Analytical Sciences

Photoinduced Redox Cycle of Riboflavin at a Water/Oil Interface

Shoji ISHIZAKA and Noboru KITAMURA

Division of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan

A photoinduced redox reaction cycle of Riboflavin (RF) at a water/CCl₄ interface was studied directly by means of both steady-state and time-resolved total internal reflection (TIR) fluorescence spectroscopies. The TIR fluorescence spectrum of RF observed at the water/CCl₄ interface with the maximum wavelength of 517 nm was assigned to the π-π^* transition from the excited singlet-state of the isoalloxazine chromophore in RF. Upon prolonged laser irradiation (400 nm) in the presence of N,N-dioctadecyl-[1,3,5]triazine-2,4,6-triamine (DTT) as a guest for RF in the CCl₄ phase, on the other hand, a new TIR fluorescence band appeared at around 480 nm. Furthermore, the fluorescence intensity at around 480 nm increased in the presence of acetic acid in the water phase. Detailed studies demonstrated that the new fluorescence band should be ascribed to 1,5-dihydoroflavin (RFH₂). The present results indicated that RFH₂ was produced through the photoreaction of the RF-DTT hydrogen-bonded complex formed at the water/CCl₄ interface, whose reaction mechanisms were discussed on the basis of the results observed by fluorescence spectra/dynamics measurements under the TIR conditions as well as by transient absorption spectroscopy.

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