Photoinduced Amplification of Separation, Analysis, and Sensing by Using Photochromic Ionophores

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(1)Design of photochromic crown ethers and photocontrol of their metal ion complexationVarious crown ether derivatives incorporating spirobenzopyran moiety, which are called crowned spirobenzopyrans, were designed and their photoresponsive metal-ion complexing behavior was investigated. Crown ether derivatives incorporating triphenylmethane moiety, crowned Malachite Green leuconitrile, realized all-or-none type photocontrol of their metal ion complexation on turning on and off UV light.(2)Photoinduced amplification in extraction-spectrophotometry of metal ions.It was found that crowned spirobenzopyrans are promising extraction-specirophotometric reagents for metal ions and that their extractability can be changed by photoirradiation. The photochromic crown ethers were also successfully applied to extraction spectrophotometric flow-injection analysis, the extractability and ion selectivity of which can be controlled by photoirradiation on the extraction coil. Moreover, photo-driven and photo-controlled membrane transports of alkali metal ions were also realized using crowned spirobenzopyrans.(3)Applications of micelle solutions containing photoresponsive crown ethers to analytical and separation chemistryMicelle solutions, in which a crowned spirobenzopyran derivative was dissolved in a surfactant aqueous solution, were applied to metal ion sensing based on absorption and fluorescence spectra. This metal ion sensing using the micelle solution suggested a possibility for highly selective alkali-metal-ion sensing. It was also found that photoirradiation modified the micellar structure, size, and aggregation number in the micelle solutions containing a crowned spirobenzopyran derivative. This in turn indicated that the uptake amount of organic compounds can be controlled photochemically by using the micellar systems.