Heterogeneous fluoridated apatites synthesized with a three-step fluoride supply system

Two types of heterogeneous fluoridated apatite, H-F-H and F-H-F, were synthesized by supplying fluoride during the middle half (H-F-H) or initial and final quarters (F-H-F) of the experimental period. Although X-ray diffraction patterns and SEM photographs of both H-F-H and F-H-F-type apatites were not significantly different, high-resolution transmission electron microscopy showed quite different features; H-F-H-type apatite crystals were elongated hexagons, while those of F-H-F-type apatite were rather wider hexagons with electron damage in three-quarters of the inner core. These results supported the previous speculations on the two different types of heterogeneous fluoridated hydroxyapatites synthesized with fluoride concentrations stoichiometrically equivalent to that of fluorapatite: hydroxyapatite covered with fluorapatite and fluorapatite covered with hydroxyapatite. F-H-F-type apatite was less soluble than that of H-F-H-type apatite.     

Importance of intrinsic calf vasodilator capacity in determining distribution of skeletal muscle perfusion during supine bicycle exercise in patients with left ventricular dysfunction

Although there is interest in forming synthetic analogs of hard tissues at physiologic temperature, significant gaps in knowledge exist with respect to the mechanisms by which precursor solids convert to apatites and also with respect to the apatite compositions that may be formed. In this study calcium-deficient HAp [Ca9(HPO4)(PO4)5OH] was prepared by hydrolysis of tricalcium phosphate (TCP), alpha-Ca3(PO4)2. The kinetics of HAp formation were studied as a function of temperature by isothermal calorimetry. TCP hydrolyzed completely within about 12 h, and the hydrolysis reaction evolved 133 kJ/mol of HAp formed. Although the kinetics of hydrolysis exhibited a strong temperature dependence, the mechanistic path taken appeared independent of temperature. The fluoridation of hydroxyapatite compositions having Ca/P ratios higher than 1.59 previously has been investigated. However, little work has been done on the fluoridation of more calcium-deficient hydroxyapatite. Ca9(HPO4)(PO4)5OH was formed at temperatures between 37.4 degrees and 55 degrees C to vary its morphology. These preparations then were reacted in NaF solution and the kinetics of fluoride incorporation studied. Solution chemical analyses were used to determine the amounts of fluoride incorporated. The extent of hydroxyl replacement by fluoride ranged from 17 to 72% and correlated with the surface area of the parent HAp.     

Oral health profile of schoolchildren, mothers and schoolteachers in Zanzibar

The piped water of Kuopio, Finland, was fluoridated in 1959. Owing to strong opposition by different civic groups, water fluoridation was stopped at the end of 1992. OBJECTIVES: The aim of this study was to examine the consequences of the discontinuation on dental health. METHODS: In 1992 and 1995, independent random samples of all children aged 6, 9, 12 and 15 years were drawn from Kuopio and Jyv?skyl?, a nearby low fluoride town whose distribution of demographic and socio-economic characteristics was fairly similar to Kuopio's. The total number of subjects examined was 550 in 1992 and 1198 in 1995. Caries was registered clinically and radiographically by the same two calibrated dentists in both towns. RESULTS: In 1992, the mean DMFS values were lower in the fluoridated town for the two older age groups, the percentage differences for 12- and 15-year-olds being 37% and 29%, respectively. For the two younger age groups no meaningful differences could be found. In 1995, the only difference with possible clinical significance was found in the 15-year-olds in favor of the fluoridated town (18%). In 1995, a decline in caries was seen in the two older age groups in the nonfluoridated town. In spite of discontinued water fluoridation, no indication of an increasing trend of caries could be found in Kuopio. The mean numbers of fluoride varnish and sealant applications decreased sharply in both towns between 1992 and 1995. In spite of that caries declined. CONCLUSIONS: These findings suggest that the decline of caries has little to do with professional preventive measures performed in dental clinics.     

