Mn(Ⅲ)-四芳基卟啉与高碘酸四丁基铵催化羧酸的氧化脱羧:金属、取代基和轴向阴离子配体的影响

锰四芳基卟啉与高碘酸四丁基铵(n-Bu4NIO4)和咪唑(ImH)组合,为羧酸氧化脱羧提供了一个有效的催化剂体系.中位含有吸电子基团和/或大体积芳基的中位-四芳基卟啉使金属卟啉的活性降低.咪唑的存在和金属中心的选择对金属卟啉的催化性能起关键性作用,催化体系中的反离子也有重要影响.Mn(TPP)CN/n-Bu4NIO4/ImH体系的催化活性最好.二苯基乙酸的氧化脱羧可能涉及高价的含氧锰物种与反应物间的相互作用,提出了可能的反应机理.     

CaO对Pt/C催化硬脂酸脱羧反应性能的影响

以硬脂酸(C₁₇H₃₅COOH)脱羧为探针反应,研究了亚临界水中CaO对Pt/C催化脱羧反应性能的影响.实验表明,CaO可以促进脱羧反应,对十七烷选择性没有影响.CaO/硬脂酸物质的量比为0.5时,在330 ℃反应1 h,硬脂酸转化率由未添加CaO时的46.06%提高到66.99%.硬脂酸催化脱羧的最佳反应温度为350 ℃,高于这一温度时,烷基链上碳碳键断裂的副反应增加,导致十七烷选择性降低.亚临界水中硬脂酸脱羧反应符合一级动力学,建立的动力学方程可以较好地预测不同反应条件下十七烷的产率.根据实验结果推测,氧化钙与硬脂酸反应生成硬脂酸钙,催化剂表面的吸附态羧酸盐增加,从而提高了脱羧反应的速率.     

白喉毒素活性中心的量子化学计算与149位突变体的酶学动力学

通过量子化学计算确定白喉毒素分子催化区活性中心的关键氨基酸残基, 评价其取代后的酶活性的改变, 为导向性抗癌药物研究提供高效杀伤细胞工具. 结合目前关于白喉毒素结构与功能的研究状况和量子化学计算结果, 将白喉毒素催化区的第149位酪氨酸突变为苯丙氨酸, 对其酶活性和与底物的结合能力进行评价. Y149位酪氨酸位于正电中心, 起受电子作用, 与野生白喉毒素相比, 苯丙氨酸突变体的酶催化活性增加约一倍, 而与底物结合能力没有变化. Y149是酶活性中心的关键氨基酸残基, 对其取代能够影响蛋白质的生物活性.     

利用L-半胱氨酸自组装膜和混合溶剂协同作用手性拆分DL-谷氨酸

基于L-半胱氨酸(L-Cys)自组装膜(SAMs)在乙醇-水混合溶剂体系中对外消旋谷氨酸展现出的手性识别能力,在含60%(体积分数)乙醇的乙醇-水混合溶剂中,利用L-Cys SAMs对不同手性谷氨酸的选择性结晶作用,通过多次重结晶,分离出纯D-谷氨酸晶体,从而实现了对DL-谷氨酸的手性拆分.     

硫酸钠对胰岛素淀粉样纤维化及其细胞毒性的作用

超过20种人类疾病与蛋白质或者多肽淀粉样纤维化密切相关,探究影响蛋白质的结构稳定性及其淀粉样纤维化的环境条件具有重要意义.本文采用牛胰岛素作为模型蛋白质,研究了Na2SO4对蛋白质淀粉样纤维化的作用.实验结果表明,不同浓度的Na2SO4对胰岛素淀粉样纤维化过程具有不同的影响,低浓度条件下可促进纤维化,较高浓度可明显抑制淀粉样纤维的形成,更高的浓度则使胰岛素形成非纤维状聚集体.ANS荧光分析结果表明,所有浓度的Na2SO4均可减小胰岛素聚集体的表面疏水性,并导致聚集体对细胞膜的损害作用降低.Na2SO4的上述作用可能与其改变蛋白质分子间的静电作用力及溶剂效应有关.     

代谢指纹分析筛选调节金橙黄微小杆菌ATCC49676乳酸产量的代谢物

金橙黄微小杆菌ATCC49676具有巨大的产乳酸潜力. 为筛查可能影响或调节乳酸产量的代谢物, 研究首先通过全因子实验设计优化并确定了最大乳酸产量的培养基组成. 然后, 通过气相色谱质谱联用技术对在基础培养基和优化培养基培养条件下的培养物进行代谢指纹分析. 显著性分析发现, 两种培养条件下胞内的谷氨酸变化最为显著. 当ATCC49676在外加谷氨酸培养时, 乳酸的产量随着谷氨酸浓度的增加而下降. 相对酶定量证实了谷氨酸可降低胞内乳酸脱氢酶含量. 研究证实了代谢指纹分析在探究表型特异性胞内代谢物上的价值以及它在改进工业发酵效率上的潜在作用.     

