Nanoparticle-Assisted Cation Adduction and Fragmentation of Small Metabolites
Nanoparticle-Assisted Cation Adduction and Fragmentation of Small Metabolites
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DOI：
10.1002/anie.202100734
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发表时间：
2021-03-24
影响因子：
16.6
通讯作者：
Qian, Kun
中科院分区：
文献类型：
--
作者：
Sun, Shiyu;Liu, Wanshan;Qian, Kun
质谱法（MS）承诺小代谢物分析作为未来的工具，并要求全面了解关键程序，以提高其能力。在此，我们研究了阳离子加合和小代谢物的碎片化的理论和实验相结合的方法，通过纳米粒子辅助激光解吸/电离（LDI）-MS和MS/MS。我们计算的能量加合构象和原子键级建立规则的阳离子代谢物的亲和力和多个阳离子加合的电荷转移。此外，我们证明了加合离子的反应路径，并绘制了势能面，以表征在碎裂过程中给定基团的损失。最后，我们通过选择性和多次加合成功地控制了代谢物碎片化，以提高原子/碎片覆盖率，如代谢物鉴定所定义的。考虑到MS在大生物分子分析中的成功，我们的工作可能会对小代谢物的高级分析产生影响和指导。
Mass spectrometry (MS) promises small-metabolite profiling as a tool of the future and calls for the comprehensive understanding of key procedures to enhance its capability. Herein, we studied cation adduction and fragmentation of small metabolites by a combination of theoretical and experimental approaches, via nanoparticle-assisted laser desorption/ionization (LDI)-MS and MS/MS. We calculated the energies of adduction conformers and atomic bond orders to establish the rules of cation-metabolite affinity and multiple cation adductions in charge transfer. Further, we demonstrated the reaction paths of adducted ions and mapped the potential energy surfaces to characterize the loss of given groups during fragmentation. Finally, we successfully controlled metabolite fragmentation by selected and multiple adductions to enhance the atomic/fragment coverage as defined for metabolite identification toward profiling. Considering the success of MS in the analysis of large biomolecules, our work may have an impact and guide to advanced analysis of small metabolites.