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  1. Poor electrochemical communication between biocatalysts and electrodes is a ubiquitous limitation to bioelectrocatalysis efficiency. An extensive library of polymers has been developed to modify biocatalyst-electrode interfaces to alleviate this limitation. As such, conducting redox polymers (CRPs) are a versatile tool with high structural and functional tunability. While charge transport in CRPs is well characterized, the understanding of charge transport mechanisms facilitated by CRPs within decisively complex photobioelectrocatalytic systems remains very limited. This study is a comprehensive analysis that dissects the complex kinetics of photobioelectrodes into fundamental blocks based on rational assumptions, providing a mechanistic overview of charge transfer during photobioelectrocatalysis. We quantitatively compare two biohybrids of metal-free unbranched CRP (polydihydroxy aniline) and photobiocatalyst (intact chloroplasts), formed utilizing two deposition strategies ( “mixed” and “layered” depositions). The superior photobioelectrocatalytic performance of the “ layered” biohybrid compared to the “ mixed” counterpart is justified in terms of rate ( D app ), thermodynamic and kinetic barriers (H ≠ , E a ), frequency of molecular collisions ( D 0 ) during electron transport across depositions, and rate and resistance to heterogeneous electron transfer ( k 0 , R CT ). Our results indicate that the primary electron transfer mechanism across the biohybrids, constituting the unbranched CRP, is thermally activated intra- and inter-molecular electron hopping, as opposed to a non-thermally activated polaron transfer model typical for branched CRP- or conducting polymer (CP)-containing biohybrids in literature. This work underscores the significance of subtle interplay between CRP structure and deposition strategy in tuning the polymer-catalyst interfaces, and the branched/unbranched structural classification of CRPs in the bioelectrocatalysis context. 
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  2. Abstract

    Time‐dependent density functional theory (TDDFT) was applied to gain insights into the electronic and vibrational spectroscopic properties of an important electron transport mediator, methyl viologen (MV2+). An organic dication, MV2+has numerous applications in electrochemistry that include energy conversion and storage, environmental remediation, and chemical sensing and electrosynthesis. MV2+is easily reduced by a single electron transfer to form a radical cation species (MV•+), which has an intense UV–visible absorption near 600 nm. The redox properties of the MV2+/MV•+couple and light‐sensitivity of MV•+have made the system appealing for photo‐electrochemical energy conversion (e.g., solar hydrogen generation from water) and the study of photo‐induced charge transfer processes through electronic absorption and resonance Raman spectroscopic measurements. The reported work applies leading TDDFT approaches to investigate the electronic and vibrational spectroscopic properties of MV2+and MV•+. Using a conventional hybrid exchange functional (B3‐LYP) and a long‐range corrected hybrid exchange functional (ωB97X‐D3), including with a conductor‐like polarizable continuum model to account for solvation, the electronic absorption and resonance Raman spectra predicted are in good agreement with experiment. Also analyzed are the charge transfer character and natural transition orbitals derived from the TDDFT vertical excitations calculated. The findings and models developed further the understanding of the electronic properties of viologens and related organic redox mediators important in renewable energy applications and serve as a reference for guiding the interpretation of electronic absorption and Raman spectra of the ions.

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  3. Cyclic voltammetry was applied to investigate the permselective properties of electrode-supported ion-exchange polymer films intended for use in future molecular-scale spectroscopic studies of bipolar membranes. The ability of thin ionomer film assemblies to exclude mobile ions charged similarly to the polymer (co-ions) and accumulate ions charged opposite to the polymer (counterions) was scrutinized through use of the diffusible redox probe molecules [Ru(NH3)6]3+and [IrCl6]2−. With the anion exchange membrane (AEM) phase supported on a carbon disk electrode, bipolar junctions formed by addition of a cation exchange membrane (CEM) overlayer demonstrated high selectivity toward redox ion extraction and exclusion. For junctions formed using a Fumion®AEM phase and a Nafion®overlayer, [IrCl6]2−ions exchanged into Fumion®prior to Nafion®overcoating remained entrapped and the Fumion®excluded [Ru(NH3)6]3+ions for durability testing periods of more than 20 h under conditions of interest for eventualin situspectral measurements. Experiments with the Sustainion®anion exchange ionomer uncovered evidence for [IrCl6]2−ion coordination to pendant imidazolium groups on the polymer. A cyclic voltammetric method for estimation of the effective diffusion coefficient and equilibrium extraction constant for redox active probe ions within inert, uniform density electrode-supported thin films was applied to examine charge transport mechanisms.

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  4. Infrared and Raman spectroscopy techniques were applied to investigate the drying and aggregation behavior of Nafion ionomer particles dispersed in aqueous solution. Gravimetric measurements aided the identification of gel-phase development within a series of time-resolved spectra that tracked transformations of a dispersion sample during solvent evaporation. A spectral band characteristic of ionomer sidechain end group vibration provided a quantitative probe of the dispersion-to-gel change. For sets of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectra, adherence to Beer’s law was attributed to the relatively constant refractive index in the frequency region of hydrated -SO3 - group vibrations as fluorocarbon-rich ionomer regions aggregate in forming the structural framework of membranes and thin films. Although vibrational bands associated with ionomer backbone CF2 stretching vibrations were affected by distortion characteristic of wavelength-dependent refractive index change within a sample, the onset of band distortion signaled gel formation and coincided with ionomer mass % values just below the critical gelation point for Nafion aqueous dispersions. Similar temporal behavior was observed in confocal Raman microscopy experiments that monitored the formation of a thin ionomer film from an individual dispersion droplet. For the ATR FTIR spectroscopy and confocal Raman microscopy techniques, intensity in the water H-O-H bending vibrational band dropped sharply at the ionomer critical gelation point and displayed a time dependence consistent with changes in water content derived from gravimetric measurements. The reported studies lay groundwork for examining the impact of dispersing solvents and above-ambient temperatures on fluorinated ionomer transformations that influence structural properties of dispersion-cast membranes and thin films. 
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  5. Electrodeposited conductive copolymer films with predictable relative properties (quantities of functional groups for further modification and capacitance) are of interest in sensors, organic electronic materials and energy applications. Potentiodynamic copolymerization of films in aqueous solutions of two different thiophene derivatives, (2,3-dihydrothieno[3,4-b]dioxin-2-yl)methanol (1) and 4-((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)-methoxy)-4-oxobutanoic acid (2), containing 0.02 M total monomer (0, 25, 34, 50, 66, 75, 100 mol%2), 0.05 M sodium dodecyl sulfate, and 0.1 M LiClO4, on gold microelectrodes in an array was investigated. Decreasing monomer deposited (m)from 0 to 100 mol%2is attributed to a decreasing pH that inhibits electropolymerization. Molar ratios of1and2in the films, determined by micro-attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, tracks closely with the ratio in the deposition solutions. Capacitances measured from cyclic voltammetry in aqueous buffer and electron transfer of ferrocyanide at the films are unaffected by copolymer composition, except for the 100 mol%2case. Ratios of reverse-to-forward faradaic peak currents suggest that films with high content of1expand in the anodic form and contract in the cathodic form and vice versa for films with high content of2, where anions and cations dominate counterion transport from solution, respectively.

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