...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Physical chemistry chemical physics: PCCP >Graph theory-based reaction pathway searches and DFT calculations for the mechanism studies of free radical-initiated peptide sequencing mass spectrometry (FRIPS MS): a model gas-phase reaction of GGR tri-peptide
【24h】

Graph theory-based reaction pathway searches and DFT calculations for the mechanism studies of free radical-initiated peptide sequencing mass spectrometry (FRIPS MS): a model gas-phase reaction of GGR tri-peptide

机译：基于图理论的反应途径搜索和DFT计算，用于自由基引发肽测序质谱（FRIPS MS）的机制研究：GGR三肽的模型气相反应

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Graph theory-based reaction pathway searches (ACE-Reaction program) and density functional theory calculations were performed to shed light on the mechanisms for the production of [a(n) + H](+), x(n)(+), y(n)(+), z(n)(+), and [y(n) + 2H](+) fragments formed in free radical-initiated peptide sequencing (FRIPS) mass spectrometry measurements of a small model system of glycine-glycine-arginine (GGR). In particular, the graph theory-based searches, which are rarely applied to gas-phase reaction studies, allowed us to investigate reaction mechanisms in an exhaustive manner without resorting to chemical intuition. As expected, radical-driven reaction pathways were favorable over charge-driven reaction pathways in terms of kinetics and thermodynamics. Charge- and radical-driven pathways for the formation of [y(n) + 2H](+) fragments were carefully compared, and it was revealed that the [y(n) + 2H](+) fragments observed in our FRIPS MS spectra originated from the radical-driven pathway, which is in contrast to the general expectation. The acquired understanding of the FRIPS fragmentation mechanism is expected to aid in the interpretation of FRIPS MS spectra. It should be emphasized that graph theory-based searches are powerful and effective methods for studying reaction mechanisms, including gas-phase reactions in mass spectrometry.
机译：图表理论的反应途径搜索（ACE-反应程序）和密度函数理论计算对揭示荧光对[A（n）+ h]（+），x（n）（+）， Y（n）（+），z（n）（+）和[y（n）+ 2h]（+）片段形成，其在自由基引发的肽测序（FRIPS）质谱测量的小型甘氨酸系统的质谱测量 - 甘氨酸 - 精氨酸（GGR）。特别地，基于图表的基于图表的搜索，即很少适用于气相反应研究，使我们能够以详尽的方式研究反应机制，而不诉诸化学直觉。正如预期的那样，在动力学和热力学方面，基于电荷驱动的反应途径是有利的。用于形成[Y（n）+ 2H]（+）片段的形成的充电和自由基驱动的途径，并揭示了在我们的FRIPS MS中观察到的[Y（N）+ 2H]（+）片段光谱源自激进的途径，与一般期望相反。预期对FRIPS碎片机制的理解有助于解释FRIPS MS Spectra。应该强调的是，基于图表理论的搜索是研究反应机制的强大且有效的方法，包括质谱法中的气相反应。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号