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Osteoproductive materials that induce quick bone regeneration are needed for the developing area of scaffold-based bone engineering. Bioactive silica-based glasses, ceramics, and hybrids are called to play an important role in this field. Organic–inorganic hybrid materials based on SiO2-modified PDMS–P2O5–CaO are studied in this work. These materials are synthesized by the sol–gel method, and the influence of the composition on the reaction kinetic, obtained porosities, degradation and bioactive behavior, and cytotoxicity is studied. Materials with greater contents in CaO yield faster reaction kinetics and produce porous materials that favor a quicker degradation, whereas with greater P2O5 contents produce denser and more stable materials. The incorporation of CaO and P2O5 up to 5 and 25 % in weight into the SiO2 network, respectively, resulted in an increase of the apatite-forming ability in PBS. None of the studied compositions are cytotoxic, showing cellular viability over 70 % at all times.

Though hydroxyapatite has the ability to promote bone growing, devices based on OHAp are mechanically weak and need to be reinforced for load bearing applications or in the manufacturing of scaffolds for bone regeneration. Graphite (Gr) could provide appropriate reinforcement properties to OHAp without being deleterious for the biocompatibility of the system. This paper describes an accelerated synthesis of the OHAp with ultrasonic agitation in the presence of functionalized graphite (GO). The toxicity of the Graphite and the GO-OHAp system is evaluated. GO-OHAp was produced by a wet chemical reaction involving CaCl2 and Na2HPO4. The calcium salt solution was added first and the solution sonicated for 1 hour, before repeating the operation with the phosphate solution. Biocompatibility was tested by using a primary cell culture of HOB (ECCAC). The disappearance of the maximum at 2q = 26.32º corresponding to the d002 plane of graphite and the appearance of the maximum at 2q = 13.2º in the XRD patterns is related with an expansion of the grapheme sheets from 0.34 nm to 0.59 nm and it has been used to assess the graphite oxidation. The OHAP on GO growing has been confirmed by the appearance of a broad peak centred at 2q = 31.5º and a sharpened peak at 2q = 26.0º characteristic of low crystalline apatites. Although the employed graphite can be considered biocompatible, cellular viability is significantly improved by the presence of apatite.

This paper focuses on the preparation of siloxane-polyurethane hybrid materials using a sol-gel method. The global aim of the project is to tailor mechanical properties, degradability rate, bioactivity and biocompatibility to design scaffolds for musculoskeletal applications. A series of seven hybrid materials were synthesized with varying the proportion of polydimethylsiloxane (PDMS), and Polyurethane (PU). The organic part ratios (by weight) employed were (% PDMS:% PU) 30:0, 35:5, 20:10, 15:15, 10:20, 5:25, and 0:30. The organic part was reacted with constant 70 % TEOS to obtain the hybrid materials. A sol-gel process was selected for the synthesis of the hybrids. The characterization of materials was carried out by the fourier-infrared spectroscopy (FT-IR), x-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electronic microscopy (SEM) and proton nuclear magnetic resonance (1H-NMR) techniques in order to analyze the structure, microstructure and chemical composition of the hybrid materials. Gelification time depends on the proportion of PU used. When no PU is employed, the gel time is 8 hours but it rises up to 18 days for 30 % of polyurethane. Materials range from opaque to translucent but with a greater fragility for greater amounts of polyurethane. No differences in the bonding of materials could be appreciated.

Bisphosphonates (BPs) may play an important role in minimizing osteolysis. In this work two new bisphosphonates pertaining to second and third generations respectively, have been synthesized and incorporated onto a chemically enriched hydroxyapatite. BP synthesis has been performed by adding H3PO3, PCl3 and methanesulfonic acid over 4-aminophenyl acetic acid (APBP) and 1-H-indole-3-acetic acid (IBP) respectively at 65°C in a N2 atmosphere. These compounds bear a primary amine group bonded to an aromatic ring, and a secondary amine group within a heterocyclic ring respectively. A chemically enriched hydroxyapatite with a chemical content corresponding to a 50% fluorided hydroxyapatite has been synthesized. Ceramic bodies manufactured by uniaxial pressure followed by cold isostatic press have a 97% density and submicron grain size. The BP was adsorbed onto the surface by immersion in a stirred solution at 37°C for 48 hours. A 10-fold decrease of the surface energy was observed for bodies modified with the APBP whereas only a 25 % decrease is obtained for bodies loaded with the bisphosphonate loaded with the IBP.

