Skip to main content

Part of the book series: Biological Magnetic Resonance ((BIMR,volume 19))

Abstract

“Allowed” double quantum ccherences (DQC) can now be routinely generated in disordered and oriented solids containing nitroxide biradicals and random distributions of stable radicals. The Pake doublets obtained from DQC pathways can be effectively used to determine a broad range of distances in the former case whereas decay constants yield concentrations in the latter. The DQC signals are strong and often comparable to standard single quantum signals. They are free of any large undesirable signals, so the DQ experiment is easy to perform. Their strong intensity permits the study of low concentrations of spins in samples typical of those ordinarily met in the case of doubly-labeled macromolecules such as proteins and polypeptides. The upper range of distances for systems labeled with nitroxides is estimated to be ca. 80 Å. In the limit of non-selective pulses the interpretation of DQC signals becomes independent of complicating geometric features which affect other ESR distance methods. The method is compared to other existing pulse distance measurement techniques and future improvements are also discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Abragam, A. (1961) The principles of nuclear magnetism. (Oxford Univ. Press, NY ), Ch. 4.

    Google Scholar 

  • Astashkin, A.V., Hara, H. and Kawamori A. (1997) The pulsed electron-electron double resonance and “2+1” electron spin echo study of the oriented oxygen-evolving and Mndepleted preparations of photosystem II. J. Chem. Phys., 108, 3805–3812.

    Article  Google Scholar 

  • Bloom, A.L. (1955) Nuclear induction in inhomogeneous fields. Phys. Rev. 98, 1105–1112.

    Article  CAS  Google Scholar 

  • Baum, J., Munowitz, M., Garroway. A.N. and Pines, A. (1985) Multiple-quantum dynamics in solid state NMR. J. Chem. Phys. 83, 2015–2025.

    Article  CAS  Google Scholar 

  • Bax, A., de Jong, P.G., Mehlkopf, A.F. and Smidt, J. (1980) Separation of the different orders of NMR multiple-quantum transitions by the use of pulsed field gradients. Chem. Phys. Leu., 69, 567–570.

    Article  CAS  Google Scholar 

  • Borbat, P.P., Berdnikov, V.M., Milov, A.D. and Tsvetkov, Yu.D. (1977) Spatial distribution and diffusion of hydrogen atoms formed on photolysis of Fe(II) in frozen sulfuric acid water solutions. Sov. Phys. Solid State, 19, 628–663.

    Google Scholar 

  • Borbat, P.P. Crepeau, R.H. and Freed, J.H. (1997) Multifrequency two-dimensional Fourier transform ESR: X/Ku-band spectrometer. J. Magn. Reson., 127, 155–167.

    Article  PubMed  CAS  Google Scholar 

  • Borbat, P.P. and Freed, J.H. (1999) Multiple-quantum ESR and distance measurements. Chem. Phys. Lett., 313, 145–154.

    Article  CAS  Google Scholar 

  • Borbat, P.P. and Freed J.H. (1999a) Progress in multiple-quantum ESR Spectroscopy: powerful tool for distance measurements, at “41st Rocky Mountain Conference on Analytical Chemistry”, Aug. 1–5, Denver, Colorado.

    Google Scholar 

  • Borbat, P.P. and Freed, J.H. (2000) Double and single quantum coherence ESR for distance measurements: effects of microwave B1 and frequency, (To be published).

    Google Scholar 

  • Budker, V., Du, J.-L., Seiter, M., Eaton, G.,R., Eaton, S.S. (1995) Electron-electron spin-spin interaction in spin-labeled low-spin methemoglobin, Biophys. J., 68, 2531–2542.

    Article  PubMed Central  PubMed  CAS  Google Scholar 

  • Cavanagh, J., Fairbrother, W.J., Palmer III, A.G., Skelton, N.J. (1996) Protein NMR Spectroscopy. Academic Press, San Diego.

    Google Scholar 

  • Chandrasekhar, S. (1943) Stochastic problems in physics and astronomy. Revs Modern. Phys. 15, 165–191

    Article  Google Scholar 

  • Corio, P.L. (1966) Structure of high-resolution NMR spectra. Academic Press, NY.

