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Increasing the Modulation Depth of GdIII-Based Pulsed Dipolar EPR Spectroscopy (PDS) with Porphyrin–GdIII Laser-Induced Magnetic Dipole Spectroscopy

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2022

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Yao, Xuemei
Qi, Mian
Wiedmaier, Max
Godt, Adelheid

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The Journal of Physical Chemistry Letters. American Chemical Society (ACS). 2022, 13(47), pp. 10958-10964. eISSN 1948-7185. Available under: doi: 10.1021/acs.jpclett.2c02138

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Distance determination with pulsed EPR has become an important technique for the structural investigation of biomacromolecules, with double electron–electron resonance spectroscopy (DEER) as the most important method. GdIII-based spin labels are one of the most frequently used spin labels for DEER owing to their stability against reduction, high magnetic moment, and absence of orientation selection. A disadvantage of GdIII–GdIII DEER is the low modulation depth due to the broad EPR spectrum of GdIII. Here, we introduce laser-induced magnetic dipole spectroscopy (LaserIMD) with a spin pair consisting of GdIII(PymiMTA) and a photoexcited porphyrin as an alternative technique. We show that the excited state of the porphyrin is not disturbed by the presence of the GdIII complex and that herewith modulation depths of almost 40% are possible. This is significantly higher than the value of 7.2% that was achieved with GdIII–GdIII DEER.

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ISO 690SCHERER, Andreas, Xuemei YAO, Mian QI, Max WIEDMAIER, Adelheid GODT, Malte DRESCHER, 2022. Increasing the Modulation Depth of GdIII-Based Pulsed Dipolar EPR Spectroscopy (PDS) with Porphyrin–GdIII Laser-Induced Magnetic Dipole Spectroscopy. In: The Journal of Physical Chemistry Letters. American Chemical Society (ACS). 2022, 13(47), pp. 10958-10964. eISSN 1948-7185. Available under: doi: 10.1021/acs.jpclett.2c02138
BibTex
@article{Scherer2022-12-01Incre-59628,
  year={2022},
  doi={10.1021/acs.jpclett.2c02138},
  title={Increasing the Modulation Depth of Gd<sup>III</sup>-Based Pulsed Dipolar EPR Spectroscopy (PDS) with Porphyrin–Gd<sup>III</sup> Laser-Induced Magnetic Dipole Spectroscopy},
  number={47},
  volume={13},
  journal={The Journal of Physical Chemistry Letters},
  pages={10958--10964},
  author={Scherer, Andreas and Yao, Xuemei and Qi, Mian and Wiedmaier, Max and Godt, Adelheid and Drescher, Malte}
}
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