The monitoring of the level of body fluoride intake in children participating in 3 milk fluoridation projects in Russia

In Russia three milk fluoridation projects have been implemented since 1994 (cities Smolensk, Voronezh and Maykop) covering more than 10,000 children living in low fluoride areas and having high risk of caries development both in temporary and permanent dentitions. Both preliminary and monitoring studies of fluoride excretion with urine and fluoride consumption were done. Total number of subjects--663 children 3-6-years of age attending kindergartens in these three cities; 2602 urine samples were collected, twice analyzed for fluoride content and processed in accordance with the method approved by the Russian Ministry of Health. 24-month monitoring of milk fluoridation projects in Russia did really show and confirm three main facts: the concentration of fluoride 2.5 mg/l in F-milk products for children 2-6 year-olds in low fluoride areas of Russia is really optimal concentration when daily milk consumption is about 200 ml; there is no such phenomena as detectable accumulation of metabolic fluoride under physiological conditions even after 2 years of regular fluoridated milk consumption; developed technique of fluoride consumption determination proved to be a very useful tool for planning and monitoring preventive programmes based on systemic use of fluoride.     

Caries prevention

It is apparent that the use of fluoride in multiple measures has a significant impact upon the prevention of dental caries. These measures involve public health benefits of water fluoridation, professional fluoride treatments in the dental office, and the home use of effective fluoridated dentifrices, with the use of fluoride rinses and gels as adjuncts when needed. In many clinical situations, professional judgment is required to identify the most appropriate treatment measures to address the needs of individual patients.     

Fluoride profiles in dental calculus from Japanese, Chinese and British residents

Whether the fluoride concentrations and profiles differ in human dental calculus obtained from different countries was investigated. A total of 203 dental calculus deposits on 203 permanent teeth from residents (mean age, 52.1 years) of Nagoya (Japan), Shanghai (China), Leeds (Great Britain) and the Wuhan mountainous area (China, fluoridated area) were analysed. An abrasive microsampling procedure was used to examine fluoride distribution. There were five types of fluoride profiles in dental calculus in each area/country (designated types L, J, U, T, W). In supragingival calculus, type L (highest in the outermost layers) and type J (highest in the innermost layers) both had significantly higher values than type U (high in the surface and innermost layers) but were relatively identical. In subgingival calculus, type W (high in the outermost, mid and innermost layers) was characteristics. Calculus from the Wuhan mountainous area (fluoridated) had the highest fluoride concentration, followed by Leeds (non-fluoridated), and Nagoya and Shanghai (non-fluoridated) calculus had the lowest. Fluoride concentrations in supragingival calculus were higher in teeth extracted because of periodontal diseases than dental caries. It is concluded that fluoride concentrations and distribution in dental calculus differ from country to country, probably due to different fluoride environments.     

Sol-Gel Derived Nanocrystalline Fluoridated Hydroxyapatite Powders and Nanostructured Coatings for Tissue Engineering Applications

Nanocrystalline fluoridated hydroxyapatite (FHA) powders and coatings with a chemical composition of Ca₁₀(PO₄)₆OH_2–x F _x (where x values were selected equal to 0.0 ,0.5, 1.0, 1.5, and 2.0) were prepared through a modified simple sol-gel technique in comparison with conventional alkoxide-based sol-gel route. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), fourier transform infrared (FTIR) spectroscopy, pF-meter with a fluorine-sensitive electrode, and inductively coupled plasma–optical emission spectroscopy (ICP-OES) analysis techniques were employed in order to evaluate phase composition, particle size distribution, morphology, functional groups, fluorine content, and purity of prepared FHA nanopowders, respectively. SEM analysis was used to study the surface morphology and cross section of the FHA coatings, deposited on 316L stainless steel substrate. Results indicated that single-phase and homogeneous FHA nanopowders with carbonate peaks in the FTIR spectrum were synthesized through the modified sol-gel technique. TEM analysis revealed that fluorapatite (FA) powder was composed of nanosized particles, ~25 nm in size, with polyhedron shape and straight corners. In the modified sol-gel technique, polymerization and gelation kinetic of the sol were significantly improved without any need to use additives or pH control. Uniform, dense, well-adhered, and compacted FHA coatings were formed on the 316L stainless steel substrate after 24 hours of aging.     

