Functional role of inorganic trace elements in dentin apatite tissue-part III: Se, F, Ag, and B.

Dentin hydroxyapatite possesses a unique versatile structure which allows it to undergo ionic substitutions. Trace elements play pivotal roles within the oral cavity, especially in dentin apatite tissue. Therefore, it is critical to explore the role of these elements in dentin apatite structure. The roles of other inorganic elements in dentin apatite were discussed in part I (Mg, Sr, Zn, and Fe) and part II (Cu, Mn, Si, and Li) of these series. In the last part of the review series, the role of selenium, fluorine, silver, and boron in the regulation of dentin apatite structure and function was discussed. We evaluated how these elements affect the overall size, morphology, and crystallinity of dentin apatite crystals. Moreover, we investigated the importance of these elements in regulating the solubility of dentin apatite. An electronic search was performed on the role of these trace elements in dentin apatite from January 2010 to January 2022. The concentration of selenium in teeth has been explored only recently, particularly its incorporation into dentin apatite. Silver nanomaterials inhibit the growth of cariogenic microorganisms as well as arrest the degradation of collagen. Fluorine was found to have important roles in dentin remineralization and dentinal tubule occlusion, making it widely used for hydroxyapatite doping. Boron is critical for mineralized tissues like bone, dentin, and enamel, but its exact role in dentin apatite is unknown. Therefore, understanding the impact of these elements on dentin apatite is potentially transformative, as it may help to fill a significant knowledge gap in teeth mechanics.

Characterization and analyses of acid-extractable and leached trace elements in dental cements.

AIMS: Determination of the elemental constitution and investigation of the total and leachable arsenic, chromium and lead in Portland cement, pure tricalcium silicate, Biodentine, Bioaggregate and mineral trioxide aggregate (MTA) Angelus. METHODOLOGY: The chemical composition of Portland cement, MTA Angelus, tricalcium silicate cement, Biodentine and Bioaggregate was determined using X-ray fluorescence (XRF). Measurements of arsenic, lead and chromium were taken with inductively coupled plasma-mass spectrometry (ICP-MS), following acid digestion on the hydrated material and on leachates of cements soaked in Hank's balanced salt solution (HBSS). RESULTS: All the cements investigated had a similar oxide composition with the main oxide being calcium and silicon oxide. Both the Portland cement and MTA Angelus had an additional aluminium oxide. The dental cements included a radiopacifying material. All the materials tested had higher acid-extractable arsenic content than the level set by ISO 9917-1 (2007) and an acceptable level of lead. Regardless these high levels of trace elements present in the materials, the leaching in HBSS was minimal for all the dental material tested in contrast to the high levels displayed by Portland cement. CONCLUSIONS: Dental materials based on tricalcium silicate cement and MTA Angelus release minimal quantities of trace elements when in contact with simulated body fluids. The results of acid extraction could be affected by nonspecific matrix effects by the cement.

Phosphate dynamics in an urban sewer: a case study of Nancy, France.

The nature of phosphate phases present in suspended matter, biofilm, and sediment of Greater Nancy sewer system was investigated over a period of two years. The phosphate speciation was determined by two approaches: a direct identification of phosphorus mineral phases was conducted by Transmission Electron Microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS), whereas a chemical extraction of samples provided an estimate of phosphorus pools defined by the fractionation scheme. Quantitative analysis of 1340 individual particles by TEM-EDXS allowed to draw a picture of phosphate species distributions along the sewer system and over time. Amorphous Ca-phosphates (brushite, whitlockite, octacalcium phosphate, Mg-brushite, hydroxyapatite and carbapatite) were ubiquitous although brushite dominated upstream, and octacalcium phosphate and apatite prevailed downstream and in sediments. Al-Ca-phosphate minerals such as foggite, bearthite, gatumbaite, and crandallite appeared downstream and in biofilms. Ca-phosphate phase assemblages in the different locations of the sewer system were dependent on phase transformations from brushite to hydroxyapatite that were shown to be kinetically driven. The restriction of Al-Ca-phosphates to downstream of the sewer system was most probably related to the lower pHs measured at these sites. The pH dependency was confirmed by stability calculations. Chemical extractions were not reliable. TEM examination of extraction residues revealed the presence of neoformed Al-Ca-phosphate species that invalidated the fractionation scheme. Nonetheless, it confirmed that phosphate phases may undergo significant geochemical changes over a short time scale.

