Micellization of poly(oxyethylene-6-oxypropylene-6-oxyethylene) triblock copolymers (Pluronic polymers F68, P85, and F108) in aqueous solutions was studied, and critical micellization concentrations (cmc) were determined using surface tension measurements and fluorescent probes (pyrene, l,6-diphenyl-l,3,5-hexatriene). The dependence of cmc on temperature was observed, and critical micellization temperatures characterizing temperature-dependent transitions of Pluronic unimers to multimolecular micelles were measured. The molecular characteristics of P85 and F108 micelles including their dimensions, molecular masses and surfactant aggregation numbers were determined using lightscattering and ultracentrifugation techniques. Depending on the type of Pluronic, the micelles had an average hydrodynamic diameter ranging from about 15 to about 35 nm, a molecular mass of about 200 kDa and aggregation numbers ranging from one to several dozens. The partitioning of fluorescent probes between aqueous and micellar phases was analyzed within the frame of a pseudophase model, and the partitioning coefficients were determined using the fluorescence data. The results are compared with previous reports and are discussed in relationship to the application of block copolymer micelles as microcontainers for drug delivery.
Poor solubility of single-walled and multiwalled carbon nanotubes (NTs) in water and organic solvents presents a considerable challenge for their purification and applications. Macromolecules can be convenient solubilizing agents for NTs and a structural element of composite materials for them. Several block copolymers with different chemical functionalities of the side groups were tested for the preparation of aqueous NT dispersions. Poly(N-cetyl-4-vinylpyridinium bromide-co-N-ethyl-4-vinylpyridinium bromide-co-4-vinylpyridine) was found to form exceptionally stable NT dispersions. It is suggested that the efficiency of macromolecular dispersion agents for NT solubilization correlates with the topological and electronic similarity of polymer-NT and NT-NT interactions in the nanotube bundles. Raman spectroscopy and atomic force and transmission electron microcopies data indicate that the polycations are wrapped around NTs forming a uniform coating 1.0-1.5 nm thick. The ability to wind around the NT originates in the hydrophobic attraction of the polymer backbone to the graphene surface and topological matching. Tetraalkylammonium functional groups in the side chains of the macromolecule create a cloud of positive charge around NTs, which makes them hydrophilic. The prepared dispersions could facilitate the processing of the nanotubes into composites with high nanotube loading for electronic materials and sensing. Positive charge on their surface is particularly important for biological and biomedical applications because it strengthens interactions with negatively charged cell membranes. A high degree of spontaneous bundle separation afforded by the polymer coating can also be beneficial for NT sorting.
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