Advertisement

Applied Magnetic Resonance

, Volume 43, Issue 1–2, pp 237–250 | Cite as

Solvent-Free High-Field Dynamic Nuclear Polarization of Mesoporous Silica Functionalized with TEMPO

  • Aany Sofia Lilly Thankamony
  • Olivier Lafon
  • Xingyu Lu
  • Fabien Aussenac
  • Melanie Rosay
  • Julien Trébosc
  • Hervé Vezin
  • Jean-Paul Amoureux
Article

Abstract

We report high-field magic-angle spinning dynamic nuclear polarization (MAS DNP) of mesoporous silica functionalized with nitroxide radicals. These results demonstrate that co-condensation can be employed to incorporate DNP polarizing agents into inorganic materials and that solvent-free DNP is feasible for porous materials. For the investigated material, the direct MAS DNP enhances the 29Si nuclear magnetic resonance (NMR) spectra, whereas the indirect MAS DNP via protons is inapplicable owing to the inefficiency of \({}^{1}\hbox{H}\rightarrow{}^{29}\hbox{Si}\) cross polarization transfer. Furthermore, the 29Si signals in direct experiments build up in a few seconds at 100 K. This fast polarization buildup improves the NMR sensitivity and will be useful for the investigation of direct DNP below 100 K.

Keywords

Microwave Irradiation Mesoporous Silica Dynamic Nuclear Polarization Nuclear Magnetic Resonance Signal Nitroxide Radical 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

The authors are grateful for funding provided by Region Nord/Pas de Calais, Europe (FEDER), CNRS, French Minister of Science, FR-3050, USTL, ENSCL, Bruker BIOSPIN, and Contract No. ANR-2010-JCJC-0811-01.

