Effect of polyvinylidene fluoride hollow fiber membranes on mass transfer of samarium

The influence of swelling and stripping acidity on the mass transfer coefficient based on water phase and the inner diameters of membranes were studied with P507-HCl-Sm as working system in the two different kinds of hollow fiber membranes. Effects of extractant concentration, H+ concentration in aqueous phase and Sm3+ concentration on extraction rate were discussed and the corresponding reaction series were obtained. According to the investigations on the interfacial kinetics, the reaction kinetics equation and reaction rate constant were obtained.

Investigation of the electrocatalytic effect of polyaniline on the redox reaction of 2,5-dimercapto-1,3,4-thiadiazole by cyclic voltammetry

Electrochemical polymerized polyaniline(PAn) film electrode was used to investigate the electrocatalytic effect of PAn on the electrochemical redox reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT), PAn film electrode was electrochemically treated or immersed in DMcT solution before it was scanned in 1.0 mol/L HCl electrolyte. The cyclic voltammograms of PAn film electrode in 1.0 mol/L HCl solution changed with the above treatment, implying the electrocatalytic effect of PAn on the redox reaction of DMcT, The formation of electron-donor-acceptor adducts through the interaction between thiol or disulfide groups of DMcT and amine or imine groups of PAn during the treatment was probably the reason of the catalysis, The electrochemical properties of the adduct were different from those of PAn and DMcT, The adduct possessed a higher electrochemical activity and a better electrochemical reversibility than DMcT or PAn used alone.

人体血浆中15种超痕量稀土元素的电感耦合等离子体质谱法测定

本文用电感耦合等离子体质谱法测定了人体血浆中的稀土元素。在优化的条件下 ,以内标法测得的各种纯水溶液的检测限在 0 .7(Eu)～ 5 .4(Gd) ng·L- 1范围内。研究了 K,Na,Ca,Fe等基体元素对稀土测定的影响。以 In为内标元素补偿样品基体效应以及灵敏度飘移。比较了直接稀释、HNO3- H2 O2 消解及 HNO3-HCl O4消解 3种样品处理方法 ,用 1% HNO3直接稀释样品可满足轻稀土元素的定量分析要求 ,方法的定量测定下限≤ 1μg·L- 1。

两种ω-二茂铁羧酸的改进合成及其电化学行为

利用 Zn(Hg) /HCl分别对 3-二茂铁甲酰基丙酸和 4-二茂铁甲酰基丁酸进行 Clemmensen还原 ,在温和条件下高收率 (93%以上 )合成了 4-二茂铁丁酸和 5 -二茂铁戊酸。新的合成方法避免了文献中采用 40 5 .3k Pa H2 还原的苛刻条件。以FT-IR、1HNMR、13CNMR和 L D-MS确证了产物的结构。利用循环伏安技术研究了这两种 ω-二茂铁羧酸的电化学行为。

聚偏氟乙烯中空纤维膜器对钐传质性能的影响

以P50 7 煤油 HCl Sm为实验体系 ,在两种聚偏氟乙烯中空纤维膜器中研究了溶胀性能、反萃酸度对基于水相的总传质系数及中空纤维膜孔径的影响 ,考察了料液酸度、萃取剂浓度、钐离子浓度与萃取速率的关系 ,获得了相应的反应级数。根据界面反应动力学 ,得到了速率常数值和动力学方程。

Anodic voltammetry of dipyridamole at a glassy carbon electrode

The anodic voltammetric behavior of dipyridamole (DPM) in the presence of various electrolytes was studetd by direct-current voltammetry, differential-pulse voltammetry and cyclic voltammetry at a glassy carbon electrode. In a medium of 0.01 mol/L HCl, an oxidative peak of dipyridamole was obtained. The peak potential is at about 0.62 V(vs.Ag/AgCl). The peak current is linearly increased with the concentration of dipyridamole over the range of 0.05 similar to 10 mg/L. The method has been used for the direct determination of dipyridamole in tablets. The recoveries of dipyridamole in urine samples are 89%. Experimental results proved that the electrode reaction was diffustion controlled and irreversible.

