Kodama Shuji, Aizawa Sen-Ichi, Taga Atsushi, Yamashita Tomohisa, Yamamoto Atsushi
Toyama Institute of Health, Toyama, Japan.
Electrophoresis. 2006 Dec;27(23):4730-4. doi: 10.1002/elps.200600140.
Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors.
六种还原性单糖(甘露糖、半乳糖、岩藻糖、葡萄糖、木糖和阿拉伯糖)用1-苯基-3-甲基-5-吡唑啉酮(PMP)进行衍生化,并采用硼酸根阴离子作为手性选择剂的中心离子、(S)-3-氨基-1,2-丙二醇(SAP)作为手性选择剂配体的配体交换毛细管电泳法研究了这些外消旋PMP-单糖的手性拆分。PMP-甘露糖、PMP-半乳糖和PMP-岩藻糖成功实现了对映体分离。降低毛细管温度提高了PMP-甘露糖体系的分离度,但降低了PMP-半乳糖和PMP-岩藻糖体系的分离度。在PMP-甘露糖体系中,pH 8.9时获得最大分离度,而在PMP-半乳糖和PMP-岩藻糖体系中,分离度随pH逐渐增加。预期在毛细管电泳实验中会形成硼酸根与SAP和PMP-单糖的三元配合物,通过半经验分子轨道计算得到硼酸非对映异构体的优化结构,以讨论非对映异构体的结构差异与对映体拆分行为的关系。