    Google Scholar 

  • Crepeau, R.H., Dulcic, A., Gorcester, J., Saarinen, T. and Freed, J.H. (1989) Composite pulses in time-domain ESR. J. Magn. Reson., 84, 184–190.

    Google Scholar 

  • Dikanov, S.A., Tsvetkov, Yu.D. (1992) Electron spin echo envelope modulation (ESEEM) spectroscopy. CRC Press, 21.

    Google Scholar 

  • Dzuba, S.A., Bosh, M.K., Hoff, A.J. (1996) Electron spin-echo detection of quantum beats and double-quantum coherence in spin-correlated radical pairs of protonated photosynthetic reaction centers. Chem. Phys. Leu., 248, 427–433.

    Article  CAS  Google Scholar 

  • Dzuba, S.A. and Kawamori, A. (1996) Selective hole burning in EPR: spectral diffusion and dipolar broadening. Concepts in Magnetic Resonance 8, 49–61.

    Article  CAS  Google Scholar 

  • Eaton, S.S. and Eaton, G.R. (1993) Irradiated fused-quartz standard sample for time-domain EPR. J. Magn. Reson. A. 102, 354–356.

    Article  CAS  Google Scholar 

  • Emshwiller, M., Hahn, E.I., Kaplan, D. (1960) Pulsed nuclear resonance spectroscopy. Phys. Rev., 118, 414–424.

    Article  CAS  Google Scholar 

  • Ernst, R.R., Bodenhausen, G., Wokaun, A. (1987) Principles of nuclear magnetic resonance in one and two dimensions. Clarendon Press, Oxford.

    Google Scholar 

  • Ewert, U, Crepeau, R.H., Lee, S., Dunnam C.R., Xu, D. and Freed, J.H. (1991) Fourier transform electron spin resonance imaging. Chem. Phys. Lett., 184, 25–33.

    Article  Google Scholar 

  • Farhbakhsh, Z.T., Huang, Q.-L., Ding, L.-L., Altenbach, C., Steinhoff, H.J., Horwitz, J. and Hubbell, W.L. (1995) Interaction of a-crystallin with spin-labeled peptides. Biochemistry, 34, 509–516.

    Article  Google Scholar 

  • Farkas, Z.D., Spalek, G. and Wilson P.B. (1989) RF pulse compression experiment at SLAC, Proceedings of the 1989 IEEE particle accelerator conference. Chicago, March 20–23, vol. 1, 132–134.

    Google Scholar 

  • Fauth, J.-M., Schweiger, A., Braunschweiler, L., Forrer, J. and Ernst, R.R. (1986) Elimination of unwanted echoes and reduction of dead time in three-pulse electron spin-echo spectroscopy. J. Magn. Reson., 66, 74–85.

    CAS  Google Scholar 

  • Feldman, E.B., Lacelle, S. (1996) Configurational averaging of dipolar interactions in magnetically dilute spin networks. J. Chem. Phys. 104, 2000–2009.

    Article  CAS  Google Scholar 

  • Gemperle, C., Aebli, G., Schweiger, A., and Ernst, R. R., (1990) Phase cycling in pulse EPR. J. Magn. Reson., 88, 241–256.

    CAS  Google Scholar 

  • Gorcester, J. and Freed, J.H. (1988) Two-dimensional Fourier transform ESR correlation spectroscopy. J. Chem. Phys., 88, 4678–4693.

    Article  CAS  Google Scholar 

  • Hanson, P., Anderson, D.J., Martinez, G., Millhauser, G., Formaggio, F., Crisma, M., Toniolo, C. and Vita, C. (1999) Electron spin resonance and structural analysis of water soluble, alanine-rich peptides incorporating TOAC. Mol. Phys., 95, 957–966.

    Google Scholar 

  • Hanson, P., Millhauser, G., Formaggio, F., Crisma, M., Toniolo, C. (1996) ESR characterization of hexameric, helical peptides using double TOAC spin-labeling. J. Am. Chem. Soc., 118, 7618–7625.

