The effect of radical trap moieties on electron capture dissociation spectra of substance P.

The effect of radical trap moieties on electron capture dissociation spectra of substance P. Research Abstract Details 

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The effect of radical trap moieties on electron capture dissociation spectra of substance P. Abstract Text:

Marina A Belyayev,Jason J Cournoyer,Cheng Lin,Peter B O'Connor,

To further test the hypothesis that electron capture dissociation (ECD) involves long-lived radical intermediates and radical migration occurs within these intermediates before fragmentation, radical trap moieties were attached to peptides with the assumption that they would reduce fragmentation by decreasing the mobility of the radical. Coumarin labels were chosen for the radical traps, and unlabeled, singly-labeled, and doubly-labeled Substance P were analyzed by ECD. The results demonstrated a correlation between the number and position of tags on the peptide and the intensity of side-chain cleavages observed, as well as an inverse correlation between the number of tags on the peptide and the intensity of backbone cleavages. Addition of radical traps to the peptide inhibits backbone cleavages, suggesting that either radical mobility is required for these cleavages, or new noncovalent interactions prevent separation of backbone cleavage fragments. The enhancement of side-chain cleavages and the observation of new side-chain cleavages associated with aromatic groups suggest that the gas-phase conformation of this peptide is substantially distorted from untagged Substance P and involves previously unobserved interactions between the coumarin tags and the phenylalanine residues. Furthermore, the use of a double resonance (DR)-ECD experiment showed that these side-chain losses are all products of long-lived radical intermediate species, which suggests that steric hindrance prevents the coumarin-localized radical from interacting with the backbone while simultaneously increasing the radical rearrangements with the side chains.

The effect of radical trap moieties on electron capture dissociation spectra of substance P. Publishing Authors By Initials

MA Belyayev,JJ Cournoyer,C Lin,PB O'Connor,

For similar peptides: intercellular signaling peptides and proteins: kinins: tachykinins: substance p research abstracts see: peptides: intercellular signaling peptides and proteins: kinins: tachykinins: substance p research

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The effect of radical trap moieties on electron capture dissociation spectra of substance P. Journal Published:

PUBLICATION TYPE: Research Support, Non-U.S. Gov

Journal: Journal of the American Society for Mass Spectrome

VOLUME: 17

Page Numbers: 1428-36

Journal Abbreviation: J. Am. Soc. Mass Spectrom.

ISSN: 1044-0305

DAY: 27

MONTH: 07

YEAR: 2006

The effect of radical trap moieties on electron capture dissociation spectra of substance P. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 9010412

The effect of radical trap moieties on electron capture dissociation spectra of substance P. Keywords Mesh Terms:

KEYWORDS: Substance P

MESH TERMS: analysis

Chemical & Substance for Abstract: The effect of radical trap moieties on electron capture dissociation spectra of substance P. Information

Substance Name: coumarin

Registry Number: 91-64-5

Grant and Affiliation Information for The effect of radical trap moieties on electron capture dissociation spectra of substance P.

AFFILIATION: Department of Chemistry, Boston University, Boston, Massachusetts 02118, USA.

Country: United States

AGENCY: United States NCRR

GRANT: P41RR10888

ACRONYM: RR

MEDLINETA: J Am Soc Mass Spectrom

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