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新型β-环糊精键合固定相在反相高效液相色谱模式下的保留特性

Retention properties of novel beta-CD bonded stationary phases in reversed-phase HPLC mode.

作者信息

Zhao Yanyan, Guo Zhimou, Zhang Yongping, Xue Xingya, Xu Qing, Li Xiuling, Liang Xinmiao, Zhang Yukui

机构信息

Key Lab of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Graduate School of the Chinese Academy of Sciences, Chinese Academy of Sciences, Dalian 116023, China.

出版信息

Talanta. 2009 May 15;78(3):916-21. doi: 10.1016/j.talanta.2008.12.066. Epub 2009 Jan 20.

Abstract

With the given special structures, the CD bonded stationary phases are expected to have complementary retention properties with conventional C18 stationary phase, which will be helpful to enhance the polar selectivity in RP mode separation. In this work, two beta-cyclodextrin (beta-CD) bonded stationary phases for reversed-phase HPLC, including 1, 12-dodecyldiol linked beta-CD stationary phase (CD1) and olio (ethylene glycol) (OEG) linked beta-CD stationary phase (CD2), have been synthesized via click chemistry. The resulting materials were characterized with FT-IR and elemental analysis, which proved the successful immobilization of ligands. The similarities and differences in retention characteristics between the CD and C18 stationary phases have been elucidated by using comparative linear solvation energy relationships (LSERs). The force related to solute McGowan volume has no significant difference, while the hydrogen bonding and dipolar interactions between solutes and CD stationary phases are stronger than between solutes and C18, which is attributed to the special structures (CD and triazole groups) of CD stationary phases. Chemical origins are interpreted by comparison between CD1 and CD2. Similar dispersive interactions of CD1 and CD2 are attributed to their similar length of spacer arms. CD2 which contains OEG spacer arm has relative weaker HBD acidity but stronger HBA basicity. CD stationary phases display no serious different methylene selectivity and higher polar selectivity than in the case of C18. Higher acid selectivity and lower basic selectivity are observed on CD2 than on CD1. Distinctive retention properties and good complementary separation selectivity to C18 make the novel CD bonded stationary phases available for more application in RPLC.

摘要

具有给定特殊结构的环糊精键合固定相有望与传统的C18固定相具有互补的保留特性,这将有助于提高反相模式分离中的极性选择性。在本工作中,通过点击化学合成了两种用于反相高效液相色谱的β-环糊精(β-CD)键合固定相,包括1,12-十二烷二醇连接的β-CD固定相(CD1)和聚(乙二醇)(OEG)连接的β-CD固定相(CD2)。通过傅里叶变换红外光谱(FT-IR)和元素分析对所得材料进行了表征,证明了配体的成功固定。通过比较线性溶剂化能关系(LSERs)阐明了CD固定相和C18固定相在保留特性上的异同。与溶质麦高恩体积相关的力没有显著差异,而溶质与CD固定相之间的氢键和偶极相互作用比溶质与C18之间更强,这归因于CD固定相的特殊结构(CD和三唑基团)。通过比较CD1和CD2来解释化学起源。CD1和CD2相似的色散相互作用归因于它们间隔臂的相似长度。含有OEG间隔臂的CD2具有相对较弱的氢键供体酸度但较强的氢键受体碱度。CD固定相显示出没有严重不同的亚甲基选择性,并且比C18情况下具有更高的极性选择性。在CD2上观察到比CD1更高的酸选择性和更低的碱选择性。独特的保留特性和对C18良好的互补分离选择性使得新型CD键合固定相可在反相液相色谱中有更多应用。

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