CARLOS EUGENIO (Tutorships)
VARELA CARRETE, JESUS ANGEL (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Preparation of ruthenium-palladium complexes with phosphine-derived thiosemicarbazones
Authorship
E.L.P.
Bachelor of Chemistry
E.L.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
In this Final Degree Project, the preparation of Pd(II), Ru(II) and Ru(III) complexes with two tridentate phosphine-thiosemicarbazone HLPn ligands and with a [NPS] donor system was addressed. Thus, [Pd(LPn)Cl] monomers were obtained for the two ligands in the case of Pd(II), which was confirmed by all characterisation techniques, including the structures of the [Pd(LPn)Cl] planar-square complexes. In the case of Ru(II) and Ru(III) the different characterisation techniques employed point to coordination between the metal ions and the ligand, although regardless of the metal: ligand stoichiometry employed (1:1 or 1:2) the reactions lead to a mixture of complexes. Nevertheless, the crystal structure of one of the species, the mixed-valence complex [RuII RuIII(LP1)2(DMSO)Cl3] was obtained.
In this Final Degree Project, the preparation of Pd(II), Ru(II) and Ru(III) complexes with two tridentate phosphine-thiosemicarbazone HLPn ligands and with a [NPS] donor system was addressed. Thus, [Pd(LPn)Cl] monomers were obtained for the two ligands in the case of Pd(II), which was confirmed by all characterisation techniques, including the structures of the [Pd(LPn)Cl] planar-square complexes. In the case of Ru(II) and Ru(III) the different characterisation techniques employed point to coordination between the metal ions and the ligand, although regardless of the metal: ligand stoichiometry employed (1:1 or 1:2) the reactions lead to a mixture of complexes. Nevertheless, the crystal structure of one of the species, the mixed-valence complex [RuII RuIII(LP1)2(DMSO)Cl3] was obtained.
Direction
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Improvement of metals recovery from lithium batteries.
Authorship
A.R.S.
Bachelor of Chemistry
A.R.S.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This bachelor’s final project deals with the development of a method for improving the extraction of metals from lithium batteries. Nowadays, the main methods for batteries recycling imply hydrometallurgical and pyrometallurgical processes which require large amounts of acid and base. In addition, they are not suitable for lithium which is inevitably lost and generate many byproducts and wastewater. Therefore, research on recycling the compounds inside batteries has become an important challenge. The goal was focused on the extraction of lithium (and other coextracted elements) using ionic liquids, which provide a “greener” liquid-liquid and solid-liquid extraction since they are not toxic and can be used several times; and by using organic acids, also less pollutants and toxic than mineral acids. To achieve this objective, an initial dismantling step of lithium batteries was conducted, followed by analysis of the main elements contained in the cathode by ICP-OES. Finally, a comparison of the extraction yields after using several ionic liquids and organic acids was stablished.
This bachelor’s final project deals with the development of a method for improving the extraction of metals from lithium batteries. Nowadays, the main methods for batteries recycling imply hydrometallurgical and pyrometallurgical processes which require large amounts of acid and base. In addition, they are not suitable for lithium which is inevitably lost and generate many byproducts and wastewater. Therefore, research on recycling the compounds inside batteries has become an important challenge. The goal was focused on the extraction of lithium (and other coextracted elements) using ionic liquids, which provide a “greener” liquid-liquid and solid-liquid extraction since they are not toxic and can be used several times; and by using organic acids, also less pollutants and toxic than mineral acids. To achieve this objective, an initial dismantling step of lithium batteries was conducted, followed by analysis of the main elements contained in the cathode by ICP-OES. Finally, a comparison of the extraction yields after using several ionic liquids and organic acids was stablished.
Direction
MOREDA PIÑEIRO, ANTONIO (Tutorships)
HERBELLO HERMELO, PALOMA (Co-tutorships)
MOREDA PIÑEIRO, ANTONIO (Tutorships)
HERBELLO HERMELO, PALOMA (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Estimation of drugs of abuse consumption through wastewater analysis.
Authorship
V.B.C.
Bachelor of Chemistry
V.B.C.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The abuse of drugs impacts the economic and social development of a population. Therefore, it is necessary to monitor the use of these substances in order to develop of awareness-raising and prevention policies. Wastewater-Based Epidemiology (WBE) is one of the strategies employed to provide data on the consumption of a population in real time, allowing the identification of consumption trends over time and geographical distribution. In this study, the consumption of nicotine, cocaine, cannabis, amphetamine, methamphetamine and MDMA was analyzed through the determination of their biomarkers in the wastewater of three Spanish cities in Galicia and Euskadi. Composite samples of 24 h were collected over one week, in both spring and autumn seasons. Two analytical methodologies were employed: enzymatic deconjugation for nicotine metabolites and Solid-Phase Extraction for the remainder of the drugs, both followed by liquid chromatography coupled to tandem mass spectrometry analysis. The two methods were validated by assessing accuracy, precision and limits of detection and quantification. Comparing the consumption estimation of the different localities studied, it was observed that cannabis is the most used illicit drug. Furthermore, with the exception of nicotine and methamphetamine, there is a weekly pattern with higher consumption on weekends due to possible recreational use. It was also found that consumption is lower in Galicia than in Euskadi, especially in the case of amphetamine.
The abuse of drugs impacts the economic and social development of a population. Therefore, it is necessary to monitor the use of these substances in order to develop of awareness-raising and prevention policies. Wastewater-Based Epidemiology (WBE) is one of the strategies employed to provide data on the consumption of a population in real time, allowing the identification of consumption trends over time and geographical distribution. In this study, the consumption of nicotine, cocaine, cannabis, amphetamine, methamphetamine and MDMA was analyzed through the determination of their biomarkers in the wastewater of three Spanish cities in Galicia and Euskadi. Composite samples of 24 h were collected over one week, in both spring and autumn seasons. Two analytical methodologies were employed: enzymatic deconjugation for nicotine metabolites and Solid-Phase Extraction for the remainder of the drugs, both followed by liquid chromatography coupled to tandem mass spectrometry analysis. The two methods were validated by assessing accuracy, precision and limits of detection and quantification. Comparing the consumption estimation of the different localities studied, it was observed that cannabis is the most used illicit drug. Furthermore, with the exception of nicotine and methamphetamine, there is a weekly pattern with higher consumption on weekends due to possible recreational use. It was also found that consumption is lower in Galicia than in Euskadi, especially in the case of amphetamine.
Direction
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Tutorships)
GONZALEZ GOMEZ, XIANA (Co-tutorships)
RODIL RODRIGUEZ, MARIA DEL ROSARIO (Tutorships)
GONZALEZ GOMEZ, XIANA (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Influence of bulky groups in the ligand on the formation of helicoidal complexes
Authorship
R.S.C.
Bachelor of Chemistry
R.S.C.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This Final Degree Project is framed within the research field “Supramolecular Chemistry” of the group Química Bioinrgánica y Supramolecular (SUPRABIOIN), and its goal is the study of the influence of small modifications in the structure of the ligand over the final architecture of the metallosupramolecular derived species. In order to achieve this, two potential dianionic and tetradentated Schiff base ligands H2Ln (n= 1 and 2) were synthesized, which are functionalized with bulky groups on the side branches (H2L1 and H2L2) and on the spacer (H2L2). Once both of them were fully characterized by the usual techniques, an electrochemical synthesis methodology was carried out as a way to obtain the cobalt, nickel, copper and zinc neutral derived complexes. The complexes were also characterized with the purpose of knowing both their stoichiometry and their final architecture in those cases where it was possible.
This Final Degree Project is framed within the research field “Supramolecular Chemistry” of the group Química Bioinrgánica y Supramolecular (SUPRABIOIN), and its goal is the study of the influence of small modifications in the structure of the ligand over the final architecture of the metallosupramolecular derived species. In order to achieve this, two potential dianionic and tetradentated Schiff base ligands H2Ln (n= 1 and 2) were synthesized, which are functionalized with bulky groups on the side branches (H2L1 and H2L2) and on the spacer (H2L2). Once both of them were fully characterized by the usual techniques, an electrochemical synthesis methodology was carried out as a way to obtain the cobalt, nickel, copper and zinc neutral derived complexes. The complexes were also characterized with the purpose of knowing both their stoichiometry and their final architecture in those cases where it was possible.
Direction
GONZALEZ NOYA, ANA MARIA (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
GONZALEZ NOYA, ANA MARIA (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Initiation of the synthesis of vitamin D analogues functionalized in the side chain with an ortho-carborane unit
Authorship
A.T.T.
Bachelor of Chemistry
A.T.T.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
Due to the properties and functions of vitamin D3 and its metabolites in the organism, the synthesis of derivatives functionalized in the side chain with different carborane units was proposed in these laboratories. Biological assays demonstrated that the corresponding carboranium analogues are as active as the native hormone 1,25D3, but less calcemic. The objective of this project is the synthesis of ester 7 as a precursor of hydroxy-carborane analogues. Ester 7 was obtained from Inhoffen-Lythgoe diol (8) (48% overall yield, 5 steps, Scheme 1).
Due to the properties and functions of vitamin D3 and its metabolites in the organism, the synthesis of derivatives functionalized in the side chain with different carborane units was proposed in these laboratories. Biological assays demonstrated that the corresponding carboranium analogues are as active as the native hormone 1,25D3, but less calcemic. The objective of this project is the synthesis of ester 7 as a precursor of hydroxy-carborane analogues. Ester 7 was obtained from Inhoffen-Lythgoe diol (8) (48% overall yield, 5 steps, Scheme 1).
Direction
PAZ CASTAÑAL, MANUEL MARIA (Tutorships)
PAZ CASTAÑAL, MANUEL MARIA (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Automated determination of pH and alkalinity in discrete samples of seawater from the coastal radial of the IEO of A Coruña: fine-tuning of the equipment and comparison with traditional manual systems
Authorship
A.V.M.
Bachelor of Chemistry
A.V.M.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
The study of the ocean's carbon cycle is of paramount importance, given that the ocean serves as a significant reservoir for both organic and inorganic carbon. In the post-industrial era, it is estimated that the ocean absorbs approximately 30% of the CO2 emitted to the atmosphere from anthropogenic sources, resulting in the general and continuous acidification of the ocean. It is therefore of great importance to control the basic variables of the CO2 system in the ocean, which are dissolved inorganic carbon, pH, total alkalinity and partial pressure of carbon dioxide. This Final Degree Project compares automatic and manual systems for measuring two key variables in the study and control of ocean acidification: pH and total alkalinity. The comparison is based on samples collected in a time series of the coastal ocean in the A Coruña estuary. The aim is to increase the capacity for analysing these variables and reduce human error.
The study of the ocean's carbon cycle is of paramount importance, given that the ocean serves as a significant reservoir for both organic and inorganic carbon. In the post-industrial era, it is estimated that the ocean absorbs approximately 30% of the CO2 emitted to the atmosphere from anthropogenic sources, resulting in the general and continuous acidification of the ocean. It is therefore of great importance to control the basic variables of the CO2 system in the ocean, which are dissolved inorganic carbon, pH, total alkalinity and partial pressure of carbon dioxide. This Final Degree Project compares automatic and manual systems for measuring two key variables in the study and control of ocean acidification: pH and total alkalinity. The comparison is based on samples collected in a time series of the coastal ocean in the A Coruña estuary. The aim is to increase the capacity for analysing these variables and reduce human error.
Direction
YEBRA BIURRUN, MARIA DEL CARMEN (Tutorships)
Álvarez Rodríguez, Marta (Co-tutorships)
YEBRA BIURRUN, MARIA DEL CARMEN (Tutorships)
Álvarez Rodríguez, Marta (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Interaction study between pesticides and the environment in the field of viticulture
Authorship
L.D.L.C.
Bachelor of Chemistry
L.D.L.C.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
In the current context of viticulture, the use of pesticides is a common practice to control pests and diseases that can affect grape production. Therefore, it is crucial to understand the interaction of these pesticides with the environment to ensure the long-term sustainability of the viticulture sector, as well as to protect the health of consumers exposed to these compounds through consumption of products obtained in the winemaking process, particularly wine. This study focuses on investigating the evolution of various families of fungicides in the soil-grape-wine system through two trials conducted on two plots with different soil and climatic characteristics, also employing two different grape varieties, as to better understand how these factors affect the persistence of pesticides in the soil and in products derived from this sector (grapes, wine, and pomace).
In the current context of viticulture, the use of pesticides is a common practice to control pests and diseases that can affect grape production. Therefore, it is crucial to understand the interaction of these pesticides with the environment to ensure the long-term sustainability of the viticulture sector, as well as to protect the health of consumers exposed to these compounds through consumption of products obtained in the winemaking process, particularly wine. This study focuses on investigating the evolution of various families of fungicides in the soil-grape-wine system through two trials conducted on two plots with different soil and climatic characteristics, also employing two different grape varieties, as to better understand how these factors affect the persistence of pesticides in the soil and in products derived from this sector (grapes, wine, and pomace).
Direction
RODRIGUEZ PEREIRO, ISAAC (Tutorships)
RODRIGUEZ PEREIRO, ISAAC (Tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Heavy metal mobility and bioavailability on mine soil: changes induced by the use of phytotechnologies for its environmental rehabilitation.
Authorship
L.D.C.
Double bachelor degree in Chemistry and Biology
L.D.C.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 11:00
07.18.2024 11:00
Summary
Mining is an anthropogenic activity that impacts soil, mainly due to the accumulation of heavy metals that stunts plant development. The risk associated with this contamination is determined by metal speciation which is directly related to its potential mobility and bioavailability. Several rehabilitation techniques can be used to improve the condition of mine soil. One of them is phytotechnologies where plant species and edaphic amendments such as organic compost are used to modify soil metal mobility and bioavailability. This project aimed to study the possible effects of rehabilitation treatments in the mobility and bioavailability of metals in a Pb/Zn mine. To achieve this, a fractionation analysis of Fe, Mn, Zn, Pb and Cd was performed in order to evaluate the dominant metal species in the soil and its potential mobility/bioavailability. The results were used to make correlations between different treatments and metal mobility. It was found that the addition of compost to the soil resulted in a reduction in mobility and bioavailability of metals. The opposite effect (higher mobility) was detected with the establishment and growth of short cycle plant species.
Mining is an anthropogenic activity that impacts soil, mainly due to the accumulation of heavy metals that stunts plant development. The risk associated with this contamination is determined by metal speciation which is directly related to its potential mobility and bioavailability. Several rehabilitation techniques can be used to improve the condition of mine soil. One of them is phytotechnologies where plant species and edaphic amendments such as organic compost are used to modify soil metal mobility and bioavailability. This project aimed to study the possible effects of rehabilitation treatments in the mobility and bioavailability of metals in a Pb/Zn mine. To achieve this, a fractionation analysis of Fe, Mn, Zn, Pb and Cd was performed in order to evaluate the dominant metal species in the soil and its potential mobility/bioavailability. The results were used to make correlations between different treatments and metal mobility. It was found that the addition of compost to the soil resulted in a reduction in mobility and bioavailability of metals. The opposite effect (higher mobility) was detected with the establishment and growth of short cycle plant species.
Direction
MONTERROSO MARTINEZ, MARIA DEL CARMEN (Tutorships)
MONTERROSO MARTINEZ, MARIA DEL CARMEN (Tutorships)
Court
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Drug Residue Analysis on Drug User's Syringes
Authorship
L.D.C.
Double bachelor degree in Chemistry and Biology
L.D.C.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
Drug use is a growing practice that can lead to an increased risk of medical issues among users. This risk is heightened in intra-venous drug users as it can lead to a higher incidence of HIV or hepatitis infection. The risk is also increased in intravenous Chemsex users, where the use of drugs in a consensual sexual environment can lead to higher rates of sexually transmitted diseases. The use of analytical methods is fundamental to achieve the objective of consumption patterns understanding in intravenous drug users and stablish the necessary harm reduction plans. Through this approach, the variety of drugs and adulterants present in the market can be assessed. In this project, syringe extracts from two populations (general consumption and Chemsex users) were analyzed by UHPLC-QTOF-MS/MS (Ultra High Performance Liquid Chromatography - Quadrupole Time-of-Flight Tandem Mass Spectrometry), for compound identification and GC-QTOF-MS (Gas Chromatography - Quadrupole Time-of-flight Mass Spectrometry) for the detection of specific isomers. The results obtained were also used to assess the differences between the two populations. Through this evaluation a differentiated pattern of consumption was observed in general population compared to Chemsex users. The most common substances in general consumption were cocaine, opiates and several adulterants, while in Chemsex samples most of the syringes contained synthetic cathinones and methamphetamine derivates. It is also important to note that several drugs were detected simultaneously in most of the syringes.
