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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 29, Number 12
BKCSDE 29(12)
December 20, 2008 

 
Title
Kinetics and Mechanism for the Formation of b- and y-type Ions from Singly Protonated Peptides on a Microsecond Time Scale: The Arginine Mystery
Author
Yeon Ji Chung, So Hee Yoon, Myung Soo Kim*
Keywords
Oxazolone pathway, b-y Ions, RRKM, Arginine
Abstract
A kinetic model was built for the formation of b and y ions ? which are the main product ions generated from singly protonated peptides at low internal energy regime ? on a microsecond time scale based on the potential energy diagram along the oxazolone pathway reported previously. The rate constants were evaluated using the Rice-Ramsperger-Kassel-Marcus theory. Even though migration of the extra proton to an amide nitrogen is a prerequisite in the oxazolone mechanism, it was found highly unlikely when this proton was sequestered at an arginine side chain. Possibility of migration of a proton from other locations such as a carboxyl group is discussed.
Page
2427 - 2433
Full Text
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