Ion mobility-mass spectrometry for the separation and analysis of procyanidins.

Ion mobility-mass spectrometry for the separation and analysis of procyanidins.
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DOI:
10.1002/jms.4377
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发表时间:
2020-02
期刊:
Journal of mass spectrometry : JMS
影响因子:
--
通讯作者:
van Breemen RB
van Breemen RB
中科院分区:
其他
文献类型:
--
作者:
Rue EA;Glinski JA;Glinski VB;van Breemen RB

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原花青素是一种存在于多种植物中的多聚黄烷酮类化合物,具有抗氧化和其他有益的生物活性。由儿茶素和表儿茶素单体单元组成,通过包含碳-碳和碳-氧-碳键的单一碳-碳B型键或A型键连接。它们的聚合物结构使原花青素混合物的分析一直很困难。用高效液相色谱法根据聚合度(DP)来评价原花青素是很耗时的,最多只能分解高达DP-17的聚合物族。为了加快原花青素的研究,研究了阳离子电喷雾离子迁移率-质谱仪(IM-MS)在混合物中原花青素的快速分离和表征中的应用。应用IM-MS分析含有多达5个亚基的结构定义的标准品,原花青素不仅可以根据聚合度而且根据连接类型在不到6ms的时间内被拆分。A型原花青素可以从B型原花青素中分离出来,两者都可以从同一DP的混合型原花青素中至少部分分离出来。IM-MS从蔓越莓提取物中分离出解离常数至少为24的高阶原花青素。随着DP的增加,多电荷原花青素的丰度也增加。在相同m/z离子的IM-MS过程中,离子漂移时间随电荷态的增加而减小。因此,IM-MS不仅根据DP,而且根据亚基之间的连接类型和电荷状态,在不到16ms的时间内分离包含至少24个相互连接的亚基的原花青素混合物。
Procyanidins are polymeric flavan-3-ones occurring in many plants with antioxidant and other beneficial bioactivities. Composed of catechin and epicatechin monomeric units connected by single carbon-carbon B-type linkages or A-type linkages containing both carbon-carbon and carbon-oxygen-carbon bonds. Their polymeric structure makes analysis of procyanidin mixtures always difficult. Evaluation of procyanidins according to degree of polymerization (DP) using HPLC is time consuming and at best has resolved polymeric families up to DP-17. To expedite studies of procyanidins, the utility of positive ion electrospray ion mobility-mass spectrometry (IM-MS) was investigated for the rapid separation and characterization of procyanidins in mixtures. Applying IM-MS to analyze structurally defined standards containing up to 5 subunits, procyanidins could be resolved in less than 6 ms not only by degree of polymerization but also by linkage type. A-type procyanidins could be resolved from B-type and both could be at least partially resolved from mixed-type procyanidins of the same DP. IM-MS separated higher order procyanidins with DP of at least 24 from extracts of cranberry. As DP increased, the abundances of multiply charged procyanidins also increased. During IM-MS of ions of similar m/z, the ion drift times decreased inversely with increasing charge state. Therefore, IM-MS was shown to separate mixtures of procyanidins containing at least 24 interconnected subunits in less than 16 ms, not only according to DP, but also according to linkage type between subunits, and charge state.
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