Drug use is a growing practice that can lead to an increased risk of medical issues among users. This risk is heightened in intra-venous drug users as it can lead to a higher incidence of HIV or hepatitis infection. The risk is also increased in intravenous Chemsex users, where the use of drugs in a consensual sexual environment can lead to higher rates of sexually transmitted diseases. The use of analytical methods is fundamental to achieve the objective of consumption patterns understanding in intravenous drug users and stablish the necessary harm reduction plans. Through this approach, the variety of drugs and adulterants present in the market can be assessed. In this project, syringe extracts from two populations (general consumption and Chemsex users) were analyzed by UHPLC-QTOF-MS/MS (Ultra High Performance Liquid Chromatography - Quadrupole Time-of-Flight Tandem Mass Spectrometry), for compound identification and GC-QTOF-MS (Gas Chromatography - Quadrupole Time-of-flight Mass Spectrometry) for the detection of specific isomers. The results obtained were also used to assess the differences between the two populations. Through this evaluation a differentiated pattern of consumption was observed in general population compared to Chemsex users. The most common substances in general consumption were cocaine, opiates and several adulterants, while in Chemsex samples most of the syringes contained synthetic cathinones and methamphetamine derivates. It is also important to note that several drugs were detected simultaneously in most of the syringes.
Direction
MONTES GOYANES, ROSA MARIA (Tutorships)
QUINTANA ALVAREZ, JOSE BENITO (Co-tutorships)
MONTES GOYANES, ROSA MARIA (Tutorships)
QUINTANA ALVAREZ, JOSE BENITO (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Antimicrobial activity of synthetic hydrogels encapsulating antibiotics
Authorship
N.R.C.
Double bachelor degree in Chemistry and Biology
N.R.C.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 10:00
07.18.2024 10:00
Summary
Antimicrobial resistance is a global concern due to the diffusion of multi-resistant bacterial strains and the difficulties associated with the development of new therapies. In this context, hydrogels with antibiotics and other encapsulated antimicrobials are presented as an innovative and promising solution. This work analyzes the use of hydrogels to improve the effectiveness of antimicrobial treatments and reduce the appearance of resistance through a controlled and sustained release of drugs. The main objective was to carry out an exhaustive bibliographic review on the advances in the development of hydrogels that encapsulate antimicrobials. The specific objectives include reviewing the mechanism of formation of hydrogels and their different types, studying their ability to encapsulate drugs and exploring the possible biomedical applications of these hydrogels. To do this, a systematic bibliographic review was carried out using academic databases such as PubMed, Scopus and Google Scholar. According to the analyzed literature, synthetic hydrogels with encapsulated antibiotics represent an innovative strategy to improve the administration of antimicrobials and combat bacterial resistance. They have potential applications in the treatment of infections, as well as in tissue engineering and even in the food industry. However, more studies are required to overcome technical challenges and evaluate their effectiveness in real clinical applications.
Antimicrobial resistance is a global concern due to the diffusion of multi-resistant bacterial strains and the difficulties associated with the development of new therapies. In this context, hydrogels with antibiotics and other encapsulated antimicrobials are presented as an innovative and promising solution. This work analyzes the use of hydrogels to improve the effectiveness of antimicrobial treatments and reduce the appearance of resistance through a controlled and sustained release of drugs. The main objective was to carry out an exhaustive bibliographic review on the advances in the development of hydrogels that encapsulate antimicrobials. The specific objectives include reviewing the mechanism of formation of hydrogels and their different types, studying their ability to encapsulate drugs and exploring the possible biomedical applications of these hydrogels. To do this, a systematic bibliographic review was carried out using academic databases such as PubMed, Scopus and Google Scholar. According to the analyzed literature, synthetic hydrogels with encapsulated antibiotics represent an innovative strategy to improve the administration of antimicrobials and combat bacterial resistance. They have potential applications in the treatment of infections, as well as in tissue engineering and even in the food industry. However, more studies are required to overcome technical challenges and evaluate their effectiveness in real clinical applications.
Direction
LEMOS RAMOS, MANUEL LUIS (Tutorships)
AFONSO LAGES, MARTA CAROLINA (Co-tutorships)
LEMOS RAMOS, MANUEL LUIS (Tutorships)
AFONSO LAGES, MARTA CAROLINA (Co-tutorships)
Court
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
Antibiotic-carrying hydrogels
Authorship
N.R.C.
Double bachelor degree in Chemistry and Biology
N.R.C.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The study of gels has emerged as a fascinating field in chemistry as these materials stand out for their flexibility, thermal insulation, low density and high specific surface area, qualities that make them attractive for multiple applications ranging from cooking to space missions. In the context of biomedicine, their ability to retain other substances, their biocompatibility and their biodegradability are transforming the way drugs are developed and delivered, allowing a controlled and regulated release. This work focuses on the synthesis and evaluation of four low molecular weight organic gelling agents (LMWOGs), derived from 2-aminocyclohexanocarboxylic acids. Their synthesis, their ability to form gels in different solvents and their potential as drug-eluting systems are being investigated, especially for applications in biomedicine, where problems such as antibiotic resistance pose significant challenges. Preliminary results suggest that these LMWOGs could hold promise for prolonged local delivery of antimicrobial drugs, leveraging the unique properties of the gels to meet current clinical demands.
The study of gels has emerged as a fascinating field in chemistry as these materials stand out for their flexibility, thermal insulation, low density and high specific surface area, qualities that make them attractive for multiple applications ranging from cooking to space missions. In the context of biomedicine, their ability to retain other substances, their biocompatibility and their biodegradability are transforming the way drugs are developed and delivered, allowing a controlled and regulated release. This work focuses on the synthesis and evaluation of four low molecular weight organic gelling agents (LMWOGs), derived from 2-aminocyclohexanocarboxylic acids. Their synthesis, their ability to form gels in different solvents and their potential as drug-eluting systems are being investigated, especially for applications in biomedicine, where problems such as antibiotic resistance pose significant challenges. Preliminary results suggest that these LMWOGs could hold promise for prolonged local delivery of antimicrobial drugs, leveraging the unique properties of the gels to meet current clinical demands.
Direction
ESTEVEZ CABANAS, JUAN CARLOS (Tutorships)
ESTEVEZ CABANAS, JUAN CARLOS (Tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Study of the role of lysophosphatidic acid in cancer immune evasion through computational simulations.
Authorship
U.L.V.
Double bachelor degree in Chemistry and Biology
U.L.V.
Double bachelor degree in Chemistry and Biology
Defense date
07.17.2024 10:00
07.17.2024 10:00
Summary
Cancer remains one of the leading causes of mortality worldwide, with significant impacts on patients' quality of life and healthcare systems. Immune evasion of tumour cells represents a critical challenge in developing effective therapies. In this context, the present research explores the hypothesis that lysophosphatidic acid contributes to immune evasion by competing with antimicrobial peptides. The main objective of this work was to study the interaction between antimicrobial peptides and different model cell membranes to understand how lysophosphatidic acid may affect these interactions. For this purpose, molecular dynamics simulations were carried out using CM15 as a model antimicrobial peptide and membranes composed of phosphatidylserine and phosphatidic acid in different protonation states (net charge -1 and -2). The main results indicate that antimicrobial peptides have a higher affinity for phosphatidic acid lipids, especially when phosphatidic acid is more negatively charged (at low pH, characteristic of cancerous environments). This suggests that lysophosphatidic acid in the tumour microenvironment may effectively compete with antimicrobial peptides, decreasing their efficacy. Membrane structural analysis also revealed low peptide insertion during the simulation time, highlighting that the conditions under which the simulations were carried out may limit peptide penetration. The importance of this study lies in providing new evidence for the role of lysophosphatidic acid in the immune evasion of cancer cells. These findings may guide the rational design of new antimicrobial peptides with improved therapeutic properties, contributing to the development of more effective strategies in the fight against cancer. However, longer simulations and additional replicates are recommended to ensure the robustness and reproducibility of the results obtained.
Cancer remains one of the leading causes of mortality worldwide, with significant impacts on patients' quality of life and healthcare systems. Immune evasion of tumour cells represents a critical challenge in developing effective therapies. In this context, the present research explores the hypothesis that lysophosphatidic acid contributes to immune evasion by competing with antimicrobial peptides. The main objective of this work was to study the interaction between antimicrobial peptides and different model cell membranes to understand how lysophosphatidic acid may affect these interactions. For this purpose, molecular dynamics simulations were carried out using CM15 as a model antimicrobial peptide and membranes composed of phosphatidylserine and phosphatidic acid in different protonation states (net charge -1 and -2). The main results indicate that antimicrobial peptides have a higher affinity for phosphatidic acid lipids, especially when phosphatidic acid is more negatively charged (at low pH, characteristic of cancerous environments). This suggests that lysophosphatidic acid in the tumour microenvironment may effectively compete with antimicrobial peptides, decreasing their efficacy. Membrane structural analysis also revealed low peptide insertion during the simulation time, highlighting that the conditions under which the simulations were carried out may limit peptide penetration. The importance of this study lies in providing new evidence for the role of lysophosphatidic acid in the immune evasion of cancer cells. These findings may guide the rational design of new antimicrobial peptides with improved therapeutic properties, contributing to the development of more effective strategies in the fight against cancer. However, longer simulations and additional replicates are recommended to ensure the robustness and reproducibility of the results obtained.
Direction
GARCIA FANDIÑO, REBECA (Tutorships)
GARCIA FANDIÑO, REBECA (Tutorships)
Court
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
The importance of cell membranes in the fight against infections: A view through computational chemistry
Authorship
U.L.V.
Double bachelor degree in Chemistry and Biology
U.L.V.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Antimicrobial peptides (AMPs) target certain membranes specifically depending on the lipid composition, which makes them potential alternatives to current antimicrobial agents. Molecular Dynamics (MD) computational simulations may be useful in order to obtain a more detailed view of the mechanism of action of AMPs on membranes and facilitate their design. In this work, MD simulations of CM15 -cationic AMP- in aqueous solution and mammalian and bacterial model membranes were performed. To test the reproducibility of the simulations, 50 replicas of each type of system were carried out. The analysis revealed good reproducibility of CM15 in aqueous solution, which aggregates due to its amphipathic nature. This aggregate initially makes contact with the polar heads of both types of membranes through its positively charged residues. The hydrophobic residues are then exposed towards the lipid tails of the membrane, decreasing the stability of the aggregate which results in the segregation into two possible final conformations: (i) clusters of two antiparallel peptides or (ii) individual peptides. The results suggest that the observed trends are not random artefacts, but inherent features of the peptide behaviour in the presence of both membranes. These findings underline the importance of performing multiple replicates in MD studies to ensure the validity of the results and allow the design of new AMPs with improved selectivity.
Antimicrobial peptides (AMPs) target certain membranes specifically depending on the lipid composition, which makes them potential alternatives to current antimicrobial agents. Molecular Dynamics (MD) computational simulations may be useful in order to obtain a more detailed view of the mechanism of action of AMPs on membranes and facilitate their design. In this work, MD simulations of CM15 -cationic AMP- in aqueous solution and mammalian and bacterial model membranes were performed. To test the reproducibility of the simulations, 50 replicas of each type of system were carried out. The analysis revealed good reproducibility of CM15 in aqueous solution, which aggregates due to its amphipathic nature. This aggregate initially makes contact with the polar heads of both types of membranes through its positively charged residues. The hydrophobic residues are then exposed towards the lipid tails of the membrane, decreasing the stability of the aggregate which results in the segregation into two possible final conformations: (i) clusters of two antiparallel peptides or (ii) individual peptides. The results suggest that the observed trends are not random artefacts, but inherent features of the peptide behaviour in the presence of both membranes. These findings underline the importance of performing multiple replicates in MD studies to ensure the validity of the results and allow the design of new AMPs with improved selectivity.
Direction
GARCIA FANDIÑO, REBECA (Tutorships)
Suárez Lestón, Fabián (Co-tutorships)
GARCIA FANDIÑO, REBECA (Tutorships)
Suárez Lestón, Fabián (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Crimean-Congo haemorrhagic fever: systematic review and situation in Spain
Authorship
N.M.V.
Double bachelor degree in Chemistry and Biology
N.M.V.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 10:00
07.18.2024 10:00
Summary
Crimean-Congo haemorrhagic fever is a viral zoonotic disease transmitted by Hyalomma genus ticks. The disease is endemic in areas of southern Europe, Asia and Africa, but globalisation is causing the emergence of cases in other places, including Spain. Since infected ticks parasitize several hosts but humans are the only ones that develop the disease after infection, it is necessary to evaluate the risk of human infection by the virus. Taking into account that Spain has experimented 12 cases of human infection to date, 4 of them fatalities, it is interesting to assess the risk associated with the spread of the disease across the country. Therefore, a necessity arises to carry out the present project. Through a systematic review and search for additional information, not only a snapshot of the most relevant current information associated with the disease is provided, but also an assessment of the virus mobility in the Spanish territory, in the light of threats such as climate change or migration. Results suggest a migration of the viral vectors towards the North of the peninsula in the short-term, but that we should not underestimate the potential of the virus although the risk of human infection is not expected to alarmingly increase.
Crimean-Congo haemorrhagic fever is a viral zoonotic disease transmitted by Hyalomma genus ticks. The disease is endemic in areas of southern Europe, Asia and Africa, but globalisation is causing the emergence of cases in other places, including Spain. Since infected ticks parasitize several hosts but humans are the only ones that develop the disease after infection, it is necessary to evaluate the risk of human infection by the virus. Taking into account that Spain has experimented 12 cases of human infection to date, 4 of them fatalities, it is interesting to assess the risk associated with the spread of the disease across the country. Therefore, a necessity arises to carry out the present project. Through a systematic review and search for additional information, not only a snapshot of the most relevant current information associated with the disease is provided, but also an assessment of the virus mobility in the Spanish territory, in the light of threats such as climate change or migration. Results suggest a migration of the viral vectors towards the North of the peninsula in the short-term, but that we should not underestimate the potential of the virus although the risk of human infection is not expected to alarmingly increase.
Direction
López Romalde, Jesús Ángel (Tutorships)
López Romalde, Jesús Ángel (Tutorships)
Court
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
Affidendrons: Multivalent Recognition for Advanced Diagnosis
Authorship
N.M.V.
Double bachelor degree in Chemistry and Biology
N.M.V.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Imaging agents that incorporate recognition proteins such as affitins or affibodies facilitate early disease detection. Although these biomolecules stand out for their smaller size, greater solubility and ease of large-scale production when compared to antibodies, they do have a major handicap: a lower affinity for their targets. In order to solve this issue, our research group has recently described “affidendrons”, bioconjugates based on affitins and dendrimers that exponentially increase protein affinity for their targets by laying on the dendrimer’s multivalent surface, thus making them competitive against antibodies. However, the impossibility to control the number of dendrimer-binding affitins limits the develpment of this technology. In consequence, the present project, which is part of a macro-project aimed at the strategic synthesis of affidendrons, deals with the synthesis of a long-armed, labellable, stable, biocompatible dendrimer with a limited number of affitin-binding positions. The dendrimer synthesis is performed by green “click” chemistry, being the reactions used azide-alkyne cycloadditions in the absence of metal catalysis and the synthesis procedure divergent.
Imaging agents that incorporate recognition proteins such as affitins or affibodies facilitate early disease detection. Although these biomolecules stand out for their smaller size, greater solubility and ease of large-scale production when compared to antibodies, they do have a major handicap: a lower affinity for their targets. In order to solve this issue, our research group has recently described “affidendrons”, bioconjugates based on affitins and dendrimers that exponentially increase protein affinity for their targets by laying on the dendrimer’s multivalent surface, thus making them competitive against antibodies. However, the impossibility to control the number of dendrimer-binding affitins limits the develpment of this technology. In consequence, the present project, which is part of a macro-project aimed at the strategic synthesis of affidendrons, deals with the synthesis of a long-armed, labellable, stable, biocompatible dendrimer with a limited number of affitin-binding positions. The dendrimer synthesis is performed by green “click” chemistry, being the reactions used azide-alkyne cycloadditions in the absence of metal catalysis and the synthesis procedure divergent.
