The experience of a clinical trial of bioceramic-based materials in dentistry

Bioceramics-based materials manufactured in Russia were experimentally and clinically tried with the aim of optimizing repair osteogenesis of the jaws. Powder, granules, and porous blocks of hydroxyapatite alone and mixed with tricalcium phosphate may be effectively used for plastic repair of osseous pouches and post-operative defects of the jaws in surgical treatment of periodontitis, periradicular cysts of the jaws, and for filling the wells after removal of teeth.     

几种骨组织工程复合支架材料在模拟生理溶液中的生物矿化性能比较

采用生物活性玻璃(BG)、磷酸三钙(TCP)、羟基磷灰石(HA)等生物活性陶瓷与3-羟基丁酸酯-3-羟基戊酸酯的共聚物(PHBV)复合,制备了性能良好的骨组织工程支架材料,分析了PHBV/BG,PHBV/TCP,PHBV/HA三种复合多孔支架在模拟生理溶液中的一系列化学反应,以及多孔材料在模拟生理溶液中浸泡后的成分、结构和微观形貌的变化。研究结果表明,三种复合支架材料在模拟生理溶液中发生了降解反应而失重;PHBV/BG和PHBV/TCP在模拟生理溶液中还发生了生物矿化反应,在表面形成矿化沉积层,为具有骨生物活性的结晶态类骨碳酸羟基磷灰石;而PHBV/HA在模拟生理溶液中没有明显的生物活性反应。     

Biphasic calcium phosphate concept applied to artificial bone, implant coating and injectable bone substitute

The development of calcium phosphate ceramics and other related biomaterials for bone graft involved a better control of the process of biomaterials resorption and bone substitution. The bioactive concept was developed for biphasic calcium phosphate ceramics (BCP). An optimum balance of the more stable phase of HA and more soluble TCP was obtained for controlling gradual dissolution in the body, seeding new bone formation as it releases calcium and phosphate ions into the biological medium. The bone/material interface and the events occurring in the development of this dynamic interface such as cellular response, biodegradation or bioresorption of the materials and their transformation to carbonate hydroxyapatite (CHA) were described. These processes were observed in both bulk samples, implant coating and injectable bone substitute (IBS).     

Influence of magnesium substitution on a collagen-apatite biomaterial on the production of a calcifying matrix by human osteoblasts

The induction of a calcifying matrix is of great interest in the restoration of bone defects. In a previous in vitro study we demonstrated that a collagen sponge constituted of type I collagen fibrils, chondroitin sulfates, and hydroxyapatite crystals induces an earlier and a more abundant synthesis of a new extracellular calcifying matrix than do other biomaterials such as collagen or hydroxyapatite alone. Bone mineral contains various amounts of magnesium ions, either adsorbed at the surface of apatite crystals or incorporated inside the crystal structure. Magnesium is known to reduce the degradation rate of tricalcium phosphate ceramics and to influence the crystallization of mineral substance. Thus we evaluated two sponges modified with different substituted apatites. The substituted low magnesium-containing apatite sample decreased the osteoinductive properties of the sponge whereas the substituted high magnesium-containing apatite sample had a toxic effect on bone cells and prevented the formation of any extracellular matrix. Such a toxic effect can be explained by the presence of large numbers of magnesium ions released into the culture medium even though at physiological level magnesium is able to promote bone mineralization and to control the growth of hydroxyapatite crystals. Thus collagen sponges containing hydroxyapatite remain one of the most appropriately evaluated biomaterials used for the restoration of periodontal pockets and bone defects.     

Characterization of calcium phosphates precipitated from simulated body fluid of different buffering capacities

The purpose of this experiment was to study the properties of calcium phosphate precipitated from simulated body fluids (SBFs) with different buffering capacities. The Ca/P molar ratios of the precipitates were determined and the microstructure of a sintered precipitate was studied. The results indicate that the pH of the SBF increases during calcium phosphate precipitations, which affects the Ca/P molar ratios and chemical compositions of these precipitates. A precipitate with a Ca/P molar ratio close to the stoichiometric molar ratio of hydroxyapatite was obtained when the pH of the SBF was continuously adjusted to 7.26 during precipitation. This precipitate has a fine-grained and laminated microstructure after sintering at 1000 degrees C in air. It seems that SBF can be used as a tool to study apatite-like precipitation in vitro when the pH of the solution is carefully controlled.     