Nine samples of Ca-deficient apatite (Ca-def Ap) were prepared from suspensions of CaHPO4 (monetite) at 90 degrees C by raising the pH from approximately 4 through release of NH3 produced by the hydrolysis of urea. Products were dried at 100 degrees C for 24h and studied by chemical analyses, X-ray powder diffraction (XRPD) (and Rietveld analysis of this data), Ca/P ratio determination (quantitative phase analysis of samples after heating to 900 degrees C from Rietveld analysis of XRPD data), scanning electron microscopy, He pycknometry, 1H and 31P MAS NMR spectrometry and Fourier transform infrared and Raman spectroscopy. All samples contained apatite, but three also contained monetite. Infrared and Raman spectroscopy confirmed the presence of HPO4(2-) and absence of carbonate ions in the six monetite-free samples. Mean results for the six samples were: a = 9.4320(40), c = 6.8751(31) A; unit cell formula from chemical analysis neglecting protonation of phosphate ion, Ca(9.303(50))(PO4)6(OH)(0.606(99)).1.97(12)H2O; theoretical density 3.10 g cm(-3); experimental density (mean for three samples) 3.15 g cm(-3); and Ca/P mole ratio from chemical analysis and phase analysis after heating to 900 degrees C, 1.550(8) and 1.550(2), respectively. An earlier assignment of a line at 6 ppm in the 1H NMR spectrum of similar samples to HPO4(2-) ions could not be confirmed; hence no information about the HPO4(2-) ion content could be derived, in disagreement with the previous NMR study. A shoulder at approximately 0.9 ppm relative to 85 wt% H3PO4 in the 31P NMR spectrum was assigned to HPO4(2-) ions. Occupancies from the Rietveld structure refinements indicated preferential loss of Ca from Ca2 sites compared with Ca1, but the loss was substantially smaller than expected from chemical analyses. It is suggested that imperfect modelling of the structure in the refinement, particularly disorder associated with the Ca2 site, resulted in errors in Ca2 occupancies. The P-O bonds were slightly shorter than those in stoichiometric hydroxyapatite, rather than longer as might be expected from protonation of phosphate tetrahedra. However, consideration of known acid phosphate structures indicated that it was unlikely that the increase in P-O lengths would be sufficient to be detected. The observed decrease was tentatively assigned to the presence of Ca2+ ion vacancies.

Hydroxyapatite has been frequently described as an osteoconductive but not osteoinductive material based on failure to observe bone formation in nonbony sites. Bisphosphonates (BPs) are stable pyrophosphate analogs, that enhance the proliferation, differentiation and bone forming activity of osteoblasts and are potent inhibitors of bone resorption. In this paper, the modification of a calcium hydroxyfluor carbonate apatite with sodium alendronate and (4-(aminomethyl)benzene)bisphosphonic acid is described. The surface modification is carried out by refluxing the apatite in a bisphosphonate acetone solution. Modified particles are characterized by thermal analysis, ATR-IR spectroscopy and contact angle between other techniques. A weight loss between 150 and 500ºC can be observed for the modified apatites. IR spectra show the appearance of bisphosphonate bands on modified powders. The surface energy of the modified apatite is reduced up to a 74% from the total apatite value after the alendronate surface modification with a decrease of 58% of the polar component main responsible of the cellular interaction of biomaterials., Financial support through research project MAT2002-04147-C02-02, CICYT (Spain) is acknowledged. LMRL has been supported by CAM regional government (Spain) through the program to incorporate doctors to the Madrid research system.