Solid state 31phosphorus nuclear magnetic resonance of iron-, manganese-, and copper-containing synthetic hydroxyapatites.

The incorporation of micronutrients into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in the National Aeronautics and Space Administration's (NASA's) Advanced Life Support (ALS) program for Lunar or Martian outposts. Solid state 31P nuclear magnetic resonance (NMR) was utilized to examine the paramagnetic effects of Fe3+, Mn2+, and Cu2+ to determine if they were incorporated into the SHA structure. Separate Fe3+, Mn2+, and Cu2+ containing SHA materials along with a transition metal free SHA (pure-SHA) were synthesized using a precipitation method. The proximity (<1 nm) of the transition metals to the 31P nuclei of SHA were apparent when comparing the integrated 31P signal intensities of the pure-SHA (87 arbitrary units g-1) with the Fe-, Mn-, and Cu-SHA materials (37-71 arbitrary units g-1). The lower integrated 31P signal intensities of the Fe-, Mn-, and Cu-SHA materials relative to the pure-SHA suggested that Fe3+, Mn2+, and Cu2+ were incorporated in the SHA structure. Further support for Fe3+, Mn2+, and Cu2+ incorporation was demonstrated by the reduced spin-lattice relaxation constants of the Fe-, Mn-, and Cu-SHA materials (T'=0.075-0.434s) relative to pure-SHA (T1=58.4s). Inversion recovery spectra indicated that Fe3+, Mn2+, and Cu2+ were not homogeneously distributed about the 31P nuclei in the SHA structure. Extraction with diethylene-triamine-penta-acetic acid (DTPA) suggested that between 50 and 80% of the total starting metal concentrations were incorporated in the SHA structure. Iron-, Mn-, and Cu-containing SHA are potential slow release sources of Fe, Mn, and Cu in the ALS cropping system.

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.

The use of high-phosphorus supplements to inhibit dental enamel demineralisation by ice lollies.

Five new formulations of water ice lollies with a high-phosphorus (low Ca) supplementation ratio were tested for their erosiveness of dental enamel or hydroxylapatite in vitro. Compared with the basic unsupplemented lolly, all five formulations that had been prepared with additional calcium and phosphorus, but in a low Ca/P ratio, as potential inhibitors of demineralisation, were associated with significantly less attack on dental mineral, as measured by the dissolution of calcium and phosphorus.

Stoichiometry of fluoride release from fluorhydroxyapatite during acid dissolution.

Release of F from fluorhydroxyapatite (FHAp) during acid dissolution was studied to validate the use of this mineral as a plaque reservoir of F. FHAp minerals having a wide range of F concentrations were synthesised by aqueous precipitation, and samples repeatedly exposed to 50 mM lactic acid solution, pH 4.5, or similar lactic/acetic/formic acid mixtures, until dissolution was complete. While the Ca/P ratio in solution remained relatively constant and close to the ratio in the solid, the solution F/Ca ratio invariably changed during dissolution. During initial stages the F/Ca solution ratio was lower than in the solid but rose to reach a plateau higher than in the solid as dissolution progressed, an effect that was more pronounced with low-F FHAp. With these minerals the plateau F/Ca level never reached 0.2, suggesting that a F-enriched FHAp rather than pure fluorapatite precipitates during dissolution. It is concluded that a high-F FHAp mineral would best serve as an apatitic plaque reservoir of F.

Morphogenesis of calcification in porcine bioprosthesis: insight from high resolution electron microscopic investigation at molecular and atomic resolution.

