Department of Chemistry, Wuhan University, Wuhan, 430072, PR China.
Department of Chemistry, Lanzhou University, Lanzhou, 730000, PR China.
Anal Chim Acta. 2021 Jun 8;1163:338505. doi: 10.1016/j.aca.2021.338505. Epub 2021 Apr 13.
Gibberellins (GAs) play crucial roles in plant growth and development, and their regulatory functions rely on complex metabolic networks and signaling pathways. Therefore, the exploration of GAs metabolic network is of great importance. However, limited GAs have been found in given plant species, which makes it difficult to comprehensively study the GAs metabolic network. Herein, a structure-guided strategy for GAs screening based on liquid chromatography-mass spectrometry analysis assisted by chemical isotope labeling (CIL-LC-MS) was developed. In the proposed strategy, N,N-dimethyl ethylenediamine (DMED) and its isotopologue d-DMED were used to label GAs. In light of the characteristic fragmentation patterns exhibited by the labeled GAs, four principles were summarized to screen the potential GAs from plant tissues. Subsequently, the MS/MS fragmentation behavior and quantitative structure-retention relationship (QSRR) model were employed to assist in deciphering structures of GA candidates. With this strategy, thirty potential GAs were screened out and identified from five plant species. Seven of them were confirmed by the authentic standards. Twenty-two of them have not been reported before in the five plant species used in this study, including thirteen that have been reported in other plant species and nine that have never been reported in any plant species. Noteworthily, a total of nine potential GAs were speculated to be novel 16, 17-double hydrated GAs, which indicated that the 16, 17-double hydration may be a ubiquitous metabolic pathway of GAs in plants. This study was the first attempt to establish a structure-guided screening strategy for GAs. Our findings have enriched the GA species in plants and expanded the GAs family, which may be helpful for study of the metabolic pathway and physiological function of GAs.
赤霉素（GAs）在植物生长发育中起着至关重要的作用，其调节功能依赖于复杂的代谢网络和信号通路。因此，探索 GAs 代谢网络具有重要意义。然而，给定植物物种中发现的 GAs 有限，这使得全面研究 GAs 代谢网络变得困难。在此，开发了一种基于液相色谱-质谱分析辅助化学同位素标记（CIL-LC-MS）的 GAs 筛选结构导向策略。在提出的策略中，使用 N,N-二甲基乙二胺（DMED）及其同位素 d-DMED 对 GAs 进行标记。根据标记 GAs 表现出的特征碎片模式，总结了四条原则从植物组织中筛选潜在的 GAs。随后，采用 MS/MS 碎片行为和定量结构保留关系（QSRR）模型协助解析 GA 候选物的结构。利用该策略，从五种植物中筛选出并鉴定出三十种潜在的 GAs。其中七种通过标准品确证。在本研究中使用的五种植物中，有二十两种以前没有报道过，包括在其他植物物种中报道过的十三种和在任何植物物种中都没有报道过的九种。值得注意的是，共推测出九种潜在的 GAs 是新型的 16、17-双水合 GAs，这表明 16、17-双水合可能是植物中 GAs 的普遍代谢途径。这是首次尝试建立 GAs 的结构导向筛选策略。我们的研究结果丰富了植物中的 GA 种类，扩展了 GA 家族，这可能有助于研究 GAs 的代谢途径和生理功能。
