Isothermal calorimetric titrations of aqueous solutions of poly(ethylene glycol) (PEG) with sodium dodecyl sulfate (SDS) are known to exhibit a peculiar trend consisting of endothermic and exothermic effects. This behavior was explained with the formation of two different mixed micellar aggregates, one characterized by hydrophobic interactions and the second by ion-dipole association. Present NMR measurements on 13C, 1H, and 23Na nuclei do not support the formation of a number of PEG-SDS aggregates characterized by interactions of different nature. Our data are rather in accordance with the initial formation, at low surfactant concentration, of a polymer-surfactant aggregate in which the polymeric chain assumes a strained conformation in order to bind a small micellar cluster. The subsequent growing of the aggregate with increasing surfactant concentration allows the polymer to relax to a more expanded, energetically favored, conformation. Further calorimetric titrations with a set of PEG samples of different molecular weight (200 to 20000 Daltons) allowed to establish a few points so far unclear. The minimum molecular weights necessary for observing the onset and the settling, respectively, of polymer-surfactant interaction were identified and the characteristic multiple peak curve of the titration of the polymer with molecular weight of 8000 Dalton was found related to the discrete binding of two successive SDS micellar clusters on the same polymeric chain

Recent experimental studies have shown a preferential interaction of poly(vinylpyrrolidone) (PVP) toward the alkyl sulfate surfactants rather than toward those belonging to the alkyl sulfonate series. To gain information on the complex formation between PVP and the alkyl sulfate surfactants, we have performed 1 H and 13 C NMR and NOESY measurements on aqueous solutions of sodium decyl sulfate (C10OS) in the presence and absence of PVP at 1wt %. The results show that C10OS interacts with PVP, forming micellelike clusters bound onto the polymer, and furthermore suggest that the PVP-C10OS complex formation implies the synergic effects of the electrostatic attractions between the surfactant headgroup and the nitrogen and oxygen atoms in the pyrrolidone ring of PVP and of the hydrophobic interaction between the surfactant alkyl moiety and the ring carbons of PVP.

Polysaccharide networks, in the form of hydrogels and dried membranes based on chitosan and on the cross-linker tripolyphosphate (TPP), were developed using a novel approach. TPP was incorporated into chitosan by slow diffusion to favor a controlled gelation. By varying chitosan, TPP, and NaCl concentration, transition from inhomogeneous to homogeneous systems was achieved. Rheology and uniaxial compression tests enabled to identify the best performing hydrogel composition with respect to mechanical properties. FTIR, (31)P NMR, and spectrophotometric methods were used to investigate the interaction chitosan-TPP, the kinetics of phosphates diffusion during the dialysis and the amount of TPP in the hydrogel. A freeze-drying procedure enabled the preparation of soft pliable membranes. The lactate dehydrogenase assay demonstrated the biocompatibility of the membranes toward fibroblasts. Overall, we devised a novel approach to prepare homogeneous macroscopic chitosan/TPP-based biomaterials with tunable mechanical properties and good biocompatibility that show good potential as novel polysaccharide derivatives.

No abstract

The present contribution aims at testing experimentally the theoretical model previously devised (Donati, I.; Cesaro, A.; Paoletti, S.; Biomacromolecules 2006, 7, 281-287) for the description of the interaction between alginate and nongelling Mg(2+) ions. The model, based on an extension of the counterion condensation theory, introduces a contribution of free energy of affinity, DeltaG(aff,0), which depends on the monomer composition of the polyuronate. In the present work, three different alginates separately mimicking the mannuronan (polyM), the guluronan (polyG), and the polyalternating (polyMG) components of alginate, together with a natural alginate isolated from Laminaria hyperborea ( L. hyperborea ), were examined. They were treated with Mg(2+) ions, and relative variations in scattered light intensity, isothermal calorimetry (DeltaH(mix)), specific viscosity, and (23)Na NMR longitudinal relaxation rates were monitored with respect to samples at the same ionic strength but containing only Na(+) ions. The fraction of condensed magnesium counterions was found to be strongly dependent on alginate composition, increasing along the series mannuronan < polyalternating approximately L. hyperborea < guluronan, thus in good agreement with the theoretical predictions.

No abstract

Here we focus the attention on the physical characteristics of a highly biocompatible hydrogel made up of crosslinked alginate and Pluronic F127 (PF127). This is a composite polymeric blend we propose for artery endoluminal delivery of an emerging class of molecules named nucleic acid based drugs (NABDs). The physical characterization of our composite gel, i.e. mesh size distribution and PF127-alginate mutual organization after crosslinking, can significantly determine the NABDs release kinetics. Thus, to explore these aspects, different technical approaches, i.e. rheology, low/high field NMR and TEM, were used. While rheology provided information at the macroscopic and nano-level, the other three approaches gave details at the nano-level. We observe that Pluronic micelles, organizing in cubic ordered domains, generate, upon alginate crosslinking, the formation of meshes (≈ 150 nm) larger than those occurring in a Pluronic-free alginate network (≈ 25 nm). Nevertheless, smaller alginate meshes are still on and can just host un-structured Pluronic micelles and water. Accordingly, the gel structure is quite inhomogeneous, where big meshes (filled by crystalline Pluronic) co-exist with smaller meshes (hosting water and un-structured PF127 micelles). While big meshes offer a considerable hindering action on a diffusing solute, smaller ones represent a sort of free space where solute diffusion is faster. The presence of big and small meshes indicates that drug release may follow a double kinetics characterized by a fast and slow release. Notably, this behavior is considered appropriate for endoluminal drug release to the arterial wall.

No abstract