A major low-energy fragmentation reaction of many protonated dipeptides inv
olves cleavage of the amide bond resulting in formation of either the y(1)"
ion or the a(1) ion. For a series of protonated dipeptides H-Val-Xxx-OH it
is observed that log(y(1)"/a(1)) is a linear function of the proton affini
ty of the variable C-terminal amino acid. For the series of protonated dipe
ptides H-Xxx-Phe-OH log(a(1)/y(1)") gives a poor correlation with the proto
n affinity or gas-phase basicity of H-Xxx-OH. However, a good limited corre
lation of log(a(1)/y(1)") with the Taft-Topsom sigma(alpha) for the alkyl g
roup is observed when Xxx is an aliphatic amino acid. It is proposed that f
ragmentation occurs by initial formation of a proton-bound complex of an az
iridinone and an amino acid which may fragment to form either a protonated
amino acid (y(1)") or an N-protonated aziridinone with the corresponding ne
utrals being an aziridinone and an amino acid. Ab initio calculations show
that the N-protonated aziridinone is unstable and fragments by loss of CO t
o form the al immonium ion. However, the proton-bound complex of an aziridi
none and an amine base is a stable species which exists in a potential well
. Copyright (C) 2000 John Wiley & Sons, Ltd.