Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Seed-mediated growth of large, monodisperse core-shell gold-silver nanoparticles with Ag-like optical properties

Large, monodisperse core-shell Au-Ag nanoparticles with Ag-like optical properties have been prepared by the seeding growth method in micellar media.

Crystal transformation of Nylon 11 using in situ WAXD

alpha Form Nylon 11 films were found to exist a non-linear transformation at 70 degrees C during the heating process using in situ WAXD. The alpha Form disappeared but delta Form appeared when the temperature was higher 70 degrees C.

A novel electrochemical SPR biosensor

In this paper, we demonstrate for the first time that upon electrochemical oxidation/reduction, the transition in the conductivity of polyaniline (PAn) film on gold electrode surface leads to a large change of surface plasmon resonance (SPR) response due to a change in the imaginary part of dielectric constant of PAn film. Based on the amplifying response of SPR to the redox transformation of PAn film as a direct result of the enzymatic reaction between horseradish peroxidase (HRP) and PAn in the presence of H2O2, a novel PAn-mediated HRP sensor has been fabricated. The electrochemical SPR biosensor, unlike a usual binding assay with SPR, can afford a larger SPR response, and can also be reused by reducing the PAn film electrochemically to its reduced state. This method opens up a new route to the fabrication of SPR biosensor. (C) 2001 Elsevier Science BN. All rights reserved.

Hydrogen peroxide biosensor with enzyme entrapped within electrodeposited polypyrrole based on mediated sol-gel derived composite carbon electrode

A novel amperometric biosensor for the detection of hydrogen peroxide was described. The biosensor was constructed by electrodepositing HRP/PPy membrane on the surface of ferrocenecarboxylic acid mediated sol-gel derived composite carbon electrode. The biosensor gave response to hydrogen peroxide in a few seconds with detection limit of 5.0 x 10(-5) M (based on signal:noise = 3). Linear range was upto 0.2 mM. The biosensor exhibited a good stability. (C) 2001 Elsevier Science B.V. All rights reserved.

Molecular component structures mediated formation of self-assemblies

Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process of the self-assembly and the morphologies of the resulted self-assemblies could be mediated by modifying the structures of the molecular components used. The effect of the structures of the molecular components on the formation of the self-assemblies was discussed in terms of intermolecular interactions.

Potential-induced transformation for surfactant aggregates on a metal surface

Surfactant adsorption on metal surfaces has been used to limit the activity of the electrode surface and to stabilize colloidal clusters and nanoparticles in solution, but the adsorption and relative potential-induced structure change of the surfactant were not known. Here, the adsorption of sodium dodecyl sulfate (SDS) on a Au(111) surface under potential control was investigated by in situ scanning tunneling microscopy (STM). The STM images showed that the morphology of SDS on Au(111) was changed from a hemi-cylindrical micellar monolayer to a compact and uniform bilayer through control of the potential. The transition between the hemimicellar monolayer and the compact bilayer is not reversed after a period of time. The model of potential-induced transformation for SDS aggregates on Au(111) was established. (C) 2001 Elsevier Science B.V. All rights reserved.

Enhanced crystallization and phase transformation of amorphous silicon nitride under high pressure

The crystallization and phase transformation of amorphous Si3N4 ceramics under high pressure (1.0-5.0 GPa) between 800 and 1700 degreesC were investigated. A greatly enhanced crystallization and alpha-beta transformation of the amorphous Si3N4 ceramics were evident under the high pressure, as characterized by that, at 5.0 GPa, the amorphous Si3N4, began to crystallize at a temperature as low as 1000 degreesC (to transform to alpha modification). The subsequent alpha-beta transformation occurred completed between 1350 and 1420 degreesC after only 20 min of pressing at 5.0 GPa. In contrast, under 0.1 MPa N-2, the identical amorphous materials were stable up to 1400 degreesC without detectable crystallization, and only a small amount of a phase was detected at 1500 degreesC. The crystallization temperature and the alpha-beta transformation temperatures are reduced by 200-350 degreesC compared to that at normal pressure. The enhanced phase transformations of the amorphous Si3N4, were discussed on the basis of thermodynamic and kinetic consideration of the effects of pressure on nucleation and growth.

Conformation transformation of syndiotactic polypropylene induced by stretching and annealing

Conformation transformation of syndiotactic polypropylene(sPP) induced by stretching and annealing processes has been investigated by WAXD, IR and DSC, The results indicate that not only the quenched samples but also the isothermally crystallized samples can form the crystals with all-trans conformation by means of uniaxially stretching at room temperature. The all-trans conformation crystals are of metastability, which can transform to stable crystals with (TTGG)(2) helical conformation at higher annealing temperatures.

Mechanism-transformation synthesis and characterization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer

By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.

Functionalized inorganic-organic composite material derivated by sol-gel for construction of mediated amperometric hydrogen peroxide biosensor

A novel functionalized inorganic-organic hybrid material with cation exchange property was prepared by sol-gel method. The H2O2 biosensor was fabricated by simply dipping the horseradish peroxidase-containing functionalized membrane modified electrode into Meldola's blue (MDB) solution. MDB was adsorbed and firmly immobilized within the membrane. The electrochemical behavior of MDB incorporated in the membrane was more reversible compared with that of the solution species and suitable as mediator for the horseradish peroxidase. The response time was less than 25 s. Linear range is up to 0.6 mM (COH. coeff. 0.9998) with detection Limit of 9 x 10(-7) M. High sensitivity of 75 nA mu M cm(-2) was obtained due to high MDB-loading. The biosensor exhibited a good stability. (C) 1999 Elsevier Science B.V. All rights reserved.

Ion/neutral complex-mediated reactions generated from some ionized tetrahydroimidazole-substituted methylene beta-diketones

The dissociation of gaseous metastable ions of m/z 153 and the formation of ions of m/z 139 from the unimolecular fragmentations of ionized tetrahydroimidazole-substituted methylene beta-diketones were examined by tandem mass spectrometry. In addition, some other fragments accompanying the elimination of either an H2O molecule or an CHO. radical were also observed in the collision-induced dissociation spectra of molecular ions of the compounds bearing an aromatic ring. Collision-induced dissociation and isotopic labeling showed that these processes may involve reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms are discussed. (C) 1997 by John Wiley & Sons, Ltd.

ASYMMETRIC ALKYLATION MEDIATED BY CHIRAL PHASE-TRANSFER CATALYSTS

Seven chiral phase-transfer catalysts, among which three have not been reported so far, have been prepared and applied to the asymmetric alkylation of alpha-isopropyl benzyl cyanide and alpha-isopropyl-p-chlorobenzyl cyanide. The result showed that short reaction time, low temperature, high catalyst concentration and non-polar solvent would improve the optical yield. The influence of structure of the catalyst on the asymmetric reaction was preliminarily studied. The optical purity of the products were evaluated by gas chromatography with a chiral column.