The influence of the chirality of chitosan ascorbate on the gelation kinetics and the properties of hybrid silicon-chitosan-containing glycerohydrogels were studied with a deep estimation of the stereospecificity of chitosan polysalts with l- and d-ascorbic acid diastereomers and their biological effects. It has been established that l- and d-diastereomerically enriched chitosan ascorbates are characterized by a positive Cotton effect and differ in the wavelength of the maximum of the dichroic band (250 and 240 nm), as well as in the values of its specific ellipticity (21.8 × 105 and 39.2 × 105 deg·mL·dm−1·g−1), the sign of specific optical rotation (+ and −), the type of dispersion curves (anomalous and smooth), as well as the condensed phase morphology (anisodiametric particles with optical anisotropy and confocal domains of spherical shape, respectively). In the biomimetic sol-gel synthesis of silicon-chitosan-containing glycerohydrogels using silicon tetraglycerolate as a precursor, it was found that chitosan d-ascorbate retarded gelation. Thin congruent plates obtained from the corresponding glycerohydrogels based on chitosan d-ascorbate have higher mechanical strength and elasticity under uniaxial stretching and lower values of Young’s modulus. It has been shown that the systems based on chitosan d-ascorbate show the greatest antibacterial activity against Staphylococcus aureus 209P and Escherichia coli 113-13 and significantly promote the viability of normal human dermal fibroblasts. The results of our assessment of the biological properties of chitosan polysalts are unexpected, since ascorbic acid exhibits biological activity as its l-isomer only.
The preparation of 3D chitosan microtubes from polymer solutions in citric and lactic acids by the wet and dry molding methods is described. The mechanism of formation of the insoluble polymeric layer constructing the walls of these microtubes is characterized. The microtubes obtained from chitosan solutions in citric acid are found to have a fragile porous inner layer. For those obtained from chitosan solutions in lactic acid the morphology, elastic-deformation properties, physicomechanical properties, and biocompatibility were assessed. These samples have smooth outer and inner surfaces with no visible defects and high values of elongation at break. The strength of the microtubes obtained by the dry method is much higher than in the case of the wet one. A high adhesion and high proliferative activity of the epithelial-like MA-104 cellular culture on the surface of our microtubular substrates in modelin vitroexperiments were revealed. Prospects of using chitosan microtubes as vascular prostheses are suggested.
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