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PubMed2002

Controlled synthesis of hydroxyapatite-supported palladium complexes as highly efficient heterogeneous catalysts.

Achieving precise control of active species on solid surfaces is one of the most important goals in the development of highly functionalized heterogeneous catalysts. The treatment of hydroxyapatites with PdCl(2)(PhCN)(2) gives two new types of hydroxyapatite-bound Pd complexes. Using the stoichiometric hydroxyapatite, Ca(10)(PO(4))(6)(OH)(2), we found that monomeric PdCl(2) species can be grafted on its surface, which are easily transformed into Pd(0) particles with narrow size distribution in the presence of alcohols. Such metallic Pd species can effectively promote alcohol oxidation using molecular oxygen and are shown to give a remarkably high TON of up to 236 000. Another monomeric Pd(II) phosphate complex can be generated at a Ca-deficient site of the nonstoichiometric hydroxyapatite, Ca(9)(HPO(4))(PO(4))(5)(OH), affording a catalyst with Pd(II) structure and high activity for the Heck and Suzuki reactions. To the best of our knowledge, the PdHAP are one of the most active heterogeneous catalysts for both alcohol oxidation under an atmospheric O(2)() pressure and the Heck reaction reported to date. These Pd catalysts are recyclable in the above organic reactions. Our approach to catalyst preparation based on the control of Ca/P ratios of hydroxyapatites represents a particularly attractive method for the nanoscale design of catalysts.

Catalysis↗
PubMedDate not supplied

Clinical and microbiological findings on newly inserted hydroxyapatite-coated and pure titanium human dental implants.

The clinical and microbiologic features of 30 hydroxyapatite-coated root-form endosseous dental implants (Tri-Stage) were compared to 10 similar pure titanium implants without hydroxyapatite coatings. In 7 of 9 partially edentulous patients studied, pure titanium fixtures were placed adjacent to hydroxyapatite-coated implants. Implants in the maxilla were submerged beneath mucosal tissues after implant placement for a minimum of 6 months, and in the mandible for at least 4 months. All patients were prescribed short-term beta-lactam antibiotic therapy after fixture placement, and 8 of 9 used chlorhexidine mouthrinses after fixture exposure. Clinical and microbiological examination was carried out 7-10 months after fixed prosthetic loading of the implants. Clinical measurements included the gingival index, plaque index, bleeding on probing and peri-implant probing depths determined with the Florida Probe system. Subgingival microbial samples were collected with paper points and transported in VMGA III. Specimens were examined by direct phase-contrast microscopy and were plated onto nonselective and selective culture media for anaerobic and aerobic incubation. No significant mean clinical or microbiological differences were found between the implant types, although one hydroxyapatite-coated implant exhibited deep probing depths, bleeding on probing and marked radiographic crestal bone loss. Streptococcus sanguis and Streptococcus mitis were the most predominant organisms recovered from clinically stable implants, whereas high proportions of Fusobacterium species and Peptostreptococcus prevotii were isolated from the ailing hydroxyapatite-coated implant. One or more implants in 8 of the study subjects yielded enteric rods, pseudomonads, enterococci or staphylococci. The prognosis of implants with varying early microbiotas needs to be established in longitudinal studies.

Aged↗
PubMed1979

The nature of the hydroxyapatite-binding site in salivary acidic proline-rich proteins.

Protein A and C, which are major components of the acidic proline-rich proteins in human saliva, were digested, before or after adsorption to hydroxyapatite, with alkaline phosphatase, trypsin, thermolysin and a proteinase preparation from salivary sediment. The results demonstrate that the binding site is located in the proline-poor N-terminal part of the protein, possibly between residues 3 and 25. Phosphoserine is necessary for maximal adsorption of the proteins to hydroxyapatite. When proteins A and C are adsorbed to hydroxyapatite before proteolytic digestion there is a protection of some of the susceptible bonds in the N-terminal part of the proteins and a gradual removal of the proline-rich C-terminal part. Thermolysin can cleave susceptible bonds in the part of the protein that remains bound to hydroxyapatite, but at least some of the resulting peptides are retained on the mineral. Since the ability of the proteins to inhibit hydroxyapatite formation and to bind calcium is located in the N-terminal proline-poor part, it is possible that these activities are retained after proteolytic digestion of the adsorbed proteins.

