手性流动相添加剂法拆分苯磺酸氨氯地平对映体

目的用磺丁基醚-β-环糊精(SBE-β-CD)作为手性选择剂,建立RP-HPLC法分离苯磺酸氨氯地平对映体。方法使用Hypersil BDS C8色谱柱(150 mm×4.6 mm,5μm),流动相为25 mmol.L-1SBE-β-CD水溶液(pH值2.5)-甲醇(体积比55∶45),流速0.8 mL.min-1,检测波长为238 nm,进样量为20μL,柱温20℃。考察了环糊精种类、SBE-β-CD浓度、有机改性剂的种类和浓度、水相pH值、柱温、流速等因素对对映体分离的影响。结果在优化的色谱条件下,苯磺酸氨氯地平对映体达到完全分离,分离度R为1.6,分离因子α为1.1。结论方法简单、经济,为苯磺酸氨氯地平对映体的拆分提供了新的方法。     

α_1-酸性糖蛋白柱分离甲溴后马托品溴化物及硫酸阿托品对映体

目的以α1-酸性糖蛋白(α1-AGP)为固定相,建立甲溴后马托品溴化物及硫酸阿托品的对映体拆分方法。方法采用HPLC法分离。考察流动相中有机改性剂种类和比例、pH值、缓冲盐溶液的浓度、流速、柱温等对对映体分离的影响。结果甲溴后马托品溴化物最佳色谱条件:流动相为10 mmol.L-1醋酸铵(pH值5.5)缓冲液,流速为0.5 mL.min-1,室温;硫酸阿托品最佳色谱条件:流动相为10 mmol.L-1醋酸铵(pH值6.5)缓冲液,流速为0.5 mL.min-1,室温。结论甲溴后马托品溴化物及硫酸阿托品对映体可以在α1-AGP固定相上得到完全分离。     

Synthesis of Polyanilines Bearing Optically Active Substituents

Summary: Optically active polyanilines were prepared by an interfacial polymerization with (NH₄)₂S₂O₈ in a water/perchloric acid/chloroform system. The pristine polymer obtained in this way is in the oxidized (doped) form. The polymers display the mirror‐image Cotton effect. The doping process in solution allows a change in the circular dichroism of the polymer. The procedure has great potential in the improved preparation of durable optoelectrical devices based on the good film‐forming properties of chiral polymers.

CD spectra of R ‐ P2 (solid line) and S ‐ P2 (dashed line) in 4.0 × 10^?4 M THF solution.     

Synthesis of Optically Active Photoresponsive Multifunctional Polymer Containing the Side‐Chain Azocarbazole Chromophore

Summary: A new optically active photochromic polymethacrylate containing the carbazole moiety, deriving from the chiral monomer (S)‐(4‐cyanophenyl)‐(3‐{9‐[2‐(2‐methacryloyloxypropanoyloxy)ethyl]carbazolyl})diazene [(S)‐ MLECA ] has been prepared and fully characterized with the aim to obtain a multifunctional derivative possessing at the same time chemical moieties suitable to NLO and optical storage, to chiroptical switches, and to photorefractive and photoconductive applications. Spectroscopic, thermal and chiroptical characterizations clearly indicate the occurrence of dipolar interactions between chromophores and the presence of an ordered chiral conformation of one prevailing helical handedness, at least for chain segments of the macromolecules.

Structure of poly[(S)‐ MLECA ].     

