Circular dichroism spectro electrochemical and voltammetric studies of vitamin B-2

Electroreduction of vitamin B-2 (VB2) was studied by in situ circular dichroism (CD) spectroelectrochemistry (SEC) with a long optical path length thin layer cell (LOPLTLC). The results showed that the electroreduction of VB2 in phosphate buffer solution (PBS) (PH 6.8) was a two-electron electrochemical process with weak adsorption of the reactant at the glassy carbon (GC) electrode surface. The CD spectra change of VB2 in the reduction process was explained with the theory of electronic states. We also treated the CD spectra with a singular value decomposition least square (SVDLS) method, and have found not only the number of components and their spectra, but also the fraction distribution of each component in the electroreduction process of VB2.

Influence of the size of ultrafine CaCO3 powder on PP crystallization

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD. The average sizes of the CaCO3 powders used were 0.1 mum (UC) and 0.5 mum (GC), respectively. The PP/CaCO3 composites at compositions of 1 phr and 10 phr were investigated. The results showed that the addition of CaCO3 reduced the supercooling, the rate of nucleation and the overall rate of crystallization (except for the 10 phr UC/PP sample). The crystallinity of PP was increased and the size distribution of the crystallites of alpha -PP; was: broadened. On the other hand,the crystallization rate of 10 phr UC/PP is 1.5 times higher than that of neat PP. It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity. The sizes of crystallites and the unit cell parameters of alpha -PP were varied by the addition of CaCO3. beta -PP was formed by addition of Ge and was not detected by addition of UC. The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.

In situ infrared spectroelectrochemical studies on adsorption and oxidation of nucleic acids at glassy carbon electrode

The adsorption and oxidation of yeast RNA and herring sperm DNA (HS DNA) at glass carbon (GC) electrode are studied by differential pulse voltammetry (DPV) and in situ FTIR spectroelectrochemistry. Two oxidation peaks of yeast RNA are obtained by DPV, whose peak potentials shift negatively with increasing pH. The peak currents decrease gradually in successive scans and no corresponding reduction peaks occur, thus indicating that the oxidation process of yeast RNA is completely irreversible. The IR bands in the 1200-1800 cm-l range, attributed to the stretching and ring vibrations of nucleic acid bases, show the main spectral changes when the potential is shifted positively, which gives evidence that the oxidation process takes place in the base residues. The oxidation process of HS DNA is similar to that of yeast RNA. The results both from DPV and in situ FTIR spectroelectrochemistry confirm that the guanine and adenine residues can be oxidized at the electrode surface, which is consistent with the oxidation mechanism of nucleic acids proposed previously. (C) 2001 Elsevier Science B.V. All rights reserved.

A facile approach to immobilize protein for biosensor: self-assembled supported bilayer lipid membranes on glassy carbon electrode

A kind of solid substrate, glassy carbon (GC) electrode. was selected to support self-assembled lipid layer membranes. On the surface of GC electrode. we made layers of dimyristoylphosphatidylcholine (DMPG, a kind of lipid). From electrochemical impedance experiments. we demonstrated that the lipid layers on the GC electrode were bilayer lipid membranes. We immobilized horseradish peroxidase (HRP) into the supported bilayer lipid membranes (s-BLM) to develop a kind of mediator-free biosensor for H2O2. The biosensor exhibited fine electrochemical response, stability and reproducibility due to the presence of the s-BLM. As a model of biological membrane, s-BLM could supply a biological environment for enzyme and maintain its activity. So s-BLM is an ideal choice to immobilize enzyme for constructing the mediator-free biosensor based on GC electrode. (C) 2001 Elsevier Science B.V. All rights reserved.

In-situ FTIR study on adsorption and oxidation of native and thermally denatured calf thymus DNA at glassy carbon electrodes

In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

人参茎叶挥发油中倍半萜烯化合物的分离与鉴定

对人参茎叶挥发油的有效成分进行分离纯化 ,利用薄层层析 (TL C)、红外光谱 (IR)、气相色谱 (GC)、气相色谱 -质谱 (GC/MS)联机技术从该挥发油中分离鉴定 6个倍半萜烯类化合物 .

Langmuir-Blodgett film formation from surfactant-capped zinc sulfide nanoparticles spread on water surface

The surfactant-capped ZnS nanoparticulate multilayer film has been fabricated by Langmuir-Blodgett(LB) technique. ZnS LB firm was investigated by the small-angle x-ray diffraction(XRD), atomic force microscopy(AFM) and transmission electron microscopy(TEM). The results indicate that ZnS nanoparticulate LB film is one-dimensional superlattice.

Preparation of SnO2 thin films with extremely preferred orientation along (101) plane by LB deposition technique

SnO2 thin films with extremely preferred orientation along (101) plane were made by LB technique and characterized by FTIR,, UV-visible, X-ray diffraction, X-ray photoelectron spectroscopy and SEM.

Particulate multilayers prepared from surfactant-stabilized SnO2 nanoparticles

Surfactant-stabilized SnO2 nanoparticulate organosol was prepared. The organosol mixed with arachidic acid was spread on water surfaces in a Langmuir-Blodgett (LB) balance. Surface pressure versus surface area isotherms were determined. The surfactant-stabilized SnO2 nanoparticulate monolayers were transferred, layer-by-layer by the LB technique, to solid substrates. Then the multilayers were characterized by Fourier transform IR spectroscopy, UV-visible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The results indicate that the multilayer is composed of SnO2 nanoparticles and arachidic acid. It forms a Z-type periodic structure with a long spacing of 7.48 nm, i.e. a kind of three-dimensional superlattice. (C) 1999 Elsevier Science S.A. All rights reserved.

