Study of conductive polymers for bioelectronics

138 p.Durante esta tesis doctoral se han desarrollado nuevos polímeros orgánicos conductores para su aplicación en bioelectrónica. Partiendo del material más famoso y utilizado hoy en día el PEDOT:PSS, se han podido mejorar propiedades como la biocompatibilidad, estabilidad y funcionabilidad. Todo ello, nos ha llevado a nuevos materiales que pueden servir para mejorar diferentes aplicaciones como sensores, electrodos cutáneos o scaffolds para ingeniería tisular. En el primer capítulo hemos sustituido el polímero aniónico PSS con otros más bio-tolerante los Glicosaminoglicanos (GAGs). Estos polímeros están presentes en nuestro cuerpo y llevan grupos sulfonatos y carboxilatos, los cuales pueden interaccionar con la cadena de PEDOT y estabilizar la carga positiva. El material final presenta efecto antiinflamatorio muy útil en vista de un implante corporal, para contrastar la inflamación resultante. En el segundo capítulo nos hemos enfocado en introducir en la formulación de PEDOT:PSS un nuevo agente reticulante. La divinilsulfona (DVS), es un reticulante muy conocido en bioquímica, que se utiliza para reticular, biomoléculas. Sustituyendo GOPS, el reticulante más utilizado, por DVS, se puede llegar a una conductividad tres veces mayor, sin perder propiedades mecánicas. El exceso es fácil de quitar y es muy estables a lo largo de los días en contacto con una solución acuosa de tampón fosfato, medio ideal para células. En el último capítulo, hemos hablado de como intervenir directamente en la estructura molecular de la parte conductora. Para pode llevarlo a cabo hemos elegido cambiar el enfoque del EDOT a ProDOT mucho más fácil de sintetizar. Hemos desarrollado una síntesis, que, en solo tres pasos, permite de conectar un grupo carboxílico al ProDOT. Finalmente lo hemos fácilmente funcionalizado con 3 moléculas útiles en bioelectronica: tetraetileneglycol, Dopamine y un radical libre (TEMPO)

Carbon Nanomaterials Embedded in Conductive Polymers: A State of the Art

Carbon nanomaterials are at the forefront of the newest technologies of the third millennium, and together with conductive polymers, represent a vast area of indispensable knowledge for developing the devices of tomorrow. This review focusses on the most recent advances in the field of conductive nanotechnology, which combines the properties of carbon nanomaterials with conjugated polymers. Hybrid materials resulting from the embedding of carbon nanotubes, carbon dots and graphene derivatives are taken into consideration and fully explored, with discussion of the most recent literature. An introduction into the three most widely used conductive polymers and a final section about the most recent biological results obtained using carbon nanotube hybrids will complete this overview of these innovative and beyond belief materials.The European Union is acknowledged for funding this research through Horizon 2020 MSCA-IF-2018 No 838171 (TEXTHIOL). IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV- 2016-0686). European Regional Development fund Project “MSCAfellow4 @ MUNI” supported by MEYS CR (No. CZ.02.2.69/0.0/0.0/20_079/0017045) is acknowledged. N.A. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 753293, acronym NanoBEAT

Poly(3,4-ethylenedioxythiophene) (PEDOT) Derivatives: Innovative Conductive Polymers for Bioelectronics

Poly(3,4-ethylenedioxythiophene)s are the conducting polymers (CP) with the biggest prospects in the field of bioelectronics due to their combination of characteristics (conductivity, stability, transparency and biocompatibility). The gold standard material is the commercially available poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). However, in order to well connect the two fields of biology and electronics, PEDOT: PSS presents some limitations associated with its low (bio) functionality. In this review, we provide an insight into the synthesis and applications of innovative poly(ethylenedioxythiophene)-type materials for bioelectronics. First, we present a detailed analysis of the different synthetic routes to (bio) functional dioxythiophene monomer/polymer derivatives. Second, we focus on the preparation of PEDOT dispersions using different biopolymers and biomolecules as dopants and stabilizers. To finish, we review the applications of innovative PEDOT-type materials such as biocompatible conducting polymer layers, conducting hydrogels, biosensors, selective detachment of cells, scaffolds for tissue engineering, electrodes for electrophysiology, implantable electrodes, stimulation of neuronal cells or pan-bio electronics.The work was supported by EU through the projects FP7-PEOPLE-2012-ITN 316832-OLIMPIA and FP7-PEOPLE-2013-ITN 607896-OrgBio. Ana Sanchez-Sanchez is thankful for the Postdoctoral Funding for Doctoral Research Staff Improvement Grant from the Basque Government. David Mecerreyes thanks Becas de Practicas en el Extranjero "Global Training"

