Natural Substrate Mimetic Aziridines for Irreversible Inhibition of Enzymes Involved in Bacterial Virulence
Authorship
A.A.L.
Master's Degree in Chemical Research and Industrial Chemistry
A.A.L.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
The most widely used strategy to combat bacterial infections is based on disrupting bacterial viability by preventing the synthesis and assembly of key components for bacterial survival. Although this strategy is highly effective, and many clinically used antibiotics are based on this principle, it causes considerable stress to the bacteria, which favors the emergence of antibiotic-resistant strains. To avoid this problem, in recent years, considerable effort has been devoted to developing agents capable of reducing the bacteria's ability to cause infection (pathogenicity). In this context, Professor Concepción González-Bello's group has focused on developing antivirulence agents based on the inhibition of the enzyme dehydrokinase type I (DHQ1), an in vivo virulence agent in Enterobacteriaceae. This Master's thesis is aimed at developing an analogue of the natural substrate in which the ketone group is replaced by an aziridine group, thereby causing irreversible inhibition of the enzyme.
The most widely used strategy to combat bacterial infections is based on disrupting bacterial viability by preventing the synthesis and assembly of key components for bacterial survival. Although this strategy is highly effective, and many clinically used antibiotics are based on this principle, it causes considerable stress to the bacteria, which favors the emergence of antibiotic-resistant strains. To avoid this problem, in recent years, considerable effort has been devoted to developing agents capable of reducing the bacteria's ability to cause infection (pathogenicity). In this context, Professor Concepción González-Bello's group has focused on developing antivirulence agents based on the inhibition of the enzyme dehydrokinase type I (DHQ1), an in vivo virulence agent in Enterobacteriaceae. This Master's thesis is aimed at developing an analogue of the natural substrate in which the ketone group is replaced by an aziridine group, thereby causing irreversible inhibition of the enzyme.
Direction
GONZALEZ BELLO, CONCEPCION (Tutorships)
GONZALEZ BELLO, CONCEPCION (Tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
QUIÑOA CABANA, EMILIO (Chairman)
Vaz Araújo, Belén (Secretary)
Castro García, Socorro (Member)
Sanmartin Matalobos, Jesus (Coordinator)
QUIÑOA CABANA, EMILIO (Chairman)
Vaz Araújo, Belén (Secretary)
Castro García, Socorro (Member)
Synthesis, optimization and physicochemical characterization of fluorescent magnetic nanocapsules.
Authorship
V.A.T.
Master's Degree in Chemical Research and Industrial Chemistry
V.A.T.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Since their discovery, nanomaterials have been employed for a wide variety of applications in many different fields. The properties of these materials such as controlled size synthesis, tunable fluorescence emission, chemical versatility and the enhancement of the catalytic and photocatalytic properties observed in the nanoscale have caught the attention of researchers to find possible applications in biomedicine. In this regard, the work carried out in the laboratories of the Nanotechnology and Magnetism (NANOMAG) group at iMATUS, Santiago de Compostela, has focused on the synthesis of novel fluorescent and magnetic nanocapsules that can be used for medical imaging and advances biomedical therapies. Therefore, a fluorescent nanocapsule was created consisting of SPIONs nuclei coated with gelatin and functionalized with FeNCs. First, SPIONs were prepared by co-precipitation method and coated with gelatin to obtain gelatin nanoparticles by desolvation. Alongside, the FeNCs were synthesized by chemical reduction and then, the assembly on the surface of gelatin nanoparticles was carried out through electrostatic/covalent methods. All nanomaterials have been characterized by different methodologies such as TGA, ATR-FTIR, XRD, DLS, or TEM/STEM to verify if the desired properties were obtained. Finally, confocal microscopy was performed to asses the potential of these fluorescent magnetic nano capsules for biomedical applications.
Since their discovery, nanomaterials have been employed for a wide variety of applications in many different fields. The properties of these materials such as controlled size synthesis, tunable fluorescence emission, chemical versatility and the enhancement of the catalytic and photocatalytic properties observed in the nanoscale have caught the attention of researchers to find possible applications in biomedicine. In this regard, the work carried out in the laboratories of the Nanotechnology and Magnetism (NANOMAG) group at iMATUS, Santiago de Compostela, has focused on the synthesis of novel fluorescent and magnetic nanocapsules that can be used for medical imaging and advances biomedical therapies. Therefore, a fluorescent nanocapsule was created consisting of SPIONs nuclei coated with gelatin and functionalized with FeNCs. First, SPIONs were prepared by co-precipitation method and coated with gelatin to obtain gelatin nanoparticles by desolvation. Alongside, the FeNCs were synthesized by chemical reduction and then, the assembly on the surface of gelatin nanoparticles was carried out through electrostatic/covalent methods. All nanomaterials have been characterized by different methodologies such as TGA, ATR-FTIR, XRD, DLS, or TEM/STEM to verify if the desired properties were obtained. Finally, confocal microscopy was performed to asses the potential of these fluorescent magnetic nano capsules for biomedical applications.
Direction
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
González Gómez, Manuel Antonio (Co-tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
González Gómez, Manuel Antonio (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Master Dissertation
Authorship
A.A.G.
Master in Organic Chemistry (3ª ed)
A.A.G.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Recent studies have shown that the use of broad-spectrum antibiotics compromises microbiome stability and promotes resistance, leading to a reconsideration of the therapeutic approach used in the treatment of bacterial infections. Inspired by advances in precision medicine in oncology, antibiotic discovery is now shifting towards the development of narrow-spectrum antibiotics. Precision antibiotics with focused and well-defined activities are emerging as a strategy to treat infections without disrupting the microbiome or promoting resistance. Pseudomonas aeruginosa, one of the most concerning pathogens identified by the World Health Organization (WHO), is responsible for some of the most challenging multidrug-resistant infectious diseases today. Therefore, there is an urgent need to develop new anti-Pseudomonas drugs with novel mechanisms of action that selectively disable clinically unexploited bacterial targets. An innovative antibacterial strategy involves the inhibition of the bacterium's ability to cause infection (pathogenesis). This project aims to discover novel inhibitors of LasB (Pseudomonas elastase B, pseudolysin, encoded by the lasB gene, EC 3.4.24.26). The proposed inhibitor, a phosphoramidon derivative, seeks to improve selectivity against other proteases by incorporating a boronate group, which mimics the tetrahedral transition state (addition-elimination mechanism) involved in LasB catalysis.
Recent studies have shown that the use of broad-spectrum antibiotics compromises microbiome stability and promotes resistance, leading to a reconsideration of the therapeutic approach used in the treatment of bacterial infections. Inspired by advances in precision medicine in oncology, antibiotic discovery is now shifting towards the development of narrow-spectrum antibiotics. Precision antibiotics with focused and well-defined activities are emerging as a strategy to treat infections without disrupting the microbiome or promoting resistance. Pseudomonas aeruginosa, one of the most concerning pathogens identified by the World Health Organization (WHO), is responsible for some of the most challenging multidrug-resistant infectious diseases today. Therefore, there is an urgent need to develop new anti-Pseudomonas drugs with novel mechanisms of action that selectively disable clinically unexploited bacterial targets. An innovative antibacterial strategy involves the inhibition of the bacterium's ability to cause infection (pathogenesis). This project aims to discover novel inhibitors of LasB (Pseudomonas elastase B, pseudolysin, encoded by the lasB gene, EC 3.4.24.26). The proposed inhibitor, a phosphoramidon derivative, seeks to improve selectivity against other proteases by incorporating a boronate group, which mimics the tetrahedral transition state (addition-elimination mechanism) involved in LasB catalysis.
Direction
GONZALEZ BELLO, CONCEPCION (Tutorships)
GONZALEZ BELLO, CONCEPCION (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Photooxidation of pharmaceutical contaminants catalyzed by atomic quantum clusters
Authorship
P.B.R.
Master's Degree in Chemical Research and Industrial Chemistry
P.B.R.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 15:30
07.17.2025 15:30
Summary
Pharmaceutical-derived pollutants represent an increasing environmental concern, as conventional water treatment methods cannot effectively remove them. In this context, innovative technologies based on advanced oxidation processes AOPs are emerging as promising alternatives for their removal. Among these, photocatalysis using titanium dioxide TiO2 stands out, enabling the photooxidation of organic molecules. However, TiO2 has limitations such as low photocatalytic efficiency and poor selectivity. In this study, the activity of catalysts based on silver atomic quantum clusters AgMM@P25, synthesized by NANOGAP, was evaluated for the photodegradation of two pharmaceutical pollutants ibuprofen and diclofenac under two light sources UVA lamp and solar simulator. The experiments demonstrated the feasibility of degrading ibuprofen and diclofenac under simulated sunlight and UVA-LED illumination. Based on the results obtained with different catalysts, it was confirmed that the presence of AgMM improves the degradation capacity of TiO2 P25 compared to unmodified P25, highlighting the potential of this system for future research.
Pharmaceutical-derived pollutants represent an increasing environmental concern, as conventional water treatment methods cannot effectively remove them. In this context, innovative technologies based on advanced oxidation processes AOPs are emerging as promising alternatives for their removal. Among these, photocatalysis using titanium dioxide TiO2 stands out, enabling the photooxidation of organic molecules. However, TiO2 has limitations such as low photocatalytic efficiency and poor selectivity. In this study, the activity of catalysts based on silver atomic quantum clusters AgMM@P25, synthesized by NANOGAP, was evaluated for the photodegradation of two pharmaceutical pollutants ibuprofen and diclofenac under two light sources UVA lamp and solar simulator. The experiments demonstrated the feasibility of degrading ibuprofen and diclofenac under simulated sunlight and UVA-LED illumination. Based on the results obtained with different catalysts, it was confirmed that the presence of AgMM improves the degradation capacity of TiO2 P25 compared to unmodified P25, highlighting the potential of this system for future research.
