Facile synthesis of a three-dimensional hydroxyapatite monolith for protein adsorption.

Hydroxyapatite (HA) shows promising applications in the clinical treatment of bone defects owing to its excellent physicochemical properties, such as biocompatibility, bioactivity, and osteoconductivity. However, it is difficult to maintain a porous structure in HA materials because of processing difficulties. In this study, a hard template method was developed to prepare a porous HA monolith with a hierarchical pore structure and high porosity. The cellulose monolith template was prepared from cellulose acetate using a thermally induced phase separation method. The cellulose monoliths were then immersed into the HA slurry to form a cellulose_HA composite monolith, which was converted to an HA monolith by burning in air to remove the cellulose monolith. Owing to the hierarchically porous structure of the cellulose monolith template, the obtained HA monolith demonstrated a hierarchically porous structure. Furthermore, the HA monolith was explored to study the adsorption and release properties of bovine serum albumin (BSA), which indicated that the HA monolith had a high adsorption capacity (388.6 mg g-1) and sustained release from the BSA-loaded HA monolith. Thus, HA monoliths have potential applications in the field of protein purification and biomaterials.

Porous Biphasic Calcium Phosphate Granules from Oyster Shell Promote the Differentiation of Induced Pluripotent Stem Cells.

Oyster shells are rich in calcium, and thus, the potential use of waste shells is in the production of calcium phosphate (CaP) minerals for osteopathic biomedical applications, such as scaffolds for bone regeneration. Implanted scaffolds should stimulate the differentiation of induced pluripotent stem cells (iPSCs) into osteoblasts. In this study, oyster shells were used to produce nano-grade hydroxyapatite (HA) powder by the liquid-phase precipitation. Then, biphasic CaP (BCP) bioceramics with two different phase ratios were obtained by the foaming of HA nanopowders and sintering by two different two-stage heat treatment processes. The different sintering conditions yielded differences in structure and morphology of the BCPs, as determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface area analysis. We then set out to determine which of these materials were most biocompatible, by co-culturing with iPSCs and examining the gene expression in molecular pathways involved in self-renewal and differentiation of iPSCs. We found that sintering for a shorter time at higher temperatures gave higher expression levels of markers for proliferation and (early) differentiation of the osteoblast. The differences in biocompatibility may be related to a more hierarchical pore structure (micropores within macropores) obtained with briefer, high-temperature sintering.

In vivo evaluation of interactions between biphasic calcium phosphate (BCP)-niobium pentoxide (Nb2O5) nanocomposite and tissues using a rat critical-size calvarial defect model.

Natural or synthetic biomaterials are increasingly being used to support bone tissue repair or substitution. The combination of natural calcium phosphates with biocompatible alloys is an important route towards the development of new biomaterials with bioperformance and mechanical responses to mimic those of human bones. This article evaluated the structural, physical, mechanical and biological properties of a new mechanical improved nanocomposite elaborated by association of fish biphasic calcium phosphate (BCP) and niobium pentoxide (Nb2O5). The nanocomposite (Nb-BCP) and the pure BCP, used as a positive control, were obtained by powder metallurgy. The density, porosity and microhardness were measured. The structural analysis was determined by X-ray diffraction (XRD) and the biological properties were studied in histological sections of critical size calvaria defects in rats, 7, 15, 30, 45 and 60 days after implantation of disks of both materials. Morphological description was made after scanning electron microscopy (SEM) and optical microscopy analysis. After sintering, the Nb-BCP nanocomposite presented four crystalline phases: 34.36% calcium niobate (CaNb2O6), 21.68% phosphorus niobium oxide (PNb9O25), 42.55% ß-tricalcium phosphate (Ca3(PO4)2) and 1.31% of niobium pentoxide (Nb2O5) and exhibited increases of 17% in density, 66% in Vickers microhardness and 180% in compressive strength compared to pure BCP. In vivo study, showed biocompatibility, bioactivity and osteoconductivity similar to pure BCP. SEM showed the formation of globular accretions over the implanted nanocomposites, representing one of the stages of bone mineralization. In conclusion, the BCP and Nb2O5 formed a nanocomposite exhibiting characteristics that are desirable for a biomaterial, such as bioperformance, higher ß-TCP percentage and improved physical and mechanical properties compared to pure BCP. These characteristics demonstrate the promise of this material for supporting bone regeneration.

