Alginate and Silk Fibroin Based Technologies for Biosensing

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Alginate and Silk Fibroin Based Technologies for Biosensing ADVERTIMENT. Lʼaccés als continguts dʼaquesta tesi queda condicionat a lʼacceptació de les condicions dʼús establertes per la següent llicència Creative Commons: http://cat.creativecommons.org/?page_id=184 ADVERTENCIA. El acceso a los contenidos de esta tesis queda condicionado a la aceptación de las condiciones de uso establecidas por la siguiente licencia Creative Commons: http://es.creativecommons.org/blog/licencias/ WARNING. The access to the contents of this doctoral thesis it is limited to the acceptance of the use conditions set by the following Creative Commons license: https://creativecommons.org/licenses/?lang=en ALGINATE AND SILK FIBROIN BASED TECHNOLOGIES FOR BIOSENSING Augusto Márquez Maqueda Doctoral Thesis PhD in Chemistry Supervised by: Dr. Xavier Muñoz Berbel Dr. Carlos Domínguez Horna Tutored by: Dr. Julián Alonso Chamorro Departament de Química Facultat de Ciències 2020 The present thesis, entitled “Alginate and Silk Fibroin based Technologies for Biosensing”, is submitted by Augusto Márquez Maqueda as a partial fulfilment of the requirements for the Doctor of Philosophy degree in Chemistry. This thesis was carried out at the Institute of Microelectronics of Barcelona (IMB-CNM, CSIC), in the Group of Chemical Transducers (GTQ), under the supervision of Dr. Xavier Muñoz Berbel and Dr. Carlos Domínguez Horna. This thesis was supported by the Spanish R & D National Program (MEC Project TEC2014-54449-C3-1-R) and by the MICINN for the award of a research studentship within the FPI program (BES-2015-072946). With the approval of: Dr. Xavier Muñoz Berbel Dr. Carlos Domínguez Horna (Director) (Director) Dr. Julián Alonso Chamorro Augusto Márquez Márquez (Tutor) (Author) Agradecimientos Son muchas las personas a las que he de agradecer el hecho de haber podido realizar esta tesis. Algunas contribuyeron a ello hace tanto tiempo que ni ellas, ni siquiera yo, nos acordamos ya. Es por ello que trataré de hacer un recorrido por los más recientes, sin desmerecer todos aquellos que me han enseñado durante mi vida. En primer lugar, quiero agradecer a mis directores, Carlos Domínguez y Xavier Muñoz, por brindarme la oportunidad de pasar estos últimos cuatro años en el CNM y dotarme de todos los recursos necesarios, tanto materiales como intelectuales, para ir avanzando en el trabajo y poder compartirlo además en muchos congresos internacionales. Está de más decirlo, pero por supuesto que nada de lo que continúa en estas páginas hubiese sido posible sin vosotros. He de agradecer también al Grupo de Transductores Químicos en su conjunto por su colaboración, por su contribución y por sus recomendaciones en los seminarios de grupo. En especial me gustaría agradecer a Juan Manuel Ríos, a Alfredo Cadarso y a Pablo Giménez por guiarme cuando comencé en el laboratorio. Por otro lado, también me gustaría agradecer a Tobias Ackermann el tiempo compartido estos años. Ha sido un referente constante durante mi tesis y de él he aprendido bastante más de lo que se pueda imaginar. Me gustaría agradecer a Gonzalo Guirado su buena disposición para colaborar y las contribuciones científicas que han surgido de ello. I also would like to thank Fiorenzo Omenetto for his kind reception at his Silklab in Tufts University and Moliria Dos Santos as well for the interesting collaboration we carried out together during those four months. Le doy las gracias a todos mis compañeros, con los que he pasado momentos inolvidables tanto en el centro como fuera de él. Por suerte son muchos, ellos lo saben, y no tiene sentido enumerarlos aquí. Habéis sido el apoyo fundamental durante todos estos años, así como yo también espero haber sido parte del vuestro. Algunos han marchado ya del CNM y, el día que me toque a mí, sé que lo haré con buenos amigos, con los que cuentas para siempre por muy lejos que estés. Aunque hayan pasado más de seis años, me gustaría agradecer a Juan A. Anta la oportunidad que me dio para unirme a su grupo de investigación de Nanostructured Solar Cells en la Universidad Pablo de Olavide, donde comenzó toda mi andadura científica y donde pude realizar mi TFG y TFM. A Thomas Berger. Creo que nunca podré agradecerte lo suficiente el tiempo que dedicaste a enseñarme casi todo lo que sé, desde el día en que entré por primera vez en el laboratorio de Juan hasta el día que me marché de Salzburgo. Este trabajo tiene mucho de ti. Me gustaría dedicar este trabajo a mi familia y amigos. Cada vez que he pasado por Carmona, Sevilla, Zahara, Badajoz o a Madrid he encontrado ese cariño incondicional y ese respiro necesario. Y gracias a ti Abril, por convencerme para venir, por escucharme y por consultarme, por ser mi apoyo y por sentir que soy el tuyo. Vendrán nuevos retos, y aquí estaremos. Contents List of Abbreviations, Units and Symbols ....................................................................... i List of Tables and Figures .............................................................................................. iv Summary ......................................................................................................................viii Resumen ........................................................................................................................ xii 1. Motivation ................................................................................................................... 