PMID- 12056570
OWN - NLM
STAT- MEDLINE
DCOM- 20020626
LR  - 20181113
IS  - 1044-0305 (Print)
IS  - 1044-0305 (Linking)
VI  - 13
IP  - 6
DP  - 2002 Jun
TI  - Electrospray low energy CID and MALDI PSD fragmentations of protonated 
      sulfinamide cross-linked peptides.
PG  - 709-18
AB  - Murine S100A8 (A8) is a major cytoplasmic neutrophil protein and is converted to 
      novel oxidation products containing Cys-epsilon amino-Lys sulfinamide cross-links 
      and Met-sulfoxide by the neutrophil oxidant HOCl. Seven products were separated 
      using RP-HPLC, with electrospray ionization mass spectrometry (ESI-MS) masses 
      after deconvolution of 10,354, 10,388, +/- 1, and 20,707, +/- 3 Da, and all were 
      resistant to reduction by dithiothreitol. The major products with masses of 
      10,354 Da contained Cys41-Lys34/35 intramolecular cross-links. Additional 
      isomeric products with identical masses (10,354 Da) were isolated and peptide 
      mapping and ESI/MS indicated that Cys41 forms covalent sulfinamide cross-links 
      with either Lys6, Lys76, Lys83, or Lys87 present in A8. Electrospray low energy 
      collisionally induced (CID) spectra of multiply-charged AspN digest peptides with 
      sulfinamide cross-links contained characteristic fragmentations that corresponded 
      to simple cleavage of the nitrogen-sulfur bond with charge retention on either of 
      the fragment ions, allowing conformation of cross-linked peptides. 
      Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) post 
      source decay spectra of [M + H] + ions of the same sulfinamide-containing 
      cross-linked peptides fragment similarly, but additional facile fragmentation 
      reactions corresponding to formation of a protonated peptide containing 
      de-hydroalanine were attributed to cleavage of the carbon-sulfur bond. In 
      addition, lose of methanesulfenic acid from Met-sulfoxide was observed. A 
      sulfinamide-containing adduct was isolated after incubation of the A8/HOCl 
      reaction mixture with Lys or alpha N-acetyl Lys with masses of 10,500 or 10,542 
      Da. ESI/MS/MS and MALDI/post decay source (PSD) analysis of 
      A8(32)-(57)-sulfinamide showed the same characteristic fragmentations as those in 
      the sulfinamide cross-linked peptides, confirming the Cys41-Lys sulfinamide 
      cross-link and suggesting that peptide-peptide sulfinamides may all fragment 
      similarly, allowing ready identification of these cross-links in proteins from 
      more complex biological materials.
FAU - Raftery, Mark J
AU  - Raftery MJ
AD  - Cytokine Research Unit, School of Medical Sciences, University of New South 
      Wales, Kensington, Australia. m.raftery@unsw.edu.au
FAU - Geczy, Carolyn L
AU  - Geczy CL
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PL  - United States
TA  - J Am Soc Mass Spectrom
JT  - Journal of the American Society for Mass Spectrometry
JID - 9010412
RN  - 0 (Amino Acids)
RN  - 0 (Cross-Linking Reagents)
RN  - 0 (Indicators and Reagents)
RN  - 0 (Peptides)
RN  - 0 (Protons)
RN  - 0 (S100 Proteins)
RN  - 0 (Sulfur Compounds)
RN  - 712K4CDC10 (Hypochlorous Acid)
SB  - IM
MH  - Amino Acid Sequence
MH  - Amino Acids/chemistry
MH  - Animals
MH  - Cross-Linking Reagents
MH  - Hypochlorous Acid/chemistry
MH  - Indicators and Reagents
MH  - Mice
MH  - Molecular Sequence Data
MH  - Oxidation-Reduction
MH  - Peptide Mapping
MH  - Peptides/*chemistry
MH  - Protons
MH  - S100 Proteins/chemistry
MH  - Spectrometry, Mass, Electrospray Ionization
MH  - Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
MH  - Sulfur Compounds/*chemistry
EDAT- 2002/06/12 10:00
MHDA- 2002/06/27 10:01
CRDT- 2002/06/12 10:00
PHST- 2002/06/12 10:00 [pubmed]
PHST- 2002/06/27 10:01 [medline]
PHST- 2002/06/12 10:00 [entrez]
AID - 10.1016/S1044-0305(02)00359-8 [doi]
PST - ppublish
SO  - J Am Soc Mass Spectrom. 2002 Jun;13(6):709-18. doi: 
      10.1016/S1044-0305(02)00359-8.