Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

水解聚合铝溶液中Al30形态的研究

水解聚合铝形态一直是分析、催化、土壤、地球化学、新材料、环境科学和生物毒理学等众多领域研究的前沿和热点。Keggin 结构的Al₃₀ 形态是迄今为止发现的电荷最高的水解铝聚合阳离子,具有独特的分子结构和纳米分子尺寸,它对催化化学、新型功能材料、高效絮凝剂的开发以及铝的水解聚合转化规律研究具有重要意义。本文主要论述了Al₃₀形态的形成、形态分析方法、结构模型以及形成机理等方面的最新研究进展,并对水解聚合铝溶液的研究发展趋势进行了展望。     

烯烃氢甲酰化催化剂活性物种的原位~1H NMR研究

有机磷配位铐或钴联基配合物是生产难或醇的工业催化剂，一般公认金属氢化物是反应的催化活性物种．通常反应活性物种仅存在干反应状态下，其结构表征非常困难，在许多研究中只能关联催化剂母体与其活性的关系［‘1；而未能揭示出催化的本质，给催化剂设计造成很大困难，因而对催化剂活性物种的直接表征受到普遍关注．B。wn问、Morrista］及本文作者研究组＊均采用加压原位红外光谱方法，在烯烃氢甲酸化反应条件下捕捉到HCO（CO）3L存在的信息·但用相同方法在反应条件下，在RhH键特征吸收谱带195O－2200Cm‘内未观测到错氢化物的Rh－…     

Synthesis of silk-like FeS2/NiS2 hybrid nanocrystals with improved reversible oxygen catalytic performance in a Zn-air battery

The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS₂/NiS₂ hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j = 10 mA cm^?2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS₂/NiS₂ hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS₂/NiS₂ hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS₂/NiS₂ hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.     

Overproduction of riboflavin by anArthrobacter sp. mutant resistant to 5-fluorouracil

Effects of pH and dissolved oxygen concentration on batchwise riboflavin production by a 5-fluorouracil (5-FU)-resistant mutant ofArthrobacter sp. were investigated. The reaction was carried out in a jar fermentor. The optimal pH of culture medium was around 7.3. Dissolved oxygen concentration was almost constant during fermentation at 600 rpm of agitation rate. Production of riboflavin reached a maximum of 160 mg/L after 70 h fermentation under the agitation rate of 600 rpm, aeration rate of 1.0 L/min, and pH 7.0.     

Determination of molecular orientation distribution of a stable paramagnetic probe in oriented 4-cyano-4’-<Emphasis Type="Italic">n</Emphasis>-pentylbiphenyl

The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005.     

Kinetic model of a DC oxygen glow discharge

A simple kinetic model predicting the concentration of oxygen atoms, metastable singlet molecules O₂(a ¹) and negative ions O — in the positive column of a DC glow discharge is developed. The calculated O and O₂(a ¹) concentrations are compared to previously reported measurements for pressuresp=0.2–2 Torr and discharge currentsI=10–80 mA. The electron density calculated from the continuity equationj=n _e e v _d agrees well with experiment. The rate coefficients for electron impact processes used in the balance equations of O, O₂(a ¹), and O^– were taken from the literature as a function of the reduced electric fieldE/N forE/N=40–80 Td. A reasonable agreement is obtained between the model and the experiment with a set of 10 reactions for the production and destruction of the above-mentioned species     

Flow injection system with in-line Winkler's procedure using 16-way valve and spectrofluorimetric determination of dissolved oxygen in environmental waters

Flow injection spectrofluorimetry with in-line Winklers procedure was developed for the dissolved oxygen (DO) determination. 2-Thionaphthol reacted with iodine produced by Winkler’s method to form fluorescence inactive disulfide compound. To automate the process completely, a 5-channel flow system with a newly designed 16-way valve was assembled. The system consisted of a dispersion coil (DC), a precipitate formation coil (PFC), a precipitate dissolving coil (PDC), and extraction coil (EC). A calibration can be constructed by using a standard iodine solution for dissolved oxygen. The calibration graph was linear over the range 1.2×10⁻⁴∼6.0×10⁻⁴ mol l⁻¹ iodine (1.96∼9.80 mg O l⁻¹)). The relative standard deviation (n=6) was below 0.3% for the 4×10⁻⁴ mol l⁻¹ iodine (6.27 mg O l⁻¹) determination. The sample throughput was 12/h.     

V-Ag-Ni系氧化物的表面氧性质与甲苯选择性氧化的催化性能

制备了一系列Ｖ，Ａｇ，Ｎｉ原子比不同的三元氧化物，应用ＴＰＤ－ＭＳ技术研究了样品表面氧的性质，并测定了甲苯选择性氧化生成苯甲醛的催化活性。实验结果表明，样品表面存在有多种吸附的氧物种。在脱附温度＜９００℃：当Ｎｉ含量对Ａｇ（或Ｖ）的原子比为０．２５或０．５０时，仅在低温处出现有表面的Ｏ＾－和Ｏ＾２＾－两种氧物种的脱附峰；当Ｎｉ含量对Ａｇ（或Ｖ）的原子比增高到＞０．７５时，除有表面的Ｏ＾－和Ｏ＾２＾