Development of hydroxyapatite derived from Indian coral

A simple method of converting the calcium carbonate skeleton of the corals available in the Indian coast into hydroxyapatite granules has been developed. By heating the coral to 900 degrees C, the organic materials were eliminated. Powder X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were employed to characterize the coral and to optimize the processing parameters as well as to confirm the hydroxyapatite formation. The coral used exhibits the presence of both aragonite and calcite phases (dimorphism). At a temperature of 900 degrees C the coral was found to decompose all the carbonate phases. The pre-heated coral is converted into hydroxyapatite by a chemical exchange reaction with di-ammonium phosphate under hydrothermal conditions. The hydroxyapatite obtained was in powder form and does not contain any impurities. The in vitro solubility test of the apatite granules performed in Gomoris, Michalelis, Sorensens, Ringer's and phosphate buffer of pH 7.2 and de-ionized water indicated the stability of the coralline hydroxyapatite.     

Structural arrangements at the interface between plasma sprayed calcium phosphates and bone

Plasma sprayed coatings of tetracalcium phosphate, magnesium whitlockite and three types of hydroxyapatite, varying in degree of crystallinity, were evaluated with light microscopy, scanning electron microscopy and backscatter electron microscopy (BSE) after implantation periods of 1, 2 and 4 wk in rat femora. BSE revealed that both tetracalcium phosphate and semi-crystalline hydroxyapatite underwent distinct bulk degradation and loss of relatively large particles. Amorphous hydroxyapatite showed a gradual surface degradation, indicated by a transition zone varying in grey level between that of the coating and bone tissue, while degradation was negligible with the highly crystalline material and magnesium whitlockite. Degradation appeared to be related to bone apposition, since more bone seemed to be present on amorphous hydroxyapatite and tetracalcium phosphate, as compared to highly crystalline hydroxyapatite and magnesium whitlockite coatings. At the interface between bone and magnesium whitlockite, a seam of unmineralized bone-like tissue was frequently seen with light microscopy, while few areas with bone contact were present. X-ray microanalysis revealed that both the magnesium whitlockite coating and the unmineralized bone-like tissue contained substantial amounts of aluminium which, in addition to possible influences of magnesium, may have caused the impaired mineralization. The results of this preliminary study indicate that, with regard to early bone formation, amorphous hydroxyapatite coatings seem to be beneficial over highly crystalline coatings. However, further experiments should be performed to give conclusive data on (i) the statistical significance of the differences in bone apposition rate, and (ii) the long-term behaviour of both amorphous and highly crystalline coatings in bone and their relation to implant performance.     

Dissolution behaviour of calcium phosphate coatings obtained by laser ablation

Pulsed laser deposited calcium phosphate coatings on titanium alloy have been tested under simulated physiological conditions in order to evaluate the changes in morphology, composition and structure. The coatings were deposited under different conditions to obtain different crystalline structures, ranging from amorphous and mixed crystalline phases to pure crystalline hydroxyapatite (HA). The coated samples were immersed in a Ca-free Hank's balanced salt solution for up to 5 days. Characterization of the coatings was performed by X-ray diffraction, scanning electron microscopy and Fourier-transform Raman spectroscopy before and after immersion. Their dissolution behaviour was also monitored through their mass loss and calcium release. Coatings of pure HA preserve their morphology and structure during the exposure time in solution. In multiphasic coatings, consisting of HA with tetracalcium phosphate (TetraCP) or beta-tricalcium phosphate (beta-TCP) with a-tricalcium phosphate (alpha-TCP), microporosity is induced by the complete dissolution of TetraCP or gamma-TCP. Amorphous calcium phosphate coatings totally dissolve.     

