【作者】 张丽丽； 沈军； 岡本佳男；

【Author】 Lili Zhang;Jun Shen;Yoshio Okamoto;Polymer Materials Research Center, College of Materials Science and Chemical Engineering,Harbin Engineering University;

【机构】 哈尔滨工程大学材料科学与化学工程学院高分子材料研究中心；

【摘要】 高效液相色谱手性固定相法(HPLC-CSP)是目前最高效快速和最受欢迎的手性分离分析方法,其中手性固定相的制备是该技术的关键内容。目前,已经有超过200种手性固定相实现商品化。在已开发的手性固定相中,以多糖的纤维素和直链淀粉基苯基氨基甲酸酯的手性识别性能最为优秀,它们可以对超过90%的外消旋体进行有效的拆分[1,2]。壳聚糖是地球上资源仅次于纤维素的第二类天然生物大分子甲壳素和纤维素的N-脱乙酰化方法获得。除了糖单元2-位上的基团外,壳聚糖其它的结构与甲壳素和纤维素的结构类似,而正是这一结构上的差异,可能导致壳聚糖类衍生物具有不同于纤维素衍生物的手性识别性能[3]。在Yamamoto[4]和Kuse[5]等人的研究基础上,本文通过控制异氰酸酯的用量和反应时间等条件合成了四种壳聚糖甲基苯基氨基甲酸酯-脲基衍生物(Figure.1)。将这些产品涂覆在氨丙基硅胶表面制备成HPLC的手性固定相。这些涂覆型手性固定相依靠于衍生物的结构显示出不同的手性识别能力,并且添加少量极性溶剂作为洗脱液成分能够有效地改进一些対映体的手性拆分能力。更多还原

【Abstract】 High-performance liquid chromatography with chiral stationary phases(HPLC-CSPs) has become the most efficient and popular technique for chiral separation and analysis. The preparation of CSPs with a high chiral recognition ability is the key of this technique, and till now, more than 200 CSPs have been commercialized. Among the CSPs developed by far, polysaccharide-based CSPs,especially those utilizing phenylcarbamate derivatives of cellulose and amylose, are well-known to exhibit high chiral recognition to more than 90% of racemic compounds. On the other hand, chitosan has the similar structure to those of chitin and cellulose, except for the 2-position of glutamine unit. Preparation of chitosan-based CSPs with quite different chiral recognition ability from that of cellulose derivatives may be possible due to this structural difference. In this study,based on the synthesis method reported by Yamamoto, et al.3and Kuse, et al.4four chitosan derivatives with different methylphenylcarbamate-urea structures were synthesized by changing the reaction time and the amount of the isocyanate. The obtained products with different structures were coated on silica gel to be used as CSPs for HPLC. These coated-type CSPs exhibited different recognition abilities depending on the their structures, and could be used with some polar solvents as the eluent, which often efficiently improved the resolution for some racemates.更多还原