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Phys Chem Chem Phys. 2005 Dec 21;7(24):4054-60. Epub 2005 Oct 25.

Electrochemical multi-tagging of cysteinyl peptides during microspray mass spectrometry: numerical simulation of consecutive reactions in a microchannel.

Author information

1
Laboratoire d'Electrochimie Physique et Analytique, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.

Abstract

On-line electrogeneration of mass tags in a microspray emitter is used to quantify the number of cysteine groups in a given peptide. A finite-element simulation of the multi-step process yields the relative distribution and concentration of tags, untagged and tagged species in the microchannel before the spray event. The work focuses on the tagging of cysteine moieties in peptides or proteins by electrogenerated quinone mass probes. The main chemical parameters determining the kinetics of the labelling are assessed and discussed considering the microfluidic aspects of the process. The control of the tagging extent allows the simultaneous MS analysis of both the unmodified and modified peptide(s). The number of cysteine groups corresponds to the number of characteristic mass shifts observed from the unmodified peptide. The present theoretical work establishes the range of optimum conditions for the determination of the number of cysteine groups in peptides containing up to five cysteine groups.

PMID:
16474869
DOI:
10.1039/b511334b
[Indexed for MEDLINE]

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