A glucose electrode based on carbon paste chemically modified with a ferrocene-containing siloxane polymer and glucose oxidase,coated with a poly(ester-sulfonic acid) cation-exchanger

A carbon-paste chemically modified with glucose oxidase and a ferrocene-containing siloxane polymer was further modified by coating the electrode surface with a poly(ester-sulfonic acid) cation-exchanger, Eastman AQ-29D. The polymer is obtained as a homogeneous aqueous dispersion at pH 5–6; when dried, the polymer coating is not water-soluble. The coating was shown not to be detrimental to the enzyme activity but to prevent electrochemically active anionic interferents such as ascorbate and urate from reaching the electrode surface. The polymer coating also prevented glucose oxidase from leaking out of the carbon paste into the contacting solution and protected the electrode surface from fouling agents present in urine and bovine serum albumin. Uncoated electrodes lost some 10-2-15% of their original response to glucose after storage in buffer for three weeks whereas the response of the coated electrodes remained constant. Calibration curves for glucose were strictly linear up to about 5 mM for uncoated and up to 20 mM for coated electrodes. The response current to glucose was not decreased after coating.     

Synthesis and properties of polyenic oligosulfides derived from acetylene and elemental sulfur

Oligosulfides derived from ethyne-1,2-dithiol were synthesized in up to 96% yield via insertion of elemental sulfur into the Na-C_sp bond of sodium acetylides (HC≡CNa, NaC≡CSNa) in liquid ammonia, followed by hydrolysis and spontaneous oligomerization of ethynethiols, ethynedithiols, and mono-and bis-(polysulfanyl)ethynes (HC≡CSH, HSC≡CSH, HC≡CS_xH, HS_xC≡CS_yH). The resulting polyenic oligosulfides were isolated as brown powders melting in the temperature range from 122 to 203°C and containing up to 77% of sulfur; they are sparingly soluble in organic solvents and are high-resistance semiconductors (10^?13–10^?14 S cm^?1) possessing paramagnetic (10¹⁷–10¹⁸ spin g^?1) and redox properties. According to the data of IR and ESR spectroscopy and cyclic voltammetry, the oligomers obtained consist mainly of different oligosulfide units, including oligothienothiophene structures. They also ensure a high discharge capacity (345–720 mA h g^?1) of lithium sulfur rechargeable batteries.     

The effect of the steric hindrance on metallic cation conduction in polymer electrolytes

2,6-Di-t-butylphenol and oligo(ethylene oxide) bound covalently to polyisocyanate were synthesized and characterized. The ionic conductivities of their Li, Na, and K phenolates were studied at various temperatures. The conductivities were in the range of 10^?7?10^?5 S/cm at 30°C. The conductivity of Na and K salts was approximately 10² greater than that of the Li salts. The t-butyl groups serve to dissociate K and Na ions from the phenoxide. The cations, therefore, are more mobile as a result increasing the conductivity. The temperature dependence of ionic conductivity suggests that the migration of ions is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel–Tammann–Fulchere plots. The polyisocyanate backbone is a rather stiff structure, however, a flexible oligo(ethylene oxide) side chain forms complexes with metal ion. Since the ion transport is associated with the local movement of polymer segments, the rigidity of the polymer backbone does not have much influence on the ion mobility.     

New Electrochemically Active Highly Sulfurized Polyconjugated Polymers

The electrochemical activity of new highly sulfurized polyconjugated polymers is studied. The polymers, polythienothiophene, poly(4,5,6,7-tetrathieno-4,5,6,7-tetrahydro-2,3-dehydrobenzothiophene), poly(6-methylthieno[2,3-b]pyridine-4-thione-5-thiol), and poly(6H-thieno[2,3-b]-azepine-6,7(8H)-dithione) are obtained in a deep sulfurization of polyethylene, polystyrene, and poly(5-vinyl-2-methylpyridine) by elemental sulfur. Employed as active cathodic material in lithium batteries, these polymers ensure their prolonged cycling with specific discharge capacity of up to 339 mA h/g. The effect of the conducting additive and electrolyte on the energy capacity and cycling of polymer cathodes in lithium batteries is discussed.     

Sulfurization of polymers

Polydiethylsiloxane reacts with elemental sulfur at 300–320 °C (ZnCl₂ slightly accelerates the process) with evolution of hydrogen sulfide and formation of black lustrous paramagnetic powders (sulfur content up to 38.50%), which possess a noticeable electric conductivity (3.20·10⁻⁷ S cm⁻¹ when doped with I₂) and redox properties. Polydimethylsiloxanes are stable under the same conditions. In rechargeable lithium batteries, the sulfurized polydiethylsiloxane behaves as an active cathode material allowing charging and discharging of the battery. The specific capacities of the cathodic and anodic processes (80–100 (mA h) g⁻¹) change insignificantly. The hydrolytic stability, elemental analysis, IR and ESR spectra, DSC-TGA and derivatographic analyses data, the electric conductivity, and the character of the electrochemical activity of the polymers synthesized indicate that the polymers contain the polyvinylene disulfide blocks cross-linked by the polysiloxane chain.     

Reagentless biosensor based on PQQ-depended glucose dehydrogenase and partially hydrolyzed polyarbutin

Partially hydrolyzed polyarbutin-containing benzoquinone groups were synthesized by using chemoenzymatic methods. This polymer was used as a mediator for the oxidation of pyrroloquinoline quinone-dependent glucose dehydrogenase. Polymer was covalently attached to the enzyme through the glucose moiety of the polymer and amine residues in the protein. Electrochemical studies show that the oxidized benzoquinone attached to the enzyme can act as a mediator for the reoxidation of the enzyme at carbon electrode surfaces. The apparent Michaelis constant and inactivation rate constant of the coupled enzyme were found to be similar to these parameters of the native enzyme.     

Polypyrrole - Semiconductor photovoltaic devices

Abstract

A new approach is given for obtaining fast electro-optical response and good angular-viewing characteristics in a liquid-crystal variable-retardation device. The improved characteristics make the new device well suited for use in field-sequential color systems.     

Sulfurization of polymers

Polyethylene exhaustively sulfurized with elemental sulfur shows paramagnetic (spin concentration 2.7–9.7·10¹⁹ sp g⁻¹,g=2.0041–2.0045, ΔH=0.53–0.62 mT) and redox properties, which was demonstrated by both voltammetric and chemical methods (sodium reduction in liquid ammonia). The high concentration of unpaired electrons, the character of the electrochemical activity, and the chemical properties are in agreement with the presence in the polymers of polyconjugated ladder polythiophene and parquet polynaphtho-thienothiophene structures along with polyene-polysulfide blocks. The use of the polymers under consideration as an active cathode material in lithium batteries enables their repeated cycling with a specific charge capacitance of 150–340 mA hg⁻¹.