New monolithic nanocomposite silica biomaterials were synthesized on the basis of various natural polysaccharides and recently introduced completely water-soluble precursor tetrakis(2-hydroxyethyl) orthosilicate. The sol-gel processes were performed in aqueous solutions without the addition of organic solvents and catalysts. The silica polymerization was promoted by the polysaccharides through acceleration and catalytic effect on the processes. By introducing poly(vinyl alcohol) or poly(ethylene oxide) in the precursor solution, it was shown that the jellification took place in the case of the hydroxyl-containing polymer. Therefore, it was suggested that the catalysis was caused by a formation of hydrogen bonds between hydroxyl groups in macromolecules and products of precursor hydrolysis (silanols). It was also demonstrated that the polysaccharides radically changed the structure of biomaterials. In place of the cross-linked nanoparticles, there was a three-dimensional network from crossed or branched fibers and uncrossed spherical particles that filled the mesh space. The density of network, thickness of fibers, and properties of synthesized biomaterials depended on the polysaccharide type, charged degree of their macromolecule, and concentration. By varying these parameters, it was possible to manipulate the structural organization of hybrid polysaccharide-silica nanocomposites.

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