Well-defined homopolymers of pentafluorophenyl acrylate (PFPA) and AB diblock copolymers of N,N-dimethylacrylamide (DMA) and poly(ethylene glycol) methyl ether acrylate (PEGA) with PFPA were prepared by reversible addition-fragmentation chain transfer (RAFT) radical polymerization. Three PFPA homopolymers of different molecular weights were reacted with the commercially available amidine and guanidine species histamine (HIS) dihydrochloride and L-arginine methyl ester (ARG) dihydrochloride in the presence of S-methyl methanethiosulfonate to yield, quantitatively, the corresponding amidine and guanidine-based acrylamido homopolymers. Both the HIS and ARG homopolymers are known to reversibly bind CO2 with, in the case of the former, CO 2 fixation being accompanied with a switch from a hydrophobic to hydrophilic state. The RAFT synthesis of PFPA-DMA and PEGA-PFPA diblock copolymers yielded well-defined materials with a range of molar compositions. These precursor materials were converted to the corresponding HIS and ARG block copolymers whose structure was confirmed using 1H NMR spectroscopy. Employing a combination of dynamic light scattering and transmission electron microscopy, we demonstrate that the DMA-HIS and PEGA-HIS diblock copolymers are able to undergo reversible and cyclable self-directed assembly in aqueous media using CO2 and N2 as the triggers between fully hydrophilic and amphiphilic (assembled) states. For example, in the case of the 54:46 DMA-HIS diblock, aggregates with hydrodynamic diameters of about 40.0 nm are readily formed from the molecularly dissolved state.
|Number of pages||11|
|Journal||Journal of Polymer Science, Part A: Polymer Chemistry|
|Publication status||Published - 15 Jan 2013|
- gas responsive
- reversible addition fragmentation chain transfer (RAFT)
- stimulus responsive