对映体制备性分离方法的进展

旋光性化合物越来越引起人们的关注。外消旋体拆分法是获得单一手性化合物的重要途径。本文综述了近年来制备性对映体拆分中发展比较快的手性固定相液相色谱法和膜拆分法。     

高效液相色谱手性固定相法直接拆分外消旋雷诺嗪

在反相以及正相争件下，利用自制的涂敷型纤维素-三（3，5-二甲基苯基氨基甲酸酯）手性固定相直接拆分了外消旋雷诺嗪，并考察了不同流动相对手性拆分的影响，特别是醇类物质对拆分影响。结果表明，醇的立体结构、极性对雷诺嗪的手性拆分均有影响。实验结果显示无论在正相条件下还是在反相条件下，涂敷型纤维素-三（3，5-二甲基苯基氨基甲酸酯）手性固定相均可以很好的拆分外消旋体雷诺嗪。     

羟乙基-β-环糊精作为手性选择剂对手性药物的毛细管电泳拆分

目前市场上销售的手性合成药物,大多数都是以外消旋体形式面市。但是药物外消旋体的两个对映体,只有一个对映体对生物体具有活性和治疗作用,而另一对映体则是非活性或是有毒副作用,所以它们表现出不同的疗效和毒理学性能,因而药物对映体的拆分在药物、临床以及生命科学中具有十     

正反相模式下键合纤维素手性固定相对手性化合物的拆分

在自行合成的键合型纤维素-(3,5-二甲基苯基氨基甲酸酯)(CDMPC-CSP)手性固定相上,在正相模式下对苯偶姻和甲霜灵外消旋体进行了拆分,考察了流动相中醇以及温度在手性识别中对手性分离的影响。同时考察了反相模式下外消旋体的拆分。     

支链淀粉-三(苯基氨基甲酸酯)手性固定相的制备及对外消旋环酮和环醇的直接拆分

在参照文献基础上，合成并制备了支链淀粉－三（苯基氨基甲酸酯）手性固定相，以此手性固定相为基础，利用高效液相色谱首次直接拆分了３种外消旋环酮和一种外消旋环醇，并考察了流动相中异丙醇含量对拆分的影响。     

支链淀粉—三（苯基氨基甲酸酯）手性固定相的制备及对外消旋环酮和环醇的直？

在参照文献基础上上，合成并制备了支链淀粉－三（苯基氨基甲酸酯）手性固定相，以此手性固定相为基础，利用高效液相色谱首次直接拆分了３种外消旋环酮和一种外消旋环醇，并考察了流动相中异丙醇含量对拆分的影响。     

乙酸丁酸纤维素手性固定相的制备及对手性化合物的拆分

将乙酸丁酸纤维素涂敷在硅烷化的硅胶上制备了涂渍型高效液相色谱固定相,在40MPa压力下将所得固定相装入色谱柱.在正相的条件下,对20种手性化合物进行拆分,包括醇类,胺类,氨基酸类手性化合物以及外消旋体药物,有13种手性化合物得到了较好的分离.     

酸性外消旋联苯类药物在纤维素-三(3,5-二甲基苯基氨基甲酸酯)固定相上的直接拆分

 合成了纤维素 三 ( 3,5 二甲基苯基氨基甲酸酯 ) (CDMPC)衍生物 ,并将其涂敷于自制的球形硅胶上 ,制备出用于高效液相色谱手性拆分的固定相。在正相条件下 ,用该固定相对 5种酸性外消旋联苯类药物进行了直接拆分 ,并考察了流动相组成和样品结构对保留和拆分的影响 ,讨论了固定相对样品的作用模式。结果表明 ,在正己烷 /异丙醇流动相体系中加入少量三氟乙酸 ,可对外消旋羧酸类化合物进行有效的手性拆分。     

酸性外消旋联苯类药物在纤维素-三(3,5-二甲基苯基氨基甲酸酯)固定相上的直接拆分

合成了纤维素 三 ( 3,5 二甲基苯基氨基甲酸酯 ) (CDMPC)衍生物 ,并将其涂敷于自制的球形硅胶上 ,制备出用于高效液相色谱手性拆分的固定相。在正相条件下 ,用该固定相对 5种酸性外消旋联苯类药物进行了直接拆分 ,并考察了流动相组成和样品结构对保留和拆分的影响 ,讨论了固定相对样品的作用模式。结果表明 ,在正己烷 /异丙醇流动相体系中加入少量三氟乙酸 ,可对外消旋羧酸类化合物进行有效的手性拆分。     