Hydroxyapatite (OHAp) particles with a specific surface area of 9 m2/g were obtained through a thermal treatment at 900 °C followed by deagglomeration by ball milling in ethanol for 20 h. Slurries with a 50-vol.% solids loading were prepared by mixing the particles with water. Organic inclusions with particles sizes from 55 to 750 μm were added and ceramic bodies were consolidated by slip casting. Dense and porous ceramic bodies were obtained with densities as low as 30% and as high as 94% and pore sizes up to 750 μm. The possibility of manufacturing ceramic bodies with porosity gradients designed according to the features of the porous ceramic bodies was studied in order to adapt them to the severe requirements of tissue engineering scaffolds.

Hydroxy-fluorapatites (OH-FAps) occur biologically in teeth and form the basis for application as biomaterials. This work aims to synthesize a series of fluoride substituted calcium hydroxyapatites (OHAps) to determine how fluoride influences the synthesis and the resulting characteristics of solid solutions. OH-FAPs powders were synthesized with a chemical composition of Ca(10)(PO(4))(6)(OH)(2-x) F(x), with x=0.0, 0.4, 0.8, 1.2, 1.6 and 2.0. The synthesis of partially substituted OHAp yields materials with lower crystallinity and higher specific surface area than OHAp or fluorapatite (FAp). The smallest crystal size of 263A, occurs at less than 50% hydroxyl substitution with fluoride at x=0.4, and the highest surface area of 132m(2)/g occurs at x=0.8. Reaction kinetics occur faster at higher fluoride content, producing the expected Ca/P ratio of 1.67 only for x=2.0. X-ray and IR studies show that OH-FAPs are homogeneous solid solutions instead of mixtures of OHAp and FAp. The presence of a high fluoride concentration increases the driving force for crystal growth during the calcination process.

Hydroxyapatite/solgel glass biphasic material has been obtained in order to improve the bioactivity of the hydroxyapatite (OHAp). A mixture of stoichiometric OHAp and the precursor gel of a solgel glass, with nominal composition in mol% CaO-26, SiO2-70, P205-4, has been prepared. The amounts of components used have been selected to obtain a final relationship for OHAp/solgel glass of 60/40 on heating. Two different thermal treatments have been used: (i) 700 degrees C, temperature of solgel glass stabilisation and (ii) 1000 degrees C, lower temperature of hydroxyapatite sintering. The bioactivity of the resulting materials has been examined in vitro by immersion in simulated body fluid at 37 degrees C. The results obtained show that both materials are bioactive. The apatite-like layer grown is greater for the new materials than for the OHAp and the solgel glass themselves.

Reliable bioceramics are needed to implement the high requirements that living tissues demand. This work focuses on the processing steps necessary to manufacture advanced ceramics that can be used as implant devices. The influence of the heat treatment temperature on the characteristics of a precipitated hydroxyapatite (OHAp) powder was evaluated in order to obtain an appropriate specific surface area for colloidal processing. Ball milling of the calcined powders for 20 h was required to improve the rheological properties of the suspensions and the packing ability during consolidation. Different dispersing agents were tested and the first trial was made based on their effect on the zeta potential. The most promising ones were then selected and their efficiency was evaluated from rheological measurements and slip-casting performance of suspensions prepared at different solids loading. Targon 1128 was revealed to be the most efficient dispersant, enabling to prepare fluid suspensions containing 50 vol% solids and the highest green and sintered density values to be obtained.