References

  1. 1.
    K. Na, C. Jo, J. Kim, K. Cho, J. Jung, Y. Seo, R.J. Messinger, B.F. Chmelka, R. Ryoo, Science 333, 328 (2011)ADSCrossRefGoogle Scholar
  2. 2.
    I. Farnan, H. Cho, W.J. Weber, Nature 445, 190 (2007)ADSCrossRefGoogle Scholar
  3. 3.
    B. Key, R. Bhattacharyya, M. Morcrette, V. Seznéc, J.M. Tarascon, C.P. Grey, J. Am. Chem. Soc. 131, 9239 (2009)CrossRefGoogle Scholar
  4. 4.
    S. Cadars, B.J. Smith, J.D. Epping, S. Acharya, N. Belman, Y. Golan, B.F. Chmelka, Phys. Rev. Lett. 103, 136802 (2009)ADSCrossRefGoogle Scholar
  5. 5.
    J.S. Hartman, A. Narayanan, Y. Wang, J. Am. Chem. Soc. 116, 4019 (1994)CrossRefGoogle Scholar
  6. 6.
    T.R. Carver, C.P. Slichter, Phys. Rev. 92, 212 (1953)ADSCrossRefGoogle Scholar
  7. 7.
    A. Abragam, J. Combrisson, I. Solomon, C. R. Acad. Sci. 246, 1035 (1958)Google Scholar
  8. 8.
    R. Wind, M. Duijvestijn, C. van der Lugt, A. Manenschijn, J. Vriend, Prog. Nucl. Magn. Reson. Spectrosc. 17, 33 (1985)CrossRefGoogle Scholar
  9. 9.
    H. Lock, R. Wind, G. Maciel, N. Zumbulyadis, Solid State Commun. 64, 41 (1987)ADSCrossRefGoogle Scholar
  10. 10.
    M. Afeworki, J. Schaefer, Macromolecules 25, 4097 (1992)ADSCrossRefGoogle Scholar
  11. 11.
    H. Lock, G.E. Maciel, C.E. Johnson, J. Mater. Res. 7, 2791 (1992)ADSCrossRefGoogle Scholar
  12. 12.
    H. Lock, R.A. Wind, G.E. Maciel, C.E. Johnson, J. Chem. Phys. 99, 3363 (1993)ADSCrossRefGoogle Scholar
  13. 13.
    R.A. Wind, in Encyclopedia of Magnetic Resonance, ed. by R.K. Harris, R.E. Wasylishen (Wiley, Ltd, Chichester, published online 15th March 2007). doi: 10.1002/9780470034590.emrstm0140
  14. 14.
    A.E. Dementyev, D.G. Cory, C. Ramanathan, Phys. Rev. Lett. 100, 127601 (2008)ADSCrossRefGoogle Scholar
  15. 15.
    A. Lesage, M. Lelli, D. Gajan, M.A. Caporini, V. Vitzthum, P. Miéville, J. Alauzun, A. Roussey, C. Thieuleux, A. Mehdi, G. Bodenhausen, C. Copéret, L. Emsley, J. Am. Chem. Soc. 132, 15459 (2010)CrossRefGoogle Scholar
  16. 16.
    M. Lelli, D. Gajan, A. Lesage, M.A. Caporini, V. Vitzthum, P. Miéville, F. Héroguel, F. Rascón, A. Roussey, C. Thieuleux, M. Boualleg, L. Veyre, G. Bodenhausen, C. Copéret, L. Emsley, J. Am. Chem. Soc. 133, 2104 (2011)CrossRefGoogle Scholar
  17. 17.
    O. Lafon, M. Rosay, F. Aussenac, X. Lu, J. Trébosc, O. Cristini, C. Kinowski, N. Touati, H. Vezin, J.P. Amoureux, Angew. Chem. Int. Ed 50, 8367 (2011)CrossRefGoogle Scholar
  18. 18.
    A.J. Rossini, A. Zagdoun, M. Lelli, J. Canivet, S. Aguado, O. Ouari, P. Tordo, M. Rosay, W.E. Maas, C. Copéret, D. Farrusseng, L. Emsley, A. Lesage, Angew. Chem. Int. Ed 51, 123 (2012)CrossRefGoogle Scholar
  19. 19.
    V. Vitzthum, P. Mieville, D. Carnevale, M.A. Caporini, D. Gajan, C. Copéret, M. Lelli, A. Zagdoun, A.J. Rossini, A. Lesage, L. Emsley, G. Bodenhausen, Chem. Commun. 48, (2012)Google Scholar
  20. 20.
    L.R. Becerra, G.J. Gerfen, R.J. Temkin, D.J. Singel, R.G. Griffin, Phys. Rev. Lett. 71, 3561 (1993)ADSCrossRefGoogle Scholar
  21. 21.
    C. Song, K.N. Hu, C.G. Joo, T.M. Swager, R.G. Griffin, J. Am. Chem. Soc. 128, 11385 (2006)CrossRefGoogle Scholar
  22. 22.
    A. Zagdoun, A.J. Rossini, D. Gajan, A. Bourdolle, O. Ouari, M. Rosay, W.E. Maas, P. Tordo, M. Lelli, L. Emsley, A. Lesage, C. Coperet, Chem. Commun. 48, 654 (2012)CrossRefGoogle Scholar
  23. 23.
    R. Ciriminna, J. Blum, D. Avnir, M. Pagliaro, Chem. Commun. pp. 1441–1442 (2000)Google Scholar
  24. 24.
    R. Ciriminna, C. Bolm, T. Fey, M. Pagliaro, Adv. Synth. Catal. 344, 159 (2002)CrossRefGoogle Scholar
  25. 25.
