Paramagnetic Perturbation of the F-19 NMR Chemical Shift in Fluorinated Cysteine by O-2: A Theoretical Study

Paramagnetic Perturbation of the F-19 NMR Chemical Shift in Fluorinated Cysteine by O-2 : A Theoretical Study

QC 20100525
We present a combined molecular dynamics and density functional theory study of dioxygen-induced perturbation of the F-19 NMR chemical shifts in an aqueous solution of fluorinated cysteine under 100 atm of O-2 partial pressure. Molecular dynamics Simulations are carried out to determine the dominant structures of O-2 and the fluorinated cysteine complexes in water, and the collected structural information is exploited in computation of F-19 chemical shifts using density functional theory. The obtained results indicate that the density redistribution of the O-2 unpaired electrons between the dioxygen and fluorinated cysteine is responsible for the experimentally observed perturbation of the F-19 NMR chemical shifts, where the Fermi contact interaction plays the key role. The O-2-induced paramagnetic F-19 chemical shift, averaged over the simulation trajectory, is comparable with the reported experimental values, proving the availability of the developed strategy for modeling F-19 NMR chemical shifts in the presence of paramagnetic agents in ail aqueous solution. The applicability of the combined molecular dynamics/density functional theory approach for dioxygen NMR perturbation to all resonating nuclei including H-1, C-13, N-15, and F-19 is emphasized, and the ramification of this for investigations of membrane protein structures is discussed.

Rinkevicius, ZilvinasKTH,Teoretisk kemi(Swepub:kth)u1ad7nfi (författare)
Tu, YaoquanÖrebro universitet,Akademin för naturvetenskap och teknik,Biophysical Chemistry(Swepub:oru)ytu (författare)
Tian, He (författare)
Ågren, HansKTH,Teoretisk kemi(Swepub:kth)u1l2s96v (författare)
KTHTeoretisk kemi (creator_code:org_t)

Ingår i:Journal of Physical Chemistry BWashington, D. C. : American Chemical Society (ACS)113:31, s. 10916-109221520-61061520-5207

Av författaren/redakt...: Li, Xin; Rinkevicius, Zil ...; Tu, Yaoquan; Tian, He; Ågren, Hans

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