We investigate the mechanism of organic electron transfer reactions based on electrochemical and spectroscopic measurements with the aid of quantum chemical calculations and thermodynamic analyses. The results are extended to the research on development of functional molecules. We also develop the new separation methods using capillary electrophoresis and HPLC integrated with sensitivity improvement of MS, fluorometric, optical and electrochemical detections. These technologies are applied to the determination of bioactive molecules in biological samples and endcrine disrupting chemicals in environment samples in the field of life science and clinical chemistry. Interaction between superoxide and hydroquinones are investigated from the point of view of concerted proto and electron transfers（CPET）, as a series of studies on organic electron transfer chemistry. We have proposed the mechanism of electron transfer reactions induced by two proton transfers between superoxide and hydroquinone, and revealed the structural characteristics of polyphenols associated with their function. We have also revealed that the crucial step in the mechanism for oxidative DNA damage by superoxide is the CPET process from DNA to hydroperoxy radical derived from superoxide. On the other hand, we have successfully developed the high-performance separation systems involving capillary electrophoresis, focused on the dynamic structural partitioning-phase in electrokinetic chromatography. The advanced analytical systems developed in our laboratory are applied to highly sensitive determination of DNA adducts from acetaldehyde, and contribute to investigation of their involvement in carcinogenesis.
- Development of electroorganic chemistry in the field of molecular science: electrochemistry for discovery and molecular analysis of functional molecules
- Study on bioactivity based upon concerted proton and electron transfer reaction
- Development of highly selective and sensitive capillary electrophoresis systems and their applications in the field of life science
- Application of a LC-MS system in the fields of life science and clinical chemistry
- Development of highly sensitive fluorescent and electrochemical detection for biofunctional molecules and environmental pollutants
- Nakayama T., Uno B., Importance of Proton-Coupled Electron Transfer from Natural Phenolic Compounds in Superoxide Scavenging, Chem. Pharm. Bull., 63, 967–973(2015).
- Murakami H., Ohtani E., Iwata T., Esaka Y., Aoyama T., Kawasaki M., Tanaka T., Minatoguchi S., Uno B., Simple Pretreatment and HILIC Separation for LC-ESI-MS/MS Determination of Adenosine in Human Plasma, Anal. Sci., 31, 1189–1192 (2015).
- Taniguchi K., Sugito N., Kumazaki M., Shinohara H., Yamada N., Nakagawa Y., Ito Y., Otsuki Y., Uno B., Uchiyama K., Akao Y., MicroRNA-124 Inhibits Cancer Cell Growth through PTB1/PKM1/PKM2 Feedback Cascade in Colorectal Cancer, Cancer Lett., 363, 17–27 (2015).
- Esaka Y., Kato N., Murakami H., Uno B., Murata H., Iinuma M., Tanaka T., Simultaneous Analysis of Polymethoxyflavones and Flavanone Glycosides in Citrus Fruits by Micellar Electrokinetic Chromatography Using Sodium Deoxycholate, Chromatography, 35, 155–162 (2014).
- Esaka Y., Rin F., Kobayashi M., Osako R., Murakami H., Uno B., Stepwise Elusion Method in Micellar Electrokinetic Chromatography via Sequential Use of Lithium Perfluorooctadecyl Sulfonate and Lithium Dodecyl Sulfate, J. Chromatogr. A., 1358, 261–268 (2014).