Adsorption↗
PubMed1992

Calvarial reconstruction in baboons with porous hydroxyapatite.

The growth of bone into porous hydroxyapatite implanted in nonhealing calvarial defects of adult baboons is evaluated. Seventy-two anterior and posterior calvarial defects, 25 mm in diameter, were prepared in 24 adult male baboons (Papio ursinus). In each animal, one defect was implanted with a disc of porous hydroxyapatite obtained after hydrothermal conversion of the calcium carbonate exoskeleton of coral (genus Goniopora); pores averaged 600 microns in diameter, pore interconnections averaged 260 microns in diameter, and the void fraction was 70% (Interpore 500). Another defect was grafted with autogenous corticocancellous bone harvested from the iliac crest. The third defect was left ungrafted and used as a control. Histology and histomorphometry on nondecalcified and decalcified sections prepared from specimens harvested at 3, 6, and 9 months after surgery showed that substantial bone growth had occurred in the hydroxyapatite implants (p < 0.01 vs bone grafts at 3 mos), culminating in complete penetration of bone within the tridimensional porous spaces. Anterior untreated defects showed greater amounts of bone when compared to posterior defects. The extent of bone growth in hydroxyapatite implants, however, appeared to be independent of the site of surgical implantation. This finding suggests that bone deposition within the porous spaces was a function of the implanted matrix rather than the healing potential of specific regions within the calvaria. Of concern was the presence of nonunions at the hydroxyapatite/calvarial interfaces, despite the often extensive bone deposition within the center of the hydroxyapatite implants. Further studies are required to identify the reasons for nonunion and to evaluate the mechanical performance of the bone-porous matrix complex.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗
PubMed1989

The rate of vascularization of coralline hydroxyapatite.

Coralline hydroxyapatite (CHAP) is a porous, biocompatible bone-graft substitute manufactured by the Replamineform process. The use of this material in the experimental and clinical settings for maxillofacial onlay grafting has been recently described. This study was designed to quantitate the rate of vascularization of coralline hydroxyapatite when used in an onlay application to membranous bone in an animal model. Sixteen onlay grafts of coralline hydroxyapatite (0.5 X 0.5 X 1.0 cm Interpore 200) were placed in a subperiosteal location on the nasal dorsum of 2- to 3-kg male New Zealand white rabbits. The grafts and nasal bones were harvested en bloc at 1, 2, 3 and 4 weeks after onlay. Prior to harvest, injectable silicone visualizing agent (Microfil*) was injected by means of carotid artery cutdown. The decalcified specimens were examined on a digitizing pad to count the number of vessels appearing in the blocks of hydroxyapatite. Counting was summed and integrated by an Apple IIe microcomputer. A significant difference (p less than 0.05) was noted in both the number of vessels and the fraction of implants infiltrated by vessels between 1 and 4 weeks. The usefulness of these previously undescribed data may be in their extrapolation to onlay grafts of coralline hydroxyapatite in maxillofacial reconstruction in humans.

Animals↗
PubMed2002

Anterior lumbar interbody fusion with processed sea coral (coralline hydroxyapatite) as part of a circumferential fusion.

STUDY DESIGN: A retrospective review of 20 patients undergoing circumferential lumbar fusion with coralline hydroxyapatite blocks anteriorly and autograft with transpedicular or translaminar facet screw fixation posteriorly. OBJECTIVES: To examine the efficacy of coralline hydroxyapatite as a bone graft substitute for anterior lumbar interbody fusion. SUMMARY OF BACKGROUND DATA: Autograft is the gold standard for bone grafting in the anterior lumbar spine. Harvesting bone from the iliac crest leads to significant postoperative pain and morbidity. Femoral ring allograft is a widely used alternative to autograft but has some inherent problems. Coralline hydroxyapatite was shown to be 100% successful for anterior cervical fusion when combined with rigid plating. METHODS: A retrospective review of 20 patients with low back pain and indicated for surgical intervention. A circumferential instrumented fusion was performed with coralline hydroxyapatite blocks anteriorly and transpedicular or translaminar facet fixation and autograft posteriorly. All patients reached a minimum 3-year clinical and radiologic follow-up. RESULTS: Radiographic follow-up yielded a solid arthrodesis rate of 93.8% by level (30 of 32 disc spaces) and 90% by patient (18 of 20). Clinical follow-up generated a mean pain reduction of 61.8% with clinical success demonstrated in 80% (16 of 20) of all patients who reported good or excellent pain relief. Eight of 12 (66.7%) patients employed before surgery returned to work in some capacity. CONCLUSIONS: Coralline hydroxyapatite is a practicable anterior lumbar interbody fusion alternative to autograft and allograft as part of a circumferential fusion with rigid posterior fixation. It is not recommended for stand-alone anterior lumbar interbody fusion without further study.

