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Multi-Gaussian Monte Carlo Analysis of PELDOR Data in the Frequency Domain

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Published/Copyright: October 26, 2016
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 231 Issue 3

Abstract

Pulsed double electron–electron resonance technique (PELDOR or DEER) is often applied to study conformations and aggregation of spin-labelled macromolecules. Because of the ill-posed nature of the integral equation determining the distance distribution function, a regularization procedure is required to restrict the smoothness of the solution. In this work, we performed PELDOR measurements for new flexible nitroxide biradicals based on trolox, which is the synthetic analogue of α-tocopherol; spin-labelled trolox derivatives are investigated as potential anti-cancer drugs. We use regularization by an approximation of the solution with a sum of limited number of Gaussians, by varying their positions, widths and amplitudes. Their best-fitted values were found by a completely random Monte Carlo process. The use of the frequency-domain PELDOR data allowed diminution of the artifacts induced by spin–spin electron–nuclear and intermolecular electron–electron interactions. It was found that for the all biradicals studied, the use of three Gaussians was enough for good agreement with the experiments. The number of trials for obtaining satisfactory result was found to be quite reasonable, which is explained by presence of the singularity in the core of integral equation. The maxima of inter-spin distance distribution for different biradicals were found to vary between 1.5 and 2.3 nm, depending on the linkers between the Trolox core and nitroxides. The distance distributions around these positions reflect flexibility of the biradicals.

Keywords: biradicals; DEER; DNA; Fredholm equation regularization; Monte Carlo fitting; peptide antibiotics; RNA; spin labels; Trolox

Dedicated to: Kev Salikhov on the occasion of his 80th birthday.

Acknowledgments

This work was supported by the Russian Science Foundation, project # 15-15-00021.

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Received: 2016-6-17
Accepted: 2016-10-6
Published Online: 2016-10-26
Published in Print: 2017-3-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Intramolecular Electron Transfer from Tryptophan to Guanosyl Radicals in a Linked System as a Model of DNA Repair
  4. SABRE Hyperpolarization of Bipyridine Stabilized Ir-Complex at High, Low and Ultralow Magnetic Fields
  5. Relaxation of Multiple Quantum NMR Coherences in Quasi-One-Dimensional Spin Systems
  6. Exciting Wide NMR Spectra of Static Solid Samples with Weak Radiofrequency Fields
  7. Spin Dynamics and Establishing of Internal Quasi-Equilibrium in Dilute Paramagnetic Solids
  8. Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla
  9. Gas-Phase Hydrogenation with Parahydrogen Over Immobilized Vaska’s Complex
  10. Triplet Charge Recombination in Heliobacterial Reaction Centers Does Not Produce a Spin-Polarized EPR Spectrum
  11. Photoinduced Electron Transfer in Dyads with (R)-/(S)-Naproxen and (S)-Tryptophan
  12. Toward Matching Optically and NMR Active Volumes for Optimizing the Observation of Photo-Induced Reactions by NMR
  13. Pulsed EPR Signals from Triplets
  14. 31P-Solid-State NMR Characterization and Catalytic Hydrogenation Tests of Novel heterogenized Iridium-Catalysts
  15. Multi-Gaussian Monte Carlo Analysis of PELDOR Data in the Frequency Domain
  16. Concept of Phase Cycling in Pulsed Magnetic Resonance Using Sinusoidal Magnetic Field Modulation
https://doi.org/10.1515/zpch-2016-0830
Keywords for this article
biradicals; DEER; DNA; Fredholm equation regularization; Monte Carlo fitting; peptide antibiotics; RNA; spin labels; Trolox

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Intramolecular Electron Transfer from Tryptophan to Guanosyl Radicals in a Linked System as a Model of DNA Repair
  4. SABRE Hyperpolarization of Bipyridine Stabilized Ir-Complex at High, Low and Ultralow Magnetic Fields
  5. Relaxation of Multiple Quantum NMR Coherences in Quasi-One-Dimensional Spin Systems
  6. Exciting Wide NMR Spectra of Static Solid Samples with Weak Radiofrequency Fields
  7. Spin Dynamics and Establishing of Internal Quasi-Equilibrium in Dilute Paramagnetic Solids
  8. Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla
  9. Gas-Phase Hydrogenation with Parahydrogen Over Immobilized Vaska’s Complex
  10. Triplet Charge Recombination in Heliobacterial Reaction Centers Does Not Produce a Spin-Polarized EPR Spectrum
  11. Photoinduced Electron Transfer in Dyads with (R)-/(S)-Naproxen and (S)-Tryptophan
  12. Toward Matching Optically and NMR Active Volumes for Optimizing the Observation of Photo-Induced Reactions by NMR
  13. Pulsed EPR Signals from Triplets
  14. 31P-Solid-State NMR Characterization and Catalytic Hydrogenation Tests of Novel heterogenized Iridium-Catalysts
  15. Multi-Gaussian Monte Carlo Analysis of PELDOR Data in the Frequency Domain
  16. Concept of Phase Cycling in Pulsed Magnetic Resonance Using Sinusoidal Magnetic Field Modulation
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