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One step synthesis of silver nanorods by autoreduction of aqueous silver ions with hydroxyapatite: An inorganic-inorganic hybrid nanocomposite.

In this report, a novel method for the synthesis of silver nanoparticles on the surface of hydroxyapatite is described. Hydroxyapatite crystals are synthesized from acid mineralized solution, a byproduct of bone glue industries, by a simple chemical precipitation method, which results in the formation of hydroxyapatite nanocrystals. The reduction of silver ions occurs by the electron transfer from the hydroxyl groups on the surface of hydroxyapatite. This results in the formation of silver nanorods and needle shaped nanoparticles that are bound on the surface of hydroxyapatite, and the observed silver nanocrystals show anisotropic structure. Thus, hydroxyapatite crystals can be used as a new class of inorganic scaffolds for the synthesis of nanomaterials with implications in designing inorganic-inorganic hybrid nanocomposites for different applications.

Durapatite↗

Identification of glycosaminoglycans using high-performance liquid chromatography on a hydroxyapatite column.

Glycosaminoglycans (heparin, heparan sulfate, dermatan sulfate, chondroitin sulfate, and hyaluronic acid) were labeled with a fluorescent reagent, 2-aminopyridine. The fluoro-labeled glycosaminoglycans were subjected to high-performance liquid chromatography on a hydroxyapatite column. The binding property of each glycosaminoglycan to hydroxyapatite was different. The structural properties of glycosaminoglycans bound to hydroxyapatite were then investigated using chemical desulfated or enzymic depolymerized glycosaminoglycans. This revealed that the sulfate content and molecular weight of the glycosaminoglycans correlated with their binding properties to hydroxyapatite. Desulfated dermatan sulfate but not desulfated chondroitin 6-sulfate bound to the hydroxyapatite. These data indicate that iduronic acid residues of glycosaminoglycans are important for the binding property. The method described which uses hydroxyapatite columns facilitates rapid separation and microanalysis of the glycosaminoglycans, especially dermatan sulfate and chondroitin sulfate.

Aminopyridines↗

The influence of fluoride on the adsorption of proteoglycans and glycosaminoglycans to hydroxyapatite.

Proteoglycans and their spatial arms, the glycosaminoglycans, are known to interact with hydroxyapatite, and are considered to have a role in the regulation of mineralization. This study investigates the interactive mechanisms, with particular attention directed at the influence of fluoride on the adsorption process. Proteoglycans and glycosaminoglycans were adsorbed to hydroxyapatite in the presence of fluoride (1-20 ppm range). The adsorbates included a chondroitin 4-sulfate-rich proteoglycan extracted from rat incisor dentine, hyaluronan, chondroitin 4-sulfate, and dermatan sulfate. The order of glycosaminoglycan in decreasing affinity for hydroxyapatite was chondroitin 4-sulfate, dermatan sulfate, and hyaluronan, and the individual glycosaminoglycans showed different responses to the presence of fluoride. Graded increases in fluoride (1-4 ppm) led to 5-40% reduction of glycosaminoglycan adsorption to hydroxyapatite. The proteoglycan showed less affinity for hydroxyapatite, and demonstrated a reduction in adsorption of up to 22% with 20 ppm fluoride. The inhibitory effect of fluoride indicated an electrostatic mechanism, presumably via the calcium sites in the hydroxyapatite lattice.

Adsorption↗

Grit-blasted and hydroxyapatite-coated total hip arthroplasty: an 11- to 14-year follow-up study.

We report long-term results of the first clinical trial of hydroxyapatite-coated total hip arthroplasty conducted in Japan. The hemispherical cup and the straight-tapered stem were made of titanium alloy with a grit-blasted, hydroxyapatite-coated surface. The surface roughness before and after hydroxyapatite coating was 1.4 microm and 3.4 microm, respectively. Thirty-three patients (35 hips) were followed prospectively; of these, 1 patient was lost to follow-up, 5 were deceased at the latest follow-up, and 27 were followed for 11 to 14 years. Two cups and one stem (two patients) were revised. Survivorship, with radiological acetabular loosening as the endpoint, was 62.3% at 14 years. At the latest radiological follow-up, stable fixation with bone ongrowth was achieved in 46% of the acetabular cups and 89% of the femoral stems. Acetabular cups with host bone coverage of less than 60% had a high rate of failure. The suboptimal result of the hydroxyapatite-coated smooth cup indicates that porous coatings under the hydroxyapatite coating would be beneficial for hydroxyapatite-coated total hip implants, especially for the acetabular components.

