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A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons

Abstract

Highlights: • Structural modifications in sulfur containing biomolecules were investigated. • Significant modifications were observed in insulin irradiated NEXAFS spectra. • Degradation of insulin can be observed even at low temperature. • Alterations in insulin spectrum were characterized according to the state of sulfur. - Abstract: We have performed a NEXAFS (S 1s) and mass spectrometry study of solid samples of cysteine, cystine and insulin irradiated with 0.8 keV electrons. The measured mass spectra point out to processes of desulfurization, deamination, decarbonylation and decarboxylation in the irradiated biomolecules. Electron beam irradiation was also conducted at low temperatures in order to evaluate the possible contribution from thermal degradation processes. The NEXAFS spectra of irradiated cysteine and cystine did not show substantial changes when compared to the same spectra obtained using non-irradiated samples. The sulfur K-edge photoabsorption spectrum of irradiated insulin, however, showed clear modifications when compared to the spectrum of the non-irradiated protein, even when the irradiation was conducted at low temperature. Using an empirical combination of the photoabsorption spectra of cysteine and cystine (which are associated respectively with reduced and oxidized forms of sulfur) we have been able to reproduce the absorption spectrum of irradiated insulin.
Authors:
Simões, G., E-mail: simoes.grazieli@gmail.com; [1]  Rodrigues, F. N.; [1]  Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil)]; Bernini, R. B.; [1]  Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil)]; Castro, C. S.C.; [2]  Souza, G. G.B. de, [1] 
  1. Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro (Brazil)
  2. Instituto Nacional de Metrologia, Qualidade e Tecnologia – Inmetro, 25250-020 Rio de Janeiro (Brazil)
Publication Date:
Mar 01, 2014
Product Type:
Journal Article
Resource Relation:
Journal Name: Journal of Electron Spectroscopy and Related Phenomena; Journal Volume: 193; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: Austria
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ABSORPTION SPECTROSCOPY; CYSTEINE; CYSTINE; FINE STRUCTURE; INSULIN; IRRADIATION; MASS SPECTROSCOPY; SULFUR; X-RAY SPECTROSCOPY
OSTI ID:
22344686
Country of Origin:
Netherlands
Language:
English
Other Identifying Numbers:
Journal ID: ISSN 0368-2048; CODEN: JESRAW; Other: PII: S0368-2048(14)00041-3; TRN: NL15R1394051020
Availability:
Available from http://dx.doi.org/10.1016/j.elspec.2014.02.002
Submitting Site:
NLN
Size:
page(s) 21-26
Announcement Date:
Jun 19, 2015

Citation Formats

Simões, G., E-mail: simoes.grazieli@gmail.com, Rodrigues, F. N., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil)], Bernini, R. B., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil)], Castro, C. S.C., and Souza, G. G.B. de,. A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons. Netherlands: N. p., 2014. Web. doi:10.1016/J.ELSPEC.2014.02.002.
Simões, G., E-mail: simoes.grazieli@gmail.com, Rodrigues, F. N., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil)], Bernini, R. B., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil)], Castro, C. S.C., & Souza, G. G.B. de,. A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons. Netherlands. https://doi.org/10.1016/J.ELSPEC.2014.02.002
Simões, G., E-mail: simoes.grazieli@gmail.com, Rodrigues, F. N., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil)], Bernini, R. B., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil)], Castro, C. S.C., and Souza, G. G.B. de,. 2014. "A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons." Netherlands. https://doi.org/10.1016/J.ELSPEC.2014.02.002.
@misc{etde_22344686,
title = {A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons}
author = {Simões, G., E-mail: simoes.grazieli@gmail.com, Rodrigues, F. N., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil)], Bernini, R. B., Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil)], Castro, C. S.C., and Souza, G. G.B. de,}
abstractNote = {Highlights: • Structural modifications in sulfur containing biomolecules were investigated. • Significant modifications were observed in insulin irradiated NEXAFS spectra. • Degradation of insulin can be observed even at low temperature. • Alterations in insulin spectrum were characterized according to the state of sulfur. - Abstract: We have performed a NEXAFS (S 1s) and mass spectrometry study of solid samples of cysteine, cystine and insulin irradiated with 0.8 keV electrons. The measured mass spectra point out to processes of desulfurization, deamination, decarbonylation and decarboxylation in the irradiated biomolecules. Electron beam irradiation was also conducted at low temperatures in order to evaluate the possible contribution from thermal degradation processes. The NEXAFS spectra of irradiated cysteine and cystine did not show substantial changes when compared to the same spectra obtained using non-irradiated samples. The sulfur K-edge photoabsorption spectrum of irradiated insulin, however, showed clear modifications when compared to the spectrum of the non-irradiated protein, even when the irradiation was conducted at low temperature. Using an empirical combination of the photoabsorption spectra of cysteine and cystine (which are associated respectively with reduced and oxidized forms of sulfur) we have been able to reproduce the absorption spectrum of irradiated insulin.}
doi = {10.1016/J.ELSPEC.2014.02.002}
journal = []
volume = {193}
journal type = {AC}
place = {Netherlands}
year = {2014}
month = {Mar}
}