Direction
FERNANDEZ MEGIA, EDUARDO (Tutorships)
FERNANDEZ MEGIA, EDUARDO (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Analysis of microplastics in sludge using spectroscopic techniques
Authorship
A.F.C.
Bachelor of Chemistry
A.F.C.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
Plastics and microplastics waste are highly polluting due to the high number of chemical compounds that are used to synthesize them and their low capacity of degradation. They generate huge problems in the environment, because of the pollution that takes place in all kinds of ecosystems, and they also create problems for living beings, since many microplastics are ingested indirectly, causing damage to the organism. A high amount of microplastics can be found in wastewaters. This is due to the actual incalculable sources of pollution that appear due to the large number of plastic products that exist. There are so many risks that make microplastics analysis in sewage sludges extremely important. This project is going to use Raman spectroscopy to characterize different types of microplastics that can be found in sewage sludges. The sample is going to be pretreated using a double digestion with hydrogen peroxide and Fenton´s reagent as a catalyst. Later, two densities separation are going to take place. Por the first one NaCl will be used, and methanol will be employed for the second one. A vacuum filtering will be carried out, comparing five filters of different materials, which are: nitrocellulose, polycarbonate, polyvinylidene fluoride, filter paper and glass microfiber. Finally, the best filter to carry out the experiment will be selected.
Plastics and microplastics waste are highly polluting due to the high number of chemical compounds that are used to synthesize them and their low capacity of degradation. They generate huge problems in the environment, because of the pollution that takes place in all kinds of ecosystems, and they also create problems for living beings, since many microplastics are ingested indirectly, causing damage to the organism. A high amount of microplastics can be found in wastewaters. This is due to the actual incalculable sources of pollution that appear due to the large number of plastic products that exist. There are so many risks that make microplastics analysis in sewage sludges extremely important. This project is going to use Raman spectroscopy to characterize different types of microplastics that can be found in sewage sludges. The sample is going to be pretreated using a double digestion with hydrogen peroxide and Fenton´s reagent as a catalyst. Later, two densities separation are going to take place. Por the first one NaCl will be used, and methanol will be employed for the second one. A vacuum filtering will be carried out, comparing five filters of different materials, which are: nitrocellulose, polycarbonate, polyvinylidene fluoride, filter paper and glass microfiber. Finally, the best filter to carry out the experiment will be selected.
Direction
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Síntesis de Cápsulas basadas en Ciclopéptidos para el reconocimiento de iones y moléculas
Authorship
M.R.M.
Bachelor of Chemistry
M.R.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
In recent years, multiple research groups have conducted studies and developed novel supramolecular systems based on structures with internal cavities capable of encapsulating various types of guests. The specific characteristics of their interior allow for multiple applications such as molecular transport, substrate recognition, or catalysis. Based on this, our research group has focused on developing supramolecular systems using cyclic peptides capable of stacking. In this way, using the fundamental concepts of synthesis and design employed in previous works of this group, dimer-forming cyclopeptides have been synthesized with enormous potential for the development of supramolecular capsules.In the present project, we carried out the synthesis and modification of a cyclopeptide with the ability to form dimers, which was designed through a convergent synthesis from an alfa-aa and a gamma-aa. The latter was modified with a propargylic chain with a terminal alkyne, allowing us to make various modifications to the peptide backbone. Moreover, two reactions were performed on this alkyne: a Sonogashira reaction for the anchoring of imidazole groups forming a decorated dimer, and on the other hand, the Click Chemistry strategy was used to anchor a molecular cap that, upon binding, forms triazole groups with very specific characteristics for the selective transport of molecules.
In recent years, multiple research groups have conducted studies and developed novel supramolecular systems based on structures with internal cavities capable of encapsulating various types of guests. The specific characteristics of their interior allow for multiple applications such as molecular transport, substrate recognition, or catalysis. Based on this, our research group has focused on developing supramolecular systems using cyclic peptides capable of stacking. In this way, using the fundamental concepts of synthesis and design employed in previous works of this group, dimer-forming cyclopeptides have been synthesized with enormous potential for the development of supramolecular capsules.In the present project, we carried out the synthesis and modification of a cyclopeptide with the ability to form dimers, which was designed through a convergent synthesis from an alfa-aa and a gamma-aa. The latter was modified with a propargylic chain with a terminal alkyne, allowing us to make various modifications to the peptide backbone. Moreover, two reactions were performed on this alkyne: a Sonogashira reaction for the anchoring of imidazole groups forming a decorated dimer, and on the other hand, the Click Chemistry strategy was used to anchor a molecular cap that, upon binding, forms triazole groups with very specific characteristics for the selective transport of molecules.
Direction
Granja Guillán, Juan Ramón (Tutorships)
AMORIN LOPEZ, MANUEL (Co-tutorships)
Granja Guillán, Juan Ramón (Tutorships)
AMORIN LOPEZ, MANUEL (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Metal complexes of lanthanides as molecular magnets
Authorship
X.M.B.
Bachelor of Chemistry
X.M.B.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
In the present work, the results obtained in the attempt to synthesize Dy+3 and Tb+3 metal complexes with pentaaza or hexaazamacrocyclic ligands and triphenylsilanolate ligands, starting from precursors containing acetate or hydroxy ligands, are described. Thus, the use of hexa- and pentadentate nitrogen-donating macrocycles allows for the isolation of the precursors [Tb(LN6en)(OAc)2](BPh4)(H2O)2 (1), [Dy(LN6prop)(OAc)2](BPh4) (2), [Dy(LN6PhenF)(OH)2](BPh4)(H2O)2 (3) and [Dy(LN5,bipy)(OAc)2](OAc)(H2O)4 (4). Complexes 1 and 2 undergo ligand exchange from acetate to triphenylsilanolate, leading to the highly pure compound [Tb(LN6en)(OSiPh3)2](BPh4)·2CH2Cl2 (5·2CH2Cl2) and [Dy(LN6prop)(OAc)(OSiPh3)](BPh4)·0.5CH2Cl2 (6·0.5CH2Cl2) in a mixture of compounds. Both were characterized crystallographically, showing the sought-after hexagonal bipyramidal geometry in 5·2CH2Cl2, and a spherical square antiprism in 6·0.5CH2Cl2. Magnetic studies of 5·2CH2Cl2 demonstrate that it is a single-molecule magnet induced by an external magnetic field, where the spin relaxes through Raman and quantum tunneling mechanisms of magnetization.
In the present work, the results obtained in the attempt to synthesize Dy+3 and Tb+3 metal complexes with pentaaza or hexaazamacrocyclic ligands and triphenylsilanolate ligands, starting from precursors containing acetate or hydroxy ligands, are described. Thus, the use of hexa- and pentadentate nitrogen-donating macrocycles allows for the isolation of the precursors [Tb(LN6en)(OAc)2](BPh4)(H2O)2 (1), [Dy(LN6prop)(OAc)2](BPh4) (2), [Dy(LN6PhenF)(OH)2](BPh4)(H2O)2 (3) and [Dy(LN5,bipy)(OAc)2](OAc)(H2O)4 (4). Complexes 1 and 2 undergo ligand exchange from acetate to triphenylsilanolate, leading to the highly pure compound [Tb(LN6en)(OSiPh3)2](BPh4)·2CH2Cl2 (5·2CH2Cl2) and [Dy(LN6prop)(OAc)(OSiPh3)](BPh4)·0.5CH2Cl2 (6·0.5CH2Cl2) in a mixture of compounds. Both were characterized crystallographically, showing the sought-after hexagonal bipyramidal geometry in 5·2CH2Cl2, and a spherical square antiprism in 6·0.5CH2Cl2. Magnetic studies of 5·2CH2Cl2 demonstrate that it is a single-molecule magnet induced by an external magnetic field, where the spin relaxes through Raman and quantum tunneling mechanisms of magnetization.
Direction
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Electrochemical synthesis and characterization of metallic complexes of Zn and Pb
Authorship
S.T.P.
Bachelor of Chemistry
S.T.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This work presents the electrochemical synthesis of lead and zinc metal complexes using two ligands, named in this report as H1PYZ and H4PYZ, which were previously synthesized. The characterization of the complexes is carried out using X-ray diffraction (XRD), elemental analysis, infrared spectroscopy (IR), and proton nuclear magnetic resonance (1H NMR), confirming their acquisition as pure products. The ligands H1PYZ [(Z)-N'-benzoylpyrazine-2-carbohydrazonamide] and H4PYZ [(Z)-N'-(4-methylbenzoyl)pyrazine-2-carbohydrazonamide] were synthesized through condensation reactions and duly characterized. The results obtained demonstrate that the electrochemical procedure employed in the synthesis is an appropriate methodology for obtaining complexes, highlighting its versatility and interest for the development of new research possibilities in coordination chemistry.
This work presents the electrochemical synthesis of lead and zinc metal complexes using two ligands, named in this report as H1PYZ and H4PYZ, which were previously synthesized. The characterization of the complexes is carried out using X-ray diffraction (XRD), elemental analysis, infrared spectroscopy (IR), and proton nuclear magnetic resonance (1H NMR), confirming their acquisition as pure products. The ligands H1PYZ [(Z)-N'-benzoylpyrazine-2-carbohydrazonamide] and H4PYZ [(Z)-N'-(4-methylbenzoyl)pyrazine-2-carbohydrazonamide] were synthesized through condensation reactions and duly characterized. The results obtained demonstrate that the electrochemical procedure employed in the synthesis is an appropriate methodology for obtaining complexes, highlighting its versatility and interest for the development of new research possibilities in coordination chemistry.
Direction
LABISBAL VIQUEIRA, MARIA ELENA (Tutorships)
LABISBAL VIQUEIRA, MARIA ELENA (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Gold-promoted cascade reactions in biological media
Authorship
X.S.I.
Bachelor of Chemistry
X.S.I.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
In recent years, the possibility of introducing abiotic reactions inside living systems in a biocompatible way has aroused great interest, thanks to the multiple applications in chemical biology and biomedicine that could lead to the development of new therapies and treatments. Within these reactions, the use of transition metals as catalytic structures can open the door to new reactivities to be carried out within biological systems. Among them, gold, a precious metal long considered highly inert, has begun to gain importance in the field of Bioorthogonal Chemistry. In this Final Degree Project, it is proposed the development of a gold-promoted double cyclization through a cascade mechanism within biological media. Thus, the study involves the optimization of the transformation towards biological conditions, that is, high dilution, water and air compatibility, as well as the tolerance to the presence of different biomolecules and complex media. We have obtained promising results suggesting the viability of these cascade processes in biological environments and even in live mammalian cells (A549). This strategy constitutes an important new approach to build up high complexity molecules from simple compounds in a straightforward, elegant and bioorthogonal manner in living cells.
In recent years, the possibility of introducing abiotic reactions inside living systems in a biocompatible way has aroused great interest, thanks to the multiple applications in chemical biology and biomedicine that could lead to the development of new therapies and treatments. Within these reactions, the use of transition metals as catalytic structures can open the door to new reactivities to be carried out within biological systems. Among them, gold, a precious metal long considered highly inert, has begun to gain importance in the field of Bioorthogonal Chemistry. In this Final Degree Project, it is proposed the development of a gold-promoted double cyclization through a cascade mechanism within biological media. Thus, the study involves the optimization of the transformation towards biological conditions, that is, high dilution, water and air compatibility, as well as the tolerance to the presence of different biomolecules and complex media. We have obtained promising results suggesting the viability of these cascade processes in biological environments and even in live mammalian cells (A549). This strategy constitutes an important new approach to build up high complexity molecules from simple compounds in a straightforward, elegant and bioorthogonal manner in living cells.
Direction
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Electrochemical synthesis of bisthiosemicarbazone-derived metal complexes for the study of their spectroscopic properties
Authorship
A.F.P.
Bachelor of Chemistry
A.F.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This Final Degree Project is part of a line of study of the research group and covers the synthesis of metal complexes derived from a tetradentate bisthiosemicarbazone ligand obtained from 1,3-diacetylbenzene and 4-(1-naphthyl)-3-thiosemicarbazide. Once the ligand was isolated and characterised, the syntheses of complexes derived from manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I), gold(I) and lead(II) were carried out by electrochemical synthesis. They were then characterised by the usual characterisation techniques in solution and in the solid state. Finally, studies of the spectroscopic properties of both the ligand and the complexes were carried out by UV-Vis absorption and fluorescence emission experiments.
This Final Degree Project is part of a line of study of the research group and covers the synthesis of metal complexes derived from a tetradentate bisthiosemicarbazone ligand obtained from 1,3-diacetylbenzene and 4-(1-naphthyl)-3-thiosemicarbazide. Once the ligand was isolated and characterised, the syntheses of complexes derived from manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I), gold(I) and lead(II) were carried out by electrochemical synthesis. They were then characterised by the usual characterisation techniques in solution and in the solid state. Finally, studies of the spectroscopic properties of both the ligand and the complexes were carried out by UV-Vis absorption and fluorescence emission experiments.
Direction
MARTINEZ CALVO, MIGUEL (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
MARTINEZ CALVO, MIGUEL (Tutorships)
VELO HELENO, MARIA ISABEL (Co-tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
The importance of the H2+ molecule in the development of quantum chemistry
Authorship
S.R.M.
Bachelor of Chemistry
S.R.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
The molecular hydrogen ion, also known as H2+, has been a key piece in the history of quantum chemistry since its inception, both in its early development and in its evolution to the present day, largely due to its simplicity and ease of use for to validate quantum theories and also for the validation of different methodologies in this discipline. This work will study its importance in the evolution of quantum chemistry from its early days, its impact on both the development and the validation of different theories, such as the chemical bond theory or the theory of molecular orbitals, its importance in the development of computational methods or the advantages provided by their use in the field of education to create in students a solid basis to be able to use this knowledge later on in more complex molecular systems.
The molecular hydrogen ion, also known as H2+, has been a key piece in the history of quantum chemistry since its inception, both in its early development and in its evolution to the present day, largely due to its simplicity and ease of use for to validate quantum theories and also for the validation of different methodologies in this discipline. This work will study its importance in the evolution of quantum chemistry from its early days, its impact on both the development and the validation of different theories, such as the chemical bond theory or the theory of molecular orbitals, its importance in the development of computational methods or the advantages provided by their use in the field of education to create in students a solid basis to be able to use this knowledge later on in more complex molecular systems.
Direction
FERNANDEZ RAMOS, ANTONIO (Tutorships)
FERNANDEZ RAMOS, ANTONIO (Tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Tetrel bond in lead complexes derived from 4-methylbenzoylpyrazine-2-carbohydrazonamide
Authorship
C.T.G.
Bachelor of Chemistry
C.T.G.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The final degree project presents the synthesis of the ligand (Z)-N'-(4-methylbenzoyl)pyrazine2-carbohydrazonamide by the reaction of 2-cyanopyridine with 4- methylbenzohydrazide using sodium and dry methanol. Subsequently, the ligand is reacted with different lead(II) salts, incorporating auxiliary ligands into certain reactions that allow the following complexes to be obtained: [Pb(4PYZ)(NO3)(H2O)], [Pb(4PYZ)(NO2)(H2O)].0.59[Pb(4PYZ)(NO3)(H2O)].0.41, [Pb(4PYZ)(NO2)], 6 {[Pb(4PYZ)(MeOH)](ClO4)2}n, [Pb(H4PYZ)(Cl)2]2 and [Pb(4PYZ)(SCN)(H2O)]. Once the complexes are isolated, they are characterized by different experimental techniques such as 1H NMR spectroscopy, elemental analysis, IR spectroscopy and X-ray diffraction, the latter being very important to be able to study the tetrel interactions of these complexes.