Direction
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
Rodríguez Arias, Iria (Co-tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
Rodríguez Arias, Iria (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
SARANDESES DA COSTA, LUIS ALBERTO (Chairman)
PARAJO MONTES, MARIA MERCEDES (Secretary)
Sánchez Vázquez, Pablo Breogán (Member)
Sanmartin Matalobos, Jesus (Coordinator)
SARANDESES DA COSTA, LUIS ALBERTO (Chairman)
PARAJO MONTES, MARIA MERCEDES (Secretary)
Sánchez Vázquez, Pablo Breogán (Member)
Determination of ketamine consumption through wastewater analysis
Authorship
M.C.R.
Master's Degree in Chemical Research and Industrial Chemistry
M.C.R.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
This project focuses on the application of the wastewater-based epidemiology (WBE) approach for determining population-level ketamine consumption and the potential routes of use (illicit or prescribed) detected in wastewater. To this end, an analytical method was developed and validated based on the direct injection of samples into a high-performance liquid chromatography system coupled to tandem mass spectrometry (HPLC-QqQ-MS/MS), using a chiral column for enantiomeric separation. The methodology was optimized to achieve appropriate accuracy, precision, and good detection and quantification limits in a complex matrix such as wastewater. Samples collected from four wastewater treatment plants corresponding to different cities were analyzed to evaluate population-level ketamine use. Furthermore, through the enantiomeric profile, the available data on hospital ketamine dispensing, and the analysis of real illicit ketamine samples, it was possible to distinguish between legal use (both racemic and S-ketamine, or esketamine) and illicit use (exclusively racemic). The results showed that ketamine concentrations in wastewater were, in all cases, significantly higher than those attributable to hospital dispensing, indicating the existence of an additional source of ketamine in the urban environment. The enantiomeric profile showed values of R-ketamine enantiomeric fractionslightly higher than 0.5 in most cases, indicating an equimolar presence of the R and S enantiomers, characteristic of racemic ketamine. Although this information alone does not allow for a clear distinction between hospital and illicit use, combining this profile with prescription data suggests that a significant proportion of the ketamine found in wastewater originates from unregulated consumption. This is further supported by the analysis of samples from the illicit market, which also showed a racemic composition, confirming the nature of the product distributed for recreational purposes.
This project focuses on the application of the wastewater-based epidemiology (WBE) approach for determining population-level ketamine consumption and the potential routes of use (illicit or prescribed) detected in wastewater. To this end, an analytical method was developed and validated based on the direct injection of samples into a high-performance liquid chromatography system coupled to tandem mass spectrometry (HPLC-QqQ-MS/MS), using a chiral column for enantiomeric separation. The methodology was optimized to achieve appropriate accuracy, precision, and good detection and quantification limits in a complex matrix such as wastewater. Samples collected from four wastewater treatment plants corresponding to different cities were analyzed to evaluate population-level ketamine use. Furthermore, through the enantiomeric profile, the available data on hospital ketamine dispensing, and the analysis of real illicit ketamine samples, it was possible to distinguish between legal use (both racemic and S-ketamine, or esketamine) and illicit use (exclusively racemic). The results showed that ketamine concentrations in wastewater were, in all cases, significantly higher than those attributable to hospital dispensing, indicating the existence of an additional source of ketamine in the urban environment. The enantiomeric profile showed values of R-ketamine enantiomeric fractionslightly higher than 0.5 in most cases, indicating an equimolar presence of the R and S enantiomers, characteristic of racemic ketamine. Although this information alone does not allow for a clear distinction between hospital and illicit use, combining this profile with prescription data suggests that a significant proportion of the ketamine found in wastewater originates from unregulated consumption. This is further supported by the analysis of samples from the illicit market, which also showed a racemic composition, confirming the nature of the product distributed for recreational purposes.
Direction
QUINTANA ALVAREZ, JOSE BENITO (Tutorships)
ESTEVEZ DANTA, ANDREA (Co-tutorships)
QUINTANA ALVAREZ, JOSE BENITO (Tutorships)
ESTEVEZ DANTA, ANDREA (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Analytical methodology for the extraction and determination of pharmaceutical residues in sludge samples.
Authorship
I.D.V.
Master's Degree in Chemical Research and Industrial Chemistry
I.D.V.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
The determination of pharmaceutical residues in urban wastewater treatment plant (WWTP) sludge has been the subject of various studies in recent years, particularly regarding its potential use in sectors like industry and agriculture. These studies aim to find a sustainable use for this residue, considering both economic and environmental criteria. In this work, an analytical methodology for the extraction of different pharmaceuticals from WWTP sludge was validated and applied. The method is based on extracting pharmaceuticals with acetonitrile (ACN) in presence of various salts, followed by their determination using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The sludge samples analyzed were obtained from different WWTPs located in Galicia. The developed analytical procedure showed quantification limits in the low ng/g range for most compounds, high extraction efficiencies, and acceptable accuracy for 46 out of 49 initially selected compounds. The processed WWTP sludges contained residues of most of the selected microcontaminants, with a group of 28 compounds (all of them pharmaceuticals or excretion metabolites) present in all samples at levels above the LOQs of the analytical procedure.
The determination of pharmaceutical residues in urban wastewater treatment plant (WWTP) sludge has been the subject of various studies in recent years, particularly regarding its potential use in sectors like industry and agriculture. These studies aim to find a sustainable use for this residue, considering both economic and environmental criteria. In this work, an analytical methodology for the extraction of different pharmaceuticals from WWTP sludge was validated and applied. The method is based on extracting pharmaceuticals with acetonitrile (ACN) in presence of various salts, followed by their determination using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The sludge samples analyzed were obtained from different WWTPs located in Galicia. The developed analytical procedure showed quantification limits in the low ng/g range for most compounds, high extraction efficiencies, and acceptable accuracy for 46 out of 49 initially selected compounds. The processed WWTP sludges contained residues of most of the selected microcontaminants, with a group of 28 compounds (all of them pharmaceuticals or excretion metabolites) present in all samples at levels above the LOQs of the analytical procedure.
Direction
RODRIGUEZ PEREIRO, ISAAC (Tutorships)
RAMIL CRIADO, MARIA (Co-tutorships)
RODRIGUEZ PEREIRO, ISAAC (Tutorships)
RAMIL CRIADO, MARIA (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Optimization, validation, and application of various methods for the determination of plastic additives in marine samples from the Galician Rías.
Authorship
N.D.F.
Master's Degree in Chemical Research and Industrial Chemistry
N.D.F.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 15:00
07.17.2025 15:00
Summary
In recent years, the presence of certain chemical compounds has begun to attract attention. Although they are not new, they are now considered emerging contaminants of concern because they tend to persist in the environment and can affect living beings even at very low concentrations. These include phthalates, rubber additives such as 6PPD (and its transformation product, 6PPD-quinone), bisphenols, and perfluorinated compounds, which will be studied in this work. Therefore, this study focused on determining the concentration of these contaminants in the marine environment of Galicia. To this end, several methods were developed and applied based on the one hand, solid-phase extraction (SPE) coupled with gas chromatography-mass spectrometry (GC-MS) to analyze seawater for phthalates, rubber additives, and bisphenols. And, secondly, matrix solid-phase dispersion (MSPD) followed by liquid chromatography-mass spectrometry (LC-MS) to determine perfluorinated compounds in mussels. The data obtained provide a fairly clear idea of the presence of these pollutants in Galician estuaries, which can be very useful for better understanding the state of the marine environment and providing a basis for future environmental risk assessments.
In recent years, the presence of certain chemical compounds has begun to attract attention. Although they are not new, they are now considered emerging contaminants of concern because they tend to persist in the environment and can affect living beings even at very low concentrations. These include phthalates, rubber additives such as 6PPD (and its transformation product, 6PPD-quinone), bisphenols, and perfluorinated compounds, which will be studied in this work. Therefore, this study focused on determining the concentration of these contaminants in the marine environment of Galicia. To this end, several methods were developed and applied based on the one hand, solid-phase extraction (SPE) coupled with gas chromatography-mass spectrometry (GC-MS) to analyze seawater for phthalates, rubber additives, and bisphenols. And, secondly, matrix solid-phase dispersion (MSPD) followed by liquid chromatography-mass spectrometry (LC-MS) to determine perfluorinated compounds in mussels. The data obtained provide a fairly clear idea of the presence of these pollutants in Galician estuaries, which can be very useful for better understanding the state of the marine environment and providing a basis for future environmental risk assessments.
Direction
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
Carro Mariño, Maria de las Nieves (Co-tutorships)
PEÑA VAZQUEZ, ELENA MARIA (Tutorships)
Carro Mariño, Maria de las Nieves (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Synthesis of multifunctional 1,5-dienes via cooperative copper/palladium catalysis.
Authorship
D.D.F.
Master in Organic Chemistry (3ª ed)
D.D.F.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Multicomponent reactions can afford highly functionalized products through the employment of three or more simple starting materials; however, they become quite challenging when there is a single wanted product to be isolated, as the chemo-, regio- and enantioselectivity of the reaction must be perfectly controlled. Among these reactions, the allylborations of allenes stand out, as the in-situ generated allyl copper species can couple at the alpha or gamma position with the alpha prime or gamma prime position of the allylic electrophile, leading to the formation of up to four different possible regioisomers of 1,5-diene compounds. Based on this, in this work the development of a synergistic copper and palladium catalytic system for the coupling of allenes, B2Pin2 and allylic carbonates that leads to the formation of borylated 1,5-dienes with a gamma,alpha prime type selectivity is presented.
