CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; Key Laboratory of Synthetic and Natural Function Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.
CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Talanta. 2019 Jun 1;198:432-439. doi: 10.1016/j.talanta.2019.02.046. Epub 2019 Feb 11.
Although various click polymerization reactions (thiol-ene, thiol-yne, thiol-Michael, thiol-epoxy and amine-epoxy) have been utilized to prepare either hybrid or organic monolithic columns with homogeneous network structures, there were few reports on fabrication of monolithic CSPs via click polymerization. Herein, a fast and robust approach was explored to fabricate cinchona-based monolithic hybrid CSPs via photo-initiated thiol-ene polymerization within 10 min in one step. A self-synthesized octakis(3-mercaptopropyl) octasilsesquioxane (POSS-SH) was polymerized with phenylisocyanate cinchonidine (PCD) and (+)-N,N'-diallyl-L-tartardiamide (DATDA) or 1,2,4-trivinylcyclohexane (TVCH). The resulting two kinds of as-synthesized monolithic CSPs, poly(POSS-co-DATDA-co-PCD) and poly(POSS-co-TVCH-co-PCD), were evaluated for cLC enantioseparation of acidic racemates. It was found that they exhibited different enantioseparation ability due to using different multivinyl crosslinkers. The influence of ACN content in mobile phase on the enantioseparation of acidic racemates was investigated. The separation mechanism was also discussed on the basis of a comparison of enantioseparation on two kinds of hybrid monolithic CSPs.
尽管已经有多种点击聚合反应（硫醇-烯、硫醇-炔、硫醇-Michael、硫醇-环氧和胺-环氧）被用于制备具有均匀网络结构的混合或有机整体柱，但通过点击聚合制备整体 CSP 的报道很少。在此，探索了一种快速而稳健的方法，通过一步光引发的硫醇-烯聚合在 10 分钟内制备基于金鸡纳的整体混合 CSP。一种自合成的八（3-巯丙基）倍半硅氧烷（POSS-SH）与苯异氰酸酯奎宁（PCD）和（+）-N，N'-二烯丙基-L-酒石二酰胺（DATDA）或 1,2,4-三乙烯基环己烷（TVCH）聚合。合成的两种整体 CSP，聚（POSS-co-DATDA-co-PCD）和聚（POSS-co-TVCH-co-PCD），用于手性 LC 拆分酸性外消旋体。结果发现，由于使用了不同的多乙烯基交联剂，它们表现出不同的手性分离能力。考察了流动相中 ACN 含量对酸性外消旋体拆分的影响。还根据两种混合整体 CSP 上的手性拆分比较，讨论了分离机制。