Adult↗
PubMed2003

A prospective randomized comparison of coralline hydroxyapatite with autograft in cervical interbody fusion.

STUDY DESIGN: A prospective randomized trial with independent clinical and radiographic outcome review of patients receiving either hydroxyapatite or tricortical iliac crest graft for cervical interbody fusion was conducted. OBJECTIVE: To determine whether coralline-derived hydroxyapatite is a suitable bone graft substitute in cervical interbody fusion. SUMMARY OF BACKGROUND DATA: Tricortical iliac crest bone is the "gold standard" graft material for cervical interbody fusion. Various bone substitutes have been used for this procedure to avoid potential donor site morbidity. ProOsteon 200 is a coralline-derived hydroxyapatite product, the use of which remains unclear for cervical interbody fusion. METHODS: In this study, 29 patients undergoing anterior cervical fusion and plating were randomized to receive either ProOsteon 200 or iliac crest grafts. The SF-36 and Oswestry Disability Index were used to measure clinical outcome. Postoperative radiographs were analyzed for graft fragmentation, loss of height, angular alignment, and hardware failure to assess structural integrity of the graft material. Plain radiographs and computed tomography scans were used to evaluate fusion. RESULTS: Both the ProOsteon 200 and iliac crest groups demonstrated significant improvement in clinical outcome scores. There was no significant difference in clinical outcome or fusion rates between the two groups. Graft fragmentation occurred in 89% of the hydroxyapatite grafts and 11% of the autografts (P = 0.001). Significant graft settling occurred in 50% of the hydroxyapatite grafts, as compared with 11% of the autografts (P = 0. 009). One patient in the ProOsteon 200 group required revision surgery for graft failure. CONCLUSIONS: ProOsteon 200 does not possess adequate structural integrity to resist axial loading and maintain disc height or segmental lordosis during cervical interbody fusion.

Bone Transplantation↗
PubMed1985

Elution of fibronectin proteolytic fragments from a hydroxyapatite chromatography column. A simple procedure for the purification of fibronectin domains.

Human plasma fibronectin is composed of at least five distinct domains which we refer to as Hep-1/Fib-1, Gel, Cell, Hep-2 and Fib-2 depending on their affinity for heparin (Hep), gelatin (Gel), the cell surface (Cell) or fibrin (Fib). These domains are aligned from the NH2 to the COOH terminus in the above order and can be separated from each other by mild proteolytic digestion. We have studied the elution of fibronectin thermolysin digest from a hydroxyapatite column using a linear gradient (0.5-190 mM) of sodium phosphate buffer. The five major fibronectin domains were eluted from the hydroxyapatite chromatography column in the following order: Gel, Fib-2, Cell, Hep-1/Fib-1 and Hep-2. They were identified on the basis of their molecular mass, affinity to different macromolecules and reaction with domain-specific monoclonal antibodies. All domains except the Cell and Hep-2 domains eluted as single homogeneous peaks. The Cell domain eluted as two different peaks and the Hep-2 domain eluted as four different peaks. This is the first time that heterogeneity of these two domains has been observed. Since chromatography of a fibronectin thermolysin digest on a hydroxyapatite column provides a good separation of the five major fibronectin domains, we have elaborated a procedure in which each fibronectin domain is purified by no more than two steps; hydroxyapatite and molecular exclusion chromatography. Fractionation of fibronectin proteolytic digest on a hydroxyapatite chromatography column should be of great value in the comparative analysis of fibronectin from different sources and in the study of fibronectin heterogeneity. Its use in combination with molecular exclusion chromatography offers a simple and high-yield method for the purification of large amounts of fibronectin domains.

Chemical Phenomena↗
PubMed1980

Adherence of Streptococcus salivarius HB and HB-7 to oral surfaces and saliva-coated hydroxyapatite.

