N. N. Saprykina

Triple-responsive inorganic–organic hybrid microcapsules as a biocompatible smart platform for the delivery of small molecules

We designed novel hybrid inorganic/organic capsules with unique physicochemical features enabling multimodal triggering by physical (UV light, ultrasound) and chemical (enzymatic treatment) stimuli. Notably, the UV- and ultrasound response was achieved by a synergetic combination of TiO2 and SiO2 nanostructures which were in situ deposited into the polymer shell of microcapsules during sol-gel synthesis. This results in the formation of a composite hybrid shell with enhanced mechanical stability. Such sol-gel modification reduces the permeability of the capsule shell to allow for small molecule encapsulation. At the same time, these hybrid capsules consist of degradable polypeptides and polysaccharides and can be decomposed in response to enzymatic reaction. Upon employing different modes of treatment (UV-light, ultrasound or enzymatic degradation) we can stimulate different mechanisms of cargo release at desired times. Importantly, such capsules have been shown to be non-cytotoxic and can be internalized into human mesenchymal stem cells (MSCs) and cervical cancer cell lines (HeLa) revealing intracellular degradation. This work demonstrates that our hybrid capsules possess a triple stimuli-responsive effect, which is of capital importance for the future design and application of multimodal responsive platforms to improve externally stimulated release of bioactive compounds and their healthcare performance.

Structure and characteristics of chitosan-based fibers containing chrysotile and halloysite

With the use of the methods of X-ray diffraction and electron microscopy, chitosan fibers prepared by coagulation into an alcohol-alkali mixture are shown to possess a two-phase structure containing C- and O-type crystallites. These fibers and composite fibers containing halloysite and Mg chrysotile nanotubes are characterized by anisotropic structure, i.e., by the orientation of both chitosan crystallites and Mg chrysotile particles along the fiber axis. A comparison of the rates of shear induced by passing of a polymer solution through a die and the data of rheological studies allows the conclusion that the structuring of chitosan solution under the applied field of shear stresses and the orientation of polymer macromolecules and filler nanotubes occur. An increase in the draw ratio during fiber spinning does not assist orientation of polymer crystallites but, in contrast, increases surface defectiveness and leads to the nucleation of longitudinal cracks; as a result, the strength of fibers decreases. The introduction of 5 wt % Mg chrysotile into the chitosan matrix markedly increases the mechanical characteristics of the composite fibers owing to the reinforcing action of oriented filler nanotubes.

Mixed Matrix Membranes Based on Polyamide/Montmorillonite for Pervaporation of Methanol–Toluene Mixture

Novel mixed matrix membranes were obtained by the dispersion of montmorillonite (MMT) nanoparticles in poly(phenylene-iso-phtalamide) (PA) matrix. Membrane structure was determined on the basis of density measurement and morphology study by SEM. The effect of MMT inclusion on membrane hydrophilic properties was estimated by the measurement of contact angles of water, methanol, and toluene, respectively, and the calculation of surface tension. Transport properties of PA/MMT membranes were studied by use of swelling and pervaporation tests. The prepared membranes were used in the pervaporation of methanol–toluene mixtures. Total fluxes and separation factors, such as permeabilities and selectivities, were determined. It was established that the improvement of some physicochemical properties and transport parameters occurs only by inclusion up to 3 wt% MMT in the PA matrix.

Electrochemical activity and structure of new composite systems based on cross-linked polyacrylamide and polyaniline

A procedure was developed for preparing electroactive composite systems based on polyacrylamide hydrogel and a conducting polymer, polyaniline. The overall electrical conductivity of the composite systems was measured by chronoamperometry, and the contributions of the electronic and ionic constituents were calculated. The specific capacity of the composites was calculated using galvanostatic charge-discharge cycles, and the stability of the capacity at cycling was evaluated.

