Institute of Environmental Research, Faculty of Chemistry, Technical University of Dortmund, Otto-Hahn Strasse 6, D-44221 Dortmund, Germany.
J Org Chem. 2013 Feb 15;78(4):1377-89. doi: 10.1021/jo3019522. Epub 2013 Jan 28.
A naphthalimide-based fluorescent indicator monomer 1 for the integration into chromo- and fluorogenic molecularly imprinted polymers (MIPs) was synthesized and characterized. The monomer was equipped with a urea binding site to respond to carboxylate-containing guests with absorption and fluorescence changes, namely a bathochromic shift in absorption and fluorescence quenching. Detailed spectroscopic analyses of the title compound and various models revealed the signaling mechanism. Titration studies employing benzoate and Z-L-phenylalanine (Z-L-Phe) suggest that indicator monomers such as the title compound undergo a mixture of deprotonation and complex formation in the presence of benzoate but yield hydrogen-bonded complexes, which are desirable for the molecular imprinting process, with weakly basic guests like Z-l-Phe. Compound 1 could be successfully employed in the synthesis of monolithic and thin-film MIPs against Z-L-Phe, Z-L-glutamic acid, and penicillin G. Chromatographic assessment of the selectivity features of the monoliths revealed enantioselective discrimination and clear imprinting effects. Immobilized on glass coverslips, the thin-film MIPs of 1 displayed a clear signaling behavior with a pronounced enantioselective fluorescence quenching dependence and a promising discrimination against cross-analytes.
一种萘酰亚胺基荧光指示剂单体 1 被合成并用于将显色和荧光分子印迹聚合物（MIP）集成。该单体配备有脲结合位点，可通过吸收和荧光变化对含有羧酸盐的客体进行响应，即吸收和荧光猝灭的红移。标题化合物和各种模型的详细光谱分析揭示了信号机制。使用苯甲酸和 Z-L-苯丙氨酸（Z-L-Phe）进行的滴定研究表明，指示剂单体（如标题化合物）在存在苯甲酸时经历去质子化和配合物形成的混合物，但与弱碱性客体（如 Z-L-Phe）形成氢键配合物，这对于分子印迹过程是有利的。化合物 1 可成功用于合成针对 Z-L-Phe、Z-L-谷氨酸和青霉素 G 的整体式和薄膜 MIP。对整体柱的选择性特征的色谱评估显示出对映体选择性的区分和明显的印迹效应。固定在玻璃载玻片上，1 的薄膜 MIP 表现出明显的信号行为，表现出明显的对映体选择性荧光猝灭依赖性和对交叉分析物的有希望的区分。
