用固体核磁共振波谱和从头计算确定5 ' -三磷酸腺苷三水合物二钠的化学屏蔽和电场梯度张量

IF 2.624
Gurpreet Singh , Usha D. Phalgune , Perunthiruthy K. Madhu , Niels Chr. Nielsen , Subramanian Ganapathy
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引用次数: 0

摘要

利用高分辨率固体核磁共振波谱和从头计算研究了结晶良好的5′三磷酸三水合腺苷二钠(ATP•3H2O)中的三磷酸和钠离子环境。根据实验结果和31P化学屏蔽张量的理论从头算量子化学计算,确定了在31P MAS光谱中分辨出的6个不等价磷位,提高了数值精度。利用DQ-SQ相关实验中建立的31P-31P偶极连通性和在B3LYP/(aug-cc-pDVZ(3s,2p,1d), 6-31G (d,p))水平上进行的DFT计算,对MAS光谱中的磷进行了共振赋值,并确定了分子固定框架中31P的化学屏蔽各向异性和张量取向。发现31P屏蔽张量的屏蔽度最高的方向几乎垂直于两个相邻氧的O-P-O面。在7.05 T下进行的3Q-MAS实验实现了四个钠位的完全分辨,这使得23Na四极参数可以通过实验确定并与理论计算进行比较。除了有助于23Na 3Q-MAS谱的部分共振分配外,我们对23Na EFG张量的HF/ 6-311 ++G(2d,2p)计算表明,对于紧密协调的两个钠位,EFG张量的取向是不同的。它们表现出独特的方向,沿着这些方向,场梯度最小和最大。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Chemical shielding and electric field gradient tensors of disodium 5′-adenosine triphosphate trihydrate determined by solid-state NMR spectroscopy and ab initio calculations

Chemical shielding and electric field gradient tensors of disodium 5′-adenosine triphosphate trihydrate determined by solid-state NMR spectroscopy and ab initio calculations

The tri-phosphate and sodium ion environments in well crystallized disodium 5′adenosine triphosphate trihydrate (ATP•3H2O) are investigated using high-resolution solid-state NMR spectroscopy and ab initio calculations. The six inequivalent phosphorus sites resolved in 31P MAS spectra have been assigned on the basis of experimentally obtained results and theoretical ab initio quantum chemical calculations of 31P chemical shielding tensors with increased numerical accuracy. Aided by 31P-31P dipolar connectivity established in DQ-SQ correlation experiment and DFT calculations carried out at the B3LYP/(aug-cc-pDVZ(3s,2p,1d), 6–31G(d,p)) level, phosphorus resonance assignments in MAS spectra have been made and the 31P chemical shielding anisotropies and tensor orientations in the molecule-fixed frame have been determined. 31P shielding tensors are found to be oriented with the most shielded direction nearly perpendicular to the O-P-O plane involving the two adjoining oxygens. The complete resolution of the four sodium sites has been achieved from 3Q-MAS experiments performed at 7.05 T and this has enabled 23Na quadrupole parameters to be determined experimentally and compared with theoretical calculations. Besides aiding a partial resonance assignment of the 23Na 3Q-MAS spectrum, our HF/6–311++G(2d,2p) calculations of 23Na EFG tensors show that for two sodium sites which are tightly coordinated the orientation of the EFG tensor is distinct. These exhibit unique directions along which the field gradient is the smallest and largest.

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