Mayes A G, Andersson L I, Mosbach K
Chemical Center, University of Lund, Sweden.
Anal Biochem. 1994 Nov 1;222(2):483-8. doi: 10.1006/abio.1994.1521.
Noncovalent molecular imprinting of sugar compounds in ethylene glycol dimethacrylate-methacrylic acid copolymers yielded materials containing highly selective sugar binding sites. Investigation of a range of polymers demonstrated that the resulting polymer imprints have a high degree of both anomeric and epimeric selectivity favoring the original print molecule. In HPLC assays, a polymer imprinted using p-nitrophenyl-alpha-D-galactoside could separate the alpha and beta anomers of the same compound with near baseline resolution. A polymer imprinted using p-nitrophenyl-beta-D-galactoside showed similar results but with the beta anomers retained longer as expected. Anomeric discrimination of closely related sugars was also possible, with the degree of separation depending on the structural resemblance to the print molecule. Similarly, a polymer imprinted with p-nitrophenyl-alpha-L-fucoside could separate alpha/beta mixtures of p-nitrophenyl-L-fucoside with baseline resolution. Using radioligand displacement assays a polymer imprinted using octyl-alpha-D-glucoside was shown to bind methyl-alpha-D-glucoside with a 40-fold higher affinity than that for the beta-anomer. The epimeric selectivity was even more impressive: methyl-alpha-D-mannoside and methyl-alpha-D-galactoside had 130- and 240-fold lower affinity, respectively, than methyl-alpha-D-glucoside. The results are discussed in relation to possible uses of such polymers in separation and analysis.
在乙二醇二甲基丙烯酸酯 - 甲基丙烯酸共聚物中对糖类化合物进行非共价分子印迹，得到了含有高度选择性糖结合位点的材料。对一系列聚合物的研究表明，所得的聚合物印迹对异头物和差向异构体都具有高度选择性，有利于原始印迹分子。在高效液相色谱分析中，用对硝基苯基 - α - D - 半乳糖苷印迹的聚合物能够以接近基线分离度分离同一化合物的α和β异头物。用对硝基苯基 - β - D - 半乳糖苷印迹的聚合物显示出类似的结果，但正如预期的那样，β异头物保留时间更长。对密切相关糖类的异头物鉴别也是可能的，分离程度取决于与印迹分子的结构相似性。同样，用对硝基苯基 - α - L - 岩藻糖苷印迹的聚合物能够以基线分离度分离对硝基苯基 - L - 岩藻糖苷的α/β混合物。使用放射性配体置换分析表明，用辛基 - α - D - 葡萄糖苷印迹的聚合物与甲基 - α - D - 葡萄糖苷的结合亲和力比对β - 异头物高40倍。差向异构体选择性更令人印象深刻：甲基 - α - D - 甘露糖苷和甲基 - α - D - 半乳糖苷与甲基 - α - D - 葡萄糖苷的亲和力分别低130倍和240倍。讨论了这些聚合物在分离和分析中的可能用途。
