Supramolecular Interaction-Assisted Fluorescence and Tunable Stimuli-Responsiveness of l-Phenylalanine-Based Polymers

Supramolecular host-guest interactions between randomly methylated β-cyclodextrin (RM β-CD) and side-chain phenylalanine (Phe) and Phe-Phe dipeptide-based homopolymers have been employed for the amplification of fluorescence emission of otherwise weakly fluorescent amino acid Phe. The host-guest complex has been characterized by ¹H and ¹³C NMR spectroscopy, two-dimensional rotating-frame overhauser spectroscopy, Fourier-transform infrared spectroscopy, UV-visible spectroscopy, and fluorescence spectroscopy. To gain insights into the origin of fluorescence in homopolymers, density functional theory calculations were performed where phenyl moieties inside the less polar core of β-CD were observed to form a π-π coupled complex resulting in an enhanced emission. Furthermore, the complex-forming ability of Phe, the guest molecule, has been employed in tuning the cloud point temperature (T_CP) of statistical copolymers derived from side-chain Phe/Phe-Phe-based methacrylate monomers and N-isopropylacrylamide. By varying the co-monomer feed ratios in the statistical copolymer and hence the concentration of RM β-CD throughout the polymer chain, host-guest interaction-assisted broad tunability in T_CP of the supramolecular polymeric complex has been achieved.