Periradicular healing in response to Diaket root-end filling material with and without tricalcium phosphate

The healing of the periradicular tissues was evaluated when the polyvinyl resin Diaket with and without tricalcium phosphate was used as surgical root-end filling material. Non-surgical root canal treatment was performed on 56 mandibular premolar roots in mongrel dogs. Following root-end resection, root-end cavity preparations were filled with Diaket, the comparative material, or Diaket in combination with tricalcium phosphate, the experimental material. Postsurgically, healing of the tissues adjacent to the filling materials and in the surrounding surgical site were evaluated at 30 and 60 days. There was virtually no statistically significant difference between the experimental and comparative group at or within the 30- or 60-day period with regard to inflammation, connective tissue formation, root-end encapsulation, cementum formation, or bone apposition. Findings suggest that cementogenesis occurred over both materials. The overall healing of the periradicular tissues was favourable.     

Stability of hydroxyapatite while processing short-fibre reinforced hydroxyapatite ceramics

Reinforcement by short fibres has been adapted from modern ceramic processing technologies to achieve an improvement of structural properties of hydroxyapatite. However, the influence of the reinforcement fibres on the thermochemical behaviour of the hydroxyapatite has yet to be clarified comprehensively. Titanium, alumina and 316L-stainless steel, all materials with a proven record as implant materials, were chosen as reinforcement materials. Short fibres of these materials were incorporated in a matrix of hydroxyapatite to toughen the hydroxyapatite. Composites were processed by sintering in air, hot isostatic pressing and a method combining sintering in inert gas atmosphere and hot isostatic pressing.     

Intracranial tuberculoma mimicking metastasis from renal tumor--case report

In vitro study of encrustation is an important part of assessment of materials as potential alloplasts or devices in the urinary tract. This modified semi-automated technique comprises a circular reaction chamber with an encrustation mixture, the level of which is controlled by a float switch which operates the exit peristaltic pump. The composition of the reactants used simulates infected urine with alkaline pH. Results of a preliminary study of the deposits by scanning electron micrography (SEM) and energy dispersive X-ray (EDX) microanalysis are consistent with struvite and hydroxyapatite, similar to the main minerals deposited on urinary catheters. It is a relatively simple, effective and inexpensive set-up for study of encrustation on materials.     

A quantitative study of the sintering and mechanical properties of hydroxyapatite/phosphate glass composites

Previous work has shown that small additions of a phosphate glass (CaO-P2O5) can significantly enhance the sinterability and strength of hydroxyapatite. However, there are no quantitative phase analyses available for these materials which would provide indicators of biocompatibility and resorbability. Similarly, there is little information available about the mechanical properties, especially with high glass additions. In this study, the effects of sintering hydroxyapatite with phosphate glass additions of 2.5, 5, 10, 25, and 50 wt.% are quantified. Each composition was sintered over a range of temperatures, and quantitative phase analysis was carried out using XRD. In addition, the microstructures were studied using RLOM and SEM, and mechanical properties (Vickers hardness, KIC, and MOR) measured. These results may be used to indicate which compositions and processing conditions may provide materials suitable for use in hard tissue replacement. Composites containing up to 10 wt.% glass additions formed dense HA/TCP composite materials possessing flexural strength and fracture toughness values up to 200% those of pure HA. The HA/TCP ratio was strongly dependent on the percentage glass addition. Higher glass additions resulted in composites containing beta-TCP together with large amounts of alpha- or beta-calcium pyrophosphate, and having similar mechanical strengths to pure HA.     

Phosphates precipitating from artificial urine and fine structure of phosphate renal calculi

Phosphates precipitating from artificial urine in the pH range 6-8 were identified using X-ray diffraction, chemical analysis and scanning electron microscopy. The influence of magnesium and citrate on phases precipitating from urine was established. From urine containing a normal quantity of magnesium (around 70 ppm), brushite accompanied by hydroxyapatite (HAP) precipitated at pH < or = 7.0 and struvite with HAP at pH > 7.0. HAP was formed exclusively from magnesium deficient urine at pH 7.0. Newberyite, octacalcium phosphate and whitlockite were not identified. The chemical and phase composition and inner fine structure of 14 phosphate calculi were studied. Three types of stones were distinguished based on their magnesium content: (i) stones rich in magnesium composed of struvite, hydroxyapatite and abundant organic matter, (ii) stones with low magnesium content constituted by calcium deficient hydroxyapatite, up to 5% of struvite, considerable amount of organic matter and occasionally brushite, and (iii) calculi without magnesium consisting of brushite, hydroxyapatite and little organic matter. Conditions prevaling during stone-formation assessed for each type of stone were confirmed by corresponding urinary biochemical data and corroborate the in vitro studies of phosphates precipitation.     

