The benchmark of P-31 NMR parameters in phosphate: a case study on structurally constrained and flexible phosphate

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F17%3A10378304" target="_blank" >RIV/00216208:11320/17:10378304 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/17:00483858 RIV/68407700:21230/17:00317371

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=T1vHu5HNk5" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=T1vHu5HNk5</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/C7CP06969C" target="_blank" >10.1039/C7CP06969C</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The benchmark of P-31 NMR parameters in phosphate: a case study on structurally constrained and flexible phosphate

Popis výsledku v původním jazyce

A benchmark for structural interpretation of the 31P NMR shift and the 2JP,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 31P NMR parameters for highly flexible and structurally constrained phosphate in a one-to-one relationship with the corresponding experiment. The calculated 31P NMR shifts were referenced employing three different NMR reference schemes to highlight the effect of the 31P NMR reference on the accuracy of the calculated 31P NMR shift. The relative Δδ(31P) 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 2JP,C coupling in DEP and cDEP calculated employing the MD/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 31P NMR parameters in phosphate must involve both the structural and the dynamical components.

Název v anglickém jazyce

The benchmark of P-31 NMR parameters in phosphate: a case study on structurally constrained and flexible phosphate

Popis výsledku anglicky

A benchmark for structural interpretation of the 31P NMR shift and the 2JP,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 31P NMR parameters for highly flexible and structurally constrained phosphate in a one-to-one relationship with the corresponding experiment. The calculated 31P NMR shifts were referenced employing three different NMR reference schemes to highlight the effect of the 31P NMR reference on the accuracy of the calculated 31P NMR shift. The relative Δδ(31P) 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 2JP,C coupling in DEP and cDEP calculated employing the MD/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 31P NMR parameters in phosphate must involve both the structural and the dynamical components.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

19

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

31830-31841

Kód UT WoS článku

000417295800034

EID výsledku v databázi Scopus

2-s2.0-85038407283