用高效液相色谱手性固定相法拆分芳香仲醇及芳香乙二 醇类手性化合物

在ChiralcelOD和ChiralcelOJ两支多糖类手性固定相上，以各种不同配比的正己烷-异丙醇为洗脱剂对38种带有不同取代基的芳香仲醇及芳香乙二醇类手性化合物的对映体进行拆分，考察了这些外消旋体在这两支手性柱上的色谱行为。结果表明，扬长避短一柱对这些化合物的拆分能力与化合物取代基的性质和位置有关，这些化合物与手性固定相之间的氢键作用和π-π作用是影响手性拆分的重要原因。拆分方法已应用于潜手性酮不对称还原产物的光学纯度的鉴定，并取得了很好的效果。     

Embedment of Well Dispersed Nickel Nanoparticles in Sulfonate and Benzimidazole Functionalized Poly (Arylene Ether Ketone) Film for the Electrocatalytic Oxidation of Glucose

Stable and well dispersed nickel nanoparticles (NiNPs) were fabricated and embedded in a novel polymer sulfonate and benzimidazole functionalized poly (arylene ether ketone) (S‐BI‐PAEK) film. After drop‐casting the mixed solution of S‐BI‐PAEK and NiSO₄ on glassy carbon electrode (GCE) surface, the uniformly distributed NiNPs were formed and stably embedded in S‐BI‐PAEK film by in‐situ electrochemical reduction method. The embedment and well dispersity of NiNPs in S‐BI‐PAEK film was probably attributed to the strong chelation of sulfonate and benzimidazole functional groups contained in S‐BI‐PAEK toward Ni²⁺ ions, as well as the transferability of Ni²⁺ ions in S‐BI‐PAEK film. The NiNPs/S‐BI‐PAEK composite film was characterized by scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). It exhibited good electrocatalytic activity toward glucose oxidation in 0.1 mol L⁻¹ NaOH solution with high stability. The NiNPs/S‐BI‐PAEK/GCE showed a fast amperometric response with a wide linear range from 1 μM to 4 mM and a low detection limit of 200 nmol L⁻¹ (S/N=3) for the determination of glucose by amperometry at a potential of 0.55 V. Finally it was successfully employed to determine glucose in human serum. Therefore, the novel fabrication method of nickel nanoparticles was promising for the future development of non‐enzymatic glucose sensor.     

Poly(aryl ether ketone) composite membrane as a high‐performance lithium‐ion batteries separator

We described the design and synthesis of a modified poly(aryl ether ketone) bearing phenolphthalein and allyl groups (P‐PAEK) via nucleophilic polycondensation. A new kind of composite separator, crosslinked P‐PAEK/polyvinylidene fluoride (c‐P‐PAEK/PVDF) membrane was successfully prepared using phase separation, phase inversion method, and UV crosslinking technique. As a separator of lithium‐ion battery, c‐P‐PAEK/PVDF membrane demonstrates high porosity and uniform distribution of pores with interconnected pathways. Low thermal shrinkage, distinct shut‐down effect, high liquid electrolyte uptake capacity, and exciting liquid electrolyte wettability of the prepared c‐P‐PAEK/PVDF membrane have been revealed through comprehensive study. Moreover, the c‐P‐PAEK/PVDF membrane was applied to assemble a conventional Li/LiFePO₄ coin cell, which exhibited hopeful cell performance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2714–2721     

Thermal,mechanical and dielectric behaviour of poly(aryl ether ketone) with low melting temperature

New poly(aryl ether ketone)s (PAEKs) with a low melting temperature (relative to PEEK) are of interest in order to simplify the manufacturing of high-performance polymers or composites. In this study, we propose to investigate the physical properties of a new PAEK from Victrex, namely PAEK LM. Combinations of thermal analyses were used as follows: standard and modulated temperature differential scanning calorimetry, dynamic mechanical analysis, dynamic dielectric analysis and guarded hot plate technique. We found that the global mechanical, dielectric and thermal properties are very similar to the PEEK reference. The glass transition temperature was observed in the same range than PEEK (∼ 150 °C) while the melting temperature T_m was measured at 307 °C for PAEK LM which is about 35 °C below the melting temperature of PEEK. The degree of crystallinity of PAEK LM was found to be 27% while for PEEK it is 38%, depending on the processing conditions. This work explored crystalline structure–property relationships to explain the behaviour of PAEK LM.