Kinetic mechanism of phosphate/phosphate and phosphate/OH- antiports catalyzed by reconstituted phosphate carrier from beef heart mitochondria

In an optimized reconstituted system, the basic kinetic properties of the phosphate carrier from bovine heart mitochondria, e.g. the influence of membrane potential, pH, and proton gradient, were investigated for the two physiological modes of transport (Pi-/Pi- antiport and electroneutral, unidirectional phosphate transport). On the basis of these data, which closely resemble the function known from mitochondria, the reaction mechanism of the phosphate carrier was determined using bireactant initial velocity studies in both transport modes. Translocation occurred according to a simultaneous (sequential) mechanism, involving a ternary complex in transport catalysis. This mechanism indicates that the phosphate carrier falls into the same functional family as most other mitochondrial carriers. A detailed analysis of the different effects of pH on transport substrates and carrier protein in both possible transport modes, in combination with the identity of the kinetic mechanism in both modes, provides evidence that the unidirectional phosphate transport is catalyzed by Pi-/OH- antiport rather than by Pi-/H+ symport. We furthermore observed noncompetitive inhibition of phosphate transport by other anions. The consequences of this result with respect to a functional model of the carrier protein are discussed.     

Formation of hydroxyapatite in new calcium phosphate cements

Tetracalcium phosphate (TTCP) has been shown previously to be an essential component of self-setting calcium phosphate cements that form hydroxyapatite (HA) as the only end-product. We report herein on a new self-setting calcium phosphate cement that does not contain TTCP. These cements consist of dicalcium phosphate anhydrous (DCPA), dicalcium phosphate dihydrate (DCPD), alpha-tricalcium phosphate, or amorphous calcium phosphate and, as an additional source of calcium, calcium hydroxide or calcium carbonate. These cements require the use of a phosphate (0.2 moll(-1) or higher) solution or a high pH solution as the cement liquid. The cements harden in relatively short time (5-30 min) and form HA as the dominant end-product in 24 h. The diametral tensile strengths of the 24-h samples are in the range of 0.2 to 7.5 MPa. Results from X-ray diffraction studies suggest that the cement setting is caused by rapid HA formation induced by the high phosphate concentration of the cement liquid. Because DCPA and DCPD are highly soluble at pH values above 12.7, which is the pK3 of phosphoric acid, high phosphate concentration in the slurry solution was also attainable by using a highly alkaline solution as the cement liquid. The physicochemical properties of these cements are comparable to those of TTCP-containing cements, and the new cements may be expected to have in vivo characteristics similar to those of TTCP-containing cements as well.     

DNA degradation during standard alkaline of thermal denaturation

Essential degradation 8 DNA (up to 10 per cent) with liberation of acid-soluble fragments takes place on the standard alkaline (0,01 M sodium phosphate, pH 12, 60 degrees, 15 min) or thermal (0.06 M sodium phosphate buffer, pH 6.8, 102 degrees C, 15 min) denaturation. This degradation is more or less selective: fraction of low molecular weight fragments, isolated by hydroxyapatite cromatography and eluted by 0.06 M sodium phosphate buffer, pH 6.8 is rich in adenine and thymine and contains about 2 times less 5-methylcytosine than the total wheat germ DNA. The degree of degradation of DNA on thermal denaturation is higher than on alkaline degradation. Therefore while studying reassociation of various DNA, one and the same standard method of DNA denaturation should be used. Besides, both the level of DNA degradation and the nature of the resulting products (fragments) should be taken into account.     