The effect of drinking water fluoridation on the natural course of hearing in patients with otosclerosis

The effect of drinking water fluoridation on the course of hearing of non-operated otosclerotic ears was assessed in an area where the natural waters have a very low fluoride content. The study population consisted of 150 patients with surgically proven otosclerosis. Patients having an additional known cause of hearing loss were excluded from the study. Every patient had a follow-up of at least 5 years, the mean follow-up period being 8.8 years. At last follow-up examination, air conduction thresholds of patients drinking fluoridated tap water were found to be significantly better than those of patients drinking fluoride-poor water, likewise there were significant differences in bone conduction thresholds at 1, 2, and 4 kHz. It was concluded that drinking water fluoridation has a beneficial effect on hearing levels of non-operated otosclerotic ears.     

Synthesis and Characterization of Arsenate/Phosphate Fluorapatite Solid Solutions

A series of arsenate-substituted fluorapatite (FA) was directly prepared through the aqueous precipitation method. Characterization studies from elemental analysis, X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, and scanning electron microscopy (SEM) have confirmed the formation of the arsenate/phosphate fluorapatite solid solutions (AsPFAs), i.e., Ca₅(P _x As_1–x O₄)₃F, which had a single phase of apatite structure. The analysis of the measurements indicated that the unit cell a and c parameters did not vary smoothly with the degree of substitution, as expected by Vegard’s law. The morphology was dependent of the arsenate/phosphate ratio. The solids with high As/(P + As) molar ratio of 0.29 to 1.0 were typically needlelike crystals, which developed along the c-axis; all apatites with the As/(P + As) molar ratio of <0.09 were large tabular. The phosphate peaks and the arsenate peaks in the FT-IR spectra were observed for the entire series of substituted apatites. The area of the phosphate peak was gradually suppressed and that of the arsenate peak increased as the proportion of the arsenate increased.     

Functional skills after rehabilitation for patients with spinal cord injury

The purpose of this case-control study was to determine the association between very-mild-to-moderate enamel fluorosis and exposure during early childhood to fluoridated water, mainly through ingestion of powdered milk. Analysis was performed on 136 residents of the optimally fluoridated community of San Felipe in the Chilean Fifth Region, who were categorised into one of three groups according to their age when water fluoridation was introduced in 1986: Group I was born after 1986; Group II was 16-24 months old in 1986; and Group III was >24 months of age. The case and control subjects were selected on the basis of a clinical examination given in July 1996. Dean's scoring system was used to determine fluorosis status. Risk factor exposure was ascertained by a questionnaire used in interviews with mothers of participating children. Logistic regression analysis, after adjustment for confounding variables, revealed that very-mild-to-moderate enamel fluorosis of permanent central maxillary incisors (CMI) was strongly associated both with the age of the subjects when water fluoridation began and with breast-feeding duration for children belonging to Group I. Subjects in Group I were 20.44 times more likely (95% CI: 5.00-93.48) to develop CMI fluorosis than children who were older than 24 months (Group III) when fluoridation began. Subjects who were between 16 and 24 months old when water fluoridation began were 4.15 times more likely (95% CI: 1.05-16.43) to have CMI fluorosis than children older than 24 months. An inverse association was found with breastfeeding duration (OR=0.86, 95% CI: 0.75-0.98) among Group I subjects but not in Groups II and III. Results obtained suggest that the current fluoride concentration in drinking water may be contributing to fluorosis. Further studies will be necessary to determine the relative competing risks of dental fluorosis and dental caries in Chilean children in order to establish the most appropriate water fluoridation level in Chile.     

