Polymer coatings based on polycations represent a perspective class of protective antimicrobial coatings. Polydiallyldimethylammonium chloride (PDADMAC) and its water-soluble complexes with sodium polystyrenesulfonate (PSS) were studied by means of dynamic light-scattering, laser microelectrophoresis and turbidimetry. It was shown that addition of six mol.% of polyanion to polycation results in formation of interpolyelectrolyte complex (IPEC) that was stable towards phase separation in water-salt media with a concentration of salts (NaCl, CaCl2, Na2SO4, MgSO4) up to 0.5 M. Most of the polyelectrolyte coatings are made by layer-by-layer deposition. The utilization of water-soluble IPEC for the direct deposition on the surface was studied. The coatings from the PDADMAC and the PSS/PDADMAC complex were formed on the surfaces of hydrophilic glass and hydrophobic polyvinylchloride. It was found that formation IPEC allows one to increase the stability of the coating towards wash-off with water in comparison to individual PDADMAC coating on both types of substrates. The visualization of the coatings was performed by atomic force microscopy and scanning electron microscopy.
In this work, the preparation procedure and properties of anionic magnetic microgels loaded with antitumor drug doxorubicin are described. The functional microgels were produced via the in situ formation of iron nanoparticles in an aqueous dispersion of polymer microgels based on poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-PAA). The composition and morphology of the resulting composite microgels were studied by means of X-ray diffraction, Mössbauer spectroscopy, IR spectroscopy, scanning electron microscopy, atomic-force microscopy, laser microelectrophoresis, and static and dynamic light scattering. The forming nanoparticles were found to be β-FeO(OH). In physiological pH and ionic strength, the obtained composite microgels were shown to possess high colloid stability. The average size of the composites was 200 nm, while the zeta-potential was −27.5 mV. An optical tweezers study has demonstrated the possibility of manipulation with microgel using external magnetic fields. Loading of the composite microgel with doxorubicin did not lead to any change in particle size and colloidal stability. Magnetic-driven interaction of the drug-loaded microgel with model cell membranes was demonstrated by fluorescence microscopy. The described magnetic microgels demonstrate the potential for the controlled delivery of biologically active substances.
Due to the presence of cationic units interpolyelectrolyte complexes (IPECs) can be used as a universal basis for preparation of biocidal coatings on different surfaces. Metallopolymer nanocomposites were successfully synthesized in irradiated solutions of polyacrylic acid (PAA) and polyethylenimine (PEI), and dispersions of non-stoichiometric IPECs of PAA–PEI containing silver ions. The data from turbidimetric titration and dynamic light scattering showed that pH 6 is the optimal value for obtaining IPECs. Metal polymer complexes based on IPEC with a PAA/PEI ratio equal to 3/1 and 1/3 were selected for synthesis of nanocomposites due to their aggregative stability. Studies using methods of UV–VIS spectroscopy and TEM have demonstrated that the size and spatial organization of silver nanoparticles depend on the composition of polymer systems. The average sizes of nanoparticles are 5 nm and 20 nm for complexes with a molar ratio of PAA/PEI units equal to 3/1 and 1/3, respectively. The synthesized nanocomposites were applied to the glass surface and exhibited high antibacterial activity against both gram-positive (Staphylococcus aureus) and gram-negative bacteria (Salmonella). It is shown that IPEC-Ag coatings demonstrate significantly more pronounced biocidal activity not only in comparison with macromolecular complexes of PAA–PEI, but also coatings of PEI and PEI based nanocomposites.
An elegant method of one-pot reaction at room temperature for the synthesis of nanocomposites consisting of cerium containing nanoparticles stabilized by carboxymethyl cellulose (CMC) macromolecules was introduced. The characterization of the nanocomposites was carried out with a combination of microscopy, XRD, and IR spectroscopy analysis. The type of crystal structure of inorganic nanoparticles corresponding to CeO2 was determined and the mechanism of nanoparticle formation was suggested. It was demonstrated that the size and shape of the nanoparticles in the resulting nanocomposites does not depend on the ratio of the initial reagents. Spherical particles with a mean diameter 2–3 nm of were obtained in different reaction mixtures with a mass fraction of cerium from 6.4 to 14.1%. The scheme of the dual stabilization of CeO2 nanoparticles with carboxylate and hydroxyl groups of CMC was proposed. These findings demonstrate that the suggested easily reproducible technique is promising for the large-scale development of nanoceria-containing materials.
Biocidal compositions based on interpolyelectrolyte complexes and a low molecular weight antibiotic can become a promising material for creating biocidal coatings, as they combine wash-off resistance and dual biocidal action due to the biocide and the polycation. Molecular mass characteristics of polymers play an essential role in the physics and mechanical properties of the coatings. In this work, the properties of polydiallyldimethylammonium chloride (PDADMAC) coatings of various molecular weights are investigated and assumptions are made about the optimal molecular weight needed to create antibacterial compositions. To study the resistance to washing off and moisture saturation of the coatings, the gravimetric method was used, and the adhesive properties of the coatings were studied by dynamometry. It has been established that an increase in molecular weight affects the wash-off resistance of coatings, but does not affect moisture absorption and adhesion mechanics of coatings. All samples of PDADMAC were demonstrated to exhibit the same antibacterial activity. Thus, when developing systems for creating antibacterial coatings, it must be taken into account that in order to create stable coatings, the requirement to use PDADMAC with a high degree of polymerization is necessary for the coating desorption control during wash off-but not mandatory for the control of mechanical and antibacterial properties of the coating.
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