Revisiting the System Silanes-Polysaccharides: The Cases of THEOS-Chitosan and MeTHEOS-Chitosan.

The glycol alkoxysilanes, tetrakis(2-hydroxyethyl)silane (THEOS), and tris(2-hydroxyethyl)methyl silane (MeTHEOS) are water soluble derivatives of tetraethoxysilane (TEOS) and methyltriethoxysilane (MeTEOS) and precursors of the system silane-chitosan reviewed in this work. The glycol modified alkoxysilanes are obtained by transesterification reaction of TEOS or MeTEOS with ethylene glycol. The reaction evolution is monitored by 29 Si NMR. It is possible to observe the formation of the various species of glycol alkoxysilanes in equilibrium as the reaction proceeds showing that the oligomers formation is favored at longer reaction times with the final product tendency to gel keeping the complete water solubility. The glycol alkoxysilanes are synthesized at moderated reaction conditions, by using the Piers-Rubinsztajn (PR) reaction. Additionally, it is already known that THEOS is compatible with different natural polysaccharides as chitosan and the same behavior has been demonstrated in this work for MeTHEOS. Several reports refer studies regarding the system THEOS-polysaccharides to synthesize hybrid materials. The system THEOS-chitosan is known but the characterization as well as the way silane-chitosan interact has not been studied in detail. In the present report, chemical evidence of the covalent interactions THEOS- and MeTHEOS-chitosan based on NMR studies (13 C and 29 Si) are presented as intended.

An Approach to the Use of Glycol Alkoxysilane-Polysaccharide Hybrids in the Conservation of Historical Building Stones.

Stone consolidants have been widely used to protect historical monuments. Consolidants and hydrophobic formulations based on the use of tetraethoxysilane (TEOS) and alkylalkoxysilanes as precursors have been widely applied, despite their lack of solubility in water and requirement to be applied in organic media. In the search for a "greener" alternative based on silicon that has potential use in this field, the use of tetrakis(2-hydroxyethyl)silane (THEOS) and tris(2-hydroxyethyl)methyl silane (MeTHEOS) as precursors, due their high water solubility and stability, is proposed in this paper. It is already known that THEOS and MeTHEOS possess remarkable compatibility with different natural polysaccharides. The investigated approach uses the water-soluble silanes THEOS-chitosan and MeTHEOS-chitosan as a basis for obtaining hybrid consolidants and hydrophobic formulations for the conservation of siliceous and calcareous stones. In the case of calcareous systems, their incompatibility with alkoxysilanes is known and is expected to be solved by the developed hybrid consolidant. Their application in the conservation of building stones from historical and archeological sites from Guanajuato, México was studied. The evaluation of the consolidant and hydrophobic formulation treatment was mainly conducted by determining the mechanical properties and contact angle measurements with satisfactory results in terms of the performance and compatibility with the studied stones.

Crystal structure and Hirshfeld surface analysis of 3-cyano-phenyl-boronic acid.

In the title compound, C7H6BNO2, the mean plane of the -B(OH)2 group is twisted by 21.28 (6)° relative to the cyano-phenyl ring mean plane. In the crystal, mol-ecules are linked by O-H⋯O and O-H⋯N hydrogen bonds, forming chains propagating along the [101] direction. Offset π-π and B⋯π stacking inter-actions link the chains, forming a three-dimensional network. Hirshfeld surface analysis shows that van der Waals inter-actions constitute a further major contribution to the inter-molecular inter-actions, with H⋯H contacts accounting for 25.8% of the surface.