The final degree project presents the synthesis of the ligand (Z)-N'-(4-methylbenzoyl)pyrazine2-carbohydrazonamide by the reaction of 2-cyanopyridine with 4- methylbenzohydrazide using sodium and dry methanol. Subsequently, the ligand is reacted with different lead(II) salts, incorporating auxiliary ligands into certain reactions that allow the following complexes to be obtained: [Pb(4PYZ)(NO3)(H2O)], [Pb(4PYZ)(NO2)(H2O)].0.59[Pb(4PYZ)(NO3)(H2O)].0.41, [Pb(4PYZ)(NO2)], 6 {[Pb(4PYZ)(MeOH)](ClO4)2}n, [Pb(H4PYZ)(Cl)2]2 and [Pb(4PYZ)(SCN)(H2O)]. Once the complexes are isolated, they are characterized by different experimental techniques such as 1H NMR spectroscopy, elemental analysis, IR spectroscopy and X-ray diffraction, the latter being very important to be able to study the tetrel interactions of these complexes.
Direction
GARCIA SANTOS, MARIA ISABEL (Tutorships)
GARCIA SANTOS, MARIA ISABEL (Tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
Evaluation of Reference Genes for the Analysis of the Immune Response in Senegalensis Sole to Viral Nervous Necrosis Virus
Authorship
L.R.N.
Double bachelor degree in Chemistry and Biology
L.R.N.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 10:00
07.18.2024 10:00
Summary
The Senegalese sole (Solea senegalensis) is a significant species in the field of aquaculture. With a view to optimizing the analysis of its gene expression by RT-qPCR for application in studies evaluating the immune response to infection caused by the nervous necrosis virus or vaccination against it, this work tested eight reference genes. The candidate genes are: beta-actin (ACTB1), a paralog of beta-actin (ACTB2), glyceraldehyde-3-phosphate dehydrogenase (GAPDH2), hypoxanthine-guanine phosphoribosyltransferase 1 (HPRT1), ubiquitin (UBQ), elongation factor 1 alpha (eEF1A1), 18S ribosomal RNA (18S), and ribosomal protein S4 (RPS4). The interferon-induced GTP-binding protein Mx (mx) was used as the gene of interest. Kidney samples from control and virus-inoculated soles were analyzed. The BioRad CFX Maestro 1.1 software, version 4.1.2433.1219, indicates that all the reference genes tested in this study are acceptable, with the most stable being GAPDH2 and ACTB2, followed by RPS4 and UBQ. It also indicates that including two reference genes is sufficient for proper normalization. In summary, this study recommends the use of GAPDH2 and ACTB2 as reference genes for the correct normalization of RT-qPCR analysis of kidney samples from soles infected with nervous necrosis virus. Future studies will be necessary to verify that these genes are suitable for the analysis of other organs.
The Senegalese sole (Solea senegalensis) is a significant species in the field of aquaculture. With a view to optimizing the analysis of its gene expression by RT-qPCR for application in studies evaluating the immune response to infection caused by the nervous necrosis virus or vaccination against it, this work tested eight reference genes. The candidate genes are: beta-actin (ACTB1), a paralog of beta-actin (ACTB2), glyceraldehyde-3-phosphate dehydrogenase (GAPDH2), hypoxanthine-guanine phosphoribosyltransferase 1 (HPRT1), ubiquitin (UBQ), elongation factor 1 alpha (eEF1A1), 18S ribosomal RNA (18S), and ribosomal protein S4 (RPS4). The interferon-induced GTP-binding protein Mx (mx) was used as the gene of interest. Kidney samples from control and virus-inoculated soles were analyzed. The BioRad CFX Maestro 1.1 software, version 4.1.2433.1219, indicates that all the reference genes tested in this study are acceptable, with the most stable being GAPDH2 and ACTB2, followed by RPS4 and UBQ. It also indicates that including two reference genes is sufficient for proper normalization. In summary, this study recommends the use of GAPDH2 and ACTB2 as reference genes for the correct normalization of RT-qPCR analysis of kidney samples from soles infected with nervous necrosis virus. Future studies will be necessary to verify that these genes are suitable for the analysis of other organs.
Direction
BANDIN MATOS, MARIA ISABEL (Tutorships)
LOPEZ VAZQUEZ, M. DEL CARMEN (Co-tutorships)
BANDIN MATOS, MARIA ISABEL (Tutorships)
LOPEZ VAZQUEZ, M. DEL CARMEN (Co-tutorships)
Court
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
Study on the Effect of Exposure to TiO2 Nanoparticles on the Elemental Content of Seaweed
Authorship
L.R.N.
Double bachelor degree in Chemistry and Biology
L.R.N.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The increase in the production of titanium dioxide nanoparticles (nTiO2) leads to a rise in their concentration in nature. Multiple studies have demonstrated that the presence of nTiO2 affects living organisms, but significant knowledge gaps still exist. This study investigated the effect of 5 nm nTiO2 on the elemental content of green algae (Ulva sp.) through multielemental analysis using ICP-MS. The elemental content was measured in Ulva sp. samples exposed to different concentrations of nTiO2 (0, 0.1, and 1 mg/L) over exposure periods of 0, 7, 14, 21, and 28 days. The elements measured (As, Cd, Ce, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sb, Se, V, and Zn) were chosen due to their significant variation observed in a preliminary semiquantitative analysis also conducted using ICP-MS. It was demonstrated that an increase in titanium concentration caused an increase in the elemental content of As, Cd, Ce, Co, Cr, Cu, Mo, Ni, Rb, and V in Ulva sp. At high concentrations of nTiO2, the exposure time showed different effects depending on the element analyzed. Co, Cu, and Mo concentrations increased with exposure time, while As, Cd, and Ce concentrations decreased. Rb and V did not show any variation. Therefore, it is concluded that the presence of nTiO2 affects the metallic content of Ulva sp.
The increase in the production of titanium dioxide nanoparticles (nTiO2) leads to a rise in their concentration in nature. Multiple studies have demonstrated that the presence of nTiO2 affects living organisms, but significant knowledge gaps still exist. This study investigated the effect of 5 nm nTiO2 on the elemental content of green algae (Ulva sp.) through multielemental analysis using ICP-MS. The elemental content was measured in Ulva sp. samples exposed to different concentrations of nTiO2 (0, 0.1, and 1 mg/L) over exposure periods of 0, 7, 14, 21, and 28 days. The elements measured (As, Cd, Ce, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sb, Se, V, and Zn) were chosen due to their significant variation observed in a preliminary semiquantitative analysis also conducted using ICP-MS. It was demonstrated that an increase in titanium concentration caused an increase in the elemental content of As, Cd, Ce, Co, Cr, Cu, Mo, Ni, Rb, and V in Ulva sp. At high concentrations of nTiO2, the exposure time showed different effects depending on the element analyzed. Co, Cu, and Mo concentrations increased with exposure time, while As, Cd, and Ce concentrations decreased. Rb and V did not show any variation. Therefore, it is concluded that the presence of nTiO2 affects the metallic content of Ulva sp.
Direction
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
BARCIELA ALONSO, Ma CARMEN (Co-tutorships)
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
BARCIELA ALONSO, Ma CARMEN (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Optimize New Biological Platforms for New Bioorthogonal Reactions
Authorship
M.G.A.
Double bachelor degree in Chemistry and Biology
M.G.A.
Double bachelor degree in Chemistry and Biology
Defense date
07.17.2024 10:00
07.17.2024 10:00
Summary
Biological chemistry is a broad field that studies biological mechanisms from a chemical point of view. One of the branches of biological chemistry is bioorthogonal chemistry, which focuses on designing non-natural chemical transformations in biological systems without interfering with their functioning. Advances in this field have opened up the possibility of developing new drug action mechanisms, for example, strategies based on the specific recognition of membrane proteins of affected cells, leading to innovative selectivity that enhances the performance of these drugs and helps reduce the number of side effects, which could lead to an expansion of tools for biomedical purposes. Despite the great interest and potential of this new field, developing new biological models to study these reactions is a priority. In this work, new biological models were studied for the optimization of bioorthogonal reactions in vivo and in vitro. Firstly, the design of a new buffer based on energetic molecules and cytoplasmic salts, called Cell-free, was carried out to mimic the composition of the cytoplasm as a tool for studying bioorthogonal reactions in vitro. In parallel, cell lines were characterized in which a bioorthogonal reaction employing the RGD peptide as a carrier could be used. The results obtained in this undergraduate thesis are the first step to optimizing and developing new bioorthogonal reactions targeted at specific cell types. The design of the photocatalytic species and the reaction is detailed in the Chemistry undergraduate thesis.
Biological chemistry is a broad field that studies biological mechanisms from a chemical point of view. One of the branches of biological chemistry is bioorthogonal chemistry, which focuses on designing non-natural chemical transformations in biological systems without interfering with their functioning. Advances in this field have opened up the possibility of developing new drug action mechanisms, for example, strategies based on the specific recognition of membrane proteins of affected cells, leading to innovative selectivity that enhances the performance of these drugs and helps reduce the number of side effects, which could lead to an expansion of tools for biomedical purposes. Despite the great interest and potential of this new field, developing new biological models to study these reactions is a priority. In this work, new biological models were studied for the optimization of bioorthogonal reactions in vivo and in vitro. Firstly, the design of a new buffer based on energetic molecules and cytoplasmic salts, called Cell-free, was carried out to mimic the composition of the cytoplasm as a tool for studying bioorthogonal reactions in vitro. In parallel, cell lines were characterized in which a bioorthogonal reaction employing the RGD peptide as a carrier could be used. The results obtained in this undergraduate thesis are the first step to optimizing and developing new bioorthogonal reactions targeted at specific cell types. The design of the photocatalytic species and the reaction is detailed in the Chemistry undergraduate thesis.
Direction
OROSA PUENTE, BEATRIZ (Tutorships)
Mascareñas Cid, Jose Luis (Co-tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
OROSA PUENTE, BEATRIZ (Tutorships)
Mascareñas Cid, Jose Luis (Co-tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Court
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
RODRIGUEZ-MOLDES REY, MARIA ISABEL (Chairman)
DOMINGUEZ GERPE, MARIA LOURDES (Secretary)
RODRIGUEZ GACIO, MARIA DEL CARMEN (Member)
Visible-light photocatalysis in biological media
Authorship
M.G.A.
Double bachelor degree in Chemistry and Biology
M.G.A.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
In recent years, Bioorthogonal Chemistry has gained significant relevance in the field of medicine. Recent studies demonstrate the possibility of carrying out chemical transformations with transition metals in biological environments and within living cells without interfering with the biomolecules present, allowing for the selective manipulation of biological processes. Therefore, advances related to the discovery of new bioorthogonal processes are highly relevant in fields such as biological chemistry and biomedicine, enabling the development of new treatments based on selective drugs. In this work, we propose adapting a reaction previously studied by Professor J.L. Mascareñas's research group to make it selective for cancer cell lines that overexpress integrin membrane proteins. Parallelly, as part of the equivalent Biology thesis, the integrin levels of different cell lines are characterized. Additionally, the study focuses on a tandem reaction, combining a photochemical reaction with a transformation based on metal photocatalysis, allowing for the development of new coordinated processes within cells. The design and synthesis of a new ruthenium catalyst with an RGD motif, providing selective properties for cells, is presented. The synthesis of a fluorescent probe containing reactive positions for the aforementioned reactivity is also detailed, enabling monitoring of the tandem process in question.
In recent years, Bioorthogonal Chemistry has gained significant relevance in the field of medicine. Recent studies demonstrate the possibility of carrying out chemical transformations with transition metals in biological environments and within living cells without interfering with the biomolecules present, allowing for the selective manipulation of biological processes. Therefore, advances related to the discovery of new bioorthogonal processes are highly relevant in fields such as biological chemistry and biomedicine, enabling the development of new treatments based on selective drugs. In this work, we propose adapting a reaction previously studied by Professor J.L. Mascareñas's research group to make it selective for cancer cell lines that overexpress integrin membrane proteins. Parallelly, as part of the equivalent Biology thesis, the integrin levels of different cell lines are characterized. Additionally, the study focuses on a tandem reaction, combining a photochemical reaction with a transformation based on metal photocatalysis, allowing for the development of new coordinated processes within cells. The design and synthesis of a new ruthenium catalyst with an RGD motif, providing selective properties for cells, is presented. The synthesis of a fluorescent probe containing reactive positions for the aforementioned reactivity is also detailed, enabling monitoring of the tandem process in question.
Direction
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Investigating the potential role of IGF-ALS (Insulin-Like Growth Factor Acid-Labile Subunit) in moderate to severe allergic asthma
Authorship
I.G.B.
Double bachelor degree in Chemistry and Biology
I.G.B.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 10:00
07.18.2024 10:00
Summary
Asthma is a chronic disease with a prevalence of 4,3%. IGF-ALS is a biomarker of severe allergic phenotype, but it is unknown whether it participates in the pathophysiological mechanism (i.e., primary biomarker) or not. The severity of asthma could be dependent on epithelial-mesenchymal transition, a phenomenon that might be involved in bronchial remodeling, and IGF-ALS could cooperate with LPS and TGFb in the induction of this process. If confirmed, IGF-ALS should be produced near bronchial epithelial cells, and macrophages could be a possible source. To validate both hypotheses, human bronchial epithelial cells (BEAS-2B) were treated with IGF-ALS, LPS, and TGFb, alone or in combination with inhibitors of TGFb- or LPS-induced signaling, and various studies were conducted to analyze the induction of epithelial-mesenchymal transition. Additionally, human monocytes were isolated and polarized in vitro to M1/M2 macrophages, evaluating the expression of the IGF-ALS gene by RT-qPCR. The results show that IGF-ALS reduces E-cadherin levels in BEAS-2B cells, which is consistent with the existence of epithelial-mesenchymal transition, and may use a signaling pathway similar to that used by LPS/CD14/TLR4. Finally, macrophages express IGF-ALS mRNA, especially M2, suggesting they could be a local source of this protein in the bronchial tissue of patients with moderate to severe asthma.
Asthma is a chronic disease with a prevalence of 4,3%. IGF-ALS is a biomarker of severe allergic phenotype, but it is unknown whether it participates in the pathophysiological mechanism (i.e., primary biomarker) or not. The severity of asthma could be dependent on epithelial-mesenchymal transition, a phenomenon that might be involved in bronchial remodeling, and IGF-ALS could cooperate with LPS and TGFb in the induction of this process. If confirmed, IGF-ALS should be produced near bronchial epithelial cells, and macrophages could be a possible source. To validate both hypotheses, human bronchial epithelial cells (BEAS-2B) were treated with IGF-ALS, LPS, and TGFb, alone or in combination with inhibitors of TGFb- or LPS-induced signaling, and various studies were conducted to analyze the induction of epithelial-mesenchymal transition. Additionally, human monocytes were isolated and polarized in vitro to M1/M2 macrophages, evaluating the expression of the IGF-ALS gene by RT-qPCR. The results show that IGF-ALS reduces E-cadherin levels in BEAS-2B cells, which is consistent with the existence of epithelial-mesenchymal transition, and may use a signaling pathway similar to that used by LPS/CD14/TLR4. Finally, macrophages express IGF-ALS mRNA, especially M2, suggesting they could be a local source of this protein in the bronchial tissue of patients with moderate to severe asthma.
Direction
NIETO FONTARIGO, JUAN JOSE (Tutorships)
Miguéns Suárez, Pablo (Co-tutorships)
NIETO FONTARIGO, JUAN JOSE (Tutorships)
Miguéns Suárez, Pablo (Co-tutorships)
Court
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
Estimation of the oral bioaccessibility of Cu, CuO nanoparticles and ZnO
Authorship
I.G.B.
Double bachelor degree in Chemistry and Biology
I.G.B.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The use of nanoparticles and nanomaterials is increasing in more and more sectors. One of these industries would be the food industry, where copper nanoparticles (Cu NPs), copper oxide (CuO NPs), and zinc oxide (ZnO NPs) are primarily used in food packaging. Due to the lack of knowledge about the potential negative effects that nanoparticles may have on our bodies, it is necessary to perform more studies to thoroughly assess their safety and better understand their long-term impact on human health. A first step, following the recommendations of the European Food Safety Authority (EFSA), would be to conduct in vitro digestion studies to evaluate whether these compounds can be absorbed by our intestines and enter the bloodstream. In this work, a bioaccessibility study of Cu NPs, CuO NPs, and ZnO NPs was carried out using an in vitro gastrointestinal digestion model. The results show that, in the case of Cu and CuO nanoparticles, the bioaccessibility for low concentration levels exceeds the 12% threshold set by EFSA, while at higher levels, agglomeration occurs during the in vitro digestion process. In contrast, ZnO nanoparticles degrade, resulting in exceptionally low bioaccessibility.