Multicomponent reactions can afford highly functionalized products through the employment of three or more simple starting materials; however, they become quite challenging when there is a single wanted product to be isolated, as the chemo-, regio- and enantioselectivity of the reaction must be perfectly controlled. Among these reactions, the allylborations of allenes stand out, as the in-situ generated allyl copper species can couple at the alpha or gamma position with the alpha prime or gamma prime position of the allylic electrophile, leading to the formation of up to four different possible regioisomers of 1,5-diene compounds. Based on this, in this work the development of a synergistic copper and palladium catalytic system for the coupling of allenes, B2Pin2 and allylic carbonates that leads to the formation of borylated 1,5-dienes with a gamma,alpha prime type selectivity is presented.
Direction
FAÑANAS MASTRAL, MARTIN (Tutorships)
FAÑANAS MASTRAL, MARTIN (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Lanthanide complexes as luminescent sensors
Authorship
C.D.F.
Master's Degree in Chemical Research and Industrial Chemistry
C.D.F.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
In this work, the results obtained from the synthesis and characterization of heteronuclear EuIII and TbIII metal complexes derived from LN6-type macrocyclic ligands are described, with the aim of evaluating their performance as ratiometric luminescent sensors for both anion detection in aqueous solution and temperature determination in the solid state. Thus, acetate complexes {[Ln(LN6,en,r)(OAc)2](OAc)} of EuIII and TbIII, 1xH2O and 2xH2O, were first synthesized and characterized, serving as precursors for the synthesis of heteronuclear EuIII:TbIII complexes {[EuxTb1-x(LN6,en,r)(OAc)2](OAc)} with different molar ratios. The behaviour of these heteronuclear complexes as ratiometric anion sensors in solution was studied, demonstrating that the complex {[Eu0.9Tb0.1(LN6,en,r)(OAc)2](OAc)}x0.5CHCl3 (4x0.5CHCl3) detects F-, H2PO4- and HSO4- individually, as well as HSO4- in a mixture of the three analytes. On the other hand, acetate complexes of EuIII and TbIII derived from the LN6,prop macrocyclic ligand were synthesized and characterized in order to prepare the heteronuclear complex {[Eu0.1Tb0.9(LN6,prop)(OAc)2](BPh4)}xH2O (8xH2O). The behaviour of this metal complex as a potential ratiometric temperature sensor was evaluated, demonstrating that it acts as an efficient temperature sensor in the range of 200-325 K, with a maximum relative sensitivity of 8.9 %xK-1 and an uncertainty of 0.25 K at 325 K.
In this work, the results obtained from the synthesis and characterization of heteronuclear EuIII and TbIII metal complexes derived from LN6-type macrocyclic ligands are described, with the aim of evaluating their performance as ratiometric luminescent sensors for both anion detection in aqueous solution and temperature determination in the solid state. Thus, acetate complexes {[Ln(LN6,en,r)(OAc)2](OAc)} of EuIII and TbIII, 1xH2O and 2xH2O, were first synthesized and characterized, serving as precursors for the synthesis of heteronuclear EuIII:TbIII complexes {[EuxTb1-x(LN6,en,r)(OAc)2](OAc)} with different molar ratios. The behaviour of these heteronuclear complexes as ratiometric anion sensors in solution was studied, demonstrating that the complex {[Eu0.9Tb0.1(LN6,en,r)(OAc)2](OAc)}x0.5CHCl3 (4x0.5CHCl3) detects F-, H2PO4- and HSO4- individually, as well as HSO4- in a mixture of the three analytes. On the other hand, acetate complexes of EuIII and TbIII derived from the LN6,prop macrocyclic ligand were synthesized and characterized in order to prepare the heteronuclear complex {[Eu0.1Tb0.9(LN6,prop)(OAc)2](BPh4)}xH2O (8xH2O). The behaviour of this metal complex as a potential ratiometric temperature sensor was evaluated, demonstrating that it acts as an efficient temperature sensor in the range of 200-325 K, with a maximum relative sensitivity of 8.9 %xK-1 and an uncertainty of 0.25 K at 325 K.
Direction
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Study of Microphysiological Systems (Organ-on-a-Chip) to Evaluate the Toxicity of Nanoparticles in Food
Authorship
I.D.R.
Master's Degree in Chemical Research and Industrial Chemistry
I.D.R.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Given the widespread use of nanomaterials in the food industry, there is an increasing need to optimize methods for the detection and characterization of nanoparticles (NPs) in biological matrices, as well as to assess their oral bioaccessibility and bioavailability. In this study, inductively coupled plasma mass spectrometry operating in single-particle mode (spICP-MS) was employed to determine the concentration and size distribution of NPs in various samples. The in vitro digestion model proposed by EFSA (INFOGEST) was selected to estimate the bioaccessibility of the most commonly used food-related NPs, namely titanium dioxide (TiO2) and silver (Ag) nanoparticles, found in food products or packaging materials. Furthermore, to evaluate the bioavailability of these NPs, the potential use of various microphysiological systems (Organ on a Chip, OoC) was explored to simulate the intestinal barrier and its dynamic physiological conditions.
Given the widespread use of nanomaterials in the food industry, there is an increasing need to optimize methods for the detection and characterization of nanoparticles (NPs) in biological matrices, as well as to assess their oral bioaccessibility and bioavailability. In this study, inductively coupled plasma mass spectrometry operating in single-particle mode (spICP-MS) was employed to determine the concentration and size distribution of NPs in various samples. The in vitro digestion model proposed by EFSA (INFOGEST) was selected to estimate the bioaccessibility of the most commonly used food-related NPs, namely titanium dioxide (TiO2) and silver (Ag) nanoparticles, found in food products or packaging materials. Furthermore, to evaluate the bioavailability of these NPs, the potential use of various microphysiological systems (Organ on a Chip, OoC) was explored to simulate the intestinal barrier and its dynamic physiological conditions.
Direction
Domínguez González, María Raquel (Tutorships)
MOREDA PIÑEIRO, ANTONIO (Co-tutorships)
Domínguez González, María Raquel (Tutorships)
MOREDA PIÑEIRO, ANTONIO (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Determination of pregabalin in blood by GCMS.
Authorship
L.F.G.
Master's Degree in Chemical Research and Industrial Chemistry
L.F.G.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Pregabalin is a drug that corresponds to the enantiomer S of 3aminomethyl5methylhexaenoic acid and has an important inhibitory function of the nervous system, so it is used to treat epilepsy, generalized anxiety or neuropathic pain. There is currently a significant misuse and abuse of pregabalin, due to its side effects similar to those of different drugs, the potentiation of these through the simultaneous use of opioids or even its use for suicidal purposes. The present work aims to develop and validate an analytical method using GCMS for the detection and quantification of pregabalin in blood. An analytical method was developed and optimized using GCMS that could solve these current analytical needs in an efficient, reproducible, fast, economical and green way. To this end, different extraction techniques, drug derivatization reactions, working conditions and detection were evaluated. The final designed method involves a liquid liquid extraction of the drug into human blood, derivatization by acetylation and determination by GCMS. This was validated under the criteria recommended by the FDA Food and Drug Administration for a linear range of concentrations 0,4 12 microg mL and finally applied and evaluated in real postmortem human blood samples.
Pregabalin is a drug that corresponds to the enantiomer S of 3aminomethyl5methylhexaenoic acid and has an important inhibitory function of the nervous system, so it is used to treat epilepsy, generalized anxiety or neuropathic pain. There is currently a significant misuse and abuse of pregabalin, due to its side effects similar to those of different drugs, the potentiation of these through the simultaneous use of opioids or even its use for suicidal purposes. The present work aims to develop and validate an analytical method using GCMS for the detection and quantification of pregabalin in blood. An analytical method was developed and optimized using GCMS that could solve these current analytical needs in an efficient, reproducible, fast, economical and green way. To this end, different extraction techniques, drug derivatization reactions, working conditions and detection were evaluated. The final designed method involves a liquid liquid extraction of the drug into human blood, derivatization by acetylation and determination by GCMS. This was validated under the criteria recommended by the FDA Food and Drug Administration for a linear range of concentrations 0,4 12 microg mL and finally applied and evaluated in real postmortem human blood samples.
Direction
SÁNCHEZ SELLERO, INÉS (Tutorships)
Álvarez Freire, Iván (Co-tutorships)
SÁNCHEZ SELLERO, INÉS (Tutorships)
Álvarez Freire, Iván (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Rare Earth Complexes (Y, Dy, Gd) with Three-Dimensional PAHs
Authorship
I.F.A.
Master's Degree in Chemical Research and Industrial Chemistry
I.F.A.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Given their magnetic and luminescent properties, rare earth metal complexes have stimulated global technological development over the past few decades, with interesting applications in medicine, sensors, and all kinds of electronic and magnetic devices. The enhanced electronic properties offered by non-planar, curved PAHs have increased their use as ligands for metal complexes. An attractive synthetic approach to such non-planar PAHs, in particular those with eight-membered rings, is based on the cyclotrimerization of COTynes via a 2+2+2 cycloaddition. This TFM project addresses the synthesis of a non-planar PAH that can be considered an open structure of a hypothetical three-dimensional carbon allotrope known as cubic graphite. Given its pi-donor capabilities, its potential as a ligand to complex rare earth metals will be explored.
Given their magnetic and luminescent properties, rare earth metal complexes have stimulated global technological development over the past few decades, with interesting applications in medicine, sensors, and all kinds of electronic and magnetic devices. The enhanced electronic properties offered by non-planar, curved PAHs have increased their use as ligands for metal complexes. An attractive synthetic approach to such non-planar PAHs, in particular those with eight-membered rings, is based on the cyclotrimerization of COTynes via a 2+2+2 cycloaddition. This TFM project addresses the synthesis of a non-planar PAH that can be considered an open structure of a hypothetical three-dimensional carbon allotrope known as cubic graphite. Given its pi-donor capabilities, its potential as a ligand to complex rare earth metals will be explored.
