Light-induced dipolar spectroscopy : A quantitative comparison between LiDEER and LaserIMD

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Journal of Magnetic Resonance. 2018, 296, pp. 29-35. ISSN 1090-7807. eISSN 1096-0856. Available under: doi: 10.1016/j.jmr.2018.08.006
Zusammenfassung

Nanometric distance measurements with EPR spectroscopy yield crucial information on the structure and interactions of macromolecules in complex systems. The range of suitable spin labels for such measurements was recently expanded with a new class of light-inducible labels: the triplet state of porphyrins. Importantly, accurate distance measurements between a triplet label and a nitroxide have been reported with two distinct light-induced spectroscopy techniques, (light-induced) triplet-nitroxide DEER (LiDEER) and laser-induced magnetic dipole spectroscopy (LaserIMD). In this work, we set out to quantitatively compare the two techniques under equivalent conditions at Q band. Since we find that LiDEER using a rectangular pump pulse does not reach the high modulation depth that can be achieved with LaserIMD, we further explore the possibility of improving the LiDEER experiment with chirp inversion pulses. LiDEER employing a broadband pump pulse results in a drastic improvement of the modulation depth. The relative performance of chirp LiDEER and Laser-IMD in terms of modulation-to-noise ratio is found to depend on the dipolar evolution time: While LaserIMD yields higher modulation-to-noise ratios than LiDEER at short dipolar evolution times (τ=2μs), the high phase memory time of the triplet spins causes the situation to revert at τ=6μs.

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540 Chemie
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EPR; Pulsed EPR; Light-induced dipolar spectroscopy; Triplet state; LaserIMD; LiDEER; Light-induced; PELDOR; DEER; PELDOR; Porphyrins; Chirp pulses; AWG
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ISO 690BIEBER, Anna, Dennis BÜCKER, Malte DRESCHER, 2018. Light-induced dipolar spectroscopy : A quantitative comparison between LiDEER and LaserIMD. In: Journal of Magnetic Resonance. 2018, 296, pp. 29-35. ISSN 1090-7807. eISSN 1096-0856. Available under: doi: 10.1016/j.jmr.2018.08.006
BibTex
@article{Bieber2018-11Light-44328,
  year={2018},
  doi={10.1016/j.jmr.2018.08.006},
  title={Light-induced dipolar spectroscopy : A quantitative comparison between LiDEER and LaserIMD},
  volume={296},
  issn={1090-7807},
  journal={Journal of Magnetic Resonance},
  pages={29--35},
  author={Bieber, Anna and Bücker, Dennis and Drescher, Malte}
}
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