Electron transport membrane: Preparation of polypeptide membrane with spacers between the polymer matrix and viologen moiety and their application to an electron transfer reaction

Polypeptide membranes with several lengths of spacers [? (CH₂)_n? ; n = 3, 6, 12] between the polymer matrix and viologen moiety as a functional group were prepared. Reduction of K₃Fe(CN)₆ with Na₂S₂O₄ across the obtained membrane in aqueous media were carried out and reduction rate of K₃Fe(CN)₆ across the membrane of n = 6 was faster than that of n = 3. However, the reduction of the membrane (n = 12) did not proceed chemically and electrochemically at all.     

Preparation of Polymers with Viologen Moieties and Their Application to the Selective Reduction of Substituted Nitroarenes

Abstract

Polymers with viologen moieties were synthesized by using poly-chlorethyl vinyl ether (PCEVE) as mother supports. These polymers were used as electron-transfer catalysts (ETC) for the reduction of substituted nitroarenes under heterophase conditions (reductant: Na₂S₂O₄ in CH₂CI₂-H₂O). The experimental results show that the substituted nitroarenes were reduced selectively and efficiently to the corresponding aniline derivatives in the presence of viologen polymers. The catalytic active species of viologen were detected by ESR and electrochemical methods. It was found that the viologen cation radical (V⁺) acts as the active species during the viologen-mediated reduction of substituted nitroarenes.     

Carbon‐Nanotube‐Mediated Electrochemical Transition in a Redox‐Active Supramolecular Hydrogel Derived from Viologen and an l‐Alanine‐Based Amphiphile

A two‐component hydrogelator (16‐A)₂‐V²⁺ , comprising an l ‐alanine‐based amphiphile ( 16‐A ) and a redox‐active viologen based partner ( V²⁺ ), is reported. The formation the hydrogel depended, not only on the acid‐to‐amine stoichiometric ratio, but on the choice of the l ‐amino acid group and also on the hydrocarbon chain length of the amphiphilic component. The redox responsive property and the electrochemical behavior of this two‐component system were further examined by step‐wise chemical and electrochemical reduction of the viologen nucleus (V²⁺/V⁺ and V⁺/V⁰). The half‐wave reduction potentials (E_1/2) associated with the viologen ring shifted to more negative values with increasing amine component. This indicates that higher extent of salt formation hinders reduction of the viologen moiety. Interestingly, the incorporation of single‐walled carbon nanotubes in the electrochemically irreversible hydrogel (16‐A)₂‐V²⁺ transformed it into a quasi‐reversible electrochemical system.     

基于羧苄基紫精配体构筑的三种多重响应配合物

以羧苄基紫精配体1,1''-双（4-羧苄基）-4,4''-联吡啶二氯化物（（H₂Bpybc） Cl₂）为功能主体,引入辅助配体1,3,5-苯三甲酸（H₃BTC）,与不同金属离子自组装反应,合成了3个配合物{[Cd （Bpybc）_0.5（HBTC）（H₂O）]·0.6H₂O}_n （1）、[Ni （Bpybc）_0.5（HBTC）（H₂O）₄]（2）和[Co （Bpybc）_0.5（HBTC）（H₂O）₄]（3）。其中,配合物1为2D结构,而配合物2和3为0D结构。同时,3种配合物表现出不同的变色性能。配合物1是由于产生紫精自由基而具有光致变色行为,而配合物2和3的光致变色行为是光诱导形成紫精自由基及金属离子的氧化反应共同导致的。此外,配合物2还表现出由电子转移而导致的热致变色行为,而配合物3表现出脱水和吸水引起的可逆结构改变而导致的颜色变化。这些结果表明,金属离子对紫精配合物的结构及变色性能具有明显的调控作用。     

Synthesis and Electrochemical Characterization of a New Electropolymerizable Hydrophilic Viologen Designed for Enzyme Wiring

A new viologen derivative functionalized by an electropolymerizable pyrrole group via a long hydrophilic spacer has been synthesized. This redox monomer has been electrochemically characterized both for its presence in organic and in aqueous media. Its electrooxidation in both solvents leads to the formation of a polymeric film exhibiting the regular electrochemical behaviour of the viologen groups. The electropolymerization process was applied to the immobilization of isocitrate dehydrogenase as an enzyme model. An electrical connection between the redox polymer and the immobilized enzyme molecules has been observed in the presence of oxoglutarate and CO₂.     

