磺丁基醚-β-环糊精修饰毛细管电色谱拆分地平类药物对映体

采用甲基丙烯酸缩水甘油酯原位聚合物基质, 将磺丁基醚-β-环糊精修饰到毛细管内壁, 制得了一种毛细管电色谱手性柱(SECDP), 并通过红外光谱(IR)和扫描电子显微镜(SEM)表征了其结构. 磺酸基可提供足够稳定的正向电渗流(EOF), 基于磺丁基醚-β-环糊精在固定相和流动相中的协同作用, 通过优化手性添加剂浓度、 pH值、 施加电压、 温度及有机调节剂含量等条件, 利用该开管电色谱柱拆分了氨氯地平、 尼莫地平和尼卡地平等10种地平类手性药物对映体. 优化的流动相组成为20 mmol/L NaH₂PO₄(pH=4.0), 含4.0 mmol/L 磺丁基醚-β-环糊精, 乙腈的体积分数为10%~25%, 施加电压15~25 kV, 温度为15 ℃, 电动进样2 kV×5 s, 检测波长为236 nm. 在上述条件下, 分离度(R_S)可达3.62, 柱效达61011块/m, 分析时间一般为6~15 min. 基于色谱分离数据, 探讨了相关的手性分离机理.     

毛细管区带电泳法测定卷烟中的生物碱

在磷酸缓冲体系中采用毛细管区带电泳法测定卷烟中的生物碱时,检测灵敏度低,分离度差。考察了卷烟中生物碱的 提取条件,分离缓冲溶液的类型、pH值和浓度,卷烟中生物碱测定方法的线性范围、检出限、重现性和回收率。结果发 现,当采用410 mmol/L的酒石酸溶液（pH 2.8）为缓冲体系时,卷烟中生物碱的检测灵敏度和分离度均有明显改善,烟碱 的线性范围为0.06~0.80 mg/L（其他生物碱为0.006~0.10 mg/L）,检出限为0.002~0.01 mg/L,相对标准偏差为2.2%~10%,回收率为87.6%~102%。     

去甲万古霉素键合毛细管电色谱硅胶整体柱的制备及应用

采用溶胶-凝胶技术制备了具有高机械强度和良好通透性的毛细管硅胶整体柱。以国产大环抗生素去甲万古霉素为 手性选择试剂对所制备的整体柱进行化学衍生,成功地制备了去甲万古霉素键合手性硅胶整体柱。在反相和极性有机相模 式下考察了所制备柱的手性识别能力,并详细考察了流动相条件对分离的影响。研究结果表明,β-受体阻滞剂类药物在极 性有机流动相组成为甲醇-乙腈-乙酸-三乙胺(体积比为80∶20∶0.1∶0.1)时,可获得最佳分离。在反相色谱条件下,电 渗流仍主要由整体硅胶基质材料产生,而手性选择试剂的贡献甚小。在反相色谱条件下,多种不同结构类型的手性药物在 所制备的色谱柱上获得了分离。     

脂质体在液相色谱和毛细管电泳中的应用

脂质体具有与细胞膜相似的封闭双层结构,是接近天然生物膜的理想模型。该文综述了脂质体的制备和性质表征方法,固定脂质体色谱用于药物在脂质体膜上的吸收和蛋白质与脂质体膜的相互作用研究,脂质体毛细管电泳在药物分离、蛋白质分离和蛋白质相互作用方面的应用研究。     

有机酸类化感物质的血清蛋白输运机制研究

利用亲和毛细管电泳(Affinity Capillary Electrophoresis,ACE)建立有机酸类化感物质与血清白蛋白(Bovine serum albumin,BSA)结合反应的分析方法。模拟典型有机酸类化感物质与血清白蛋白的结合反应,构建配体(有机酸)-受体(BSA)相互作用体系,采用ACE法研究不同浓度柠檬酸(Citric Acid,CA)/磺基水杨酸(Sulfosalicylic acid,SA)与BSA的结合反应机制并比较不同有机酸作用机理异同。结果表明,有机酸类化感物质CA/SA与BSA发生结合反应形成复合物CABSA和SA-BSA。依据有效淌度变化,理论方程非线性拟合结合反应的表观结合常数KCA-BSA=(1.82±0.11)×104L·mol-1、KSA-BSA=(2.12±0.12)×104L·mol-1,结合反应均为快平衡反应。相关工作阐明了血清蛋白输运有机酸类化感物质的生理作用,为化感物质与生物大分子结合反应的深入研究提供相应理论参考。     