    Article  CAS  Google Scholar 

  • Hara, H., and Kawamori, A. (1997) A selective hole burning method applied to determine distances between paramagnetic species in Photosystems. Appl. Magn. Reson., 13, 241–257.

    Article  CAS  Google Scholar 

  • Höfer, P., Grupp, A., Nebenfuhr, H. and Mehring, M. (1986) Hyperfine sublevel correlation (HYSCORE) spectroscopy: A 2D ESR investigation of the squaric acid radical. Chem. Phys. Lett., 132, 279–282.

    Article  Google Scholar 

  • Hoult, D.I. and Richards (1975) Critical factors in the design of sensitive high resolution nuclear magnetic resonance spectrometers. Proc. Roy. Soc., (Load), 344, 311–340.

    Article  CAS  Google Scholar 

  • Hustedt, E.J., Smirnov, A.I., Laub, C.F., Beth, A.H. (1997). Molecular distances from dipolar coupled spin-labels: the global analysis of multifrequency continuous wave electron paramagnetic resonance data. Biophys. J. 72, 1861–1877.

    Article  PubMed Central  PubMed  CAS  Google Scholar 

  • Hustedt, E.J. and Beth, A.H. (1999) Nitroxide spin-spin interactions: applications to protein structure and dynamics. Annu. Rev. Biophys. Biomed. Struct., 28, 129–153.

    Article  CAS  Google Scholar 

  • Ichikawa, T., Wakasugi, S.Ichi and Yoshida, H. (1985) Structure of spurs in y-irradiated alcohol matrices by electron spin-echo method. J. Phys. Chem., 89, 3583–3586.

    Article  CAS  Google Scholar 

  • Jeschke, G., Bauer C., Pannier M., Leporini D. and Spiess, H.W. (2000) Pulse high-field EPR on nitroxide spin probes in polymers, at “High frequency electron paramagnetic resonance: technology and applications”, Amsterdam, April 12–14.

    Google Scholar 

  • Kurshev, V.V., Astashkin, A.V., and Raitsimring, A.M (1988) Modulation Effects in 2+1 Electron spin echo pulse sequence. J. Struct. Chem., 29, 62–68.

    Article  Google Scholar 

  • Kurshev, V.V., Raitsimring, A.M. and Tsvetkov, Yu.D. (1989) Selection of dipolar interaction by the “2+1” pulse train ESE. J. Magn. Reson., 81, 441–454.

    CAS  Google Scholar 

  • Larsen R.G. and Singel, D.J. (1993) Double electron-electron resonance spin-echo modulation. Spectroscopic measurement of electron spin pair separation in orientationally disordered solids. J. Chem. Phys., 98, 5134–5146.

    Article  CAS  Google Scholar 

  • Lee, S., Patyal, B.R. and Freed, J.H. (1993) A two-dimensional Fourier transform electron spin resonance (ESR) study of nuclear modulation and spin relaxation in irradiated malonic acid. J. Chem. Phys., 98, 3665–3689.

    Article  CAS  Google Scholar 

  • Lee, S., Budil, D.E. and Freed, J.H. (1994) Theory of two-dimensional electron spin-resonance for ordered and viscous fluids. J. Chem. Phys., 101, 5529–5558.

    Article  CAS  Google Scholar 

  • Levitt, M.H. (1979) Composite pulses. Progr. NMR. Spectr., 18, 61–122.

    Article  Google Scholar 

  • Lindgren, M., Eaton, G.R., Eaton, S.S., Johnsson, B-H, Hamarström, P., Svensson, M. and Carlsson, U. (1997) Electron spin echo decay as a probe of aminoxyl environment in spinlabeled mutants of human carbonic anhydrase II. J. Chem. Soc., Perkin Trans. 2, 2549–2554.

    Google Scholar 

  • Maryasov, A.G., Tsvetkov, Yu.D., Raap, J. (1998) Weakly-coupled radical pairs in solids: ELDOR in ESE structure studies. Appl. Magn. Reson., 14, 101.