Direction
SAA RODRIGUEZ, CARLOS EUGENIO (Tutorships)
VARELA CARRETE, JESUS ANGEL (Co-tutorships)
SAA RODRIGUEZ, CARLOS EUGENIO (Tutorships)
VARELA CARRETE, JESUS ANGEL (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
QUIÑOA CABANA, EMILIO (Chairman)
Vaz Araújo, Belén (Secretary)
Castro García, Socorro (Member)
Sanmartin Matalobos, Jesus (Coordinator)
QUIÑOA CABANA, EMILIO (Chairman)
Vaz Araújo, Belén (Secretary)
Castro García, Socorro (Member)
Design of Atomic Quantum Clusters for the Detection and Treatment of Bacterial Infections
Authorship
S.F.G.
Master's Degree in Chemical Research and Industrial Chemistry
S.F.G.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Nanotechnology has become a revolutionary field, with applications ranging from biomedicine to catalysis and optics. Its importance has increased exponentially in the last years 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. Therefore, this project focused on the electrochemical synthesis and characterization of low-nuclearity iron clusters, with the aim of evaluating their potential as antibacterial agents. Clusters with different size distributions were synthesized in order to compare their antibacterial performance as a function of this parameter. The results showed promising catalytic activity in reactions associated with oxidative stress generation, which led to testing their antibacterial properties. These assays also yielded interesting results, revealing antibacterial activity worthy of further investigation.
Nanotechnology has become a revolutionary field, with applications ranging from biomedicine to catalysis and optics. Its importance has increased exponentially in the last years 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. Therefore, this project focused on the electrochemical synthesis and characterization of low-nuclearity iron clusters, with the aim of evaluating their potential as antibacterial agents. Clusters with different size distributions were synthesized in order to compare their antibacterial performance as a function of this parameter. The results showed promising catalytic activity in reactions associated with oxidative stress generation, which led to testing their antibacterial properties. These assays also yielded interesting results, revealing antibacterial activity worthy of further investigation.
Direction
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
BLANCO TRILLO, JOSE MANUEL (Co-tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
BLANCO TRILLO, JOSE MANUEL (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Characterization of UF, MUF, and PF resins by thermal analysis, FT-IR spectroscopy, and determination of the rheological profile, free monomer content, and other physicochemical and structural parameters.
Authorship
M.G.A.
Master's Degree in Chemical Research and Industrial Chemistry
M.G.A.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 15:00
07.17.2025 15:00
Summary
FORESA is a company commercially positioned in the wood industry, and its main activity focuses on the design and synthesis of chemical compounds related to the manufacturing of wood-based products, such as medium-density fiberboards (MDF), plywood, and others. Among its products are all types of aminoplastic and phenolic resins, primarily urea-formaldehyde (UF), melamine-formaldehyde (MF), melamine-urea-formaldehyde (MUF), and phenol-formaldehyde (PF) resins, as well as other surface coating products such as surfactants and agents that provide fire-retardant, thermal insulation, and electrical insulation properties, among others. Its core commercial activity is the sale of formaldehyde, the main raw material used in the production of wood adhesives. The company is also involved in the production of AdBlue, which is widely used in the automotive industry. In the present work, carried out in the instrumentation laboratory of the Research Department at Foresa Technologies under the supervision of the department head, Dr. Luis Alberto Otero, the characterization of three different resins was conducted: one UF, one MUF, and one PF. The characterization process included the analysis of the rheological profile of the resins, the determination of physicochemical properties such as viscosity, pH, and density, as well as structural and compositional tests, such as the analysis of molecular weight distribution and the content of monomers and/or free monomers.
FORESA is a company commercially positioned in the wood industry, and its main activity focuses on the design and synthesis of chemical compounds related to the manufacturing of wood-based products, such as medium-density fiberboards (MDF), plywood, and others. Among its products are all types of aminoplastic and phenolic resins, primarily urea-formaldehyde (UF), melamine-formaldehyde (MF), melamine-urea-formaldehyde (MUF), and phenol-formaldehyde (PF) resins, as well as other surface coating products such as surfactants and agents that provide fire-retardant, thermal insulation, and electrical insulation properties, among others. Its core commercial activity is the sale of formaldehyde, the main raw material used in the production of wood adhesives. The company is also involved in the production of AdBlue, which is widely used in the automotive industry. In the present work, carried out in the instrumentation laboratory of the Research Department at Foresa Technologies under the supervision of the department head, Dr. Luis Alberto Otero, the characterization of three different resins was conducted: one UF, one MUF, and one PF. The characterization process included the analysis of the rheological profile of the resins, the determination of physicochemical properties such as viscosity, pH, and density, as well as structural and compositional tests, such as the analysis of molecular weight distribution and the content of monomers and/or free monomers.
Direction
Sanmartin Matalobos, Jesus (Tutorships)
Otero Vázquez, Luís Alberto (Co-tutorships)
Sanmartin Matalobos, Jesus (Tutorships)
Otero Vázquez, Luís Alberto (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Photodegradation of agricultural wastewater contaminants catalyzed by Atomic Quantum Clusters.
Authorship
M.J.G.P.
Master's Degree in Chemical Research and Industrial Chemistry
M.J.G.P.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 15:30
07.17.2025 15:30
Summary
In this Final Project, the photocatalytic reduction of nitrates in contaminated water was studied using TiO2 modified with silver quantum clusters (Ag5-MM) as photocatalysts under simulated solar radiation. Different Ag5-MM samples were compared alongside TiO2 (P25) under identical experimental conditions, evaluating both the reduction kinetics and the overall efficiency of the process. In addition, the effects of inhibitory species, such as sulfates, and the influence of the medium's pH were analyzed. Finally, the impact of sonication on the stability of the samples was investigated. This study provides new findings demonstrating the potential of five-atom silver quantum clusters (Ag5-MM) to enhance photocatalytic efficiency compared to TiO2 (P25), as well as highlighting the critical role of experimental conditions in the process.
In this Final Project, the photocatalytic reduction of nitrates in contaminated water was studied using TiO2 modified with silver quantum clusters (Ag5-MM) as photocatalysts under simulated solar radiation. Different Ag5-MM samples were compared alongside TiO2 (P25) under identical experimental conditions, evaluating both the reduction kinetics and the overall efficiency of the process. In addition, the effects of inhibitory species, such as sulfates, and the influence of the medium's pH were analyzed. Finally, the impact of sonication on the stability of the samples was investigated. This study provides new findings demonstrating the potential of five-atom silver quantum clusters (Ag5-MM) to enhance photocatalytic efficiency compared to TiO2 (P25), as well as highlighting the critical role of experimental conditions in the process.
Direction
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
Rodríguez Arias, Iria (Co-tutorships)
VAZQUEZ VAZQUEZ, CARLOS (Tutorships)
Rodríguez Arias, Iria (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
SARANDESES DA COSTA, LUIS ALBERTO (Chairman)
PARAJO MONTES, MARIA MERCEDES (Secretary)
Sánchez Vázquez, Pablo Breogán (Member)
Sanmartin Matalobos, Jesus (Coordinator)
SARANDESES DA COSTA, LUIS ALBERTO (Chairman)
PARAJO MONTES, MARIA MERCEDES (Secretary)
Sánchez Vázquez, Pablo Breogán (Member)
Preparation of potential palladium and platinum metallodrugs with thiosemicarbazone ligands
Authorship
E.L.P.
Master's Degree in Chemical Research and Industrial Chemistry
E.L.P.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
This Master's Final Project (TFM) focused on the synthesis of palladium(II) and platinum(II) complexes from tetradentate bisthiosemicarbazone ligands H2Ln, lacking a donor atom in the spacer, using electrochemical and chemical synthesis methodologies from different salts. Electrochemical synthesis generated mononuclear species [PdLn], while chemical synthesis produced species of different nuclearity depending on the palladium(II) or platinum(II) salt used. Particularly, a trinuclear mixed organometallic and coordination palladium(II) compound was obtained. In any case, the absence of the donor atom in the spacer only allows the formation of potentially helical dinuclear [Pd2Ln2] complexes for ethyl- and methoxyphenyl-substituted ligands when using PdCl2 and [Pd(CH3CN)4](BF4)2 salts, as well as [PtLn]m complexes obtained from K2PtCl4.
This Master's Final Project (TFM) focused on the synthesis of palladium(II) and platinum(II) complexes from tetradentate bisthiosemicarbazone ligands H2Ln, lacking a donor atom in the spacer, using electrochemical and chemical synthesis methodologies from different salts. Electrochemical synthesis generated mononuclear species [PdLn], while chemical synthesis produced species of different nuclearity depending on the palladium(II) or platinum(II) salt used. Particularly, a trinuclear mixed organometallic and coordination palladium(II) compound was obtained. In any case, the absence of the donor atom in the spacer only allows the formation of potentially helical dinuclear [Pd2Ln2] complexes for ethyl- and methoxyphenyl-substituted ligands when using PdCl2 and [Pd(CH3CN)4](BF4)2 salts, as well as [PtLn]m complexes obtained from K2PtCl4.
Direction
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
MARTINEZ CALVO, MIGUEL (Co-tutorships)
PEDRIDO CASTIÑEIRAS, ROSA MARIA (Tutorships)
MARTINEZ CALVO, MIGUEL (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Dysprosium molecular magnetic materials
Authorship
X.M.B.
