Fluorescent molecular thermometers based on thermo-responsive linear polymer molecules such as poly(N-isopropylacrylamide) (PNIPAM) labelled with a polarity-responsive fluorescent molecule benzofurazan (BD) are the most sensitive known. Thermo-responsive PNIPAM and some related polymer microgel particles labelled with BD by emulsion polymerization have been prepared and their fluorescence properties in water as fluorescent thermometers studied. All the cross-linked polymer microgel particles dispersed in water fluoresce strongly as soon as each threshold temperature is exceeded. The nine kinds of microgel dispersion developed in this work thoroughly cover the sensitivity range from 18 to 47 °C. They are not only more sensitive than the previous fluorescent molecular thermometers based on other principles but also highly reproducible in their behaviour.

In order to clarify the local environment during interpolymer complex formation between poly(carboxylic acids) and poly(acrylamide derivatives) with different N-substitutions, a fluorescence label technique was used. 3-(2-propenyl)-9-(4-N,N-dimethylaminophenyl) phenanthrene (VDP) was used as an intramolecular fluorescence probe. All polymers were synthesized by free radical polymerization. Interpolymer complexation was monitored by charge transfer emission from the VDP unit. Both of the poly(carboxylic acids) formed interpolymer complexes with poly(N,N-dimethylacrylamide) (polyDMAM). The micro-environments around the VDP unit in the acidic pH region for the poly(methacrylic acid) (polyMAAc) and polyDMAM mixed systems were more hydrophobic than those of the poly(acrylic acid) (polyAAc) and polyDMAM mixed systems, as the α-methyl group of the MAAc unit contributed to hydrophobicity around the polymer chain during hydrogen bond formation. This suggests that, when the poly(carboxylic acids) and poly(acrylamide derivatives) were mixed, with a subsequent decrease in the solution pH, a hydrogen bond was partially formed, following which the hydrophobicity of the micro-environment around the polymer chains was changed, resulting in the formation of interpolymer complexes. Moreover, the electron-donating ability of the carbonyl group in the poly(acrylamide derivatives) had an effect on complexation with poly(carboxylic acids).