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Characterization of a titanium(IV)–porphyrin complex as a highly sensitive and selective reagent for the determination of hydrogen peroxide: a computational chemistry approach and a critical review

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Abstract

The Ti–TPyP reagent, i.e. an acidic aqueous solution of the oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato] titanium(IV) complex, TiO(tpyp), was developed as a highly sensitive and selective spectrophotometric reagent for determination of traces of hydrogen peroxide. Using this reagent, determination of hydrogen peroxide was performed by flow-injection analysis with a detection limit of 0.5 pmol per test. The method was actually applied to determination of several constituents of foods, human blood, and urine mediated by appropriate oxidase enzymes. The reaction specificity of the TiO(tpyp) complex for hydrogen peroxide was clarified from the viewpoint of the reaction mechanisms and molecular orbitals based on ab initio calculations. The results provided a well-grounded argument for determination of hydrogen peroxide using the Ti–TPyP reagent experimentally. This review deals with characterization of the high sensitivity and reaction specificity of the Ti–TPyP reagent for determination of hydrogen peroxide, to prove its reliability in analytical applications.

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Acknowledgements

The authors are grateful to Emeritus Professor C. Matsubara of Tokyo University of Pharmacy and Life Sciences, for her collaboration throughout the experiments, and to Professor P. K. Dasgupta of Texas University, for his efforts to extend the application of the Ti–TPyP reagent to the measurement of the atmospheric hydrogen peroxide. The authors thank Dr K. Higuchi of Ogawa and Co., Ltd. (formerly Tokyo Kasei Industries Co. Ltd.) for his kind help in synthesizing the TiO(tpyp) complex at the beginning of these studies.

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Correspondence to Kiyoko Takamura.

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Takamura, K., Matsumoto, T. Characterization of a titanium(IV)–porphyrin complex as a highly sensitive and selective reagent for the determination of hydrogen peroxide: a computational chemistry approach and a critical review. Anal Bioanal Chem 391, 951–961 (2008). https://doi.org/10.1007/s00216-008-1942-y

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