Microcontainers with electrochemically reversible permeability

The present study demonstrates a novel application of polyelectrolyte microcapsules as microcontainers with electrochemically reversible flux of redox active materials into and out of the capsule volume. Incorporation of the capsules inside the conducting polymer (polypyrrole) film results in a new composite electrode combining electrocatalytic and conducting properties of the polypyrrole with the storage and release properties of the capsules. This electrode, if loaded with electrochemical fuels, can possess electrochemically controlled switching between "open/closed" states of the capsule shell and be of practical interest for a new type of chemically rechargeable batteries or fuel cells. A special explanation for the potential depending loading and unloading of the capsule inner volume may be related to the fact that the polyelectrolyte capsules experience a potential gradient in the polypyrrole matrix within which the polyions of the shell can be moved.     

Thermal transition of electrochemically synthesized polyaniline

The thermal stability of polyaniline (PAni) is of great importance in commercial applications. PAni and its emeraldine base form (PAni-EB) were electrochemically synthesized and subjected to thermogravimetric analysis (TGA) in inert atmosphere, which illustrated that the dopant HClO₄ could act as the oxidizing agent at elevated temperature and caused serious decomposition of PAni. Combined with differential scanning calorimetry (DSC), in-situ X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) analyses, the crosslinking reaction among PAni-EB molecules at about 250 °C was characterized, and the kinetic parameters were calculated by applying different heating rates in the DSC measurement.     

An electrochemically tuneable cyclodextrin-based molecular adapter

We report the synthesis of a cyclodextrin-based molecular adapter which has the propensity to form an electrochemically tuneable ternary complex with cyclophanes 2 or 3 and ferrocene 4 in non-aqueous and aqueous environments, respectively.     

Abiotic metallofoldamers as electrochemically responsive molecules

Described are the design, synthesis, and study of nonbiological molecules based on salophen and salen ligands that fold into single-stranded helices in the presence of either Ni(II) or Cu(II). X-ray diffraction studies show that the materials fold into helical structures in the solid state, and a series of NMR studies provide strong evidence that the folded structures are conserved in solution. Metal coordination is required for folding, as NMR and X-ray show that the free ligands do not adopt helical structures. Two of the racemic metallofoldamers spontaneously resolve during crystallization from CHCl3/acetonitrile, and CD spectroscopy and optical rotation show that the resolved, crystalline materials racemize quickly when dissolved at 5 degrees C. This shows that the secondary structures can reorganize easily and can, therefore, provide the basis for responsive materials. By comparison, an analogue from enantiomerically pure (R,R)-(-)-trans-cyclohexanediamine showed a strong CD signal and a large specific rotation. Electrochemical experiments show that a structural reorganization occurs upon metal-centered reduction of a Cu(II)-containing foldamer. When the reduction is carried out in the presence of coordinating ligands, it is proposed that apical binding of those ligands gives square pyramidal complexes. Semiempirical (AM1) calculations support that the helical structure would be disrupted by the reduction to Cu(I) with concomitant reorganization to a square pyramidal complex.     

A perchlorate-promoted electrochemically induced nitride coupling reaction

The osmium nitride complex [Os^VI(NH₃)₄N]³⁺ undergoes a one-electron reduction in acetonitrile to give [Os^V(N)(NH₃)₄]²⁺, which further reacts by nitride coupling to give the μ-dinitrogen osmium complex [(CH₃CN)(NH₃)₄Os^II(N₂)Os^II(NH₃)₄(CH₃CN)]⁴⁺. The formation of the μ-dinitrogen osmium complex is promoted by the presence of perchlorate anion, which causes the deposition of [(CH₃CN)(NH₃)₄Os^II(N₂)Os^II(NH₃)₄(CH₃CN)](ClO₄)₄ on the electrode surface upon repetitive voltammetric scans.     

