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Issue 29, 2014
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Selectivity in fragmentation of N-methylacetamide after resonant K-shell excitation

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Abstract

The fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways. Comparison between the excitation of six different resonances in the vicinity of the C1s, N1s and O1s edges suggests evidence for site-selective bond breaking. In particular the breaking of the peptide bond and the N–Cα bond show a clear correlation with resonant excitation at the N1s edge. Also, stronger tendencies towards site-selective bond breaking are found for the generation of single ions compared with ion pairs. Analysis of angular distributions of ions from breakage of the peptide bond yields a fragmentation time of <400 fs.

Graphical abstract: Selectivity in fragmentation of N-methylacetamide after resonant K-shell excitation

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Article information


Submitted
12 Mar 2014
Accepted
14 May 2014
First published
18 Jun 2014

Phys. Chem. Chem. Phys., 2014,16, 15231-15240
Article type
Paper

Selectivity in fragmentation of N-methylacetamide after resonant K-shell excitation

P. Salén, M. Kamińska, R. J. Squibb, R. Richter, M. Alagia, S. Stranges, P. van der Meulen, J. H. D. Eland, R. Feifel and V. Zhaunerchyk, Phys. Chem. Chem. Phys., 2014, 16, 15231
DOI: 10.1039/C4CP01067A

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