Hyperbranched polymers with thermoresponsive property highly sensitive to ions.

The salt effects on the water solubility of thermoresponsive hyperbranched polyethylenimine and polyamidoamine possessing large amounts of isobutyramide terminal groups (HPEI-IBAm and HPAMAM-IBAm) were studied systematically. Eight anions with sodium as the counterion and ten cations with chloride as the counterion were used to measure the anion and cation effects on the cloud point temperature (T(cp)) of these dendritic polymers in water. It was found that the T(cp) of these dendritic polymers was much more sensitive to the addition of salts than that of the traditional thermoresponsive linear polymers. At low anion concentration, the electrostatic interaction between anions and the positively charged groups of these polymers was dominant, resulting in the unusual anion effect on the T(cp) of these polymers in water, including (1) T(cp) of these dendritic polymers decreasing nonlinearly with the increase of kosmotropic anion concentration; (2) the chaotropic anions showing abnormal salting-out property at low salt concentration and the stronger chaotropes having much pronounced salting-out ability; (3) anti-Hofmeister ordering at low salt concentration. At moderate to high salt concentration, the specific ranking of these anions in reducing the T(cp) of HPEI-IBAm and HPAMAM-IBAm polymers was PO(4)(3-) > CO(3)(2-) > SO(4)(2-) > S(2)O(3)(2-) > F(-) > Cl(-) > Br(-) > I(-), in accordance with the well-known Hofmeister series. At moderate to high salt concentration, the specific ranking order of inorganic cations in reducing the T(cp) of HPEI-IBAm polymer was Sr(2+) ≈ Ba(2+) > Na(+) ≈ K(+) ≈ Rb(+) > Cs(+) > NH(4)(+) ≈ Ca(2+) > Li(+) ≈ Mg(2+). This sequence was only partially similar to the typical Hofmeister cation series, whereas at low salt concentration the cation effect on T(cp) of the dendritic polymer was insignificant and no obvious specific ranking order could be found.

Multifunctional covalently stabilized vesicles acting simultaneously as the template of gold nanoparticle cluster and the nanocarrier of guest molecules.

The terminal hydroxyl groups of amphiphilic multiarm star copolymers with a hydrophilic hyperbranched polyethylenimine (PEI) core and hydrophobic poly(ε-caprolactone) (PCL) arms were partially or completely transformed into the radical-crosslinkable methacrylate (MA) groups (PEI-b-PCL-MA). The resulting PEI-b-PCL-MA polymers with 100% MA substitution self-assembled in water into simple vesicles, whereas those with partial MA substitution aggregated into complex vesicles. These structures could be proved by transmission electron microscopy and dynamic light scattering only after crosslinking the intra-vesicular MA groups that generated the covalently stabilized vesicles (CSVs). The obtained CSVs could be used as host for the formation of gold nanoparticle (AuNP) cluster, and the AuNP clusters stabilized by the CSVs were stable under a wider range of CSV/AuNP feed ratio than those stabilized by the uncrosslinked precursors. The diameter of AuNPs in the clusters was in the range of 4-6 nm, and the distance of adjacent AuNPs could be modulated through altering the feed ratio of CSV/AuNP. The color of the solutions of AuNPs with CSV could be tuned from brown to red, purple, even blue. The composites of CSV and AuNPs could be further used as nanocarriers to accommodate hydrophobic guest of pyrene, and a higher amount of AuNPs in the nanocarriers led to a lower encapsulation capacity for pyrene guests.