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Abstract

PELDOR or DEER spectroscopy is a magnetic resonance method to probe spin interactions between free radicals. It was proposed and demonstrated in the 1980s and has developed into a powerful means to routinely measure distances in non-crystalline chemical, macromolecular and biological systems on the nanometer length scale. The basis of PELDOR spectroscopy is introduced using a simple model with two unpaired electron spins.

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References

  1. Milov AD, Salikhov KM, Shirov MD (1981) Application of eldor in electron-spin echo for paramagnetic center space distribution in solids. Fiz Tverd Tela 23(4):975–982

    CAS  Google Scholar 

  2. Stein RA, Beth AH, Hustedt EJ (2015) A straightforward approach to the analysis of double electron-electron resonance data. Methods Enzymol 563:531–567. https://doi.org/10.1016/bs.mie.2015.07.031

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Milov AD, Ponomarev AB, Tsvetkov YD (1984) Modulation beats of signal of double electron-electron resonance in spin-echo for biradical systems. J Struct Chem 25(5):710–713. https://doi.org/10.1007/Bf00747913

    Article  Google Scholar 

  4. Klauder JR, Anderson PW (1962) Spectral diffusion decay in spin resonance experiments. Phys Rev 125(3):912–932. https://doi.org/10.1103/PhysRev.125.912

    Article  CAS  Google Scholar 

  5. Hahn EL (1950) Spin echoes. Phys Rev 80(4):580–594

    Article  Google Scholar 

  6. Salikhov KM, Semenov AG, Tsvetkov YD (1976) Electron spin echo and its applications. Nauka, Novosibirsk

    Google Scholar 

  7. Pannier M, Veit S, Godt A, Jeschke G, Spiess HW (2000) Dead-time free measurement of dipole-dipole interactions between electron spins. J Magn Reson 142(2):331–340. https://doi.org/10.1006/jmre.1999.1944

    Article  CAS  PubMed  Google Scholar 

  8. Kaplan DE, Hahn EL (1958) Experiences de double irradiation en resonance magnetique par la methode dimpulsions. J Phys-Paris 19(11):821–825. https://doi.org/10.1051/jphysrad:019580019011082100

    Article  Google Scholar 

  9. Graf R, Demco DE, Gottwald J, Hafner S, Spiess HW (1997) Dipolar couplings and internuclear distances by double-quantum nuclear magnetic resonance spectroscopy of solids. J Chem Phys 106(3):885–895. https://doi.org/10.1063/1.473169

    Article  CAS  Google Scholar 

  10. Emshwiller M, Hahn EL, Kaplan D (1960) Pulsed nuclear resonance spectroscopy. Phys Rev 118(2):414–424. https://doi.org/10.1103/PhysRev.118.414

    Article  CAS  Google Scholar 

  11. Maryasov AG, Tsvetkov YD (2000) Formation of the pulsed electron-electron double resonance signal in the case of a finite amplitude of microwave fields. Appl Magn Reson 18(4):583–605. https://doi.org/10.1007/Bf03162305

    Article  Google Scholar 

  12. Milov AD, Maryasov AG, Tsvetkov YD (1998) Pulsed electron double resonance (PELDOR) and its applications in free-radicals research. Appl Magn Reson 15(1):107–143. https://doi.org/10.1007/Bf03161886

    Article  CAS  Google Scholar 

  13. Tsvetkov YD (1989) ELDOR in ESE study of magnetic dipole-dipole interactions. In: Keijzers CP, Reijerse EJ, Schmidt J (eds) Pulsed EPR: a new field of applications. North Holland, Amsterdam, pp 206–218

    Google Scholar 

  14. Maryasov AG, Tsvetkov YD, Raap J (1998) Weakly coupled radical pairs in solids: ELDOR in ESE structure studies. Appl Magn Reson 14(1):101–113. https://doi.org/10.1007/Bf03162010

    Article  CAS  Google Scholar 

  15. Parmon VN, Kokorin AI, Zhidomirov GM (1980) Stable biradicals. Nauka, Moscow

    Google Scholar 

  16. Bowman MK, Maryasov AG, Kim N, DeRose VJ (2004) Visualization of distance distribution from pulsed double electron-electron resonance data. Appl Magn Reson 26(1–2):23–39. https://doi.org/10.1007/Bf03166560

