X-Ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation States in Fe–NO Complexes†
Corresponding Author
Prof. Tsai-Te Lu
Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorCorresponding Author
Dr. Tsu-Chien Weng
SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Wen-Feng Liaw
Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Tsai-Te Lu
Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorCorresponding Author
Dr. Tsu-Chien Weng
SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Wen-Feng Liaw
Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Tsai-Te Lu, Department of Chemistry, Chung Yuan Christian University, No. 200, Chung Pei Rd. Chungli, 32023 (Taiwan)
Tsu-Chien Weng, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd. Menlo Park, CA 94025 (USA)
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Rd. Hsinchu, 30013 (Taiwan)
Search for more papers by this authorWe gratefully acknowledge the support from staff at ID26 of ESRF. W.-F.L. and T.-T.L. acknowledge financial support from the Ministry of Science and Technology (Taiwan). We also thank Dr. Wei-Ming Ching for helpful discussion.
Abstract
Extensive study of the electronic structure of Fe-NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe 3d orbitals complicate the bonding interaction within FeNO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark–Feltham notation, {Fe(NO)x}n, was devised to circumvent this puzzle. This 40-year puzzle is revisited using valence-to-core X-ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔEσ2s*-σ2p of NO and its oxidation state. V2C Fe XES study of FeNO complexes reveals the ΔEσ2s*-σ2p of NO derived from NO σ2s*/σ2p→Fe1s transitions and determines NO oxidation state in FeNO complexes. Quantitative assignment of NO oxidation state will correlate the feasible redox process of nitric oxide and Fe-nitrosylation biology.
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References
- 1
- 1aW. P. Arnold, C. K. Mittal, S. Katsuki, F. Murad, Proc. Natl. Acad. Sci. USA 1977, 74, 3203–3207;
- 1bL. J. Ignarro, R. E. Byrns, G. M. Buga, K. S. Wood, Circ. Res. 1987, 61, 866–879;
- 1cD. E. Koshland, Jr., Science 1992, 258, 1861;
- 1dY. Zhao, P. E. Brandish, D. P. Ballou, M. A. Marletta, Proc. Natl. Acad. Sci. USA 1999, 96, 14753–14758;
- 1eD. T. Hess, A. Matsumoto, S. O. Kim, H. E. Marshall, J. S. Stamler, Nat. Rev. Mol. Cell Biol. 2005, 6, 150–166;
- 1fR. Radi, Proc. Natl. Acad. Sci. USA 2004, 101, 4003–4008;
- 1gN. S. Bryan, T. Rassaf, R. E. Maloney, C. M. Rodriguez, F. Saijo, J. R. Rodriguez, M. Feelisch, Proc. Natl. Acad. Sci. USA 2004, 101, 4308–4313.
- 2
- 2aB. D’Autreaux, N. P. Tucker, R. Dixon, S. Spiro, Nature 2005, 437, 769–772;
- 2bM. C. Kennedy, W. E. Antholine, H. Beinert, J. Biol. Chem. 1997, 272, 20340–20347;
- 2cR. N. Watts, C. Hawkins, P. Ponka, D. R. Richardson, Proc. Natl. Acad. Sci. USA 2006, 103, 9745–9745.
- 3
- 3aC. A. Bosworth, J. C. Toledo, Jr., J. W. Zmijewski, Q. Li, J. R. Lancaster, Jr., Proc. Natl. Acad. Sci. USA 2009, 106, 4671–4676;
- 3bM. Lee, P. Arosio, A. Cozzi, N. D. Chasteen, Biochemistry 1994, 33, 3679–3687.
- 4Y.-J. Chen, W.-C. Ku, L.-T. Feng, M.-L. Tsai, C.-H. Hsieh, W.-H. Hsu, W.-F. Liaw, C.-H. Hung, Y.-J. Chen, J. Am. Chem. Soc. 2008, 130, 10929–10938.
- 5
- 5aT.-T. Lu, S.-H. Lai, Y.-W. Li, I.-J. Hsu, L.-Y. Jang, J.-F. Lee, I.-C. Chen, W.-F. Liaw, Inorg. Chem. 2011, 50, 5396–5406;
- 5bJ. L. Hess, C. H. Hsieh, S. M. Brothers, M. B. Hall, M. Y. Darensbourg, J. Am. Chem. Soc. 2011, 133, 20426–20434;
- 5cS. Ye, F. Neese, J. Am. Chem. Soc. 2010, 132, 3646–3647;
- 5dM.-C. Tsai, F.-T. Tsai, T.-T. Lu, M.-L. Tsai, Y.-C. Wei, I.-J. Hsu, J.-F. Lee, W.-F. Liaw, Inorg. Chem. 2009, 48, 9579–9591;
- 5eT. C. Harrop, D. Song, S. J. Lippard, J. Am. Chem. Soc. 2006, 128, 3528–3529;
- 5fL. E. Goodrich, F. Paulat, V. K. Praneeth, N. Lehnert, Inorg. Chem. 2010, 49, 6293–6316;
- 5gJ. E. M. N. Klein, B. Miehlich, M. S. Holzwarth, M. Bauer, M. Milek, M. M. Khusniyarov, G. Knizia, H. J. Werner, B. Plietker, Angew. Chem. Int. Ed. 2014, 53, 1790–1794; Angew. Chem. 2014, 126, 1820–1824.
- 6J. H. Enemark, R. D. Feltham, Coord. Chem. Rev. 1974, 13, 339–406.
- 7
- 7aP. Glatzel, U. Bergmann, Coord. Chem. Rev. 2005, 249, 65–95;
- 7bK. M. Lancaster, M. Roemelt, P. Ettenhuber, Y. Hu, M. W. Ribbe, F. Neese, U. Bergmann, S. DeBeer, Science 2011, 334, 974–977;
- 7cC. J. Pollock, K. Grubel, P. L. Holland, S. DeBeer, J. Am. Chem. Soc. 2013, 135, 11803–11808.
- 8
- 8aM. U. Delgado-Jaime, S. DeBeer, M. Bauer, Chem. Eur. J. 2013, 19, 15888–15897;
- 8bC. J. Pollock, S. DeBeer, J. Am. Chem. Soc. 2011, 133, 5594–5601.
- 9T.-T. Lu, S.-J. Chiou, C.-Y. Chen, W.-F. Liaw, Inorg. Chem. 2006, 45, 8799–8806.
- 10K. S. Hagen, J. G. Reynolds, R. H. Holm, J. Am. Chem. Soc. 1981, 103, 4054–4063.
- 11
- 11aK. C. Prince, A. Santoni, A. Morgante, G. Comelli, Surf. Sci. 1994, 317, 397–406;
- 11bK. Siegbahn, ESCA applied to free molecules, North-Holland Pub. Co., Amsterdam, 1969.
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