High resolution electron microscopy (HREM) coupled with energy dispersive X-ray microanalysis were used to investigate the morphogenesis of calcification in 28 explanted porcine bioprosthetic heart valves. Different morphology and compositions of calcific deposits were consistently observed in various valvular structures of all explanted porcine bioprostheses. The most common forms of calcific deposits were present as spherical particles and needle-shaped structures. HREM investigation of spherical particles of calcium phosphate revealed very fine electron-dense dots about 0.3-1.0 nm in diameter which were packed to form sphere-like clusters of about 2.0-3.5 nm in diameter in the particles. HREM observations of the microneedle-shaped structures even as small as 1.9 nm in thickness could identify the lattice fringes with center-to-center spacings of about 0.8-0.9 nm. Energy dispersive X-ray microanalysis defined the components of needle-shaped calcification as calcium and phosphorus in a ratio typical of hydroxyapatite crystals. The calcific deposits in the collagen tissue have been shown to be at discrete sites on or in the collagen fibrils as the spherical particles or homogeneous electron-dense masses. Based on HREM observations of different types of morphogenesis of calcification it is suggested that chemical processes of calcification accompanying the deposition of calcium in the implanted bioprosthetic heart valves are specific to each substrate system. The formation of amorphous calcium phosphate precursors and direct deposition of microcrystalline hydroxyapatites are considered to be the primary mechanisms of calcification occurring in implanted porcine bioprostheses.

Physical, chemical, and mineralogical characterization of carbonate-hydroxyapatite concretions of the human pineal gland.

Physical, chemical, and mineralogical investigations of mineral concretions found in the human pineal gland were performed by means of optical microscopy and modern techniques of analytical electron microscopy and x-ray powder diffraction (OM,SEM + EDS,TEM + EDS,XRD). The mineral concretions were found to be nano-crystalline carbonate-hydroxyapatite with a mean Ca/P molar ratio equal to 1.65, very close to the theoretical value of 1.67. TEM and XRD showed that this is the only inorganic phase present in the concretions without the presence of amorphous phosphate as precursor. SEM and EDS, performed on cross-sectioned samples, showed a concentric layered distribution of the inorganic phase permeated by organic matter, within the concretions, with a slight increasing of the Ca/P molar ratio in their internal part.

Notes on the dissolution of human dental enamel in dilute acid solutions at high solid/solution ratio.

The aim of the present study was to elucidate the nature of the relationship between enamel apatite and lesion fluid during demineralization. Powdered enamel in samples of 1.0 g was suspended in 3 ml of 10, 30, 50, or 70 mmol/l HCl under gentle agitation for up to 24 h at 20 degrees C. After 20 min and 24 h, pH and the concentrations of calcium and phosphate were determined and the degree of saturation with respect to various calcium phosphates calculated. The experiments were replicated 15 times using the same enamel samples. Twenty minutes after the start of dissolution, both pH and concentrations of calcium and phosphate had increased, and the solution became supersaturated with respect to hydroxyapatite, and in some runs also with respect to brushite. During the subsequent 23 h and 40 min, pH continued to increase, despite the supersaturation with respect to apatite, whilst the concentrations of calcium and phosphate decreased due to formation of apatite and, occasionally, brushite mineral. The data indicated that release of carbonate from enamel and its conversion to H2CO3 caused the increase in pH and thus, played a major role in the dissolution-reprecipitation process.

Calcification inhibitors in human ligamentum flavum.

To examine the presence of substances which inhibit calcification in human ligamentum flavum, the inhibitory effect of an Na2HPO4 extract of the flavum was determined in terms of the in vitro calcium uptake of the ligamentum flavum matrix. Additionally, grafts of extracted and non-extracted dry ligamentum flavum matrices were transplanted into the dorsal muscles of rats, and calcification in the grafts was examined radiologically and histochemically. In order to determine if component cells of human ligamentum flavum produce calcification inhibitors, ligamentum flavum cells were cultured, and the crystal inhibitor activity of the culture medium was measured by a seed test which used hydroxyapatite as the nucleus of precipitation. The calcification reaction system demonstrated that the ligamentum flavum extract contains an inhibitory factor for calcium uptake by the ligamentum flavum matrix. The seed test revealed that human ligamentum flavum cells produce calcification inhibitor activity.

[Diagnosis of hydroxyapatite disease]. / Beitrag zur Diagnostik der Hydroxyapatitkrankheit.