Rapid regeneration of enamel-like-oriented inorganic crystals by using rotary evaporation.

Enamel, the hardest tissue in the human body, has excellent mechanical properties, mainly due to its highly ordered spatial structure. Fabricating enamel-like structure is still a challenge today. In this work, a simple and highly efficient method was introduced, using the silk fibroin as a template to regulate calcium- and phosphate- supersaturated solution to regenerate enamel-like hydroxyapatite crystals on various substrates (enamel, dentin, titanium, and polyethylene) under rotary evaporation. The enamel-like zinc oxide nanorod array structure was also successfully synthesized using the aforementioned method. This strategy provides a new approach to design and fabricate mineral crystals with particular orientation coatings for materials.

Pulsed laser deposition temperature effects on strontium-substituted hydroxyapatite thin films for biomedical implants.

Substituting small molecule drugs with abundant and easily affordable ions may have positive effects on the way countless disease treatments are approached. The interest in strontium cation in bone therapies soared in the wake of the success of strontium ranelate in the treatment of osteoporosis. A new method for producing thin strontium-containing hydroxyapatite (Sr-HA, Ca9Sr(PO4)6(OH)2) films as coatings that render bioinert titanium implant bioactive is reported here. The method is based on the combination of a mechanochemical synthesis of Sr-HA targets and their deposition in form of thin films on top of titanium with the use of laser ablation at low pressure. The films were 1-2 µm in thickness and their formation was studied at different temperatures, including 25, 300, and 500 °C. Highly crystalline Sr-HA target transformed during pulsed laser deposition to a fully amorphous film, whose degree of long-range order recovered with temperature. Particle edges became somewhat sharper and surface roughness moderately increased with temperature, but the (Ca+Sr)/P atomic ratio, which increased 1.5 times during the film formation, remained approximately constant at different temperatures. Despite the mostly amorphous structure of the coatings, their affinity for capturing atmospheric carbon dioxide and accommodating it as carbonate ions that replace both phosphates and hydroxyls of HA was confirmed in an X-ray photoelectron spectroscopic analysis. As the film deposition temperature increased, the lattice voids got reduced in concentration and the structure gradually "closed," becoming more compact and entailing a linear increase in microhardness with temperature, by 0.03 GPa/°C for the entire 25-500 °C range. Biocompatibility and bioactivity of Sr-HA thin films deposited on titanium were confirmed in an interaction with dental pulp stem cells, suggesting that these coatings, regardless of the processing temperature, may be viable candidates for the surface components of metallic bone implants.

Structural modification of nanohydroxyapatite Ca10(PO4)6(OH)2 related to Eu3+ and Sr2+ ions doping and its spectroscopic and antimicrobial properties.

The Eu3+ and Sr2+ ions co-doped hydroxyapatite nanopowders (Ca10(PO4)6(OH)2) were synthesized via a precipitation method and post heat-treated at 500 °C. The concentration of Eu3+ ions was established in the range of 0.5-5 mol% to investigate the site occupancy preference. The concentration of Sr2+ ions was set at 5 mol%. The structural and morphological properties of the obtained materials were studied by an X-ray powder diffraction, a transmission electron microscopy techniques and infrared spectroscopy. As synthesized nanoparticles were in the range of 11-17 nm and annealed particles were in the range of 20-26 nm. The luminescence properties in dependence of the dopant concentration and applied temperature were investigated. The 5D0 → 7F0 transition shown the abnormally strong intensity for annealed materials connected with the increase of covalency character of Eu3+-O2- bond, which arise as an effect of charge compensation mechanism. The Eu3+ ions occupied three possible crystallographic sites in these materials revealed in emission spectra: one Ca(1) site with C3 symmetry and two Ca(2) sites with Cs symmetry arranged as cis and trans symmetry. The antibacterial properties of Eu3+ and Sr2+ ions doped and co-doped hydroxyapatite nanopowders were also determined against Gram-negative pathogens such as Pseudomonas aeruginosa, Klebsiella pneumoniae and Escherichia coli. Obtained results suggest that both europium and strontium ions may implement antibacterial properties for hydroxyapatites. In the most cases, better antibacterial effect we noticed for dopants at 5 mol% ratio. However, the effect is strongly species- and strain-dependent feature.