Fluorescence spectra of hemorrhagin III from the snake venom of Agkistrodon acutus

Hemorrhagin III (AaH III) was separated and purified from the crude snake venom of Agkistrodon acutus, and its molecule weight was determined accurately to be 23; 284.4 +/- 0.1 by LDI1700-MALDI-TOF-MS. Emission spectra of AaH III showed that Trp residues were located by a great degree in the hydrophobic area. Addition of SDS and guanidine-HCl led to change of the molecular conformation of AaH III, and caused the fluorescence quenching of Trp residues. The red-shifted emission band of AaH III after adding guanidine-HCl showed that Trp residues exposed in polar solvents. The effects of pH, EDTA and metal ions on the fluorescence spectra of AaH III were also investigated.

Synthesis and characterization of soluble polyimides from 2,2-bis(4-aminophenyl)cycloalkane derivatives

New aromatic diamines [(1) and (2)] containing polycycloalkane structures between two benzene rings were synthesized by HCl-catalyzed condensation reaction of aniline hydrochloride and corresponding polycycloalkanone derivatives. The structures of diamines were identified by H-1-NMR, C-13-NMR, FTIR spectroscopy, and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The inherent viscosities of the resulting polyimides were in the range of 0.34-1.02 dL/g. The polyimides showed good thermal stabilities and solubility. All the polymers were readily soluble in N-methyl-2-pyrrolidone, m-cresol, tetrachloroethane, etc. Some of them were soluble even in chloroform at room temperature. The glass transition temperatures were observed in the range of 323-363 degrees C, and all of the polymers were stable up to 400 degrees C under nitrogen atmosphere. (C) 1999 John Wiley & Sons, Inc.

In-situ Fourier transform infrared spectroelectrochemistry as a probe of the glassy carbon electrode chemically modified by nickel (II)-cyanometallates

A new nickel (II)-cyanometallates modified on glassy carbon electrode was prepared by a new method and studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroelectrochemistry. It was found that the NiHCF film existed in two forms: Ni2Fe(II)-(CN)(6) and M2NiFe(II)(CN)(6), Fe(CN)(3)(6-) codeposited in the NiHCF film existing in free cation or bridged-bond state depended on the property of the cations in electrolyte: in NaCl and LiCl solution, it is in bridges-bonded, but in HCl and KCl, it is free.

Catalytic oxidization polymerization of aniline in an H2O2-Fe2+ system

Polyaniline is prepared by chemical polymerization of aniline in an acidic solution using H2O2 as an oxidant and ferrous chloride as a catalyst. A wide variety of synthesis parameters are studied, such as the amount of the catalyst, reaction temperature, reaction time, initial molar ratio of oxidant, monomer and catalyst, and aniline and HCl concentrations. The polymerization of aniline can be initiated by a very small amount of catalyst. The yield and the conductivity of product depend on the initial molar ratio of the oxidant and monomer. The polyaniline with a conductivity of about 10 degrees S/cm and a yield of 60% is prepared under optimum conditions. The process of polymerization was studied by in situ ultraviolet-visible spectroscopy and open-circuit potential technology. Compared to the polymerization process in a (NH4)(2)S2O8 system, the features of the H2O2-Fe2+ system are pointed out, and the chain growth mechanism is proposed. (C) 1999 John Wiley & Sons, Inc.

