Development of Reaction and Analysis Systems based on Liquid / Liquid Interfaces

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Chemistry in Oil-in-Water Emulsion and Single Microdroplets/Water Systems : On the basis of the knowledge about ion/mass transfer across oil/water interfaces, new and novel photoreactions of single microdroplets in water have been developed. In the case of a photocyanation reaction of pyrene via a photoinduced electron transfer mechanism (PET), photoirradiation of benzonitrile microdroplets containing pyrene and 1,4-dicyanobenzene dispersed in an aqueous NaCN solution gave rise to formation of 1-cyanopyrene with the quantum yield of 0.68 under the optimum conditions. Analogous photoreactions were developed for carbazole derivatives and other aromatic hydrocarbons.Oil/Water Interfacial Systems in Microchannel Chips : Photchemical, electrochemical, and thermal reactions were explored in polymer microchannel, microchannel-microelectrode, or microchannel-microheter chips. As a typical example, the photocyanation reaction of pyrene via a PET mechanism mentioned above was conducted in microc … More hannel chips. An aqueous NaCN solution and a propylene carbonate solution of pyrene and 1,4-dicyanobenzene were introduced to a microchannel chip at the same flow velocity and the whole of the chip was irradiated. The photocyanation reaction of pyrene proceeded along parallel solution flow in the microchannel with the yield of 72% and the reaction time of 210 s. Furthermore, 1-cyanopyrene as a product was extracted completely into the oil phase. A photochemical microreactor was thus demonstrated.Laser-Induced Photo-Thermal Liquid-to-Droplet Extraction : A novel method of laser-induced microdroplet formation was developed and the phenomena was applied to liquid-to-single microdroplet extraction of a solute. When an aqueous triethylamine (TEA) solution was irradiated by a focused 1064 nm laser beam under an optical microscope, a single TEA microdroplet was produced by photo-thermal effects of the solution. The droplet was optically trapped simultaneously. In the presence of p-chlorophenol in aqueous TEA solution, laser irradiation gave rise to single microdroplet formation and simultaneous liquid-to-TEA droplet extraction of p-chlorophenol as revealed by in situ Raman microspectroscopy. The extraction efficiency in the single microdroplet system was shown to be much higher than that in the relevant bulk solution system. Analogous laser-induced liquid-to-droplet extraction was confirmed in an aqueous 1-BuOH solution. On the basis of fluorescence microspectroscopy, a solute as low as 10-8 M was simultaneously concentrated and detected by the laser-induced method. Less