The use of nanoparticles and nanomaterials is increasing in more and more sectors. One of these industries would be the food industry, where copper nanoparticles (Cu NPs), copper oxide (CuO NPs), and zinc oxide (ZnO NPs) are primarily used in food packaging. Due to the lack of knowledge about the potential negative effects that nanoparticles may have on our bodies, it is necessary to perform more studies to thoroughly assess their safety and better understand their long-term impact on human health. A first step, following the recommendations of the European Food Safety Authority (EFSA), would be to conduct in vitro digestion studies to evaluate whether these compounds can be absorbed by our intestines and enter the bloodstream. In this work, a bioaccessibility study of Cu NPs, CuO NPs, and ZnO NPs was carried out using an in vitro gastrointestinal digestion model. The results show that, in the case of Cu and CuO nanoparticles, the bioaccessibility for low concentration levels exceeds the 12% threshold set by EFSA, while at higher levels, agglomeration occurs during the in vitro digestion process. In contrast, ZnO nanoparticles degrade, resulting in exceptionally low bioaccessibility.
Direction
Domínguez González, María Raquel (Tutorships)
MOREDA PIÑEIRO, ANTONIO (Co-tutorships)
Domínguez González, María Raquel (Tutorships)
MOREDA PIÑEIRO, ANTONIO (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Characterization of plastic particles present in nests, pellets, and feathers of Ciconia ciconia and analysis of associated variables.
Authorship
A.F.D.
Double bachelor degree in Chemistry and Biology
A.F.D.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 11:00
07.18.2024 11:00
Summary
Plastics are materials currently present in all environments, including soil, water, air, and even within organisms. Their effects on the health of ecosystems are yet to be fully discovered in detail, especially the smaller particles known as microplastics, which are known to have the capacity to bioaccumulate within organisms. In this work, a study and characterization of plastic particles found in samples from storks was carried out, specifically in nests (and their surroundings) and pellets. For this purpose, the samples were collected and subjected to chemical digestion to isolate the possible microplastics present, as well as characterized using FTIR spectroscopy. After the identification and classification of all the particles found, it was concluded that there is a significant amount of plastic particles in stork nests, while plastics do not seem to accumulate in the pellets. Furthermore, there does not appear to be a relationship between the number of particles found in the nests and their age, nor their proximity to various sources of pollution.
Plastics are materials currently present in all environments, including soil, water, air, and even within organisms. Their effects on the health of ecosystems are yet to be fully discovered in detail, especially the smaller particles known as microplastics, which are known to have the capacity to bioaccumulate within organisms. In this work, a study and characterization of plastic particles found in samples from storks was carried out, specifically in nests (and their surroundings) and pellets. For this purpose, the samples were collected and subjected to chemical digestion to isolate the possible microplastics present, as well as characterized using FTIR spectroscopy. After the identification and classification of all the particles found, it was concluded that there is a significant amount of plastic particles in stork nests, while plastics do not seem to accumulate in the pellets. Furthermore, there does not appear to be a relationship between the number of particles found in the nests and their age, nor their proximity to various sources of pollution.
Direction
VARELA RIO, ZULEMA (Tutorships)
LAZZARI , MASSIMO (Co-tutorships)
VARELA RIO, ZULEMA (Tutorships)
LAZZARI , MASSIMO (Co-tutorships)
Court
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Model microplastic study
Authorship
A.F.D.
Double bachelor degree in Chemistry and Biology
A.F.D.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Los plásticos son considerados uno de los mayores contaminantes actuales, debido a su amplia distribución y durabilidad. Concretamente, el efecto de los microplásticos, así como su comportamiento, es un campo de estudio muy reciente, por lo que su investigación es enormemente necesaria. En este trabajo se realizó una caracterización de estos, así como un estudio de fotoenvejecimiento acelerado, con el fin de simular su proceso de degradación en el medio ambiente y estudiar su mecanismo. Para hacer el seguimiento de esta degradación se utilizaron distintos métodos de identificación tradicionales, como la espectroscopía FTIR o la calorimetría diferencial de barrido. Tras el análisis de los resultados se propuso un mecanismo de oxidación para las principales unidades funcionales de cada polímero estudiado. Para acabar, se llegó a la conclusión de que el PS es más resistente a la foto-oxidación que el ABS y que el SBC. Además, a menor tamaño de partícula, la radiación parece tener un menor efecto degradativo.
Los plásticos son considerados uno de los mayores contaminantes actuales, debido a su amplia distribución y durabilidad. Concretamente, el efecto de los microplásticos, así como su comportamiento, es un campo de estudio muy reciente, por lo que su investigación es enormemente necesaria. En este trabajo se realizó una caracterización de estos, así como un estudio de fotoenvejecimiento acelerado, con el fin de simular su proceso de degradación en el medio ambiente y estudiar su mecanismo. Para hacer el seguimiento de esta degradación se utilizaron distintos métodos de identificación tradicionales, como la espectroscopía FTIR o la calorimetría diferencial de barrido. Tras el análisis de los resultados se propuso un mecanismo de oxidación para las principales unidades funcionales de cada polímero estudiado. Para acabar, se llegó a la conclusión de que el PS es más resistente a la foto-oxidación que el ABS y que el SBC. Además, a menor tamaño de partícula, la radiación parece tener un menor efecto degradativo.
Direction
LAZZARI , MASSIMO (Tutorships)
VARELA RIO, ZULEMA (Co-tutorships)
LAZZARI , MASSIMO (Tutorships)
VARELA RIO, ZULEMA (Co-tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Preparation of printles with personalized doses of lithium
Authorship
P.B.R.
Bachelor of Chemistry
P.B.R.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
Bipolar disorder is a mental illness that consists on the cyclical alteration of mood, alternating between episodes of mania and depression. For the control of this disorder, it is common to include a mood stabilizer in the treatment, being lithium carbonate the most prominent. Currently, the commercialization of this medication is limited and, in Spain, the only available medication comes in a fixed dose of 400 mg. Since continuous monitoring of lithium levels in the blood is required, the treatment needs to be adjusted to the needs of each patient. To achieve this, recent developments in pharmaceutical technology, especially regarding 3D printing, are remarkable. With the correct selection of excipients for the formulation of pharmaceutical inks, printels can be achieved, offering more advantages over traditional tablets. It is also necessary to adjust the printing conditions to these formulations to achieve good mechanical properties of the medications. Different excipients and different printing conditions have been studied to include the drug, lithium carbonate, in this type of personalized medicine. Additionally, various tests have been conducted on each batch in accordance with the specifications set by the European Pharmacopoeia (Ph. Eur.) for medications to measure their quality as pharmaceuticals.
Bipolar disorder is a mental illness that consists on the cyclical alteration of mood, alternating between episodes of mania and depression. For the control of this disorder, it is common to include a mood stabilizer in the treatment, being lithium carbonate the most prominent. Currently, the commercialization of this medication is limited and, in Spain, the only available medication comes in a fixed dose of 400 mg. Since continuous monitoring of lithium levels in the blood is required, the treatment needs to be adjusted to the needs of each patient. To achieve this, recent developments in pharmaceutical technology, especially regarding 3D printing, are remarkable. With the correct selection of excipients for the formulation of pharmaceutical inks, printels can be achieved, offering more advantages over traditional tablets. It is also necessary to adjust the printing conditions to these formulations to achieve good mechanical properties of the medications. Different excipients and different printing conditions have been studied to include the drug, lithium carbonate, in this type of personalized medicine. Additionally, various tests have been conducted on each batch in accordance with the specifications set by the European Pharmacopoeia (Ph. Eur.) for medications to measure their quality as pharmaceuticals.
Direction
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Effect of aromatic substitution on direction of rotation induction in a helical polymer
Authorship
L.F.G.
Bachelor of Chemistry
L.F.G.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
With the aim of deepening the field of chiral helical materials, in this work the synthesis of ortho-, meta- and para-substituted polymethoxyphenylacetylenes was carried out, in its two configurations (R) and (S). To reach the target polymers, a previous synthetic route was carried out, obtaining the corresponding monomers, as well as the study of the characterization of each of the compounds obtained in its course. The main objective of the work is the study of the helical conformational variation of polymers in response to different external stimuli, such as the polarity of the solvent and the presence of mono- and divalent metal ions. To do this, the initial helical structures of each polymer were observed and then their dynamism (chirality amplification capacity) was studied in different external stimuli such as: solvents of different polarities and coordination with metal cations (Li+ and Ca+2). These studies demonstrate the different behavior of a helical polymer depending on its substitution position, stating that para-substituted polymers tend to present more compressed structures, while meta- and ortho-substituted polymers are increasingly stretched, due to the gradual increase of steric impediment generated in the polyenic skeleton.
With the aim of deepening the field of chiral helical materials, in this work the synthesis of ortho-, meta- and para-substituted polymethoxyphenylacetylenes was carried out, in its two configurations (R) and (S). To reach the target polymers, a previous synthetic route was carried out, obtaining the corresponding monomers, as well as the study of the characterization of each of the compounds obtained in its course. The main objective of the work is the study of the helical conformational variation of polymers in response to different external stimuli, such as the polarity of the solvent and the presence of mono- and divalent metal ions. To do this, the initial helical structures of each polymer were observed and then their dynamism (chirality amplification capacity) was studied in different external stimuli such as: solvents of different polarities and coordination with metal cations (Li+ and Ca+2). These studies demonstrate the different behavior of a helical polymer depending on its substitution position, stating that para-substituted polymers tend to present more compressed structures, while meta- and ortho-substituted polymers are increasingly stretched, due to the gradual increase of steric impediment generated in the polyenic skeleton.
Direction
FREIRE IRIBARNE, FELIX MANUEL (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
FREIRE IRIBARNE, FELIX MANUEL (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Formulation of a Glass-Boron Nitride Composite for 3D Printing
Authorship
M.B.M.
Bachelor of Chemistry
M.B.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
This work focuses on the design and formulation of an ink for 3D printing a composite material composed of glass and boron nitride (BN). It includes a detailed analysis of the materials and methods used in the ink's fabrication, emphasizing its synthesis and characterization. The procedure for formulating the ink and the printing tests conducted are explained in detail. The ink is composed of 95% glass and 5% BN, with isopropanol as the dispersant and polyethyleneglycol and polyvinylbutyral as plasticizers and viscosity regulators additives. Ultimately, the goal of producing reproducible structures through 3D printing of this composite was successfully achieved and demonstrated.
This work focuses on the design and formulation of an ink for 3D printing a composite material composed of glass and boron nitride (BN). It includes a detailed analysis of the materials and methods used in the ink's fabrication, emphasizing its synthesis and characterization. The procedure for formulating the ink and the printing tests conducted are explained in detail. The ink is composed of 95% glass and 5% BN, with isopropanol as the dispersant and polyethyleneglycol and polyvinylbutyral as plasticizers and viscosity regulators additives. Ultimately, the goal of producing reproducible structures through 3D printing of this composite was successfully achieved and demonstrated.
Direction
GIL GONZALEZ, ALVARO (Tutorships)
GIL GONZALEZ, ALVARO (Tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
MetalloSupramolecular helicoidal polymers
Authorship
S.T.M.
Bachelor of Chemistry
S.T.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This work focuses on the study and formation of metallosupramolecular helical polymers. For this purpose, three pairs of monomers were synthesized and characterized, differentiated by the -ortho, -meta, or -para position of the chiral subunit. These monomers, derived from oligo(p-phenyleneethynylene)s (OPEs), will be coordinated through their terminal alkyne to Ag+ cations leading to the formation of supramolecular helicoidal fibers, which will be studied using different techniques such as Circular Dichroism (CD), Ultraviolet-Visible (UV-Vis), Field Emission Scanning Electron Microscopy (FESEM) and Circular Dichroism/Ultraviolet-Visible Variable Temperatura (VT-CD/VT-UV-Vis). In this way, the existence of chirality amplification phenomena between monomers and aggregates can be verified and will be obtained information about the optimal conditions to achieve self-assembly between the OPEs and Ag+ cations, which will act as the driving force in the process.
This work focuses on the study and formation of metallosupramolecular helical polymers. For this purpose, three pairs of monomers were synthesized and characterized, differentiated by the -ortho, -meta, or -para position of the chiral subunit. These monomers, derived from oligo(p-phenyleneethynylene)s (OPEs), will be coordinated through their terminal alkyne to Ag+ cations leading to the formation of supramolecular helicoidal fibers, which will be studied using different techniques such as Circular Dichroism (CD), Ultraviolet-Visible (UV-Vis), Field Emission Scanning Electron Microscopy (FESEM) and Circular Dichroism/Ultraviolet-Visible Variable Temperatura (VT-CD/VT-UV-Vis). In this way, the existence of chirality amplification phenomena between monomers and aggregates can be verified and will be obtained information about the optimal conditions to achieve self-assembly between the OPEs and Ag+ cations, which will act as the driving force in the process.
Direction
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Fluorimetric screening of tacrolimus in blood based on quantum dots and molecularly imprinted polymers
Authorship
J.R.V.P.
Bachelor of Chemistry
J.R.V.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
Possibilities of the use of molecularly imprinted polymer-quantum dot composites (MIP-QDs) for the fluorometric screening of tacrolimus in blood have been explored in this work. MIP-QDs combine the high sensitivity of quantum dot (QDs)-based sensors and the high selectivity of molecularly imprinted polymers (MIPs). The synthesis of manganese-doped zinc sulfide QDs (Mn-ZnS QDs) was performed using an ultrasound procedure and coating with 3-aminopropyltriethoxysilane (APTES). The MIP-QDs were characterized by X-ray diffraction, showing spacing values that indicate their crystalline structure and size. Analyte detection was based on the alteration of the QDs' luminescence, observed as a variation in fluorescence intensity due to interaction with tacrolimus. Fluorescence studies showed a significant decrease in emission upon analyte incorporation, attributed to hydrogen bond interactions between tacrolimus and the amine residues of APTES on the MIP-QDs surface. The developed methodology shows considerable potential for creating miniaturized and low-cost devices for tacrolimus 5 monitoring in plasma, facilitating appropriate dosage control in patients through rapid analysis using a smartphone.
Possibilities of the use of molecularly imprinted polymer-quantum dot composites (MIP-QDs) for the fluorometric screening of tacrolimus in blood have been explored in this work. MIP-QDs combine the high sensitivity of quantum dot (QDs)-based sensors and the high selectivity of molecularly imprinted polymers (MIPs). The synthesis of manganese-doped zinc sulfide QDs (Mn-ZnS QDs) was performed using an ultrasound procedure and coating with 3-aminopropyltriethoxysilane (APTES). The MIP-QDs were characterized by X-ray diffraction, showing spacing values that indicate their crystalline structure and size. Analyte detection was based on the alteration of the QDs' luminescence, observed as a variation in fluorescence intensity due to interaction with tacrolimus. Fluorescence studies showed a significant decrease in emission upon analyte incorporation, attributed to hydrogen bond interactions between tacrolimus and the amine residues of APTES on the MIP-QDs surface. The developed methodology shows considerable potential for creating miniaturized and low-cost devices for tacrolimus 5 monitoring in plasma, facilitating appropriate dosage control in patients through rapid analysis using a smartphone.
Direction
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
MOREDA PIÑEIRO, ANTONIO (Tutorships)
GOYANES GOYANES, ALVARO (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Optimization of the paper impregnation process
Authorship
S.M.R.
Bachelor of Chemistry
S.M.R.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This final degree project was undertaked at the company Financiera Maderera S.A. in order to analyze the polymerization of the resins use in the paper impregnation process and subsequent lamination of the boards. For this, physochemical tests were carryed out on the resins for several days and at two different temperatures (20ºC and 30º) simulating their storage in the factory tanks. As the resins polymerizes, an increase in viscosity and density is observed, and water tolerance and cloud time decrease. Another problem to be solved in this work takes place in the production lines with the obstruction of the mesh that covers the rollers that transfer the resin to the impregnates paper. To resolve this, pilot tests were completed at a laboratory scale using the lines formula and varying the amount of water. Subsequently, tests were executed on both impreganated paper and laminated board to observe how the properties varied.