玻碳电极上六氰亚铁酸钯膜的现场FTIR光谱电化学研究

本文报道六氰亚铁酸钯膜修饰电极在HCL，KCL和NaCl溶液中的现场反射FTIR光谱电化学研究，结果表明该修饰膜具有内外两层结构，分别为Pd2Fe(CN)6和M2PdFe(CN)6，其中M为支持电解质一价阳离子．在1mol/L NaCl中，内层的氧化电位Em＝0.87V(vs．Ag/AgCl)，外层为0.77V．在1mol/L HCl或KCl中两层的氧化还原波重叠为一个大CV波峰而难以分辨，然而现场FTIR光谱电化学清晰地分辨出这两种结构在所有3种溶液中CN的不同振动频率，发现H+离子是最佳的支持电解质，能使这两种结构同时发生氧化反应

Chemical polymerization of aniline with hydrogen peroxide as oxidant

Oxidative polymerization of aniline in the presence of H2O2/Fe2+/HCl was carried out, and polyaniline obtained showed similar molecular structure compared to that prepared in (NH4)(2)S2O8 system.

Interaction of brilliant cresyl blue and methylene green with DNA studied by spectrophotometric and voltammetric methods

The binding behavior of two cationic dyes, brilliant cresyl blue (BCB) and methylene green (MG) to calf thymus DNA was studied by spectrophotometric and voltammetric methods. A red shift of the adsorption spectra and hypochromism accompany the binding of BCB and MG to calf thymus DNA. In 5 x 10(-2) mol dm(-3) NaCl, 5 x 10(-3) mol dm(-3) tris-HCl pH 6.87 buffer solution, the apparent binding constants are: K-BCB+ 3.0 x 10(4)M(-1) (N = 4.13) and K-MG+ = 8.8 x 10(4)M(-1) (n = 4.44). Electrochemical studies show that the formal potentials shift negatively upon addition of DNA, indicating that the oxidized forms of the dyes have stronger affinity to DNA than the reduced ones. K-BCB+/K-BCBH and K-MG+/K-MGH are evaluated to be 10.39 and 7.04. respectively. Our investigation suggests that the two cationic dyes interact with DNA predominantly via electrostatic interaction.

The fabrication and performance of an Ag/AgCl reference electrode in human serum

A simple set of electric circuits was used to assemble a pulse generator. With pulse potentials and under galvanostatical control, a clean silver wire was anodized electrochemically for 0.2-0.5 min in 1.0 moll(-1) HCl with a pulse current density of 20 mA cm(-2), and the pulse wave parameters of t(a)/t(c) = 1 and a cycle of 4 s forming an Ag/AgCl reference electrode. Even though the AgCl layer was consumed during the working period when the Ag/AgCl electrode was used as a cathode, the AgCl layer could be in situ recovered electrochemically in serum used when a reversed potential was applied to the electrode system immediately after the measuring program was finished. The current response curve of the anode indicated that an AgCl layer in high density was basically accomplished during the first 6 pulse cycles in human serum. In order to keep a stable and uniform AgCl layer on the reference electrode after each measuring cycle, the ratio of the recovery time (t(r)) to the working time (t(w)) was measured and the smallest value was obtained at 0.03. The open-circuit potential of the Ag/AgCl electrode with respect to a SCE in 0.1 moll(-1) KCl was monitored over a period of 14 days and the mean value was 40.09 mV vs SCE with a standard deviation of 2.55 mV. The potential of the Ag/AgCl reference electrode did remain constant when the measurements were repeated more than 600 times in undiluted human serum with a standard deviation of 1.89 mV. This study indicated that the Ag/AgCl reference electrode could been rapidly fabricated with a pulse potential and could be used as a reference electrode with long-term stable properties in human serum samples.

Adsorption of PMo12 and SiMo12 on activated carbon in aqueous and acidic media

In various acidic media, such as H2SO4, HCl, H3PO4, acetic acid of 3 M in hydrogen ion concentration, and pure acetic acid, the adsorption of heteropolyacids composed of molybdenum with the Keggin structures PMo12 and SiMo12 on different activated carbons is studied. In acidic media, the adsorbed amount of heteropolyacids is much higher than that in water. By considering the relation between adsorbed amount and the acid strength of the media, as far as SiMo12 and PMo12 are concerned, there exist different trends.