Search Results (3)

A series of N-methyl quaternized derivatives of poly(4-vinylpyridine) (PVP) were synthesized in high yields with different degrees of quaternization, obtained by varying the methyl iodide molar ratio and affording products with unexplored optical and solvation properties. The impact of quaternization on the physicochemical properties of the copolymers, and notably the solvation properties, was further studied. The structure of the synthesized polymers and the quaternization degrees were determined by infrared and nuclear magnetic spectroscopies, while their thermal characteristics were studied by differential scanning calorimetry and their thermal stability and degradation by thermogravimetric analysis (TG-DTA). Attention was given to their optical properties, where UV-Vis and diffuse reflectance spectroscopy (DRS) measurements were carried out. The optical band gap of the polymers was calculated and correlated with the degree of quaternization. The study was further orientated towards the solvation properties of the polymers in binary solvent mixtures that strongly depend on the degree of quaternization, enabling a better understanding of the key polymer (solute)-solvent interactions. The assessment of the underlying solvation phenomena was performed in a system of different ratios of DMSO/H₂O and the solvatochromic indicator used was Reichardt’s dye. Solvent polarity parameters have a significant effect on the visible spectra of the nitrogen quaternization of PVP studied in this work and a detailed path towards this assessment is presented. Full article

The core of micelles self-assembled from amphiphiles is hydrophobic and contains little water, whereas complex coacervate core micelles co-assembled from oppositely charged hydrophilic polymers have a hydrophilic core with a high water content. Co-assembly of ionic surfactants with ionic-neutral copolymers yields surfactant–copolymer complexes known to be capable of solubilizing both hydrophilic and hydrophobic cargo within the mixed core composed of a coacervate phase with polyelectrolyte-decorated surfactant micelles. Here we formed such complexes from asymmetric (PUI-A2) and symmetric (PUI-S2), sequence-controlled polyurethane ionomers and poly(N-methyl-2-vinylpyridinium iodide)₂₉-b-poly(ethylene oxide)₂₀₄ copolymers. The complexes with PUI-S2 were 1.3-fold larger in mass and 1.8-fold larger in radius of gyration than the PUI-A2 complexes. Small-angle X-ray scattering revealed differences in the packing of the similarly sized PUI micelles within the core of the complexes. The PUI-A2 micelles were arranged in a more ordered fashion and were spaced further apart from each other (10 nm vs. 6 nm) than the PUI-S2 micelles. Hence, this work shows that the monomer sequence of amphiphiles can be varied to alter the internal structure of surfactant–copolymer complexes. Since the structure of the micellar core may affect both the cargo loading and release, our findings suggest that these properties may be tuned through control of the monomer sequence of the micellar constituents. Full article

Tetrakis (4-carboxyphenyl) porphyrin (TCPP) and polyelectrolyte poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) (PMVP₄₁-b-PEO₂₀₅) can self-aggregate into polyion complex (PIC) micelles in alkaline aqueous solution. UV-vis spectroscopy, fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering were carried out to study PIC micelles. Density functional theory (DFT) calculation method was applied to study the interaction of TCPP and PMVP₄₁-b-PEO₂₀₅. We found that the H-aggregates and J-dimers of anionic TCPP transformed in PIC micelles. H-aggregates of TCPP formed at the charge ratio of TCPP/PMVP₄₁-b-PEO₂₀₅ 1:2 and J-dimer species at the charge ratio above 1:4, respectively. It is worth noting that the transformation from H-aggregates to J-dimer species of TCPP occurred just by adjusting the ratio of polymer and TCPP rather than by changing other factors such as pH, temperature, and ions. Full article