双功能方酰胺荧光探针手性识别研究  

Bifunctional Squaramide Fluorescent Probes for Chiral Recognition

作　　者：白蕾 霍淑慧 韩振刚 陈晶 BAI Lei;HUO Shu-Hui;HAN Zhen-Gang;CHEN Jing(College of Chemistry and Chemical Engineering,Northwest Normal University,Key Laboratory of Bioelectrochemistry&Environmental Analysis of Gansu Province,Lanzhou 730070,China)

机构地区：[1]西北师范大学化学化工学院甘肃省生物电化学与环境分析重点实验室

出　　处：《分析化学》2019年第8期1219-1226,I0019-I0026,共16页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.21462036);甘肃省自然科学基金项目(Nos.18JR3RA085,145RJYA239);甘肃省高等学校科研项目(No.2015A-027)资助~~

摘　　要：合成了4个双功能方酰胺探针分子,其中1和3为新化合物,2和4为已知化合物,并通过核磁共振(1H NMR、13 C NMR)和高分辨质谱(HRMS)确认其结构。采用荧光光谱法,系统研究了这4个手性探针分子对Boc-苯丙氨酸、苯丙氨酸、苯甘氨酸、脯氨酸、缬氨酸、酒石酸、扁桃酸和联二萘酚的荧光手性识别效果。通过组合筛选发现,探针分子4对缬氨酸有较好的识别效果。进一步的研究结果表明,探针分子4与缬氨酸的摩尔比为1∶2时,加入L-缬氨酸后,荧光光谱峰大幅蓝移,且荧光强度大幅减弱;加入D-缬氨酸后,荧光光谱没有变化,荧光强度比值(I D/I L)达到1.35。据此提出了探针分子4的叔胺基团和方酰胺基团分别通过静电作用和氢键作用各结合一分子L-缬氨酸的双手性中心识别机理。Four chiral bifunctional squaramide fluorescent probes were synthesized,including new compounds 1 and 3,and known compounds 2 and 4,and their structure were confirmed by 1H NMR,13 C NMR and HRMS spectra.The fluorescence chiral recognition effects of these four probes on Boc-phenylalanine,phenylalanine,phenylglycine,proline,valine,tartaric acid,mandelic acid,and binaphthol were systematically investigated by fluorescence spectroscopy.By combinatorial screening,it was found that the probe 4 had good recognition effect on valine.Further research showed that the fluorescence peak showed a sharp blue shift and the fluorescence intensity was greatly reduced after addition of L-valine at 1∶2 molar ratio of probe 4 to valine.By contrast,there was no obvious change on the fluorescence intensity after addition of D-valine,and the fluorescence intensity ratio(I D/I L)value was up to 1.35.Based on this,a two-chiral-centers recognition mechanism was proposed.The tertiary amine and squaramide group of the probe 4 separately combined with one molecule of L-valine by electrostatic and hydrogen bonding interactions.

关 键 词：手性识别 荧光探针 方酰胺 双功能 非衍生氨基酸 

分 类 号：O62[理学—有机化学]