Intramolecular hydrophobic aggregation of amphiphilic polysulfobetaine with various hydrophobic groups in aqueous solution

The copolymers derived from zwitterionic DMAPAMAIPS and hydrophobic monomer (AdMAI or NaMAI) were studied in terms of the surface tension, viscometric s, and photophysical measurements. The surface tension of poly(DMAPAMAIPS) was shown to be larger than that of both the copolymer [poly(DMPAMAIPS/ NaM AI)] with an aromatic hydrophobic residue (naphthalene group) and [poly(DMA PAMAIPS/AdMAI)] with an aliphatic hydrophobic residue (adamantane group). T he copolymer [poly( DMAPAMAIPS/NaMAI)] has a larger surface activity than t hat of [poly(DMAPAMAIPS/AdMAI)]. The reduced viscosity of the copolymers re vealed that both zwitterionic and hydrophobic associations were important i n polymer aggregation. The aromatic hydrophobic units of the copolymer [pol y(DMAPAMAIPS/NaMAI)] were more strongly associated than the units of alipha tic hydrophobic copolymer [poly(DMAPAMAIPS/AdMAI)] due to the stronger hydr ophobic aggregation of naphthyl groups. The fluorescence experiment showed that when the hydrophobic adamantyl group was incorporated into the polymer , the environmental polarity of the pyrene residue increases. Coil expansio n was due to weaker hydrophobic associations of the adamantane moieties.