Startseite Naturwissenschaften Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants
Artikel
Lizenziert
Nicht lizenziert Erfordert eine Authentifizierung

Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants

  • Andrey A. Kuzhelev , Victor M. Tormyshev EMAIL logo , Olga Yu. Rogozhnikova , Dmitry V. Trukhin , Tatiana I. Troitskaya , Rodion K. Strizhakov , Olesya A. Krumkacheva , Matvey V. Fedin und Elena G. Bagryanskaya EMAIL logo
Veröffentlicht/Copyright: 5. Oktober 2016
Zeitschrift für Physikalische Chemie
Aus der Zeitschrift Zeitschrift für Physikalische Chemie Band 231 Heft 4

Abstract

Triarylmethyl (TAM) radicals are widely used in electron paramagnetic resonance (EPR) spectroscopy as spin labels and in EPR imaging as spin probes for in vivo oxymetry. One of the key advantages of TAMs is the extremely narrow EPR line, especially in case of deuterated analogs (~2.5 μT). Another advantage is their slow spin relaxation even at physiological temperatures; in particular, this characteristic enables the use of pulsed dipolar EPR methods for distance measurements in biomolecules. In this study, a large series of TAM radicals and their deuterated analogs was synthesized, and the corresponding spectroscopic parameters including 13C hyperfine constants were determined for the first time. We observed negligible dependence of 13C hyperfine constants on the solvent or on the structure or number of substituents at para-C atoms of the aromatic rings. In addition, we demonstrated that 13C signals at natural abundance can be used for successful distance measurements at room temperature by pulsed electron double resonance (PELDOR or DEER).

Keywords: triarylmethyl radical

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

Acknowledgments

This work was supported by the Russian Science Foundation (grant No. 14-14-00922). We thank Dr. Georgiy Shevelev and Prof. Dmitrii Pyshnyi for providing the TAM-labeled DNA duplex in trehalose.

  1. Conflict of interest statement: The authors declare that they have no competing financial interests.

References

1. S. Anderson, K. Golman, F. Rise, H. Wikstrom, L. Wistrand, US Patent 5530140 (1996).Suche in Google Scholar

2. S. Andersson, F. Radner, A. Rydbeck, R. Servin, L. G. Wistrand, US5728370 A (1998).Suche in Google Scholar

3. M. Thaning, WO1998039277 A1 (1998).Suche in Google Scholar

4. J. H. Ardenkjaer-Larsen, I. Leunbach, WO1997009633 A1 (1997).Suche in Google Scholar

5. B. Epel, G. Redler, C. Pelizzari, V. M. Tormyshev, H. J. Halpern, in: C. E. Elwell, T. S. Leung, D. K. Harrison (Eds.), Oxygen transport to tissue XXXVII, Springer, New York (2016), p. 185.10.1007/978-1-4939-3023-4_23Suche in Google Scholar

6. B. Epel, G. Redler, V. Tormyshev, H. J. Halpern, in: C. E. Elwell, T. S. Leung, D. K. Harrison (Eds.), Oxygen transport to tissue XXXVII, Springer, New York (2016), P. 363.10.1007/978-1-4939-3023-4_45Suche in Google Scholar

7. I. Dhimitruka, A. A. Bobko, T. D. Eubank, D. A. Komarov, V. V. Khramtsov, J. Am. Chem. Soc. 135 (2013) 5904.10.1021/ja401572rSuche in Google Scholar PubMed PubMed Central

8. I. Dhimitruka, A. A. Bobko, C. M. Hadad, J. L. Zweier, V. V. Khramtsov, J. Am. Chem. Soc. 130 (2008) 10780.10.1021/ja803083zSuche in Google Scholar PubMed PubMed Central

9. I. Dhimitruka, M. Velayutham, A. A. Bobko, V. V. Khramtsov, F. A. Villamena, C. M. Hadad, J. L. Zweier, Bioorg. Med. Chem. Lett. 17 (2007) 6801.10.1016/j.bmcl.2007.10.030Suche in Google Scholar PubMed PubMed Central

10. L. Yong, J. Harbridge, R. W. Quine, G. A. Rinard, S. S. Eaton, G. R. Eaton, C. Mailer, E. Barth, H. J. Halpern, J. Magn. Reson. 152 (2001) 156.10.1006/jmre.2001.2379Suche in Google Scholar PubMed

11. R. Owenius, G. R. Eaton, S. S. Eaton, J. Magn. Reson. 172 (2005) 168.10.1016/j.jmr.2004.10.007Suche in Google Scholar PubMed