Template-oriented synthesis of hydroxyapatite nanoplates for 3D bone printing.

The design of hydroxyapatite (HA) nanoarchitecture is critical for fabricating artificial bone tissues as it dictates the biochemical and the mechanical properties of the final product. Herein, we incorporated a simple hard-template approach to synthesise single crystal nanoplates of HA. We used the 2D graphitic nitride (g-C3N4) material to prepare an HA sol-gel under hydrothermal conditions. A new HA nanostructure was then formed during the calcination and removal of g-C3N4 at a higher temperature, which finally led to the production of nanoplates (thickness of ∼100 nm) while in lateral dimension the average size was in the micrometre scale. We characterised the synthesised HA nanoplates with XRD, TEM, and HRTEM. The theoretically predicted nanostructure construction based on Wulff's method is in full agreement with the experimental observations. We then prepared different weight ratios of HA and polylactic acid (PLA) composites for artificial 3D bone fabrication. The strong interaction between PLA and HA's (110) facet, which was the second most prevalent, resulted in the composite's mechanical robustness. After mechanical testing, an optimum ratio was selected for biological studies and 3D printing. Biological experiments demonstrated that the synthesised composite had excellent viability in vitro.

Corrosion resistance and drug release profile of gentamicin-loaded polyelectrolyte multilayers on magnesium alloys: Effects of heat treatment.

Magnesium (Mg) alloys have received considerable attentions as the emerging biodegradable implant materials in orthopedic surgery applications. However, the rapid corrosion rate and the susceptibility to bacterial infection have prevented their wide spread applications to date. In this work, the gentamicin-loaded multilayers have been constructed on Mg alloys through spin-assisted layer-by-layer (SLbL) assembly. Heat treatment is applied for improving the corrosion resistance and prolonging the drug release profile. In addition, the treated multilayer can promote the formation of hydroxyapatite (HA) during the long-time immersion in Hank's balanced salt solution (HBSS).

Synthesis and characterization of calcium phosphate compounds with strontium and magnesium ionic substitutions / Síntetis y caracterización del compuestos de fosfato de calcio con substituto iónico de estroncio y magnesio

Bioceramics offer advantages in the repair and regeneration of hard tissues and are used as bone void fillers and particulate fillers in bone cements with surgical applications. Regeneration and osteosynthesis stimulation via the release of essential ions such as strontium (Sr2+) and magnesium (Mg2+) is a relatively new field. Therefore, there is great interest in investigating various ionic substitutions on crystallographic structure and characteristics for use in osteoporosis prevent and increase bone formation and decrease bone resorption. In this study, we synthesize calcium phosphate samples with Sr2+ and Mg2+ ionic substitutions. The samples are characterized using X-ray diffraction, Fourier transform infrared spectroscopy, and inductively coupled plasma mass spectroscopy. Hydroxyapatite, beta tricalcium phosphate, and amorphous phases were observed. Depending on the ionic substitution, the crystal size and crystallinity varied from 22 nm to 130 nm and from 84% to 99.6%, respectively. The Ca/P ratio ranged from 0.72 to 1.82. The results demonstrated the effect of Sr2+ and Mg2+ inclusions in calcium phosphate on important parameters used in several bioceramic applications.