Adult↗

Priming effect of hydroxyapatite on the chemiluminescence response in human polymorphonuclear leukocytes.

In order to determine whether hydroxyapatite modulates the response of polymorphonuclear leukocyte (PMN) to oxidative stimuli, human PMNs were incubated with a non-activating concentration (1 or 10 micrograms/ml) of hydroxyapatite prior to stimulation with N-formyl-methionyl-leucyl-phenylalanine (FMLP; 0.1 or 1 microM), phorbol 12-myristate 13-acetate (PMA; 100 pg/ml), sodium fluoride (50 microM), zymosan (1 microgram/ml), or the calcium ionophore A23187 (0.1 microM). Chemiluminescence was measured with an automatic microcomputer-controlled luminescence analyzer at 37 degrees C. Hydroxyapatite alone did not stimulate chemiluminescence at concentrations below 10 micrograms/ml. Levels 300-400% higher than 'stimulus only' controls without preincubation with hydroxyapatite have been recorded. This synergism between hydroxyapatite and subsequent stimuli reveals a new activity of hydroxyapatite and suggests that particulate material may prepare PMNs for an exaggerated inflammatory response to other phlogistic mediators. This is the first report demonstrating PMNs primed with particulate material.

Calcimycin↗

Polymethylmethacrylate composites: disturbed bone formation at the surface of bioactive glass and hydroxyapatite.

The effects of polymethylmethacrylate on bone formation were studied alone and as composites in combination with hydroxyapatite and bioactive glass in the rabbit subchondral femur. Radiographs, histology, computer assisted histomorphometry, scanning electron microscopy and energy dispersive X-ray analysis were used for evaluation. A total of 60 cones were implanted for 3, 6 and 12 weeks. The composite cones consisted of granules of bioactive glass (S56.5P4) or hydroxyapatite embedded in polymethylmethacrylate. Pure polymethylmethacrylate cones served as controls. At the interface of the cones, bone contact was observed only when bioactive glass or hydroxyapatite was present at the cone surface. Fibrous tissue was always found at the polymethylmethacrylate-tissue interface. The osteoconductive bone formation at the surface of bioactive glass and hydroxyapatite was disturbed by polymethylmethacrylate. It seemed to resist bone formation at the interface of both bioactive glass and hydroxyapatite. However, bioactive glass was better able to withstand the detrimental effect of polymethylmethacrylate than hydroxyapatite.

Animals↗

Systematic evolution of a porous hydroxyapatite-poly(vinylalcohol)-gelatin composite.

Hydroxyapatite (HAp)-poly(vinylalcohol) (PVA)-gelatin nanocomposite was biomimetically synthesized and characterized. Fourier transform infrared spectroscopy (FT-IR) analysis of hydroxyapatite, hydroxyapatite-poly(vinylalcohol) and hydroxyapatite-poly(vinylalcohol)-gelatin composites show modification of hydroxyl, amide and phosphate bands as a result of chemical interaction of hydroxyapatite with the above composite matrices. Transmission electron microscopy (TEM) confirmed the time-dependent development of a porous structure of hydroxyapatite-poly(vinylalcohol)-gelatin as a consequence of nucleation at the HAp aggregate-matrix interface. A literature survey holds great promise for the above as scaffolds in terms of increased mechanical properties and bioactivity.

Biocompatible Materials↗

Mechanical properties of visible light-cured resins reinforced with hydroxyapatite for dental restoration.