The possibility of detecting hydroxyapatite crystals in synovia in a routine setting has been studied prospectively. Coloration of the crystals with alizarin red-S was the method of choice. The diagnostic results were markedly improved by simultaneous observation of a freshly prepared positive control synovia.

FT-IR microscopic mappings of early mineralization in chick limb bud mesenchymal cell cultures.

Chick limb bud mesenchymal cells differentiate into chondrocytes and form a cartilaginous matrix in culture. In this study, the mineral formed in different areas within cultures supplemented with 4 mM inorganic phosphate, or 2.5, 5.0, and 10 mM beta-glycerophosphate (beta GP), was characterized by Fourier-transform infrared (FT-IR) microscopy. The relative mineral-to-matrix ratios, and distribution of crystal sizes at specific locations throughout the matrix were measured from day 14 to day 30. The only mineral phase detected was a poorly crystalline apatite. Cultures receiving 4 mM inorganic phosphate had smaller crystals which were less randomly distributed around the cartilage nodules than those in the beta GP-treated cultures. beta GP-induced mineral consisted of larger, more perfect apatite crystals. In cultures receiving 5 or 10 mM beta GP, the relative mineral-to-matrix ratios (calculated from the integrated intensities of the phosphate and amide I bands, respectively) were higher than in the cultures with 4 mM inorganic phosphate or in the in vivo calcified chick cartilage.

Effect of short-term hypomagnesemia on the chemical and mechanical properties of rat bone.

Magnesium is known to have an essential role in determining the properties of bone, but the way in which Mg exerts its actions remains unclear. Although long-term Mg deficiency is known to produce osteopenia, the effects of short-term Mg deficiency have not been established. To test the hypothesis that Mg deficiency results in an altered pattern of initial mineralization and concomitant altered bone properties, the radiographic, histologic, chemical, and mechanical properties of the bones of rats given a Mg-deficient diet were compared to those of rats pair-fed the same diet supplemented with Mg. Short-term Mg-deficiency in the diet of growing rats produced a significant decrease in both the trabecular bone volume and the mineral content of the newly formed metaphysis, a significant increase in the Ca:P ratio, and a slight, but significant increase in hydroxyapatite crystallite size and/or perfection in the metaphysis. Comparable, but not significant, trends were found in the diaphyses. Metaphyseal bone osteocalcin levels were reduced in the Mg-deficient rats and lipid was more easily extracted from their bones. No detectable alterations in radiographic microstructure were noted. Mechanically, a significant decrease in the maximum three-point bend strength of the femurs of Mg-deficient rats was observed. These data support the hypothesis that short-term Mg deficiency affects the pattern of bone mineral formation.

Nail-patella syndrome associated with mixed crystal deposition arthropathy.

This report describes a case of nail-patella syndrome in a woman with a strong family history who presented with effusions in her shoulder and knees. Microscopic examination of the shoulder fluid suggested the presence of calcium pyrophosphate dihydrate (CPPD) crystals, and examination of the knee fluid suggested both hydroxyapatite (HAP) and CPPD crystals. To our knowledge, the coexistence of these two conditions has not been reported in the past. Moreover, it brings up a new element regarding the inflammatory origin of the nail-patella syndrome.

Technical note: mineral deposits on Dacron bags during ruminal incubation.

Extensive DM contamination was found on Dacron bags that were incubated for prolonged periods of time in the rumen of steers fed alfalfa hay. The ash content of the contaminant was high, and most of it was acid-soluble X-ray analysis indicated the presence of hydroxylapatite and synthetic calcium magnesium phosphate or whitlockite. The contaminant appeared as a smooth coating on the Dacron fiber, suggesting that contamination was a gradual process rather than the result of entrapment of dislodged crystals from plant material. Contamination seemed to occur exponentially within the range of observations (0 to 42 d). Contamination also occurred in steers fed orchardgrass, although to a lesser extent than in steers fed alfalfa hay. The DM contamination was less than .04 g per bag (average bag weight was 1.2 g) during the first 10 d of incubation. However, correction for contamination might be required for studies involving longterm incubation or mineral digestion.

Examination by X-ray photoelectron spectroscopy of the adsorption of chlorhexidine on hydroxyapatite.

