Predicting Precursor Ions Combined with Fragmentation Pathway for Screening and Identification of Flavan-3-ol Oligomers in Tea (Camellia sinensis. var. assamica).

IF 3.1 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS Journal of the American Society for Mass Spectrometry Pub Date : 2025-01-01 Epub Date: 2024-12-18 DOI:10.1021/jasms.4c00390
Min Feng, Yonglin Li, Yanfang Qin, Wensi Ma, Dabing Ren, Lunzhao Yi
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Abstract

Flavan-3-ol oligomers (FLOs), including proanthocyanidins (PAs) and theasinensins (TSs), contribute greatly to the flavor and bioactivity of the tea beverage. Ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry has been widely used in profiling a wide range of compounds in tea. However, the detection and identification of FLOs with low concentration and high structural diversity remain meaningful yet challenging work. Herein, we propose a strategy that enables efficient discovery and annotation of FLOs, especially those with a relatively high degree of polymerization (DP, ≥3). Based on the known monomers and the specific polymerization pattern between them, the strategy predicted a theoretical list of precursor ions of FLO. Matching the predicted list against the experimental ion features screened out 490 features as the candidate of FLOs from over 10 000 raw features. Investigation of the fragmentation pathways of 17 known FLOs found that both PAs and TSs are easily subjected to RDA cleavage, which produced a series of characteristic fragmentation ions and neutral losses. Moreover, successive cleavage of the C4 → C8 bond between monomer units is observed for PAs, leading to the generation of characteristic fragmentation ions corresponding to monomeric flavan-3-ols. Assisted by the characteristic fragmentation pathways, 52 FLOs (DP: 2-6) were finally annotated from the 490 retained features. Their chemical structures were verified by depolymerization experiments using menthofuran as the nucleophilic trapping reagent. Among them, the pentamers and hexamers were detected in a Yunnan large leaf tea for the first time. Semiquantitation and multivariate statistical analysis indicate that PAs exhibit higher contents in green tea, and TSs show higher levels in black and white tea.

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预测前体离子结合断裂途径筛选和鉴定茶树黄烷-3-醇低聚物var. assamica)。
黄烷-3-醇低聚物(FLOs),包括原花青素(PAs)和茶素(TSs),对茶饮料的风味和生物活性有很大贡献。高效液相色谱-高分辨率质谱联用技术已广泛应用于茶叶中多种化合物的分析。然而,低浓度、高结构多样性的FLOs的检测和鉴定仍然是一项有意义但具有挑战性的工作。在此,我们提出了一种能够有效发现和注释FLOs的策略,特别是那些聚合度相对较高的FLOs (DP,≥3)。基于已知的单体和它们之间特定的聚合模式,该策略预测了FLO前驱体离子的理论列表。将预测列表与实验离子特征进行匹配,从10000多个 000个原始特征中筛选出490个特征作为候选的FLOs。对17种已知FLOs的断裂途径的研究发现,PAs和TSs都容易受到RDA裂解,产生一系列特征断裂离子和中性损失。此外,PAs的单体单元之间的C4→C8键连续断裂,导致产生与黄烷-3-醇单体相对应的特征断裂离子。在特征碎片化路径的辅助下,最终从490个保留的特征中注释了52个FLOs (DP: 2-6)。以薄荷呋喃为亲核捕获剂,通过解聚实验验证了它们的化学结构。其中五聚体和六聚体首次在云南大叶茶中检出。半定量和多元统计分析表明,绿茶中PAs含量较高,红茶和白茶中TSs含量较高。
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来源期刊
CiteScore
5.50
自引率
9.40%
发文量
257
审稿时长
1 months
期刊介绍: The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role. Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives
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