Chemotaxonomic investigation of Apocynaceae for retronecine-type pyrrolizidine alkaloids using HPLC-MS/MS
Chemotaxonomic investigation of Apocynaceae for retronecine-type pyrrolizidine alkaloids using HPLC-MS/MS
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DOI：
10.1016/j.phytochem.2021.112662
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发表时间：
2021-03-27
期刊：
影响因子：
3.8
通讯作者：
Minbiole, Kevin P. C.
中科院分区：
文献类型：
--
作者：
Barny, Lea A.;Tasca, Julia A.;Minbiole, Kevin P. C.
罗布麻科植物以种类繁多的特殊代谢物而闻名，这些代谢物以系统发育信息的方式分布。吡咯里西丁生物碱(PA)在该科的APSA分支中有零星的报道，但到目前为止很少有物种被研究。我们首次对罗布麻科植物进行了系统的调查，采用高效液相-质谱仪/质谱仪对APSA分支内16个主要谱系中的13个物种的231个种的叶片进行了采样。我们还跟踪了Echites umellatus Jacq中PA可检出性的亚种间差异的初步证据。开发了四种前体离子扫描(PREC)，用于高通量调查含有许多PA共有的结构部分的化学物质，Rtronecine核心。我们在8个样本中的7个Eiteae属中高度确定了Pas，但在与之密切相关的齿齿亚科和中线亚科的样本中没有发现Pas，证实了Pas作为分类特征在部落划分中的作用。Pas在Maloutieae中的出现是在Schomburgkiana Woodson和Eucorymbia Alba Stapf中报道的，但目前我们对它们在Holarrena pubescens Wall中的存在信心较低。以及在Holarrena curtisii King&Gamble和Kibatalia macPhylla(Pierre Ex Hua)Woodson中发现。Wright tia R.Br.某些种的候选Pas。(Wright Tieae)和Marsdenia R.Br.(Marsdenieae)是以中等信心提出的，但这些分类群中呈现PA样碎裂模式的化合物的子集更有可能是氨基苯甲酰糖苷。已报道的候选PA在其高精胺合成酶样基因中具有预测的(VXXXD)和意外的(IXXXN)氨基酸基序。猪笼草Pas的可探测性在不同的Echites Ubellatus样品中是不同的，个体内的可塑性导致了这种差异。具有重要毒理学意义的是，在药用植物Wright tia tincVictoria R.Br.和食用植物Marsdenia novra Cost中发现了新的人类接触亲有毒PA的潜在来源。和Echites panuratus A.DC.，需要立即进行进一步的研究，以阐明所确定的候选Pas的结构。讨论了方法的发展和局限性。
Apocynaceae are well known for diverse specialized metabolites that are distributed in a phylogenetically informative manner. Pyrrolizidine alkaloids (PAs) have been reported sporadically in one lineage in the family, the APSA clade, but few species have been studied to date. We conducted the first systematic survey of Apocynaceae for retronecine-type PAs, sampling leaves from 231 species from 13 of 16 major lineages within the APSA clade using HPLC-MS/MS. We also followed up preliminary evidence for infra-specific variation of PA detectability in Echites umbellatus Jacq. Four precursor ion scans (PREC) were developed for a high-throughput survey for chemicals containing a structural moiety common to many PAs, the retronecine core. We identified with high confidence PAs in 7 of 8 sampled genera of tribe Echiteae, but not in samples from the closely related Odontadenieae and Mesechiteae, confirming the utility of PAs as a taxonomic character in tribal delimitation. Occurrence of PAs in Malouetieae is reported with moderate confidence in Galactophora schomburgkiana Woodson and Eucorymbia alba Stapf, but currently we have low confidence of their presence in Holarrena pubescens Wall. ex G. Don (the one Malouetieae species where they were previously reported), as well as in Holarrena curtisii King & Gamble and in Kibatalia macrophylla (Pierre ex Hua) Woodson. Candidate PAs in some species of Wrightia R. Br. (Wrightieae) and Marsdenia R. Br. (Marsdenieae) are proposed with moderate confidence, but a subset of the compounds in these taxa presenting with a PA-like fragmentation pattern are more likely to be aminobenzoyl glycosides. Candidate PAs are reported in species with predicted (VXXXD) and unexpected (IXXXN) amino acid motifs in their homospermidine synthase-like genes. Detectability of PAs varies among samples of Echites umbellatus and intra-individual plasticity contributes to this variation. Of toxicological importance, novel potential sources of human exposure to pro-toxic PAs were identified in the medicinal plant, Wrightia tinctoria R.Br., and the food plants, Marsdenia glabra Cost. and Echites panduratus A. DC., warranting immediate further research to elucidate the structures of the candidate PAs identified. Method development and limitations are discussed.