This final degree project was undertaked at the company Financiera Maderera S.A. in order to analyze the polymerization of the resins use in the paper impregnation process and subsequent lamination of the boards. For this, physochemical tests were carryed out on the resins for several days and at two different temperatures (20ºC and 30º) simulating their storage in the factory tanks. As the resins polymerizes, an increase in viscosity and density is observed, and water tolerance and cloud time decrease. Another problem to be solved in this work takes place in the production lines with the obstruction of the mesh that covers the rollers that transfer the resin to the impregnates paper. To resolve this, pilot tests were completed at a laboratory scale using the lines formula and varying the amount of water. Subsequently, tests were executed on both impreganated paper and laminated board to observe how the properties varied.
Direction
Sanmartin Matalobos, Jesus (Tutorships)
Sanmartin Matalobos, Jesus (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
PAZ CASTAÑAL, MANUEL MARIA (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Computerised development of liquid chromatographic separation methods for quality control and single sample analysis.
Authorship
A.D.A.
Bachelor of Chemistry
A.D.A.
Bachelor of Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
The state-of-the-art methodology for developing separations of compounds in solution, using Ultra performance liquid chromatography (UPLC), in reversed phase, is examined. The incorporation of novel computerised tools, using computer-aided methods (CAMD), allows the substitution of more laborious experiments by simulation of processes that imply substantial time and cost savings. Mchrom Scout (Mestrelab Research S.L.) allows the separation of mixtures of both known and unknown composition, thus differentiating it from other software that is limited to a specific type of problem. A general strategy is followed to extract the information from the spectra of the components in the mixture chromatograms obtained experimentally using multivariate alternating least squares curve resolution (MCR-ALS) tools. This technique allows estimating the actual spectra for the individual components as well as their elution profiles. In this way, a retention model is constructed for each component, which allows an efficient optimisation process to be developed. Following this approach, strategies for samples of unknown composition only differ from those of known composition in the need for an initial spectrum discovery process by the computer application and thus a general and flexible tool for the development of computer-aided liquid chromatography methods is available. Mchrom Scout (Mestrelab Research) is the only computer-aided chromatographic software that adopts the same strategy for both types of problems. Drylab is currently the software per excellence used in many laboratories and, therefore, the comparison of the two software is also the subject of this study.
The state-of-the-art methodology for developing separations of compounds in solution, using Ultra performance liquid chromatography (UPLC), in reversed phase, is examined. The incorporation of novel computerised tools, using computer-aided methods (CAMD), allows the substitution of more laborious experiments by simulation of processes that imply substantial time and cost savings. Mchrom Scout (Mestrelab Research S.L.) allows the separation of mixtures of both known and unknown composition, thus differentiating it from other software that is limited to a specific type of problem. A general strategy is followed to extract the information from the spectra of the components in the mixture chromatograms obtained experimentally using multivariate alternating least squares curve resolution (MCR-ALS) tools. This technique allows estimating the actual spectra for the individual components as well as their elution profiles. In this way, a retention model is constructed for each component, which allows an efficient optimisation process to be developed. Following this approach, strategies for samples of unknown composition only differ from those of known composition in the need for an initial spectrum discovery process by the computer application and thus a general and flexible tool for the development of computer-aided liquid chromatography methods is available. Mchrom Scout (Mestrelab Research) is the only computer-aided chromatographic software that adopts the same strategy for both types of problems. Drylab is currently the software per excellence used in many laboratories and, therefore, the comparison of the two software is also the subject of this study.
Direction
MONTES GOYANES, ROSA MARIA (Tutorships)
MONTES GOYANES, ROSA MARIA (Tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Biosorption: a green alternative for the preconcentration and speciation of trace metals in environmental samples
Authorship
A.D.C.
Bachelor of Chemistry
A.D.C.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
The increase of pollutants in the environment is a significant environmental concern that affects the health of ecosystems and humanity. This issue has intensified in recent decades due to human practices such as industrialization and deforestation, causing irreversible damage. To mitigate the effects of these impacts, chemistry advocates for a sustainable practice known as green chemistry. In this literature review, various studies on biosorption for the preconcentration and speciation of trace metals in environmental samples are analyzed. Biosorption is considered an alternative to traditional solid-phase extraction, but unlike the latter, it is committed to green chemistry. The biosorbents referenced in the literature include bacteria, fungi, yeasts, algae, and animal and plant derivatives. These are applied to a variety of samples, but environmental analyses frequently use natural sorbents. The most common metal contaminants in water and soil are pollutants such as mercury and lead. Through various procedures, we can quantitatively study the different species thanks to spectroscopic detection methods, which are the most employed in biosorption. This alternative achieves low LODs and high selectivities, with results similar to those obtained with traditional separation techniques. Therefore, the use of biosorbents is a very valid green alternative to incorporate into analytical methodologies aimed at determining metals in environmental samples.
The increase of pollutants in the environment is a significant environmental concern that affects the health of ecosystems and humanity. This issue has intensified in recent decades due to human practices such as industrialization and deforestation, causing irreversible damage. To mitigate the effects of these impacts, chemistry advocates for a sustainable practice known as green chemistry. In this literature review, various studies on biosorption for the preconcentration and speciation of trace metals in environmental samples are analyzed. Biosorption is considered an alternative to traditional solid-phase extraction, but unlike the latter, it is committed to green chemistry. The biosorbents referenced in the literature include bacteria, fungi, yeasts, algae, and animal and plant derivatives. These are applied to a variety of samples, but environmental analyses frequently use natural sorbents. The most common metal contaminants in water and soil are pollutants such as mercury and lead. Through various procedures, we can quantitatively study the different species thanks to spectroscopic detection methods, which are the most employed in biosorption. This alternative achieves low LODs and high selectivities, with results similar to those obtained with traditional separation techniques. Therefore, the use of biosorbents is a very valid green alternative to incorporate into analytical methodologies aimed at determining metals in environmental samples.
Direction
YEBRA BIURRUN, MARIA DEL CARMEN (Tutorships)
YEBRA BIURRUN, MARIA DEL CARMEN (Tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Identification of lactate-producing microbial communities in anaerobic fermentation
Authorship
X.G.D.D.
Double bachelor degree in Chemistry and Biology
X.G.D.D.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 10:00
07.18.2024 10:00
Summary
The valorization of waste and by-products through anaerobic fermentation represents a promising strategy to transform organic carbon into products with high added value, contributing to a circular economy. Metabolic pathways that have lactate as an intermediate and give rise to volatile fatty acids are particularly relevant because they allow greater selectivity towards odd chain acids and greater production of medium chain acids through the chain elongation mechanism. The experiments were designed according to the metabolic pathways and factors that favor lactate production. The 16S amplicons were sequenced and the microbial populations involved in the conversion of organic carbon via lactate were characterized by analyzing the reactor over time. The technique used was DNA sequencing using metabarcoding. The alpha and beta structure and diversity of the microbial community, the common and stable microbiome under all conditions in which significant amounts of lactate as an intermediate are produced, were studied. The results obtained indicate that the Firmicutes phylum, specifically the Bacilli class, is related to the production of lactic acid in anaerobic fermentation. This approach will allow a deep understanding of how to optimize anaerobic fermentation for the production of valuable compounds and how microbial communities contribute to these processes. The results may have practical applications in the design of more efficient and sustainable biorefineries.
The valorization of waste and by-products through anaerobic fermentation represents a promising strategy to transform organic carbon into products with high added value, contributing to a circular economy. Metabolic pathways that have lactate as an intermediate and give rise to volatile fatty acids are particularly relevant because they allow greater selectivity towards odd chain acids and greater production of medium chain acids through the chain elongation mechanism. The experiments were designed according to the metabolic pathways and factors that favor lactate production. The 16S amplicons were sequenced and the microbial populations involved in the conversion of organic carbon via lactate were characterized by analyzing the reactor over time. The technique used was DNA sequencing using metabarcoding. The alpha and beta structure and diversity of the microbial community, the common and stable microbiome under all conditions in which significant amounts of lactate as an intermediate are produced, were studied. The results obtained indicate that the Firmicutes phylum, specifically the Bacilli class, is related to the production of lactic acid in anaerobic fermentation. This approach will allow a deep understanding of how to optimize anaerobic fermentation for the production of valuable compounds and how microbial communities contribute to these processes. The results may have practical applications in the design of more efficient and sustainable biorefineries.
Direction
Balboa Méndez, Sabela (Tutorships)
MAURICIO IGLESIAS, MIGUEL (Co-tutorships)
Balboa Méndez, Sabela (Tutorships)
MAURICIO IGLESIAS, MIGUEL (Co-tutorships)
Court
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
ESTEVEZ TORANZO, MARIA ALICIA CAROLINA (Chairman)
COVELO ARTOS, GUILLERMO (Secretary)
CANDAL SUAREZ, EVA MARIA (Member)
Stimulation of metabolic pathways for the production of carboxylic acids via lactate in anaerobic fermentation
Authorship
X.G.D.D.
Double bachelor degree in Chemistry and Biology
X.G.D.D.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
Mixed open culture fermentation to produce volatile fatty acids can become an effective way to recover organic carbon present in wastewater and organic waste, contributing to circular chemistry. For this technique to be effective, it is necessary to have control over the products that are generated. One way to achieve this control could be through lactic acid, an intermediate that is produced during the fermentation of organic waste. In this way, the catabolic pathways carried out by microorganisms could be directed to produce odd-chain carboxylic acids, medium-chain acids through chain elongation, and especially propionic acid. Controlled experiments were designed and conducted for these mixed cultures with various strategies, such as modifying pH, carbohydrate abundance, and using nutritionally rich media. In this way, the conversion and selectivity towards carboxylic acids was studied and the factors that favor the production of lactic acid as an intermediate were determined. The results obtained indicate that the relationship between the substrate and the inoculum is a crucial factor when it comes to promoting lactate production, but not the type of medium and the type of carbohydrates, although some of these factors are necessary for certain microorganisms or to facilitate the production of volatile fatty acids. In addition, an analysis of the microbial population present in the different conditions was carried out. Well, knowing the microorganisms present responsible for lactate production will help optimize the process.
Mixed open culture fermentation to produce volatile fatty acids can become an effective way to recover organic carbon present in wastewater and organic waste, contributing to circular chemistry. For this technique to be effective, it is necessary to have control over the products that are generated. One way to achieve this control could be through lactic acid, an intermediate that is produced during the fermentation of organic waste. In this way, the catabolic pathways carried out by microorganisms could be directed to produce odd-chain carboxylic acids, medium-chain acids through chain elongation, and especially propionic acid. Controlled experiments were designed and conducted for these mixed cultures with various strategies, such as modifying pH, carbohydrate abundance, and using nutritionally rich media. In this way, the conversion and selectivity towards carboxylic acids was studied and the factors that favor the production of lactic acid as an intermediate were determined. The results obtained indicate that the relationship between the substrate and the inoculum is a crucial factor when it comes to promoting lactate production, but not the type of medium and the type of carbohydrates, although some of these factors are necessary for certain microorganisms or to facilitate the production of volatile fatty acids. In addition, an analysis of the microbial population present in the different conditions was carried out. Well, knowing the microorganisms present responsible for lactate production will help optimize the process.
Direction
MAURICIO IGLESIAS, MIGUEL (Tutorships)
Balboa Méndez, Sabela (Co-tutorships)
MAURICIO IGLESIAS, MIGUEL (Tutorships)
Balboa Méndez, Sabela (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Assessment of the use of Fontinalis antipyretica as a biomonitor for the presence of Ag nanoparticles in river courses, Part B
Authorship
I.D.R.
Double bachelor degree in Chemistry and Biology
I.D.R.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
This work focuses on evaluating the adsorption capacity of silver nanoparticles by the bryophyte Fontinalis antipyretica Hedw. To determine the evolution of adsorption over time, an initial laboratory experiment was proposed. This experiment evaluates the adsorption capacity using two suspensions of nanoparticles at different concentration levels during ten days of exposure. Once the results were obtained and the necessary exposure time was established, the experiment was conducted in the Sar River. Four points were selected before and after two wastewater treatment plants, aiming to detect and monitor the presence of silver nanoparticles in the river. The amount of silver nanoparticles adsorbed by the aquatic moss, as well as the amount of ionic silver present on its surface, was determined.
This work focuses on evaluating the adsorption capacity of silver nanoparticles by the bryophyte Fontinalis antipyretica Hedw. To determine the evolution of adsorption over time, an initial laboratory experiment was proposed. This experiment evaluates the adsorption capacity using two suspensions of nanoparticles at different concentration levels during ten days of exposure. Once the results were obtained and the necessary exposure time was established, the experiment was conducted in the Sar River. Four points were selected before and after two wastewater treatment plants, aiming to detect and monitor the presence of silver nanoparticles in the river. The amount of silver nanoparticles adsorbed by the aquatic moss, as well as the amount of ionic silver present on its surface, was determined.
Direction
Domínguez González, María Raquel (Tutorships)
HERBELLO HERMELO, PALOMA (Co-tutorships)
Domínguez González, María Raquel (Tutorships)
HERBELLO HERMELO, PALOMA (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Use of Fontinalis antipyretica Hedw. as an active biomonitor for silver nanoparticles
Authorship
I.D.R.
Double bachelor degree in Chemistry and Biology
I.D.R.
Double bachelor degree in Chemistry and Biology
Defense date
07.18.2024 11:00
07.18.2024 11:00
Summary
This work focuses on evaluating the adsorption capacity of silver nanoparticles by the bryophyte Fontinalis antipyretica Hedw. With the aim of determining the evolution of adsorption over time, an initial laboratory experiment was proposed to assess the adsorption capacity using two nanoparticle suspensions at different concentration levels over ten days of exposure. Once the results were obtained and the necessary exposure time established, the experiment was carried out in the Sar River. Four points located before and after two treatment plants were selected, with the aim of detecting and monitoring the presence of silver nanoparticles in the river, as well as evaluating the proper functioning of the corresponding WWTPs.
This work focuses on evaluating the adsorption capacity of silver nanoparticles by the bryophyte Fontinalis antipyretica Hedw. With the aim of determining the evolution of adsorption over time, an initial laboratory experiment was proposed to assess the adsorption capacity using two nanoparticle suspensions at different concentration levels over ten days of exposure. Once the results were obtained and the necessary exposure time established, the experiment was carried out in the Sar River. Four points located before and after two treatment plants were selected, with the aim of detecting and monitoring the presence of silver nanoparticles in the river, as well as evaluating the proper functioning of the corresponding WWTPs.
Direction
ABOAL VIÑAS, JESUS RAMON (Tutorships)
FERNANDEZ ESCRIBANO, JOSE ANGEL (Co-tutorships)
ABOAL VIÑAS, JESUS RAMON (Tutorships)
FERNANDEZ ESCRIBANO, JOSE ANGEL (Co-tutorships)
Court
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Ortiz Nuñez, Santiago (Chairman)
SANCHEZ VILAS, JULIA (Secretary)
PRIETO LAMAS, BEATRIZ LORETO (Member)
Dendrimeric vectors for gene therapy: structure-activity relationship. PART B
Authorship
N.M.P.
Double bachelor degree in Chemistry and Biology
N.M.P.
Double bachelor degree in Chemistry and Biology
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Gene therapy offers a revolutionary hope for the treatment of numerous diseases. Despite significant advances in the development of viral vectors, their high production cost and severe associated adverse effects have driven the search for non-viral alternatives. In this context, polymeric vehicles appear as a promising option to overcome these limitations. However, polymeric systems face other challenges, notably endosomal capture. This work explores the functionalization of dendritic systems to address this issue. The combination of dendrimers properties with boronic acid chemistry allows for the specific functionalization of the dendritic systems through variations in the subunits that reversibly bind to boronic acids. In the present work, the focus is on the search for vectors that achieve endosomal escape. Thus, the effect of different molecular subunits on the system's efficiency was studied, hoping that they could serve as enhancers of endosomal escape and, therefore, gene expression. The synthesis of the subunits, functionalized with catechol groups, was carried out following two synthetic strategies, depending on the nature of the final product. After their synthesis and characterization, they were assembled into the system previously designed by the group, through the formation of pH-sensitive boronate bonds, and their in vitro transfection capacity was evaluated. The results achieved were not satisfactory, so further studies will be required to optimize the system.