Master's Degree in Chemical Research and Industrial Chemistry
X.M.B.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
This work presents the synthesis and characterization of a series of dysprosium(III) acetate complexes with hexaazamacrocyclic ligands: {[Dy(LN6,prop)(OAc)2](BPh4)} (1), {[Dy(LN6,propr)(OAc)2](OAc)}xH2O (2xH2O) and {[Dy(LN6,propr)(OAc)2](BPh4)} (3) as well as the results of ligand exchange reactions of these precursors with triphenylsilanolate.. Complexes 1 and 3 undergo partial or complete substitution of acetate ligands by triphenylsilanolate, yielding {[Dy(LN6,prop)(OAc)(OSiPh3)](BPh4)}x0.5CH2Cl2 (4x0.5CH2Cl2) and {[Dy(LN6,propr)(OSiPh3)2](BPh4)}x3THF (5x3THF), respectively. Compound 4x0.5CH2Cl2 was structurally characterized by single-crystal X-ray diffraction, revealing a distorted square antiprismatic geometry tending toward a muffin-shaped conformation. Magnetic studies of 4x0.5CH2Cl2 demonstrate typical single-molecule magnet behavior, with spin relaxation occurring through Orbach and quantum tunneling of magnetization mechanisms.
This work presents the synthesis and characterization of a series of dysprosium(III) acetate complexes with hexaazamacrocyclic ligands: {[Dy(LN6,prop)(OAc)2](BPh4)} (1), {[Dy(LN6,propr)(OAc)2](OAc)}xH2O (2xH2O) and {[Dy(LN6,propr)(OAc)2](BPh4)} (3) as well as the results of ligand exchange reactions of these precursors with triphenylsilanolate.. Complexes 1 and 3 undergo partial or complete substitution of acetate ligands by triphenylsilanolate, yielding {[Dy(LN6,prop)(OAc)(OSiPh3)](BPh4)}x0.5CH2Cl2 (4x0.5CH2Cl2) and {[Dy(LN6,propr)(OSiPh3)2](BPh4)}x3THF (5x3THF), respectively. Compound 4x0.5CH2Cl2 was structurally characterized by single-crystal X-ray diffraction, revealing a distorted square antiprismatic geometry tending toward a muffin-shaped conformation. Magnetic studies of 4x0.5CH2Cl2 demonstrate typical single-molecule magnet behavior, with spin relaxation occurring through Orbach and quantum tunneling of magnetization mechanisms.
Direction
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
FONDO BUSTO, MARIA MATILDE (Tutorships)
CORREDOIRA VAZQUEZ, JULIO (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Tunning Peptide Conformation through Compositionally Designed Deep Eutectic Solvents
Authorship
M.M.G.
Master in Organic Chemistry (3ª ed)
M.M.G.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Peptides show great potential as chemical tools, so their behaviour and folding are crucial to understanding the extent of their use beyond the frontiers of living systems. Deep Eutectic Solvents (DES) are alternative environments where peptides can be solubilised, thus expanding the applications beyond aqueous buffers. Notably, the “design” character of DES could be exploited to tailor the conformational landscape of peptides, potentially providing à-la-carte solvents that control peptide topology. However, nowadays DES effects on peptide structure can not be easily predicted, so developing a fundamental framework to understand peptide topology as a function of DES properties is becoming a key theme in supramolecular chemistry. In this research line, we aim to stablish correlations between the DES composition and the topology of model peptides. To do so, we synthesized a series of peptides by solid-phase peptide synthesis with different overall charge. We reveal that peptides undergo conformational changes from a fully random coil structure in pH 7 phosphate buffer to ordered secondary structures once dissolved in DES with pre-designed properties. Importantly, this topology depends on the composition of the DES and peptide, where specific counterion condensation drives the degree of local ordering. These observations can lead to the precise design of solvents capable of finely controlling the conformation of peptides, aiming to open new possibilities in the field of biomaterial development and stimuli-response systems.
Peptides show great potential as chemical tools, so their behaviour and folding are crucial to understanding the extent of their use beyond the frontiers of living systems. Deep Eutectic Solvents (DES) are alternative environments where peptides can be solubilised, thus expanding the applications beyond aqueous buffers. Notably, the “design” character of DES could be exploited to tailor the conformational landscape of peptides, potentially providing à-la-carte solvents that control peptide topology. However, nowadays DES effects on peptide structure can not be easily predicted, so developing a fundamental framework to understand peptide topology as a function of DES properties is becoming a key theme in supramolecular chemistry. In this research line, we aim to stablish correlations between the DES composition and the topology of model peptides. To do so, we synthesized a series of peptides by solid-phase peptide synthesis with different overall charge. We reveal that peptides undergo conformational changes from a fully random coil structure in pH 7 phosphate buffer to ordered secondary structures once dissolved in DES with pre-designed properties. Importantly, this topology depends on the composition of the DES and peptide, where specific counterion condensation drives the degree of local ordering. These observations can lead to the precise design of solvents capable of finely controlling the conformation of peptides, aiming to open new possibilities in the field of biomaterial development and stimuli-response systems.
Direction
MONTENEGRO GARCIA, JAVIER (Tutorships)
SANCHEZ FERNANDEZ, ADRIAN (Co-tutorships)
MONTENEGRO GARCIA, JAVIER (Tutorships)
SANCHEZ FERNANDEZ, ADRIAN (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Photocatalytic Cascade Cyclization using Isobutane: Unveiling a Regioselective Disparity
Authorship
N.M.A.
Master in Organic Chemistry (3ª ed)
N.M.A.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
In this work, we present a novel photocatalytic hydrogen atom transfer (HAT)-based cascade cyclization of N-aryl acrylamides with isobutane. This method enables efficient and regioselective incorporation of isobutane into non-cyclic substrates under mild conditions, followed by intramolecular cyclization to yield indolinone derivatives. Optimal conditions afforded cyclized products in moderate to good yields with high linear selectivity. Substrate scope studies revealed good tolerance, particularly for electron-withdrawing groups. Mechanistic studies using TEMPO as a radical trap showed a 96:4 linear:branched ratio in the C-H activation of isobutane, indicating a highly regioselective HAT pathway. Control experiments using FeCl3 and TBADT as alternative HAT photocatalysts suggest that the active species may originate from a Fe-NFSI complex generating a nitrogen-centered radical via ligand-to-metal charge transfer (LMCT). To showcase the method's synthetic utility, a Suzuki cross-coupling reaction was performed, obtaining a derivative with pharmacologically relevant structures such as an indolinone core and a naphthyl group. This is the first reported use of isobutane as an alkylating agent in a photocatalytic cascade cyclization, highlighting the untapped potential of gaseous alkanes in synthetic chemistry.
In this work, we present a novel photocatalytic hydrogen atom transfer (HAT)-based cascade cyclization of N-aryl acrylamides with isobutane. This method enables efficient and regioselective incorporation of isobutane into non-cyclic substrates under mild conditions, followed by intramolecular cyclization to yield indolinone derivatives. Optimal conditions afforded cyclized products in moderate to good yields with high linear selectivity. Substrate scope studies revealed good tolerance, particularly for electron-withdrawing groups. Mechanistic studies using TEMPO as a radical trap showed a 96:4 linear:branched ratio in the C-H activation of isobutane, indicating a highly regioselective HAT pathway. Control experiments using FeCl3 and TBADT as alternative HAT photocatalysts suggest that the active species may originate from a Fe-NFSI complex generating a nitrogen-centered radical via ligand-to-metal charge transfer (LMCT). To showcase the method's synthetic utility, a Suzuki cross-coupling reaction was performed, obtaining a derivative with pharmacologically relevant structures such as an indolinone core and a naphthyl group. This is the first reported use of isobutane as an alkylating agent in a photocatalytic cascade cyclization, highlighting the untapped potential of gaseous alkanes in synthetic chemistry.
Direction
FAÑANAS MASTRAL, MARTIN (Tutorships)
FAÑANAS MASTRAL, MARTIN (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Scale-up of bioactive compound extraction from natural sources.
Authorship
F.J.M.V.
Master's Degree in Chemical Research and Industrial Chemistry
F.J.M.V.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 15:00
07.17.2025 15:00
Summary
This work focuses on obtaining, characterizing, and analyzing extracts rich in bioactive compounds from holm oak acorns (Quercus ilex). The study was conducted using a rapid, simple, economical, and environmentally friendly extraction technique: the MSAT (medium scale and ambient temperature) system, which employs mild conditions and solvents generally recognized as safe (GRAS). The work consists of three parts. First, the extraction method was optimized to maximize the total polyphenol index (TPI) and antioxidant activity (AA). In addition, the influence of the solvent ratio was studied and the complete bioactive profile of the extracts was obtained, quantifying the TPI, AA using the DPPH method, and the mean inhibitory concentration (IC50). The best results were obtained with 50% ethyl lactate and water, both in TPI and AA. In the second part, individual characterization of the polyphenols was performed using ultra-high-performance liquid chromatography coupled with mass spectrometry (UHPLC-QToF), detecting 19 compounds of interest. Among the main compounds identified were ellagic acid, gallic acid, 1,2,3,4,6-pentagalloylglucose, 1,2,3,6-tetragalloylglucose, and 1,3,6-trigalloylglucose. Finally, in the third phase, the optimized technique was applied to oak acorns (Quercus robur), allowing for a comparison of the bioactive parameters and chromatographic profile of both extracts.
This work focuses on obtaining, characterizing, and analyzing extracts rich in bioactive compounds from holm oak acorns (Quercus ilex). The study was conducted using a rapid, simple, economical, and environmentally friendly extraction technique: the MSAT (medium scale and ambient temperature) system, which employs mild conditions and solvents generally recognized as safe (GRAS). The work consists of three parts. First, the extraction method was optimized to maximize the total polyphenol index (TPI) and antioxidant activity (AA). In addition, the influence of the solvent ratio was studied and the complete bioactive profile of the extracts was obtained, quantifying the TPI, AA using the DPPH method, and the mean inhibitory concentration (IC50). The best results were obtained with 50% ethyl lactate and water, both in TPI and AA. In the second part, individual characterization of the polyphenols was performed using ultra-high-performance liquid chromatography coupled with mass spectrometry (UHPLC-QToF), detecting 19 compounds of interest. Among the main compounds identified were ellagic acid, gallic acid, 1,2,3,4,6-pentagalloylglucose, 1,2,3,6-tetragalloylglucose, and 1,3,6-trigalloylglucose. Finally, in the third phase, the optimized technique was applied to oak acorns (Quercus robur), allowing for a comparison of the bioactive parameters and chromatographic profile of both extracts.
