ABSTRACT
This study investigates the formation mechanisms of oligomeric phenyl silanols, focusing on polyhedral oligomeric silsesquioxane (POSS) and double-decker silsesquioxane (DDSQ) derivatives. Combining literature reports and crystal structures of solvated derivatives obtained in our laboratory, we show that the solvent choice significantly influences their structures. POSS-based silanols prefer aprotic solvents like THF, preserving dimerization, while double-deckers form stable architectures in protic solvents like isopropanol. This discrepancy arises from different stabilization mechanisms. Our findings enhance our understanding of hydrolytic condensation involving trimethoxyphenylsilane and suggest aprotic solvents for efficient reactions with POSS-based silanols.
ABSTRACT
In this article, we explore theoretical validations of experimental findings pertaining to the classical corner-capping reactions of a commercially available heptaisobutyltrisilanol cage to mono-substituted phenylhepta(isobutyl)-POSS cages. Additionally, the process of opening a fully condensed cage is tracked to assess the possibility of isolating and separating the resulting isomers. The corner-capping reactions of potential silanotriols, both as monomers and dimers, and the impact of these structural motifs on their closing to bifunctional POSS cages are also investigated. Our studies highlight that analyzing experimental results alone, without incorporating complex theoretical investigations, does not offer a clear understanding of the reactions involving multiple simultaneously reacting substrates, which may also undergo further transformations, potentially complicating the conventional pathways of classic corner-opening/capping reactions.
ABSTRACT
The CuAAC active-template approach was exploited to construct rotaxanes incorporating cage-like silsesquioxane stoppers, namely, POSSaxanes. The compounds were characterized in the solution and solid state, providing the unprecedented molecular structures of POSS-incorporating rotaxanes.
Subject(s)
Rotaxanes , Rotaxanes/chemistry , Molecular StructureABSTRACT
An easy, efficient, and scalable synthetic procedure is described to obtain novel amide-functionalized double-decker silsesquioxanes (DDSQs). The use of mild conditions of deprotection of the BOC group, which does not result to the cleavage of the cage-like silsesquioxane structure, is reported. This method leads to the so far undescribed hydrochloride salt of aminoalkyl-DDSQ. Interestingly, the cis/trans-isomerization of DDSQ molecules was observed during the reaction. The resulting compounds are characterized using multinuclear NMR (1H, 13C, and 29Si), MALDI-TOF, FT-IR, and elemental analysis. Moreover, crystal structures are reported for three trans DDSQs. The chloride salt of aminoalkyl derivative, obtained in one of the steps of the synthetic pathway, shows an intriguing structure of the crystal lattice in which large channels are present, caused by ionic interactions in the lattice. The described approach opens the way to synthesizing new DDSQ derivatives and materials using BOC-blocked amines. We believe our findings would advance investigations about new materials based on little known organic-inorganic DDSQ-based hybrids.
ABSTRACT
The use of diverse biomaterials for regenerative medicine is constantly evolving. Therefore, looking for easy-to-scale-up materials in terms of preparation, less complex composition, and featuring structural and chemical stability seems justified. In this work, we report the preparation of double-decker silsesquioxane-based (DDSQ-based) composites, which, according to our best knowledge, have never been used as biomaterials. A family of methacrylate-substituted DDSQs was obtained starting from the previously reported hydroxyalkyl double-decker silsesquioxanes. In the resulting hybrids, methacrylate groups are attached to each other's lateral silicon atoms of DDSQ in trans positions, providing an excellent geometry for forming thin layers. In contrast to pure organic methacrylates, the covalent bonding of methacrylate derivatives to inorganic silsesquioxane core improves mechanics, cell adhesion, and migration properties. Furthermore, to increase the hydrophilicity of the resulting DDSQ-based hybrids, polyvinyl alcohol (PVA) was added. The entire system forms an easy-to-obtain two-component (DDSQ-PVA) composite, which was subjected without any upgrading additives to biological tests later in the research. The resulting biomaterials fulfill the requirements for potential medical applications. Human fibroblasts growing on prepared hybrid composites are characterized by proper spindle-shaped morphology, proliferation, and activation status similar to control conditions (cells cultured on PVA), as well as increased adhesion and migration abilities. The obtained results suggest that the prepared biomaterials may be used in regenerative medicine in the future.