We compared the binding of Streptococcus salivarius HB and the mutant HB-7 to oral surfaces in vivo. Mutant HB-7 does not aggregate with saliva nor does it bind to buccal epithelium, but it does retain its ability to coaggregate with Veillonella and Fusobacterium. At 1 h after inoculation into the oral cavity of six volunteers, significantly more S. salivarius HB than HB-7 cells were found adhering to the buccal mucosa (P < 0.05) and to a cleaned tooth surface (P < 0.01); there was no significant difference in the numbers adhering to the tongue. The ratio of HB to HB-7 on the tongue increased in samples taken 1, 3, and 9 days after inoculation. The average time required to clear the mutant HB-7 from the oral cavity was 7 days, whereas that for the parent HB was greater than 20 days, and in some cases strain HB was still present 3 months after its inoculation. A representative S. salivarius serotype II strain, designated T3, behaved similarly to mutant HB-7 with respect to its adherence to the buccal mucosa. Strain HB adhered better to hydroxyapatite treated with human saliva than mutant HB-7; both strains adhered in similar numbers to untreated hydroxyapatite. Hydroxyapatite treated with rat saliva bound less HB than hydroxyapatite treated with human saliva, corresponding to the lower aggregating activity of rat saliva. Extraction of saliva with aggregating strains of S. salivarius reduced the ability of saliva to mediate attachment of strain HB to hydroxyapatite.

Adsorption↗
PubMed1982

Influence of sublethal antibiotic concentrations on bacterial adherence to saliva-treated hydroxyapatite.

The influence of growth in the presence of sublethal concentrations of nine antibiotics on the ability of certain potentially odontopathic bacteria to attach to saliva-treated hydroxyapatite surfaces which mimic teeth was studied. Cells of Actinomyces viscosus LY7 and S2, Bacteroides gingivalis 381, Capnocytophaga ochraceus 6, and Actinobacillus actinomycetemcomitans N27 attached in lower numbers to saliva-treated hydroxyapatite when grown in the presence of 50% of the minimum inhibitory concentration of tetracycline. Electron microscopic observations of negatively stained preparations indicated that tetracycline-grown A. viscosus LY7 cells had fewer fimbriae than did untreated cells, which may account for the impaired ability of the treated cells to attach. However, cells of Actinomyces naeslundii L13 and S4 attached in higher numbers when grown in the presence of tetracycline, clindamycin, erythromycin, chloramphenicol, or neomycin. Streptococcus mutans strains H12 and JBP also exhibited increased adherence to saliva-treated hydroxyapatite when grown in the presence of 50 or 25% of the minimum inhibitory concentration of penicillin. Thus, growth in the presence of sublethal antibiotic concentrations could increase as well as decrease the adherence of bacteria to saliva-treated hydroxyapatite. Antibiotic-grown cells of the Actinomyces strains showed enhanced hemagglutination activity, but this did not correlate with their ability to attach to saliva-treated hydroxyapatite. Sublethal concentrations of antibiotics in the growth media also affected the coaggregation reactions of several organisms; the effects were specific for one member of the coaggregation pair.

Actinobacillus↗
PubMed1989

Hydroxyapatite and urate crystal induced cytokine release by macrophages.

Destructive osteoarthritis is characterised by rapidly progressive joint destruction associated with intra-articular deposition of hydroxyapatite crystals. The possible role of such crystals in the pathogenesis of this condition was investigated by testing the ability of hydroxyapatite crystals to stimulate the production of bone resorbing activity from mouse peritoneal macrophages. Urate crystals were used for comparison. Culture supernatants were tested for bone resorbing activity using the mouse calvarial bone resorption assay, for interleukin 1 using a standard lymphocyte activation assay, and for prostaglandin E2 by radioimmunoassay. Culture supernatants from macrophages incubated with hydroxyapatite crystals contained dialysable bone resorbing activity, high concentrations of prostaglandin E2, but no interleukin 1 like activity. The production of the bone resorbing agent was prevented by culturing macrophages with hydroxyapatite crystals in the presence of indomethacin. By contrast, culture supernatants from macrophages incubated with urate crystals contained bone resorbing activity, which was only partly removed by dialysis, and interleukin 1 like activity. The latter was shown to be increased in culture supernatants from macrophages incubated with urate crystals in the presence of indomethacin, while production of bone resorbing activity was partially inhibited. It is considered that the bone resorbing activity liberated from macrophages stimulated by hydroxyapatite crystals can be explained by the presence of prostaglandin E2 alone, whereas the activity liberated by urate crystals is due to both prostaglandin E2 and interleukin 1.

