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Title: Energetics and Dynamics of Fragmentation of Protonated Leucine Enkephalin from Time-and Energy-Resolved Surface-Induced Dissociation Studies

Abstract

Dissociation of singly protonated leucine enkephalin (YGGFL) was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of seven primary dissociation channels were deduced from modeling the time- and energy-resolved fragmentation efficiency curves for different fragment ions using an RRKM based approach developed in our laboratory. The following threshold energies and activation entropies were determined in this study: E0=1.20 eV and ΔS‡=-20 e.u.1 (MH+→b5); E0=1.14 eV and ΔS‡=-14.7 e.u. (MH+→b4); E0=1.42 eV and ΔS‡=-2.5 e.u. (MH+→b3); E0=1.30 eV and ΔS‡=-4.1 e.u. (MH+→a4); E0=1.37 eV and ΔS‡=-5.2 e.u. (MH+→y ions); E0=1.50 eV and ΔS‡=1.6 e.u. (MH+→internal fragments); E0=1.62 eV and S‡=5.2 e.u. (MH+→F). Comparison with Arrhenius activation energies reported in the literature demonstrated for the first time the reversal of the order of activation energies as compared to threshold energies for dissociation.

Authors:
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
890103
Report Number(s):
PNNL-SA-47768
14395; KC0302020; TRN: US200620%%53
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 110(27):8554-8562
Additional Journal Information:
Journal Name: Journal of Physical Chemistry A, 110(27):8554-8562
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; DISSOCIATION; ENKEPHALINS; FRAGMENTATION; ION CYCLOTRON-RESONANCE; LEUCINE; MASS SPECTROMETERS; DYNAMICS; ACTIVATION ENERGY; DATA; Environmental Molecular Sciences Laboratory

Citation Formats

Laskin, Julia. Energetics and Dynamics of Fragmentation of Protonated Leucine Enkephalin from Time-and Energy-Resolved Surface-Induced Dissociation Studies. United States: N. p., 2006. Web. doi:10.1021/jp063263+.
Laskin, Julia. Energetics and Dynamics of Fragmentation of Protonated Leucine Enkephalin from Time-and Energy-Resolved Surface-Induced Dissociation Studies. United States. https://doi.org/10.1021/jp063263+
Laskin, Julia. 2006. "Energetics and Dynamics of Fragmentation of Protonated Leucine Enkephalin from Time-and Energy-Resolved Surface-Induced Dissociation Studies". United States. https://doi.org/10.1021/jp063263+.
@article{osti_890103,
title = {Energetics and Dynamics of Fragmentation of Protonated Leucine Enkephalin from Time-and Energy-Resolved Surface-Induced Dissociation Studies},
author = {Laskin, Julia},
abstractNote = {Dissociation of singly protonated leucine enkephalin (YGGFL) was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of seven primary dissociation channels were deduced from modeling the time- and energy-resolved fragmentation efficiency curves for different fragment ions using an RRKM based approach developed in our laboratory. The following threshold energies and activation entropies were determined in this study: E0=1.20 eV and ΔS‡=-20 e.u.1 (MH+→b5); E0=1.14 eV and ΔS‡=-14.7 e.u. (MH+→b4); E0=1.42 eV and ΔS‡=-2.5 e.u. (MH+→b3); E0=1.30 eV and ΔS‡=-4.1 e.u. (MH+→a4); E0=1.37 eV and ΔS‡=-5.2 e.u. (MH+→y ions); E0=1.50 eV and ΔS‡=1.6 e.u. (MH+→internal fragments); E0=1.62 eV and S‡=5.2 e.u. (MH+→F). Comparison with Arrhenius activation energies reported in the literature demonstrated for the first time the reversal of the order of activation energies as compared to threshold energies for dissociation.},
doi = {10.1021/jp063263+},
url = {https://www.osti.gov/biblio/890103}, journal = {Journal of Physical Chemistry A, 110(27):8554-8562},
number = ,
volume = ,
place = {United States},
year = {Thu Jul 13 00:00:00 EDT 2006},
month = {Thu Jul 13 00:00:00 EDT 2006}
}