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The role of nucleophile–electrophile interactions in the unimolecular and bimolecular gas‐phase ion chemistry of peptides and related systems †
Author(s) -
O'Hair Richard A. J.
Publication year - 2000
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/1096-9888(200012)35:12<1377::aid-jms83>3.0.co;2-7
Subject(s) - chemistry , nucleophile , electrophile , protonation , molecule , computational chemistry , ion , ionic bonding , combinatorial chemistry , organic chemistry , catalysis
This account describes the experimental tools (multi‐stage mass spectrometric experiments, isotopic and structural labelling, kinetics and theoretical modelling) and physical organic concepts (influence of charge, the intermediacy of ion–molecule complexes, etc.) that can be used to unravel the mechanisms of gas‐phase unimolecular and bimolecular ionic reactions of peptides. The role that nucleophile–electrophile interactions play in charge‐directed reactions is highlighted for both unimolecular fragmentations (examples are illustrated for protonated sulfur‐containing amino acids and peptides) and bimolecular ion–molecule reactions which cleave peptide bonds. Copyright © 2000 John Wiley & Sons, Ltd.