RAFT-synthesis and self-assembly-induced emission of pendant diphenylalanine-tetraphenylethylene copolymers.

Manipulation of the properties of aggregation-induced emission luminogens (AIEgens) by combining self-assembling motifs has attracted significant interest as a promising approach to developing various advanced materials. In this study, pendant diphenylalanine-tetraphenylethylene (TPE) copolymers exhibiting the ability for self-assembly and AIE properties were synthesized via reversible addition-fragmentation chain-transfer (RAFT) copolymerization. The resulting anionic and non-ionic amphiphilic copolymers with a carbon-carbon main chain bearing diphenylalanine-TPE through-space interactions self-assembled into nanorods and nanofibers, showing blue emissions originating from the aggregation of TPE side chains in the assembled structures. Suitable tuning of the comonomer composition, monomer structure, and environmental conditions (e.g., solvent polarity) enables manipulation of the self-assembled structures, AIE properties, and aggregation-induced circular dichroism by achiral TPE units via through-space interactions with diphenylalanine moieties.

Mixed Polyplex Micelles with Thermoresponsive and Lysine-Based Zwitterionic Shells Derived from Two Poly(vinyl amine)-Based Block Copolymers.

Two series of poly(vinyl amine) (PVAm)-based block copolymers with zwitterionic and thermoresponsive segments were synthesized by the reversible addition-fragmentation chain transfer polymerization. A mixture of the two copolymers, poly(N-acryloyl-l-lysine) (PALysOH) and poly(N-isopropylacrylamide) (PNIPAM), which have the same cationic PVAm chain but different shell-forming segments, were used to prepare mixed polyplex micelles with DNA. Both PVAm-b-PALysOH and PVAm-b-PNIPAM showed low cytotoxicity, with characteristic assembled structures and stimuli-responsive properties. The cationic PVAm segment in both block copolymers showed site-specific interactions with DNA, which were evaluated by dynamic light scattering, zeta potential, circular dichroism, agarose gel electrophoresis, atomic force microscopy, and transmission electron microscopy measurements. The PVAm-b-PNIPAM/DNA polyplexes showed the characteristic temperature-induced formation of assembled structures in which the polyplex size, surface charge, chiroptical property of DNA, and polymer-DNA binding were governed by the nitrogen/phosphate (N/P) ratio. The DNA binding strength and colloidal stability of the PVAm-b-PALysOH/DNA polyplexes could be tuned by introducing an appropriate amount of zwitterionic PALysOH functionality, while maintaining the polyplex size, surface charge, and chiroptical property, regardless of the N/P ratio. The mixed polyplex micelles showed temperature-induced stability originating from the hydrophobic (dehydrated) PNIPAM chains upon heating, and remarkable stability under salty conditions owing to the presence of the zwitterionic PALysOH chain on the polyplex surface.