手性气相色谱法拆分及测定3-环己烯甲酸甲酯及3-环己烯甲酸  

Separation and Determination of 3-Cyclohexene-1-carboxylic Acid Methyl Ester and 3-Cyclohexene Carboxylic Acid by Chiral Gas Chromatography

作　　者：张振永 李东阳 解艺璇 张辰元 陈闵敏 许瑞 阎振鑫 康健 ZHANG Zhen-yong;LI Dong-yang;XIE Yi-xuan;ZHANG Chen-yuan;CHEN Min-min;XU Rui;YAN Zhen-xin;KANG Jian(Shimadzu(Shanghai)Global Laboratory Consumables Co.,Ltd.,Shanghai 200233,China;Shimadzu(China)Co.,Ltd.,Shanghai 200233,China;HZYMES BIOTECH Co.,Ltd.,Shanghai 201401,China)

机构地区：[1]岛津(上海)实验器材有限公司,上海200233 [2]岛津企业管理(中国)有限公司,上海200233 [3]武汉瀚海新酶生物科技有限公司,上海201401

出　　处：《分析测试学报》2025年第4期714-719,共6页Journal of Instrumental Analysis

摘　　要：开发了一种可同时拆分及测定手性3-环己烯甲酸甲酯及手性3-环己烯甲酸的气相色谱法。外消旋3-环己烯甲酸甲酯作为底物,可经脂肪酶立体选择性催化生成产物手性3-环己烯甲酸。采用正交试验法,研究了色谱柱类型、载气线速度、初始柱温和升温速率对3-环己烯甲酸甲酯及3-环己烯甲酸对映异构体的拆分效果。极差分析结果表明,采用SH-βDEXsm色谱柱、载气线速度为30.0 cm/s、初始柱温为70.0℃、升温速率为1.00℃/min时,可得到最优分离效果。此时,3-环己烯甲酸甲酯对映异构体的分离度为2.15,3-环己烯甲酸对映异构体的分离度为3.50。(R)-和(S)-3-环己烯甲酸甲酯、(R)-和(S)-3-环己烯甲酸的线性范围分别为3.50~350 mg/L和15.8~315 mg/L,相关系数均为0.999,4个化合物的检出限为0.550~3.16 mg/L,定量下限为1.85~9.56 mg/L。(R)-和(S)-3-环己烯甲酸甲酯和(R)-和(S)-3-环己烯甲酸在3个不同浓度下的加标回收率分别为91.4%~97.1%、91.4%~95.7%、89.9%~95.6%和88.6%~96.0%,相对标准偏差(RSD)均不大于4.7%。该方法一次进样可同时手性拆分3-环己烯甲酸甲酯和3-环己烯甲酸。A gas chromatography method has been developed for the simultaneous separation and determination of chiral 3-cyclohexene-1-carboxylic acid methyl ester(CHCM)and chiral 3-cyclohexene carboxylic acid(CHCA).The racemic CHCM serves as a substrate that can be stereoselectively catalyzed by lipase to produce the product chiral CHCA.By employing the orthogonal experimental design,the effects of chromatographic column type,carrier gas linear velocity,initial column temperature and temperature ramp rate on the enantiomeric separation of CHCM and CHCA were investigated.The analysis of variance(ANOVA)indicated that the optimal separation was achieved using an SH-βDEXsm chromatographic column,with a carrier gas linear velocity of 30.0 cm/s,an initial column temperature of 70.0℃,and a temperature ramp rate of 1.00℃/min.Under these conditions,the separation factor for the enantiomers of CHCM was 2.15,and for CHCA,it was 3.50.The linearity range for(R)-and(S)-CHCM and(R)-and(S)-CHCA were determined to be 3.50-350 mg/L and 15.8-315 mg/L,respectively,with correlation coefficients of 0.999.The limits of detection(LODs)for the four compounds ranged from 0.550 mg/L to 3.16 mg/L,and the limits of quantification(LOQs)ranged from 1.85 mg/L to 9.56 mg/L.The recoveries for(R)-and(S)-CHCM and(R)-and(S)-CHCA at three different concentrations were between 91.4%to 97.1%,91.4%to 95.7%,89.9%to 95.6%,and 88.6%to 96.0%,respectively,with relative standard deviations(RSDs)not more than 4.7%.This method allows for the simultaneous separation of chiral CHCM and CHCA in a single injection.

关 键 词：手性气相色谱 3-环己烯甲酸甲酯 3-环己烯甲酸 正交试验 对映异构体 

分 类 号：O657.7[理学—分析化学]