Electrocatalytic mechanism for formaldehyde oxidation on the highly dispersed gold microparticles and the surface characteristics of the electrode

Electrocatalytic mechanism for the electrochemical oxidation of formaldehyde (HCHO) on the highly dispersed Au microparticles electrodeposited on the surface of the glass carbon (GC) electrode in the alkaline Na2CO3/NaHCO3 solution and the surface characteristics of the Au microparticle-modified glass carbon (Au/GC) electrode were studied with in situ FTIR spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the final products of HCHO oxidation is HCOO- at the Au/GC electrode and CO2 at the bulk Au electrode. The difference may be ascribed to the different surface characteristics between the Au/GC electrode and the bulk Au electrode. (C) 1999 Elsevier Science B.V. All rights reserved.

Investigation of the self-accelerating process of ascorbic acid by in-situ circular dichroism spectroelectrochemistry

The electrode reaction process of ascorbic (Vc) was studied by in-situ circular dichroic(CD) spectroelectrochemistry with a long optical path thin layer cell on glassy carbon(GC) electrode. The spectroelectrochemical data were analyzed by the double logarithmic method together with nonlinear regression. The results suggested that the mechanism of Ve in pH 7.0 phosphate buffer solution at GC electrode was a two-electron irreversible electrooxidation followed by adsorption of the oxidation product. That is a self-accelerated process. Some kinetic parameters at free and at adsorbed electrode surface, i.e, the formal potentials, E-0' = 0.09 V, E-a(0') = 0.26 +/- 0.02 V; the electron transfer coefficient and number of transfered electron, alpha n = 0.41, alpha(a)n = 0.07;the standard heterogeneous electron transfer rate constant, k(0) = 8.0 x 10(-5) cm.s(-1), k(a)(0) = 1.9 x 10(-4) cm.s(-1) and adsorption constant, beta = 102.6 were also estimated.

Effects of La3+ and Gd3+ on Ca2+ influx in rat hepatoma H-35 cells

Effects of La3+ and Gd3+ on Ca2+ influx were investigated in rat hepatoma H-35 cells by measuring the initial rate of Ca-45(2+) uptake. It was found that the maximum initial rate of Ca2+ uptake was increased six- to ten-fold at low concentrations of La3+ and Gd3+. Kinetic analyses by measuring the initial rate of Ca2+ influx at different external Ca2+ concentrations indicated the existence of two intracellular exchangeable components in the basal Ca2+ system, with low and high affinities for Ca2+, and only one class of Ca2+ binding sites was observed in the La3+- or Gd3+-treated cells. For high affinity, La3+ and Gc(3+) increased both kinetic parameters K-m and V-max of basal Ca2+ influx. La3+ and Gd3+ compete directly with Ca2+ for Ca2+ binding site for low affinity. The kinetics is competitive.

Ti-Al系金属间化合物的价电子结构及其合金化行为

由固体和分子经验电子理论(EET)分析了Ti-Al系金属间化合物合金化前后的价电子结构,再计算了该系合金各相的均匀变形因子α和解理能Gc 值,据此分析了合金化对该系金属间化合物脆性的影响。结果表明,常量合金化元素Nb使Ti3Al基合金的α2相无序化,增加了韧的第二相,减弱了Ti-Ti共价键,综合导致α和Gc 值增大,使Ti3Al的脆性有本质改善;微量合金化元素Mn减弱了TiAl基合金的Al-Al共价键,并诱发孪生,使α和Gc 有所提高,在一定程度上降低了TiAl的脆性;TiAl3极低的α和Gc导致恶劣的本征脆性,Mn也难以改变其脆性本质

六氰亚铁酸镍修饰玻碳电极的现场红外光谱电化学研究

报道了一种制备六氰亚铁酸镍玻碳修饰电极(NiHCF/GC)的电化学方法,并用循环伏安(CV)和现场红外光谱电化学(FTIRs)方法对该修饰电极进行了研究.结果表明该电极上的NiHCF修饰膜有两种结构:Ni_2Fe(Ⅱ)(CN)_6和M_2NiFe(Ⅱ)(CN)_6,M为碱金属离子.M_2NiFe(CN)_6结构具有阳离子选择性,而阳离子对Ni_2Fe(Ⅱ)(CN)_6电化学反应的影响是间接的.FTLRs研究还表明在膜制备过程中Fe(CN)_6~(4-)发生了共沉积,其存在形式与支持电解质中阳离子的性质有关:在Na~+和Li~+溶液中,主要以桥式结构存在;而在K~-和H~-溶液中,主要为离子对形式.

谷物中噻吩甲氯残留量的气相色谱-质谱测定

应用气相色谱－ 质谱法确证及测定谷物( 糙米、玉米) 中噻吩甲氯的残留含量，试样采用水—丙酮提取，提取液经与石油醚液—液分配后， 再以硅酸镁载体(Florisil)柱净化，气相色谱—质量选择检测器选择离子监测方式(GC-MSD-SIM)进行测定和阳性确证。噻吩甲氯选择监测离子的种类为m/z287、288、323，其丰度比约为46:100:11。采用外标法定量，方法检出限为0.010 ×10-6。