精炼塔尔油在磷酸盐浮选中的应用及QCM-D吸附研究

对Georgia-Pacific公司新开发的精炼塔尔油捕收剂GP193G75在佛罗里达CF Industries公司的磷酸盐浮选中应用效果进行了研究.采用具有测定能量耗散功能的石英晶体微天平(QCM-D)研究了GP193G75在羟基磷灰石(HAP)表面的吸附过程,并与油酸钠和CF Industries公司目前所用的药剂粗塔尔油脂肪酸PR1进行了比较.考察了捕收剂用量、pH值、柴油用量和浮选时间等参数对GP193G75浮选效果的影响.结果表明,当pH值为10,捕收剂用量为0.45kg·t^-1,且与柴油用量的比例为9∶8时,GP193G75的正浮选P₂O₅回收率最高可达到91.7%.QCM-D测定结果显示,GP193G75与油酸钠有相似的吸附过程,但GP193G75比油酸钠更易于且更快在羟基磷灰石表面吸附.在相同条件下,与PR1相比,GP193G75形成的吸附层密度更大,而且吸附更牢固,因此可以使羟基磷灰石表面的疏水性更强,从而得到较高的浮选效果.     

Clinical and histologic observation of replacement of biphasic calcium phosphate by bone tissue in monkeys

Biphasic calcium phosphate, consisting of beta-tricalcium phosphate and hydroxyapatite, was implanted in wide and deep periodontal osseous defects of monkeys in combination with the guided tissue regeneration technique. After 12 weeks, sites treated with a combination of biphasic calcium phosphate and guided tissue regeneration maintained the shape of the ridge, but both guided tissue regeneration and control sites (untreated) showed extreme resorption. A histopathologic investigation revealed that numerous macrophages contained small particles of ceramic within their vesicles and the active bone replacement occurred from the surrounding bone. Biphasic calcium phosphate has osteoconductive potential and this potential may be related to degradation by macrophage phagocytosis.     

Preparation and physical characteristics of a lithium-beryllium-substituted fluorapatite

A lithium-beryllium-substituted fluorapatite, Li_0.50Be_0.25Ca_4.50(PO₄)₃F, has been prepared by means of a high-temperature reaction between lithium beryllium fluoride, Li₂BeF₄, and tricalcium phosphate, Ca₃(PO₄)₂. This material has potential application as a waste form for radioactive and toxic fluoride salts. Monitoring of the reaction progress by differential scanning calorimetry indicated that the reaction was initiated by melting of the fluoride salt and that it was fast and complete. While reactive sintering of lithium beryllium fluoride with tricalcium phosphate led to a rather porous product, melting of the reactants with subsequent solidification readily produced a substituted fluorapatite with a near-theoretical bulk density.     

Setting reaction and hardening of an apatitic calcium phosphate cement

The combination of self-setting and biocompatibility makes calcium phosphate cements potentially useful materials for a variety of dental applications. The objective of this study was to investigate the setting and hardening mechanisms of a cement-type reaction leading to the formation of calcium-deficient hydroxyapatite at low temperature. Reactants used were alpha-tricalcium phosphate containing 17 wt% beta-tricalcium phosphate, and 2 wt% of precipitated hydroxyapatite as solid phase and an aqueous solution 2.5 wt% of disodium hydrogen phosphate as liquid phase. The transformation of the mixture was stopped at selected times by a freeze-drying techniques, so that the cement properties at various stages could be studied by means of x-ray diffraction, infrared spectroscopy, and scanning electron microscopy. Also, the compressive strength of the cement was measured as a function of time. The results showed that: (1) the cement setting was the result of the alpha-tricalcium phosphate hydrolysis, giving as a product calcium-deficient hydroxyapatite, while beta-tricalcium phosphate did not participate in the reaction; (2) the extent of conversion of alpha-TCP was nearly 80% after 24 hr; (3) both the extent of conversion and the compressive strength increased initially linearly with time, subsequently reaching a saturation level, with a strong correlation observed between them, indicating that the microstructural changes taking place as the setting reaction proceeded were responsible for the mechanical behavior of the cement; and (4) the microstructure of the set cement consisted of clusters of big plates with radial or parallel orientations in a matrix of small plate-like crystals.