    A. Michaud, G. Gingras, M. Morin, F. Béland, R. Ciriminna, D. Avnir, M. Pagliaro, Org. Process Res. Dev. 11, 766 (2007)CrossRefGoogle Scholar
  26. 26.
    R. Ciriminna, M. Pagliaro, Org. Process Res. Dev. 14, 245 (2009)CrossRefGoogle Scholar
  27. 27.
    L. Tebben, A. Studer, Angew. Chem. Int. Ed 50, 5034 (2011)CrossRefGoogle Scholar
  28. 28.
    H. Dorn, T. Glass, R. Gitti, K. Tsai, Appl. Magn. Reson. 2, 9 (1991)Google Scholar
  29. 29.
    E.R. McCarney, S. Han, J. Magn. Reson. 190, 307 (2008)ADSCrossRefGoogle Scholar
  30. 30.
    M.H. Lim, A. Stein, Chem. Mater. 11, 3285 (1999)CrossRefGoogle Scholar
  31. 31.
    V. Vitzthum, F. Borcard, S. Jannin, M. Morin, P. Miéville, M.A. Caporini, A. Sienkiewicz, S. Gerber-Lemaire, G. Bodenhausen, ChemPhysChem 12, 2929 (2011)CrossRefGoogle Scholar
  32. 32.
    M. Rosay, L. Tometich, S. Pawsey, R. Bader, R. Schauwecker, M. Blank, P.M. Borchard, S.R. Cauffman, K.L. Felch, R.T. Weber, R.J. Temkin, R.G. Griffin, W.E. Maas, Phys. Chem. Chem. Phys. 12, 5850 (2010)CrossRefGoogle Scholar
  33. 33.
    D.G. Cory, W.M. Ritchey, J. Magn. Reson. 80, 128 (1988)Google Scholar
  34. 34.
    B.M. Fung, A.K. Khitrin, K. Ermolaev, J. Magn. Reson. 142, 97 (2000)ADSCrossRefGoogle Scholar
  35. 35.
    Mathworks Inc. http://www.mathworks.com
  36. 36.
    D. Baute, V. Frydman, H. Zimmermann, S. Kababya, D. Goldfarb, J. Phys. Chem. B 109, 7807 (2005)CrossRefGoogle Scholar
  37. 37.
    V.A. Atsarkin, Sov. Phys. Solid State 21, 725 (1978)ADSGoogle Scholar
  38. 38.
    C.T. Farrar, D.A. Hall, G.J. Gerfen, S.J. Inati, R.G. Griffin, J. Chem. Phys. 114, 4922 (2001)ADSCrossRefGoogle Scholar
  39. 39.
    C.E. Bronnimann, R.C. Zeigler, G.E. Maciel, J. Am. Chem. Soc. 110, 2023 (1988)CrossRefGoogle Scholar
  40. 40.
    A. Abragam, The Principles of Nuclear Magnetism (Oxford University Press, Oxford, 1961)Google Scholar
  41. 41.
    D. Hirsemann, T.K.J. Koster, J. Wack, L. van Wullen, J. Breu, J. Senker, Chem. Mater. 23, 3152 (2011)CrossRefGoogle Scholar
  42. 42.
    V.S. Bajaj, P.C. van der Wel, R.G. Griffin, J. Am. Chem. Soc. 131, 118 (2008)CrossRefGoogle Scholar
  43. 43.
    T. Kobayashi, J.A. DiVerdi, G.E. Maciel, J. Phys. Chem. C 112, 4315 (2008)CrossRefGoogle Scholar
  44. 44.
    E.C. Kelusky, C.A. Fyfe, J. Am. Chem. Soc. 108, 1746 (1986)CrossRefGoogle Scholar
  45. 45.
    R.C. Zeigler, G.E. Maciel, J. Am. Chem. Soc. 113, 6349 (1991)CrossRefGoogle Scholar
  46. 46.
    R.C. Zeigler, G.E. Maciel, J. Phys. Chem. 95, 7345 (1991)CrossRefGoogle Scholar
  47. 47.
    A.W. Overhauser, Phys. Rev. 92, 411 (1953)ADSzbMATHCrossRefGoogle Scholar
  48. 48.
    C. Griesinger, M. Bennati, H. Vieth, C. Luchinat, G. Parigi, P. Hfer, F. Engelke, S. Glaser, V. Denysenkov, T. Prisner, Prog. Nucl. Magn. Reson. Spectrosc. (2012, in press)Google Scholar
  49. 49.
    E. Brunner, D. Freude, B. Gerstein, H. Pfeifer, J. Magn. Reson. 90, 90 (1990)Google Scholar
  50. 50.
    V.E. Zorin, S.P. Brown, P. Hodgkinson, J. Chem. Phys. 125, 144508 (2006)ADSCrossRefGoogle Scholar
  51. 51.
    D.H. Levy, K.K. Gleason, J. Phys. Chem. 96, 8125 (1992)CrossRefGoogle Scholar
  52. 52.
    G.R. Khutsishvili, Phys. Usp. 11, 802 (1969)ADSCrossRefGoogle Scholar
  53. 53.
    C. Ramanathan, Appl. Magn. Reson. 34, 409 (2008)CrossRefGoogle Scholar
  54. 54.
    C.F. Hwang, D.A. Hill, Phys. Rev. Lett. 19, 1011 (1997)ADSCrossRefGoogle Scholar
  55. 55.
    K.N. Hu, C. Song, H.H. Yu, T.M. Swager, R.G. Griffin, J. Chem. Phys. 128, 052302 (2008)ADSCrossRefGoogle Scholar
  56. 56.
    K.N. Hu, G.T. Debelouchina, A.A. Smith, R.G. Griffin, J. Chem. Phys. 134, 125105 (2011)ADSCrossRefGoogle Scholar
