Synthesis of derivatives of ketocarboxylic acids by the decomposition of 1,4-cyclohexanedione monoethyleneketal hydroperoxide

The decomposition of 1,4-dihydroxy-1,4-dihydroperoxycyclohexane under the action of FeSO₄ and the decomposition of 1,4-cyclohexanedione monoethyleneketal hydroperoxide under the action of Fe^II salts in the presence of various ligands or under the action of Cu^II sulfate have been studied. A preparative method for the synthesis of derivatives of diketodicarboxylic or -functionally substituted ketocarboxylic acids from 1,4-cyclohexanedione monoethyleneketal has been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1231–1235, July, 1993.     

A Siloxane Homopolymer with Interacting Ferrocenes as a New Material for the Preparation of Sensors Based on the Detection of Hydrogen Peroxide

The electrochemical characterization of a hydrogen peroxide sensor based on a ferrocene‐containing polymer electrochemically deposited onto a platinum electrode is described. The redox polymer consists of a siloxane‐based homopolymer, with pendant electronically communicated ferrocenyl moieties. The electrodes were used as the transducer for glucose and lactate‐sensing enzyme sensors. Amperometric biosensors were prepared by immobilization of glucose oxidase (Gox) or lactate oxidase (Lox) onto these modified electrodes. The steady‐state amperometric response of the sensors is investigated as a function of the applied potential and substrate concentration. Interferences, sensitivity and stability of the sensors were also studied.     

Habit modification of calcium carbonate in the presence of malic acid

The ability of malic acid to control calcium carbonate morphology has been investigated by aging calcium chloride solution in the presence of urea in a 90 °C bath. Malic acid favors the formation of calcite. A transition from single block to aggregate with special morphology occurs upon increasing malic acid concentration. The morphological development of CaCO₃ crystal obviously depends on the starting pH. CaCO₃ crystal grows from spindle seed to dumbbell in the pH regime from 7 to 11; while it evolves from spindle seed, through peanut, to sphere at pH=11.5. Both dumbbell and sphere consist of rods that are elongated along c-axis and capped with three smooth, well-defined rhombic {1 0 4} faces. A tentative growth mechanism is proposed based on the fractal model suggested by R. Kniep and S. Busch [Angew. Chem. Int. Ed. Engl. 35 (1996) 2624].     

用同步荧光法研究细胞色素C在水溶液中的存在形态

用同步荧光光谱法研究细胞色素Ｃ在水溶液中的存在形态，发现细胞色素Ｃ中色氨酸残基的同步荧光光谱随浓度改变而发生变化，在较稀的溶液中，只观察到色氨酸残基的一个荧光峰，在较浓的溶液中也观察到一个荧光峰，而在这两个浓度之间时，这两个峰共存，可能反映了细胞色素Ｃ在不同浓度溶液中聚集状态的不同，当向存在两个荧光峰的溶液中加入不同浓度的脲，在一定脲浓度范围内，细胞色素Ｃ不发生变性，脲的作用使细胞色素Ｃ的单体浓度     

聚苯基（聚苄基）甲基硅氧烷的氟烷基化反应研究

通过苯基甲基二乙氧基硅烷和苄基甲基二乙氧基硅烷的缩合反应制备了聚苯基甲基和聚苄基甲基硅氧烷。研究了它们与含氟酰基过氧化物间的反应。经酸碱滴定及ＩＲ、＾１Ｈ ＮＭＲ和＾１９Ｆ ＮＭＲ光谱分析确证反应主要生成苯环上氟烷基取代产物。通过测定经氟烷基化后聚硅氧烷处理的玻璃表面的接触角，初步评价了氟烷基化率对其表现性能变化的影响。     

Selective synthesis of di(propen-1-yl)sulfone and di(propen-1-yl)sulfoxide

Convenient selective methods of synthesis of the title compounds, based on oxidation of di(propen-1-yl)sulfide with 30% H₂O₂, have been developed.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 675–679, March, 1992.     

丝网印刷普鲁士蓝修饰电极催化还原测定过氧化氢

制备了普鲁士蓝修饰的丝网印刷过氧化氢传感器,研究了过氧化氢在该修饰电极上的电催化还原特性,考察了有关修饰膜制备和试验条件对传感器性能的影响。结果表明,pH4.0的0.2mol·L-1KH2PO4 K2HPO4缓冲溶液(PBS)中,修饰电极对过氧化氢显示出快速的电化学响应,较高的稳定性、重现性和催化活性,测定的线性范围为1.0×10-5～1.0×10-3mol·L-1,相关系数为0.999,检出限为6.0×10-6mol·L-1(3σ)。电极制作方法简便,可用于实际样品的测定。     

固定化过氧化物酶在过氧化物测定中的应用

采用聚丙烯酰胺凝胶迭氮法固定了辣根过氧化物酶，其作为催化剂用于荧光法测定过氧化物，并探讨了固定酶测定过氧化物的最佳条件，如溶液pH值、温度、反应时间、荧光剂用量等。结果表明：酶固定化后，反应pH值范围变宽，为pH5.0-7.0和7.5-9.0，最佳pH为7.8左右；酶的热稳定性与储存稳定性也都得到提高，在室温下便可用固定酶进行长时间测定，且可较长时间保存。采用固定酶制成的酶柱用于HPLC测定过氧化物，固定酶可反复使用，简化了测定操作，并降低了成本。     

Kinetic determination of trace levels of selenium(IV) and total selenium by Nile Blue A/hydrogen peroxide method

A kinetic method for the determination of selenium(IV) traces is proposed, based on its inhibitory action on the oxidation of Nile Blue A by hydrogen peroxide in phosphate buffer (pH 10.5). A linear dependence was established between the rate of the proposed indicator reaction and selenium concentration in the range 9.5 × 10^–2-1.58 ng cm^–3. The experimental conditions of maximal selenium effect were established. Selenium, determined by the tangent method, was determined at concentrations over the range 0.22–1.26 ng cm^–3, with relative standard deviations up to 4.5%. The reaction rate was followed spectrophotometrically. The effect of foreign ions on the accuracy of this method was also investigated. The method was applied to the determination of selenium in pharmaceutical preparations and wheat flour.     

Oxidative aromatization of Hantzsch 1,4-dihydropyridines by aqueous hydrogen peroxide-acetic acid

A simple method for the oxidative aromatization of Hantzsch 1,4-dihydropyridines to the corresponding pyridines is achieved by using hydrogen peroxide as green oxidant and acetic acid as catalyst in aqueous solution.