    Article  CAS  Google Scholar 

  • Meirovitch, E., Igner, D., Igner, E., Moro, G. and J.H. Freed, J.H. (1982) Electron-spin relaxation and ordering in smectic and supercooled nematic liquid crystals. J. Chem. Phys., 77, 3915–3937.

    Article  CAS  Google Scholar 

  • Milov, A.D., Salikhov, K.M. and Tsvetkov, Yu.D. (1973) Phase relaxation of hydrogen atoms stabilized in an amorphous matrix. Sov. Phys. Solid State. 15, 802–806.

    Google Scholar 

  • Milov, A.D., Salikhov, K.M., Shirov, M.D. (1981) Application of the double resonance method to electron spin echo in a study of the spatial distribution of paramagnetic centers in solids. Sov. Phys. Solid State, 23, 565–569.

    Google Scholar 

  • Milov, A.D., Maryasov, A.G. and Tsvetkov, Yu.D. (1998) Pulsed electron double resonance (PELDOR) and its applications in free-radical research. Appl. Magn. Reson., 15, 107–143.

    Article  CAS  Google Scholar 

  • Milov, A.D., Maryasov, A.G., Tsvetkov, Yu.D., Raap, J. (1999) Pulsed ELDOR in spinlabeled polypeptides. Chem. Phys. Lett., 303, 135–143.

    Article  CAS  Google Scholar 

  • Milov, A.D., Ponomarev, A.B. and Tsvetkov, Yu.D. (1985) Modulation beats of double electron-electron resonance in spin echo for biradical systems. J. Chem. Struct., 25, 710–713.

    Article  Google Scholar 

  • Ohba, Y., Satoh, R., Kikuchi, T., Yamauchi. S. and Iwazumi. M. (1993) A new technique for accurate measurement and adjustment of the phase of the microwave pulse in pulsed EPR spectroscopy. J. Magn. Reson., A103, 282–287.

    Article  CAS  Google Scholar 

  • Pake, G.E. (1948) Nuclear resonance absorption in hydrated crystals: fine structure of the proton line. J.Chem.Phys., 16, 327–336.

    Article  CAS  Google Scholar 

  • Pannier, M., Veit, S., Godt, A., Jeshke, G. and Spiess, H.W. (2000) Dead time free measurement of dipole-dipole interactions between electron spins. J. Magn. Reson., 142, 331–340.

    Article  PubMed  CAS  Google Scholar 

  • Pfannebecker, V., Klos, H., Hubrich, M., Volkmer, T., Heuer, A., Wiesner, U. and Spiess, H.W. (1996) Determination of end-to-end distances in oligomers by pulsed EPR. J. Phys. Chem., 100, 13428–13432.

    Article  CAS  Google Scholar 

  • Rabenstein, M.D. and Shin, Y.-K. (1995) Determination of the distance between two spin labels attached to a macromolecule. Proc. Natl. Acad. Sci., USA, 92, 8239–8243.

    Article  PubMed Central  PubMed  CAS  Google Scholar 

  • Rabenstein, M.D., Shin, Y.-K. (1996), HIV-1 gp41 tertiary structure studied by EPR spectroscopy. Biochemistry, 35, 13922–13928.

    Article  PubMed  CAS  Google Scholar 

  • Raitsimring, A.M. and Salikhov, K.M. (1985) Electron spin echo method as used to analyze the spatial distribution of paramagnetic centers Bulletin of Magn. Reson., 7, 184–217.

    CAS  Google Scholar 

  • Raitsimring, A., Crepeau, R.H. and Freed, J.H. (1995) Nuclear modulation effects in “2+1” electron spin-echo correlation spectroscopy. J. Chem. Phys., 102, 8746–8762.

    Article  CAS  Google Scholar 

  • Rakowsky, M.H., Zecevic, A., Eaton, G.R. and Eaton, S.S. (1998) Determination of high — spin iron(11)-nitroxyl distances in spin-labeled porphyrins by time-domain EPR. J. Magn. Reson., 11, 97–110.

