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Gold, Silver and Platinum Nanoparticles: from New Synthetic Adrián Fernández Lodeiro Gold, Silver and Platinum Nanoparticles: From New Synthetic Routes to Sensing, Catalysis and Bio-Applications Dissertação para a obtenção do Grau de Doutor em Química Sustentável Orientador Doutor José Luís Capelo Martínez Professor Associado com Agregação Faculdade de Ciências e Tecnologia (FCT) Universidade Nova de Lisboa (UNL), Portugal Co-Orientadores Doutora Julia Lorenzo Rivera Visiting Professor, Universitat Autònoma de Barcelona, UAB, Spain Doutor Hugo Miguel Baptista Carreira dos Santos Investigador Auxiliar, FCT Investigator Programme, FCT, UNL, Portugal Júri Presidente Prof. Doutor Manuel Luís De Magalhães Nunes Da Ponte Vogais Prof. Doutor Gilberto Paulo Peixoto Igrejas Prof. Doutor José Luís Capelo Martínez Prof. Doutor Jorge Pérez Juste Doutora Elisabete De Jesus Oliveira Marques March - 2019 Adrián Fernández Lodeiro Gold, Silver and Platinum Nanoparticles: From New Synthetic Routes to Sensing, Catalysis and Bio-Applications Dissertação para a obtenção do Grau de Doutor em Química Sustentável (Sustainable Chemistry) Orientador Doutor José Luís Capelo Martínez Professor Associado com Agregação Faculdade de Ciências e Tecnologia (FCT) Universidade Nova de Lisboa (UNL), Portugal Co-Orientadores Doutora Julia Lorenzo Rivera Visiting Professor, Universitat Autònoma de Barcelona, UAB, Spain Doutor Hugo Miguel Baptista Carreira dos Santos Investigador Auxiliar, FCT Investigator Programme, FCT, UNL, Portugal Júri Presidente Prof. Doutor Manuel Luís De Magalhães Nunes Da Ponte Vogais Prof. Doutor Gilberto Paulo Peixoto Igrejas Prof. Doutor José Luís Capelo Martínez Prof. Doutor Jorge Pérez Juste Doutora Elisabete De Jesus Oliveira Marques March - 2019 II Gold, Silver and Platinum Nanoparticles: From New Synthetic Routes to Sensing, Catalysis and Bio-Applications Copyright © Adrián Fernández Lodeiro, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal A Faculdade de Ciências e Tecnologia e a Universidade Nova de Lisboa (Portugal) têm o direito, perpétuo e sem limites geográficos, de arquivar e publicar esta dissertação através de exemplares impressos reproduzidos em papel ou de forma digital, ou por qualquer outro meio conhecido ou que venha a ser inventado, e de a divulgar através de repositórios científicos e de admitir a sua cópia e distribuição com objectivos educacionais ou de investigação, não comerciais, desde que seja dado crédito ao autor e editor. III IV A mis padres, José Manuel y María Pilar V VI Acknowledgments First of all, I want to thanks the “Fundação para a Ciencia e Tecnología” (FCT), as well as the “Faculdade de Ciências e Tecnologia” (FCT), the “Universidade Nova de Lisboa” (UNL), and all the professors responsible for the “Programa Doutoral em Química Sustentável” (PDQS), for the grant number SFRH/BD/52528/2014. I want to thanks all the people involved in the REQUIMTE-Chemistry Department of the FCT. To the research units, UCIBIO-REQUIMTE first, and to the LAQV-REQUIMTE later, for their support and help during this period. Thanks to the Analytical Laboratory at the REQUIMTE-Chemistry Department for their support, and specially the help to Dr. Luz Fernandes, Ms. Carla Rodrigues, Mr. Nuno Costa and Ms. Ana Teresa Lopes. Thanks also to laboratory technicians at the 4th floor of the Chemistry Department, Ms. Idalina Martins e Ms. Conceição Luis for their help and kindness. I want to thanks my supervisor Professor Dr José Luís Capelo Martinez, as well as the co-supervisors, Professor Dr Julia Lorenzo Rivera and Dr Hugo Santos, for giving me the opportunity to do my PhD under their guidance and supervision. Thanks a lot. I want to thanks the Proteomass Scientific Society for the support during the PhD, in the form of reagents, general funding and for the last year contract. I want to do a special thanks to all the people (past and present) of the Bioscope group and Proteomass Scientific Society. It has been several years where I have worked with many people. I can say, happy and proud, that I learned something positive from every person with whom I have coincided, and that without you none of this would be possible. I want to give my sincere thanks, extendible to the others members with whom I have coincided during this "adventure", to the heads of the group, the "catalysts" of all the work present here, Professor Jose Luis Capelo Matínez and Professor Carlos Lodeiro Espiño. Without your tireless work and support, none of this would be possible. I would also like to thank very much the support of two persons who have shared with me these years of work, such as Dr Javier Fernández and Ms Jamila Djafari (almost Dr too). Their constant support in the laboratory, when things didn’t go as expected, as well as their help in understanding when they did, leading me to learn more than I could have thought at the beginning of the thesis. Their