Caries prevalence and salt fluoridation among 9-year-old schoolchildren in Strasbourg, France

The 9-year-old group (236 children) of an epidemiological study carried out in 1991 in Strasbourg on children aged 6 to 15 years was selected with the aim of determining if the caries prevalence reduction observed could be related to the use of salt fluoridation (FS) introduced in France in 1987. From these 236 children, 143 answered a questionnaire which showed that 36 of them were fluoridated salt users and 107 were not. The dft index was significantly lower in the FS consumers which showed 35.5% dft reduction compared to the non-FS-consuming children. When using the Generalized Linear Model, this reduction was significant (P = 0.03). Although lower in the FS group, the DMFT and DMFS indices showed no statistical significant difference. It appeared that 72.2% of the users took simultaneously fluoride tablets but no dental fluorosis was observed. The use of fluoride tablets had a significant effect on the DMFS (P = 10(-2)). The children who consumed FS used more frequently fluoridated mouthrinses (P = 10(-3)) and had more frequent professional application of fluoridated gel and varnishes than non-consumers (P = 0.02). The DMFS index increased with the number of meals (P = 10(-6)), which was the most significant variable entered into the Generalized Linear Model. The children who brushed their teeth once a day had a DMFS value 2.6 times higher than those who brushed regularly three times a day (P = 10(-3)). The DMFS value was 4.4 times higher among the children who brushed their teeth irregularly when compared with those who brushed three times a day (P = 10(-2)).     

Recognition of a non-standard base pair by thermostable DNA polymerases

Fluoride is a potent preventive agent of caries. It acts at two levels: local and systemic. At the local level it prevents the surface demineralisation of enamel by strengthening the superficial layers, and inhibiting the local bacterial activity. At the systemic level it improves the resistance of the enamel by forming with calcium, fluorapatite which is stronger than hydroxyapatite. Main sources are naturally fluorinated water, artificially enriched water, fluorinated salt, and fluoride medication. Recommended mean daily intake is 0.05 mg/kg, the risk of dental fluorosis occurring when daily intake exceeds 1 mg/kg. The large benefits of regular fluoride supplementation on children dental health must not live down the risk of dental fluorosis resulting from over administration. Therefore when prescribing fluoride to a child, the practitioner must carefully examine his/her possible other fluoride sources.     

低C、O含量氟化稀土的制备工艺研究

以氯化钇为原料,采用碳酸氢铵制备的碳酸盐,通过复合氟化剂转化生成氟化钇,经过烘干和粒子整合之后得到无水氟化钇。考察了碳酸盐晶体质量、复合氟化剂的配比和浓度、反应温度、稀土浓度、pH值等对稀土氟化物中C、O含量的影响。结果表明:在选定条件下,用复合氟化剂将碳酸钇晶体转化生成氟化稀土,可明显降低氟化稀土中C、O的含量。     

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.     

Hydroxyapatite and Fluoridated Hydroxyapatite Coatings and Their Effects on Commercially Pure Magnesium Corrosion Response

Dicalcium-phosphate dehydrate, converted to hydroxyapatite by post-treatment in sodium hydroxide, and fluoridated hydroxyapatite were electrodeposited on commercially pure magnesium substrates that were pretreated with sodium hydroxide. The coatings’ crystalline structure, thickness, scratch hardness, morphology and chemical composition were characterised by GIXRD, microscratch testing platform, SEM and EDS. The results showed that the apatite coatings had highly crystalline structure, acceptable scratch hardness, flake-like morphology and acceptable chemical composition. Corrosion behaviour of the uncoated and coated substrates was investigated by potentiodynamic polarization and immersion tests in simulated body fluid. The coated substrates, especially fluoridated hydroxyapatite coated substrates, showed significantly lower corrosion rates compared to uncoated substrates. The polarisation curves showed that the coatings hindered anodic reactions; the corrosion potentials were shifted toward less-negative. In general, this study concluded that the corrosion rate of commercially pure magnesium could be significantly decreased to be a candidate for future cost-effective biodegradable orthopaedic implants.     

Apoptosis: a role in skin aging?

