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Insights into the Post‐Translational Methylation of Arginine from Studies of Guanidinium–Water Nanodroplets
Author(s) -
McQuinn Keri,
McIndoe J. Scott,
Hof Fraser
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800101
Subject(s) - arginine , methylation , chemistry , electrospray ionization , ion , mass spectrometry , guan , biophysics , crystallography , computational chemistry , biochemistry , chromatography , amino acid , organic chemistry , dna , biology , paleontology
Highly solvated methylated guanidinium ions ([Me n Guan(H 2 O) m ] + ; n =0–4 and 6; m =1–>50), which model the various post‐translationally methylated states of arginine, were generated in the electrospray ionization (ESI) source of an unmodified commercial tandem mass spectrometer. The dehydration processes of highly solvated [Me n Guan(H 2 O) 21 ] + ions were monitored by using energy‐dependent ESI MS. These data, together with supporting calculations, provide a detailed picture of the interplay of methylation and hydration, and both the calculations and the experimental evidence suggest a specific structural basis for the observed effects. The ramifications for biochemical binding events that are controlled by the post‐translational methylation of arginine to give dimethylarginines are discussed.