12. A. A. Kuzhelev, D. V. Trukhin, O. A. Krumkacheva, R. K. Strizhakov, O. Y. Rogozhnikova, T. I. Troitskaya, M. V. Fedin, V. M. Tormyshev, E. G. Bagryanskaya, J. Phys. Chem. B 119 (2015) 13630.10.1021/acs.jpcb.5b03027Suche in Google Scholar PubMed PubMed Central

13. N. Khan, H. Swartz, Mol. Cell. Biochem. 234 (2002) 341.10.1023/A:1015938528432Suche in Google Scholar

14. P. Kuppusamy, P. H. Wang, M. Chzhan, J. L. Zweier, Magn. Reson. Med. 37 (1997) 479.10.1002/mrm.1910370402Suche in Google Scholar PubMed

15. Y. P. Liu, F. A. Villamena, Y. G. Song, J. A. Sun, A. Rockenbauer, J. L. Zweier, J. Org. Chem. 75 (2010) 7796.10.1021/jo1016844Suche in Google Scholar PubMed PubMed Central

16. R. Halevy, V. Tormyshev, A. Blank, Biophys. J. 99 (2010) 971.10.1016/j.bpj.2010.05.002Suche in Google Scholar PubMed PubMed Central

17. Y. P. Liu, F. A. Villamena, J. Sun, T. Y. Wang, J. L. Zweier, Free Radical Biol. Med. 46 (2009) 876.10.1016/j.freeradbiomed.2008.12.011Suche in Google Scholar PubMed PubMed Central

18. Y. Liu, F. A. Villamena, J. Sun, Y. Xu, I. Dhimitruka, J. L. Zweier, J. Org. Chem. 73 (2008) 1490.10.1021/jo7022747Suche in Google Scholar PubMed

19. C. Rizzi, A. Samouilov, V. K. Kutala, N. L. Parinandi, J. L. Zweier, P. Kuppusamy, Free Radical Biol. Med. 35 (2003) 1608.10.1016/j.freeradbiomed.2003.09.014Suche in Google Scholar PubMed

20. M. Elas, D. Hleihel, E. D. Barth, C. R. Haney, K. H. Ahn, C. A. Pelizzari, B. Epel, R. R. Weichselbaum, H. J. Halpern, Mol. Imaging. Biol. 13 (2011) 1107.10.1007/s11307-010-0436-4Suche in Google Scholar PubMed PubMed Central

21. M. Elas, K. H. Ahn, A. Parasca, E. D. Barth, D. Lee, C. Haney, H. J. Halpern, Clin. Cancer Res. 12 (2006) 4209.10.1158/1078-0432.CCR-05-0446Suche in Google Scholar PubMed

22. M. Elas, B. B. Williams, A. Parasca, C. Mailer, C. A. Pelizzari, M. A. Lewis, J. N. River, G. S. Karczmar, E. D. Barth, H. J. Halpern, Magn. Reson. Med. 49 (2003) 682.10.1002/mrm.10408Suche in Google Scholar PubMed

23. B. Driesschaert, V. Marchand, P. Leveque, B. Gallez, J. Marchand-Brynaert, Chem. Commun. (Camb) 48 (2012) 4049.10.1039/c2cc00025cSuche in Google Scholar PubMed

24. A. A. Bobko, I. Dhimitruka, D. A. Komarov, V. V. Khramtsov, Anal. Chem. 84 (2012) 6054.10.1021/ac3008994Suche in Google Scholar PubMed PubMed Central

25. Y. Talmon, L. Shtirberg, W. Harneit, O. Y. Rogozhnikova, V. Tormyshev, A. Blank, Phys. Chem. Chem. Phys. 12 (2010) 5998.10.1039/b922060gSuche in Google Scholar PubMed

26. J. Leggett, R. Hunter, J. Granwehr, R. Panek, A. J. Perez-Linde, A. J. Horsewill, J. McMaster, G. Smith, W. Kockenberger, Phys. Chem. Chem. Phys. 12 (2010) 5883.10.1039/c002566fSuche in Google Scholar PubMed

27. J. H. Ardenkjaer-Larsen, B. Fridlund, A. Gram, G. Hansson, L. Hansson, M. H. Lerche, R. Servin, M. Thaning, K. Golman, Proc. Natl. Acad. Sci. USA. 100 (2003) 10158.10.1073/pnas.1733835100Suche in Google Scholar

28. Z. Y. Yang, Y. P. Liu, P. Borbat, J. L. Zweier, J. H. Freed, W. L. Hubbell, J. Am. Chem. Soc. 134 (2012) 9950.10.1021/ja303791pSuche in Google Scholar