passion for science is indeed contagious, and with them, the desire to learn and experiment seems endless. I wanted to leave my sincere thanks, once again, to the Bioscope and the Proteomass, for everything. I want to thank all the collaborators which have contributed in my work, with the characterization techniques as well as bacterial, cellular or catalytic properties. VII Dr Benito Rodríguez-González from the University of Vigo, CACTI (Spain) for some of the TEM, HRTEM, EDS, EELS and HAADF-STEM characterizations. Dr Fernando Novio Vazquez and Dr Daniel Ruiz Molina from the Universitat Autònoma de Barcelona (Spain) for some Raman, SEM and XPS analysis. Mr David Lopez-Tejedor, Mr Carlos Perez-Rizquez and Dr Jose M. Palomo, from the Consejo Superior de Investigaciones Científicas (Spain), for some of the HRTEM and catalytic analisys. Mr Carlos Fernández Lodeiro from the University of Vigo (Spain) for some of the TEM images. Mr Sergi Rodriguez Calado and Dr Julia Lorenzo Rivera, from Universitàt Autónoma de Barcelona, for the cell toxicity experiments. Dr Elisabete Muchagato Mauricio from the Universidade Lusófona (Portugal) and Dr Maria Paula Duarte from the Universidade Nova de Lisboa (Portugal) for the antibacterial studies. A modo personal, me gustaría agradecer a mis todos compañeros del programa doctoral en química sostenible. Al inicio, cuando una persona cambia de país e idioma, la transición entre lo conocido y lo nuevo puede llegar a ser ciertamente complicada. Gracias a su recibimiento, comportamiento y amabilidad, puedo decir que me he sentido como en casa desde el principio. Un agradecimiento especial a mis compañeros “lisboetas” del programa doctoral, que más que compañeros, considero amigos. Muito Obrigado rapazes! Creo que lo que hace especial a un lugar no son sus monumentos, sus comidas ni sus paisajes naturales. Lo que hace especial a un lugar son sus gentes. Y no solo creo, si no que puedo afirmar, que las personas con las que compartí muchos de mis mejores momentos en estos últimos años, tanto fuera como dentro del laboratorio, hacen grande a Portugal. Muchas gracias a todos los “vicentinos”, y en especial a mi gran compañero y amigo Eduardo. ¡Por muchos años más! Quería agradecer a todos mis amigos de Santiago y alrededores que me han dado su apoyo durante este tiempo. Sobre todo a Ángela, que ha sido una parte importante en estos años. Un agradecimiento especial a una gran persona, a mi amigo el Dr. Rodrigo Lamelas, con quien empecé compartiendo estudios en primero de carrera, y acabé compartiendo autoría en artículos científicos. No serían agradecimientos completos sin dar las gracias a todos mis amigos “estradenses”, a la familia que se escoge. Si hay mejores personas en este mundo, no quiero saberlo. Saber que al volver a casa, a pesar del tiempo y la distancia, siempre se puede contar con vosotros, para lo bueno y para lo malo, es lo mejor que se puede desear. Han sido muchos años hasta llegar aquí, pero no sería posible sin vuestros ánimos y apoyo. Vuestra amistad no solo hace bien a la mente, sino también al corazón. Dicen que si una amistad dura más de siete años, es para toda la vida. Con vosotros, toda la vida hasta me parece VIII poco. Mención especial a Paula y Rubén. Gracias por vuestra visita, pero ¡aún espero la del resto! ¡Muchas gracias a todos! A Silvia, por todo el cariño y apoyo en este tramo final. Lo importante no es como se empieza, es como se acaba, y no podría haber acabado mejor. A mi familia perruna. Por el inmenso cariño que dan sin pedir nada a cambio. En ese sentido, son un ejemplo a seguir. Por último, a mi familia. Creo que todavía no se han inventado las palabras necesarias que consigan reflejar mi enorme gratitud hacia todos ellos. A mis abuelos, José, Hermitas, Esther y Avelino. Los abuelos pasan mucha sabiduría a sus nietos, y ellos, tanto directa como indirectamente, son los mejores profesores. A mis hermanos, Abel, Javier y Carlos. Mira que vivimos cosas juntos, y más que vendrán. Sois los mejores. A mis cuñadas, Paula, Jamila y Paula. Muchas gracias por ser como sois, vuestro apoyo, cariño y por soportar a mis hermanos. Eso sí que tiene mérito. A mi sobrina Valentina. No podría encontrar mejor uso de mí tiempo, que el invertido jugando y aprendiendo contigo. ¡No crezcas tan rápido! A mis tíos, Carlos y Jose. Por todo el apoyo y cariño. Pero sobre todo por sus incontables consejos, sin los cuales nada de esto sería posible. De hecho, recuerdo una conversación con Jose en el año 2005 sobre la importancia de aportar valor a la sociedad mediante nuestro trabajo diario. Ese día, en un Peugeot 205 de color verde, en la IC20 camino del Almada Forum, en ese preciso día, me decanté por la elección de la química como futuro profesional. Y no puedo estar más agradecido. No por ser donde mas dinero se puede ganar, si no por, como bien apuntó mi tio, ser donde la satisfacción personal es mas elevada.
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