Thiophene-Based Trimers and Their Bioapplications: An Overview

Certainly, the success of polythiophenes is due in the first place to their outstanding electronic properties and superior processability. Nevertheless, there are additional reasons that contribute to arouse the scientific interest around these materials. Among these, the large variety of chemical modifications that is possible to perform on the thiophene ring is a precious aspect. In particular, a turning point was marked by the diffusion of synthetic strategies for the preparation of terthiophenes: the vast richness of approaches today available for the easy customization of these structures allows the finetuning of their chemical, physical, and optical properties. Therefore, terthiophene derivatives have become an extremely versatile class of compounds both for direct application or for the preparation of electronic functional polymers. Moreover, their biocompatibility and ease of functionalization make them appealing for biology and medical research, as it testifies to the blossoming of studies in these fields in which they are involved. It is thus with the willingness to guide the reader through all the possibilities offered by these structures that this review elucidates the synthetic methods and describes the full chemical variety of terthiophenes and their derivatives. In the final part, an in-depth presentation of their numerous bioapplications intends to provide a complete picture of the state of the art.Operational Program Research, Development, and Education Project “MSCAfellow4@MUNI” (No. CZ.02.2.69/0.0/0.0/20_079/0017045) is acknowledged. The European Union is acknowledged for funding this research through Horizon 2020 MSCA-IF-2018 No 838171 (TEXTHIOL)

Comparison of the Corrosion Inhibition Ability of Different Coumarate-Based Compounds Incorporated into Waterborne Binders

One of the most widely applied methods for the mitigation of corrosion is to cover metallic surfaces with polymeric coatings; however, the barrier properties provided by the polymer may not be enough to prevent corrosion. To improve the performance of the coatings, the incorporation of corrosion inhibitors in their formulation can be done to provide active protection to the system. Among the organic corrosion inhibitors, p-coumaric acid (p-CA) is promising for corrosion protection. Therefore, in this work, the corrosion protection efficiency of four p-coumaric-based inhibitors, methyl (H1), butyl (H4), trifluoromethoxy (HCF3), and p-4-ethyloxymethacrylate p-coumaric acid (HMA), is investigated. The inhibitors are incorporated into environmentally friendly waterborne polymeric binders by batch miniemulsion polymerization. The barrier corrosion protection of the coatings produced from these hybrid latexes is analyzed by electrochemical impedance spectroscopy (EIS) of the intact and scratched coated steel substrates. Of the intact coatings, the one with H1 showed the best response, with impedances of 10(6.3)-10(6.7) Omega and phase angles of 82-84 degrees, considerably higher than the control without inhibitor (10(5)-10(5.2) Omega and 60-66 degrees, respectively). The better performance of H1 has been attributed to its higher solubility in the media. However, the best impedance results for the scratched films have been obtained for the coating with HMA, as the impedance was maintained at similar to 10(4.3) Omega for 24 h, while the impedance drops from similar to 10(4.6) to 10(4.1) Omega for the control scratched sample. As HMA is attached to the polymeric chains, it is likely able to protect the exposed metallic area without completely leaching from the coating, thus explaining why it is able to maintain its performance. The EIS analysis also strongly suggests that the inhibitors have an additional protective effect through increasing pore resistance and decreasing metal corrosion as indicated from the higher R-pore and lower C-dl data extracted from the fits.We are thankful for the financial support received from the Basque Government (IT-1525-22), from the Spanish Government (MINECO PID2021-123146OB-I00 and MICINN PDC2021-121416-I00), and from Deakin University

New poly(ionic liquid)s based on poly(azomethine-pyridinium) salts and its use as heterogeneous catalysts for CO2 conversion

A fast and simple synthetic route towards a new family of poly(ionic liquids) based on aromatic crosslinked poly(azomethine-pyridinium) salts is described. These new polymers were prepared in one step from new diamine methyl pyridinium salts and isopthaldehyde, in 30 min under microwave irradiation. By this method, poly(azomethine-pyridinium) containing chloride (Cl), bis(trifluoromethylsulfonyl)imide (TFSI) and hexaflorophosphate (PF6) as counter-anions were synthetized. This new pyridinium poly(ionic liquid)s were obtained as insoluble powders showing high thermal stability. The poly(azomethine-pyridinium)s were tested as heterogeneous catalysts in the cycloaddition of CO2 to epichlorohydrin to obtain chloropropylene carbonate. The polymers containing chloride anion shows high content of catalytically active sites and the best performance of the series, with 100% selectivity towards the chloropropylene carbonate in a reaction without solvent at 3 bar of CO2, 100 °C and low catalyst loading (0.5 mol%).Spanish Government, MINECO (Projects MAT2014-52085-C2-2-P and MAT2017-82288-C2-2-P, MAT2017-83373-R

