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Gas-phase conjugation to arginine residues in polypeptide ions via N-hydroxysuccinimide ester-based reagent ions.

ABSTRACT: Gas-phase conjugation to unprotonated arginine side-chains via N-hydroxysuccinimide (NHS) esters is demonstrated through both charge reduction and charge inversion ion/ion reactions. The unprotonated guanidino group of arginine can serve as a strong nucleophile, resulting in the facile displacement of NHS from NHS esters with concomitant covalent modification of the arginine residue. This reactivity is analogous to that observed with unprotonated primary amines such as the N-terminus or ?-amino group of lysine. In solution, however, the arginine residues tend to be protonated at pH values low enough to prevent hydrolysis of NHS esters, which would render them relatively unreactive with NHS esters. This work demonstrates novel means for gas-phase conjugation to arginine side chains in polypeptide ions.

SUBMITTER: McGee WM

PROVIDER: S-EPMC3404623 | biostudies-literature | 2012 Jul

REPOSITORIES: biostudies-literature

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Gas-phase conjugation to arginine residues in polypeptide ions via N-hydroxysuccinimide ester-based reagent ions.

McGee William M WM Mentinova Marija M McLuckey Scott A SA

Journal of the American Chemical Society 20120706 28

Gas-phase conjugation to unprotonated arginine side-chains via N-hydroxysuccinimide (NHS) esters is demonstrated through both charge reduction and charge inversion ion/ion reactions. The unprotonated guanidino group of arginine can serve as a strong nucleophile, resulting in the facile displacement of NHS from NHS esters with concomitant covalent modification of the arginine residue. This reactivity is analogous to that observed with unprotonated primary amines such as the N-terminus or ε-amino ...[more]

PMID: 22769013

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