高效液相色谱法拆分奥硝唑对映体

目的：建立奥硝唑对映体的手性拆分方法,并用于测定左旋奥硝唑原料和制剂中的右旋异构体。方法：采用高效液相色谱法,Ultron ES OVM手性柱(150mm×4.6mm,5μm,Agilent),通过考察影响分离的一些因素,最终确定拆分的最佳条件,即以20mmol[DK]?L-1醋酸钠(pH 5.4)-乙腈（98[DK]∶2）为流动相,流速为0.6mL[DK]?min-1,检测波长为320nm。结果：在此条件下,奥硝唑对映体之间的分离度为2.5,奥硝唑对映体最小检出浓度为0.1μg[DK]?mL-1。结论：所建立的方法简便、快速,可用于分离和测定左旋奥硝唑原料和制剂中的右旋异构体。     

*研究快报* 通过Bergman环化聚合反应合成侧链含有苯丙氨酸的手性聚合物

以直径为140 mm水力旋流器作为研究对象,采用计算流体力学（CFD）技术对旋流器内部流场进行数值模拟,并对所建立的模型进行激光粒子图像测速（PIV）实验验证。基于数值模拟和实验结果,分析了旋流器内部压力、切向速度、轴向速度和径向速度的分布。利用PIV技术对旋流器内部流场进行测量,考察了不同入口速度下旋流器圆柱段区域瞬态速度场。通过对比数值计算与测试结果表明：CFD模拟可以有效预测水力旋流器内部流场分布,帮助探索旋流器内的流动状态和分离机理;利用PIV技术测量旋流器内部流动特性和速度分布,其测量结果与CFD计算结果吻合良好,验证了数值模型的准确性。     

黏蛋白质手性合成多肽疫苗对BALB/c小鼠CTL的诱导作用

目的：研究由具有局部手性特征的合成多肽D-MUC1和小鼠血清白蛋白(mouse serum albumin,MSA)构成的多肽疫苗对小鼠MUCl特异性CTL的诱导作用．方法：用固相合成法合成含有D-Ser的多肽D-MUC1,纯化后与载体蛋白MSA偶联,分别以细胞因子重组人粒细胞-巨噬细胞集落刺激因子(GM-CSF)和胸腺肽(TP)为佐剂,免疫BALB／c小鼠,测定淋巴细胞增殖活性、MUCl特异性CTL杀伤活性．结果：合成肽经HPLC纯化后,质谱分析证明目的肽的分子量与理论值相符;D-MUCl多肽疫苗对BALB／c小鼠淋巴细胞增殖有明显的促进作用;D-MUCl多肽疫苗诱导出的特异性CTL杀伤MUCl阳性肿瘤细胞GZ．A5．3H．4．结论：研究结果表明D．MUCl合成肽疫苗可以在小鼠体内诱导出MUC1特异性CTL,为具有局部手性特征的MUCl合成肽疫苗进行肿瘤免疫治疗提供了实验依据。     

Synthesis and Fluorescence Properties of Chiral Near‐Infrared Emissive Polymers Incorporating BODIPY Derivatives and (S)‐Binaphthyl

A new series of π‐conjugated chiroptical polymers consisting of styryl BODIPYs moieties and (S)‐binaphthyl units has been firstly synthesized via Sonogashira polymerization. The resulting polymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography (GPC), UV–Vis absorption spectroscopy, cyclic voltammetry (CV), circular dichroism (CD), and density functional theory (DFT) calculations. The chiral polymers have moderate molecular weights, high solubility in commonly solvents and stable chiroptical conformation. And more importantly, the four chiral polymers can exhibit near‐infrared (NIR) emissive and good anisotropic fluorescence. We anticipate these chiral NIR polymers will be useful in biological measurements and cellular imaging where NIR emission is beneficial.     

Aqueous Emulsion Polymerization of Substituted Acetylenes: Effects of Organic Solvent and Analysis of Blue Shifts and Emulsion Polymerization Mechanism

A series of optically active nanoparticles composed of helical substituted polyacetylene is prepared via emulsion polymerization. A specific organic solvent is required for solid substituted acetylene monomers to undergo emulsion polymerization. The effects of this organic solvent are investigated. Its amount is found to be decisive for obtaining stable polymer emulsions. The helical conformations of the substituted polyacetylenes in nanoparticle state are identified with the help of CD and UV‐vis spectra. A blue shift occurs in CD and UV‐vis spectra of some of the polyacetylene emulsions. The underlying driving force for the blue shift is discussed, and an emulsion polymerization mechanism is proposed.