29. G. Y. Shevelev, O. A. Krumkacheva, A. A. Lomzov, A. A. Kuzhelev, O. Y. Rogozhnikova, D. V. Trukhin, T. I. Troitskaya, V. M. Tormyshev, M. V. Fedin, D. V. Pyshnyi, E. G. Bagryanskaya, J. Am. Chem. Soc. 136 (2014) 9874.10.1021/ja505122nSuche in Google Scholar

30. G. Y. Shevelev, O. A. Krumkacheva, A. A. Lomzov, A. A. Kuzhelev, D. V. Trukhin, O. Y. Rogozhnikova, V. M. Tormyshev, D. V. Pyshnyi, M. V. Fedin, E. G. Bagryanskaya, J. Phys. Chem. B 119 (2015) 13641.10.1021/acs.jpcb.5b03026Suche in Google Scholar

31. Z. Yang, M. D. Bridges, C. J. López, O. Y. Rogozhnikova, D. V. Trukhin, E. K. Brooks, V. Tormyshev, H. J. Halpern, W. L. Hubbell, J. Magn. Reson. 269 (2016) 50.10.1016/j.jmr.2016.05.006Suche in Google Scholar

32. A. D. Milov, K. M. Salikhov, M. D. Shirov, Fiz. Tverd. Tela 23 (1981) 975.Suche in Google Scholar

33. M. Pannier, S. Veit, A. Godt, G. Jeschke, H. W. Spiess, J. Magn. Reson. 142 (2000) 331.10.1006/jmre.1999.1944Suche in Google Scholar

34. S. Saxena, J. H. Freed, J. Chem. Phys. 107 (1997) 1317.10.1063/1.474490Suche in Google Scholar

35. P. P. Borbat, J. H. Freed, Chem. Phys. Lett. 313 (1999) 145.10.1016/S0009-2614(99)00972-0Suche in Google Scholar

36. G. Jeschke, M. Pannier, A. Godt, H. W. Spiess, Chem. Phys. Lett. 331 (2000) 243.10.1016/S0009-2614(00)01171-4Suche in Google Scholar

37. H. Jager, A. Koch, V. Maus, H. W. Spiess, G. Jeschke, J. Magn. Reson. 194 (2008) 254.10.1016/j.jmr.2008.07.012Suche in Google Scholar PubMed

38. S. Razzaghi, E. K. Brooks, E. Bordignon, W. L. Hubbell, M. Yulikov, G. Jeschke, ChemBioChem 14 (2013) 1883.10.1002/cbic.201300165Suche in Google Scholar

39. D. Akhmetzyanov, P. Schöps, A. Marko, N. Kunjir, S. T. Sigurdsson, T. Prisner, Phys. Chem. Chem. Phys. 17 (2015) 24446.10.1039/C5CP03671BSuche in Google Scholar

40. A. A. Kuzhelev, G. Y. Shevelev, O. A. Krumkacheva, V. M. Tormyshev, D. V. Pyshnyi, M. V. Fedin, E. G. Bagryanskaya, J. Phys. Chem. Lett. 7 (2016) 2544.10.1021/acs.jpclett.6b01024Suche in Google Scholar

41. V. Meyer, M. A. Swanson, L. J. Clouston, P. J. Boratyński, R. A. Stein, H. S. Mchaourab, A. Rajca, S. S. Eaton, G. R. Eaton, Biophys. J. 108 (2015) 1213.10.1016/j.bpj.2015.01.015Suche in Google Scholar

42. A. A. Kuzhelev, R. K. Strizhakov, O. A. Krumkacheva, Y. F. Polienko, D. A. Morozov, G. Y. Shevelev, D. V. Pyshnyi, I. A. Kirilyuk, M. V. Fedin, E. G. Bagryanskaya, J. Magn. Reson. 266 (2016) 1.10.1016/j.jmr.2016.02.014Suche in Google Scholar

43. G. W. Reginsson, N. C. Kunjir, S. T. Sigurdsson, O. Schiemann, Chem-Eur. J. 18 (2012) 13580.10.1002/chem.201203014Suche in Google Scholar

44. B. Mohos, F. Tüdös, L. Jókay, Phys. Lett. A 24 (1967) 310.10.1016/0375-9601(67)90597-XSuche in Google Scholar

45. K. Schreiner, A. Berndt, F. Baer, Mol. Phys. 26 (1973) 929.10.1080/00268977300102181Suche in Google Scholar

46. M. K. Bowman, C. Mailer, H. J. Halpern, J. Magn. Reson. 172 (2005) 254.10.1016/j.jmr.2004.10.010Suche in Google Scholar PubMed

