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Self-Assembly of Electroactive Supramolecular Architectures: a Bio-Inspired Approach

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Self-Assembly of Electroactive Supramolecular Architectures: a Bio-Inspired Approach UNIVERSIDAD COMPLUTENSE DE MADRID FACULTAD DE CIENCIAS QUÍMICAS TESIS DOCTORAL Self-assembly of electroactive supramolecular architectures: a bio-inspired approach Auto-ensamblaje de estructuras supramoleculares electroactivas: estrategias bio-inspiradas MEMORIA PARA OPTAR AL GRADO DE DOCTORA PRESENTADA POR Alicia López Andarias DIRECTORES Nazario Martín León Carmen María Atienza Castellanos Madrid © Alicia López Andarias, 2019 UNIVERSIDAD COMPLUTENSE DE MADRID FACULTAD DE CIENCIAS QUÍMICAS Departamento de Química Orgánica Self-assembly of electroactive supramolecular architectures: a bio-inspired approach Auto-ensamblaje de estructuras supramoleculares electroactivas: estrategias bio-inspiradas TESIS DOCTORAL Alicia López Andarias Madrid, 2019 Self-assembly of electroactive supramolecular architectures: a bio­ inspired approach Auto-ensamblaje de estructuras supramoleculares electroactivas: estrategias bio-inspiradas Directores: Dr. Nazario Martín León Dra. Carmen Mª Atienza Castellanos Memoria para optar al grado de DOCTORA EN CIENCIAS QUÍMICAS que presenta Alicia López Andarias Madrid, 2019 DECLARACION DE AUTORiA Y ORIGINALIDAD DE LA TESIS PRESENTADA PARA OBTENER EL TITULO DE DOCTOR D./Diia. Alicia L6pez Andarias, estudiante en el Programa de Doctorado en Quimica Organica, de la Facultad de Ciencias Quimicas de la Universidad Complutense de Madrid, como autora de la tesis presentada para la obtencion del titulo de Doctor y titulada: Seif-assembly of e/ectroactive supramo!ecular architectures: a bio-inspired approach; Auto-ensamblaje de estructuras supramolecu!ares electroactivas: estrategias bio-inspiradas y dirigida por: D. azario Martin Leon y Diia. Carmen M 3 Atienza Castellanos, DECLARO QUE: La tesis es una obra original que no infringe los derechos de propiedad intelectual ni los derechos de propiedad industrial u otros, de acuerdo con el ordenamiento juridico vigente, en particular, la Ley de Propiedad Intelectual (R.D. legislative 1/1996, de 12 de abril, por el que se aprueba el texto refundido de la Ley de Propiedad lntelectual, modificado por la Ley 2/2019, de 1 de marzo, regularizando, aclarando y armonizando las disposiciones legates vigentes sobre la materia), en particular, las disposiciones referidas al derecho de cita. Del mismo modo, asumo frente a la Universidad cualquier responsabilidad que pudiera derivarse de la autoria o falta de originalidad del contenido de la tesis presentada de conformidad con el ordenamiento juridico vigente. En Madrid, a 12 de Septiembre de 2019 D. Nazario Martín León, Catedrático de Universidad del Departamento de Química Orgánica de la Universidad Complutense de Madrid y Dª. Carmen Mª Atienza Castellanos, Profesora Titular del Departamento de Química Orgánica de la Universidad Complutense de Madrid, CERTIFICAN: Que la presente Memoria titulada: Self-assembly of electroactive supramolecular architectures: a bio-inspired approach; Auto-ensamblaje de estructuras supramoleculares electroactivas: estrategias bio-inspiradas, se ha realizado bajo su dirección en el Departamento de Química Orgánica de la Facultad de Ciencias Químicas de la Universidad Complutense de Madrid por la Licenciada en Química Dª. Alicia López Andarias y autorizan su presentación para ser calificada como Tesis Doctoral. Y para que conste firman el presente certificado en Madrid, a 12 de Septiembre de 2019. Fdo. Dra. Carmen Mª Atienza Castellanos Fdo. Dr. Nazario Martín León A mis padres y mi hermano, Agradecimientos Esta Tesis Doctoral se ha llevado a cabo en el Departamento de Química Orgánica de la Universidad Complutense de Madrid bajo la dirección de los Profesores Carmen Mª Atienza y Nazario Martín, a los que agradezco enormemente la orientación, sugerencias y estímulo durante estos años. También Nazario, muchas gracias por la confianza depositada desde el primer momento. La realización del presente trabajo es también fruto de la colaboración con otros grupos de investigación, a los que quiero agradecer su contribución: Al grupo del Prof. José L. Carrascosa (CNB-CSIC), por los estudios de Crio­ microscopía electrónica expuestos en el primer capítulo. En especial a Javi Chichón, por su contribución y ayuda también en la preparación de las muestras. Al grupo de la Prof. Silvia Osuna (Universidad de Girona), por su contribución en la modelización computacional del capítulo 2. Al grupo del Prof. Shu Seki (Kyoto University) por la realización de las medidas de fotocorriente. Especialmente quiero dar las gracias al grupo de la Prof. Aitziber L. Cortajarena (CIC biomaGUNE), no solo por su gran contribución al desarrollo del capítulo dos, sino también por darme la oportunidad de realizar una estancia