加压毛细管电色谱-激光诱导荧光法检测4种黄曲霉毒素

建立了三氟乙酸( TFA)柱前衍生,加压毛细管电色谱-激光诱导荧光( pCEC-LIF)快速测定黄曲霉毒素B1、B2、G1、G2方法。使用粒径1.8μm的C18毛细管色谱柱,以甲醇-水(45：55, V/V,含0.05%甲酸)为流动相,泵流速为0.05 mL/min,分离电压为15 kV,激发波长为375 nm,发射波长为450 nm,黄曲霉毒素B1, B2, G1, G2达到基线分离。各组分的检出限(S/N=3)分别为0.02,0.016,0.008和0.01μg/L,在0.1~10μg/L,0.1~10μg/L,0.1~3.0μg/L,0.1~3.0μg/L 范围内分别呈线性相关,相关系数 R2分别为0.9999,1.0000,0.9995,0.9997。将本方法应用于花生酱的分析,加标回收率在90.0%~112.0%之间,RSD在0.5%~1.9%之间。     

A new zwitterionic electrochromatographic stationary phase based on poly(3‐chloro‐2‐hydroxypropyl methacrylate‐co‐ethylene dimethacrylate) reactive monolith

A new reactive monolith, poly(3‐chloro‐2‐hydroxypropyl methacrylate‐co‐ethylene dimethacrylate), poly(HPMA‐Cl‐co‐EDMA) was synthesized and post‐functionalized by taurine (2‐aminoethane sulfonic acid) to obtain a zwitterionic stationary phase for capillary electrochromatography. The new stationary phase contained charged groups such as secondary amine providing anodic electroosmotic flow and sulfonic acid groups providing cathodic electroosmotic flow. Hence, the capillary electrochromatography separations with the new zwitterionic monolith were performed with either anodic or cathodic electroosmotic flow. The electrochromatographic separation of alkylbenzenes and phenols was successfully performed. The zwitterionic monolith also allowed the separation of nucleosides using only electrokinetic mode. Theoretical plate numbers up to ~10⁵ plates/m were achieved. Our study is the first report based on poly(HPMA‐Cl‐co‐EDMA) reactive monolith post‐functionalized with a zwitterionic ligand allowing to operate in both anodic and cathodic electroosmotic flow modes. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization of interactions between methoxatin disodium salt and human serum albumin by pressure‐assisted capillary electrophoresis/frontal analysis and circular dichroism spectroscopy

Pressure‐assisted capillary electrophoresis (PACE)/frontal analysis (FA) and circular dichroism spectroscopy were utilized to investigate the interactions between methoxatin disodium salt (PQQ‐2Na) and human serum albumin (HSA). With the PACE/FA method, sodium phosphate buffer solution (67 mm , pH 7.4) was used as the background electrolyte. Hydrodynamic injection at 50 mbar for 50 s and external pressure of 50 mbar were applied. The binding constant and the number of primary binding sites to HSA were obtained under fixed concentration of PQQ‐2Na (100 µm ) and increasing HSA concentration (0~475 µm ). The thermodynamic parameters characterized the main acting forces of hydrophobic and electrostatic interactions. The displacement experiments using phenylbutazone and flurbiprofen as ligand markers suggested that the binding site was the Sudlow site I of the HSA molecule. Circular dichroism spectroscopy was further employed to evaluate the conformation changes of HSA under the interaction of PQQ‐2Na. This work provides comprehensive information for understanding the interactions between PQQ‐2Na and HSA. Copyright © 2014 John Wiley & Sons, Ltd.     

毛细管电泳法测定复方制剂中的硝酸咪康唑

毛细管电泳;高频电导检测;非接触式电导检测;硝酸咪康唑;复方制剂     

中药大黄多糖中单糖组成的毛细管区带电泳分析

以1-苯基-3-甲基-5-吡唑啉酮(PMP)为单糖的衍生化试剂,建立毛细管区带电泳(CZE)同时分离分析8种常见还原单糖PMP衍生物的方法。将该方法用于中药大黄多糖(RTP)的单糖组成及其摩尔比率的测定。结果表明,在pH 10.8和150 mmol/L硼砂缓冲溶液、10kV分离电压、25℃柱温的优化条件下,8种单糖衍生物实现了良好的分离,并证实RTP由阿拉伯糖、葡萄糖、半乳糖、葡萄糖醛酸和半乳糖醛酸5种单糖组成,其摩尔比为8.01∶5.01∶30.30∶1.00∶1.56;样品测定回收率为96.4%~105.3%。该方法灵敏、快速、准确,可用于中药RTP的组成分析。