Los biocerámicos ofrecen ventajas en la reparación y regeneración de tejidos duros utilizándose como relleno en cavidades óseas y como relleno particulado en cementos óseos de aplicaciones quirúrgicas. Regeneración y estimulación de la osteosíntesis a través de la liberación de iones esenciales, como el estroncio (Sr) y magnesio (Mg) es un campo relativamente nuevo. Por lo tanto, existe un gran interés en la investigación de diversas sustituciones iónicos sobre la estructura cristalográfica y las características para su uso en la prevención de osteoporosis y aumento de la formación ósea con disminuir la resorción ósea. En este estudio, se sintetizó muestras de fosfato de calcio con sustituciones iónicos Sr y Mg. Las muestras se caracterizaron usando difracción de rayos X, espectroscopia infrarroja por transformada de Fourier, y la espectroscopia de masas con plasma acoplado inductivamente. Se observó hidroxiapatita, fosfato tricálcico beta, y las fases amorfas. Dependiendo de la sustitución iónica, el tamaño del cristal y cristalinidad variaron de 22 nm a 130 nm y de 84% a 99,6%, respectivamente. La relación Ca/P varió desde 0,72 hasta 1,82. Los resultados demostraron el efecto de las inclusiones de Sr y Mg en fosfato de calcio en parámetros importantes que se utilizan en varias aplicaciones de biocerámicos.

Effects on growth and osteogenic differentiation of mesenchymal stem cells by the strontium-added sol-gel hydroxyapatite gel materials.

In the present study, strontium-modified hydroxyapatite gels (Sr-HA) at different concentrations were prepared using sol-gel approach and their effect on human-bone-marrow-derived mesenchymal stem cells, were evaluated. The effect of Strontium on physico-chemical and morphological properties of hydroxyapatite gel were evaluated. Morphological analyses (SEM and TEM) demonstrate that an increasing in the amount of Sr ions doped into HA made the agglomerated particles smaller. The substitution of large Sr2+ for small Ca2+ lead to denser atomic packing of the system causing retardation of crystals growth. The biological results demonstrated that hydroxyapatite gel containing from 0 to 20 mol% of Sr presented no cytotoxicity and promote the expression of osteogenesis related genes including an early marker for osteogenic differentiation ALP; a non-collagen protein OPN and a late marker for osteogenic differentiation OCN. Finally, the Sr-HA gels could have a great potential application as filler in bone repair and regeneration and used in especially in the osteoporotic disease.

Preparation, evaluation, and first clinical use of 177Lu-labeled hydroxyapatite (HA) particles in the treatment of rheumatoid arthritis: utility of cold kits for convenient dose formulation at hospital radiopharmacy.

While radiation synovectomy (RSV) constitutes a successful paradigm for the treatment of arthritis, a major cornerstone of its success resides in the selection of appropriate radiolabeled agent. Among the radionuclide used for RSV, the scope of using (177)Lu [T1/2 = 6.65 d, Eß(max) = 497 keV, Eγ = 113 KeV (6.4%), 208 KeV (11%)] seemed to be attractive owing to its suitable decay characteristics, easy availability, and cost-effective production route. The present article describes a formulation of (177)Lu-labeled hydroxyapatite (HA) using ready-to-use kits of HA particles of 1-10 µm size range. The developed kits enable convenient one-step preparation of (177)Lu-HA (400 ± 30 MBq doses) in high radiochemical purity (>99%) and stability at hospital radiopharmacy. The preparation showed promising results in pre-clinical studies carried out in Wistar rats bearing arthritis in knee joints. In preliminary clinical investigation, significant improvement in the disease conditions was reported in 10 patients with rheumatoid arthritis of knee joints treated with 333 ± 46 MBq doses of (177)Lu-HA. The studies reveal that while (177)Lu labeled HA particles holds considerable promise as a cost-effective agent for RSV, the adopted strategy of using HA kits could be a potential step toward wider clinical utilization of radiolanthanide-labeled HA particles.

Novel mineralized heparin-gelatin nanoparticles for potential application in tissue engineering of bone.