en su grupo. Gracias también a Antonio, Aline, Edu, Leire, Aldo, Dani y Elena por el buen recibimiento en el grupo. En especial gracias también a Mantas, por todo lo que aprendí durante la estancia y por su ayuda. También quiero dar las gracias a las personas que conforman los diferentes CAI y centros que han sido indispensables para la realización de muchos de los experimentos recogidos en esta Tesis. A Ángel Sánchez, a la Dra. Dolores Molero y a la Dra. Elena Sáez, del CAI de RMN por su gran dedicación y ayuda en los experimentos de RMN. A los CAI de Espectrometría de Masas de la Facultad de Ciencias Químicas de la UCM y del SIdI de la UAM. Al Centro de Microscopía Electrónica, especialmente a Ana Soubrié (AFM) y Javier García y Adrián Gómez (TEM) por la realización de las imágenes de microscopía. Por último, agradecer a los técnicos de laboratorio, Laura García y Javier Cornejo su ayuda y disposición y, también, a Francisco Javier García la realización de los espectros de FTIR. Muchísimas gracias también a todos mis compañeros y amigos del departamento, por todo lo que hemos disfrutado juntos. Me llevo muy buenos recuerdos, repletos de risas, con todos vosotros: Alberto, Paula, Elena, Mayka, Dani, Yago, Canario, Sergio, Matías, Paloma. Muy en especial, gracias Jorge, por los cafés (sin que faltase el horóscopo), cervecitas en el Paraninfo (que se complicaban de vez en cuando), sesiones de “cine” y todos los momentos divertidos que he vivido contigo estos años. Gracias también al grupo de Luís Sánchez, Julia, Yeray, Elisa, Cris y Manu, por su ayuda y los buenos ratitos que echamos durante las comidas. Mª Ángeles, Beti, Ángel, Andreas, David y Luis, gracias por vuestra ayuda. Agradecer también a Salvo sus bromas y el buen humor que siempre transmite. Gracias Virginia por tu simpatía. Por último, muchas gracias Ana por estar siempre pendiente y ayudarnos tanto. Por supuesto, agradecer a todos mis compañeros del grupo: Alfon, Rosa, Miki, Javi, Laura, Chus, Paul, Sonia, Marina, muchas gracias por hacer el día a día ameno, repleto de risas y tonterías que hacen que a cualquiera se le olvide un mal día. Gracias también a Valentina, Marta y Sarita, con las que lo he pasado tan bien y a las que he echado mucho de menos este último tiempo. A mis compañeros de IMDEA: Agus, Jose, Javi, Eider, Inés y Rafa, gracias por su ayuda y compañía. Quiero agradecer ahora a todos los amigos que me han acompañado no solo estos años, sino toda una vida, y lo seguirán haciendo. Al team Swim Happy, con los que he vivido tantísimos buenos momentos y que siempre están ahí. Además, aún sin saber mucho de Química, siempre os habéis preocupado de cómo iban las cosas y saber “de qué va la Tesis”. También quiero dar las gracias a mis gemelillos, Sergio y Raúl, por tantos años tan buenos a vuestro lado. También a las pajarillas, con las que tan buenos momentos he pasado en la Universidad. También agradecer a toda mi familia por su apoyo incondicional. Por último, dar las gracias a las personas que más quiero: A Andrés, el gran regalo de esta etapa. En los momentos difíciles siempre me has escuchado y apoyado, y me has ayudado a superarlos. Gracias por ser tan positivo, por tantos buenos momentos juntos y porque siempre me motivas para conseguir lo que me proponga. A mi hermano, por acompañarme siempre, hasta en mis primeros meses de esta Tesis tuve la suerte de estar contigo. Me has enseñado muchísimo, y no hablo sólo de Química, eres la mejor guía que podría tener y un ejemplo a seguir. Por supuesto, mil gracias a mis padres, por los que soy como soy y he conseguido todo lo que tengo. Porque siempre nos habéis dado todo lo que habéis podido y habéis confiado plenamente en nosotros. Gracias por vuestro cariño, paciencia, entusiasmo y darnos siempre vuestra ayuda con la mejor sonrisa. Os quiero. Abbreviations and acronyms 1D One dimensional 2D Two dimensional 3D Three dimensional a. u. Arbitrary units AFM Atomic force microscopy APCI Atmospheric-pressure chemical ionization CD Circular dichroism CNT Carbon nanotube CT Charge transfer CTPR Consensus tricopeptide repeat CV Cyclic voltammetry DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene DMF N,N-Dimethylformamide DMSO Dimethylsulfoxyde DNA Deoxyribonucleic acid DTT DL-Dithiotreitol ESI Electrospray ionization exTTF π-Extended tetrathiafulvalene FTIR Fourier transform infrared Fmoc Fluorenylmethyloxycarbonyl FP-TRMC Flash-photolysis time-resolved microwave conductivity FPLC Fast protein liquid chromatography HBTU o-(Benzotriazole-1-yl)-N,N,N’,N’-tetramethyluronium hexafluorophosphate HBC Hexabenzocoronene HIVP Human immunodeficiency virus protease HOMO Highest occupied molecular orbital HR High resolution LUMO Lowest unoccupied molecular orbital MALDI Matrix-assisted laser desorption/ionization MS Mass spectrometry MW Molecular weight NMR Nuclear magnetic resonance PBI Perylenebisimide PBS Phosphate buffered
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