Chiral separations by host-guest complexation with cyclodextrin and crown ether in capillary zone electrophoresis

Summary Capillary zone electrophoresis using cyclodextrins and a chiral crown ether as buffer constituents was studied for the enantiomeric separation of drugs and amino acids. Based on results obtained from separation of racemic -amino acids both chiral selectors are compared with respect to resolution, efficiency and retention time. For (±)-Quinagolide effects of buffer composition and temperature are examined using -cyclodextrin as chiral agent. Optimum conditions were pH 2.5 at 30 mmol L^–1 -cyclodextrin. A linear dependence of retention on -cyclodextrin concentration allowed calculation of formation constants of the host-guest complexes. Buffer concentration and temperature also influence resolution. The application of a chiral crown ether to the separation of optical isomers in capillary zone electrophoresis is described for the first time. Chiral recognition of solutes depends on the formation of protonated alkyl amines and separation is attributed to the formation of diastereomeric host-guest complexes with different interactions for each enantiomer. The effects of crown ether concentration on resolution are presented.     

毛细管电泳-柱端安培检测法用于抗癌药物2-氨基-6-巯基嘌呤和8-氮杂鸟嘌呤的研究

采用毛细管电泳-安培检测法建立一种简单、快速、有效的同时分析抗癌药物2-氨基-6-巯基嘌呤和8-氮杂鸟嘌呤的新方法.在长50 cm、内径为25μm的未涂层毛细管中,采用20 mmol/L磷酸盐(pH为7.0)缓冲液作为运行液,当分离电压为21 kV时,两组分在12 min内达到基线分离.在上述最佳分离条件下,当电极电位为1.050V、进样时间为10 s时,2-氨基-6-巯基嘌呤和8-氮杂鸟嘌呤的峰电流和浓度之间呈良好的线性关系,其相关系数分别为0.999 20、.999 0,检测限分别为3.0×10-7、2.0×10-7mol/L.7次重复实验2-氨基-6-巯基嘌呤和8-氮杂鸟嘌呤的日间峰电流RSD分别为2.44%3、.46%.利用该法检测了牛血清蛋白中的2-氨基-6-巯基嘌呤和8-氮杂鸟嘌呤,回收率分别为100%-113%,93.0-102%.     

SPS法研究ZnTPP对TiO_2的光谱敏化

本文利用表面光电压谱(Surface Photovohage spectroscopy,简称SPS)研究了ZnTPP对TiO_2粉末的光谱敏化,发现用ZnTPP修饰后的TiO_2(金红石和锐钛矿)粉末在可见区420、550和590nm附近有三个光伏响应带,它们分别对应于ZnTPP的Soret、Q(1,0)和Q(0,0)带。经过严格的实验和分析,证明这三个带是由ZnTPP对TiO_2的敏化光电压引起的,而不是ZnTPP自身的光伏响应。在敏化效果上,亚稳的锐钛矿优于金红石。同时,我们对这种光敏表面的光诱导电荷转移机制和SPS作为一种研究光谱敏化方法的可行性进行了讨论。     

高效毛细管电泳的电导检测和紫外光度检测研究

本文自制商效毛细管电泳装置.研究了毛细管区带电泳电导检测和毛细管胶束电动色谱紫外光度检测。在电导检测中,制作铂丝微电导池,并由用电池隔膜制作的导电接口连接电泳毛细管和电导池,高压被有效隔离,实现柱后电导检测,用内径200μm、长70cm(到接口)石英毛细管在10kV电压下分离检测Li~-、Na~-、K~-。在电动色谱中将高效液相色谱仪与高压电源组成电泳装置,用内径100μm,长50cm(到检测器)石英毛细管和SDS胶束溶液在14kV电压下分离检测电中性化合物。     

Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

毛细管电泳法快速分离和检测肠毒性大肠杆菌

 建立了快速分离和检测引起仔猪腹泻的肠毒性大肠杆菌K88、K99和 987P细菌细胞的毛细管区带电泳方法 ,并进行了腹泻仔猪粪便中肠毒性大肠杆菌的应用检测分析。结果表明 ,在电泳缓冲液为 0 0 5mol/LNa2 CO3 NaHCO3(pH 9 9)、分离电压为 1 4 1kV、检测波长为 2 1 0nm的电泳条件下 ,E coliK88、K99和 987P的细胞分别具有单一、稳定的特征谱峰 ,其保留时间的相对标准偏差RSD≤ 0 9% ;在确定的实验条件下 ,实现了腹泻仔猪粪便中肠毒性大肠杆菌的快速检测分析 ,发现将出生 5d～ 6d的腹泻仔猪粪便引入培养基中增殖后主要检出K88。     

