Solvent extraction of sodium picrate with 15-crown-5 into carbon tetrachloride. The determination of the dimer-formation constant of a crown ether-univalent metal salt 1∶1∶1 complex

The theory is derived to determine the dimer-formation constant,K ₂, of a crown ethermetal salt 111 complex in organic solvents of low dielectric constant by solvent extraction. The theoretical predictions are verified experimentally by extraction of sodium picrate (NaA) with 15-crown-5 (15C5) into carbon tetrachloride. All the experiments were conducted at 25°C. The logK ₂ value of the Na(15C5)A complex in carbon tetrachloride has been determined to be 4.05±0.11. Moreover, the partition constant of the complex is calculated.     

邻菲啰啉对固定尿酸酶催化反应动力学的影响

The activation energy of the enzyme-catalyzed reaction for uric acid decreases markedly in the presence of o-phenanthroline, which activates the bioelectrochemicla activity of the polypyrrole uricase electrode. The response current of the enzyme electrodeis independent of the concentration of o-phenanthroline. Based on the experimental results, the mechamsm of the enzyme-catalyzed reaction for uric acid in the presence of o-phenanthroline is presented as follows: E+A→EA, EA+S EAS, EAS→EA+P, where E, A, S and P are the enzyme, activator, substrate and product, respectively. The effects of pH value, potential and the uric acid concentration on the response currents of the uricase electrode have been studied in the presence of o-phenanthroline. In the presence of o-phenanthroline, the response current of the enzyme electrode increase linearly with increasing concentration of uric acid in the region of 0.07 to 0.67 mmol·L~(-1), therefore the polypyrrole uricase electrode which has once lost its activity can be activated and used again to determine the substrate concentration.     

Synthesis of protected peptides from the human IgG1 hinge region on PEG support using disulfide bond synthons and alkaline or enzymatic detachment

Peptides from the hinge region of human IgG1 are potential defined carriers of synthetic immunogens. Their synthesis was carried out on the soluble support—PEG-OMe 2000 using disulfide bond synthons. The loading capacity of the polymer was increased twofold by anchoring the lysine as a simple branching unit. The amino acid leucine was used as an enzymatically cleavable linker. Peptide detachment from the polymer was performed either by classical ester bond saponification or newly by peptide bond cleavage catalyzed by thermolysin in water.     

Influence of conjugated nitrogenous bases on the spectra and structure of mixed-ligand nickel(II) chelates containing β-diones

The infrared and electronic excitation spectra of a series of new nickel(II) chelates containing an-diimine (or nitrogenous base, enR) and the anion of a-dione (1,3-ketoenol or 1,3-ketoester,H) were obtained in the solid state and in solution. The composition and the overall structure of the new chelates in the solid state depends on ligand concentration, the substituents within the-dionato moiety and the counterion present. The IR and electronic excitation spectra of [Ni(enR)₂ ]NO₃ and [Ni(enR)(O₂NO)] indicate, in conjunction with other physicochemical measurements, bidentate coordination of the ligands, while the spectral shifts reveal replacement of the (O,O)nitrato group by basic solvents. The existence of the nickel(II) in an octahedral environment is confirmed by an X-ray structure analysis of [Ni(dpamH)₂acac]NO₃ · CH₃OH (monoclinic, space groupP2_l/n, a=17.296(1),b=7.462(1),c=21.604(3) å,=95.65(1),Z=4, R=0.0534,Rw=0.0600), where dpamH denotes the 2,2-dipyridylamine.     

Adsorption of Pd, Ni, and Cu ions on anode-oxidized carbon fiber materials

The anodic oxidation of the carbon felt Carbonetcalon results in the formation of surface defects which serve as centers of strong adsorption of Pd^II, Ni^II, and Cu^II ions. The electrochemical reduction of adsorbed ions makes it possible to obtain metallic catalysts, which undergo multiple redox cycles without loss of metal. The catalysts are characterized by high dispersity of the reduced phase, high adsorption capacity with respect to hydrogen, and 100% selectivity in hydrogenation of acetophenone. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–85, January 1997     

ELECTRON PARAMAGNETIC RESONANCE STUDIES OF SINGLE CRYSTAL SODIUM HEXAMOLYBDOCHROMATE (Ⅲ)Cr~(3+)/Na_3(AlMo_6O_(24)H_6)·8H_2O

An X-band EPR study on a Na_3(CrMo_6O_(24)H_6)·8H_2O single crystal diluted by its isomor-phic compound Na_3(AlMo_6O_(24)H_6)·8H_2O at room temperature is reported. Using the least squares-fitting method to simulate the EPR data for principal planes, the Hamiltonian parameterswere obtained. The principal values of the g tensors are g_(ZZ) = 1.904, g_(XX)= 1.973, g_(YY)=1.933. The zero field splitting tensor parameters are D = 0.275 cm~(-1), E = 0.05 cm~(-1). The fielddependence of Cr~(3+) energy levels with field at different angles from the principal axes whenthe field is along the principal planes is calculated based on these experimental parameters.The isofrequency plots of calculated field vs. angle are also shown. They agree well with theexperimental results.     