OBJECTIVE: This paper reports findings for dental caries and dental fluorosis in 8-10- and 13-16-year-old schoolchildren who were lifelong residents of communities having either naturally occurring low (Broken Bow and Holdrege, NE; < 0.3 ppm) or optimal (Kewanee, IL; 1 ppm) levels of fluoride in drinking water. METHODS: Findings are reported for participants who received both dental caries and dental fluorosis examinations (n = 495). The DMFS and TSIF indices, respectively, were used to assess dental caries and dental fluorosis. RESULTS: The mean DMFS score adjusted for age, sealant presence, and fluoride use was significantly lower in Kewanee (1.8) than was the adjusted mean caries score in either Holdrege (2.9) or Broken Bow (3.6). Adjusted mean DMFS scores in Broken Bow and Holdrege were not statistically different. The mean percent of fluorosed tooth surfaces per person, adjusted for age and use of dietary fluoride supplements, was similar in the three communities (approximately 15%); more than 80 percent of tooth surfaces in all participants were fluorosis-free. CONCLUSIONS: Findings from the present study suggest that water fluoridation still is beneficial and that dental sealants can play a significant role in preventing dental caries. In addition, findings from this survey appear to support the premise that the difference in dental fluorosis prevalence between fluoridated and nonfluoridated communities has narrowed considerably in recent years.     

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.     

Hydrolysis of CaHPO4 in sodium fluoride solutions at 37.4 degrees C

A possible chemical process occurring during caries reversal is conversion of acidic calcium phosphates to apatite. The role of fluoride in this process is of particular interest. The effects of fluoride on the rate of CaHPO4 hydrolysis at 37.4 degrees C were studied by a multimethod analysis involving X-ray diffraction, analyses of variations in solution chemistry, and observation of microstructural evolution. Hydrolysis in low NaF concentrations results in the formation of discrete fluorapatite crystals on the surfaces of the CaHPO4 crystallites. At CaHPO4/NaF molar ratios from approximately 9:1 to 10:2, fluorapatite formed in approximately 3 h as the only crystalline product and complete hydrolysis of CaHPO4 occurred; a pH value as low as 2.4 was attained with solution species being predominantly sodium phosphate. At NaF concentrations beyond those which result in pH minima, fluorapatite and CaF2 are the crystalline products. At 0.6 M NaF, pseudomorphs composed of fluorapatite and CaF2 crystals form without developing morphologies characteristic of individual fluorapatite and CaF2 crystals. CaHPO2 can hydrolyze completely to fluorapatite and CaF2 within a few hours depending on NaF concentration and liquid-to-solids ratio.     

Combined Raman and SEM study on CaF2 formed on/in enamel by APF treatments

Raman spectra containing the distinct band at 322 cm-1 due to CaF2 or CaF2-like material formed in/on fluoridated bovine enamel were recorded using a micro-Raman spectrograph. Due to increasing levels of background fluorescence with increasing thickness of enamel, the Raman measurements were carried out on thin regions of wedged enamel sections. The distribution of the CaF2 or CaF2-like material was estimated using a simple model. The results indicate that 1/3 of the total CaF2 was concentrated within the narrow depth < 2 microns with high CaF2 concentrations (> 10 wt%), and that the majority of the CaF2 was distributed over the depths up to 26 microns (1 wt% CaF2). SEM observations on fractured fluoridated enamel confirmed that morphological changes were present in the depth range comparable to that of the high CaF2 concentration region expected from the Raman analysis. In deeper regions where lower concentration (< 10%) but a large amount of CaF2 was still expected, the SEM images failed to distinguish between the normal and fluoridated enamel. After KOH treatment, the Raman spectra did not show evidence of the CaF2 peak and the SEM micrographs also confirmed the removal of globules. The peak position of the Raman band of the CaF2 formed by the fluoridation was identical to that of pure CaF2. However, the linewidth was 23 cm-1 (FWHM) and a factor of 2 broader than that of pure CaF2 (12 cm-1). This implies that the lattice dynamics of the CaF2 formed by fluoridation is different from of pure CaF2, and that the material formed is 'CaF2-like' or 'disordered CaF2'.     

稀土氧化物氟化反应过程的研究

本文对Ｙ２Ｏ３与无水ＨＦ气体的反应过程进行了热力学计算，并根据实验结果，计算了该反应在３００～７００℃的活化能，研究了氟化反应时间、温度等因素对氟化反应的影响，同时对氟化产物进行了Ｘ射线衍射分析，探讨了氟化反应过程的机理，为合理确定制备高质量稀土氟化物的工艺条件提供了理论依据。