The Theoretical 77Se Chemical Shift as a Probe of Selenium State in Selenoproteins and Their Mimics

Theoretical 77Se chemical shifts of a series of simple organoselenium compounds are compared to known NMR data for various
derivatives of selenoenzymes and selenoamino acids. Since the
theoretical data only differs from the biochemical data set by an
overall ∼15−30 ppm downfield shift, simple theoretical model
studies are suggested as an additional tool for the interpretation
of selenoenzyme spectra. Further studies demonstrate that model
systems can be extended to incorporate the effects of intramolecular interactions (such as Se···N bonds).

本研究对比了一系列简单有机硒化合物的理论77Se化学位移与已知硒酶及其硒氨基酸衍生物的核磁共振（NMR）数据。鉴于理论数据与生物化学数据集的差异仅体现在整体约15-30 ppm的化学位移向低场方向偏移，故建议将简单的理论模型研究作为解读硒酶光谱的辅助工具。进一步的研究还表明，模型体系可以扩展以纳入分子内相互作用（如Se···N键）的影响。