ma201089j_si_001.pdf (5.65 MB)
Tetraphenylthiophene-Functionalized Poly(N-isopropylacrylamide): Probing LCST with Aggregation-Induced Emission
journal contributionposted on 2011-08-23, 00:00 authored by Chung-Tin Lai, Rong-Hong Chien, Shiao-Wei Kuo, Jin-Long Hong
A hydrophobic tetraphenylthiophene (TP) center with novel aggregation-induced emission (AIE) property was chemically linked to two poly(N-isoprppylacrylamide) (PNIPAM) chains to obtain thermoresponsive polymers to study the relationships between the lower critical solution transitions (LCSTs) and the AIE-operative fluorenscence (FL) emission. Three ethynyl-terminated PNIPAMs with different molecular weights were synthesized via controlled atom transfer radical polymerization (ATRP) using ethynyl-functionalized initiator. The PNIPAMs were then coupled with diazide-funtionalized TP (TPN3) via click reaction to obtain the desired TP-embedded polymers of Px (x = 1, 2, and 3). All three polymers show AIE-property from their solution fluorescence behavior in THF/hexane mixtures. In the aqueous solution, the TP-center served as a fluorogenic probe that reveals the LCSTs of polymers and its relation to the degree of TP labeling in terms of polymer concentration. The thermoresponsiveness of Px was demonstrated by the complete emission quench when heated at temperatures above LCST. Dissociation of the TP aggregates above LCST is responsible for the emission quench, which was evaluated through the uses of transmittance measurement, dynamic light scattering, and 1H NMR spectra.