Nanoparticles (NPs) were prepared from succinylated gelatin (s-GL) cross-linked with aldehyde heparin (a-HEP) and used subsequently as a nano-template for the mineralization of hydroxyapatite (HAP). Gelatin was functionalized with succinyl groups that made it soluble at room temperature. Heparin was oxidized to generate aldehyde groups and then used as a cross-linker that can react with s-GL to form NPs via Schiff's base linkage. The polymer concentrations, feed molar ratios and pH conditions were varied to fabricate NPs suspension. NPs were obtained with a spheroid shape of an average size of 196 nm at pH 2.5 and 202 nm at pH 7.4. These NPs had a positive zeta potential of 7.3 ± 3.0 mV and a narrow distribution with PDI 0.123 at pH 2.5, while they had a negative zeta potential of -2.6 ± 0.3 mV and formed aggregates (PDI 0.257) at pH 7.4. The NPs prepared at pH 2.5 with a mean particle size of 196 nm were further used for mineralization studies. The mineralization process was mediated by solution without calcination at 37 °C. The HAP formed on NPs was analyzed by Fourier transform infrared spectroscopy and X-ray diffraction. HAP coated s-GL/a-HEP NPs developed in this study may be used in future as osteoinductive fillers enhancing the mechanical properties of injectable hydrogel or use as potential multifunctional device for nanotherapeutic approaches.

Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method. Optimisation, characterisation and rheology.

OBJECTIVES: Currently, most titanium implant coatings are made using hydroxyapatite and a plasma spraying technique. There are however limitations associated with plasma spraying processes including poor adherence, high porosity and cost. An alternative method utilising the sol-gel technique offers many potential advantages but is currently lacking research data for this application. It was the objective of this study to characterise and optimise the production of Hydroxyapatite (HA), fluorhydroxyapatite (FHA) and fluorapatite (FA) using a sol-gel technique and assess the rheological properties of these materials. METHODS: HA, FHA and FA were synthesised by a sol-gel method. Calcium nitrate and triethylphosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride (NH4F) were incorporated for the preparation of the sol-gel derived FHA and FA. Optimisation of the chemistry and subsequent characterisation of the sol-gel derived materials was carried out using X-ray Diffraction (XRD) and Differential Thermal Analysis (DTA). Rheology of the sol-gels was investigated using a viscometer and contact angle measurement. RESULTS: A protocol was established that allowed synthesis of HA, FHA and FA that were at least 99% phase pure. The more fluoride incorporated into the apatite structure; the lower the crystallisation temperature, the smaller the unit cell size (changes in the a-axis), the higher the viscosity and contact angle of the sol-gel derived apatite. SIGNIFICANCE: A technique has been developed for the production of HA, FHA and FA by the sol-gel technique. Increasing fluoride substitution in the apatite structure alters the potential coating properties.

[Preparation of alpha-tricalcium phosphate/HA whisker/carboxymethyl chitosan-gelatin composite porous bone cement].

In order to investigate the effects of HA whisker and carboxymethyl chitosan-gelatin(CMC-Gel) on the mechanical properties of porous calcium phosphate cement, a series of alpha-tricalcium phosphate (alpha-TCP), HA whisker and L-sodium glutamate porogen with different mass fractions were mixed, and setting liquid was added to them to prepare alpha-TCP/HA whisker composite porous bone cement. Then, the cement was immersed in a series of CMC-Gel solutions which had different weight ratios of CMC to Gel to prepare alpha-TCP/HA whisker/CMC-Gel composite porous bone cement. The compressive strengths and microstructure of cement were characterized by mechanical testing machine and SEM. The results showed that when the mass fraction of HA whisker is 4%, the compressive strength of alpha-TCP/HA whisker composite porous bone cement reaches 2.57MPa, which is 1.81 times that of alpha-TCP bone cement. When the weight ratio of CMC to Gel is 50:50, the compressive strength of alpha-TCP/HA whisker/CMC-Gel composite porous bone cement is 3. 34MPa, which is 2.35 times that of alpha-TCP bone cement, and the toughness of the composite cement is greatly improved as well.

Fabrication and characterization of novel nano hydroxyapatite/ß-tricalcium phosphate scaffolds in three different composition ratios.

