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对映体拆分农药的气相色谱法。手性选择剂与对映体的结合常数的测定。

Enantioseparation of pesticides by gas chromatography. Measurement of association constants enantiomer-chiral selector.

机构信息

Laboratorio de Investigación y Desarrollo de Métodos Analíticos, LIDMA, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CIC-PBA, 47 y 115 (B1900AJL), La Plata, Argentina.

Laboratorio de Investigación y Desarrollo de Métodos Analíticos, LIDMA, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CIC-PBA, 47 y 115 (B1900AJL), La Plata, Argentina..

出版信息

J Chromatogr A. 2024 Aug 30;1731:465172. doi: 10.1016/j.chroma.2024.465172. Epub 2024 Jul 20.

DOI:10.1016/j.chroma.2024.465172
PMID:39053254
Abstract

In this study, the association constants of sixteen pesticides with the chiral selector octakis(6-O-tert-butyldimethylsilyl-2,3-di-O-acetyl)-γ-cyclodextrin were determined. The procedure only involved a few experimental measurements; namely, gas hold-up time and retention time of pesticides in capillary columns, as well as column phase ratio at each temperature condition. Fundamental equations of gas-liquid chromatography were used to estimate association constants. Two sets of columns containing different concentrations of the mentioned chiral selector dissolved in (14 %-cyanopropyl-phenyl)-86 %-methyl-polysiloxane were used. One set included capillary columns without any chemical treatment and the other group included columns that were crosslinked. The systematic comparison between both groups indicated a deleterious effect of the crosslinking on enantioselectivity. Our main objective is to promote the use of gas chromatography for the analysis of volatile and semi-volatile chiral pesticides. Thus, we proposed a simple methodology, based only on chromatographic measurements, to obtain information about the enantiorecognition ability of a particular chiral selector constituting the stationary phase and the influence of the selected polymer on the selectivity experimentally obtained.

摘要

在这项研究中,测定了 16 种农药与手性选择剂十六(6-O-叔丁基二甲基硅基-2,3-二-O-乙酰基)-γ-环糊精的缔合常数。该方法仅涉及几个实验测量,即农药在毛细管柱中的气体保留时间和保留时间,以及在每个温度条件下的柱相比例。使用气液色谱的基本方程来估算缔合常数。使用两组包含不同浓度上述手性选择剂的(14%-氰丙基苯基)-86%-甲基聚硅氧烷填充的毛细管柱。一组包含未经任何化学处理的毛细管柱,另一组包含交联柱。两组之间的系统比较表明交联对对映选择性有不利影响。我们的主要目标是促进使用气相色谱法分析挥发性和半挥发性手性农药。因此,我们提出了一种简单的方法,仅基于色谱测量,以获得关于构成固定相的特定手性选择剂的对映体识别能力以及所选聚合物对实验获得的选择性的影响的信息。

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