OBJECTIVES: The purpose of this study was to measure and analyze the mechanical properties of several composite materials designed for dental restoration. METHODS: The materials were composed of a visible light-curing monomer mixture (either Bis-GMA+TEGDMA or Bis-GMA+HEMA) as a matrix and hydroxyapatite (either microscopic or nanoscopic particles) as a reinforcing filler. The surface of the hydroxyapatite particles was modified by using a coupling agent (citric, malic, acrylic or methacrylic acid). Five specimens of 14 different composites were prepared for each mechanical test: flexural strength, Young's modulus and Vickers hardness. Mean values and standard deviations were calculated, and ANOVA and Student Newman Keuls multiple comparison tests were applied (P < 0.05). RESULTS: The addition of 50-60 wt% of hydroxyapatite particles to the unfilled monomer mixtures led to the increase of both Young's modulus and surface hardness of the material, while the flexural strength decreased. In general, when microscopic instead of nanoscopic hydroxyapatite was used as a reinforcing filler, mechanical properties were favored. The mechanical properties were also improved by adding citric, acrylic or methacrylic acid as a coupling agent. CONCLUSIONS: An adequate surface modification of the hydroxyapatite particles conferred enhanced mechanical properties to the final dental composite. Microscopic-hydroxyapatite particles are preferred to nanoscopic ones.

Acrylates↗

Chemically coupled hydroxyapatite-polyethylene composites: structure and properties.

Silanation of hydroxyapatite and acrylic acid grafting of polyethylene were employed to improve bonding between hydroxyapatite and polyethylene. The structure and properties of chemically coupled hydroxyapatite reinforced high-density polyethylene (HA/HDPE) composites were subsequently investigated using various techniques. It was shown that there existed a silicon-containing interphase between the hydroxyapatite particle and the polyethylene matrix. The silane coupling agent used promoted chemical adhesion between hydroxyapatite particles and the polymer. The use of the silane coupling agent also facilitated the penetration of polymer into cavities in individual ceramic particles, which resulted in enhanced mechanical interlocking at the matrix-reinforcement interface. With a strong bond (both mechanical and chemical) being formed between hydroxyapatite and polyethylene, chemically coupled HA/HDPE composites possessed improved mechanical properties and fracture behaviour.

Durapatite↗

Comparative motility of hydroxyapatite and alloplastic enucleation implants.

OBJECTIVE: To compare the motility of scleral-covered hydroxyapatite and alloplastic enucleation implants. DESIGN: Retrospective, nonrandomized comparative trial. PARTICIPANTS: Measurements were obtained after surgery in 76 anophthalmic patients who had received either hydroxyapatite or alloplastic enucleation implants. METHODS/MAIN OUTCOME MEASURES: Horizontal and vertical excursions of the enucleation implants. RESULTS: There is no clinically important difference between the movement of hydroxyapatite and alloplastic enucleation implants. Implant movement appears to decline with advancing age. CONCLUSION: Scleral-covered alloplastic and hydroxyapatite enucleation implants show similar movement. Although directly coupling hydroxyapatite implants to the prosthesis via the motility peg provides enhanced prosthetic movement, there appears to be no motility benefit of nonpegged hydroxyapatite over spherical alloplastic implants.

Adolescent↗

Removal of formaldehyde by hydroxyapatite layer biomimetically deposited on polyamide film.

Some harmful volatile organic compounds (VOCs), such as formaldehyde, are regulated atmospheric pollutants. Therefore, development of a material to remove these VOCs is required. We focused on hydroxyapatite, which had been biomimetically coated on a polyamide film, as an adsorbent and found that formaldehyde was successfully removed by this adsorbent. The amount of formaldehyde adsorbed increased with the area of the polyamide film occupied by hydroxyapatite. The amount of adsorbed formaldehyde and its rate of adsorption were larger for hydroxyapatite deposited on polyamide film than for the commercially available calcined hydroxyapatite powder. This high adsorption ability is achieved by the use of nanosized particles of hydroxyapatite with low crystallinity and containing a large number of active surface sites. Therefore, hydroxyapatite biomimetically coated on organic substrates can become a candidate material for removing harmful VOCs such as formaldehyde.

Adsorption↗

The effect of partially stabilized zirconia on the mechanical properties of the hydroxyapatite-polyethylene composites.

The effect of partially stabilized zirconia (PSZ) on the mechanical properties of the hydroxyapatite-high density polyethylene composites was studied by investigating the effect of hydroxyapatite and the simultaneous effect of hydroxyapatite and PSZ volume fractions on fracture strength, modulus of elasticity, and absorbed energy in the composite samples. The results showed a decrease in fracture strength, and absorbed energy with an increase in the volume fraction of hydroxyapatite content in the hydroxyapatite-polyethylene samples. Partial replacement of hydroxyapatite with PSZ particles was beneficial in the improvement of both the fracture strength and failure energy values in the composite samples. A transition from ductile to brittle behavior was observed as the volume fraction of ceramic filler particles increased in the samples.

