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Laser ion beam photodissociation studies of model amino acids and peptides

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00186a001· OSTI ID:5115513

Visible (458-514.5 nm) and uv (333-385 nm) photodissociation of the (M + H){sup +} ions of dinitrophenyl (DNP) derivatized amino acids and peptides is reported. Photoexcitation of the DNP peptides by a visible proton results in fragmentation of the peptide chain with little fragmentation within the chromophore. Conversely, uv photoexcitation of the DNP peptides results in fragmentation of the chromophore as well as the peptide chain, but loss of NO or NO{sub 2} (within the chromophore) often dominates the photofragment ion spectrum. These results are rationalized with particular emphasis on energy-selective dissociation channels of large ionic systems. DNP-leucine and DNP-isoleucine (M + H){sup +} can be differentiated on the basis of photodissociation reactions which yield distonic radical cations. The rate of dissociation of photoexcited ions of DNP peptides is shown to decrease with increasing molecular weight (degrees of freedom). Lastly, comparisons between photodissociation and collision-induced dissociation as a structural probe are presented. 55 refs., 8 figs., 3 tabs.

DOE Contract Number:
AS05-82ER13023
OSTI ID:
5115513
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:4; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English