1 2. Introduction ................................................................................................................. 4 3. Fundamentals ............................................................................................................ 25 4. Objectives .................................................................................................................. 45 5. Materials and Methods .............................................................................................. 47 6. Results ....................................................................................................................... 69 6.1 Electrodepositable Alginate Membranes for Amperometric Glucose Biosensing ........................................................................................................................... 70 6.2. Alginate Membrane Integration in POC Device for Glucose and Lactate Determination .................................................................................................... 88 6.3. Silk-Fibroin Micro-Capillary Pads for Glucose Determination in Whole Blood ......................................................................................................................... 104 6.4. Silk Bio-Cladding Fiber Optics Biosensor for Glucose Detection in Whole Blood ......................................................................................................................... 118 6.5. Photo-Electro-Enzymatic Glucose Biosensor using dithienylethene derivatives as Reusable mediators ......................................................................................... 131 6.6. Light-Renewable Enzymatic Silk Biosensors Incorporating Diarylethene Mediators For Continuous Glucose Monitoring ............................................. 143 7. General Discussion .................................................................................................. 155 8. Conclusions ............................................................................................................. 161 9. Future Scope ............................................................................................................ 163 10. Bibliography .......................................................................................................... 168 List of Abbreviations, Units and Symbols Abbreviations ABTS 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) ATR Attenuated total reflectance CV Cyclic voltammetry, Coefficient of variation DET Direct electron transfer DNA Deoxyribonucleic acid DTE 1,2-bis (5-carboxy-2-methylthien-3-yl) cyclopentene DTEc Closed DTE DTEo Open DTE e-beam Electron beam ELISA Enzyme-linked immunosorbent assay FBS Fetal bovine serum FOCS Fiber optics chemical and biochemical sensors FTIR Fourier transformed infrared GOx Glucose oxidase HRP Horseradish peroxidase Instituto de Microelectrónica de Barcelona – Centro Nacional de IMB-CNM Microelectrónica IUPAC International Union of Pure and Applied Chemistry LOC Lab on chip LOD Limit of detection LOx Lactate oxidase NP Nanoparticle PBS Phosphate buffer saline PDMS Polydimethylsiloxane PECVD Plasma enhanced chemical vapour deposition PMMA Poly(methyl methacrylate) POC Point of Care ▲ I ▼ PSA Pressure sensitive adhesive RI Refractive index SEM Scanning electron microscopy SF Silk Fibroin SPGE Screen-printed gold electrodes T, A, R Transmittance, Absorbance, Reflectance (Optics) TMB 3,3′,5,5′-Tetramethylbenzidine UV Ultraviolet WE, CE, Working, Counter and Reference electrode RE Units A Ampere Å Angstrom C Coulomb ºC Celsius degree g Gram K Kelvin degree L Litre m Metre min minutes psi Pound per square inch s Second V Volt W Watt Symbols c Concentration (M) E Potential (V) ε Molar attenuation coefficient (M-1 cm-1) ▲ II ▼ F Faraday constant (96485 C mol-1) h Plank’s constant (6,62 kg m2 s1) i Current intensity (A) l Length (m) λ Wavelength (nm) m Mass (g) M Molar (mol L-1) n Number of electrons, number of samples Q Electric charge (C) R Gas Constant (8,31 J K-1 mol-1) t Time (s) T Temperature (ºC) ▲ III ▼ List of Tables and Figures Table 1.1. Number of millions of people with diabetes worldwide …………….. 3 Figure
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