Bone Substitutes↗

Maxillary sinus augmentation using different grafting materials and dental implants in monkeys. Part IV. Evaluation of hydroxyapatite-coated implants.

The aim of this study was to evaluate clinically, histologically and histometrically the use of hydroxyapatite-coated dental implants in conjunction with maxillary sinus augmentation procedures. In 4 adult male Rhesus monkeys (Macaca mulatta) the 3 maxillary molars on 1 side of the jaws were extracted and the remaining bone between the alveolar crest and the floor of the sinus was reduced to 3-4 mm. After 3 months, maxillary sinus augmentation procedures were performed in each monkey and the sinuses were grafted with a porous hydroxyapatite bone graft (Interpore-200). At the same time, 2 hydroxyapatite-coated cylinder implants (IMZ) were immediately placed into the augmented sinuses (i.e. simultaneous-implants-loaded group). Four months later, 2 additional similar implants were placed into the previously augmented sinuses (i.e. delayed-implants-loaded group). After 4 months, the abutment connection was performed and all 4 implants were loaded with a gold-alloy bridge for 6 months (i.e. until sacrifice of the animals). The contralateral side of each monkey received the same treatment with the exception that removal of the maxillary molars was performed 7 months after those in the opposite side, and that the implants in this side were not loaded. Thus, 2 additional study groups (i.e. simultaneous-implants-unloaded group and delayed-implants-unloaded group) were obtained. Clinically, all loaded and unloaded implants were stable the day of sacrifice. Histologically, the grafted sinuses exhibited a significant amount of new bone formation with integration of the porous hydroxyapatite graft particles and hydroxyapatite-coat of the dental implants to the new bone. Histometric analysis indicated that on the loaded side the implants placed simultaneously with the sinus lift procedure exhibited greater direct mineralized bone-to-implant contact than the delayed placed implants. In addition, the percentage of direct mineralized bone-to-implant contact was significantly greater in the residual bone in comparison to the augmented area in all groups. Loading of the implants exhibited a positive effect on the percentage of direct mineralized bone-to-implant contact in the augmented area. It could be concluded that hydroxyapatite-coated implants may be of benefit when used in conjunction with sinus augmentation procedures.

Alveolar Process↗

Chimeric peptides of statherin and osteopontin that bind hydroxyapatite and mediate cell adhesion.

Extracellular matrix proteins play key roles in controlling the activities of osteoblasts and osteoclasts in bone remodeling. These bone-specific extracellular matrix proteins contain amino acid sequences that mediate cell adhesion, and many of the bone-specific matrix proteins also contain acidic domains that interact with the mineral surface and may orient the signaling domains. Here we report a fusion peptide design that is based on this natural approach for the display of signaling peptide sequences at biomineral surfaces. Salivary statherin contains a 15-amino acid hydroxyapatite binding domain (N15) that is loosely helical in solution. To test whether N15 can serve to orient active peptide sequences on hydroxyapatite, the RGD and flanking residues from osteopontin were fused to the C terminus. The fusion peptides bound tightly to hydroxyapatite, and the N15-PGRGDS peptide mediated the dose-dependent adhesion of Moalpha(v) melanoma cells when immobilized on the hydroxyapatite surface. Experiments with an integrin-sorted Moalpha(v) subpopulation demonstrated that the alpha(v)beta(3) integrin was the primary receptor target for the fusion peptide. Solid state NMR experiments showed that the RGD portion of the hydrated fusion peptide is highly dynamic on the hydroxyapatite surface. This fusion peptide framework may thus provide a straightforward design for immobilizing bioactive sequences on hydroxyapatite for biomaterials, tissue engineering, and vaccine applications.

Adsorption↗

Histological and radiological analyses of hydroxyapatite orbital implants in rabbits.

