手性衍生化试剂PPZ-Pro-NHS的合成及其在D/L-氨基酸分离中的应用  

Synthesis of chiral derivatization reagent PPZ-Pro-NHS and its application in D/L-amino acids separation

作　　者：冯磊宁 张波 金佑熙 金彪 金东日[1] FENG Leining;ZHANG Bo;JIN Youxi;JIN Biao;JIN Dongri(College of Science,Yanbian University,Yanji 133002,China;Yanji Cigarette Factory,Jilin Tobacco Industry CO.,Ltd.,Yanji 133001,China;Analysis and Testing Center,Yanbian University,Yanji 133002,China)

机构地区：[1]延边大学理学院,吉林延吉133002 [2]吉林烟草工业有限责任公司延吉卷烟厂,吉林延吉133001 [3]延边大学分析测试中心,吉林延吉133002

出　　处：《延边大学学报（自然科学版）》2021年第3期260-265,共6页Journal of Yanbian University（Natural Science Edition）

基　　金：国家自然科学基金(22064017)。

摘　　要：以(S)1(5(4甲基哌嗪1基)2,4二硝基苯基)吡咯烷2羧酸(PPZ-Pro)和N羟基琥珀酰亚胺(NHS)为反应物合成了一种新型衍生化试剂(S)2,5二氧吡咯烷1基1(5(4甲基哌嗪1基)2,4二硝基苯基)吡咯烷2羧酸酯(PPZ-Pro-NHS),并采用核磁共振波谱法(^(1)H NMR、^(13)C NMR)和质谱(MS)对其结构进行了表征.研究显示:在碱性介质中PPZ-Pro-NHS与氨基酸反应生成非对映体氨基酸衍生物,且当在反应条件为100mmol/L三乙胺介质、反应温度为25℃和反应时间为40min条件下所生成的非对映体氨基酸衍生物的色谱峰面积最大.以水乙腈为流动相,用C18柱对19种氨基酸对映体进行分离显示,其分离度(Rs)大于1.20(除天冬氨酸外),达到基线分离.因此,制备的PPZ-Pro-NHS在氨基酸对映体和手性药物的分离和分析方面具有较好的应用前景.A new derivatization reagent(S)-2,5-dioxypyrrolidine-1-yl-1-(5-(4-methylpiperazine-1-yl)-2,4-dinitrophenyl)pyrrolidine-2-carboxylic acid ester(PPZ-Pro-NHS)was synthesized from(S)-1-(5-(4-methylpiperazine-1-yl)-2,4-dinitrophenyl)pyrrolidine-2-carboxylic acid(PPZ-Pro)and N-hydroxysuccinimide(NHS).Its structure was characterized bynuclearmagnetic resonance spectroscopy(^(1)H NMR,^(13)C NMR)and mass spectroscopy(MS).The reswults showed that in alkaline medium,PPZ-Pro-NHS reacts with amino acidsto produce the diastereomeric derivatives of amino acids,and the highest peak area of amino acid derivatives was obtained when the reaction conditions were 100mmol/L triethylamine medium,reaction temperature 25℃and reaction time 40min.Nineteen kinds of amino acid enantiomers were separated by C18 column with water-acetonitrile as mobile phase.The resolution(Rs)was greater than 1.20(except aspartic acid),which reached the baseline separation.Therefore,PPZ-Pro-NHS will have a good application prospect in the separation and analysis of amino acid enantiomers and chiral drugs.

关 键 词：手性 氨基酸 衍生化试剂 PPZ-Pro-NHS 

分 类 号：O658.9[理学—分析化学]