RESUMEN

The influence of l- and d-ascorbic acid diastereomers on the structure, supramolecular ordering, energy, sorption and biological properties of heterochiral (D-L) and homochiral (D-D) salt complexes of chitosan (d-glucan)-acid was studied. The thermal effect of dissolving chitosan in l-ascorbic acid and the protonation degree of (D-L)-salts were lower than those in the medium of the d-isomer. Homochiral (D-D) salts, in contrast to heterochiral (D-L) ones, are distinguished by a more developed system of intermolecular and intramolecular contacts, a more ordered and equilibrium supramolecular organization of macrochains, a higher crystallinity degree, and a smaller amount of crystallization water. The sorption isotherms of chiral salts were approximated by the thermal equation of sorption and the superposition of the Langmuir and Flory-Huggins isotherms. Significant differences were found in the limiting value and energy of sorption, the constant of adsorption equilibrium, the limiting sorption capacity of the localized mode of water, and the Gibbs mixing energy. Biotesting on non-vascular (Scenedesmus quadricauda) and vascular eukaryotes (Linum usitatissimum) revealed the growth-stimulating effect of the D-D salts. The obtained results confirm our hypothesis of the homochiral salt complexes d-glucan-d-ascorbic acid best corresponding to the principles of the functional organization of biological objects.

Asunto(s)

Quitosano , Quitosano/química , Sales (Química) , Ácido Ascórbico , Adsorción , Glucanos , Agua/química , Cinética , Concentración de Iones de Hidrógeno

RESUMEN

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.