Surface plasmon resonance of electrochemically deposited Au-black

Au-black, a kind of gold nanostructure, was electrochemically deposited on a Au-vapor-deposited glass plate, and its optical properties were evaluated with a surface plasmon resonance (SPR) measurement system. The Au-black was found to exhibit an extraordinary high resonance angle (minimum reflectance angle) compared to that of the Au-vapor-deposited glass plate. We proposed a five-layer model, which consists of glass, Cr, Au, Au-black, and solution layers, to explain the high resonance angle of the Au-black plate. The calculation was based on the Fresnel formulas extended for multilayers. When the Bruggeman formula was used to obtain a refractive index of the Au-black layer, the numerical simulation could qualitatively explain the experimental observations. The curve fitting method by the five-layer model enabled us to simultaneously estimate the thickness of the Au-black layer and the volume fraction of Au in Au-black.     

Anionic responses of electrochemically synthesized polypyrrole films

Conducting polypyrrole films with thickness of about 8 mum were prepared on platinum by continuous scanning in 0.1M pyrrole and 0.1M electrolyte (LiCl, LiBF(4) or NaBF(4)). Scan-rates of 10, 20 and 50 mV/sec with scan-times of 30, 45 and 60 min were used. The potentiometric response of the films was tested over a range of anions. Films were found to be anion-sensitive but very non-selective. The influence of the doping cation was also investigated.     

Thermally and electrochemically controllable self-complexing molecular switches

Self-complexing molecular systems are obtained when an arm component (a pi-donor) is covalently linked to a preformed macrocycle (a pi-acceptor). The resulting self-complexing compounds are not only attractive in relation to their topology, but also for their potential to undergo reversible movements, i.e., the arm can be driven out of or into the cavity of the linked macrocycle in response to temperature or applied voltage. These structurally sensitive changes render them potential thermosensors or electroswitches.     

Influence of electrochemically activated water on lignin

It has been shown that under the action of electrochemically activated water a change in the functional composition of the macromolecule of hydrolysis lignin and of lignin sulfonate takes place and, in addition, the latter is desulfurated.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 425–427, 1987.     

Oxygen carriers based on electrochemically reduced trinitroarenes

1,3,5-Trinitrobenzene, 2,4,6-trinitrotoluene and 1-methoxy-2,4,6-trinitrobenzene undergoes reversible dimerization, after electrochemical reduction of two units of corresponding anion radical. The pi-dimer formed captures molecular oxygen (O(2)) leading to a sigma(o-o)(H)-adduct, in an atmosphere of oxygen or even air. The sigma(o-o)(H)-adduct is able to reversibly bind and remove dioxygen after an external redox stimulus.     

电化学预处理玻炭电极上的电催化

用循环伏安法、计时电流法、计时库仑法和X射线光电子能谱法研究了恒电流法电化学预处理玻炭电极上的表面性质及其对抗坏血酸、儿茶酚和对苯二酚的电催化效应。讨论了电催化机理, 证明电极表面吸附及表面功能团的催化是发生电催化的主要原因。儿茶酚、对苯二酚和抗坏血酸的混合物的预处理电极上的波峰明显分开, 有可能应用于儿茶酚和抗坏血酸的同时测定。     

Synthesis of electrochemically active pyrazine based dendrimers

A synthesis of dendrimers with pyrazine as core and m-terphenyl as surface end groups has been achieved. The electrochemical behavior of the dicationic pyrazinium dendrimers was also studied by cyclic voltammetry.     

Carbon paste electrodes electrochemically modified with cyclodextrins

Cyclic voltammetry was used in order to obtain carbon paste electrodes (CPEs) modified with α- and β-cyclodextrins (CPE_α-CD, CPE_β-CD) in HClO₄ media as electrolyte. The modified CPEs were obtained by applying 30 potential cycles, thus forming on the substrate a film with electroactive characteristics; a rise in current for the anodic and cathodic peaks became apparent as the number of cycles increased. Such behaviour confirmed the CPE modification by the species mentioned. The CPE_α-CD and CPE_β-CD exhibited significant stability before various electrolytes. In order to evaluate the sort of modification attained on the CPEs, a study was conducted, varying the potential scan rate, that confirmed the CD's presence. The modified electrodes were used to determine Pb(II) ions in solution within the range from 1×10^–5 M up to 1×10^–3 M. The CPE_α-CD and CPE_β-CD electrochemical response was studied by means of anodic stripping voltammetry of the Pb(II) ions, thereby giving a linear relation between the current for the anodic peak as a function of Pb(II) concentration with r ²=0.996 for the CPE_β-CD and 0.992 for the CPE_α-CD. Electronic Publication