【作者】 余光艳；

【导师】 翁文；

【作者基本信息】 漳州师范学院 ， 分析化学， 2011， 硕士

【摘要】 本论文主要包括以下几方面:1.简述了手性物质拆分的重要性、色谱拆分技术和环糊精及其衍生物手性固定相的研究进展。2.分别用3-缩水甘油基丙基三甲氧基硅烷(KH-560)和3-异氰酸丙基三乙氧基硅烷(IPTS)作为偶联剂,合成了β-环糊精键合手性固定相。通过比较,以KH-560为偶联剂合成的β-环糊精键合手性固定相具有键合量大,柱效高,稳定性好等优点,且对盐酸四咪唑以及安息香类化合物具有较好的拆分能力。3.制备了羟丙基-β-环糊精键合手性固定相。比较分析了羟丙基-β-环糊精键合手性固定相和β-环糊精键合手性固定相对氢化安息香、安息香和α-苯乙醇拆分的影响。结果表明,在所有流动相中,氢化安息香和安息香都获得了拆分,而α-苯乙醇未得到拆分。硼酸缓冲盐对氢化安息香拆分的影响很大。结合线性溶剂强度(LSS)模型和计量置换理论(SDM-R)对手性识别机理进行了探讨。4.利用R-1-苯基乙基异氰酸酯对β-环糊精键合固定相进行衍生,合成了不同取代度的R-1-苯基乙基氨基甲酸酯-β-环糊精键合手性固定相。填充后在反相条件下考察对氢化安息香、安息香和α-苯乙醇的手性拆分,探讨了流动相中乙腈含量、缓冲盐类型对手性拆分的影响。结果表明,乙腈作为流动相的有机添加剂时,色谱峰形对称,基线噪音小,柱效高,化合物出峰时间短。氢化安息香获得了基线分离,分离因子可达1.214,而安息香得到了部分分离,α-苯乙醇未能拆开。结合LSS模型和SDM-R模型对手性拆分及色谱保留机理进行了探讨,认为水分子和乙腈分子一起参与了溶质的置换。5.制备了3, 5-二甲基苯基氨基甲酸酯-β-环糊精键合手性固定相。在正相和反相两种模式下,考察了该固定相的手性拆分性能。更多还原

【Abstract】 Following aspects were represented in this study:1. The importance of chiral separation, the main chiral chromatographic separation techniques and the recent development of cyclodextrin-based chiral stationary phases were briefly discussed.2. The synthesis and evaluation ofβ-cyclodextrin (β-CD) bonded chiral stationary phases (CSPs) with 3-glycidoxyproryl-trimethoxysilane (KH-560) or 3-isocyanatopropyltriethoxy- silane (IPTS) for the enantioseparation of various chiral analytes by HPLC were presented. By comparison, the former was deemed to have higher bonded amount, higher enantiosparation ability and better stability.3. A hydroxypropyl-β-cyclodextrin (HP-β-CD) bonded chiral stationary phase (CSP) was prepared. Comparative evaluations of these two CSPs for the enantioseparation of hydrobenzoin, benzoin andα-phenethyl alcohol by HPLC were presented. The effects of buffer composition in the mobile phase on the retention and enantioseparation were investigated. The borate buffer had a significant influence on the retention and enantioseparation of hydrobenzoin. Linear solvent strength (LSS) retention model was used to fit the chromatographic data. Good linearity existed between the common logarithm of retention factor (k) and the volume fraction of organic modifier (φ). Another retention model, stoichiometric displacement theory for retention (SDT-R), was also tried to fit the chromatographic data. The results showed that not only acetonitrile, but also water molecules participated in the displacing process of the solute.4. R-1-Phenylethylcarbamoylatedβ-CD-CSP was prepared from R-1-Phenylethyl isocyanate andβ-cyclodextrin bonded CSP. The obtained CSP was packed by slurrying method. Then enantioseparations of hydrobenzoin, benzoin andα-phenethyl alcohol were evaluated under the reversed mode. The effects of acetonitrile amount and buffer type on the retention and enantioseparation were investigated. Hydrobenzoin obtained baseline separation, and the separation factor could reach 1.214. Benzoin obtained partial enantioseparation, and α-phenethyl alcohol could not be separated wholly. Chiral recognition mechanism was studied with the LSS and SDM-R models. Water molecules and acetonitrile molecules were considered to participate in the displacing process.5. Two 3, 5-dimethylphenyl carbamoylatedβ-cyclodextrin stationary phases were prepared in the different solvents. Then the enantioseparation ability of the CSPs was evaluated under normal-phase or reverse-phase condition by HPLC.更多还原