NMR crystallography of amino acids

IF 1.8 3区 化学 Q4 CHEMISTRY, PHYSICAL Solid state nuclear magnetic resonance Pub Date : 2024-02-19 DOI:10.1016/j.ssnmr.2024.101921
Ema Chaloupecká , Václav Tyrpekl , Kateřina Bártová , Yusuke Nishiyama , Martin Dračínský
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Abstract

The development of NMR crystallography methods requires a reliable database of chemical shifts measured for systems with known crystal structure. We measured and assigned carbon and hydrogen chemical shifts of twenty solid natural amino acids of known polymorphic structure, meticulously determined using powder X-ray diffraction. We then correlated the experimental data with DFT-calculated isotropic shieldings. The small size of the unit cell of most amino acids allowed for advanced computations using various families of DFT functionals, including generalized gradient approximation (GGA), meta-GGA and hybrid DFT functionals. We tested several combinations of functionals for geometry optimizations and NMR calculations. For carbon shieldings, the widely used GGA functional PBE performed very well, although an improvement could be achieved by adding shielding corrections calculated for isolated molecules using a hybrid functional. For hydrogen nuclei, we observed the best performance for NMR calculations carried out with structures optimized at the hybrid DFT level. The high fidelity of the calculations made it possible to assign additional signals that could not be assigned based on experiments alone, for example signals of two non-equivalent molecules in the unit cell of some of the amino acids.

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氨基酸的核磁共振晶体学
核磁共振晶体学方法的发展需要一个可靠的数据库,其中包含对已知晶体结构的系统所测量的化学位移。我们利用粉末 X 射线衍射法对二十种已知多晶型结构的固态天然氨基酸进行了测量并分配了碳和氢的化学位移。然后,我们将实验数据与 DFT 计算的各向同性屏蔽相关联。由于大多数氨基酸的单胞尺寸较小,因此可以使用不同系列的 DFT 函数(包括广义梯度近似 (GGA)、元 GGA 和混合 DFT 函数)进行高级计算。我们测试了用于几何优化和 NMR 计算的几种函数组合。在碳屏蔽方面,广泛使用的 GGA 函数 PBE 表现非常出色,不过如果加入使用混合函数为孤立分子计算的屏蔽修正,效果会更好。对于氢核,我们观察到使用混合 DFT 水平优化的结构进行 NMR 计算的性能最佳。计算的高保真度使我们有可能分配到仅靠实验无法分配的额外信号,例如某些氨基酸单胞中两个非等价分子的信号。
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来源期刊
CiteScore
5.30
自引率
9.40%
发文量
42
审稿时长
72 days
期刊介绍: The journal Solid State Nuclear Magnetic Resonance publishes original manuscripts of high scientific quality dealing with all experimental and theoretical aspects of solid state NMR. This includes advances in instrumentation, development of new experimental techniques and methodology, new theoretical insights, new data processing and simulation methods, and original applications of established or novel methods to scientific problems.
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