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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electron Spin-Echo Envelope Modulation Spectrum of Azurin at X-Band
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Electron Spin-Echo Envelope Modulation Spectrum of Azurin at X-Band

机译：天青素在X波段的电子自旋回波包络调制谱

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摘要

Frozen solutions of azurin and of its mutant His117Gly in the presence of [~(15)N]imidazole have been investigated by 9 GHz three-pulse electron spin-echo envelope modulation (ESEEM) and two-dimensional ESEEM spectroscopy. It is found that the interaction of the unpaired electron with a backbone nitrogen leads to a sizable contribution to the ESEEM spectrum. This observation provides the clue to the interpretation of the ESEEM spectrum of the prototypical blue-copper site of azurin. The modulations stem largely from the interaction of the electron spin with three nitrogen nuclei. The quadrupole bands of the remote nitrogen of histidine-117 dominate the spectrum. Smaller but significant contributions result from the backbone nitrogen and the remote nitrogen of histidine-46. Simulations of the ESEEM spectra of azurin confirm this interpretation and yield complete hyperfine and quadrupole tensors for all three nitrogens. The significant contribution of the backbone nitrogen to the ESEEM spectra of azurin nicely brings out the delocalized character of the unpaired-electron wave function of the oxidized copper center.
机译：已经通过9 GHz三脉冲电子自旋回波包络调制（ESEEM）和二维ESEEM光谱研究了[[（15）N]咪唑存在下的天青蛋白及其突变体His117Gly的冷冻溶液。发现未成对电子与主链氮的相互作用导致对ESEEM谱的相当大的贡献。该观察结果为解释天青蓝原型蓝铜位点的ESEEM光谱提供了线索。调节主要来自电子自旋与三个氮核的相互作用。组氨酸117的远端氮的四极带占主导地位。较小但重要的贡献来自组氨酸46的主链氮和偏远氮。对天青星的ESEEM谱的模拟证实了这种解释，并针对所有三个氮产生了完整的超精细和四极张量。主链氮对天青蛋白ESEEM光谱的重要贡献很好地展现了氧化铜中心的非成对电子波函数的离域特征。

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