Direction
LORES AGUIN, MARTA (Tutorships)
VERDES GOMEZ, JUAN JOSE (Co-tutorships)
LORES AGUIN, MARTA (Tutorships)
VERDES GOMEZ, JUAN JOSE (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Sanmartin Matalobos, Jesus (Coordinator)
GONZALEZ ROMERO, ELISA (Chairman)
Rodríguez Figueiras, Óscar (Secretary)
Avecilla Porto, Fernando Francisco (Member)
Dispersive solid-phase extraction using a metal-organic framework (MIL-100) for the determination of UV filters in environmental waters
Authorship
N.M.R.
Master's Degree in Chemical Research and Industrial Chemistry
N.M.R.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
In recent decades, growing awareness of the harmful effects of solar radiation on human health has significantly increased the demand for sunscreen products. Sunscreen agents are not only found in photoprotective formulations but also in a wide variety of daily-use products such as creams, body lotions or hair products. These compounds, which exhibit considerable structural diversity, belong to various families, including benzophenones, salicylates, cinnamates, and camphor derivatives. The large-scale production and widespread use of these substances have led to their massive release into the environment, making them a significant group of emerging contaminants. Ultraviolet (UV) filters enter the environment primarily through aquatic activities and due to incomplete removal in wastewater treatment plants. Most of them are persistent compounds, and their harmful effects have been reported not only in marine organisms but also in amphibians and some terrestrial species. One example of their toxicity is coral bleaching, with evidence suggesting that UV filters can cause adverse effects even at very low concentrations. Some of these substances, such as Avobenzone and Octocrylene, are banned in certain states or countries. Therefore, the development of efficient and highly sensitive analytical methods for the determination of UV filters is essential. In this study, a methodology based on ultrasound-vortex-assisted solid-phase extraction is developed, employing a metal-organic framework (MIL-100) as the sorbent phase, followed by gas chromatography coupled with tandem mass spectrometry for the simultaneous analysis of 15 UV filters in water. Extraction parameters, including extraction format, temperature, pH, extraction time, and salt addition, are optimized using experimental design. After validation, the method is applied to the extraction of analytes from environmental water, wastewater, and recreational water samples. The advantages of the developed method include high efficiency, low consumption of organic solvents, rapid sample processing, and high sensitivity.
In recent decades, growing awareness of the harmful effects of solar radiation on human health has significantly increased the demand for sunscreen products. Sunscreen agents are not only found in photoprotective formulations but also in a wide variety of daily-use products such as creams, body lotions or hair products. These compounds, which exhibit considerable structural diversity, belong to various families, including benzophenones, salicylates, cinnamates, and camphor derivatives. The large-scale production and widespread use of these substances have led to their massive release into the environment, making them a significant group of emerging contaminants. Ultraviolet (UV) filters enter the environment primarily through aquatic activities and due to incomplete removal in wastewater treatment plants. Most of them are persistent compounds, and their harmful effects have been reported not only in marine organisms but also in amphibians and some terrestrial species. One example of their toxicity is coral bleaching, with evidence suggesting that UV filters can cause adverse effects even at very low concentrations. Some of these substances, such as Avobenzone and Octocrylene, are banned in certain states or countries. Therefore, the development of efficient and highly sensitive analytical methods for the determination of UV filters is essential. In this study, a methodology based on ultrasound-vortex-assisted solid-phase extraction is developed, employing a metal-organic framework (MIL-100) as the sorbent phase, followed by gas chromatography coupled with tandem mass spectrometry for the simultaneous analysis of 15 UV filters in water. Extraction parameters, including extraction format, temperature, pH, extraction time, and salt addition, are optimized using experimental design. After validation, the method is applied to the extraction of analytes from environmental water, wastewater, and recreational water samples. The advantages of the developed method include high efficiency, low consumption of organic solvents, rapid sample processing, and high sensitivity.
Direction
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
LLOMPART VIZOSO, MARIA PILAR (Tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Inventing New Chiral “CpM” Catalysts for Asymmetric Catalysis
Authorship
S.M.R.
Master in Organic Chemistry (3ª ed)
S.M.R.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Cyclopentadienyl (Cp) ligands are highly relevant in the field of organometallic catalysis, particularly in the development of group IX metal (Co, Rh, Ir) catalysts for C-H functionalization reactions, which directly transform inert C-H bonds into specific functional groups. Unfortunately, current synthetic technologies for the preparation of chiral Cp ligands are complex and lack versatility. As a result, the development of enantioselective C-H functionalization reactions using chiral CpM catalysts has been limited. We have recently discovered a cobalt-catalyzed cycloaddition that enables the one-step synthesis of cyclopentadienyl ligands bearing a wide range of substituents, effectively tuning their steric and electronic properties. Furthermore, we have confirmed that the resulting Cp-rhodium complexes are catalytically active. Building on this foundation, our objective is to design a completely new chiral Cp ligand and evaluate its corresponding metal complex in relevant asymmetric C-H functionalization reactions. We will also explore different strategies for obtaining these Cp-rhodium catalysts in enantiopure form, paving the way for the development of asymmetric catalytic variants.
Cyclopentadienyl (Cp) ligands are highly relevant in the field of organometallic catalysis, particularly in the development of group IX metal (Co, Rh, Ir) catalysts for C-H functionalization reactions, which directly transform inert C-H bonds into specific functional groups. Unfortunately, current synthetic technologies for the preparation of chiral Cp ligands are complex and lack versatility. As a result, the development of enantioselective C-H functionalization reactions using chiral CpM catalysts has been limited. We have recently discovered a cobalt-catalyzed cycloaddition that enables the one-step synthesis of cyclopentadienyl ligands bearing a wide range of substituents, effectively tuning their steric and electronic properties. Furthermore, we have confirmed that the resulting Cp-rhodium complexes are catalytically active. Building on this foundation, our objective is to design a completely new chiral Cp ligand and evaluate its corresponding metal complex in relevant asymmetric C-H functionalization reactions. We will also explore different strategies for obtaining these Cp-rhodium catalysts in enantiopure form, paving the way for the development of asymmetric catalytic variants.
Direction
LÓPEZ GARCÍA, FERNANDO JOSÉ (Tutorships)
Mascareñas Cid, Jose Luis (Co-tutorships)
LÓPEZ GARCÍA, FERNANDO JOSÉ (Tutorships)
Mascareñas Cid, Jose Luis (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Synthesis of nanowires from self-assembled helical peptides
Authorship
A.M.T.
Master in Organic Chemistry (3ª ed)
A.M.T.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Conductive proteins are natural protein filaments capable of transporting electric current. This has motivated the design of synthetic polypeptides with applications in electronic devices with low production costs and toxicity, and environmentally sustainable. These peptide nanowires transmit electric current through charge delocalization facilitated by pi-pi stacking interactions between the side chains of aromatic amino acids. In this study, we describe the second-generation sequence (XQAXKAD)5, where X is the commercially available non-natural amino acid L-3-benzothienylalanine, a structural analogue of tryptophan in which the indole group has been replaced by a benzo[b]thiophen-3-yl side chain that given the wide application of thiophenes in conductive materials, might display enhanced electron transport properties. This peptide is capable of self-assembling into oligomers and forming homogeneous fibers with the aromatic residues stacked in the core. The peptide sequence was assembled via solid-phase peptide synthesis, purified by HPLC, and its identity confirmed by ESI-MS, and the supramolecular assembly of the oligomers was characterized using CD, UV-Vis Spectroscopy, AFM, TEM, MALDI-TOF and SAXS.
Conductive proteins are natural protein filaments capable of transporting electric current. This has motivated the design of synthetic polypeptides with applications in electronic devices with low production costs and toxicity, and environmentally sustainable. These peptide nanowires transmit electric current through charge delocalization facilitated by pi-pi stacking interactions between the side chains of aromatic amino acids. In this study, we describe the second-generation sequence (XQAXKAD)5, where X is the commercially available non-natural amino acid L-3-benzothienylalanine, a structural analogue of tryptophan in which the indole group has been replaced by a benzo[b]thiophen-3-yl side chain that given the wide application of thiophenes in conductive materials, might display enhanced electron transport properties. This peptide is capable of self-assembling into oligomers and forming homogeneous fibers with the aromatic residues stacked in the core. The peptide sequence was assembled via solid-phase peptide synthesis, purified by HPLC, and its identity confirmed by ESI-MS, and the supramolecular assembly of the oligomers was characterized using CD, UV-Vis Spectroscopy, AFM, TEM, MALDI-TOF and SAXS.
Direction
VAZQUEZ SENTIS, MARCO EUGENIO (Tutorships)
VAZQUEZ SENTIS, MARCO EUGENIO (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Preparation of quantum dots and molecularly imprinted polymer composites and their application as a sensing phase in the fluorimetric screening of tacrolimus in clinical samples
Authorship
L.O.R.
Master's Degree in Chemical Research and Industrial Chemistry
L.O.R.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Tacrolimus is an imnunosuppressive drug used in the prevention of organ transplant rejection. Although the discover of this drug revolutionized the medical field, it exhibits highly variable pharmacokinetics, which can lead to adverse effects if the administered dose is not properly controlled. For this reason, this work proposes the implementation of a new rapid fluorimetric analysis methodology, based on the use of quantum dots functionalized with molecularly imprinted polymers (MIP@QDs) as the sensing phase, with the aim of determining tacrolimus levels in saliva. The experimental work began with the synthesis of the MIP@QDs sensing phase. First, manganese-doped zinc sulfide quantum dots (Mn-ZnS QDs) were synthetized and coated with polyethilene glycol (PEG). The MIP@QDs were then obtained through a polymerization reaction using tacrolimus as a template. Once the sensing phase was formed, it was characterized by FT-IR, XRPD and HRTEM. Fluorimetric measurements were carried out based on the alteration of the QDs luminiscence, observing a decrease in the signal (quenching effect). The optimal conditions for the tacrolimus-MIP@QDs interation were determined, and the potential matrix effect was evaluated by using oral fluid as a biological matrix. The limit of detection (LOD) of the method was determined along with intra- and inter-day recovery values, which provide insight into the accuracy of the measurements. The proposed methodology shows great potential for the development of miniaturized devices to determine tacrolimus levels in the saliva of patients who require monitoring.