     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

PPEKK/PEI共混物的相容性及拉伸性能

作为相容体系 ,聚芳醚酮与聚醚酰亚胺 (ＰＥＩ)共混物体系的研究受到了研究者的重视[1～ 4] .由于现在已商品化的聚芳醚酮基本上都是半结晶型聚合物 ,所以有有关无定型聚芳醚酮与聚醚酰亚胺共混物的研究鲜见报道 .含二氮杂萘酮结构聚芳醚酮酮 (ＰＰＥＫＫ)是一种新型耐高温聚合物 ,相比于已经商品化的各种聚芳醚酮 ,ＰＰＥＫＫ除具有优异的综合性能外 ,它最大的特点表现在以下两方面 ,ＰＰＥＫＫ耐热性突出 ,玻璃化转变温度 (Ｔｇ)为 2 4 5℃左右 ,远高于各种商品化的聚芳醚酮 ;ＰＰＥＫＫ为无定型聚合物 ,易溶于多种有机极性溶剂 ,大大的扩…     

STRUCTURE AND PROPERTIES OF PHOSPHROUS-CONTAINING POLY（ARYL ETHER KETONE） WITH BISPHENOL-A MOIETY

A phosphrous-containing poly(aryl ether ketone)was synthesized derived from bisphenol-A and bis[4-(4- fluorobenzoyl)phenyl] phenyl phosphine oxide(FPPPO)by nucleophilic substitution reaction.The structure of the polymer was characterized by FT-IR,~1H-NMR and ~(31)p-NMR.The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature(T_g)of the polymer was 205℃,and the 5% weight loss temperature under nitrogen was 475℃.Good solubility of the polymer in organic solvents,such as N-methylpyrrolidone,dimethylformamide, dimethylacetamide,dimethylsulfoxide and chloroalkanes was observed,flexible film was obtained from the polymer's CH_2Cl_2 solution.The limiting oxygen index(LOI)of the PAEK was 40,which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.     

Glass transition,crystallization, and morphology relationships in miscible poly(aryl ether ketones) and poly(ether imide) blends

The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of T_g over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.     

侧链含萘可交联聚芳醚酮的合成及性能

以4,4'-二羟基苯基正戊酸和4,4'-二氟二苯酮为原料, 二甲基亚砜(DMSO)为溶剂, 采用亲核取代反应合成侧基含羧基的聚芳醚酮均聚物, 进一步与1-萘酚和2-萘酚接枝制备新型含萘可交联聚芳醚酮. 用核磁共振(NMR)、红外光谱(FTIR)、示差扫描量热(DSC)和热重分析(TGA)表征其结构和性能, 含萘聚芳醚酮在常用有机溶剂如N,N-二甲基乙酰胺(DMAc)、DMSO, 四氢呋喃(THF)中有良好的溶解性, 并具有很好的成膜性. DSC测试结果显示, 在170℃热处理2 h的交联聚合物的玻璃化转变温度(T_g)提高40℃. TGA数据显示接枝后的聚合物的5%热失重温度提高40~50℃, 证明其发生交联反应. 结果表明, 新型含萘可交联聚芳醚酮具有热固性树脂的耐溶剂和耐高温特性, 进一步拓宽了聚芳醚酮的应用前景.     

Inelastic deformation of glassy polyaryleneetherketone: Energy accumulation and deformation mechanism

The plastic deformation of glassy non-annealed polyaryleneetherketone (PAEK) was investigated via deformation calorimetry and thermally stimulated recovery of residual strain. Polymer samples were deformed at room temperature under uniaxial compression up to ε_def =–(40?50)% at a rate of 0.04 min^?1. It was found that PAEK behaves in the deformation process similarly to many other glassy polymers: It stores internal energy excess at loading and contains two types of different inelastic strain carriers, namely the delayed elastic (ε_de) and plastic (ε_pl) strain carriers. The maximum level of the accumulated energy in PAEK reaches ≈ 8.3 J/g, which is close to those for glassy polystyrene and polycarbonate. Nearly all the deformation energy stored in PAEK is carried by the delayed-elastic strain. The carriers of plastic strain carry no extra energy or a very small amount of it. The inelastic deformation of glassy PAEK proceeds in two stages. The carriers of ε_de are nucleated at the first stage of the deformation process, and the carriers of ε_pl are nucleated at the second stage. It was shown that, during glassy-polymer loading, the molecular level structures carrying ε_pl never appear by themselves, but appear only as a result of spontaneous reorganization of ε_de. In other words, the plastic deformation appears in PAEK owing to the two-step process. This situation is typical for all glassy polymers.     

Nature of the Ring‐Banded Spherulites in Blends of Aromatic Poly(ether ketone)s

Summary: The ring‐banded spherulites in liquid crystalline poly(aryl ether ketone) (LC‐PAEK) and poly(aryl ether ether ketone) (PEEK) blends with a higher content (>50%) of LC‐PAEK are investigated by polarizing light microscopy (PLM) and atomic force microscopy (AFM) techniques. The results indicate that the light core and rings of the ring‐banded spherulites under PLM are mainly composed of an LC‐PAEK phase, while the dark rings consist of coexisting phases of PEEK and a small amount of LC‐PAEK. The formation of the ring‐banded spherulites is attributable to structural discontinuity caused by a rhythmic radial growth.

PLM image of ring‐banded spherulites in a 70:30 LC‐PAEK/PEEK blend caused by rhythmic growth.