The study of sorption and transport properties of membranes containing polyaniline

The transport properties of membranes based on polyimide-polyaniline composites are studied in the pervaporation separation of a methanol-toluene binary azeotropic mixture. The morphology of the membranes is investigated by electronic microscopy, and the wettability of their surface is analyzed by contact-angle measurements. Special attention is given to the study of sorption and diffusion characteristics of membranes affecting the selectivity and rate of membrane separation. It is found that the incorporation of polyaniline into the matrix of the aromatic polyimide facilitates a reduction in the density of the composites relative to that of the nonmodified polyimide. It is shown that the membranes based on the polyimide-polyaniline composites are more selective with respect to methanol and show lower permeability during pervaporation of the methanol-toluene mixture than polyimide membranes.

Structural optimization of calcium carbonate cores as templates for protein encapsulation

Abstract The calcium carbonate (CaCO3) cores being templates for model proteins encapsulation were obtained for developing oral drug delivery systems. The influence of the characteristics of the core formation (the time, the temperature, the stirring intensity, the ultrasound treatment and drying conditions) on the size and morphology of the carbonate cores was studied. The core size was shown to decrease with increasing the stirring time and stirring intensity. Statistical analysis of the scanning electron microscopy images of the carbonate cores allowed finding a correlation between their mean diameter and the parameters of the core formation. The regularities of proteins loading into porous CaCO3 cores were determined, and different loading methods were compared quantitatively. The co-precipitation method gives cores with the proteins load about five times as much as the adsorption method. The influence of protein properties and the ionic environment of protein molecules on the loading parameters were shown.

Two-level delivery systems for oral administration of peptides and proteins based on spore capsules of Lycopodium clavatum

Two-level delivery systems (DSs) for oral administration of therapeutic proteins and peptides were developed. The first level consists of outer walls of Lycopodium clavatum spores (sporopollenin exine capsules, SECs) with included target objects; the alginate microgranules serve as the second (outer) level. Alginate (a pH-dependent natural polymer) protects peptides from gastric acidity and enzyme exposure and provides slow release of target objects in an alkaline intestinal medium. Introducing ovomucoid (a peptidase inhibitor) into alginate coatings prevents enzymatic hydrolysis of peptide objects in the intestinal medium. The elemental composition of spores and SECs was controlled using energy-dispersion spectroscopy and combustion analysis; their morphology was visualized by SEM. The efficiencies of different methods of SEC loading were compared. It was demonstrated that the load value was controlled by molecular mass and the value of the isoelectric point of target objects. A comparison of peptide in vitro release profiles from DSs of various structures into simulated gastric and intestinal fluids was carried out. The mechanism of peptide release from two-level DSs was suggested. SECs were found in rat blood after intragastric administration of the two-level DSs. Time profiles of therapeutic peptide release were obtained in vivo.

Composite hydrogels based on polyacrylamide and cellulose: Synthesis and functional properties

Biocompatible composite hydrogels based on polyacrylamide and reinforced with bacterial or vegetable cellulose were synthesized. In the mechanical characteristics and water content, these hydrogels are similar to knee joint cartilages with average rigidity level. The structure and chemical composition of the hydrogels after their residence for 45 days in laboratory animal joints were studied by scanning electron microscopy and energydispersive X-ray microanalysis. Prolonged contact of the hydrogels with bones results in formation of calcium phosphate spherulites similar in composition to hydroxyapatite.

Morphology of modified hydrolysis lignin

The morphology of hydrolysis lignin was studied. The effect of dimethyl sulfoxide, temperature, and activating additives on the surface characteristics of lignin was examined.

Microencapsulated fire-extinguishing fluids and reactive fire-extinguishing composites formed on their basis

The application of microencapsulated liquid gasifiable fire-extinguishing agents as reactive filling compounds for fire-extinguishing composites is considered. A new process for microencapsulation of environmentally friendly fire-extinguishing agents possessing enhanced stability is designed. Novel composite materials are produced with these agents. The thermal-destruction processes of microcapsules containing liquid gasifiable fire-extinguishing agents of different compositions are considered. Laboratory and bench-mark firing tests of the materials are performed.