Animals↗
PubMedDate not supplied

Hydroxyapatite ceramic as middle ear implant material: animal experimental results.

Hydroxyapatite is the main constituent of the mineral matrix of bone. The behavior of porous and dense hydroxyapatite ceramic implants was studied in normal rat middle ears, after induced infection, and in an in vitro assay by light and electron microscopic techniques. All implants were integrated into the middle ears without signs of extrusion, and their mucosal coverings did not appear to differ fundamentally from those of normal ears. The porous hydroxyapatite became filled with fibrous tissue and bone that showed normal morphology, and there was direct bonding of the bone to the implants. Minor biodegradation was established for the porous implants. Hydroxyapatite did not affect cultured middle ear mucosa significantly in vitro. Induced infection failed to show any adverse effect on the behavior of the implants. These observations suggest that hydroxyapatite is very useful for reconstructive ear surgery.

Animals↗
PubMed1991

Adsorption to hydroxyapatite of partially deglycosylated human salivary mucins in competition with phosvitin and phytate.

The effect of phosvitin and phytate on the binding of native as well as partially deglycosylated human whole salivary mucins (HWSM) to hydroxyapatite was studied. Native HWSM preadsorbed onto hydroxyapatite was completely desorbed in the presence of greater than 500 micrograms/ml phosvitin. In contrast, in similar experiments, asialo-HWSM was desorbed approximately 10%. Desorption of preadsorbed asialo-afuco-HWSM in the presence of 1 mg/ml phosvitin was approximately 20%. Further deglycosylation of HWSM resulted in preparations which, after preadsorption to hydroxyapatite, were not desorbed upon subsequent incubation with phosvitin. With phytate, a less effective competitor of HWSM for the hydroxyapatite surface, essentially the same results were obtained, i.e. increase in deglycosylation of HWSM was concomitant with decrease in desorption by phytate. Using other incubation conditions (preadsorption of a phosphocompound, and simultaneous incubation of HWSM and phosphocompounds) essentially the same conclusion was obtained. The data indicate that the ability of salivary mucins to absorb to hydroxyapatite in competition with phosphocompounds appears to be enhanced by deglycosylation.

Asialoglycoproteins↗
PubMed2004

Hydroxyapatite-coated prostheses in total hip and knee arthroplasty.

Hydroxyapatite-coated implants have demonstrated extensive bone apposition in animal models. The osseous interface develops even in the presence of gaps of 1 mm and relative motion of up to 500 mum. Development of implant-bone interfacial strength is due to the biological effects of released calcium and phosphate ions, although surface roughness leads to increased interface strength in the absence of interface gaps. The clinical results at fifteen years after total hip replacements have demonstrated that hydroxyapatite-coated femoral stems perform as well as, and possibly better than, other types of cementless devices, with the added benefit of providing a seal against wear debris. Hydroxyapatite-coated acetabular components must have a mechanical interlock with bone in order to take advantage of the coating effects. Clinical analyses of these types of designs at seven years have indicated good survivorship. The performance of a hydroxyapatite-coated implant depends on coating properties (thickness, porosity, hydroxyapatite content, and crystallinity), implant roughness, and overall design. The most reliable predictor of the performance of a device is success in long-term clinical studies.

Acetabulum↗
PubMedDate not supplied

Nutrient-substituted hydroxyapatites: synthesis and characterization.

