We examine the influence of the macromolecule chain length on the cloud point temperature (T cp ) and the temperature of the coil-to-globule transition (T M ) in aqueous solutions of hydrophobically modified (HM) telechelic poly(N-isopropylacrylamides) (PNIPAM) ranging in concentration from 0.01 to 35 g L -1 (0.1-310 mmol of NIPAM L -1 ). The telechelic HM-PNIPAM samples with n-octadecyl termini were obtained by RAFT polymerization of NIPAM in dioxane in the presence of S-1-n-octadecyl-S′-(R,R′-dimethyl-R′′-N-n-octadecylacetamide)trithiocarbonate as a chain transfer agent. Their molar mass (M n ) ranged from 12 000 to 49 000 g mol -1 with a polydispersity index lower than 1.20. The cloud point temperatures, measured by monitoring the temperatureinduced changes in scattering intensity, decreased significantly with increasing polymer concentration, this effect being more pronounced with decreasing polymer molar mass. In contrast, the temperature of the PNIPAM chain coil-to-globule collapse (30 ( 1 °C) was only slightly affected by solution concentration and polymer molecular weight. These results are interpreted in terms of the coexistence of two phenomena: association of the n-octadecyl terminal groups and hydration of the PNIPAM chains.

We report the first application of pressure perturbation calorimetry (PPC) to determine the hydration properties of poly(N-isopropylacrylamide) (PNIPAM) in H2O and in D2O as the solutions undergo a temperature-induced phase transition. The technique, which measures the heat change resulting from a pressure change above a solution of PNIPAM placed in a microcalorimeter cell, yields the temperature dependence of the coefficient of thermal expansion, αp, of the polymer in solution and the change in volume of the solvation layer around the polymer chain. In the temperature ranges below and above the phase transition, αp of PNIPAM in H2O increased linearly with temperature. It underwent a sharp increase at the transition temperature, T max, then rapidly decreased. The phase transition was accompanied by an increase in the partial specific volume of the hydrated polymer. This increase was significantly higher for solutions of PNIPAM in D2O, compared to H2O. A study by PPC of the phase transition of hydrophobically modified PNIPAM samples that undergo micellization in water demonstrated that the hydration of the polymeric micelles varies significantly as a function of the degree of hydrophobic substitution and length of the alkyl group linked to the polymer.

The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair.

We report the design of a platform for the delivery of hydrophobic drugs via a macromolecular prodrug approach combined with LbL-assembled polyelectrolyte multilayers. A hyaluronan ester prodrug of the chemotherapeutic drug paclitaxel has been synthesized. Conjugation of the drug to hyaluronan through a labile succinate ester did not inhibit its activity. Using quartz crystal microbalance, atomic force microscopy, and UV spectroscopy, we have shown that the presence of the hydrophobic paclitaxel moieties does not prohibit the layer-by-layer construction of the multilayers. Release of the drug from the paclitaxel-loaded multilayers upon hydrolysis of the ester linkage resulted in a drastic cell death. Application of this delivery platform to substrates such as colloids, biomedical implants, or vascular tissues may lead to new therapeutic strategies.