Division of Chemical and Biomolecular Engineering, College of Engineering, Nanyang Technological University, 16 Nanyang Drive, Singapore 637722, Singapore.
J Chromatogr A. 2011 Aug 19;1218(33):5597-601. doi: 10.1016/j.chroma.2011.06.020. Epub 2011 Jun 17.
Three novel chiral stationary phases (CSPs) were prepared by regioselective chemical immobilization of mono(6(A)-N-allylamino-6(A)-deoxy)perphenylcarbamoylated (PICD) α-, β-, and γ-cyclodextrins (CDs) onto silica support via hydrosilylation. Their enantioseparation properties in high performance liquid chromatography (HPLC) were evaluated with a large spectrum of racemates including flavanone compounds, β-adrenergic blockers, amines and non-protolytic compounds. The effect of CD's cavity size on enantioseparation abilities was studied and discussed. The results indicated that CD's surface loading at silica support played an important role in the enantioseparation on these CSPs under normal-phase conditions while inclusion phenomena contributed the major driving force under reverse-phase conditions. As expected, α-PICD demonstrated the best resolutions towards flavonone and most aromatic alcohols under normal-phase conditions with the highest surface loading; while Fujimura's competitive inclusion model can be applied to explain the better enantioseparations towards β-adrenergic blockers, amines and non-protolytic compounds with α- and β-PICD CSPs. γ-PICD CSP showed superior enantioseparation ability for sterically encumbered analytes like flavanone compounds under both normal-phase and reversed phase conditions.
三种新型手性固定相（CSP）通过硅烷化将单（6(A)-N-烯丙基氨基-6(A)-去氧）perphenylcarbamoylated（PICD）α-、β-和γ-环糊精（CDs）区域选择性化学固定在硅胶载体上制备。使用包括黄酮类化合物、β-肾上腺素能阻滞剂、胺和非质子性化合物在内的大量外消旋体评估了它们在高效液相色谱（HPLC）中的对映体分离性能。研究并讨论了 CD 腔大小对对映体分离能力的影响。结果表明，在正相条件下，CD 在硅胶载体上的表面负载对这些 CSP 上的对映体分离起着重要作用，而包合现象是反相条件下的主要驱动力。正如预期的那样，α-PICD 在正相条件下对黄酮类化合物和大多数芳香醇表现出最佳的分辨率，其表面负载最高；而 Fujimura 的竞争包合模型可用于解释 α-和 β-PICD CSP 对β-肾上腺素能阻滞剂、胺和非质子性化合物的更好对映体分离。γ-PICD CSP 在正相和反相条件下对空间位阻较大的黄酮类化合物等分析物表现出优异的对映体分离能力。