Bisphosphonates (BP) are drugs currently administered orally to treat diseases characterised by an excessive bone resorption. Alternative and more efficient delivery routes and more potent compounds are being investigated. Three implantable delivery systems, which allow the controlled release of therapeutic agents from the device core, are examined in this paper. (4- (aminomethyl) benzene) bisphosphonic acid (ABBP) was incorporated on Ca8.8Na0.8(PO4)4.8(CO3)1.2(OH)0.4F1.6 particles by refluxing the powder in a 60 mmol suspension in acetone at 60ºC for 5 hours. 4-aminophenyl acetic bisphosphonate monosodium salt (APBP) and 1- H-indole-3-acetic bisphosphonate monosodium (IBP) were loaded on Ca10(PO4)6(OH)1F1 ceramic bodies by stirring the ceramic bodies in 0.04M BP solutions. Injectable acrylic cements based on self-curing formulations of methyl methacrylate (MMA) and vitamin E were loaded with APBP and IBP. The incorporation of ABBP was confirmed by MAS-NMR spectroscopy. Modified powder shows two different phosphorous environments, the first one at 2.91 ppm can be assigned to the apatite base and the second one at 18.0 ppm has to be attributed to the phosphonic group of the ABBP. The IBP addition on ceramic surfaces did not decrease the number of osteoclast colonies and appeared to improve the performance of the HA as a surface for osteoblast culture. A therapeutic dosage of APBP and IBP can be achieved from acrylic cements that showed lack of toxicity and an increased cellular activity and proliferation, Financial support from CICYT, Spain (MAT2004-01654) and NoE EXPERTISSUES (UE contract Nº: 500283-2) is acknowledged. Mar Fernández and Luis M. Rodríguez Lorenzo are supported by the Ramón y Cajal Programme, MEC-Spain

Fluoride substitution within hydroxyapatite is an important occurrence for biological apatites and is a promising approach for the chemical modification of synthetic hydroxyapatite. Limited information on the influence of fluoride substitution for hydroxyl groups on the mechanical properties has provided the rationale for this study. Hydroxyfluorapatites with 0%, 20%, 40%, 60%, 80% and 100% replacement of hydroxyl groups with fluoride ions were assessed for hardness, elastic modulus, fracture toughness and brittleness using microindentation of sintered pellets. The production of samples with a similar grain size and density allowed the influence of fluoride on mechanical properties to be determined. It was found that the hardness remains unaffected until 80% replacement of hydroxyl groups with fluoride, after which the hardness rapidly increases. The elastic modulus increases linearly with fluoride content. Fracture toughness is improved with fluoride incorporation into the lattice and reaches a peak of 1.8 for a 95% dense sintered pellet with a 60% fluoride replacement, followed by a rapid decrease at higher fluoride concentrations. The brittleness index is lowered to a minimum at 60%, after which a rapid increase occurs. High fluoride levels are unfavourable from a mechanical perspective, are not recommended for biomaterials, and can lead to a higher incidence of fracture where sodium fluoride, for treatment of osteoporosis, may produce a highly fluoridated hydroxyapatite.

Hydroxyapatite (OHAp) has been obtained by using a precipitation method. Thermal stability of the precipitated powder has been checked to define an appropriate working range to process ceramic bodies without the appearance of odd phases. Pellets of hydroxyapatite have been manufactured by means of uniaxial pressing and convenient thermal treatments have been investigated to achieve high density OHAp bodies. Finally, factors that could affect the ultimate mechanical properties of the sintered bodies prepared by uniaxial pressing have been discussed.

Synthetic pseudowollastonite (psW) and a nanostructured copolymer made of a biostable component, Poly(ethylmethacrylate) (PEMA) and a bioresorbable component, vinylpyrrolidone (VP) are used in this work for the preparation of a new family of bone substitutes that allow osseointegration and mechanical stability. Composites are prepared by bulk polymerization of the desired composition in 15 mm diameter cylindrical plastic moulds. Polymerization was induced thermally at 50°C using 1wt% azobis(isobutyronitrile) (AIBN) as free-radical initiator. The moulds were filled to a height of 100 mm and 1 mm height discs were cut with a diamond saw. Specimens with a ceramic/polymer ratio 58/42, 33/67,17/83 and 0/100 were obtained. Compression stress in the range 39-59 MPa and elastic modulus between 2.64 and 4.14 GPa are obtained where the greater values correspond to the specimens prepared with a 60% ceramic load. Degradation in SBF produces a porous nanostructure in the polymeric component indicating microdomains of different solubility and the formation of an apatite-like layer on the surface of the wollastonite component. All the compositions assayed present a biocompatibility at least of the level or even superior than the Thermanox® control used.