    Article  Google Scholar 

  • Salikhov, K.M., Semenov, A.G. and Tsvetkov, Yu.D. (1976) Electron spin echo and its applications. Nauka, Novosibirsk, (in Russian).

    Google Scholar 

  • Salikhov, K.M., Schneider, D.J., Saxena, S., Freed, J.H. (1996) A theoretical approach to the analysis of arbitrary pulses in magnetic resonance. Chem. Phys. Lett., 262, 17–26.

    Article  CAS  Google Scholar 

  • Saxena, S., Freed, J.H. (1996) Double quantum two-dimensional Fourier transform spin resonance: distance measurements. Chem. Phys. Lett., 251, 102–110.

    Article  CAS  Google Scholar 

  • Saxena, S., Freed, J.H. (1997a) Theory of double quantum two-dimensional electron spin resonance with applications to distance measurements. J. Chem. Phys., 107, 1317–1340.

    Article  CAS  Google Scholar 

  • Saxena, S. and Freed, J.H. (1997b) Two-dimensional electron spin resonance and slow motions. J. Phys. Chem., A101, 7998–8008.

    Article  CAS  Google Scholar 

  • Schweiger, A. (1990) New trends in pulsed spin-resonance methodology. In Modern Pulsed and Continuous-wave Electron Spin Resonance, ( Kevan, L., Bowman, M.K., eds), pp 43–118, Wiley, NY.

    Google Scholar 

  • Shriver, J. (1992) Product operators and coherence transfer in multiple-pulse NMR experiments. Concepts in Magn. Reson., 4, 1–33.

    Article  Google Scholar 

  • Slichter, C.P. (1990) Principles of magnetic resonance, 3rd enl. and updated edn., Springer-Verlag, Berlin-Heidelberg-New-York.

    Book  Google Scholar 

  • Sorensen, O.W., Eich, G.W., Levitt, M.H., Bodenhausen, G. and Ernst, R.R. (1983) Product operator formalism for the description of NMR pulse experiments. Progr. NMR Spectr., 16, 163–192.

    Article  Google Scholar 

  • Suzuki, M. (1985) Decomposition formulas of exponential operators and Lie exponentials with some applications to quantum mechanics and statistical physics. J. Math. Phys., 26, 601–612.

    Article  CAS  Google Scholar 

  • Tang, J., Norris, J.R. (1995) Multiple-quantum EPR coherence in a spin-correlated radical pair system. Chem. Phys. Lett., 233, 192–200.

    Article  CAS  Google Scholar 

  • Thorgeirsson, T.E., Xiao, W., Brown, L.S., Needleman, R., Lanyi, J.K. and Shin, Y.-K. (1997) Transient channel-opening in bacteriorhodopsin: an EPR study. J. Mol. Biol., 273, 951–957.

    Article  PubMed  CAS  Google Scholar 

  • Yudanov, V.F., Salikhov, K.M., Zhidomirov, G.M. and Tsvetkov, Yu.D. (1969) Modulation effects in the electron spin echo of biradical systems. Theor. and Experim. Chem., 5, 663–668.

    CAS  Google Scholar 

  • Zecevic, A., Eaton, G.R., Eaton, S.S. and Lindgren, M. (1998) Dephasing of electron spin echoes for nitroxyl radicals in glassy solvents by non-methyl protons. Mol. Phys., 95, 1225–1263.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2002 Kluwer Academic / Plenum Publishers, New York

About this chapter

Cite this chapter

Borbat, P.P., Freed, J.H. (2002). Double-Quantum ESR and Distance Measurements. In: Berliner, L.J., Eaton, G.R., Eaton, S.S. (eds) Distance Measurements in Biological Systems by EPR. Biological Magnetic Resonance, vol 19. Springer, Boston, MA. https://doi.org/10.1007/0-306-47109-4_9

Download citation

  • DOI: https://doi.org/10.1007/0-306-47109-4_9

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4757-0575-1

  • Online ISBN: 978-0-306-47109-4

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics