Solution versus solid-state electropolymerization of regioregular conjugated fluorenone–thienylene vinylene macromonomers—voltammetric and spectroelectrochemical investigations

We present detailed voltammetric and spectroelectrochemical studies of poly(2,7-bis(5-[(E)-1,2-bis(3-octylthien-2-yl)ethylene])-fluoren-9-one) (PTVF)—a conjugated polymer consisting of thienylene, vinylene, and fluorenone subunits. PTVF can be easily obtained either by electropolymerization of its monomer ((2,7-bis(5-[(E)-1,2-bis(3-octylthien-2-yl)ethylene])-fluoren-9-one) [TVF]) dissolved in the electrolytic solution or via solid-state electropolymerization of a thin film of the monomer deposited on the electrode. UV-vis-NIR spectroscopic data indicate that the latter method leads to a polymer of a smaller degree of polymerization (DP). The possibility of the formation of a polymeric conductor on a transparent conductive substrate such as indium tin oxide, in situ, via solid-state electropolymerization, combined with its postpolymerization transformation into an organic semiconductor by electrochemical dedoping, is technologically very attractive and makes TVF and its polymer very promising materials for applications in organic electronics. Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June 2006.     

Interactions in open-shell clusters: ab initio study of pre-reactive complex O(3P) + HCl

Van der Waals interactions between the ground-state triplet O(3P) atom and the closed-shell HCl molecule are investigated in the pre-reactive region. Three adiabatic (two of A' symmetry and one of A' symmetry) and four non-relativistic diabatic potential energy surfaces are obtained by combining a restricted open-shell coupled cluster approach with the multireference configuration interaction method. The lower A' adiabatic potential surface has a single minimum (D(e) = 589 cm(-1)) for a linear O...HCl configuration. The upper A' potential has a weak (D(e) = 65 cm(-1)) minimum for a linear HCl...O configuration. The A' adiabatic potential has a weak (124 cm(-1)) T-shaped minimum. Adiabatic potentials intersect once in the O...HCl linear configuration and twice in the linear HCl...O geometry. The role of electrostatic interactions in shaping these potentials is discussed. The effects of spin-orbit coupling on this interaction are also investigated assuming a constant value of the SO parameter.     

Electrochemical charging and electrocatalysis at hybrid films of polymer-interconnected polyoxometallate-stabilized carbon submicroparticles

Using the layer-by-layer technique, carbon submicroparticles, that have been modified and stabilized with monolayers of Keggin-type phosphododecamolybdate (PMo₁₂O₄₀³⁻), can be dispersed in multilayer films of organic polymers, poly(3,4-ethylenedioxythiophene), i.e., PEDOT, or poly(diallyldimethylammonium) chloride, i.e., PDDA, deposited on glassy carbon or indium-tin oxide conductive glass electrodes. The approach involves alternate treatments in the colloidal suspension of PMo₁₂O₄₀³⁻-covered carbon submicroparticles in the solution of monomer, 3,4-ethylenedioxythiophene or in solution of PDDA polymer. Electrostatic attractive interactions between anionic phosphomolybdate-modified carbon submicroparticles and cationic polymer layers permit not only uniform and controlled growth of the hybrid organic–inorganic film but also contribute to its overall stability. The system composed of PMo₁₂O₄₀³⁻-covered carbon submicroparticles dispersed in PEDOT is characterized by fast dynamics of charge transport and has been used to construct symmetric microelectrochemical redox capacitor. The PDDA-based system has occurred to be attractive for electrocatalytic reduction of hydrogen peroxide.     

Enantiomeric differentiation of amino acids by a chiral crown ether derived fromd-mannose studied by the liquid membrane technique

Chiral 18-crown-6 incorporating ad-mannopyranoside unit displays noticeable enantioselectivity in the recognition of amino acids and their sodium and potassium salts in transport experiments across a liquid membrane containing the carrier.d-phenylalanine andd-phenylglycine were transported faster than their correspondingl-enantiomers, whereas the enantioselectivity was reversed with tryptophan.     

Determination of uranium by adsorptive stripping voltammetry at a lead film electrode

An adsorptive stripping voltammetric procedure for the determination of U(VI) at an in situ plated lead film electrode is described. The U(VI) complex with cupferron was accumulated from an acetate buffer solution of pH 4.2 at the potential −0.65 V. The measurements were carried out from undeaerated solutions. The calibration graph for an accumulation time of 180 s was linear from 5 × 10⁻¹⁰ to 2 × 10⁻⁸ mol L⁻¹. The detection limit was 2 × 10⁻¹⁰ mol L⁻¹, the relative standard deviation for 2 × 10⁻⁸ mol L⁻¹ U(VI) was 4.3%. The proposed procedure was validated in the course of U(VI) determination in water certified reference materials.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

The analysis of the electrical properties of BLT ceramics fabricated from sol-gel derived powders

The (Ba_xLa_1?x)Ti_1?x/4O₃ (BLT,0.001 ≤ x ≤ 0.005) amorphous gel was prepared by sol-gel process. The electricalproperties of obtained materials has been investigated by impedance spectroscopy. Detailedanalysis of impedance spectra allowed to propose an adequate equivalent circuit, whichdescribed the electric properties of discussed materials very well. Basing on the obtainedcircuits and the fitting procedure the grain and grain boundary resistivity was determinedas a function of temperature and La concentration. With increase of La admixture thecontribution of grain and grains impedance to the bulk impedance changes. It was foundthat the small amount of La additive decreases the blocking factor of the grain boundaryin the temperature range 600–850 K, whereas the amount of La on the level of 0.4–0.5 mol.%causes the sharp increase of the mentioned factor. The fact may be attributed to adecrease of grain activation energy and increase of the grain boundary one.     

Initiation of lipid autoxidation by ABAP at pH 4-10 in SDS micelles

The rates of radical generation, R(i), by two water soluble initiators: 2,2'-azobis(2-methylpropionamidine) and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and the lipid soluble 2,2'-azobisisobutyronitrile were measured in an SDS micellar system over a pH range of 4-10. Enhanced values of R(i) at low pH are attributed to Coulombic repulsion of protonated radicals.     

Integrated computational approach to vibrationally resolved electronic spectra: anisole as a test case

A new general and effective procedure to compute Franck-Condon spectra from first principles is exploited to elucidate the subtle features of the vibrationally resolved optical spectra of anisole. Methods based on the density functional theory and its time-dependent extension for electronic excited states [B3LYP6-311+G(d,p) and TD-B3LYP6-311+G(d,p)] have been applied to geometry optimizations and harmonic frequency calculations. Perturbative anharmonic frequencies [J. Chem. Phys. 122, 014108 (2005)] have been calculated for the ground state, and the Duschinsky matrix elements have been used to evaluate the corresponding anharmonic corrections for the first excited electronic state. The relative energetics of both electronic states has been refined by single point calculations at the coupled clusters (CC) level with the aug-cc-pVDZ basis set. Theoretical spectra have been evaluated using a new optimized implementation for the effective computation of Franck-Condon factors. The remarkable agreement between theoretical and experimental spectra allowed for revision of some assignments of fundamental vibrations in the S(1) state of anisole.     

Density functional theory study of intramolecular hydrogen bonding and proton transfer in o-hydroxyaryl ketimines

The potential energy surface and the reaction pathway for the intramolecular hydrogen transfer in o-hydroxyaryl ketimines are characterized using DFT methods. Structural changes in the proton-transfer process in quasi-aromatic hydrogen bonding are described. A transition state and a state with a low proton-transfer barrier were studied in sterically compressed o-hydroxyaryl ketimines (2(N-methyl-alpha-iminoethyl)phenols) possessing two potential minimums. The potentials for proton vibration in the OH and HN tautomers of o-hydroxyaryl ketimines were investigated and anharmonic frequencies were determined. Solvent and substituent effects were analyzed. The energies of the various conformers of the OH and HN tautomers were compared with the related forms of o-hydroxyaryl aldimine.