Frederik Romer

Bioactivity in silica/poly(γ-glutamic acid) sol–gel hybrids through calcium chelation

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.

Highly flexible silica/chitosan hybrid scaffolds with oriented pores for tissue regeneration

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. Here, silica/chitosan hybrid scaffolds with oriented structures were fabricated through the sol-gel method with a unidirectional freeze casting process. 3-Glycidoxypropyl trimethoxysilane (GPTMS) was used to obtain covalent inorganic/organic coupling. Process variables were investigated such as cooling rate, GPTMS and inorganic content, which can be used to tailor the mechanical properties and hybrid chemical coupling. Structural characterization and dissolution tests confirmed the covalent cross-linking of the chitosan and the silica network in hybrids. The scaffolds had a directional lamellar structure along the freezing direction and a cellular morphology perpendicular to the freezing direction. Compression testing showed that the scaffolds with 60 wt% organic were flexible and elastomeric perpendicular to the freezing direction whilst behaving in an elastic-brittle fashion parallel to the freezing direction. The compressive strengths are about one order of magnitude higher in the latter direction reaching values of the order of 160 kPa. This behaviour provides potential for clinicians to be able to squeeze the materials to fit tissue defect sites while providing some mechanical support from the other direction.

Poly(γ-glutamic acid)/silica hybrids with calcium incorporated in the silica network by use of a calcium alkoxide precursor

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).

Proton Conductivity of Naphthalene Sulfonate Formaldehyde Resin‐Doped Mesoporous Niobium and Tantalum Oxide Composites

Proton conductivity in a series of mesoporous niobium and tantalum metal oxide (mX2 O5 ) composites of naphthalene sulfonic acid formaldehyde resin (NSF) that are resistant to moisture loss at temperatures greater than 50 °C is reported. The investigation focuses on the effect to proton conductivity by changing pore size and metal in the mesostructure of the mX2 O5 system and thus, a series of mX2 O5 -NSF composites were synthesized with C6 , C12 , and C18 templates. These were characterized by XRD, thermogravimetric analysis, nitrogen adsorption, and scanning TEM and then studied using impedance spectroscopy to establish proton conductivity values at various temperatures ranging from 25 to 150 °C. The most promising sample displayed a conductivity of 21.96 mS cm(-1) at 100 °C, surpassing the literature value for Nafion 117 (ca. 8 mS cm(-1) ). (1) H and (13) C solid state NMR studies the mX2 O5 -NSF composites demonstrate that the oligomeric nature of the NSF is preserved while in contact with the mX2 O5 surface, thus facilitating conductivity.