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The benchmark of P-31 NMR parameters in phosphate: a case study on structurally constrained and flexible phosphate
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SYSNO ASEP 0483858 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název The benchmark of P-31 NMR parameters in phosphate: a case study on structurally constrained and flexible phosphate Tvůrce(i) Fukal, Jiří (UOCHB-X) ORCID, RID
Páv, Ondřej (UOCHB-X) RID, ORCID
Buděšínský, Miloš (UOCHB-X) RID, ORCID
Šebera, Jakub (UOCHB-X) RID, ORCID
Sychrovský, Vladimír (UOCHB-X) RID, ORCIDZdroj.dok. Physical Chemistry Chemical Physics. - : Royal Society of Chemistry - ISSN 1463-9076
Roč. 19, č. 47 (2017), s. 31830-31841Poč.str. 12 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova phosphate ; MD ; DFT ; NMR Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA16-00270S GA ČR - Grantová agentura ČR GA13-26526S GA ČR - Grantová agentura ČR Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000417295800034 EID SCOPUS 85038407283 DOI https://doi.org/10.1039/c7cp06969c Anotace A benchmark for structural interpretation of the P-31 NMR shift and the (2)J(P),(C) NMR spin-spin coupling in the phosphate group was obtained by means of theoretical calculations and NMR measurements in diethylphosphate (DEP) and 5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphinane 2-oxide (cDEP). The NMR parameters were calculated employing the B3LYP, BP86, BPW91, M06-2X, PBE0, KT2, KT3, MP2, and HF methods, and the 6-31+G(d), Iglo-n (n = II, III), cc-pVnZ (n = D, T, Q, 5), aug-cc-pVnZ (n = D, T and Q), and pcS-n and pcJ-n (n = 1, 2, 3, 4) bases, including the solvent effects described with explicit water molecules and/or the implicit Polarizable Continuum Model (PCM). The effect of molecular dynamics (MD) on NMR parameters was MD-calculated using the GAFF force field inclusive of explicit hydration with TIP3P water molecules. Both the optimal geometries and the dynamic behaviors of the DEP and cDEP phosphates differed notably, which allowed a reliable theoretical benchmark of the P-31 NMR parameters for highly flexible and structurally constrained phosphate in a one-to-one relationship with the corresponding experiment. The calculated P-31 NMR shifts were referenced employing three different NMR reference schemes to highlight the effect of the P-31 NMR reference on the accuracy of the calculated P-31 NMR shift. The relative Dd(P-31) NMR shift calculated employing the MD/B3LYP/Iglo-III/PCM method differed from the experiment by 0.16 ppm while the NMR shifts referenced to H3PO4 and/or PH3 deviated from the experiment notably more, which illustrated the superior applicability of the relative NMR reference scheme. The (2)J(P,C) coupling in DEP and cDEP calculated employing theMD/B3LYP/Iglo-III(DSO,PSO,SD)/cc-PV5Z(FC)/PCM method inclusive of correction due to explicit hydration differed from the experiment by 0.32 Hz and 0.15 Hz, respectively. The NMR calculations demonstrated that reliable structural interpretation of the P-31 NMR parameters in phosphate must involve both the structural and the dynamical components. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2018 Elektronická adresa http://pubs.rsc.org/en/content/articlepdf/2017/cp/c7cp06969c
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