Gene therapy offers a revolutionary hope for the treatment of numerous diseases. Despite significant advances in the development of viral vectors, their high production cost and severe associated adverse effects have driven the search for non-viral alternatives. In this context, polymeric vehicles appear as a promising option to overcome these limitations. However, polymeric systems face other challenges, notably endosomal capture. This work explores the functionalization of dendritic systems to address this issue. The combination of dendrimers properties with boronic acid chemistry allows for the specific functionalization of the dendritic systems through variations in the subunits that reversibly bind to boronic acids. In the present work, the focus is on the search for vectors that achieve endosomal escape. Thus, the effect of different molecular subunits on the system's efficiency was studied, hoping that they could serve as enhancers of endosomal escape and, therefore, gene expression. The synthesis of the subunits, functionalized with catechol groups, was carried out following two synthetic strategies, depending on the nature of the final product. After their synthesis and characterization, they were assembled into the system previously designed by the group, through the formation of pH-sensitive boronate bonds, and their in vitro transfection capacity was evaluated. The results achieved were not satisfactory, so further studies will be required to optimize the system.
Direction
FERNANDEZ MEGIA, EDUARDO (Tutorships)
FERNANDEZ MEGIA, EDUARDO (Tutorships)
Court
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
TOJO SUAREZ, GABRIEL (Chairman)
FONDO BUSTO, MARIA MATILDE (Secretary)
TORNEIRO ABUIN, MERCEDES (Member)
The role of hydrogen in the energy transition
Authorship
P.R.S.C.
Double bachelor degree in Physics and Chemistry
P.R.S.C.
Double bachelor degree in Physics and Chemistry
Defense date
07.18.2024 09:30
07.18.2024 09:30
Summary
This Degree Thesis presents a detailed analysis of the role of hydrogen in the energy transition. Hydrogen is a key energy vector within the framework of the transition towards sustainable systems. This work studies the role of hydrogen as an alternative for the decarbonization of various sectors, including transport and industry. Current hydrogen production and sustainable alternatives, as well as different options for its transportation and storage, are analyzed. Promoting these aspects is crucial for its industrial use, especially in the transport sector, with the aim of reducing dependence on fossil fuels. This study is framed within the Spanish government’s hydrogen roadmap, which outlines a series of actions to promote the use of hydrogen as part of its energy transition plan.
This Degree Thesis presents a detailed analysis of the role of hydrogen in the energy transition. Hydrogen is a key energy vector within the framework of the transition towards sustainable systems. This work studies the role of hydrogen as an alternative for the decarbonization of various sectors, including transport and industry. Current hydrogen production and sustainable alternatives, as well as different options for its transportation and storage, are analyzed. Promoting these aspects is crucial for its industrial use, especially in the transport sector, with the aim of reducing dependence on fossil fuels. This study is framed within the Spanish government’s hydrogen roadmap, which outlines a series of actions to promote the use of hydrogen as part of its energy transition plan.
Direction
MENDEZ MORALES, TRINIDAD (Tutorships)
MENDEZ MORALES, TRINIDAD (Tutorships)
Court
ALVAREZ MUÑIZ, JAIME (Chairman)
BELIN , SAMUEL JULES (Secretary)
CARBALLEIRA ROMERO, CARLOS (Member)
ALVAREZ MUÑIZ, JAIME (Chairman)
BELIN , SAMUEL JULES (Secretary)
CARBALLEIRA ROMERO, CARLOS (Member)
Reduction and immobilization of nitrate and phosphate in aquatic systems
Authorship
P.R.S.C.
Double bachelor degree in Physics and Chemistry
P.R.S.C.
Double bachelor degree in Physics and Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
Eutrophication is a serious global environmental problem resulting from increased concentrations of nitrate and phosphate in aquatic systems, leading to the undesired proliferation of plants and microorganisms. This phenomenon causes a decrease in oxygen levels in the water, severely affecting aquatic fauna and water quality. To design a methodology that can mitigate the problems caused by eutrophication, this study investigates the capacity of iron oxyhydroxides, such as ferrihydrite, to remove phosphate from aquatic environments and the effects that organic matter (concentration and nature), pH, and salinity may have. Additionally, the Iron Wheel hypothesis was evaluated to propose a methodology for removing nitrate from aquatic environments by reducing it to nitrite or ammonium in the presence of organic matter and ferrihydrite. The results obtained are promising and indicate that optimizing the process regarding the concentrations and precursors of iron and organic matter to be used will allow the design of a material suitable for the simultaneous removal of both nutrients.
Eutrophication is a serious global environmental problem resulting from increased concentrations of nitrate and phosphate in aquatic systems, leading to the undesired proliferation of plants and microorganisms. This phenomenon causes a decrease in oxygen levels in the water, severely affecting aquatic fauna and water quality. To design a methodology that can mitigate the problems caused by eutrophication, this study investigates the capacity of iron oxyhydroxides, such as ferrihydrite, to remove phosphate from aquatic environments and the effects that organic matter (concentration and nature), pH, and salinity may have. Additionally, the Iron Wheel hypothesis was evaluated to propose a methodology for removing nitrate from aquatic environments by reducing it to nitrite or ammonium in the presence of organic matter and ferrihydrite. The results obtained are promising and indicate that optimizing the process regarding the concentrations and precursors of iron and organic matter to be used will allow the design of a material suitable for the simultaneous removal of both nutrients.
Direction
FIOL LOPEZ, SARAH (Tutorships)
ANTELO MARTINEZ, JUAN (Co-tutorships)
FIOL LOPEZ, SARAH (Tutorships)
ANTELO MARTINEZ, JUAN (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
Carbon quantum dots for the detection of pollutants in water.
Authorship
R.S.G.
Double bachelor degree in Physics and Chemistry
R.S.G.
Double bachelor degree in Physics and Chemistry
Defense date
09.17.2024 10:30
09.17.2024 10:30
Summary
Carbon dots (CDs) are a class of carbon-based nanoparticles widely used in various sectors due to their optical and electronic properties. Their application has extended to different fields such as biomedicine and environmental science, thanks to their outstanding biocompatibility and chemical stability. The degree of graphitization and the spatial arrangement of surface functional groups determine the functionality of these particles. In this work, carbon quantum dots (CQDs), a specific type of CDs characterized by intense fluorescence due to quantum confinement, will be synthesized. Generally, the presence of an analyte causes variations in the fluorescence of the CDs due to changes in the chemical environment. In this context, the performance of these particles as detectors of various pollutants will be analyzed by monitoring the changes in their fluorescence emission. Specifically, a detailed study of 4-nitrophenol, a highly toxic and harmful pollutant commonly found in aquatic environments, will be carried out. In summary, this work aims to establish a simple and eco-friendly technique capable of accurately determining the presence and concentration of contaminants in water. Furthermore, it will be demonstrated that the results obtained can be corroborated using complementary techniques.
Carbon dots (CDs) are a class of carbon-based nanoparticles widely used in various sectors due to their optical and electronic properties. Their application has extended to different fields such as biomedicine and environmental science, thanks to their outstanding biocompatibility and chemical stability. The degree of graphitization and the spatial arrangement of surface functional groups determine the functionality of these particles. In this work, carbon quantum dots (CQDs), a specific type of CDs characterized by intense fluorescence due to quantum confinement, will be synthesized. Generally, the presence of an analyte causes variations in the fluorescence of the CDs due to changes in the chemical environment. In this context, the performance of these particles as detectors of various pollutants will be analyzed by monitoring the changes in their fluorescence emission. Specifically, a detailed study of 4-nitrophenol, a highly toxic and harmful pollutant commonly found in aquatic environments, will be carried out. In summary, this work aims to establish a simple and eco-friendly technique capable of accurately determining the presence and concentration of contaminants in water. Furthermore, it will be demonstrated that the results obtained can be corroborated using complementary techniques.
Direction
TABOADA ANTELO, PABLO (Tutorships)
CAMBON FREIRE, ADRIANA (Co-tutorships)
TABOADA ANTELO, PABLO (Tutorships)
CAMBON FREIRE, ADRIANA (Co-tutorships)
Court
Pérez Muñuzuri, Alberto (Chairman)
BORSATO , RICCARDO (Secretary)
BARBOSA FERNANDEZ, SILVIA (Member)
Pérez Muñuzuri, Alberto (Chairman)
BORSATO , RICCARDO (Secretary)
BARBOSA FERNANDEZ, SILVIA (Member)
Polyhydroxylated Octahydroisoindols: Bibliographic Study and Synthetic Approach
Authorship
S.A.G.
Bachelor of Chemistry
S.A.G.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
In the field of organic chemistry and pharmaceutical research, compounds derived from octahydro-1H-isoindole and octahydro-1H-isoindolone have garnered attention due to their various industrial and biological applications. Of particular interest are the derivatives of these compounds with hydroxyl groups on their cyclohexane ring, which are the subject of investigation in this work. The synthesis of these hydroxylated derivatives is a key process in chemical research, with the incorporation of hydroxyl groups in positions on the cyclohexane ring being of great importance. Such structural modifications influence the biological activity of the compounds, making them potentially useful in various applications. In this work, the possible applications and synthesis methods described to date for these hydroxylated derivatives of octahydro-1H-isoindole and octahydro-1H-isoindolone will be explored to further investigate them.
In the field of organic chemistry and pharmaceutical research, compounds derived from octahydro-1H-isoindole and octahydro-1H-isoindolone have garnered attention due to their various industrial and biological applications. Of particular interest are the derivatives of these compounds with hydroxyl groups on their cyclohexane ring, which are the subject of investigation in this work. The synthesis of these hydroxylated derivatives is a key process in chemical research, with the incorporation of hydroxyl groups in positions on the cyclohexane ring being of great importance. Such structural modifications influence the biological activity of the compounds, making them potentially useful in various applications. In this work, the possible applications and synthesis methods described to date for these hydroxylated derivatives of octahydro-1H-isoindole and octahydro-1H-isoindolone will be explored to further investigate them.
Direction
ESTEVEZ CABANAS, JUAN CARLOS (Tutorships)
ESTEVEZ CABANAS, JUAN CARLOS (Tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Fabrication of self-healable electroluminescent devices
Authorship
B.T.P.
Bachelor of Chemistry
B.T.P.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Electroluminescent devices (EL) are being integrated into all kinds of electronic systems because of their light-emitting properties. However, the life expectancy and reliability of these devices are often diminished by the mechanical wear and tear they go through, especially in applications where strain is a constant factor to endure. This work explores the integration of a self-healable version of polydimethylsiloxane with phosphor nanoparticles (ZnS:Cu), which provides a solution to the short life expectancy most electroluminescent devices face nowadays. This new material, apart from being thermically stable, achieved a self-healing efficiency of 64% and showed remarkable stretching capabilities, being able to reach stretch deformations of up to 1250%. In addition to this, due to the biocompatible nature of its composition and the self-healing mechanism based on hydrogen bonding, this material is perfect for integration in devices that need to be in contact with the human body, such as medical monitoring devices. The implementation of self-healing mechanisms in electroluminescent devices may open new ways of addressing the physical deadline most of these devices are deemed to reach.
Electroluminescent devices (EL) are being integrated into all kinds of electronic systems because of their light-emitting properties. However, the life expectancy and reliability of these devices are often diminished by the mechanical wear and tear they go through, especially in applications where strain is a constant factor to endure. This work explores the integration of a self-healable version of polydimethylsiloxane with phosphor nanoparticles (ZnS:Cu), which provides a solution to the short life expectancy most electroluminescent devices face nowadays. This new material, apart from being thermically stable, achieved a self-healing efficiency of 64% and showed remarkable stretching capabilities, being able to reach stretch deformations of up to 1250%. In addition to this, due to the biocompatible nature of its composition and the self-healing mechanism based on hydrogen bonding, this material is perfect for integration in devices that need to be in contact with the human body, such as medical monitoring devices. The implementation of self-healing mechanisms in electroluminescent devices may open new ways of addressing the physical deadline most of these devices are deemed to reach.
Direction
LAZZARI , MASSIMO (Tutorships)
TIWARI , NAVEEN (Co-tutorships)
LAZZARI , MASSIMO (Tutorships)
TIWARI , NAVEEN (Co-tutorships)
Court
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
MARTINEZ NUÑEZ, EMILIO (Chairman)
MONTES GOYANES, ROSA MARIA (Secretary)
RIOS RODRIGUEZ, ANA MARIA (Member)
Self-assembly of catanionic surfactants in aqueous media
Authorship
C.S.M.
Bachelor of Chemistry
C.S.M.
Bachelor of Chemistry
Defense date
07.15.2024 09:30
07.15.2024 09:30
Summary
Catanionic surfactants are a type of surfactant that arises from the combination of cationic and anionic surfactants. This novel type of surfactant brings significant advancements due to its unique properties. The introduction will cover what surfactants are, the different types of surfactants, and the structures they form upon aggregation. Catanionic/anionic mixtures will be introducen as well. This bibliographic project will address the preparation methods, properties, different phases and sructures. This study will focus primarily on the self-aggregation of catanionic vesicles, due to their remarkable properties and the advancements they bring to the scientific community. Catanionic vesicles applications in the pharmaceutical field will be studied to.
Catanionic surfactants are a type of surfactant that arises from the combination of cationic and anionic surfactants. This novel type of surfactant brings significant advancements due to its unique properties. The introduction will cover what surfactants are, the different types of surfactants, and the structures they form upon aggregation. Catanionic/anionic mixtures will be introducen as well. This bibliographic project will address the preparation methods, properties, different phases and sructures. This study will focus primarily on the self-aggregation of catanionic vesicles, due to their remarkable properties and the advancements they bring to the scientific community. Catanionic vesicles applications in the pharmaceutical field will be studied to.
Direction
GARCIA RIO, LUIS (Tutorships)
GARCIA RIO, LUIS (Tutorships)
Court
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
ABOAL SOMOZA, MANUEL (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
FERRO COSTAS, DAVID (Member)
Aggregation of ortho-, meta- and para-substituted oligo(phenylenethynylenes)
Authorship
C.R.F.
Bachelor of Chemistry
C.R.F.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
In this project, three different monomers were synthesized with substituents in different positions with their respective enantiomers of each of them R and S, the ortho substituent is called N-(2-((4-ethinylphenyl) ethinyl )phenyl)-2-methoxy-2- phenylacetamide the meta is called N-(3-((4-ethynylphenyl)ethynyl)phenyl)-2-methoxy2-phenylacetamide, the para is called N-(4- ((4-ethynylphenyl)ethynyl)phenyl)-2- methoxy-2-phenylacetamide in this case all six are OPEs with two aromatic rings in each of the monomers. From what was analyzed in the VT-CD and UV-vis studies we can see how none of the six compounds formed a supramolecular aggregate. Therefore, it is necessary to additionally add one more aromatic ring to the six molecules since this way the monomers will have a greater capacity to form pi-pi interactions and thus form a supramolecular aggregate.
In this project, three different monomers were synthesized with substituents in different positions with their respective enantiomers of each of them R and S, the ortho substituent is called N-(2-((4-ethinylphenyl) ethinyl )phenyl)-2-methoxy-2- phenylacetamide the meta is called N-(3-((4-ethynylphenyl)ethynyl)phenyl)-2-methoxy2-phenylacetamide, the para is called N-(4- ((4-ethynylphenyl)ethynyl)phenyl)-2- methoxy-2-phenylacetamide in this case all six are OPEs with two aromatic rings in each of the monomers. From what was analyzed in the VT-CD and UV-vis studies we can see how none of the six compounds formed a supramolecular aggregate. Therefore, it is necessary to additionally add one more aromatic ring to the six molecules since this way the monomers will have a greater capacity to form pi-pi interactions and thus form a supramolecular aggregate.
Direction
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Photolabile ligands for the development of precision antibiotics.
Authorship
J.C.D.
Bachelor of Chemistry
J.C.D.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
The ability of antibiotics to cure bacterial infectious diseases is now at serious risk due to the consequences of broad-spectrum antibiotic use on microbiome stability and pathogen resistance. Precision antibiotics with focused and well-defined activities are emerging as a means of addressing infections without damaging microbiomes or incentivizing resistance. This project is focused on the synthesis of photolabile compounds targeting the LpxB enzyme from Acinetobacter baumannii, an unexplored target involved in the lipid A biosynthesis, which therapeutic potential has been recently identified by our research group. The target compounds, which are mimics of the enzyme substrate, Lipid X, are aimed to get structural information of enzyme recognition, along with the enzyme key sites for inhibition. The development of a robust and reproducible synthetic strategy for the preparation of the target compounds is described.