Capillary zone electrophoresis for analysis of phytochelatins and other thiol peptides in complex biological samples derivatized with monobromobimane

A new method to improve the analysis of phytochelatins and their precursors (cysteine, gamma-Glu-Cys, and glutathione) derivatized with monobromobimane (mBrB) in complex biological samples by capillary zone electrophoresis is described. The effects of the background electrolyte pH, concentration, and different organic additives (acetonitrile, methanol, and trifluoroethanol) on the separation were studied to achieve optimum resolution and number of theoretical plates of the analyzed compounds in the electropherograms. Optimum separation of the thiol peptides was obtained with 150 mM phosphate buffer at pH 1.60. Separation efficiency was improved when 2.5% v/v methanol was added to the background electrolyte. The electrophoretic conditions were 13 kV and capillary dimensions with 30 cm length from the inlet to the detector (38 cm total length) and 50 microm inner diameter. The injection was by pressure at 50 mbar for 17 s. Under these conditions, the separation between desglycyl-peptides and phytochelatins was also achieved. We also describe the optimum conditions for the derivatization of biological samples with mBrB to increase electrophoretic sensitivity and number of theoretical plates. The improved method was shown to be simple, reproducible, selective, and accurate in measuring thiol peptides in complex biological samples, the detection limit being 2.5 microM glutathione at a wavelength of 390 nm.     

Determination of inosine 5′-monophosphate and guanosine 5′-monophosphate in pig feed by capillary zone electrophoresis

A capillary zone clectrophoresis method was developed for the determination of IMP and GIMP, commonly used as flavor enhancers in poultry feed, in a real sample of complex composition. A baseline separation of inosine 5′-monophosphate and guanosine 5′-monophosphate was achieved within 10 min and the other components in the sample did not interfere with the separation. Quantitative results obtained from pig feed samples are presented. The separation conditions and experimental reproducibility are also discussed.     

Dynamic Interfacial Tension Behavior of Water/Oil Systems Containing In situ-Formed Surfactants

Time-dependent interfacial tension (IFT) has been investigated for an interfacially reactive immiscible system composed of model-acidified oil and alkaline water. The acidified oil was composed of either lauric acid or linoleic acid dissolved in n-dodecane. Drop volume tensiometry was employed to measure the interfacial tension between the two phases. In the case of lauric acid, the IFT value was found to decrease sharply with increasing alkali concentration, even at low drop formation times. In the case of linoleic acid, the IFT decrease with the drop formation time was more gradual, especially at low alkali concentration. The rate of formation of the interfacial area was also found to be dependent on alkali concentration.     

表面能与晶体生长/溶解动力学研究的新动向

界面现象使物质在结晶过程中出现了临界现象.但最近的研究指出在物质溶解过程中,在表面能量的控制下也存在着临界现象以及尺寸效应.实验发现,当晶体自身小到一 定的程度时(通常在纳米尺度上并和临界蚀坑的大小相近),在溶解过程中其速度会自发降 低,反应被抑制乃至停止.尽管在热力学上表面能的因素可以赋予小颗粒晶体较大的溶解度 ,但表面能却也能通过对临界条件的控制而使这些微粒在动力学上不被溶解.这个发现不仅 解决了纳米颗粒在水溶液中稳定性的问题,而且还从动力学的角度解释了生物矿物选择纳米 尺度作为其基本构成单元的原因.由于表面能和晶体生长/溶解的动力学有着密切的关系, 我们可以通过对表面能的调节来修改它们的动力学速度和晶体的形貌.反过来,也可以用动力学的方法来测定表面能及表面吸附/脱附常数等.相对于常规的界面研究手段,通过生 长和溶解动力学途径所得的数据有着很好的可靠性及重复性.我们认为,晶体生长和溶解的 动力学和表面能的研究相结合,不仅为界面研究提供了新的思路和方法,而且也会推动晶体生长和材料科学的发展.