Julolidine-labelled fluorinated block copolymers for the development of two-layer films with highly sensitive vapochromic response

Fluorinated block copolymers composed of a polystyrene (S_x) first block and a polyacrylate second block carrying hydrophobic/lipophobic perfluorohexyl side chains (AF) were prepared by atom transfer radical polymerization (ATRP). Fluorescence emission properties were imparted to the copolymers by incorporation in the second block of a julolidine-based fluorescent molecular rotor (JCBF). The synthesized block copolymers were used as the fluorescent low-surface energy thin top-layer onto a polystyrene bottom-layer to produce novel two-layer film vapochromic sensors. Contact angle and X-ray photoelectron spectroscopy (XPS) measurements revealed that the two-layer film surfaces were hydrophobic and lipophobic at the same time and highly enriched in fluorine content as a result of the effective segregation of the perfluorinated tails to the polymer-air interface. The fluorescence intensity of the two-layer films decreased significantly when they were exposed to vapours of organic solvents, including tetrahydrofurane, chloroform, and trifluorotoluene. However, an AF content-dependent sensing behaviour was also observed, with the two-layer films containing the copolymer with the shorter fluorinated block giving a more rapid and almost quantitative decrease in fluorescence variation. Fluorescence emission of the films was also proved to vary with temperature. Both the vapochromic and thermochromic responses were reversible after successive solicitation cycles. The fluorescence variation of the two-layer films was much more marked than that of the corresponding PS/JCBF blend, thus providing a system potentially applicable as highly sensitive volatile organic compound (VOC) sensor, thanks to the active role of the fluorinated block in promoting the migration of the fluorophore to the outermost surface layers.