Sequencing of new beauverolides by high-performance liquid chromatography and mass spectrometry
Sequencing of new beauverolides by high-performance liquid chromatography and mass spectrometry
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DOI：
10.1002/jms.213
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发表时间：
2001-10-01
影响因子：
2.3
通讯作者：
Havlícek, V
中科院分区：
文献类型：
--
作者：
Kuzma, M;Jegorov, A;Havlícek, V
采用质谱法（MS）和串联质谱法（MSn）对白僵菌发酵液中的白僵菌内酯进行了鉴定，并对白僵菌内酯升华纯化后的产物进行了评价。升华法不仅是一种新的高效纯化途径，还可以从原复合菌丝体提取液中富集低分子量的新的小亲脂性beauverolides。比较和评价了离子阱（电喷雾电离）获得的产物离子碰撞诱导离解（CID）谱、扇形仪（大气压化学电离）获得的源内CID质谱和源后衰变基质辅助激光解吸/电离质谱。所有的MSn实验都是从单电荷前体离子开始的。通过高效液相色谱和质谱（HPLC/MS）鉴定了这类化合物的两个新代表：环-（3-羟基-4-甲基辛烷酰-丙烯酰-亮基）和环-（3-羟基-4-甲基辛烷酰-酪氨酸-丙烯酰-亮基）。单个结构通过制备分离和核磁共振波谱法得到证实。通过HPLC/MS初步确定了第三种新型的小波弗罗内酯的结构为环-(3-羟基-4-甲基癸烷基-戊酰丙烯基-Lxx), Lxx =亮基、异亮基或异亮基。版权所有John Wiley & Sons， Ltd。
Mass spectrometry (MS) and tandem mass spectrometry (MSn) were used for the identification of beauverolides in the fermentation broth of Beauveria bassiana and for evaluation of the purified fraction obtained by sublimation of beauverolides. Besides being a new efficient route for purification of beauverolides, sublimation provided an enrichment of new minor lipophilic beauverolides of lower molecular weight from the original complex mycelial extract. The product ion collision-induced dissociation (CID) spectra obtained on an ion trap (electrospray ionization), the in-source CID mass spectra on a sector instrument (atmospheric-pressure chemical ionization) and the post-source decay matrix-assisted laser desorption/ionization mass spectra of beauverolides were compared and evaluated. All MSn experiments started with singly charged precursor ions. The following two new representatives of this group of compounds were identified by high-performance liquid chromatography and MS (HPLC/MS): cyclo-(3-hydroxy-4-methyloctanoyl-valyl-alanyl-leucyl) and cyclo-(3-hydroxy-4-methyloctanoyl-tyrosyl-alanyl-leucyl). Individual structures were confirmed by preparative isolation and nuclear magnetic resonance spectroscopy. The structure of a third novel and minor beauverolide was tentatively assigned by HPLC/MS only as cyclo-(3-hydroxy-4-methyldecanoyl-valyl-alanyl-Lxx), Lxx = leucyl, isoleucyl, or allo-isoleucyl. Copyright (C) 2001 John Wiley & Sons, Ltd.