    Article  CAS  Google Scholar 

  17. Abragam A (1961) The Principles of Nuclear Magnetism. Clarendon Press, Oxford

    Google Scholar 

  18. Raitsimring AM, Salikhov KM (1985) Electron spin echo method as used to analyze the spatial distribution of paramagnetic centers. Bull Magn Reson 7(4):184–217

    CAS  Google Scholar 

  19. Kutsovsky YE, Maryasov AG, Aristov YI, Parmon VN (1990) Electron-spin echo as a tool for investigation of surface-structure of finely dispersed fractal solids. React Kinet Catal L 42(1):19–24. https://doi.org/10.1007/Bf02137612

    Article  Google Scholar 

  20. Milov AD, Samoilova RI, Tsvetkov YD, Gusev VA, Formaggio F, Crisma M, Toniolo C, Raap J (2002) Spatial distribution of spin-labeled trichogin GA IV in the gram-positive bacterial cell membrane determined from PELDOR data. Appl Magn Reson 23(1):81–95. https://doi.org/10.1007/Bf03166186

    Article  CAS  Google Scholar 

  21. Milov AD, Tsvetkov YD (1997) Double electron-electron resonance in electron spin echo: Conformations of spin-labeled poly-4-vinilpyridine in glassy solutions. Appl Magn Reson 12(4):495–504

    Article  CAS  Google Scholar 

  22. Uemura S, Okada M, Abedin KM, Nakatsuka H (1992) Fractal interpretation of Non-Lorentzian persistent hole shapes in organic glasses. Chem Phys Lett 189(2):193–196. https://doi.org/10.1016/0009-2614(92)85122-Q

    Article  CAS  Google Scholar 

  23. Tsvetkov YD (2004) Peptide aggregation and conformation properties as studied by pulsed electron-electron double resonance. In: Bender C, Berliner LJ (eds) EPR: instrumental methods. Biological magnetic resonance, vol 21. Springer, New York. https://doi.org/10.1007/978-1-4419-8951-2

    Chapter  Google Scholar 

  24. Milov AD, Maryasov AG, Tsvetkov YD, Raap J (1999) Pulsed ELDOR in spin-labeled polypeptides. Chem Phys Lett 303(1–2):135–143. https://doi.org/10.1016/S0009-2614(99)00220-1

    Article  CAS  Google Scholar 

  25. Milov AD, Tsvetkov YD (2000) Charge effect on relative distance distribution of Fremy’s radical ions in frozen glassy solution studied by PELDOR. Appl Magn Reson 18(2):217–226. https://doi.org/10.1007/Bf03162112

    Article  CAS  Google Scholar 

  26. Milov AD, Ponomarev AB, Tsvetkov YD (1984) Electron electron double-resonance in electron-spin echo—model biradical systems and the sensitized photolysis of decalin. Chem Phys Lett 110(1):67–72. https://doi.org/10.1016/0009-2614(84)80148-7

    Article  CAS  Google Scholar 

  27. Ponomarev AB, Milov AD, Tsvetkov YD (1988) Double electron-electron resonance in electron-spin echo and the spatial distribution of radicals formed by irradiation of frozen cyclohexane. Khim Fiz 7(12):1673–1679

    CAS  Google Scholar 

  28. Ponomarev AB, Milov AD, Tsvetkov YD (1990) Double electron-electron resonance in electron-spin echo—spatial distribution of radicals forming during radiolysis of polyethylene, monocarboxylic and dicarboxylic acids. Khim Fiz 9(4):498–503

    CAS  Google Scholar 

  29. Salikhov KM, Khairuzhdinov IT, Zaripov RB (2014) Three-pulse ELDOR theory revisited. Appl Magn Reson 45(6):573–619. https://doi.org/10.1007/s00723-014-0541-7

    Article  CAS  Google Scholar 

  30. Salikhov KM, Khairuzhdinov IT (2014) Four-pulse ELDOR theory of the spin ½ label pairs extended to overlapping EPR spectra and to overlapping pump and observer excitation bands. Appl Magn Reson 46(1):67–83. https://doi.org/10.1007/s00723-014-0609-4

