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Pulsed EPR Dipolar Spectroscopy under the Breakdown of the High‐Field Approximation: The High‐Spin Iron(III) Case
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-06-06 , DOI: 10.1002/chem.201900977 Dinar Abdullin 1 , Hideto Matsuoka 1, 2 , Maxim Yulikov 3 , Nico Fleck 1 , Christoph Klein 1, 4 , Sebastian Spicher 5 , Gregor Hagelueken 1 , Stefan Grimme 5 , Arne Lützen 4 , Olav Schiemann 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-06-06 , DOI: 10.1002/chem.201900977 Dinar Abdullin 1 , Hideto Matsuoka 1, 2 , Maxim Yulikov 3 , Nico Fleck 1 , Christoph Klein 1, 4 , Sebastian Spicher 5 , Gregor Hagelueken 1 , Stefan Grimme 5 , Arne Lützen 4 , Olav Schiemann 1
Affiliation
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Pulsed EPR dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling and thus the distance between electron‐spin centers. To date, PDS measurements to metal centers were limited to ions that adhere to the high‐field approximation. Here, the PDS methodology is extended to cases where the high‐field approximation breaks down on the example of the high‐spin Fe3+/nitroxide spin‐pair. First, the theory developed by Maryasov et al. (Appl. Magn. Reson. 2006, 30, 683–702) was adapted to derive equations for the dipolar coupling constant, which revealed that the dipolar spectrum does not only depend on the length and orientation of the interspin distance vector with respect to the applied magnetic field but also on its orientation to the effective g‐tensor of the Fe3+ ion. Then, it is shown on a model system and a heme protein that a PDS method called relaxation‐induced dipolar modulation enhancement (RIDME) is well‐suited to measuring such spectra and that the experimentally obtained dipolar spectra are in full agreement with the derived equations. Finally, a RIDME data analysis procedure was developed, which facilitates the determination of distance and angular distributions from the RIDME data. Thus, this study enables the application of PDS to for example, the highly relevant class of high‐spin Fe3+ heme proteins.
中文翻译：
高场近似分解下的脉冲EPR偶极光谱：高自旋铁（III）情况
脉冲EPR偶极光谱（PDS）提供了几种方法来测量偶极耦合，从而测量电子自旋中心之间的距离。迄今为止，对金属中心的PDS测量仅限于坚持高场近似的离子。在此，PDS方法扩展到了高场近似在高自旋Fe 3+ /硝基氧自旋对的例子中发生的情况。首先，Maryasov等人发展的理论。（申请MAGN。立信。2006年，30683-702）推导了偶极耦合常数方程，该方程揭示了偶极谱不仅取决于自旋间距离矢量相对于所施加磁场的长度和方向，还取决于其相对于所施加磁场的方向。Fe 3+的有效g张量离子。然后，在模型系统和血红素蛋白上显示了一种称为弛豫诱导偶极调制增强（RIDME）的PDS方法非常适合测量此类光谱，并且实验获得的偶极光谱与推导的方程式完全一致。最后，开发了RIDME数据分析程序，该程序有助于根据RIDME数据确定距离和角度分布。因此，这项研究使得PDS可以应用于高度相关的一类高旋转Fe 3+血红素蛋白。
更新日期：2019-06-06
中文翻译：
高场近似分解下的脉冲EPR偶极光谱：高自旋铁（III）情况
脉冲EPR偶极光谱（PDS）提供了几种方法来测量偶极耦合，从而测量电子自旋中心之间的距离。迄今为止，对金属中心的PDS测量仅限于坚持高场近似的离子。在此，PDS方法扩展到了高场近似在高自旋Fe 3+ /硝基氧自旋对的例子中发生的情况。首先，Maryasov等人发展的理论。（申请MAGN。立信。2006年，30683-702）推导了偶极耦合常数方程，该方程揭示了偶极谱不仅取决于自旋间距离矢量相对于所施加磁场的长度和方向，还取决于其相对于所施加磁场的方向。Fe 3+的有效g张量离子。然后，在模型系统和血红素蛋白上显示了一种称为弛豫诱导偶极调制增强（RIDME）的PDS方法非常适合测量此类光谱，并且实验获得的偶极光谱与推导的方程式完全一致。最后，开发了RIDME数据分析程序，该程序有助于根据RIDME数据确定距离和角度分布。因此，这项研究使得PDS可以应用于高度相关的一类高旋转Fe 3+血红素蛋白。
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