Synthesis and characterization of a new soluble conducting polymer and its electrochromic device

A mixture of isomers 2,5-di(4-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole, 2-(4-methyl-thiophen-2-yl)-5-(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole and 2,5-di(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole (Me-SNS(NO₂)) were synthesized. Resulting monomers were polymerized chemically, producing soluble polymers in common organic solvents. The average molecular weight has been determined by gel permeation chromatography (GPC) as Mn=5.6×10³ for the chemically synthesized polymer. The monomers were also electrochemically polymerized in the presence of LiClO₄, NaClO₄ (1:1) as the supporting electrolyte in acetonitrile solvent. Resulting polymers were characterized via CV, FTIR, NMR, SEM and UV–Vis spectroscopy. Spectroelectrochemistry analysis of polymer revealed Π–Π^* transition below 300 nm, with an electronic band gap of 2.18 ev. Switching ability of the polymer was evaluated by kinetic study measuring percent transmittance (%T) at the maximum contrast point, indicating that poly(Me-SNS(NO₂)) is a suitable material for electrochromic devices.     

Comparative studies on electrochemical activity of graphene nanosheets and carbon nanotubes

This study compares the electrochemical activity of four kinds of carbon materials, i.e. single-walled carbon nanotubes (SWNTs), pristine graphene oxide nanosheets (GONs), chemically reduced GONs, and electrochemically reduced GONs, with potassium ferricyanide (K₃Fe(CN)₆), β-nicotinamide adenine dinucleotide (NADH) and ascorbic acid (AA) as the redox probes. Cyclic voltammetry (CV) results demonstrate that the electron transfer kinetics of the redox probes employed here at the carbon materials essentially depend on the kind of the materials, of which the redox processes of the probes at SWNTs and electrochemically reduced GONs are faster than those at the pristine and chemically reduced GONs. The different electron transfer kinetics for the redox probes at the carbon materials studied here could be possibly ascribed to the synergetic effects of the surface chemistry (e.g., C/O ratio, presence of quinone-like groups, surface charge, and surface cleanness) and conductivity of the materials. This study could be potentially useful for understanding the structure/property relationship of the carbon materials and, based on this, for screening and synthesizing advanced carbon materials for electrochemical applications.     

A redox-active ionic liquid manifesting charge-transfer interaction between a viologen and carbazole and its effect on the viscosity,ionic conductivity,and redox process of the viologen

Redox-active ionic liquids (RAILs) are gaining attention as a material that can create a wide range of functions. We herein propose a charge-transfer (CT) RAIL by mixing two RAILs, specifically a carbazole-based ionic liquid ([CzC₄ImC₁][TFSI]) as a donor and a viologen-based ionic liquid ([C₄VC₇][TFSI]₂) as an acceptor. We investigated the effect of CT interaction on the physicochemical properties of the CT ionic liquid (CT-IL) using the results of temperature-dependent measurements of UV-vis absorption, viscosity, and ionic conductivity as well as cyclic voltammograms. We employed the Walden analysis and the Grunberg–Nissan model to elucidate the effect of the CT interaction on the viscosity and ionic conductivity. The CT interaction reduces the viscosity by reducing the electrostatic attraction between the dicationic viologen and TFSI anion. It also reduces the ionic conductivity by the CT association of the dicationic viologen and carbazole. The electrochemically reversible responses of the viologens in [C₄VC₇][TFSI]₂ and CT-IL are consistent with the Nernstian and the interacting two-redox site models. Notably, the transport and electrochemical properties are modulated by CT interaction, leading to unique features that are not present in individual component ILs. The inclusion of CT interaction in RAILs thus provides a powerful means to expand the scope of functionalized ionic liquids.

A redox-active ionic liquid (RAIL) consisting of a carbazole and viologen shows charge transfer (CT) interaction. The physicochemical properties are modulated by the CT interaction by comparison with the individual RAILs.     

NiAs- versus zinc-blende-type intermetallic insertion electrodes for lithium batteries: lithium extraction from Li2CuSn

The extraction of lithium from Li₂CuSn with a lithiated zinc-blende-type structure has been investigated both chemically and electrochemically. The data show that the resulting Li_xCuSn (x≈0) product has a NiAs-related structure similar to that of Cu₆Sn₅ (CuSn_0.83). The Li₂CuSn structure is described in detail; this structure type has important implications for designing new intermetallic insertion electrodes with zinc-blende-type structures.     

Polarographic catalytic wave of hydrogen

A polarographic catalytic hydrogen wave of bovine serum albumin (BSA) at about-1.80 V (vs. SCE) in NH₄Cl-NH₃ · H₂O buffer is further catalyzed by such oxidants as iodate, persulfate and hydrogen peroxide, producing a kinetic wave. Studies show that the kinetic wave is a parallel catalytic wave of hydrogen, which resulted from that hydrogen ion is electrochemically reduced and chemically regenerated through oxidation of its reduction product, atomic hydrogen, by oxidants mentioned above. It is a new type of poralographic catalytic wave of protein, which is suggested to be named as a parallel catalytic hydrogen wave.     

