Dicyanobiphenyl polysioloxane stationary phases for capillary column gas chromatography

Summary The chromatographic performance of newly developed dicyanobiphenyl polysiloxane stationary phases were evaluated and compared with the performance of other polar stationary phases, including the previously reported monocyanobiphenyl polysiloxanes. Due to the unique combination of polarizable biphenyl and polar cyano functionalities in the side chains of the flexible polysiloxane backbone, and by virtue of their mild liquid crystalline properties, the new stationary phases provide excellent resolution of a wide variety of analytes, both polar and nonpolar, in both GC and SFC. They can be easily coated and cross-linked in open tubular columns, and the resultant columns demonstrate excellent efficiency and performance at temperatures up to 280–300°C. The new stationary phases exhibit enhanced selectivities for various types of isomeric compounds.     

载铂铝交联蒙脱土的烷烃芳构化特性──Ⅰ．载铂铝交联蒙脱土对烷烃的择形芳构化作用

对比考察了Ｐｔ／ＫＬ沸石，Ｐｔ／Ａｌ２Ｏ３和载铂铝交联蒙脱土（Ｐｔ／Ａｌ－ＣＬＭ）催化剂对不同碳原子数烷烃的芳构化特性．脉冲微反的评价结果表明：Ｐｔ／Ａｌ－ＣＬＭ比Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＫＬ具有较高的转化ｎ－Ｃ８，ｎ－Ｃ９为其对应芳烃的选择性，在转化ｎ－Ｃ８时，产物中的间、对位二甲苯收率很高，而转化ｎ－Ｃ９时有高的正丙苯收率．采用１２９Ｘｅ－ＮＭＲ、ＸＲＤ和孔分布测定考察了Ｐｔ／Ａｌ－ＣＬＭ和Ｐｔ／ＫＬ、Ｐｔ／Ａｌ２Ｏ３之间孔结构的差异．结果表明：由于ｎ－Ｃ８，ｎ－Ｃ９在反应过程中其过渡态的极限尺寸与Ｐｔ／Ａｌ－ＣＬＭ０．９ｎｍ左右的层间域相匹配，因而它对ｎ－Ｃ８，ｎ－Ｃ９具有择形芳构化作用．     

Synthesis and ion selectivity of macrocyclic metacyclophanes analogous to spherand-type calixarenes

Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs₂CO₃ under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K⁺ selectivity was observed for octaethyl ester4.¹H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Substituent-dependent reactivity in the photodimerization of N-substituted dibenz[b,f]azepines

The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout.     

π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

烯胺酮与烯胺酯的交叉缩合反应及自缩合反应的区域选择性研究

烯胺酮与烯胺酯以(3C+3C)缩合反应形成多取代芳环化合物,具有区域选择性。用波谱和 X-射线衍射技术确定了产物的结构,讨论了反应机理。     

SYNTHESIS, CHARACTERIZATION, METAL-UPTAKE BEHAVIOR OF BIS（BENZIMIDAZOLE） RESIN SUPPORTED ON EPOXIDE POLYMER

The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis（2,3-epoxypropyl）benzene with the primary amine group of 1,3-bis（benzimidazol-2yl）propylamine （BBPAH）. The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2＋, Zn^2＋, Cd^2＋ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ （synthetic molar ratio = 1：1.5） under non-competitive condition were found to be 0.94 mmol/g for Cu^2＋ at pH = 2, 1.3 mmol/g for Cd^2＋ at pH = 1 and 1.75 mmol/g for Zn^2＋ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2＋ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2＋, Zn^2＋, Cd^2＋ and the contrary pH dependence.     

Dependence of the methylene selectivity on the composition of hydro-organic eluents for reversed-phase liquid chromatographic systems with alkyl bonded phases

Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol, water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile phase compositions are similar. However, significant differences in composition between the two phases are observed when binary combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents.     

Phenol methylation over CrPO4 and CrPO4?AlPO4 catalysts

The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO₄ (Cr/P=1) and CrPO₄-AlPO₄ (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol.     

Selectivity optimization for the capillary gas chromatographic analysis of bacterial cellular fatty acids

Summary The importance of selectivity in the capillary gas chromatographic analysis of the cellular fatty acids of micro-organisms is underestimated. The analysis on apolar silicone phases can lead to erratic elucidation of the fatty acid structure. Qualitative errors have been detected in commercially available standards on which computer matching identification techniques are based. Using highly polar capillary columns of the cyanopropyl silicone type, the errors could be elucidated. The exact identification of the hydrolysis products of bacteria is a must for chemotaxonomic studies applying chromatographic techniques. The fatty acid methyl ester profiles can also contain other chemical components which are very important taxonomic markers. Fatty aldehydes, for example, are main components in someClostridium species. Fractionation techniques are described for selective enrichment of fatty aldehydes and hydroxy fatty acids.Dedicated to Prof. Dr. A Liberti on the occasion of his 70th birthday