The biphasic calcium phosphate (BCP) concept was introduced to overcome disadvantages of single phase biomaterials. Different composition ratios of BCP bioceramics have been studied, yet controversies regarding the effects of ratio on biomaterial behavior still exist. In this study, BCP scaffolds were prepared from nano hydroxyapatite (HA) and ß-tricalcium phosphate (ß-TCP) that were synthesized via a solid state reaction. Three different composition ratios of pure BCP and collagen-based BCP scaffolds (%HA/%ß-TCP; 30/70, 40/60, and 50/50) were produced using a polymeric sponge method. Physical and mechanical properties of all materials and scaffolds were investigated. SEM showed overall distribution of both macropores (80-200 µm) and micropores (0.5-2 µm) with high interconnected porosities. Total porosity of pure BCP (90% ± 3%) was found to be higher than collagen-based BCP (85% ± 2%). It was observed that following sintering process, dimensional shrinkage of large scaffolds (39% ± 4%) was lower than small ones (42% ± 5%) and scaffolds with high HA ratios (50%) experienced higher dimensional changes than those with higher ß-TCP (70%) ratios (45% ± 3% and 36% ± 1%, respectively). Compressive strength of both groups was less than 0.1 MPa and collagen coating had almost no influence on mechanical behavior. Further studies may improve the physical properties of these scaffolds and investigate their exact biological behaviors.

Synthesis and characterization of biocompatible-nanohydroxyapatite crystals obtained by a modified sol-gel processing.

A modified sol-gel process for synthesizing nanocrystalline hydroxyapatite powders (nHA) for biomedical applications, using tetrahydrated calcium nitrate [Ca(NO(3))(2)∙4H(2)O] and phosphorous pentoxide [P(2)O(5)] as precursor, is presented and discussed. The powders were washed and heat-treated at different temperatures and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The total process time reached with this modified process was less than 16 h. The results showed that there was an increment in size of the HA nanocrystals (nHA) when treated at different temperatures, ranging from 30 nm for the sample treated at 600°C to 500 nm for the sample heat-treated at 1,200°C.

BisGMA/TEGDMA dental composite containing high aspect-ratio hydroxyapatite nanofibers.

OBJECTIVES: The objectives of this study are to investigate the properties of high aspect-ratio hydroxyapatite (HAP) nanofibers and the reinforcing effect of such fibers on bisphenol A glycidyl methacrylate (BisGMA)/triethylene glycol dimethacrylate (TEGDMA) dental resins (without silica microparticle filler) and dental composites (with silica microparticle filler) with various mass fractions (loading rates). METHODS: HAP nanofibers were synthesized using a wet-chemical method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermal gravimetric analysis (TGA). Biaxial flexural strength (BFS) of the HAP nanofibers reinforced dental resins without any microsized filler and dental composites with silica microparticle filler was tested and analysis of variance (ANOVA) was used for the statistically analysis of acquired data. The morphology of fracture surface of tested dental composite samples was examined by SEM. RESULTS: The HAP nanofibers with aspect-ratios of 600 to 800 can be successfully fabricated with a simple wet-chemical method in aqueous solution. Impregnation of small mass fractions of the HAP nanofibers (5 wt% or 10 wt%) into the BisGMA/TEGDMA dental resins or impregnation of small mass fractions of the HAP nanofibers (2 wt% or 3 wt%) into the dental composites can substantially improve the biaxial flexural strength of the resulting dental resins and composites. A percolation threshold of HAP nanofibers, beyond which more nanofibers will no longer further increase the mechanical properties of dental composites containing HAP nanofibers, was observed for the dental composites with or without silica microparticle filler. Our mechanical testing and fractographic analysis indicated that the relatively good dispersion of HAP nanofibers at low mass fraction is the key reason for the significantly improved biaxial flexural strength, while higher mass fraction of HAP nanofibers tends to lead to bundles that cannot effectively reinforce the dental resins or composites and may even serve as defects and thus degrade the resulting dental resin and composite mechanical properties. SIGNIFICANCE: The incorporation of small mass fraction of HAP nanofibers with good dispersion can improve the mechanical property of dental resins and dental composites.

Synthesis of spherical hydroxyapatite granules with interconnected pore channels using camphene emulsion.

