Journal
ANALYTICAL CHEMISTRY
Volume 75, Issue 21, Pages 5926-5935Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ac0346914
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Poly(N-isopropylacrylamide) in aqueous solution undergoes a phase transition at similar to32 degreesC. The fluorescence properties of benzofurazans are affected by solvent polarity. We combine these two characteristics for the first time to develop sensitive fluorescent molecular thermometers. Five fluorescent monomers having a benzofurazan skeleton were synthesized, and the copolymers of N-isopropylacrylamide (NIPAM) and a small quantity of the fluorescent monomer were obtained to investigate their fluorescence properties. With increase in temperature, the copolymers in water showed the temperature-induced phase transition at similar to32 degreesC and the fluorescence intensities of the copolymers concurrently increased. Especially, for the copolymer of 4-N-(2-acryloyloxyethyl)-N-methylamino-7-N,N-dimethylaminosulfonyl-2,1,3-benzoxadia- zole and NIPAM, the fluorescence intensity at 37 degreesC was 13.3-fold that seen at 29 degreesC. The sensitive range of temperature of these fluorescent molecular thermometers is changed by the replacement of the NIPAM units by N-isopropylmethacrylamide or N-n-propylacrylamide units in the copolymers. The basis of these fluorescent molecular thermometers is the decrease in the microenvironmental polarities near the main chains of the copolymers with increasing temperature, as confirmed from the maximum emission wavelengths of the benzofurazan units in the copolymers. The responses from the copolymers to the change in temperature are reversible and exactly repeatable during at least 10 cycles of heating and cooling.
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