Electron transfer reaction and mechanism of oxidation of Inosine

Electrochemical oxidation of Inosine has been studied in the phosphate buffers of pH range 3.3-10.9 at pyrolytic graphite electrode. In the entire pH range a single well-defined oxidation peak (I_a) was observed, when the sweep was initiated in the positive direction. In the reverse sweep no cathodic peak was obtained. The peak potential of the oxidation peak was dependent on pH and shifted to less positive potential with increase in pH. The kinetics of the UV absorbing intermediate was followed spectrophotometrically and the decay occurred in a pseudo first order reaction having k values in the range 0.50-0.92 × 10⁻³ s⁻¹ in the entire pH range studied. The value of n was found to be 2.95 ± 0.3. The products of oxidation were silylated and characterized by using GC-Mass. Two tetramers having CC, CN, NN, CON and COOC linkages were identified. A plausible mechanism for the electrooxidation of Inosine has been suggested.     

Spectroelectrochemical study of perchloroethylene reduction at copper electrodes in neutral aqueous medium

The potential-dependent chemical reaction of perchloroethylene (PCE) on copper in neutral noncomplexing aqueous media is explored by means of surface-enhanced Raman spectroscopy (SERS), linear sweep voltammetry and preparative electrolysis at controlled potential. Voltammetric peaks associated with copper oxide reduction in Na₂SO₄ solution in the presence and the absence of Cl⁻ are correlated with simultaneously acquired SER spectra. Perchloroethylene undergoes a dechlorination process at potentials at E ≤ −0.3 V vs. Ag/AgCl/KCl (3 M), as shown by the emergence of an intense CuCl stretching band at 290 cm⁻¹ and a CH stretching band together with the presence of Cl⁻ in the catholyte. In the potential region between 0 and −0.9 V vs. Ag/AgCl/KCl (3 M) a broad band assigned to CC structures is observed in the triple-bond region (∼1900 cm⁻¹, FWHM = 180 cm⁻¹). In addition, dichloroethylene (DCE) is detected (but not trichloroethylene (TCE)) in this potential region during preparative electrolysis. At potentials lower than −1 V vs. Ag/AgCl/KCl (3 M) carbon residues are the main product, detected on the copper surface by SERS (and confirmed by XPS), whereas in solution higher levels of dichloroethylene and trichloroethylene are detected with a DCE/TCE ratio below 1.     

Di-ureasil xerogels containing lithium bis(trifluoromethanesulfonyl)imide for application in solid-state electrochromic devices

In this study we report the characterization of a prototype solid-state electrochromic device based on poly(ethylene oxide) (PEO)/siloxane hybrid networks doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The polymer networks prepared, designated as di-ureasils and represented as d-U(2000), were produced by a sol-gel procedure and are composed of a siliceous framework to which both ends of polyether chains containing about 40 CH₂CH₂O units are covalently bonded through urea linkages. Samples with compositions of 200 ≥ n ≥ 0.5 (where n is the molar ratio of CH₂CH₂O to Li⁺) were characterized by thermal analysis, complex impedance measurements and cyclic voltammetry at a gold microelectrode. Electrolyte samples were obtained as self-supporting, transparent, amorphous films and at room temperature the highest conductivity was observed with the d-U(2000)₃₅LiTFSI composition (3.2 × 10⁻⁵ Ω⁻¹ cm⁻¹). We report the results of preliminary evaluation of these polymer electrolytes as multi-functional components in prototype electrochromic displays. Device performance parameters such as coloration efficiency, optical contrast and image stability were also evaluated. The electrolytes with n > 8 presented an optical density above 0.56 and display assemblies exhibited good open-circuit memory and stable electrochromic performances.     

Enhancement of ionic conductivity by mixing lithium borate with lithium aluminate

Several lithium borates (Salt A and Salt B) and a lithium aluminate (Salt C) with electron-withdrawing groups, OC₆F₅, OCOCF₃ or N(SO₂CF₃)₂, and oligoether chains (O(CH₂CH₂O)_nCH₃) directly bonded to the ate complex center, B or Al, were prepared. Lithium borate and lithium aluminate were mixed to get mix-salt electrolytes. Higher ionic conductivity was observed for the mix-salt than for the pure-salt. Conductivity as high as 1.1 × 10⁻⁴ S/cm at ambient temperature (25 °C) was achieved for the electrolyte in the optimized composition. The reason for such mixing effect on enhancement of ionic conductivity was discussed. Other electrochemical properties including electrochemical stability, compatibility with lithium anode and cyclic performance were also investigated for the mix-salt electrolytes.     

Synthesis and high electrochemical activity of poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid)

Poly(aniline-co-2-amino-4-hydroxybenzenesulfonic acid) (PAAHB) was synthesized using chemical oxidative copolymerization of aniline and 2-amino-4-hydroxybenzenesulfonic acid (AHB) in the presence of an ionic liquid at 50 °C. The conductivity of the PAAHB copolymer synthesized at the optimum conditions is 0.47 S cm⁻¹ that is lower than that of polyaniline, but is slightly affected by water. The cyclic voltammograms demonstrate that the PAAHB copolymer has excellent redox activity from highly acidic solution to pH 12.0 in a wider potential range. This is attributed to the synergistic effect of the SO₃⁻ and OH functional groups in the copolymer chain and the ionic liquid incorporated into the PAAHB film. It is evident that the pH dependence of the redox activity and conductivity of the PAAHB copolymer prepared chemically is much better than that of polyaniline, and is further improved, compared to the PAAHB copolymer prepared electrochemically. The proton NMR spectrum of the PAAHB copolymer demonstrates that the SO₃⁻ group exists in the copolymer chain instead of the SO₃H group. The ESR spectra show that the ESR signal intensity is a function of the monomer concentration ratio of AHB to aniline in the mixture. The morphology of the PAAHB copolymer is also dependent on the monomer concentration ratio in the mixture.