Tacrolimus is an imnunosuppressive drug used in the prevention of organ transplant rejection. Although the discover of this drug revolutionized the medical field, it exhibits highly variable pharmacokinetics, which can lead to adverse effects if the administered dose is not properly controlled. For this reason, this work proposes the implementation of a new rapid fluorimetric analysis methodology, based on the use of quantum dots functionalized with molecularly imprinted polymers (MIP@QDs) as the sensing phase, with the aim of determining tacrolimus levels in saliva. The experimental work began with the synthesis of the MIP@QDs sensing phase. First, manganese-doped zinc sulfide quantum dots (Mn-ZnS QDs) were synthetized and coated with polyethilene glycol (PEG). The MIP@QDs were then obtained through a polymerization reaction using tacrolimus as a template. Once the sensing phase was formed, it was characterized by FT-IR, XRPD and HRTEM. Fluorimetric measurements were carried out based on the alteration of the QDs luminiscence, observing a decrease in the signal (quenching effect). The optimal conditions for the tacrolimus-MIP@QDs interation were determined, and the potential matrix effect was evaluated by using oral fluid as a biological matrix. The limit of detection (LOD) of the method was determined along with intra- and inter-day recovery values, which provide insight into the accuracy of the measurements. The proposed methodology shows great potential for the development of miniaturized devices to determine tacrolimus levels in the saliva of patients who require monitoring.
Direction
MOREDA PIÑEIRO, ANTONIO (Tutorships)
Domínguez González, María Raquel (Co-tutorships)
MOREDA PIÑEIRO, ANTONIO (Tutorships)
Domínguez González, María Raquel (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Synthesis of ciclyc peptides for the formation of nanoreactors
Authorship
O.P.F.
Master in Organic Chemistry (3ª ed)
O.P.F.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
This work describes the synthetic strategy for preparing a new cyclopeptide designed to self assemble into supramolecular catalytic capsules. The design includes key structural modifications such as an alkylazide chain to anchor porphyrin caps through click chemistry, a methylene naphthyl group to help position the molecular cap over the cavity entrance, and a gamma amino acid to restrict the equilibrium to a single dimer. The main goal was to synthesize this cyclopeptide as a precursor for such capsules, enhancing structural rigidity and spatial control. To achieve this, a convergent solution phase synthetic strategy was used. The gamma amino acid functionalized with the alkylazide, which is essential for porphyrin anchoring, was synthesized from the commercial precursor Boc L gamma Ace OH. This process involved catalytic hydrogenation, esterification of the carboxylic group, exchange of protecting groups from Boc to Ns, and finally N alkylation of the resulting derivative. Next, two dipeptides were synthesized, named Boc D Leu MeN L gamma Acp OMe and Boc D gamma Ach MeN L gamma Acp OMe, through differential deprotection and coupling. These dipeptides were then joined to form the linear tetrapeptide. In summary, a robust precursor has been synthesized for future supramolecular catalytic capsules. Future work includes completing the synthesis of the linear peptide, its cyclization, and confirmation of its dimeric self assembly. Finally, porphyrin caps will be anchored, followed by encapsulation studies of different types of ligands, especially di and tetrapyridines, and investigation of their catalytic properties.
This work describes the synthetic strategy for preparing a new cyclopeptide designed to self assemble into supramolecular catalytic capsules. The design includes key structural modifications such as an alkylazide chain to anchor porphyrin caps through click chemistry, a methylene naphthyl group to help position the molecular cap over the cavity entrance, and a gamma amino acid to restrict the equilibrium to a single dimer. The main goal was to synthesize this cyclopeptide as a precursor for such capsules, enhancing structural rigidity and spatial control. To achieve this, a convergent solution phase synthetic strategy was used. The gamma amino acid functionalized with the alkylazide, which is essential for porphyrin anchoring, was synthesized from the commercial precursor Boc L gamma Ace OH. This process involved catalytic hydrogenation, esterification of the carboxylic group, exchange of protecting groups from Boc to Ns, and finally N alkylation of the resulting derivative. Next, two dipeptides were synthesized, named Boc D Leu MeN L gamma Acp OMe and Boc D gamma Ach MeN L gamma Acp OMe, through differential deprotection and coupling. These dipeptides were then joined to form the linear tetrapeptide. In summary, a robust precursor has been synthesized for future supramolecular catalytic capsules. Future work includes completing the synthesis of the linear peptide, its cyclization, and confirmation of its dimeric self assembly. Finally, porphyrin caps will be anchored, followed by encapsulation studies of different types of ligands, especially di and tetrapyridines, and investigation of their catalytic properties.
Direction
AMORIN LOPEZ, MANUEL (Tutorships)
Granja Guillán, Juan Ramón (Co-tutorships)
AMORIN LOPEZ, MANUEL (Tutorships)
Granja Guillán, Juan Ramón (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Novel Sulfonopenicillin Siderophore Conjugates to Restore betaLactam Antibiotic Efficacy
Authorship
D.P.R.
Master in Organic Chemistry (3ª ed)
D.P.R.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Resistant bacterial infections have become increasingly common, and certain pathogens have even developed resistance to multiple classes of antibiotics, leaving few or no treatment options available. In recent years, the most successful strategy in the discovery of antiinfective drugs for the treatment of these hard to treat infections has been the combined therapy of antibiotic plus resistance inhibitor. These inhibitors enable the reuse of antibiotics that have already been proven safe and effective for clinical use. In Gram negative bacteria, the primary resistance mechanism involves enzymatic inactivation of betalactam antibiotics, which account for 70 percent of prescriptions, catalyzed by betalactamases. These enzymes hydrolyze the betalactam ring, leading to the formation of inactive compounds. Our research group has focused on the most complex and difficult to inhibit betalactamases: class D enzymes with carbapenemase activity, which are widely distributed in clinically relevant species such as Acinetobacter baumannii e.g., OXA 23 and OXA 24 40; and Enterobacterales e.g., OXA 48. The hydrolytic activity of OXA 23 and OXA 24 40 enzymes is attributed to the uncommon structure of their active site, which features a tunnel-like entry acting as a hydrophobic filter that restricts access to specific substrates. This Master’s Thesis aims to synthesize a zwitterionic sulfonopenicillin siderophore conjugate, with the objective of developing a broad-spectrum inhibitor effective against the most challenging betalactamases.
Resistant bacterial infections have become increasingly common, and certain pathogens have even developed resistance to multiple classes of antibiotics, leaving few or no treatment options available. In recent years, the most successful strategy in the discovery of antiinfective drugs for the treatment of these hard to treat infections has been the combined therapy of antibiotic plus resistance inhibitor. These inhibitors enable the reuse of antibiotics that have already been proven safe and effective for clinical use. In Gram negative bacteria, the primary resistance mechanism involves enzymatic inactivation of betalactam antibiotics, which account for 70 percent of prescriptions, catalyzed by betalactamases. These enzymes hydrolyze the betalactam ring, leading to the formation of inactive compounds. Our research group has focused on the most complex and difficult to inhibit betalactamases: class D enzymes with carbapenemase activity, which are widely distributed in clinically relevant species such as Acinetobacter baumannii e.g., OXA 23 and OXA 24 40; and Enterobacterales e.g., OXA 48. The hydrolytic activity of OXA 23 and OXA 24 40 enzymes is attributed to the uncommon structure of their active site, which features a tunnel-like entry acting as a hydrophobic filter that restricts access to specific substrates. This Master’s Thesis aims to synthesize a zwitterionic sulfonopenicillin siderophore conjugate, with the objective of developing a broad-spectrum inhibitor effective against the most challenging betalactamases.
Direction
GONZALEZ BELLO, CONCEPCION (Tutorships)
GONZALEZ BELLO, CONCEPCION (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Detection of nanomaterials by spectrometric techniques
Authorship
M.R.Q.
Master's Degree in Chemical Research and Industrial Chemistry
M.R.Q.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Nanomaterials (NMs) are small materials whose optoelectronic properties are determinated by quantum confinement due to the reduction in size relative to the bulk material. In recent years, nanotechnology has advanced at an unstoppable rhythm, and nanomaterials are increasingly appearing in numerous fields and textile industries, cosmetics, electronics, computer industry and the environment. The objective of this work is to detect the presence of NMs in solution. Therefore, a design plan is proposed for a sensor carrying a fluorophore group capable of binding to the metal ions of NMs, modifying their optical properties linearly depending on their concentration. Various techniques were applied to characterize ligand-NP adhesion, and for detection, the feasibility of replacing Fluorescence Spectroscopy with Colorimetric Detection (RGB) was studied. The goal is to develop a more practical, rapid, affordable an low-cost method for detecting NMs. This is achieved by capturing and processing images via smarthpone, wich would eliminate the need for specialized molecular fluorescence instrumentation. Preliminaty results suggest the potential viability if the method in solution. The adhesion of NPs to the sensor causes their fluorescence decrease, an observable change in their fluorophore characteristics.