To date, only anectodal clinical data exist pertaining to the histological changes of hydroxyapatite within an enucleated socket. This study was conducted to determine the histological and radiological changes in a coralline hydroxyapatite sphere placed into the central socket, in a controlled fashion. Rabbits underwent simple enucleation with implantation of an autologous sclera-wrapped hydroxyapatite spheres with extraocular muscle reattachment. Preoperatively, the mineral density of each sphere was determined using quantitative computed tomography (CT) that was repeated 2- and 6 weeks postoperatively. The implants were harvested at 2- and 6 weeks and submitted for light and electron microscopic analysis. The results demonstrated a uniform influx of fibrovascular tissue that did not reach the center of the implant, even at 6 weeks. A marked mixed-cell inflammatory response was noted at the interface between the fibrovascular tissue and the hydroxyapatite. Giant cells were noted only at the scleral windows. This study demonstrated that the early response to hydroxyapatite implants was fibrovascular ingrowth with mixed-cell inflammation. These histological observations correlated with findings observed with quantitative CT. Quantitative CT appears to be an ideal modality for observing the early temporal tissue density changes in hydroxyapatite implants.

Animals↗

Prevention and management of complications associated with the hydroxyapatite implant.

The hydroxyapatite orbital implant offers many advantages compared to conventional implants; however, its use is not entirely free of complications. The objectives of this study are to review the complications encountered with the hydroxyapatite orbital implant, suggest mechanisms contributing to the development of these complications, and emphasize aspects of surgical technique that will minimize the risk of the most frequent complication, implant exposure. Preoperative, operative, and postoperative records of 154 patients receiving primary and secondary hydroxyapatite implants were studied retrospectively. Three clinical types of exposure defects were observed; dehiscences along the horizontal suture line, defects over holes in the hydroxyapatite, and a defect adjacent to the site of radiation plaque therapy. Most small exposures healed spontaneously. Medium and large defects were associated with anteriorly malpositioned implants, most often required surgical intervention, and were successfully managed with one or a combination of techniques including flaps, mucous membrane grafts, or repositioning of the implant more posteriorly. Placing the hydroxyapatite implant as far posteriorly as possible and advancing the extraocular muscles 3-5 mm from the apex of the implant will prevent most exposures. Unlike other types of implants, the hydroxyapatite implant does not migrate or extrude, and when exposed, usually does not require removal.

Adolescent↗

Osteogenin-enhanced bone-specific differentiation in hydroxyapatite orbital implants.

Hydroxyapatite orbital implants undergo early ingrowth of fibrovascular tissue after enucleation. This animal study determined whether control and osteogenin-impregnated hydroxyapatite orbital implants vary in their osteogenic response at 6 and 52 weeks. Rabbits underwent enucleation with implantation of control or osteogenin-impregnated hydroxyapatite spheres. Light microscopy determined fibrovascular ingrowth, and histomorphometry quantitated the amount of bone produced. Osteogenin implants vascularized at a faster rate and contained bony foci by 6 weeks that became confluent at 1 year. Spontaneous osteogenesis was not seen in control animals at 6 weeks. After 1 year they contained bone, although less than in the osteogenin implants. Mixed cell inflammation was observed at the hydroxyapatite-tissue interface in both groups. No inflammation was noted at the interface of hydroxyapatite and bone. These are the first controlled observations that bone-specific differentiation occurs in the pores of spherical hydroxyapatite implants within the soft tissues of the socket. This vascularized process can be enhanced with osteogenin to occur earlier and more uniformly in the implants at one year.

Animals↗

Histologic study of living response to artificially synthesized hydroxyapatite implant: 1-year follow-up.

We implanted artificially synthesized hydroxyapatite spheres into the orbits of 13 rabbits after enucleation. The spheres were removed 1, 2, 3, 6, and 12 months after implantation and examined by light and scanning electron microscopy. Tissue breakdown and exposure of the artificially synthesized hydroxyapatite implants were not observed. Month after month, fibrovascular tissues gradually invaded the pores of the artificially synthesized hydroxyapatite spheres deeper and deeper. Although the hydroxyapatite we used was completely artificially synthesized, we observed a mild foreign-body reaction around the artificially synthesized hydroxyapatite spheres. After 12 months, however, relief of the foreign-body reaction had occurred. Hydroxyapatite spheres for orbital implants after enucleation without scleral enveloping are appropriate.

Animals↗