Chitosan has been explored as a potential component of biomaterials and scaffolds for many tissue engineering applications. Hybrid materials, where organic and inorganic networks interpenetrate at the molecular level, have been a particular focus of interest using 3-glycidoxypropyl trimethoxysilane (GPTMS) as a covalent crosslinker between the networks in a sol-gel process. GPTMS contains both an epoxide ring that can undergo a ring opening reaction with the primary amine of chitosan and a trimethoxysilane group that can co-condense with silica precursors to form a silica network. While many researchers have exploited this ring-opening reaction, it is not yet fully understood and thus the final product is still a matter of some dispute. Here, a detailed study of the reaction of GPTMS with chitosan under different pH conditions was carried out using a combination of solution state and solid state MAS NMR techniques. The reaction of GPTMS with chitosan at the primary amine to form a secondary amine was confirmed and the rate was found to increase at lower pH. However, a side-reaction was identified between GPTMS and water producing a diol species. The relative amounts of diol and chitosan-GPTMS species were 80 and 20% respectively and this ratio did not vary with pH. The functionalisation pH had an effect on the mechanical properties of 65 wt% organic monoliths where the properties of the organic component became more dominant. Scaffolds were fabricated by freeze drying and had pore diameters in excess of 140 mm, and tailorable by altering freezing temperature, which were suitable for tissue engineering applications. In both monoliths and scaffolds, increasing the organic content disrupted the inorganic network, leading to an increase in silica dissolution in SBF. However, the dissolution of silica and chitosan was congruent up to 4 weeks in SBF, illustrating the true hybrid nature resulting from covalent bonding between the networks.

Current materials used for bone regeneration are usually bioactive ceramics or glasses. Although they bond to bone, they are brittle. There is a need for new materials that can combine bioactivity with toughness and controlled biodegradation. Sol-gel hybrids have the potential to do this through their nanoscale interpenetrating networks (IPN) of inorganic and organic components. Poly(γ-glutamic acid) (γ-PGA) was introduced into the sol-gel process to produce a hybrid of γ-PGA and bioactive silica. Calcium is an important element for bone regeneration but calcium sources that are used traditionally in the sol-gel process, such as Ca salts, do not allow Ca incorporation into the silicate network during low-temperature processing. The hypothesis for this study was that using calcium methoxyethoxide (CME) as the Ca source would allow Ca incorporation into the silicate component of the hybrid at room temperature. The produced hybrids would have improved mechanical properties and controlled degradation compared with hybrids of calcium chloride (CaCl2), in which the Ca is not incorporated into the silicate network. Class II hybrids, with covalent bonds between the inorganic and organic species, were synthesised by using organosilane. Calcium incorporation in both the organic and inorganic IPNs of the hybrid was improved when CME was used. This was clearly observed by using FTIR and solid-state NMR spectroscopy, which showed ionic cross-linking of γ-PGA by Ca and a lower degree of condensation of the Si species compared with the hybrids made with CaCl2 as the Ca source. The ionic cross-linking of γ-PGA by Ca resulted in excellent compressive strength and reduced elastic modulus as measured by compressive testing and nanoindentation, respectively. All hybrids showed bioactivity as hydroxyapatite (HA) was formed after immersion in simulated body fluid (SBF).

Inorganic/organic sol–gel hybrids have nanoscale co-networks of organic and inorganic components that give them the unique potential of tailored mechanical properties and controlled biodegradation in tissue engineering applications.

Bioactive glasses and inorganic/organic hybrids have great potential as biomedical implant materials. Sol-gel hybrids with interpenetrating networks of silica and biodegradable polymers can combine the bioactive properties of a glass with the toughness of a polymer. However, traditional calcium sources such as calcium nitrate and calcium chloride are unsuitable for hybrids. In this study calcium was incorporated by chelation to the polymer component. The calcium salt form of poly(γ-glutamic acid) (γCaPGA) was synthesized for use as both a calcium source and as the biodegradable toughening component of the hybrids. Hybrids of 40wt.% γCaPGA were successfully formed and had fine scale integration of Ca and Si ions, according to secondary ion mass spectrometry imaging, indicating a homogeneous distribution of organic and inorganic components. (29)Si magic angle spinning nuclear magnetic resonance data demonstrated that the network connectivity was unaltered with changing polymer molecular weight, as there was no perturbation to the overall Si speciation and silica network formation. Upon immersion in simulated body fluid a hydroxycarbonate apatite surface layer formed on the hybrids within 1week. The polymer molecular weight (Mw 30-120kDa) affected the mechanical properties of the resulting hybrids, but all hybrids had large strains to failure, >26%, and compressive strengths, in excess of 300MPa. The large strain to failure values showed that γCaPGA hybrids exhibited non-brittle behaviour whilst also incorporating calcium. Thus calcium incorporation by chelation to the polymer component is justified as a novel approach in hybrids for biomedical materials.

Solid state 13 C-NMR spectra of pure tannin powders from four different sources -mimosa, quebracho, chestnut and tara -are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan. Groups of signals indicative of the source, and type (condensed vs. hydrolyzable) of tannin used in the manufacture are well resolved in the spectra of the finished leathers. These fingerprints are compared with those arising from leathers tanned with other common tanning agents. Paramagnetic chromium (III) tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III) structures. Aluminium (III) and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 27 Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance. OPEN ACCESSMolecules 2011, 16 1241

Organic–inorganic hybrid materials composed of co-networks of biodegradable polymer and silica have potential to combine the properties of an elastic organic polymer and inorganic silica. The nanoscale interaction of the co-networks and formation of covalent bonds between them are expected to provide tailored mechanical properties and congruent degradation. Alginate is a natural polymer commonly used in tissue engineering applications due to its good biocompatibility and biodegradability. In this work we present new alginate–silica hybrids prepared through nucleophilic ring opening reaction of 3-glycidoxypropyl trimethoxysilane (GPTMS) by carboxylic groups of alginate and incorporation of this functionalized alginate into the sol–gel process to make a hybrid. The role of the GPTMS is to provide organic/inorganic covalent coupling. The reaction of alginate with GPTMS was followed using NMR, FTIR and ToF-SIMS and the dissolution behaviour, bioactivity and mechanical properties of the resultant alginate–silica hybrid monoliths were evaluated. While mechanical strength was high with values of 110–242 MPa comparable to that of cortical bone, the amount of GPTMS coupling to the alginate was low, with the rest of the GPTMS forming diols or a separate network

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