Incorporation of Mg, S, and plant-essential micronutrients into the structure of synthetic hydroxyapatite (HA) may be advantageous for closed-loop systems, such as will be required on Lunar and Martian outposts, because these apatites can be used as slow-release fertilizers. Our objective was to synthesize HA with Ca, P, Mg, S, Fe, Cu, Mn, Zn, Mo, B, and Cl incorporated into the structure, i.e., nutrient-substituted apatites. Hydroxyapatite, carbonate hydroxyapatite (CHA), nutrient-substituted hydroxyapatite (NHA), and nutrient-substituted carbonate hydroxyapatite (NCHA) were synthesized by precipitating from solution. Chemical and mineralogical analysis of precipitated samples indicated a considerable fraction of the added cations were incorporated into HA, without mineral impurities. Particle size of the HA was in the 1 to 40 nm range, and decreased with increased substitution of nutrient elements. The particle shape of HA was elongated in the c-direction in unsubstituted HA and NHA but more spherical in CHA and NCHA. The substitution of cations and anions in the HA structure was confirmed by the decrease of the d[002] spacing of HA with substitution of ions with an ionic radius less than that of Ca or P. The DTPA-extractable Cu ranged from 8 to 8429 mg kg-1, Zn ranged from 57 to 1279 mg kg-1, Fe from 211 to 2573 mg kg-1, and Mn from 190 to 1719 mg kg-1, depending on the substitution level of each element in HA. Nutrient-substituted HA has the potential to be used as a slow-release fertilizer to supply micronutrients, S, and Mg in addition to Ca and P.

Carbonates↗
PubMed1989

Crystallographic properties of a series of synthetic hydroxyapatites.

The crystallographic properties of hydroxyapatites synthesized at temperatures of 200 degrees C, 500 degrees C, 900 degrees C and 1250 degrees C, designated HAP200, HAP500, HAP900 and HAP1250, respectively, were studied using X-ray powder diffraction. Values of a-axis length for the hydroxyapatites ranged from 9.406 A to 9.416 A, which were smaller than the corresponding value for stoichimetric hydroxyapatite, a = 9.418 A. Generally, the a-axis length decreased with the synthesis temperature, except for HAP500 which showed the smallest value. Crystallinity of the hydroxyapatites, measured by X-ray diffraction peak broadening as full width at the half-maximum value (FWHM), increased with the synthesis temperature, although HAP500 showed a decrease. These results suggest that the synthetic hydroxyapatites contained some carbonate ions, probably at the A-site of the apatite structure, and that the structure was depleted of carbonate ions at about 500 degrees C.

Crystallography↗
PubMedDate not supplied

Epithelial reactions to hydroxyapatite. An in vivo and in vitro study.

The intention of this study was to investigate the epithelial reactions to hydroxyapatite ceramic in vivo and in vitro. Shortly after implantation in the rat middle ear, hydroxyapatite was found covered by a mucosal layer. In the early postoperative period the implant was almost completely covered by epithelial cells, which were found to proliferate and also showed migratory activity. After longer intervals the implant was completely covered by epithelium, which was composed predominantly of flat polygonal cells and a relatively small number of ciliated epithelium and goblet cells. All cells showed normal morphology. In vitro experiments showed preservation of the morphology of rat middle-ear mucosa explants with good outgrowth of epithelial cells. In these outgrows, the majority of the cells were flat polygonal, but ciliated epithelium was also seen. No difference was found between the absence and presence of hydroxyapatite. Serially cultured cells displayed normal polygonal morphology, but no ciliated cells were found. Ciliated cells were also absent in control experiments without hydroxyapatite. Growth curves obtained in the absence and presence of hydroxyapatite did not differ significantly from each other.

Animals↗
PubMed2000

[Physicochemical characterization and histological bone-formability evaluation of electrically polarized hydroxyapatite].

Acceleration and deceleration of bone-like crystal growth on electrically polarized hydroxyapatite ceramics are induced by their surface changes, as recently reported by Yamashita, et al. In this study, new-bone-forming ability of electrically polarized hydroxyapatite was physicochemically characterized and histologically evaluated using femora and tibiae of rabbits. The electrical polarizability of hydroxyapatite was demonstrated by thermally stimulated current measurements. No significant difference between polarized and non-polarized hydroxyapatite was recognized by IR spectroscopy and X-ray diffractometry. A negatively charged hydroxyapatite surface exhibited osteogenesis with direct bone contacting in early stage. A positively charged surface resulted in a small amount of bone formation on the surface. On the contrary, in the zone isolated by fibrous layer, a large volume of bone newly formed. It is useful that the outstanding bone-formability in the early stage on a negatively charged surface implies more rigid initial fixation in orthopedic and dental fields. Positively charged surfaces have a new-bone-conducting property that acts over a long distance, and the possibility of controlling osteogenesis.

Animals↗