Collision-activated dissociation studies of alkylamines formed from copper-induced dealkylation of N-alkylporphyrins.
A low-energy (5-450 eV) collision-activated dissociation (CAD) study of a series of aliphatic amines revealed that at collision energies above 200 eV, charge-site-initiated fragmentation occurs. The resulting fragment ions can be utilized in the characterization of alkyl substituents of di- and trisubstituted aliphatic amines. In the presence of Cu2+ and a suitable nucleophile, such as n-dodecylamine, N-alkyl protoporphyrins dealkylate to afford copper protoporphyrin and an alkyl-dodecylamine adduct. A CAD study of a number of alkyl-dodecylamine adducts derived from the copper-induced dealkylation of synthetic N-alkyl protoporphyrins, using charge-site-initiated fragment ions, showed that the alkyl group was trapped by the nucleophilic amine present. Subsequently this method was used to identify the alkyl group of a biologically derived N-alkyl protoporphyrin.
Naylor
S
S
MRC Toxicology Unit, Carshalton, Surrey, UK.
Gibbs
A H
AH
Lamb
J H
JH
De Matteis
F
F
D000588:Amines; D003300:Copper; D003640:Dealkylation; D007202:Indicators and Reagents; D013058:Mass Spectrometry / Q000379:methods; D011166:Porphyrins / Q000737:chemistry*
D000588:Amines; D007202:Indicators and Reagents; D011166:Porphyrins; D003300:Copper