大型多电荷离子的质子转移反应活性。
Proton transfer reactivity of large multiply charged ions.
作者信息
Williams E R
机构信息
Department of Chemistry, University of California, Berkeley 94720, USA.
出版信息
J Mass Spectrom. 1996 Aug;31(8):831-42. doi: 10.1002/(SICI)1096-9888(199608)31:8<831::AID-JMS392>3.0.CO;2-7.
Abstract
Charge-charge interactions dramatically influence the dissociation and proton transfer reactivity of large multiply protonated ions. In combination with tandem mass spectrometry, proton transfer reactions have been used to determine the charge state of an ion and to increase the effective mass resolution of electrospray ionization mass spectra. A model for the proton transfer reactivity of multiply protonated ions, in which protons are assigned to specific sites in an ion based on the intrinsic reactivity of the site and the sum of point-charge Coulomb interactions between charges, is discussed. In combination with experimentally measured rates of proton transfer to bases of known gas-phase basicity, information about the intramolecular electrostatic interactions, gas-phase ion conformation and maximum charge state of an ion produced by electrospray ionization can be obtained.
摘要
电荷-电荷相互作用极大地影响了大型多质子化离子的解离和质子转移反应活性。结合串联质谱，质子转移反应已被用于确定离子的电荷状态，并提高电喷雾电离质谱的有效质量分辨率。本文讨论了一个多质子化离子的质子转移反应活性模型，该模型基于位点的固有反应活性以及电荷之间的点电荷库仑相互作用之和，将质子分配到离子中的特定位点。结合实验测量的质子转移到已知气相碱度的碱上的速率，可以获得有关分子内静电相互作用、气相离子构象以及电喷雾电离产生的离子的最大电荷状态的信息。
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