A Low‐dimensional Viologen/Iodoargentate Hybrid [(BV)2­(Ag5I9)]n: Structure,Properties, and Theoretical Study

A new low‐dimensional benzyl viologen/iodoargentate hybrid, [(BV)₂(Ag₅I₉)]_n ( 1 ) (BV²⁺ = benzyl viologen) was prepared. In 1 , (Ag₆I₉)_n^2– chain exhibits a new type of one‐dimensional chain constructed from vertex‐sharing of Ag₅I₁₀ units, and its two‐dimensional layer structure was constructed from C–H ··· I hydrogen bonds. Strong luminescence at 404 nm can be detected in 1 . DFT calculation suggests that 1 displays a reduced bandgap, which is led by a more dispersed LUMO band of BV²⁺ compared with MV²⁺ in [MV(Ag₂I₄)]_n.     

Quartz crystal microbalance monitoring of density changes in mesoporous TiO2 phytate films during redox and ion exchange processes

Nanofilm deposits of TiO₂ nanoparticle phytates are formed on gold electrode surfaces by ‘directed assembly’ methods. Alternate exposure of a 3-mercapto-propionic acid modified gold surface to (i) a TiO₂ sol and (ii) an aqueous phytic acid solution (pH 3) results in layer-by-layer formation of a mesoporous film. Ru(NH₃)₆³⁺ is shown to strongly adsorb/accumulate into the mesoporous structure whilst remaining electrochemically active. Scanning the electrode potential into a sufficiently negative potential range allows the Ru(NH₃)₆³⁺ complex to be reduced to Ru(NH₃)₆²⁺ which undergoes immediate desorption. When applied to a gold coated quartz crystal microbalance (QCM) sensor, electrochemically driven adsorption and desorption processes in the mesoporous structure become directly detectable as a frequency response, which corresponds directly to a mass or density change in the membrane. The frequency response (at least for thin films) is proportional to the thickness of the mass-responsive film, which suggests good mechanical coupling between electrode and film. Based on this observation, a method for the amplified QCM detection of small mass/density changes is proposed by conducting measurements in rigid mesoporous structures.     

A Chemically and Electrochemically Switchable [2]Catenane Incorporating a Tetrathiafulvalene Unit

A mechanical switch in a [2]catenane , made up of a cyclobis(paraquat-p-phenylene) tetracation interlocked with a macrocyclic polyether containing a redox-active tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene ring system, can be thrown either chemically or electrochemically. The neutral TTF unit resides “inside” the tetracationic cyclophane in the reduced state and “alongside” it in the oxidized species (TTF⁺/ TTF²⁺). Switching between the reduced (I⁴⁺) and oxidized state (I⁵⁺(I⁶⁺)) is accompanied by a dramatic color change.     

Electrochemically Prepared Manganese Oxide as a Cathode Material for a Microbial Fuel Cell

This work describes the construction of a mediatorless microbial fuel cell (MFC) using the microorganism Acetobacter aceti as the biocatalyst in the anode compartment with glucose as a fuel. The periplasmic membrane bound pyrroloquinoline quinone (PQQ) containing enzymes of these genera provide fast and highly efficient oxidation of a wide variety of substrates and helps in the direct routing of electrons to the anode. We describe our preliminary findings with regard to the use of electrochemically deposited manganese oxide films on carbon substrates as cathode materials in MFCs. Manganese oxide was electrochemically deposited on carbon paper in the presence and in the absence of the surfactant, sodium lauryl sulfate (SLS). Electrochemical characterizations of the electrodeposited films are carried out by cyclic voltammetry and impedance spectroscopy. Structural characterization of the film is carried out by XRD, XPS, and SEM. The XPS studies reveal that the presence of Mn⁴⁺ (as MnO₂) in the absence of SLS and Mn^3+/2+ (as Mn₃O₄or Mn₂O₃ or MnOOH) ion in the presence of SLS. The power output obtained from MnO₂ cathode was 666 ± 9 mW m^?3 and it is the highest value reported for MFCs with cubical configuration with the same cathode.     

Chemical oxidation of a redox-active, ferrocene-containing cationic lipid: Influence on interactions with DNA and characterization in the context of cell transfection

