Fluorescent polymer films based on photo-induced electron transfer for visualizing water.

As fluorescent materials for visualization, detection, and quantification of a trace amount of water, we have designed and developed a PET (photo-induced electron transfer)-type fluorescent monomer SM-2 composed of methyl methacrylate-substituted anthracene fluorophore-(aminomethyl)-4-cyanophenylboronic acid pinacol ester (AminoMeCNPhenylBPin) and achieved preparation of a copolymer poly(SM-2-co-MMA) composed of SM-2 and methyl methacrylate (MMA). Both SM-2 and poly(SM-2-co-MMA) exhibited enhancement of the fluorescence emission with the increase in water content in various solvents (less polar, polar, protic, and aprotic solvents) due to the formation of the PET inactive (fluorescent) species SM-2a and poly(SM-2-co-MMA)a, respectively, by the interaction with water molecules. The detection limit (DL) of poly(SM-2-co-MMA) for water in the low water content region below 1.0 wt% in acetonitrile was 0.066 wt%, indicating that poly(SM-2-co-MMA) can act as a PET-type fluorescent polymeric sensor for a trace amount of water in solvents, although it was inferior to that (0.009 wt%) of SM-2. It was found that spin-coated poly(SM-2-co-MMA) films as well as 15 wt% SM-2-doped polymethyl methacrylate (PMMA) films produced a satisfactory reversible fluorescence off-on switching between the PET active state under a drying process and the PET inactive state upon exposure to moisture, which is demonstrated by the fact that the both the films are similar in hydrophilicity to each other from the measurement of the water contact angles on the polymer film surface. Herein we propose that PET-type fluorescent polymer films based on a fluorescence enhancement system are one of the most promising and convenient functional dye materials for visualizing moisture and water droplets.

Polymer films doped with fluorescent sensor for moisture and water droplet based on photo-induced electron transfer.

Anthracene-(aminomethyl)phenylboronic acid pinacol ester (AminoMePhenylBPin) OF-2 acts as a PET (photo-induced electron transfer)-type fluorescent sensor for determination of a trace amount of water: the addition of water to organic solvents containing OF-2 causes a drastic and linear enhancement of fluorescence emission as a function of water content, which is attributed to the suppression of PET. Indeed, detection limits (DLs) for OF-2 were as low as 0.01-0.008 wt% of water in solvents, that is, the PET method makes it possible to visualize, detect, and determine a trace amount of water. Thus, in this work, in order to develop fluorescent polymeric materials for visualization and detection of water, we have achieved the preparation of various types of polymer films (polystyrene (PS), poly(4-vinylphenol) (PVP), polyvinyl alcohol (PVA), and polyethylene glycol (PEG)) which were doped with OF-2, and investigated the optical sensing properties of the OF-2-doped polymer films for water. As-prepared OF-2-doped polymer films initially exhibited green excimer emission in the PET active state, but blue monomer emission in the PET inactive state upon exposure to moisture or by water droplet. Moreover, it was found that the OF-2-doped polymer films show the reversible fluorescence properties in the dry-wet process. Herein we propose that polymer films doped with PET-type fluorescent sensors for water based on a fluorescence enhancement (turn-on) system are one of the most promising and convenient functional materials for visualizing moisture and water droplets.