O'Shannessy D J, Andersson L I, Mosbach K
Department of Pure and Applied Biochemistry, University of Lund, Sweden.
J Mol Recognit. 1989 Jul;2(1):1-5. doi: 10.1002/jmr.300020102.
Molecular imprints were prepared using L-phenylalanine anilide as the print molecule and methacrylic acid as the functional monomer. Methacrylic acid interacts ionically with the primary amine of the print molecule and via hydrogen bonding with the amide function. In the HPLC mode such polymers were shown to exhibit efficient enantiomeric resolution of a racemic mixture of the original print molecule. Enantiomeric resolution was shown to be dependent on the ratio of methacrylic acid to print molecule in the pre-polymerization mixture and specific for the presence of both print molecule and functional monomer. Further analyses showed the importance of both the primary amino and amide functions in the correct stereochemistry for recognition and enantiomeric resolution of compounds on such polymers. Other amide derivatives of amino acids including p-nitroanilides, beta-naphthylamides and amides were recognized by such polymers, and enantiomeric resolution was obtained for amide derivatives of amino acid ranging from alanine to tryptophan on a single polymer. The implications of these findings with respect to the mechanism of recognition and the ability to predict enantiomeric resolution of molecules on molecularly imprinted polymers will be discussed.
以L-苯丙氨酸苯胺为印迹分子、甲基丙烯酸为功能单体制备了分子印迹聚合物。甲基丙烯酸与印迹分子的伯胺发生离子相互作用，并通过氢键与酰胺官能团相互作用。在高效液相色谱模式下，这类聚合物能够对原始印迹分子的外消旋混合物进行有效的对映体拆分。结果表明，对映体拆分取决于预聚合混合物中甲基丙烯酸与印迹分子的比例，且对印迹分子和功能单体的同时存在具有特异性。进一步分析表明，伯氨基和酰胺官能团对于此类聚合物上化合物的识别和对映体拆分的正确立体化学结构都很重要。包括对硝基苯胺、β-萘酰胺和酰胺在内的其他氨基酸酰胺衍生物也能被这类聚合物识别，并且在单一聚合物上能够对从丙氨酸到色氨酸的氨基酸酰胺衍生物进行对映体拆分。将讨论这些发现对于识别机制以及预测分子印迹聚合物上分子对映体拆分能力的意义。