We report an approach to the chemical oxidation of a ferrocene-containing cationic lipid [bis(11-ferrocenylundecyl)dimethylammonium bromide, BFDMA] that provides redox-based control over the delivery of DNA to cells. We demonstrate that BFDMA can be oxidized rapidly and quantitatively by treatment with Fe(III)sulfate. This chemical approach, while offering practical advantages compared to electrochemical methods used in past studies, was found to yield BFDMA/DNA lipoplexes that behave differently in the context of cell transfection from lipoplexes formed using electrochemically oxidized BFDMA. Specifically, while lipoplexes of the latter do not transfect cells efficiently, lipoplexes of chemically oxidized BFDMA promoted high levels of transgene expression (similar to levels promoted by reduced BFDMA). Characterization by SANS and cryo-TEM revealed lipoplexes of chemically and electrochemically oxidized BFDMA to both have amorphous nanostructures, but these lipoplexes differed significantly in size and zeta potential. Our results suggest that differences in zeta potential arise from the presence of residual Fe²⁺ and Fe³⁺ ions in samples of chemically oxidized BFDMA. Addition of the iron chelating agent EDTA to solutions of chemically oxidized BFDMA produced samples functionally similar to electrochemically oxidized BFDMA. These EDTA-treated samples could also be chemically reduced by treatment with ascorbic acid to produce samples of reduced BFDMA that do promote transfection. Our results demonstrate that entirely chemical approaches to oxidation and reduction can be used to achieve redox-based ‘on/off’ control of cell transfection similar to that achieved using electrochemical methods.     

Electron transport across artificial liposomal membranes aided by phase-transfer of the movable electron carrier. Correlationship between hydrophobicity and carrier efficiency.

Electron transport across single wall, bimolecular lecithin liposomal membranes from exterior S₂O₄ = to interior ferricyanide or FMN (riboflavin 5′-phosphate) were investigated. A series of alkylviologens were used as electron carriers. The overall electron trasport rates increased with the carbon number of the alkyl chain for C₁ – C_4′ then decreased monotonically until C₁₈. Measurement of the distribution of tne viologens, and the corresponding viologen cation radicals, between H₂O/CH₂Cl₂ or H₂O/lecithin liposome were carried out independently. These results, together with the rate measurements, clearly demonstrate that the overall electron transport rates are primarily controlled by the phase-transfer of the alkylviologen cation radicals from the exterior aqueous phase to the membrane for C₁ – C_4′ and by the phase-transfer of the cation radicals from the membrane to the interior aqueous phase for C₄ – C₁₈. This leads to optimal electron transport for the C₄ viologen.     

Novel species in the electrochemical reduction of a metalmetal bond bridged by a bidentate fluorophosphine

The purple bridged bimetallic complex [CH₃N(PF₂)₂]₃Co₂(CO)₂ undergoes successive chemically and electrochemically reversible one-electron reductions to the corresponding green radical anion and pale-yellow dianion. The radical anion is relatively unreactive towards oxygen and methyl iodide. The dianion is not only reactive towards oxygen and methyl iodide but also captures small positively charged species (e.g. Li⁺ and H⁺) with significant alteration of its chemical properties.     

Synthesis and characterization of vanadium oxide/hexadecylamine membrane and its application as pH-EGFET sensor

Vanadium oxide/hexadecylamine (V₂O₅/HDA) sensing membrane was deposited on the glassy carbon substrate and used as the sensing layer of the extended gate H⁺-ion sensitive field effect transistor (EGFET) device. The structural and morphological features of V₂O₅/HDA were studied by X-ray diffraction, Fourier transformed-infrared spectroscopy and Scanning electronic microscopy images; and the electrochemical behavior was analyzed by cyclic voltammogram. V₂O₅/HDA presents a lamellar structure as well as several rod formations. The material stabilizes electrochemically after several cycles and leads to reproducibility of Li⁺ ion insertion/de-insertion into the vanadium oxide structure. The material was investigated as a pH sensor in the pH range 2–12 and presented a sensitivity of 38.1 mV/pH. The sensitive membrane structure is simple to fabricate and the measurement is fast for application as a disposable sensor.     

Electrochemical Reduction of Phosphaallenes: Electron Spin Resonance and Theoretical Studies

Abstract

In order to check to what extent allenic systems containing one or two phosphorus atoms are likely to accept an electron, solutions of ArP?C?Cφ₂ (Ar Phenyltributyl; φ benzene) and ArP?C?PAr have been electrochemically and chemically reduced. Cyclic voltammetry shows that ArP?C?Cφ₂ undergoes irreversible reduction at -2266mV in THF while an irreversible reduction takes place at - 1900 mV (THF) for ArP?C?PAr.     

Crystalline phases of electrically conductive poly(p-phenylene vinylene)

Poly(p-phenylene vinylene) (PPV) undergoes a first-order crystal-crystal phase transition when chemically doped with AsF₅, SbF₅, or H₂SO₄ or electrochemically oxidized with ClO^-₄ as the counterion. These structures have been observed using wide-angle x-ray diffraction. Doping with these agents does not disrupt the original orientation of the PPV crystallites. The crystalline phases obtained with all dopants employed here are similar in character, indicating a closely related family of electrically conductive structures having orthorhombic symmetry. An electrically conductive phase consisting of layers of polymer chains separated by a layer of the chemical dopant is proposed.