Non‐specific retention characteristics of dissolved β‐cyclodextrin derivatives in open tubular column gas chromatography
Non‐specific retention characteristics of dissolved β‐cyclodextrin derivatives in open tubular column gas chromatography
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DOI：
10.1002/jssc.200301518
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发表时间：
2003-08
影响因子：
5.4
通讯作者：
W. Kiridena;C. Poole;M. I. Nawas;W. W. Koziol-W.
中科院分区：
文献类型：
--
作者：
W. Kiridena;C. Poole;M. I. Nawas;W. W. Koziol-W.
溶剂化参数模型是用来确定的贡献，负责非特异性保留在气相色谱三个溶解的β-环糊精衍生物在聚（氰丙基苯基二甲基硅氧烷）固定相的分子间相互作用。环糊精为全甲基化β-环糊精（Cyclodex-B）、七（2，3-二-O-甲基-6-O-叔丁基二甲基甲硅烷基）-β-环糊精（CycloSil-B）和七（2，3-二-O-乙酰氧基-6-O-叔丁基二甲基甲硅烷基）-β-环糊精（Rt-βDEXsa）。以DB-1701作为参考相的聚（氰丙基苯基二甲基硅氧烷）溶剂，它表明，占主导地位的相互作用的环糊精衍生物与它们的氢键碱性和能力的偶极型相互作用。没有一个环糊精衍生物是氢键酸，并且都是弱电子孤对排斥的。溶解相的内聚性质与溶剂的内聚性质相似，但Rt-βDEXsa的内聚性明显更高。此外，Rt-βDEXsa显示用于确定溶剂化参数模型系统常数的化合物具有显著的包合络合作用，导致统计模型较差，仅适用于定性解释。将Cyclodex-B和CycloSil-B柱与23个开管柱固定相的数据库进行比较，所述开管柱固定相彼此具有相似的选择性，但对与其他固定相类型的非特异性相互作用具有不同的选择性。
The solvation parameter model is used to identify contributions from intermolecular interactions responsible for non-specific retention in gas chromatography for three dissolved p-cyclodextrin derivatives in a poly(cyanopropylphenyldimethylsiloxane) stationary phase. The cyclodextrins are permethylated p-cyclodextrin (Cyclodex-B), heptakis(2,3-di-O-methyl-6-O-t-butyldimethylsilyl)-β-cyclodextrin (CycloSil-B) and heptakis(2,3-di-O-acetoxy-6-O-t-butyldimethylsilyl)-β-cyclodextrin (Rt-βDEXsa). Taking DB-1701 as a reference phase for the poly(cyanopropylphenyldimethylsiloxane) solvent, it is shown that the dominant interactions for the cyclodextrin derivatives are associated with their hydrogen-bond basicity and capacity for dipole-type interactions. None of the cyclodextrin derivatives are hydrogen-bond acids and all are weakly electron lone pair repulsive. The cohesive properties of the dissolved phases are similar to those of the solvent, except for Rt-βDEXsa, which is significantly more cohesive. Also, Rt-βDEXsa shows significant inclusion complexation for the compounds used to determine the system constants of the solvation parameter model resulting in poor statistical models, suitable only for qualitative interpretation. The Cyclodex-B and CycloSil-B columns are compared to a database of 23 open-tubular column stationary phases possessing similar selectivity to each other but different selectivity for non-specific interactions to the other stationary phase types.