化学修饰法表征Bacillus smithii T7产耐热菊粉酶催化活性中心的必需氨基酸残基

采用化学修饰法研究了史氏芽胞杆菌Bacillus smithiiT7产耐热菊粉酶活性中心氨基酸残基,发现该酶活性中心存在一个组氨酸残基和一个谷氨酸(或天冬氨酸)残基.修饰前后的酶动力学参数变化表明组氨酸残基参与了底物的结合和催化过程,而谷氨酸(或天冬氨酸)的羧基亲核攻击促使底物分解.邹氏作图法证明酶活性中心存在两个必需的色氨酸残基,荧光和圆二色光谱研究表明色氨酸残基在酶的催化和酶的耐热性方面起重要作用.     

Pd/MgO:一种基于芳香羧酸脱羧与卤代芳烃的交叉偶联反应体系的可循环的多相催化剂(英文)

发展了钯多相催化剂Pd/MgO(0.5 mol%Pd)参与的芳基羧酸脱羧与卤代芳烃的偶联反应体系.在与溴代芳烃甚至氯代芳烃的偶联反应中,缺电子和富电子的芳基羧酸均能进行脱羧,并以高收率得到目标产物.该体系采用的负载型钯多相催化剂制备方法简单易行,可多次循环使用,能便捷地应用于脱羧偶联的有机合成反应.     

甲酸－异丙醇体系分离蛋白质时甲酸的作用研究

 本文在反相高效液相色谱上，用甲酸－异丙醇体系作流动相，研究了甲酸浓度变化对蛋白质分离的影响。结果表明当甲酸浓度增加时，蛋白质的保留时间减小和计量置换模型之值的降低反映了甲酸在这个体系中具有洗脱剂的作用。甲酸使蛋白质在流动相中的溶解度增大，具有离子对试剂的作用。在这个体系中甲酸还具有破坏蛋白质结构的功能。     

甲酸－异丙醇体系分离蛋白质时甲酸的作用研究

本文在反相高效液相色谱上，用甲酸－异丙醇体系作流动相，研究了甲酸浓度变化对蛋白质分离的影响。结果表明当甲酸浓度增加时，蛋白质的保留时间减小和计量置换模型之值的降低反映了甲酸在这个体系中具有洗脱剂的作用。甲酸使蛋白质在流动相中的溶解度增大，具有离子对试剂的作用。在这个体系中甲酸还具有破坏蛋白质结构的功能。     

Permanganate/glycine-initiated polymerization of acrylamide

The kinetics of aqueous polymerization of acrylamide with KMnO₄/glycine redox pair was studied in an atmosphere of nitrogen at 35 ± 0.2°C. The rate of polymerization was found to be first power on monomer, activator, and catalyst concentration. The overall energy of activation was calculated to be 15.66 kcal/deg mol (65.54 kJ/mol) between 30 and 50°C. The effects of various additives (alcohols, neutral salts, complexing agents, addition of catalyst) were studied. The dependence of the polymerization rate on the activator and catalyst concentration was studied in DMF-water mixture also. The molecular weight of polymer was determined at various temperatures of the reaction medium.     

Kinetics of Alkaline Hydrolysis of Quaternary Phosphonium Salts. The Influence of Protic and Aprotic Solvents on the Hydrolysis of Alkyl Phenylphosphonium Salts

Abstract

Third order rate constants have been determined for the alkaline hydrolysis of four series of alkylphenylphosphonium salts and alkylphenylbenzylphosphonium salts at various temperatures in 50%–70% ^v/_v aqueous tetrahydrofuran and 70% ^v/_v aqueous methanol. Thermodynamic activation parameters have been calculated for the reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as revealed by trends in entropy of activation, plays a largely counter-balancing role with respect to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation parameters actually reverse.     

Theoretical and experimental study of optical second harmonic generation in new chiral thiolates salts

The second harmonic generation ability of new chiral thiolate salts is investigated. Aromatic thiolate anions ArS⁻ are expected from semi-empirical calculations with PM3 parameterization of the MNDO Hamiltonian to possess higher intrinsic polarizabilities than the parent neutral thiols ArSH.

Salts associating (hyper)polarizable aromatic thiolate anions with chiral cations, which ensure the noncentrosymmetry necessary to have second-order nonlinear optical effects have been synthesized. The first hyperpolarizabilities, β, of the salts are measured using hyper-Rayleigh scattering technique. Second harmonic generation powder tests (Kurtz and Perry method) carried out on various salts studied, were positive indicating that these materials crystallize in noncentrosymmetric space groups.     

