The Molecular Structure and Optical Recognition Mechanism for Mono Saccharide Optical Resolution Membrane

对具有糖侧链的聚合物膜，即氯甲基化聚砜[CM-PSF+AGP]、氯甲基化聚苯乙烯[P-CM-St+AGP]、聚甲基丙烯酸甲酯[PMMA+AGP]、氯甲基化聚γ -甲基- l-谷氨酸][CE-PMLG+AGP]进行了实验。1)用差示扫描量热仪（DSC）定量测定了膜中的水化行为，并将其作为冷冻水和未冷冻水的量。2)用DSC法测定单糖在膜中的溶解度，观察其冰点下降。然后，测定了d光和l光异构体的溶解度。3)测定单糖通过膜的通透性。4)确定了d -和l -消旋体混合物的光学分辨分配系数。5)测定了含糖链结构和不含糖链结构的抗致癌物质的渗透性。虽然膜的糖侧链含量相同，但由于聚合物一级结构的不同，膜的含水量（水化比）不同。在水化比为0.53 ~ 0.59的膜中，Wf和Wn占总水化量（Wt）的比例、Wf/Wt和Wn/Wt的比例依次为PMMA-AGP、CE-PMLG+AGP、P-CM-St+AGP。由于单糖对冰冻水和非冰冻水溶解度的独立测定，d -异构体对非冰冻水的溶解度明显较大。因此，可以得出结论，D-异构体在未冻结水中的大溶解度是膜对D-/ l -异构体光学分辨的原因。PMMA+APG对d -和l -葡萄糖外消旋混合物的分离因子约为2.5。P-CM-St+AGP膜对5-FU衍生的抗癌物质FUR的通透性受到膜糖侧链的强烈影响。

The following experiments were carried out for the polymer membranes having saccharide side chain, i. e., chloromethylated polysulfone [CM-PSF+AGP], chloromethylated polystirene [P-CM-St+AGP], poly (methylmethacrylate) [PMMA+AGP], and chloroethylated poly (gamma-methyl-L-glutamate) [CE-PMLG+AGP]. 1)The hydration behavior in the membranes was determined quantiatively using Deferential Scanning Calorimeter (DSC) as an amount of a frozen and un-frozen water. 2)Mono saccharide solubilities into the membranes were determined as observing their freezing point depression by DSC.Then, the solubilities were determined for D-and L-optical isomers. 3)The mono saccharide permeabilities through the membranes were determined. 4)The partition coefficients of the optical resolution were determined for a D-and L-raceme mixture. 5)The permeabilities for anti carcinogenic materials, both with and without a saccharide chain structure, were determined. Although the saccharide side chain contents were same for the membranes, their water content (hydration ratio) of the membranes were different due to the differences of the polymer primary structure. The ratio of Wf and Wn to the total hydration (Wt), Wf/Wt and Wn/Wt, in the membranes having hydration ratio ranging 0.53 to 0.59, were decreasing in order of PMMA-AGP, CE-PMLG+AGP, P-CM-St+AGP.As a result of the independent determination of the solubilities of mono saccharide to the frozen and un-frozen water, the D-isomer solubility into the un-frozen water was notably large. It is, therefore, concluded that the large D-isomer solubility into the un-frozen water is responsible for D-/L-isomer optical resolution by the membranes. The separation factor of D-and L-glucose raceme mixture was about 2.5 for PMMA+APG.The permeability of P-CM-St+AGP membrane to the anti carcinogenic material FUR derived from 5-FU was strongly affected by the saccharide side chain of the membrane.