1 Department of Physics and Astronomy, Science and Technology, Aarhus University2 Department of Chemistry, Science and Technology, Aarhus University3 unknown4 Department of Biochemistry and Molecular Biology, University of Southern Denmark5 Department of Chemistry, Science and Technology, Aarhus University6 Department of Physics and Astronomy, Science and Technology, Aarhus University
prompt versus slow dissociation
Vulnerability of biomolecules to ultraviolet radiation is intimately linked to deexcitation pathways: photostability requires fast internal conversion to the electronic ground state, but also intramolecular vibrational redistribution and cooling on a time scale faster than dissociation. Here we present a protocol to disentangle slow and non-hazardous statistical dissociation from prompt cleavage of peptide bonds by 210 nm light based on experiments on protonated peptides isolated in vacuo and tagged by 18-crown-6 ether (CE). The weakest link in the system is between the charged site and CE, which is remote from the initial site of excitation. Hence loss of CE serves as direct proof that energy has reached the charge-site end, leaving the backbone intact. Our work demonstrates that excitation of tertiary amide moieties (proline linkages) results in both prompt dissociation and statistical dissociation after energy randomisation over all vibrational degrees of freedom.
Physical Chemistry Chemical Physics, 2014, Vol 16, Issue 30, p. 15831-15838