Magnetic Nanocomposite Materials Based on Fe3O4 Nanoparticles with Iron and Silica Glycerolates Shell: Synthesis and Characterization.

Novel magnetic nanocomposite materials based on Fe3O4 nanoparticles coated with iron and silica glycerolates (MNP@Fe(III)Glyc and MNP@Fe(III)/SiGlyc) were obtained. The synthesized nanocomposites were characterized using TEM, XRD, TGA, VMS, Mössbauer and IR spectroscopy. The amount of iron and silica glycerolates in the nanocomposites was calculated from the Mössbauer spectroscopy, ICP AES and C,H-elemental analysis. Thus, it has been shown that the distribution of Fe in the shell and core for MNP@Fe(III)Glyc and MNP@Fe(III)/SiGlyc is 27:73 and 32:68, respectively. The synthesized nanocomposites had high specific magnetization values and a high magnetic response to the alternating magnetic field. The hydrolysis of shells based on Fe(III)Glyc and Fe(III)/SiGlyc in aqueous media has been studied. It has been demonstrated that, while the iron glycerolates shell of MNP@Fe(III)Glyc is resistant to hydrolysis, the silica glycerolates shell of MNP@Fe(III)/SiGlyc is rather labile and hydrolyzed by 76.4% in 24 h at 25 °C. The synthesized materials did not show cytotoxicity in in vitro experiments (MTT-assay). The data obtained can be used in the design of materials for controlled-release drug delivery.

Biocompatible Silica-Polyethylene Glycol-Based Composites for Immobilization of Microbial Cells by Sol-Gel Synthesis.

Biocatalysts based on the methylotrophic yeast Ogataea polymorpha VKM Y-2559 immobilized in polymer-based nanocomposites for the treatment of methanol-containing wastewater were developed. The organosilica composites with different matrix-to-filler ratios derived from TEOS/MTES in the presence of PEG (SPEG-composite) and from silicon-polyethylene glycol (STPEG-composite) differ in the structure of the silicate phase and its distribution in the composite matrix. Methods of fluorescent and scanning microscopy first confirmed the formation of an organosilica shell around living yeast cells during sol-gel bio-STPEG-composite synthesis. Biosensors based on the yeast cells immobilized in STPEG- and SPEG-composites are characterized by effective operation: the coefficient of sensitivity is 0.85 ± 0.07 mgO2 × min-1 × mmol-1 and 0.87 ± 0.05 mgO2 × min-1 × mmol-1, and the long-term stability is 10 and 15 days, respectively. The encapsulated microbial cells are protected from UV radiation and the toxic action of heavy metal ions. Biofilters based on the developed biocatalysts are characterized by high effectiveness in the utilization of methanol-rich wastewater-their oxidative power reached 900 gO2/(m3 × cycle), and their purification degree was up to 60%.

Individual iron(iii) glycerolate: synthesis and characterisation.

Iron(ii) and iron(iii) salts of strong acids form iron glycerolates on heating at 180 °C with glycerol in the presence of an equivalent amount of alkali. Individual iron(iii) glycerolate was obtained for the first time. When Fe3O4 magnetic nanoparticles were heated with glycerol, an iron(iii) glycerolate shell was formed on their surface.

Silicon-zinc-glycerol hydrogel, a potential immunotropic agent for topical application.

Nanoparticles synthesized using sol-gel method are promising agents for biomedical applications, in particular for the therapy and diagnosis of various diseases. Using silicon and zinc glycerolates as biocompatible precursors we synthesized by the sol-gel method a new bioactive silicon-zinc-containing glycerohydrogel combining the positive pharmacological properties of the precursors. In the present work the structural features of silicon-zinc-containing glycerohydrogel and its immunotropic properties were studied. The advanced physical methods, including XRD, TEM, dynamic and electrophoretic light scattering, were used for studying the structural features of the gel. Hydrolysis of zinc monoglycerolate was investigated under gelation conditions. Evaluation of the efficiency of silicon-zinc-containing glycerohydrogel in providing immune functions was carried out using a model of the complicated wound process behind immunosuppression induced by hydrocortisone administration in the Wistar rats. It has been shown that zinc monoglycerolate exists in the state of amorphous nanoparticles in the cells of 3D-network formed due to incomplete hydrolysis of silicon glycerolates and subsequent silanol condensation. Zinc monoglycerolate is not hydrolyzed and does not enter 3D-network of the gel with the formation of Zn-O-Si groups, but it forms a separate phase. Immunotropic action of silicon-zinc-containing glycerohydrogel was revealed by the histology and immunohistochemistry methods. Amorphous nanoparticles of zinc monoglycerolate, water-soluble silicon glycerolates, and products of their hydrolytic transformations, which are present in a aqueous-glycerol medium, are in the first place responsible for the pharmacological activity of hydrogel. The results obtained allow us to consider silicon-zinc-containing glycerohydrogel as a promising immunotropic agent for topical application.

Mechanism of structural networking in hydrogels based on silicon and titanium glycerolates.

Formation of organic/inorganic hydrogels based on silicon- and titanium-glycerol precursors synthesized by transesterification of alkoxy derivatives in excess of glycerol was investigated. The precursors in excess of glycerol and obtained gels were studied by chemical and physical methods including gelation kinetics, IR spectroscopy, XRD, dynamic and electrophoretic light scattering, mechanical deformation, which disclosed the basic difference in the gelation mechanism and structure of network in the hydrogels. Due to this difference, the gelation time of silicon- and titanium-glycerol precursors depended on pH or electrolyte addition in an opposite way. In the wide pH range, silicon-glycerol hydrogel was a polymeric single-phase system formed by the polymeric network homogeneously swollen in liquid water/glycerol medium. Flory-Rehner theory applied to the elastic modulus of these gels gave 40-180 monomer base units in the subchains of the network depending on water content in the gel. The mechanism of networking was three-dimensional polycondensation promoted by the electrically charged functional groups attached to the flexible polymeric chains. Electrolyte solutions provided the gelation according to Hofmeister series. Titanium-glycerol hydrogels were heterogeneous colloid systems at pH>1.5 and single-phase polymeric gels at lower pH. Electrolyte solutions provided the gelation according to Schultze-Hardy rule.