Engineering block copolymer materials for patterning ultra-low dimensions

Recently engineered high χ-low N block copolymers for nanolithography are evaluated. Synthetic routes together with thin film processing strategies are highlighted that could enable the relentless scaling for logic technologies at sub-10 nanometres

Incorporation of a Coumarate Based Corrosion Inhibitor in Waterborne Polymeric Binders for Corrosion Protection Applications

The incorporation of organic corrosion inhibitors into waterborne coatings is optimized in this work. Herein, p-coumaric acid (4-hydroxycinnamic acid) is modified by a butyl radical and its effectiveness as an anticorrosive free inhibitor in solution is confirmed by potentiodynamic polarization (PP). The molecule is then successfully incorporated into waterborne polymeric binders by employing different polymerization techniques in dispersed media. Whenever possible, the inhibitor is also blended into the bare latexes to compare the effect of the incorporating method. The anticorrosion performance of the obtained coatings is tested and compared by electrochemical analysis. Promising results are obtained for the coatings produced by semibatch emulsion polymerization even at the low concentration of 1.5 mg of inhibitor g(-1) latex. The intact control coating without inhibitor shows an impedance of up to 10(6) omega and a phase angle of 72 degrees after 1 h of immersion in the corrosive medium, meanwhile the coating with inhibitor shows higher values, 10(6.7) omega and 80 degrees. Active corrosion inhibition is observed in the coating with inhibitor in which a defect has been done, as the impedances drop to 10(3.9) omega after 24 h of immersion in the saline solution while in the control scratched coating it drops to 10(3.6) omega.The authors would like to thank for the financial support received from the Basque Government (IT-999-16), and the Spanish Government (MINECO CTQ -2017-87841-R and MICINN PDC2021-121416-I00)

From Plastic Waste to New Materials for Energy Storage

The use of plastic waste to develop high added value materials, also known as upcycling, is a useful strategy towards the development of more sustainable materials. More specifically, the use of plastic waste as a feedstock for synthesising new materials for energy storage devices can not only provide a route to upgrading plastic waste but can also help in the search for sustainable materials. This perspective describes recent strategies for the use of plastic waste as a sustainable, cheap and abundant feedstock in the production of new materials for electrochemical energy storage devices such as lithium batteries, sodium batteries and supercapacitors. Two main strategies are described, the development of conducting carbons by combustion of plastic waste and the depolymerization of plastics into new chemicals and materials. In both cases, catalysis has been key to ensuring high efficiency and performance. Future opportunities and challenges are highlighted and hypotheses are made on how the use of plastic waste could enhance the circularity of current energy storage devices.NG acknowledges the funding from the European Union’s Horizon 2020 framework programme under the Marie Skłodowska-Curie agreement No. 101028682. CJ acknowledges the financial support from el Ministerio de ciencia e innovación from the Juan de la Cierva Program (FJC2020-045872-I). The funding from the European Union’s Horizon 2020 framework programme under the Marie Skłodowska-Curie agreement No. 101028975 and Ministerio de ciencia e innovación under PDC2021-121461-I00 project is acknowledged

Dual redox-active porous polyimides as high performance and versatile electrode material for next-generation batteries

Energy storage will be a primordial actor of the ecological transition initiated in the energy and transport sectors. As such, innovative approaches to design high-performance electrode materials are crucial for the development of the next generation of batteries. Herein, a novel dual redox-active and porous polyimide network (MTA-MPT), based on mellitic trianhydride (MTA) and 3,7-diamino-N-methylphenothiazine (MPT) monomers, is proposed for applications in both high energy density lithium batteries and symmetric all-organic batteries. The MTA-MPT porous polyimide was synthesized using a novel environmentally-friendly hydrothermal polymerization method. Rooted in its dual redox proprieties, the MTA-MPT porous polyimide exhibits a high theoretical capacity making it a very attractive cathode material for high energy density battery applications. The cycling performance of this novel electrode material was assessed in both high energy density lithium batteries and light-weight symmetric all-organic batteries, displaying excellent rate capability and long-term cycling stability.N. Goujon acknowledges the funding from the European Union's Horizon 2020 framework programme under the Marie Sklodowska-Curie agreement No. 101028682. M. Lahnsteiner, H. M. Moura, D. A. Cerron-Infantes and M. M. Unterlass acknowledge funding through the Austrian Science Fund's (FWF) START programme under grant no. Y1037-N28. We thank Dr Jerpme Roeser and Prof. Arne Thomas (TU Berlin) for gas sorption measurements