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Solvent Polarity-Induced Conformational Unlocking of Asparagine
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0185-5724
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1763-9383
2012 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 116, no 47, 11702-11708 p.Article in journal (Refereed) Published
Abstract [en]

Classical and Car-Parrinello molecular dynamics simulations are performed to study the solvent effect on the conformational distribution of asparagine. Conformational populations obtained from the simulations in gas phase and in nonpolar chloroform solvent are in agreement with the most probable single conformation of asparagine in the gas phase measured in recent laser ablation with molecular beam Fourier transform microwave spectroscopy experiments. We rationalize that intramolecular hydrogen bonding and dipole-dipole interactions between carbonyl groups dictate such a conformational locking to a single asparagine conformer. The solvent polarity induced interlocking or intermolecular hydrogen bonding with water solvent molecules destabilizes the (NH center dot center dot center dot O=C) bonding between side chain and terminal groups of asparagine, while not essentially affecting the (NH center dot center dot center dot O=C) intramolecular hydrogen bondings within the side chain nor within the terminal groups. Such a conformational unlocking or cage effect is observed in asparagine within aqueous solution. We observed a spontaneous conversion of neutral to zwitterionic isomer of asparagine in aqueous solution, which is in agreement with interpretation of Raman spectroscopy results. Using Meller-Plesset second order perturbation theory, we show that a tautomeric shift from neutral to zwitterionic occurs on asparagine in between DMSO and water solvents. The ramification of these findings for the conformational character of asparagine is briefly discussed.

Place, publisher, year, edition, pages
2012. Vol. 116, no 47, 11702-11708 p.
Keyword [en]
Molecular-Dynamics Simulations, Density-Functional Theory, X-L Deamidation, Aspartic-Acid, Linked Glycosylation, Gas-Phase, Ab-Initio, Peptide Conformation, Transition-States, Aqueous-Solutions
National Category
Physical Chemistry
URN: urn:nbn:se:kth:diva-109636DOI: 10.1021/jp307715nISI: 000311650200024ScopusID: 2-s2.0-84870399484OAI: diva2:584889
Swedish e‐Science Research Center

QC 20130109

Available from: 2013-01-09 Created: 2013-01-08 Last updated: 2013-04-08Bibliographically approved

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Selvaraj, Ananda Rama KrishnanNatarajan Arul, MuruganÅgren, Hans
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