ABMES

Influences of the terminal group of non-ionic polymer with upper critical solution temperature on cloud points (CPs) has been one of curious research topics, however, detailed investigation has not been conducted so far. This study investigates the effect of the terminal group of poly(N-acryloyl-nipecotamide)s (PNANAms) on their CPs in aqueous solution. PNANAms with different molecular weights (Mn) ranging from 4,100 to 34,300 and different terminal end groups were successfully synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The temperature-dependent optical transmittance of aqueous solutions of the PNANAms revealed that their CP was influenced by their terminal group, in addition to their Mn and polymer concentration. PNANAms with low Mn (Mn ≥ 7,500) and a hydrophobic (dodecyl) terminal group exhibited poor solubility, whereas PNANAms with a moderate Mn (Mn ≤ 10,200) and hydrophilic (maleimide or carboxylic) terminal groups were readily soluble in aqueous solution. However, PNANAms with a high Mn (Mn = 34,300) were hardly soluble in aqueous solution. The poor solubility of such PNANAms suggests that strong inter- and intramolecular hydrogen bonds were formed among the polymer chains, increasing their CP. PNANAm with a low Mn (Mn = 4,100) and the hydrophobic terminal and that with a moderate Mn (13,200 ≤ Mn ≤ 18,200) and hydrophilic terminal groups exhibited CPs in aqueous solution. The CP of PNANAms with carboxylic terminal groups was also influenced by the solution pH owing to the deprotonation of these groups. The size of polymeric aggregates was directly observed using phase-contrast microscopy, and the temperature-dependent aggregation and dispersion of the polymers were described in terms of the inter- and intramolecular hydrogen bonds formed among PNANAm chains. Finally, a cell viability assay was conducted to explore the possibility of the applications of PNANAm in the fields of biomaterials and regenerative therapy.