  57. 57.
    M. Rosay, A.C. Zeri, N.S. Astrof, S.J. Opella, J. Herzfeld, R.G. Griffin, J. Am. Chem. Soc. 123, 1010 (2001)CrossRefGoogle Scholar
  58. 58.
    P.C.A. van der Wel, K.N. Hu, J. Lewandowski, R.G. Griffin, J. Am. Chem. Soc. 128, 10840 (2006)CrossRefGoogle Scholar
  59. 59.
    K.N. Hu, Solid State Nucl. Magn. Reson. 40, 31 (2011)ADSCrossRefGoogle Scholar
  60. 60.
    A. Zagdoun, G. Casano, O. Ouari, G. Lapadula, A.J. Rossini, M. Lelli, M. Baffert, D. Gajan, L. Veyre, W.E. Maas, M. Rosay, R.T. Weber, C. Thieuleux, C. Copéret, A. Lesage, P. Tordo, L. Emsley, J. Am. Chem. Soc. 134, 2284 (2011)CrossRefGoogle Scholar
  61. 61.
    M.M. Maricq, J.S. Waugh, J. Chem. Phys. 70, 3300 (1979)ADSCrossRefGoogle Scholar
  62. 62.
    W.P. Rothwell, J.S. Waugh, J. Chem. Phys. 74, 2721 (1981)ADSCrossRefGoogle Scholar
  63. 63.
    A.H. Linden, S. Lange, W.T. Franks, Ü. Akbey, E. Specker, van B.J. Rossum, H. Oschkinat, J. Am. Chem. Soc. 133, 19266 (2011)CrossRefGoogle Scholar
  64. 64.
    S. Lange, A.H. Linden, Akbey, W. Trent Franks, N.M. Loening, B.J.v. Rossum, H. Oschkinat, J. Magn. Reson. 216, 209 (2012)Google Scholar
  65. 65.
    N.P. Wickramasinghe, M. Kotecha, A. Samoson, J. Past, Y. Ishii, J. Magn. Reson. 184, 350 (2007)ADSCrossRefGoogle Scholar
  66. 66.
    N.P. Wickramasinghe, S. Parthasarathy, C.R. Jones, C. Bhardwaj, F. Long, M. Kotecha, S. Mehboob, L.W.M. Fung, J. Past, A. Samoson, Y. Ishii, Nat. Meth. 6, 215 (2009)CrossRefGoogle Scholar
  67. 67.
    P.S. Nadaud, J.J. Helmus, I. Sengupta, C.P. Jaroniec, J. Am. Chem. Soc. 132, 9561 (2010)CrossRefGoogle Scholar
  68. 68.
    T. Maly, L.B. Andreas, A.A. Smith, R.G. Griffin, Phys. Chem. Chem. Phys. 12, 5872 (2010)CrossRefGoogle Scholar
  69. 69.
    T. Maly, A.F. Miller, R.G. Griffin, ChemPhysChem 11, 999 (2010)CrossRefGoogle Scholar
  70. 70.
    C.A. Fyfe, Y. Zhang, P. Aroca, J. Am. Chem. Soc. 114, 3252 (1992)CrossRefGoogle Scholar
  71. 71.
    B. Dietrich, K. Holtin, M. Bayer, V. Friebolin, M. Kühnle, K. Albert, Anal. Bioanal. Chem. 391, 2627 (2008)CrossRefGoogle Scholar
  72. 72.
    G. Kervern, G. Pintacuda, Y. Zhang, E. Oldfield, C. Roukoss, E. Kuntz, E. Herdtweck, J.M. Basset, S. Cadars, A. Lesage, C. Copéret, L. Emsley, J. Am. Chem. Soc. 128, 13545 (2006)CrossRefGoogle Scholar
  73. 73.
    D. Tse, S.R. Hartmann, Phys. Rev. Lett. 21, 511 (1968)ADSCrossRefGoogle Scholar
  74. 74.
    D. Tse, I.J. Lowe, Phys. Rev. 166, 292 (1968)ADSCrossRefGoogle Scholar
  75. 75.
    K.R. Thurber, W.M. Yau, R. Tycko, J. Magn. Reson. 204, 303 (2010)ADSCrossRefGoogle Scholar
  76. 76.
    Y. Matsuki, K. Ueda, T. Idehara, R. Ikeda, K. Kosuga, S. Nakamura, M. Toda, T. Anai, T. Fujiwara, in Third International DNP Symposium on dynamic nuclear polarization (Lausanne, 2011)Google Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Aany Sofia Lilly Thankamony
    • 1
    • 2
  • Olivier Lafon
    • 1
    • 2
  • Xingyu Lu
    • 1
    • 2
  • Fabien Aussenac
    • 3
  • Melanie Rosay
    • 4
  • Julien Trébosc
    • 1
    • 2
  • Hervé Vezin
    • 1
    • 5
  • Jean-Paul Amoureux
    • 1
    • 2
  1. 1.Univ. Lille Nord de FranceLilleFrance
  2. 2.CNRS, UMR 8181, Unité de Catalyse et de Chimie du Solide, UCCSUniv. Lille 1Villeneuve d’AscqFrance
  3. 3.Bruker BioSpin SA, 34, rue de l’IndustrieWissembourg CedexFrance
  4. 4.Bruker BioSpin Corporation, 15 Fortune DriveBillericaUSA
  5. 5.CNRS, UMR 8516, Laboratoire de Spectrochimie Infrarouge et Raman, LASIRUniv. Lille 1Villeneuve d’AscqFrance

Personalised recommendations