高效液相色谱手性固定相法拆分金属簇合物

在正相条件下,ChiralcelR○OD手性色谱柱上,首次直接拆分了3种外消旋过渡金属簇合物,考察了手性化合物结构以及流动相中的醇在手性识别过程中对手性拆分的影响。     

Preparation of new poly(amide–imide)s with chiral architectures via direct polyamidation reaction

N‐trimellitylimido‐L ‐methionine ( 3 ) was prepared by reaction of trimellitic anhydride ( 1 ) with ‐L ‐methionine ( 2 ) in acetic acid solution at refluxing temperature. This diacid was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐methionine diacid chloride ( 4 ) was obtained in quantitative yield. The resulting diacid chloride was reacted with p‐aminobenzoic acid in dry acetone and bis(p‐aminobenzoic acid)‐N‐trimellitylimido‐L ‐methionine ( 5 ) was obtained as a novel optically active amide–imide diacid monomer in high yield. The direct polycondensation of amide–imide diacid monomer 5 with several aromatic diamines was carried out with tosyl chloride (TsCl)/pyridine (Py)/dimetheylformamide (DMF) system. The resulting thermally stable poly(amide–imide)s (PAIs) were obtained in good yields and inherent viscosities ranging between 0.24 and 0.46 dL g^?1 and were characterized with FTIR, ¹H NMR, CHN, and TGA techniques. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1248–1254, 2007     

Effects of Surface Relaxation on Enantiospecific Adsorption on Naturally Chiral Pt Surfaces

Many high Miller index metals surfaces are naturally chiral, offering opportunities for performing enantiospecific chemistry. Previous theoretical treatments of adsorption on these surfaces have used surfaces truncated from bulk crystals. This paper examines the effect of surface relaxation on enantiospecific adsorption on chiral Pt surfaces by using relaxed surface structures determined using density functional theory.     

纤维素衍生化手性固定相的制备和对噻吗洛尔拆分

用超声方法合成了三(3,5-二硝基苯甲酰基)纤维素(CTNB)、三(4-溴苯甲酰基)纤维素(CTBB)、三(苯甲酰基)纤维素(CTB)、三(4-甲基苯甲酰基)纤维素(CTMB)、三(4-硝基苯甲酰基)纤维素(CTPB).将此类衍生化纤维素作为薄层色谱的手性固定相,结合展开剂的优化,对噻吗洛尔对映体进行拆分研究,并对衍生化取代基对拆分效果的影响以及对映体在手性固定相上的拆分机理进行了详细的探讨.     

Application of the Stepwise-Regression Method in Calculating High-Temperature Ceramic Phases

Phase calculation for nonequilibrium multicomponent systems is attempted using the stepwise-regression method. The experimental data (the amount and composition of glassy phase in a system of Al₂O₃–SiO₂ ceramics as functions of the state of the original materials, the firing temperature, and the composition of the samples) are treated by the proposed method. The equations obtained are accurate in estimating the amount and composition of glassy phases in the system, showing that the stepwise-regression method is effective in phase calculation.     

MCM-41 Heterogenized Chiral Amines as Base Catalysts for Enantioselective Michael Reaction

Cinchonidine and cinchonine have been grafted onto pure silica MCM-41. It has been shown that both supported alkaloids are active catalysts for the Michael addition of ethyl 2-oxocyclopentanecarboxylate and methyl vinyl ketone, anchored cinchonidine being more active and enantioselective than anchored cinchonine. The study of the influence of the polarity of the solvent and reaction temperature on the optical induction shows that there is not a direct correlation between solvent polarity and enantioselectivity, and the maximum optical yield was obtained between 278 and 273 K.     

Status of aqueous surfactant phase science

Recent phase studies of several surfactant-water systems, using new or refined methods, have revealed significant errors in earlier phase diagrams. These diagrams had been determined largely using methods based on the isoplethal phase studies principle. This principle has inherent limitations which do not exist in isothermal methods. Isothermal nuclear magnetic resonance and refined calorimetric methods have been extensively used in recent surfactant phase studies. Methods based on the new lyotrope gradient (swelling) principle show great promise as a means of improving the efficiency and quality of surfactant phase studies.     

新型离子液体气相色谱固定相研究

合成了一种用作新型气相色谱固定相的室温离子液体[C7H17NO] [(CF3SO2)2N]-,并考察其色谱性能。该固定相具有较好的成膜性、较高的柱效、较强的极性,对正构烷烃、芳香族化合物以及一些位置异构体具有良好的分离效果。     

ON GENERALIZED FRACTIONAL PROCESSES

Abstract. A class of stationary long-memory processes is proposed which is an extension of the fractional autoregressive moving-average (FARMA) model. The FARMA model is limited by the fact that it does not allow data with persistent cyclic (or seasonal) behavior to be considered. Our extension, which includes the FARMA model as a special case, makes use of the properties of the generating function of the Gegenbauer polynomials, and we refer to these models as Gegenbauer autoregressive moving-average (GARMA) models. While the FARMA model has a peak in the spectrum at f = 0, the GARMA process can model long-term periodic behavior for any frequency 0 f 0.5. Properties of the GARMA process are examined and techniques for generation of realizations, model identification and parameter estimation are proposed. The use of the GARMA model is illustrated through simulated examples as well as with classical sunspot data.     

Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene

New tetradentate chelates of bis-Schiff bases were synthesized and then these chiral salen ligands were immobilized over mesoporous MCM-41 by using the ion-exchange method. The efficiency of the chiral catalyst was examined in the asymmetric epoxidation of styrene. Chiral Mn(salen) complexes immobilized onto mesoporous MCM-41 were stable during the reaction without any leaching and exhibited relatively high enantioselectivity for epoxidation as compared with homogeneous complexes. This revised version was published online in August 2006 with corrections to the Cover Date.