β-环糊精（苯基氨基甲酸酯）类手性固定相在多种模式下拆分能力的比较

发布时间：2018-12-30 10:34

【摘要】：在过去的二十年间,人们越来越关注在医药、农药、食品和功能材料等领域中手性这个概念。高效液相色谱手性固定相法不仅在分析对映异构体方面发挥着不可替代的作用,更是获得光学纯的单一对映体的最强有力的手段。在有文献记载的手性选择子中,β-环糊精(β-CDs)及其衍生物因其具有独特的空腔结构而被广泛应用于外消旋体的手性拆分。本课题分别以β-环糊精和羟丙基-β-环糊精为原料,4-氯苯基异氰酸酯和苯基异氰酸酯作为衍生试剂,酸化硅胶为载体,使用键合试剂γ-异氰酸酯基丙基三乙氧基硅烷,制得β-CD-CSP1和β-CD-CSP2。在正相、反相、添加酸碱流动相调节剂和极性有机相条件下,利用40余种样品对键合型β-CD CSPs的手性拆分性能进行了评价。结果表明以上两种自制手性填料都具有良好的手性识别能力,对多种具有酸碱性的手性药物都能够达到基线分离,在极性有机相模式下的拆分尝试与常规正、反相起到了一定的互补作用。总体而言在流动相条件一定时,CSP1的拆分能力优于CSP2。以β-环糊精为原料,4-氯苯基异氰酸酯为衍生试剂,合成β-CD衍生物并将其涂敷于新型聚多巴胺-硅胶载体上,制得β-CD-CSP3。在正相条件下,通过调整异丙醇的组分含量和改变醇的种类来考察固定相的拆分能力。β-CD-CSP3对23种样品有良好的手性分离能力。实验表明,影响手性外消旋体的分离度和保留时间的因素不仅有样品本身的结构,流动相中异丙醇的体积含量和不同醇的立体结构亦不容忽视。选用不同空间位阻的醇作为流动相改性剂对扩展手性柱的拆分范围是有一定意义的。
[Abstract]:In the past two decades, more and more attention has been paid to the concept of chirality in the fields of medicine, pesticides, food and functional materials. High performance liquid chromatography (HPLC) chiral stationary phase method not only plays an irreplaceable role in the analysis of enantiomers, but also is the most powerful means to obtain optical pure enantiomers. Among the reported chiral selectors, 尾-cyclodextrin (尾-CDs) and its derivatives have been widely used in the chiral resolution of racemes due to their unique cavity structure. In this paper, 尾 -cyclodextrin and hydroxypropyl- 尾 -cyclodextrin were used as raw materials, 4-chlorophenyl isocyanate and phenyl isocyanate were used as derivatives, and acidified silica gel was used as carrier. 尾-CD-CSP1 and 尾-CD-CSP2. were prepared by using 纬-isocyanate propyl triethoxy silane as a bonding reagent. The chiral resolution properties of bonded 尾-CD CSPs were evaluated by using more than 40 kinds of samples under the conditions of positive phase, reverse phase, acid-base mobile phase modifier and polar organic phase. The results showed that the above two kinds of self-made chiral fillers had good chiral recognition ability and could reach baseline separation for a variety of chiral drugs with acid and alkalinity. The reverse phase plays a complementary role. In general, the resolution ability of CSP1 is better than that of CSP2. when the mobile phase condition is fixed. 尾-CD derivatives were synthesized by using 尾-cyclodextrin as raw material and 4-chlorophenyl isocyanate as derivative reagent. 尾-CD derivatives were coated on a new type of polydopamine silica gel carrier. 尾-CD-CSP3. was synthesized by using 尾-cyclodextrin as raw material and 4-chlorophenyl isocyanate as derivative reagent. The resolution ability of the stationary phase was investigated by adjusting the composition of isopropanol and changing the kinds of alcohols under normal phase conditions. 尾-CD-CSP3 had good chiral separation ability for 23 kinds of samples. The experimental results show that the separation degree and retention time of chiral racemes are affected not only by the structure of the sample itself, but also by the volume content of isopropanol and the solid structure of different alcohols in the mobile phase. The use of alcohol with different steric hindrance as mobile phase modifier has certain significance for expanding the resolution range of chiral column.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.72

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