Abstract
We report a novel force-detected high-frequency electron spin resonance (HFESR) technique using a microcantilever in the terahertz region. In this technique, we attach a tiny sample on the microcantilever end and the ESR signal is detected as the cantilever bending. The bending is sensitively detected by fiber-optic Fabry–Perot interferometry. We applied this technique to a tiny amount (~16 ng) of metalloporphyrin, a model substance of hemoproteins, and successfully observed ESR signals at multiple frequencies up to 0.5 THz. This result indicates that the sample volume needed in multi-frequency HFESR can be greatly reduced by several orders of magnitude, and our novel technique would be a promising tool for HFESR studies of metalloproteins in the future.
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References
A. Abragam, B. Bleaney, Electron Paramagnetic Resonance of Transition Ions (Clarendon Press, Oxford, 1970)
H. Ohta, S. Okubo, K. Kawakami, D. Fukuoka, Y. Inagaki, T. Kunimoto, Z. Hiroi, J. Phys. Soc. Jpn. 72, Suppl. B, 26–35 (2003)
A. Tasaki, J. Otsuka, M. Kotani, Biochim. Biophys. Acta 140, 284–290 (1967)
H. Uenoyama, T. Iizuka, H. Morimoto, M. Kotani, Biochim. Biophys. Acta 160, 159–166 (1968)
M.P. Hendrich, P.G. Debrunnner, J. Magn. Reson. 78, 133–141 (1988)
Y. Miyajima, H. Yashiro, T. Kashiwagi, M. Hagiwara, H. Hori, J. Phys. Soc. Jpn. 73, 280–286 (2004)
M. Horitani, H. Yashiro, M. Hagiwara, H. Hori, J. Inorg. Biochem. 102, 781–788 (2008)
G. Hanson, L. Berliner (eds.), High Resolution EPR, Applications to Metalloenzymes and Metals in Medicine (Springer, Berlin, 2009)
K. Mobius, A. Savitsky, High-Field EPR Spectroscopy on Proteins and Their Model Systems: Characterization of Transient Paramagnetic States (Royal Society of Chemistry, Cambridge, 2009)
K. Mobius, A. Savitsky, A. Schnegg, M. Plato, M. Fuchs, Phys. Chem. Chem. Phys. 7, 19–42 (2005)
P.J.M. van Kan, E. van der Horst, E.J. Reijerse, P.J.M. van Bentum, W.R. Hagen, J. Chem. Soc. Faraday Trans. 94, 2975–2978 (1988)
J. Telser, A. Ozarowski, J. Krzystek, J. Biol. Inorg. Chem. 19, 297–318 (2014)
Y. Tokuda, D. Tsubokura, E. Ohmichi, H. Ohta, J. Magnet. 18, 173–177 (2013)
E. Ohmichi, T. Okamoto, M. Mitani, H. Takahashi, H. Ohta, J. Inorg. Biochem. 162, 190–193 (2016)
E. Ohmichi, Y. Tokuda, R. Tabuse, T. Okamoto, H. Ohta, Rev. Sci. Instrum. 87, 073904/1–8 (2016)
T. Okamoto, H. Takahashi, E. Ohmichi, H. Ohta, J. Infrared Milli. Terahertz Waves 37, 1173–1184 (2016)
M.M. Hertel, V.P. Denysenkov, M. Bennati, T.F. Prisner, Magn. Reson. Chem. 43, S248–S255 (2005)
H. Takahashi, T. Okamoto, E. Ohmichi, H. Ohta, Appl. Phys. Express 9, 126701/1-4 (2016)
K.M. Smith (ed.), Porphyrins and Metalloporphyrins (Elsevier, Amsterdam, 1975)
W.S. Caughey, Ann. Rev. Biochem. 36, 611–644 (1967)
T. Yonetani, H. Schleyer, J. Bio. Chem. 242, 3926–3933 (1967)
W.A. Rawlinson, P.B. Scutt, Aust. J. Sci. Res., Ser. A: Phys. Sci. 5, 173–188 (1952)
A.J. Bearden, T.H. Moss, W.S. Caughey, C.A. Beaudreau, Proc. Natl. Acad. Sci. USA 53, 1246–1253 (1965)
J. Nherkorn, J. Telser, K. Holldack, S. Stoll, A. Schnegg, J. Phys. Chem. B 119, 13816–13824 (2015)
E. Ohmichi, Y. Yasufuku, K. Konishi, H. Ohta, J. Magnet. 18, 163–167 (2013)
Acknowledgements
This research was partly supported by Grants-in-Aid for Scientific Research (B) (Nos. 22340101 and 26287081) and by a Grant-in-Aid for Challenging Exploratory Research (No. 26610104) from JSPS, by the Canon Foundation, by the Motizuki Fund of Yukawa Memorial Foundation, and by the Murata Science Foundation.
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The original version of this article has been revised: The equations (3) and (4) were incorrect. Now, these equations have been corrected.
An erratum to this article is available at http://dx.doi.org/10.1007/s00723-017-0881-1.
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Okamoto, T., Takahashi, H., Ohmichi, E. et al. Force-detected ESR Measurements in a Terahertz Range up to 0.5 THz and Application to Hemin. Appl Magn Reson 48, 435–444 (2017). https://doi.org/10.1007/s00723-017-0872-2
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DOI: https://doi.org/10.1007/s00723-017-0872-2