The aim of this study was to fabricate porous spherical hydroxyapatite (HA) granules with interconnected pore channels for use as a bone graft substitute. Various weights of camphene porogen were mixed with nano-sized HA powder (camphene/HA = 0, 10, 30, 50, 70, and 90% w/w) and 10% gelatin aqueous solution then added to the mixture. The water-in-oil emulsion method was employed to obtain spherical-shaped granules, of which those 1000-2000 µm in diameter were selectively classified using a standard sieve set. Thermogravimetric analysis and X-ray diffraction were used to determine optimal sintering conditions. The sintered granules were characterized using field emission-scanning electron microscopy (FE-SEM), microcomputed tomography, and porosimetry. The pore size and porosity of spherical HA granules increased with the addition of camphene. Granules with a HA/camphene ratio of 90% (HG90) demonstrated macropores (>50 µm) with interconnected pore channels (porosity: 58.49%). In addition, FE-SEM examination of HG90 coated with polycaprolactone showed that the granule may hold promise as a drug delivery carrier. We concluded that these HG90 granules merit consideration as a bone graft substitute or drug delivery carrier in bone tissue engineering.

Nanostructure-loaded mesoporous silica for controlled release of coumarin derivatives: a novel testing of the hyperthermia effect.

The synthesis of three types of mesoporous materials is reported: pure mesoporous silica (MCM-41), a nanocomposite of mesoporous silica with hydroxyapatite (MCM-41-HA) and mesoporous silica/gold nanorods nanocomposite (MCM-41-GNRs). The mesoporous materials were characterized by X-ray diffraction, N(2) adsorption isotherms, FTIR spectroscopy, transmission electron microscopy, and scanning electron microscopy. The samples were loaded with coumarin thiourea derivatives (I-IV) having functional groups of varying sizes and the in vitro release assays were monitored, and the release behavior was investigated as a function of soaking time in simulated body fluid. Two release stages were obtained in MCM-41, MCM-41-HA and MCM-41-GNRs loaded samples with the early release stages accounting for about 30% of loaded derivatives. These early release stages are characterized by Higuchi rate constant values nearly twice the values associated with the second release stages. The influence of substituent size on the release rate constants was explained in terms of sorption sites and hydrogen bonding with silanol groups on silicates. The release of coumarin derivatives loaded on MCM-41, MCM-41-HA and MCM-41-GNRs occurs over remarkably long time of the order of about 260 h with faster release rates in loaded MCM-41 and MCM-41-GNRs samples compared with MCM-41-HA ones. The role of hyperthermia effect in enhancing release rates was investigated by subjecting loaded MCM-41-GNRs to near infrared (NIR) radiation at 800 nm. This would be of significance in targeted drug release using hyperthermia effect. Unlike hydroxyl apatite, loading MCM-41 with gold nanorods does not affect the release kinetics. Only when these samples are irradiated with NIR photons, does the release occur with enhanced rates. This property could be valuable in selected targeting of drugs.

Hydrothermal synthesis and characterization of hydroxyapatite and fluorhydroxyapatite nano-size powders.

Pure hydroxyapatite (HAp) and fluoride-containing apatite powders (FHAp) were synthesized using a hydrothermal method. The powders were assessed by x-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscope (SEM) and F-selective electrode. X-ray diffraction results revealed the formation of single phase apatite structure for all the compositions synthesized in this work. However, the addition of a fluoride ion led to a systematic shift in the (3 0 0) peak of the XRD pattern as well as modifications in the FTIR spectra. It was found that the efficiency of fluoride ion incorporation decreased with the increase in the fluoride ion content. Fluorine incorporation efficiency was around 60% for most of the FHAp samples prepared in the current study. Smaller and less agglomerated particles were obtained by fluorine substitution. The bioactivity of the powder samples with different fluoride contents was compared by performing cell proliferation, alkaline phosphatase (ALP) and Alizarin red staining assays. Human osteoblast cells were used to assess the cellular responses to the powder samples in this study. Results demonstrated a strong dependence of different cell activities on the level of fluoridation.