Enhanced model protein adsorption of nanoparticulate hydroxyapatite thin films on silk sericin and fibroin surfaces.

Hydroxyapatite coated metallic implants favorably combine the required biocompatibility with the mechanical properties. As an alternative to the industrial coating method of plasma spraying with inherently potential deleterious effects, sol-gel methods have attracted much attention. In this study, the effects of intermediate silk fibroin and silk sericin layers on the protein adsorption capacity of hydroxyapatite films formed by a particulate sol-gel method were determined experimentally. The preparation of the layered silk protein/hydroxyapatite structures on glass substrates, and the effects of the underlying silk proteins on the topography of the hydroxyapatite coatings were described. The topography of the hydroxyapatite layer fabricated on the silk sericin was such that the hydroxyapatite particles were oriented forming an oriented crystalline surface. The model protein (bovine serum albumin) adsorption increased to 2.62 µg/cm2 on the latter surface as compared to 1.37 µg/cm2 of hydroxyapatite on glass without an intermediate silk sericin layer. The BSA adsorption on glass (blank), glass/c-HAp, glass/m-HAp, glass/sericin/c-HAp, and glass/sericin/m-HAp substrates, reported as decrease in BSA concentration versus contact time.

Compositional, microstructural and mechanical effects of NaCl porogens in brushite cement scaffolds.

Modification of the setting process of brushite cements by varying the concentration of ions that alter calcium phosphate crystallization kinetics, is known to enable control on the monetite conversion extent and the accompanying microporosity. This is useful because monetite serves as a suitable matrix in macroporous scaffolds due to its higher phase stability and finer crystal morphology compared to its hydrous counterpart brushite. In this study the synergistic effect of NaCl and citric acid on the microstructural evolution of brushite cement was demonstrated and microporosity of macroporous monetite-rich cement blocks was minimized by a variable NaCl porogen size distribution approach. Initially, maximum packing ratio of various combinations of NaCl size groups in PEG were determined by their rheological analysis in a range between 57% and 69%. Statistical analysis revealed a positive correlation between the amounts of NaCl particles under 38µm and 212µm and the maximum packing ratio. Further broadening the size distributions of NaCl porogens with fine cement precursors was effective in increasing the solids packing ratio of cement blocks more than the maximum packing ratio for the porogens. This improvement in packing was accompanied by a reduction in microporosity despite the increase in micropore volume with ion induced monetite formation. The detrimental effect of the microporosity introduced to the structure during monetite formation was balanced for some size distributions and not so much for others, thereby resulting in a wide range of porosities and mechanical properties. Thus, the exponential dependence of mechanical properties on porosity and the mechanical properties of monetite-rich macroporous blocks at the theoretical zero-porosity were determined according to Rice's model. Zero-porosity extrapolations were much higher than those predicted for brushite cement, contrary to the common assumption that brushite is mechanically stronger than monetite.

Monetite promoting effect of NaCl on brushite cement setting kinetics.

Brushite forming calcium phosphate cements (CPCs) have received growing interest for scaffold applications due to their high surface area and high bioresorbability. The dehydrated form of brushite, monetite, has a finer microstructure with higher surface area, higher strength and bioresorbability comparable to brushite, making it a viable alternative phase in CPCs. The increase in monetite content of the ß-tricalcium phosphate (ß-TCP)-monocalcium phosphate monohydrate (MCPM) cement system due to the reduction in its supersaturation upon addition of NaCl to excess setting liquid was investigated kinetically. The relaxation period was monitored by pH-stat titration of the cement solution by 0.1 M NaOH. Monetite growth was achieved in shorter periods at higher NaCl concentrations where the supersaturation gap between brushite and monetite is thought to be narrowed due to high ionic strength in accord with Pitzer's ion interaction model. The brushite/monetite ratio decreased consistently with increasing NaCl concentration in the 3-6 M range.