The ability of antibiotics to cure bacterial infectious diseases is now at serious risk due to the consequences of broad-spectrum antibiotic use on microbiome stability and pathogen resistance. Precision antibiotics with focused and well-defined activities are emerging as a means of addressing infections without damaging microbiomes or incentivizing resistance. This project is focused on the synthesis of photolabile compounds targeting the LpxB enzyme from Acinetobacter baumannii, an unexplored target involved in the lipid A biosynthesis, which therapeutic potential has been recently identified by our research group. The target compounds, which are mimics of the enzyme substrate, Lipid X, are aimed to get structural information of enzyme recognition, along with the enzyme key sites for inhibition. The development of a robust and reproducible synthetic strategy for the preparation of the target compounds is described.
Direction
GONZALEZ BELLO, CONCEPCION (Tutorships)
MANEIRO REY, MARIA (Co-tutorships)
GONZALEZ BELLO, CONCEPCION (Tutorships)
MANEIRO REY, MARIA (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Unraveling the formation of glycine and its isomer, glycolamide, in space.
Authorship
M.C.R.
Bachelor of Chemistry
M.C.R.
Bachelor of Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
One of the primordial conditions for the existence of life, as we know it, is the presence of amino acids such as glycine. Its origin remains unknown, which is why proving its formation in the interstellar medium (ISM) would bring us closer to understanding how life might arise, a topic widely discussed within the scientific community. Here we present a computational investigation of the possible reaction pathways leading to glycine in the cold regions of the ISM. For this purpose, we use the AutoMeKin software, which employs MOPAC for low-level calculations via the semi-empirical PM7 method and Gaussian16 for high-level calculations using density functional theory (DFT) [M08HX/6-31+G(d,p)]. Our results show that glycine can form from radical-radical barrierless collision pathways, involving precursors detected in the ISM. We have also discovered formation pathways leading to glycolamide, an isomer of glycine detected in the ISM.
One of the primordial conditions for the existence of life, as we know it, is the presence of amino acids such as glycine. Its origin remains unknown, which is why proving its formation in the interstellar medium (ISM) would bring us closer to understanding how life might arise, a topic widely discussed within the scientific community. Here we present a computational investigation of the possible reaction pathways leading to glycine in the cold regions of the ISM. For this purpose, we use the AutoMeKin software, which employs MOPAC for low-level calculations via the semi-empirical PM7 method and Gaussian16 for high-level calculations using density functional theory (DFT) [M08HX/6-31+G(d,p)]. Our results show that glycine can form from radical-radical barrierless collision pathways, involving precursors detected in the ISM. We have also discovered formation pathways leading to glycolamide, an isomer of glycine detected in the ISM.
Direction
FERNANDEZ RAMOS, ANTONIO (Tutorships)
CASTIÑEIRA REIS, MARTA (Co-tutorships)
FERNANDEZ RAMOS, ANTONIO (Tutorships)
CASTIÑEIRA REIS, MARTA (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Supramolecular Helical Polymers: Halogen Bonding
Authorship
I.M.F.
Bachelor of Chemistry
I.M.F.
Bachelor of Chemistry
Defense date
02.19.2024 10:00
02.19.2024 10:00
Summary
Supramolecular chemistry focuses on the non-covalent interactions between molecules to form larger and more complex supramolecular structures and systems. Supramolecular helical polymers are particularly notable in this field due to their helical structure and unique properties such as chirality, structural stability, optical and electronic properties, self-assembly and molecular recognition. Halogen bonding, a specialized form of non-covalent interaction, also plays a significant role in the stabilization of these polymers. This interaction occurs between halogen atoms and electronegative atoms such as oxygen, nitrogen, or sulfur. It is directional, specific and it can contribute to the formation and stability of supramolecular helical polymers. Experimental studies employ techniques such as infrared spectroscopy, X-Ray diffraction, nuclear magnetic resonance spectroscopy and UV/Vis spectroscopy to confirm the assembly of halogen-bonded supramolecular polymers. These techniques enable the determination of the presence of halogen bonds, analysis of the structure and properties of the formed polymers, and investigation of their response to external stimuli. The primary objective of these experimental studies is to understand the assembly mechanism of supramolecular polymers and their response to temperature, pH, or other stimuli. This work aims to design monomers with suitable characteristics to facilitate the self-assembly of supramolecular polymers. This understanding is crucial for the design and synthesis of materials with applications in various fields such as medicine, materials chemistry, and molecular electronics.
Supramolecular chemistry focuses on the non-covalent interactions between molecules to form larger and more complex supramolecular structures and systems. Supramolecular helical polymers are particularly notable in this field due to their helical structure and unique properties such as chirality, structural stability, optical and electronic properties, self-assembly and molecular recognition. Halogen bonding, a specialized form of non-covalent interaction, also plays a significant role in the stabilization of these polymers. This interaction occurs between halogen atoms and electronegative atoms such as oxygen, nitrogen, or sulfur. It is directional, specific and it can contribute to the formation and stability of supramolecular helical polymers. Experimental studies employ techniques such as infrared spectroscopy, X-Ray diffraction, nuclear magnetic resonance spectroscopy and UV/Vis spectroscopy to confirm the assembly of halogen-bonded supramolecular polymers. These techniques enable the determination of the presence of halogen bonds, analysis of the structure and properties of the formed polymers, and investigation of their response to external stimuli. The primary objective of these experimental studies is to understand the assembly mechanism of supramolecular polymers and their response to temperature, pH, or other stimuli. This work aims to design monomers with suitable characteristics to facilitate the self-assembly of supramolecular polymers. This understanding is crucial for the design and synthesis of materials with applications in various fields such as medicine, materials chemistry, and molecular electronics.
Direction
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
QUIÑOA CABANA, EMILIO (Tutorships)
RODRIGUEZ RIEGO, RAFAEL (Co-tutorships)
Court
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
FERNANDEZ MEGIA, EDUARDO (Chairman)
MARTINEZ CALVO, MIGUEL (Secretary)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Member)
Inhibition of the LasB enzyme for the development of new anti-virulence agents against hospital-acquired pathogenic bacteria
Authorship
C.A.C.
Bachelor of Chemistry
C.A.C.
Bachelor of Chemistry
Defense date
09.11.2024 16:30
09.11.2024 16:30
Summary
Antibiotics have saved millions of lives and revolutionised modern medicine. However, its misuse and inappropriate implementation have led to the rising emergence of antibiotic-resistant strains. Given the severity of this issue, the World Health Organization has identified a series of pathogens considered priorities for the development of new treatments, prominently including the Gram-negative bacterium Pseudomonas aeruginosa. This is an opportunistic bacterium that thrives in numerous environments and poses significant problems for immunocompromised patients, particularly those suffering from cystic fibrosis. The adaptability of the bacterium and the plasticity of its genome make it extremely resistant, complicating its eradication. The inefficiency of traditional antibiotics has driven the search for new therapies, such as anti-virulence therapies. This strategy involves inhibiting specific virulence factors rather than targeting processes essential for bacterial survival, thereby reducing the selective pressure that fosters resistance. This project addresses this strategy and specifically aims to develop inhibitors of the elastase LasB, an extracellular protease and key virulence factor in P. aeruginosa. Phosphoramidon, a transition state mimetic (addition-elimination), is one of the most notable inhibi-tors of LasB, though it lacks specificity for this metalloprotease. This work focuses on the development of a specific inhibitor for LasB, a boronic acid derivative of phospho-ramidon, which aims to improve this specificity issue.
Antibiotics have saved millions of lives and revolutionised modern medicine. However, its misuse and inappropriate implementation have led to the rising emergence of antibiotic-resistant strains. Given the severity of this issue, the World Health Organization has identified a series of pathogens considered priorities for the development of new treatments, prominently including the Gram-negative bacterium Pseudomonas aeruginosa. This is an opportunistic bacterium that thrives in numerous environments and poses significant problems for immunocompromised patients, particularly those suffering from cystic fibrosis. The adaptability of the bacterium and the plasticity of its genome make it extremely resistant, complicating its eradication. The inefficiency of traditional antibiotics has driven the search for new therapies, such as anti-virulence therapies. This strategy involves inhibiting specific virulence factors rather than targeting processes essential for bacterial survival, thereby reducing the selective pressure that fosters resistance. This project addresses this strategy and specifically aims to develop inhibitors of the elastase LasB, an extracellular protease and key virulence factor in P. aeruginosa. Phosphoramidon, a transition state mimetic (addition-elimination), is one of the most notable inhibi-tors of LasB, though it lacks specificity for this metalloprotease. This work focuses on the development of a specific inhibitor for LasB, a boronic acid derivative of phospho-ramidon, which aims to improve this specificity issue.
Direction
GONZALEZ BELLO, CONCEPCION (Tutorships)
MANEIRO REY, MARIA (Co-tutorships)
GONZALEZ BELLO, CONCEPCION (Tutorships)
MANEIRO REY, MARIA (Co-tutorships)
Court
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
SARDINA LOPEZ, FRANCISCO JAVIER (Chairman)
SAA RODRIGUEZ, CARLOS EUGENIO (Secretary)
GARCIA FERNANDEZ, MARIA ESTHER (Member)
Unraveling the Mystery of Atoms in the Molecule
Authorship
R.S.G.
Double bachelor degree in Physics and Chemistry
R.S.G.
Double bachelor degree in Physics and Chemistry
Defense date
09.11.2024 09:00
09.11.2024 09:00
Summary
The quantum theory of atoms in molecules (QTAIM), developed by Richard F.W. Bader, constitutes a powerful tool in the field of theoretical chemistry. Intended for topological analysis, this quantum theory introduces the innovation of using the electron density, which allows fragmenting the molecular space into regions called atomic basins. The evaluation of the electron density at critical points (CPs) and the calculation of integrated properties within these basins provide answers to various questions, such as the reason for the transferability of electronic properties associated with functional groups between different compounds. In this work we will present the theoretical principles of QTAIM and analyze different chemical systems to relate QTAIM properties to chemical quantities and fundamentals. The results, obtained computationally, depend on the level of calculation used, characterized by the level of theory and the basis set. In addition to isolated molecules, the course of a sigmatropic reaction will be also analyzed, detailing the associated transition state (TS) and minimum energy path (MEP).
The quantum theory of atoms in molecules (QTAIM), developed by Richard F.W. Bader, constitutes a powerful tool in the field of theoretical chemistry. Intended for topological analysis, this quantum theory introduces the innovation of using the electron density, which allows fragmenting the molecular space into regions called atomic basins. The evaluation of the electron density at critical points (CPs) and the calculation of integrated properties within these basins provide answers to various questions, such as the reason for the transferability of electronic properties associated with functional groups between different compounds. In this work we will present the theoretical principles of QTAIM and analyze different chemical systems to relate QTAIM properties to chemical quantities and fundamentals. The results, obtained computationally, depend on the level of calculation used, characterized by the level of theory and the basis set. In addition to isolated molecules, the course of a sigmatropic reaction will be also analyzed, detailing the associated transition state (TS) and minimum energy path (MEP).
Direction
FERNANDEZ RAMOS, ANTONIO (Tutorships)
FERRO COSTAS, DAVID (Co-tutorships)
FERNANDEZ RAMOS, ANTONIO (Tutorships)
FERRO COSTAS, DAVID (Co-tutorships)
Court
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
Rodríguez Prieto, María de la Flor (Chairman)
CASTRO VARELA, GABRIELA (Secretary)
ABOAL SOMOZA, MANUEL (Member)
New porous materials for energetic and catalytic applications
Authorship
P.D.C.
Double bachelor degree in Physics and Chemistry
P.D.C.
Double bachelor degree in Physics and Chemistry
Defense date
07.18.2024 09:00
07.18.2024 09:00
Summary
In this work, nanoparticles of the metal organic structure (MOF) type containing Cu in its lattice: CuMI, have been obtained through synthesis processes in aqueous medium and room temperature. The MOF has been structurally and functionally characterized by Scanning Electron Microscopy, X ray Diffraction, Thermogravimetric Analysis and N2 Adsorption Analysis. After the characterization of the standard product, we studied the influence of the synthesis parameters on the MOF: the oncentration of stabilizer, CTAB, and reaction time; and what is its effect on the structure and size of the MOF. Finally, we analyze the colloidal stability of the MOF dissolved in acetone.
In this work, nanoparticles of the metal organic structure (MOF) type containing Cu in its lattice: CuMI, have been obtained through synthesis processes in aqueous medium and room temperature. The MOF has been structurally and functionally characterized by Scanning Electron Microscopy, X ray Diffraction, Thermogravimetric Analysis and N2 Adsorption Analysis. After the characterization of the standard product, we studied the influence of the synthesis parameters on the MOF: the oncentration of stabilizer, CTAB, and reaction time; and what is its effect on the structure and size of the MOF. Finally, we analyze the colloidal stability of the MOF dissolved in acetone.
Direction
TABOADA ANTELO, PABLO (Tutorships)
VILA FUNGUEIRIÑO, JOSE MANUEL (Co-tutorships)
TABOADA ANTELO, PABLO (Tutorships)
VILA FUNGUEIRIÑO, JOSE MANUEL (Co-tutorships)
Court
Varela Cabo, Luis Miguel (Chairman)
PARAJO VIEITO, JUAN JOSE (Secretary)
ARMESTO PEREZ, NESTOR (Member)
Varela Cabo, Luis Miguel (Chairman)
PARAJO VIEITO, JUAN JOSE (Secretary)
ARMESTO PEREZ, NESTOR (Member)
Porous materials based on metal organic frameworks (MOFs) for energy and catalytic applications
Authorship
P.D.C.
Double bachelor degree in Physics and Chemistry
P.D.C.
Double bachelor degree in Physics and Chemistry
Defense date
07.15.2024 09:00
07.15.2024 09:00
Summary
In this work, nanoparticles of two types of metal organic structures (MOFs) containing Cu in their lattice: Cu3(HITP)2 and CuMI, have been obtained through synthesis processes in aqueous medium and room temperature. Both types of MOFs have been structurally and functionally characterized by Scanning Electron Microscopy, X Ray Diffraction, UV Vis Spectroscopy, Thermogravimetric Analysis and Brunauer-Emmet-Teller (BET)N2 Adsorption Analysis. Both MOFs have been compared to determine their potential in catalytic applications. In the case of Cu3(HITP)2 nanoparticles of a size of less than 100nm have been obtained, while for CuMI the size range is greater than 130nm. In addition, the percentage of mass corresponding to the organic ligand is higher (45 %) in the Cu3(HITP)2 with a more gradual degradation process. In particular, for the MOF Cu3(HITP)2 it has been possible to determine an orthorhombic structure with a cell volume of 4.83nm3. Although both MOFs have very similar pore sizes, close to 2nm, the surface area available in the Cu3(HITP)2 is double, which suggests that this compound would have greater potential in catalysis applications.
In this work, nanoparticles of two types of metal organic structures (MOFs) containing Cu in their lattice: Cu3(HITP)2 and CuMI, have been obtained through synthesis processes in aqueous medium and room temperature. Both types of MOFs have been structurally and functionally characterized by Scanning Electron Microscopy, X Ray Diffraction, UV Vis Spectroscopy, Thermogravimetric Analysis and Brunauer-Emmet-Teller (BET)N2 Adsorption Analysis. Both MOFs have been compared to determine their potential in catalytic applications. In the case of Cu3(HITP)2 nanoparticles of a size of less than 100nm have been obtained, while for CuMI the size range is greater than 130nm. In addition, the percentage of mass corresponding to the organic ligand is higher (45 %) in the Cu3(HITP)2 with a more gradual degradation process. In particular, for the MOF Cu3(HITP)2 it has been possible to determine an orthorhombic structure with a cell volume of 4.83nm3. Although both MOFs have very similar pore sizes, close to 2nm, the surface area available in the Cu3(HITP)2 is double, which suggests that this compound would have greater potential in catalysis applications.
Direction
VILA FUNGUEIRIÑO, JOSE MANUEL (Tutorships)
TABOADA ANTELO, PABLO (Co-tutorships)
VILA FUNGUEIRIÑO, JOSE MANUEL (Tutorships)
TABOADA ANTELO, PABLO (Co-tutorships)
Court
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)
LORES AGUIN, MARTA (Chairman)
RIOS RODRIGUEZ, MARIA DEL CARMEN (Secretary)
Carro Díaz, Antonia María (Member)