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Title: Guanidinium Group Remains Protonated in a Strongly Basic Arginine Solution

Abstract

Knowledge of the acid dissociation constant of an amino acid has very important ramifications in the biochemistry of proteins and lipid bilayers in aqueous environments because charge and proton transfer depend on its value. The acid dissociation constant for the guanidinium group in arginine has historically been posited as 12.5, but there is substantial variation in published values over the years. Recent experiments suggest that the dissociation constant for arginine is much higher than 12.5, which explains why the arginine guanidinium group retains its positive charge under all physiological conditions. Here, we use X-ray photoelectron spectroscopy to study unsupported, aqueous arginine nanoparticles. By varying the pH of the constituent solution, we provide evidence that the guanidinium group is protonated even in a very basic solution. By analyzing the energy shifts in the C and N X-ray photoelectron spectra, we establish a molecular level picture of how charge and proton transport in aqueous solutions of arginine occur.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1454493
Alternate Identifier(s):
OSTI ID: 1401071
Grant/Contract Number:  
AC02-05CH11231; DGE‐1106400
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 18; Journal Issue: 12; Related Information: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; acid dissociation constant; amino acids; nanoparticles; photoelectron spectroscopy; proton transport

Citation Formats

Xu, Bo, Jacobs, Michael I., Kostko, Oleg, and Ahmed, Musahid. Guanidinium Group Remains Protonated in a Strongly Basic Arginine Solution. United States: N. p., 2017. Web. doi:10.1002/cphc.201700197.
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Xu, Bo, Jacobs, Michael I., Kostko, Oleg, & Ahmed, Musahid. Guanidinium Group Remains Protonated in a Strongly Basic Arginine Solution. United States. https://doi.org/10.1002/cphc.201700197
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Xu, Bo, Jacobs, Michael I., Kostko, Oleg, and Ahmed, Musahid. Tue . "Guanidinium Group Remains Protonated in a Strongly Basic Arginine Solution". United States. https://doi.org/10.1002/cphc.201700197. https://www.osti.gov/servlets/purl/1454493.
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@article{osti_1454493,
title = {Guanidinium Group Remains Protonated in a Strongly Basic Arginine Solution},
author = {Xu, Bo and Jacobs, Michael I. and Kostko, Oleg and Ahmed, Musahid},
abstractNote = {Knowledge of the acid dissociation constant of an amino acid has very important ramifications in the biochemistry of proteins and lipid bilayers in aqueous environments because charge and proton transfer depend on its value. The acid dissociation constant for the guanidinium group in arginine has historically been posited as 12.5, but there is substantial variation in published values over the years. Recent experiments suggest that the dissociation constant for arginine is much higher than 12.5, which explains why the arginine guanidinium group retains its positive charge under all physiological conditions. Here, we use X-ray photoelectron spectroscopy to study unsupported, aqueous arginine nanoparticles. By varying the pH of the constituent solution, we provide evidence that the guanidinium group is protonated even in a very basic solution. By analyzing the energy shifts in the C and N X-ray photoelectron spectra, we establish a molecular level picture of how charge and proton transport in aqueous solutions of arginine occur.},
doi = {10.1002/cphc.201700197},
journal = {ChemPhysChem},
number = 12,
volume = 18,
place = {United States},
year = {Tue May 16 00:00:00 EDT 2017},
month = {Tue May 16 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/cphc.201700197
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    Works referencing / citing this record:

    Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine
    journal, July 2017

    • Sadybekov, Arman; Krylov, Anna I.
    • The Journal of Chemical Physics, Vol. 147, Issue 1
    • DOI: 10.1063/1.4990564
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