Synthesis, characterisation and antitubercular activities of a series of pyruvate-containing aroylhydrazones and their Cu-complexes

A series of eight pyruvate-based aroylhydrazones was synthesised and characterised. The reaction of the sodium salts of the aroylhydrazones with one equivalent of copper(II) chloride allowed the isolation of neutral 1:1 complexes in which the hydrazones occupy three basal coordination sites of a square pyramidal Cu(II)-centre, with two solvent molecules completing the coordination sphere. Structural details were obtained through the determination of the crystal structures of two representative pyruvate-based aroylhydrazones and three Cu(II) complexes. The evaluation of the antimycobacterial activity of the sodium salts of the eight pryruvate hydrazones showed that the compounds are essentially inactive in their anionic form. The corresponding neutral Cu(II) complexes, however, exhibit promising antimycobacterial activities if tested under high iron (8 μg Fe per mL) conditions. As observed for the related antimycobacterial agent isoniazid, the activity of the complexes decreases if the M. tuberculosis cells are grown under low iron (0.02 μg Fe per mL) conditions. The Cu(II) complexes may thus have a similar mode of action and may require an iron-containing heme-dependent peroxidase for activation.     

Optimization of solid-phase extraction and solid-phase microextraction for the determination of alpha- and beta-endosulfan in water by gas chromatography-electron-capture detection

The electrophoretic behaviour of ionizable and neutral alkylxanthines commonly used in pharmaceutical preparations was studied. The performance of various separation modes including capillary zone electrophoresis (CZE), cyclodextrin electrokinetic chromatography, and micellar electrokinetic chromatography (MEKC) with either sodium dodecyl sulfate (SDS) or bile salts as surfactants, was assessed. CZE in an alkaline medium successfully separates ionizable xanthines and dyphylline. The addition of carboxymethyl-β-cyclodextrin to the background electrolyte allows only partial resolution of neutral xanthines. Based on MEKC results, bile salts exhibit more discrimination ability than SDS to separate similar xanthines. The best results are provided by taurodeoxycholic acid, which ensures baseline separation of xanthines.     

5-Arylideneaminouracils: II. Synthesis of sodium and ammonium salts

In continuation of studies on the design of new 5-arylideneaminouracil derivatives possessing antimicrobial and antiviral properties, the corresponding ammonium and sodium salts were synthesized. The antimicrobial activity of water-soluble salts of substituted aminouracils in vitro was shown to be several times higher than that of parent neutral compounds.

     

磷钨杂多酸及其铯盐上的常温正戊烷异构化反应

制备了一系列用于正戊烷异构化的磷钨杂多酸及其铯盐催化剂,并对它们进行了详细的物性表征。实验结果表明, Cs含量对催化剂的比表面、孔结构、热稳定性和表面酸量有显著的影响。考察了所制备的催化剂上常温下正戊烷异构化反应的活性和选择性。利用催化剂表征结果讨论了活化温度和Cs含量等因素对催化性能的影响。磷钨杂多酸及其铯酸式盐属固体超强酸。根据35℃时正戊烷异构化反应速率常数估测H~3PW~1~2O~4~0和Cs~2~.~2~5H~0~.~7~5PW~1~2O~4~0的酸强度H~0约在-13～-12.4之间。     

Acidic peroxo salts. A new class of initiators for vinyl polymerization. I. Kinetics of polymerization of acrylonitrile initiated by potassium monopersulfate catalyzed by Ag(I)

The kinetics of polymerization of acrylonitrile initiated by KHSO₅ and catalyzed by Ag(I) have been investigated in an aqueous medium over the temperature range of 35–50°C. The rates of polymerization R_p have been calculated and studied with respect to monomer and initiator. The catalytic activity of various metal ions on the initiator has been determined from a comparison of R_p values. The effects of monomer, catalyst, neutral salts, various amines, and inhibitor (hydroquinone) on the initial rate as well as maximum conversion have been studied. From the kinetics results a suitable reaction scheme has been proposed.     

Extraction of phenols using polyurethane membrane

The extraction of various phenols from aqueous and organic solutions using polyurethane membrane has been investigated. The effects of solution concentration, extraction time, surface area, pH, salts, and temperature on extraction were studied. The phenols are extracted as neutral species and the extraction is governed by a combined effect of intra- and intermolecular hydrogen bonding and nonspecific hydrophobic interactions. The ether-type membrane showed higher extraction capability for the phenols than the ester-type polyurethane membrane.     

二甲基硅氧烷甘醇乙酸基共聚物水溶液的表面活性

通过表面张力的测定, 考察了不同无机盐和温度对二甲基硅氧烷甘醇乙酸基共聚物(PSEP)表面活性的影响, 进而研究PSEP在不同介质中胶束形成热力学性质. 研究表明, NaCl、NaBr和CaCl2的存在可提高PSEP的表面活性. 而且, PSEP的胶束化焓变对熵变呈线性相关, 说明存在焓/熵补偿现象.