    Article  CAS  Google Scholar 

  31. Edwards TH, Stoll S (2018) Optimal Tikhonov regularization for DEER spectroscopy. J Magn Reson 288:58–68. https://doi.org/10.1016/j.jmr.2018.01.021

    Article  CAS  PubMed  Google Scholar 

  32. Jeschke G, Koch A, Jonas U, Godt A (2002) Direct conversion of EPR dipolar time evolution data to distance distributions. J Magn Reson 155(1):72–82. https://doi.org/10.1006/jmre.2001.2498

    Article  CAS  PubMed  Google Scholar 

  33. Milov AD, Tsvetkov YD, Formaggio F, Oancea S, Toniolo C, Raap J (2003) Aggregation of spin labeled trichogin GA IV dimers: distance distribution between spin labels in frozen solutions by PELDOR data. J Phys Chem B 107(49):13719–13727. https://doi.org/10.1021/jp035057x

    Article  CAS  Google Scholar 

  34. Chiang YW, Borbat PP, Freed JH (2005) The determination of pair distance distributions by pulsed ESR using Tikhonov regularization. J Magn Reson 172(2):279–295. https://doi.org/10.1016/j.jmr.2004.10.012

    Article  CAS  PubMed  Google Scholar 

  35. Jeschke G, Panek G, Godt A, Bender A, Paulsen H (2004) Data analysis procedures for pulse ELDOR measurements of broad distance distributions. Appl Magn Reson 26(1–2):223–244. https://doi.org/10.1007/Bf03166574

    Article  CAS  Google Scholar 

  36. Dzuba SA (2016) The determination of pair-distance distribution by double electron-electron resonance: regularization by the length of distance discretization with Monte Carlo calculations. J Magn Reson 269:113–119. https://doi.org/10.1016/j.jmr.2016.06.001

    Article  CAS  PubMed  Google Scholar 

  37. Matveeva AG, Nekrasov VM, Maryasov AG (2017) Analytical solution of the PELDOR inverse problem using the integral Mellin transform. Phys Chem Chem Phys 19(48):32381–32388. https://doi.org/10.1039/c7cp04059h

    Article  CAS  PubMed  Google Scholar 

  38. Tikhonov AN, Arsenin VY (1977) Solutions of ill-posed problems. Scripta series in mathematics. Winston; Halsted Press, Washington, New York

    Google Scholar 

  39. Bowman MK, Maryasov AG (2007) Dynamic phase shifts in nanoscale distance measurements by double electron electron resonance (DEER). J Magn Reson 185(2):270–282. https://doi.org/10.1016/j.jmr.2006.12.011

    Article  CAS  PubMed  Google Scholar 

  40. Jeschke G, Chechik V, Ionita P, Godt A, Zimmermann H, Banham J, Timmel CR, Hilger D, Jung H (2006) DeerAnalysis2006—a comprehensive software package for analyzing pulsed ELDOR data. Appl Magn Reson 30(3–4):473–498. https://doi.org/10.1007/Bf03166213

    Article  CAS  Google Scholar 

  41. Borbat PP, Freed JH (2002) Double-quantum ESR and distance measurements. In: Berliner LJ, Eaton SS, Eaton GR (eds) Distance measurements in biological systems by EPR, vol 19. Springer, New York. https://doi.org/10.1007/b111467

    Chapter  Google Scholar 

  42. Godt A, Schulte M, Zimmermann H, Jeschke G (2006) How flexible are poly(para-phenyleneethynylene)s? Angew Chem Int Edit 45(45):7560–7564. https://doi.org/10.1002/anie.200602807

    Article  CAS  Google Scholar 

  43. Sicoli G, Mathis G, Aci-Seche S, Saint-Pierre C, Boulard Y, Gasparutto D, Gambarelli S (2009) Lesion-induced DNA weak structural changes detected by pulsed EPR spectroscopy combined with site-directed spin labelling. Nucleic Acids Res 37(10):3165–3176. https://doi.org/10.1093/nar/gkp165

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  44. Schnegg A, Dubinskii AA, Fuchs MR, Grishin YA, Kirilina EP, Lubitz W, Plato M, Savitsky A, Mobius K (2007) High-field EPR, ENDOR and ELDOR on bacterial photosynthetic reaction centers. Appl Magn Reson 31(1–2):59–98