X-ray photoelectron spectroscopy (XPS) was used for determination of the effects of chlorhexidine (CHX) solutions (0.2% and 1% solutions of the digluconate salt) on the elemental composition of hydroxyapatite surfaces. So that the nature of the adsorbed species after they were washed with water could be identified, comparisons were made with reference spectra for CHX obtained from a CHX digluconate film and CHX dichloride powder. The XPS results clearly indicated the retention of CHX moieties, which could be ascertained from the spectra by the presence of N and Cl, features unique to CHX. The spectral envelopes were virtually identical to those obtained from the reference spectra. High-resolution C 1s spectra also gave support for the retention of CHX; however, the spectra differed from those of the CHX digluconate film in that no feature attributable to the C-OH of the gluconate anion was present, consistent with the view that the CHX cation remains behind to form an electrostatic bond with the phosphate groups of the hydroxyapatite. The N:Cl ratio for the washed samples was found to be higher than that for the reference samples and may be indicative of partial decomposition of the CHX. Decomposition was also seen to be induced by x-ray exposure. While the high-resolution spectra presented here do not directly address the controversy on the mechanism for the anti-plaque efficacy of CHX, they do provide the necessary basis for the application of XPS to future in vitro studies on the retention of CHX to dental surfaces.

In vitro formation of mineralized nodules by periodontal ligament cells from the rat.

The purposes of this study were to determine whether periodontal ligament (PDL) cells are capable of producing mineralized nodules in vitro and to analyze ultrastructural features of the nodules. Rat PDL cells were obtained from coagulum in the socket at 2 days after tooth extraction and cultured at confluence in standard medium containing Dulbecco's Modified Eagle's Medium supplemented with 10% FBS and antibiotics. To test mineralized nodule formation, cells were further cultured for an additional 3 weeks in the standard medium containing (1) ascorbic acid (50 micrograms/ml) and sodium beta-glycerophosphate (10 mM), (2) ascorbic acid, sodium beta-glycerophosphate, and dexamethasone (5 microM), or (3) ascorbic acid alone. Cells were then fixed in 2.5% glutaraldehyde, postfixed in 1% OsO4, and prepared for light and electron microscopy. Three-dimensional nodules containing mineralized matrices were formed only when the cells were cultured in the presence of ascorbic acid and dexamethasone. They were composed of multilayered fibroblasts (up to 13 layers), and highly organized collagen fibrils with 64 nm cross-banding patterns between the cell layers. The fibroblasts in the nodules exhibited an elongated shape with a high degree of cytoplasmic polarity throughout the nodule, and have the morphological features of PDL fibroblasts as seen in vivo. Mineral deposition with needle-like crystals was initiated on collagen fibrils located in intercellular spaces of the upper cell layers and became increasingly heavier towards the bottom half of the nodules. X-ray microanalysis and electron diffraction analysis confirmed that mineral deposition contained calcium and phosphate in the form of immature hydroxyapatite.(ABSTRACT TRUNCATED AT 250 WORDS)

Partial defluoridation of drinking water using fluorapatite precipitation.

Ion adsorption and ion exchange are two methods commonly used in small home units to treat drinking water to bring the fluoride concentration to within acceptable limits. However, the necessary flowthrough system is often difficult to arrange where there is no piped supply and gradual exhaustion of the active agent is not easily detected. In an attempt to overcome these problems a defluoridation method based on the precipitation of a sparingly soluble fluoride salt, fluorapatite, has been studied. Samples of simulated high-fluoride drinking waters, approximately 10 ppm F, were saturated with brushite, resulting in a state of supersaturation with respect to fluorapatite. Subsequent seeding with hydroxyapatite caused a lowering of the calcium, phosphate, and fluoride concentrations in solution, indicative of fluorapatite precipitation. Repeating the process had an additive effect. Bone char was a less effective seed than hydroxyapatite with water containing fluoride only, but was a more effective seed with simulated Kenyan borehole water containing additional salts. Sixty-minute brushite saturation and apatite seeding steps were generally more effective than 10-min steps. The results suggest that apatite coprecipitation may be a convenient low-technology way to defluoridate drinking water, although prior testing might be useful to ensure adequate removal of fluoride.