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

水包油乳化液和单微滴/水系统的化学性质：基于对油/水界面离子/质传递的认识，单微滴在水中的光反应得到了新的发展。通过光致电子转移机制（PET）对芘进行光氰化反应，在最佳条件下，将含有芘和1,4-二苯基苯的苯腈微滴分散在NaCN水溶液中，光照射可生成量子产率为0.68的1-氰芘。对咔唑衍生物和其他芳香烃进行了类似的光反应。微通道芯片中的油/水界面系统：探讨了聚合物微通道、微通道-微电极或微通道-微表芯片中的光化学、电化学和热反应。作为典型的例子，利用上述PET机制在微通道芯片上进行了芘的光氰化反应。将NaCN水溶液和苯乙烯- 1,4-二氯苯的碳酸丙烯酯溶液以相同的流速引入到微通道芯片中，并对芯片进行全辐射。芘的光氰化反应在微通道中沿平行溶液流动进行，产率为72%，反应时间为210 s。1-氰芘作为产物被完全萃取到油相中。因此，光化学微反应器被证明。激光诱导光热液-液滴萃取：提出了一种激光诱导微液滴形成的新方法，并将该现象应用于溶质的液-单微液滴萃取。在光学显微镜下，用聚焦1064 nm的激光束照射三乙胺水溶液，通过溶液的光热效应产生单个TEA微滴。液滴同时被光学捕获。原位拉曼光谱分析表明，在TEA水溶液中存在对氯酚的情况下，激光照射可形成单微滴，同时液相萃取对氯酚。结果表明，单微滴体系的萃取效率远高于相应的整体溶液体系。类似的激光诱导液-液滴萃取在1-BuOH水溶液中得到了证实。在荧光显微光谱的基础上，同时浓缩低至10-8 M的溶质，并通过激光诱导方法检测。少

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