    Article  CAS  Google Scholar 

  45. Mobius K, Lubitz W, Savitsky A (2013) High-field EPR on membrane proteins—crossing the gap to NMR. Prog Nucl Mag Res Sp 75:1–49. https://doi.org/10.1016/j.pnmrs.2013.07.002

    Article  CAS  Google Scholar 

  46. Savitsky A, Dubinskii AA, Flores M, Lubitz W, Mobius K (2007) Orientation-resolving pulsed electron dipolar high-field EPR spectroscopy on disordered solids: I. Structure of spin-correlated radical pairs in bacterial photosynthetic reaction centers. J Phys Chem B 111(22):6245–6262. https://doi.org/10.1021/jp070016c

    Article  CAS  PubMed  Google Scholar 

  47. Denysenkov VP, Prisner TF, Stubbe J, Bennati M (2006) High-field pulsed electron-electron double resonance spectroscopy to determine the orientation of the tyrosyl radicals in ribonucleotide reductase. P Natl Acad Sci USA 103(36):13386–13390. https://doi.org/10.1073/pnas.0605851103

    Article  CAS  Google Scholar 

  48. Polyhach Y, Godt A, Bauer C, Jeschke G (2007) Spin pair geometry revealed by high-field DEER in the presence of conformational distributions. J Magn Reson 185(1):118–129. https://doi.org/10.1016/j.jmr.2006.11.012

    Article  CAS  PubMed  Google Scholar 

  49. Bowen AM, Tait CE, Timmel CR, Harmer JR (2013) Orientation-selective deer using rigid spin labels, cofactors, metals, and clusters. In: Timmel CR, Harmer JR (eds) Structural information from spin-labels and intrinsic paramagnetic centres in the biosciences. Springer, Berlin, Heidelberg, pp 283–327. https://doi.org/10.1007/430_2013_115

    Chapter  Google Scholar 

  50. Yang ZY, Kise D, Saxena S (2010) An approach towards the measurement of nanometer range distances based on Cu2+ ions and ESR. J Phys Chem B 114(18):6165–6174. https://doi.org/10.1021/jp911637s

    Article  CAS  PubMed  Google Scholar 

  51. Lovett JE, Bowen AM, Timmel CR, Jones MW, Dilworth JR, Caprotti D, Bell SG, Wong LL, Harmer J (2009) Structural information from orientationally selective DEER spectroscopy. Phys Chem Chem Phys 11(31):6840–6848. https://doi.org/10.1039/b907010a

    Article  CAS  PubMed  Google Scholar 

  52. Bode BE, Plackmeyer J, Prisner TF, Schiemann O (2008) PELDOR measurements on a nitroxide-labeled Cu(II) porphyrin: Orientation selection, spin-density distribution, and conformational flexibility. J Phys Chem A 112(23):5064–5073. https://doi.org/10.1021/jp710504k

    Article  CAS  PubMed  Google Scholar 

  53. Milov AD, Naumov BD, Tsvetkov YD (2004) The effect of microwave pulse duration on the distance distribution function between spin labels obtained by PELDOR data analysis. Appl Magn Reson 26(4):587–599. https://doi.org/10.1007/Bf03166585

    Article  CAS  Google Scholar 

  54. Milov AD, Tsvetkov YD, Maryasov AG, Gobbo M, Prinzivalli C, De Zotti M, Formaggio F, Toniolo C (2012) Conformational properties of the spin-labeled tylopeptin B and heptaibin peptaibiotics based on PELDOR spectroscopy data. Appl Magn Reson 44(4):495–508. https://doi.org/10.1007/s00723-012-0402-1

    Article  CAS  Google Scholar 

  55. Milov AD, Grishin YA, Dzuba SA, Tsvetkov YD (2011) Effect of pumping pulse duration on echo signal amplitude in four-pulse PELDOR. Appl Magn Reson 41(1):59–67. https://doi.org/10.1007/s00723-011-0232-6

    Article  Google Scholar 

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Correspondence to Yuri D. Tsvetkov .

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Tsvetkov, Y.D., Bowman, M.K., Grishin, Y.A. (2019). Introduction. In: Pulsed Electron–Electron Double Resonance. Springer, Cham. https://doi.org/10.1007/978-3-030-05372-7_1

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