Pseudoelementverbindungen. VIII. [1]. Zum Komplexbildungsverhalten von potentiell ambidenten Aryl-cyanamidosulfonat-Liganden

Pseudoelement Compounds. VIII. [1]. On the Coordination Behaviour of Potential Ambidentate Aryl-cyanamidosulfonate Ligands Aryl-cyanamidosulfonates form with metal(II) ions (Co, Ni, Cu, Zn, Cd, Hg, Pd, Pt) complexes of the types MX₂, [MX₂L₂], [MX₂L₄] and [MX₄]^2?. The ionic, potentially ambidentate ligand [RSO₂NCN]^? is monodentately coordinated via the terminal nitrogen atom and bidentately in a bridging function through the nitrile group end-on (equatorial) and one of the two sulfonyl oxygen atoms (axial). The new compounds are characterized by means of ir and uv-vis spectroscopy. In the case of [Ni(NCNSO₂C₆H₄Me-4)₂(py)₄] the molecular and crystal structure was determined.     

Separation of peptides and proteins by capillary electrophoresis using acidic buffers containing tetraalkylammonium cations and cyclodextrins

A method for improving separations of peptides and other positively charged species in capillary zone electrophoresis with untreated capillaries using acidic buffers containing tetraalkylammonium cations is described. Tetramethylammonium and tetrabutylammonium cations dynamically modify the capillary surface, leading to a reversal in the direction of the electroosmotic flow. As a result, the adsorption of positively charged peptides and proteins is minimized, and resolution and peak capacity are improved as the migration of cationic analytes is counterbalanced by the electroosmotic flow. The combining effect of reversing electroosmotic flow and cyclodextrin inclusion complexation on separations of closely related peptides and a protein mixture, as well as tryptic digest of hemoglobin is demonstrated.     

Synthesis of Nonracemic 9-(1-Methoxycarbonylethyl)-1,2,3,4-tetrahydrocarbazole

A new approach has been proposed to the synthesis of indole derivatives containing a chiral substituent at the nitrogen atom, comprizing Fischer indolization of phenylhydrazines with a chiral substituent at the -nitrogen atom. The initial hydrazines were obtained by the alkylation (Mitsunobu reaction applying optically active esters of lactic acid) of anilines containing an electron-accepting substituent at the amino group. Subsequent removal of the activating acceptor grouping was realized by nitrosation of the chiral secondary aniline followed by reduction of the corresponding N-nitroso compound.     

磁化作用对汽油动态挥发性影响的研究

用热重（TG）分析和自行设计的原位动态挥发实验，研究了在不同条件下汽油的挥发性，结果表明，磁化空气或磁化汽油都可提高汽油的挥发性，而汽油和空气共同磁化，可更大幅度地提高汽油的挥发性。     

超临界NaCl水溶液的分子动力学模拟

采用分子动力学模拟的方法对超临界NaCl水溶液的微观结构进行了研究.模拟发现在所研究超临界条件下,密度的变化比温度的变化对超临界NaCl水溶液的微观结构影响更大.温度及密度对Cl－ H2O径向分布函数的影响比对Na＋ H2O径向分布函数的影响要大.超临界条件下,各gNa＋－Cl－在0.261 nm处出现峰值,表明Na＋、Cl－之间发生了离子的缔合.超临界条件下,随温度增加,缔合作用增强；随密度增加,缔合作用减弱.本文工作为建立可适用于超临界条件下的电解质热力学模型提供了依据.     

6-氨基青霉烷酸在弱碱性阴离子树脂IRA67上的吸附研究

用静态法研究了6-氨基青霉烷酸在弱碱性阴离子交换树脂IRA67上的吸附行为．在溶液pH为8．0，6-APA起始浓度介子3.00mg／m1-20．00mg／ml条件下，测定了25℃时IRA67树脂的静态交换动力学曲线、吸附等温线，并求得了IRA67树脂的平衡速率常数及吸附等温线方程．分别用Langmuir型和Frendlich型方程对IRA67树脂吸附等温线进行线性回归拟合，结果表明，6-APA在IRA67树脂上的吸附更符合Langmuir型吸附．     

Thermus thermophilus 木糖异构酶与木糖醇的分子对接及模型分析

在1BXB结构基础上, 通过分子对接方法构建木糖异构酶与抑制剂木糖醇的复合物模型, 为合理设计解除木糖醇对木糖异构酶的抑制及进一步揭示木糖醇对该酶抑制机理提供参考.     

Studies on Aggregation Interaction between Reduced Denatured Egg White Lysozymes during Refolding Procedure in Urea Solution

The aggregation interaction between reduced-denatured egg white lysozymes during refolding procedure in urea solution was studied by means of reducing and non-reducing protein electrophoreses. Results of non-reducing sodium dodecyl sulphate polyacrylamide gel electrophoresis （SDS-PAGE） of the supernatant and aggregate precipitate formed in refolding process show that except being refolded to native egg white lysozymes, the reduced-denatured lysozymes can also form the aggregates with molecular weights （MW） being separately about 30.0 and 35.0 kD, while the reducing SDS-PAGE and the refolding results in the presence of sodium dodecyl sulphate show that these aggregates are formed chiefly through the misconnection of disulfide bonds between the reduced-denatured lysozymes, and the aggregate precipitates are formed through the non-covalent interactions between the aggregates with molecular weight being about 30.0 kD. From the results of electrophoresis and size-exclusion chromatographic analyses, it can be inferred that the aggregates with molecular weights being about 30.0 and 35.0 kD are bi-molecular and tri-molecular egg white lysozyme aggregates, respectively. And finally, a suggested refolding mechanism of reduced-denatured egg white lysozymes in urea solution was presented.     

Improved quantification limits in chiral capillary electrochromatography by peak compression effects

The peak compression effect has been applied to improve quantification limits in chiral capillary electrochromatography (CEC). A stationary phase based on the chiral selector vancomycin (Chirobiotic V) was used for separations of the enantiomers of mianserin. By adding solvents with a low dielectric constant, e.g. 2-propanol or tetrahydrofuran, to the sample solution, peak compression could be induced. The plate numbers for the minor enantiomer increased from approximately 100,000 to 1.4-1.6 million plates/m, when the composition of the mobile phase was adjusted so that the analyte eluted within either one of two system zones originating from the sample solution. A 10-fold improvement in the quantification limit for the minor enantiomer was obtained compared to elution under non-focused conditions.     

Asymmetric enolate alkylation via templation with chiral synthetic receptors

C₃-Symmetric chiral receptors have been developed for enantioselective alkylation of sodium enolates of active methylene compounds. It has been demonstrated that a 1:1 binding complex forms between these receptors and sodium enolates in THF-d₈/CD₃CN by ¹H NMR titration experiments. Moderate enantiomeric enrichment of the benzylation product of 2-acetylcyclohexanone has been demonstrated using this strategy. Templation of enolate alkylation by synthetic receptors represents a new approach to asymmetric induction.