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基于超高效液相色谱-四极杆-Orbitrap 串联质谱的桃金娘科植物中柠檬苦素类成分的分析及定量

Ultra-high performance liquid chromatography Q-Orbitrap MS/MS-based profiling and quantification of limonoids in Meliaceae plants.

机构信息

Chemical Biology Unit, Division of Organic Chemistry, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India.

Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India.

出版信息

Anal Bioanal Chem. 2022 Aug;414(20):6093-6106. doi: 10.1007/s00216-022-04169-2. Epub 2022 Jun 21.

DOI:10.1007/s00216-022-04169-2
PMID:35727329
Abstract

Meliaceae plants have been extensively used in agriculture, folklore, and traditional medicine. They are the major storehouses for structurally diverse limonoids (meliacins) possessing various bioactivities like antifeedant, insecticidal, antimicrobial, etc. However accurate detection of these tetranortriterpenes from the vast pool of metabolites in plant tissue extracts or biological sample is a crucial challenge. Though the mass spectrum (MS) provides the molecular mass and the corresponding elemental composition, it cannot be relied precisely. The exact identification of a specific metabolite demands the MS/MS spectrum containing the signature product ions. In the present study, we have developed the UHPLC Q-Orbitrap-based method for identification, quantification, and characterization of limonoids in different plant tissue extracts requiring minimum plant material. Using this method, we carried out the limonoid profiling in different tissue extracts of sixteen Meliaceae plants and the identification of limonoids was performed by comparing the retention time (RT), ESI-( +)-MS spectrum, and HCD-MS/MS of the purified fifteen limonoids used as reference standards. Our results revealed that early intermediates of the limonoid biosynthetic pathway such as azadiradione, epoxyazadiradione, and gedunin occurred more commonly in Meliaceae plants. The MS/MS spectrum library of the fifteen limonoids generated in this study can be utilized for identification of these limonoids in other plant tissue extracts, botanical fertilizers, agrochemical formulations, and bio pesticides.

摘要

楝科植物在农业、民间传说和传统医学中被广泛应用。它们是结构多样的 limonoids(meliacins)的主要储存库,具有各种生物活性,如抗营养、杀虫、抗菌等。然而,从植物组织提取物或生物样本中的大量代谢物中准确检测这些四环三萜是一个关键的挑战。尽管质谱(MS)提供了分子质量和相应的元素组成,但它不能被精确依赖。特定代谢物的确切鉴定需要包含特征产物离子的 MS/MS 光谱。在本研究中,我们开发了基于 UHPLC Q-Orbitrap 的方法,用于鉴定、定量和表征不同植物组织提取物中的 limonoids,所需的植物材料最少。使用这种方法,我们对 16 种楝科植物的不同组织提取物进行了 limonoid 分析,并通过比较作为参考标准的 15 种纯化 limonoids 的保留时间(RT)、ESI-(+)-MS 光谱和 HCD-MS/MS,对 limonoids 进行了鉴定。我们的结果表明,limonoid 生物合成途径的早期中间产物,如 azadiradione、epoxyazadiradione 和 gedunin,在楝科植物中更为常见。本研究生成的 15 种 limonoids 的 MS/MS 光谱库可用于鉴定其他植物组织提取物、植物肥料、农用化学品制剂和生物农药中的这些 limonoids。

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2
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Proc Natl Acad Sci U S A. 2019 Aug 20;116(34):17096-17104. doi: 10.1073/pnas.1906083116. Epub 2019 Aug 1.
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Tracing the biosynthetic origin of limonoids and their functional groups through stable isotope labeling and inhibition in neem tree (Azadirachta indica) cell suspension.
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BMC Plant Biol. 2018 Oct 11;18(1):230. doi: 10.1186/s12870-018-1447-6.
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