47. O. Y. Rogozhnikova, V. G. Vasiliev, T. I. Troitskaya, D. V. Trukhin, T. V. Mikhalina, H. J. Halpern, V. M. Tormyshev, Eur. J. Org. Chem. 2013 (2013) 3347.10.1002/ejoc.201300176Suche in Google Scholar PubMed PubMed Central

48. D. V. Trukhin, O. Y. Rogozhnikova, T. I. Troitskaya, V. G. Vasiliev, M. K. Bowman, V. M. Tormyshev, Synlett 27 (2016) 893.10.1055/s-0035-1561299Suche in Google Scholar PubMed PubMed Central

49. E. Mohacsi, Synth. Commun. 15 (1985) 723.10.1080/00397918508063864Suche in Google Scholar

50. S. Stoll, A. Schweiger, J. Magn. Reson. 178 (2006) 42.10.1016/j.jmr.2005.08.013Suche in Google Scholar PubMed

51. A. J. Fielding, P. J. Carl, G. R. Eaton, S. S. Eaton, Appl. Magn. Reson. 28 (2005) 231.10.1007/BF03166758Suche in Google Scholar

52. G. Jeschke, V. Chechik, P. Ionita, A. Godt, H. Zimmermann, J. Banham, C. R. Timmel, D. Hilger, H. Jung, Appl. Magn. Reson. 30 (2006) 473.10.1007/BF03166213Suche in Google Scholar

Supplemental Material:

The online version of this article (DOI: 10.1515/zpch-2016-0811) offers supplementary material, available to authorized users.

Received: 2016-6-7
Accepted: 2016-9-2
Published Online: 2016-10-5
Published in Print: 2017-4-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Basic and Combination Cross-Features in X- and Q-band HYSCORE of the 15N Labeled Bacteriochlorophyll a Cation Radical
  4. An EPR Study of Small Magnetic Nanoparticles
  5. Magnetic Resonance Study of the Spin-1/2 Quantum Magnet BaAg2Cu[VO4]2
  6. Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants
  7. Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group
  8. Surface Hydroxyl OH Defects of η-Al2O3 and χ-Al2O3 by Solid State NMR, XRD, and DFT Calculations
  9. THz ESR study of Spinel Compound GeCo2O4
  10. Self-Association of Glycyrrhizic Acid. NMR Study
  11. A Site-Specific Study of the Magnetic Field-Dependent Proton Spin Relaxation of an Iridium N-Heterocyclic Carbene Complex
  12. Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
  13. Electron Paramagnetic Resonance and DFT Analysis of the Effects of Bulky Perfluoroalkyl Substituents on a Vanadyl Perfluoro Phthalocyanine
  14. Coordination of the Mn4+-Center in Layered Li[Co0.98Mn0.02]O2 Cathode Materials for Lithium-Ion Batteries
  15. Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency
https://doi.org/10.1515/zpch-2016-0811
Schlagwörter für diesen Artikel
triarylmethyl radical

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Basic and Combination Cross-Features in X- and Q-band HYSCORE of the 15N Labeled Bacteriochlorophyll a Cation Radical
  4. An EPR Study of Small Magnetic Nanoparticles
  5. Magnetic Resonance Study of the Spin-1/2 Quantum Magnet BaAg2Cu[VO4]2
  6. Triarylmethyl Radicals: An EPR Study of 13C Hyperfine Coupling Constants
  7. Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group
  8. Surface Hydroxyl OH Defects of η-Al2O3 and χ-Al2O3 by Solid State NMR, XRD, and DFT Calculations
  9. THz ESR study of Spinel Compound GeCo2O4
  10. Self-Association of Glycyrrhizic Acid. NMR Study
  11. A Site-Specific Study of the Magnetic Field-Dependent Proton Spin Relaxation of an Iridium N-Heterocyclic Carbene Complex
  12. Multifrequency Multiresonance EPR Investigation of Halogen-bonded Complexes Involving Neutral Nitroxide Radicals
  13. Electron Paramagnetic Resonance and DFT Analysis of the Effects of Bulky Perfluoroalkyl Substituents on a Vanadyl Perfluoro Phthalocyanine
  14. Coordination of the Mn4+-Center in Layered Li[Co0.98Mn0.02]O2 Cathode Materials for Lithium-Ion Batteries
  15. Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency
Jetzt anmelden und 20% sparen
Institutioneller Zugang
Wie funktioniert Authentifizierung?
Haben Sie eine Idee, wie wir unsere Website verbessern können?
Bitte schreiben Sie uns.
© 2025 De Gruyter Brill
Heruntergeladen am 8.12.2025 von https://www.degruyterbrill.com/document/doi/10.1515/zpch-2016-0811/html?lang=de
Button zum nach oben scrollen