Nanomaterials (NMs) are small materials whose optoelectronic properties are determinated by quantum confinement due to the reduction in size relative to the bulk material. In recent years, nanotechnology has advanced at an unstoppable rhythm, and nanomaterials are increasingly appearing in numerous fields and textile industries, cosmetics, electronics, computer industry and the environment. The objective of this work is to detect the presence of NMs in solution. Therefore, a design plan is proposed for a sensor carrying a fluorophore group capable of binding to the metal ions of NMs, modifying their optical properties linearly depending on their concentration. Various techniques were applied to characterize ligand-NP adhesion, and for detection, the feasibility of replacing Fluorescence Spectroscopy with Colorimetric Detection (RGB) was studied. The goal is to develop a more practical, rapid, affordable an low-cost method for detecting NMs. This is achieved by capturing and processing images via smarthpone, wich would eliminate the need for specialized molecular fluorescence instrumentation. Preliminaty results suggest the potential viability if the method in solution. The adhesion of NPs to the sensor causes their fluorescence decrease, an observable change in their fluorophore characteristics.
Direction
Sanmartin Matalobos, Jesus (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
Sanmartin Matalobos, Jesus (Tutorships)
ABOAL SOMOZA, MANUEL (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Obtention of helicoidal complexes derived from ligands funcionalized with bulky groups
Authorship
R.S.C.
Master's Degree in Chemical Research and Industrial Chemistry
R.S.C.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
This Final Master Project is part of the Supramolecular Chemistry research line within the SUPRABIOIN group, and its goal is to obtain helical metallo-supramolecular complexes from ligands functionalized with bulky groups, in order to study their effect on the final architecture of the compounds. To achieve this, five Schiff base ligands H2Ln (where n=1-5), were synthetized. These ligands are potentially dianionic and tetradentate (N2O2), presenting methyl groups on the spacer and tert-butyl groups on the arms. Neutral cobalt, nickel, copper and zinc metallo-supramolecular complexes were synthesized using an electrochemical methodology. Their characterization in the solid state and solution allowed us to determine their stoichiometry and architecture.
This Final Master Project is part of the Supramolecular Chemistry research line within the SUPRABIOIN group, and its goal is to obtain helical metallo-supramolecular complexes from ligands functionalized with bulky groups, in order to study their effect on the final architecture of the compounds. To achieve this, five Schiff base ligands H2Ln (where n=1-5), were synthetized. These ligands are potentially dianionic and tetradentate (N2O2), presenting methyl groups on the spacer and tert-butyl groups on the arms. Neutral cobalt, nickel, copper and zinc metallo-supramolecular complexes were synthesized using an electrochemical methodology. Their characterization in the solid state and solution allowed us to determine their stoichiometry and architecture.
Direction
GONZALEZ NOYA, ANA MARIA (Tutorships)
Fernández Fariña, Sandra (Co-tutorships)
GONZALEZ NOYA, ANA MARIA (Tutorships)
Fernández Fariña, Sandra (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Sanmartin Matalobos, Jesus (Coordinator)
Couce Fortúnez, Delfina (Chairman)
PELAZ GARCIA, BEATRIZ (Secretary)
Martínez Cebeira, Montserrat (Member)
Bioorthogonal Gold-Catalyzed Cascade Cyclizations
Authorship
X.S.I.
Master in Organic Chemistry (3ª ed)
X.S.I.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Bioorthogonal chemistry has established itself as an essential discipline, studying high selective chemical reactions within complex biological settings without disrupting their proper functioning. In this context, introducing non-natural transformations inside living systems has emerged as a key tool in Biomedicine, providing unprecedented opportunities for the design of new treatments and therapies. Within this framework, it is interesting to consider the use of catalytic transition metal complexes to develop new biocompatible reactivities. In this project we seek to tailor a multiple cascade cyclization process to biocompatible conditions, mimicking natural mechanisms such as steroid biosynthesis. Toward this end, we explore the use of gold as a catalyst able to promote C-C multiple bonds activation for a nucleophile attack, leading to the in situ formation of complex and bioactive heterocyclic structures of interest in a straightforward manner. Thus, this work entails the optimization of a cascade process involving a double cyclization, achieving high dilution conditions, air-tolerance and water compatibility. Besides, we have evaluated its tolerance in biorelevant media and the effect of the presence of different biomolecules, with promising results. Furthermore, we have explored the expansion of the pi-system to enable the formation of fluorescent products through three consecutive gold-promoted cyclizations. Finally, we present preliminary results of the performance of this reactivity inside living mammalian cells.
Bioorthogonal chemistry has established itself as an essential discipline, studying high selective chemical reactions within complex biological settings without disrupting their proper functioning. In this context, introducing non-natural transformations inside living systems has emerged as a key tool in Biomedicine, providing unprecedented opportunities for the design of new treatments and therapies. Within this framework, it is interesting to consider the use of catalytic transition metal complexes to develop new biocompatible reactivities. In this project we seek to tailor a multiple cascade cyclization process to biocompatible conditions, mimicking natural mechanisms such as steroid biosynthesis. Toward this end, we explore the use of gold as a catalyst able to promote C-C multiple bonds activation for a nucleophile attack, leading to the in situ formation of complex and bioactive heterocyclic structures of interest in a straightforward manner. Thus, this work entails the optimization of a cascade process involving a double cyclization, achieving high dilution conditions, air-tolerance and water compatibility. Besides, we have evaluated its tolerance in biorelevant media and the effect of the presence of different biomolecules, with promising results. Furthermore, we have explored the expansion of the pi-system to enable the formation of fluorescent products through three consecutive gold-promoted cyclizations. Finally, we present preliminary results of the performance of this reactivity inside living mammalian cells.
Direction
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Mascareñas Cid, Jose Luis (Tutorships)
TOMAS GAMASA, MARIA (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Synthesis and characterization of a hexaazananographene
Authorship
M.S.P.
Master in Organic Chemistry (3ª ed)
M.S.P.
Master in Organic Chemistry (3ª ed)
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
The synthesis of large polycyclic aromatic hydrocarbons (PAHs) and nanographenes is complicated due to the absence of functional groups in their structures and their typically low solubility. However, the considerable interest and wide range of potential applications of these compounds have driven substantial progress in recent decades. Among the ongoing challenges, the incorporation of heteroatoms such as nitrogen still presents synthetic difficulties. This project yielded an unprecedented synthetic approach for the synthesis of N-containing nanographenes.
The synthesis of large polycyclic aromatic hydrocarbons (PAHs) and nanographenes is complicated due to the absence of functional groups in their structures and their typically low solubility. However, the considerable interest and wide range of potential applications of these compounds have driven substantial progress in recent decades. Among the ongoing challenges, the incorporation of heteroatoms such as nitrogen still presents synthetic difficulties. This project yielded an unprecedented synthetic approach for the synthesis of N-containing nanographenes.
Direction
PEÑA GIL, DIEGO (Tutorships)
Pozo Míguez, Iago (Co-tutorships)
PEÑA GIL, DIEGO (Tutorships)
Pozo Míguez, Iago (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Determination of gabapentin in blood and vitreous humor by GCMS
Authorship
J.R.V.P.
Master's Degree in Chemical Research and Industrial Chemistry
J.R.V.P.
Master's Degree in Chemical Research and Industrial Chemistry
Defense date
07.17.2025 10:00
07.17.2025 10:00
Summary
Gabapentin (GBP) is a drug with anticonvulsant and analgesic properties, widely used and increasingly prescribed for off-label indications, which has heightened its relevance in forensic toxicology. The aim of this study was to develop and validate a rapid and sensitive analytical method for the determination of GBP in blood and vitreous humor using gas chromatography coupled to mass spectrometry (GCMS), in accordance with the validation guideline of the US Food and Drug Administration (FDA). Various extraction techniques were evaluated, with solid-phase extraction (SPE) using Strata C18T column providing the best results in terms of recovery and precision. The method did not require derivatization, simplifying the procedure and aligning with green chemistry principles. Validation included linear calibration curves with comparable coefficients of determination in both matrices, and intra and inter-day assays that demonstrated accuracy and precision within the accepted limits. Finally, the method was applied to the analysis of real samples to verify its applicability to actual forensic cases managed by the Institute of Forensic Sciences (INCIFOR) at the University of Santiago de Compostela. Additionally, the potential use of vitreous humor as an alternative biological matrix to blood was investigated, highlighting its stability and lower susceptibility to postmortem redistribution when blood is unavailable.
Gabapentin (GBP) is a drug with anticonvulsant and analgesic properties, widely used and increasingly prescribed for off-label indications, which has heightened its relevance in forensic toxicology. The aim of this study was to develop and validate a rapid and sensitive analytical method for the determination of GBP in blood and vitreous humor using gas chromatography coupled to mass spectrometry (GCMS), in accordance with the validation guideline of the US Food and Drug Administration (FDA). Various extraction techniques were evaluated, with solid-phase extraction (SPE) using Strata C18T column providing the best results in terms of recovery and precision. The method did not require derivatization, simplifying the procedure and aligning with green chemistry principles. Validation included linear calibration curves with comparable coefficients of determination in both matrices, and intra and inter-day assays that demonstrated accuracy and precision within the accepted limits. Finally, the method was applied to the analysis of real samples to verify its applicability to actual forensic cases managed by the Institute of Forensic Sciences (INCIFOR) at the University of Santiago de Compostela. Additionally, the potential use of vitreous humor as an alternative biological matrix to blood was investigated, highlighting its stability and lower susceptibility to postmortem redistribution when blood is unavailable.
Direction
BERMEJO BARRERA, ANA MARIA (Tutorships)
CABARCOS FERNANDEZ, PAMELA (Co-tutorships)
BERMEJO BARRERA, ANA MARIA (Tutorships)
CABARCOS FERNANDEZ, PAMELA (Co-tutorships)
Court
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)
Sanmartin Matalobos, Jesus (Coordinator)
CASAIS LAIÑO, Mª DEL CARMEN (Chairman)
Ramos Berdullas, Nicolás (Secretary)
Alonso Rodríguez, Elia (Member)