Determining moisture absorption/desorption properties of commercial membranes by thermogravimetry (TG)

A series of different commercial membranes were characterized by their moisture absorption and desorption properties under controlled humidity and temperature conditions. This work was made possible by combining the features of a constant humidity conditioning chamber with those of a thermogravimetric (TG) apparatus. These two modules were interconnected by tubing, rotameters, an atmosphere-recycling microbellows pump and switching valves. Under programmed heating and isothermal conditions reproducible data were obtained in terms of weight-gain or weight-lossvs. time and pore size. Evaluation of the resulting TG curves allowed us to report reasonable differences in the materials, some of which had been previously surface-modified by the manufacturer.     

Erosion of efficiency in non-uniform linear chromatography

In linear chromatography (i.e. chromatography performed in the absence of sample overloading), when the plate height of a column is roughly uniform along its length, variations in the velocities of solutes are the only possible causes of erosion of efficiency. The sources of these variations (variations in capacity ratio and in the density of the mobile phase, etc.) play no direct role in the erosion of efficiency except through their effect on solute velocities. In other words, what eventually causes the erosion of efficiency is merely variation in the time required for solutes to traverse equally small segments of a column. Significant erosion can only arise from abrupt and deep deceleration of solutes in one or several relatively small segments of a column. If erosion of efficiency caused by pressure gradients in linear SFC is to be large, the depth and the sharpness of the deceleration of a solute must go beyond that hitherto confirmed experimentally. Many relevant examples are analyzed graphically.     

Strukturelle Abwandlungen anN-Acetylneuraminsäure, 3

From methyl-5-acetylamino-7,8-anhydro-4,9-O-bis-(t-butyldimethylsilyl)-3,5-dideoxy--D-glycero-D-galacto-2-nonulopyranosidonic acid methylester (1) the derivatives1 a and1 b were obtained by removing the 9-O-(t-butyldimethylsilyl)group withBu ₄NF, followed by acetylation. Treatment of1 b with 80% acetic acid and acetanhydride/pyridine yields the 8-epi-N-acetylneuraminic acid derivative2 a and the 7-epi-N-acetylneuraminic acid derivative3 a in a ratio of 3:1 (Scheme 1). The structure elucidation of2 b was achieved by converting2 b via the 4,9-bis-O-(tBDMSi)-8-O-tosyl-derivative2 d into the epoxide1 (Scheme 2). Using the same sequence the epoxides4 and5 were transformed into theN-acetylneuraminic acid derivative6 a and the 7,8-bis-epi-N-acetylneuraminic acid derivative7 a (Scheme 3). After treatment with sodium hydroxide and 0.025m HCl and Dowex 50 H⁺ the 8-epi-, 7-epi- and 7,8-bis-epi-N-acetylneuraminic acids2,3, and7 were obtained. These three compounds were tested withCMP-N-acetylneuraminic acid synthetase.

Herrn KollegenK. Schlögl mit den besten Wünschen zum 60. Geburtstag.     

丙酮中除虫脲溶液标准物质研制

采用重量-容量法制备丙酮中除虫脲溶液标准物质。准确称量国家二级标准物质除虫脲溶解到色谱纯丙酮中,通过A级容量瓶定容至500 mL,摇匀后分装到2 mL安瓿瓶内共460瓶,每瓶为1 mL,保持低温迅速封口,配制过程中室温保持在(20±2)℃。采用液相色谱法进行均匀性、稳定性检验和定值结果验证。从样品中随机抽取16瓶进行均匀性检验,经F检验表明,在95%的置信区间范围内该标准物质均匀性良好;采用t检验对标准物质稳定性进行检验,标准物质在12月内稳定性良好。对该标准物质的不确定度进行了评定,研制的丙酮中除虫脲溶液标准物质定值结果为100μg/mL,相对扩展不确定度为2%(k=2)。结果表明,该标准物质均匀性与稳定性良好,量值准确,可用于日常分析检测中的方法评价和仪器校准。