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Bacteria and pulpal reactions under silicate cement restorations.

Silicate cement was inserted in deep unlined cavities in 70 human teeth; 35 cavities were cleaned with an antibacterial cleanser, and the other 35 cavities in the contralateral teeth were treated with water spray only. In all teeth, invasion of bacteria from the tooth surface was prevented with a surface seal. Histologic examinations after 4 weeks revealed bacterial growth on dentinal walls in 9 of the uncleaned and in 2 cleaned cavities. Only in these 11 teeth was an inflammatory reaction seen in the pulp. Under eight cavities without bacterial growth and with silicate cement placed directly on an exposed pulp, no serious injury and no inflammatory reactions were observed. It was concluded that silicate cement per se does not seriously irritate the pulp. Infection of cavity walls should be avoided, not only by removing grinding debris and antibacterial cleansing, but also by use of a liner to prevent invasion of bacteria from the surface of the tooth.

Anti-Bacterial Agents↗

Aluminum silicate toxicity in cell cultures.

To assess the cytotoxicity of four clays containing an aluminum silicate--montmorillonite, bentonite, kaolinite and erionite--we used human umbilical vein endothelial, N1E-115 neuroblastoma, and ROC-1 oligodendroglial cells. Morphological examination, lactate dehydrogenase release and fatty acid release were used as indices of trauma. The clays were added in suspension to the cell cultures at concentrations of 0.1, 0.03 and 0.01 mg/ml of medium and the cells were incubated for 1, 6 and 24 h. The clays did not lyse ROC-1 and N1E-115 cells and did not cause a dose-dependent increase in fatty acid levels at 24 h. There were no significant increases in lactate dehydrogenase activity in N1E-115 neuroblastoma or ROC-1 oligodendroglial cells. In human umbilical vein endothelial cells, montmorillonite, kaolinite and bentonite caused a dose-dependent increase in fatty acids at 24 h. All three clays caused cell lysis. We postulate that the cytotoxicity of the clays containing an aluminum silicate towards endothelial cells may disrupt the blood-brain barrier in the affected areas, allowing the entry of the clay particle into the brain. Aluminum silicate clays caused a dose-dependent release of fatty acids in human umbilical vein endothelial cells. The clays also caused lysis of these cells. ROC-1 oligodendroglia and N1E-115 neuroblastoma cells were not lysed by the clays, suggesting that this is not a general phenomenon.

Aluminum Silicates↗

Cyclic silicate active site and stereochemical match for apatite nucleation on pseudowollastonite bioceramic-bone interfaces.

Hydroxyapatite (Ca5(PO4)3(OH)) forms on pseudowollastonite (psW) (alpha-CaSiO3) in vitro in simulated body fluid, human parotid saliva and cell-culture medium, and in vivo in implanted rat tibias. We used crystallographic constraints with ab initio molecular orbital calculations to identify the active site and reaction mechanism for heterogeneous nucleation of the earliest calcium phosphate oligomer/phase. The active site is the planar, cyclic, silicate trimer (Si3O9) on the (001) face of psW. The trimer has three silanol groups (>SiOH) arranged at 60 degrees from each other, providing a stereochemical match for O atoms bonded to Ca2+ on the (001) face of hydroxyapatite. Calcium phosphate nucleation is modeled in steps as hydrolysis of surface Ca-O bonds with leaching of Ca2+ into solution, protonation of the surface Si-O groups to form silanols, calcium sorption as an inner-sphere surface complex and, attachment of HPO4(2-). Our model explains the experimental solution and high resolution transmission electron microscopy data for epitaxial hydroxyapatite growth on psW in vitro and in vivo. We propose that the cyclic silicate trimer is the universal active site for heterogeneous, stereochemically promoted nucleation on silicate-based bioactive ceramics. A critical active site-density and a point of zero charge of the bioceramic less than physiological pH are required for bioactivity.

Aluminum↗

Modeling the competitive effect of phosphate, sulfate, silicate, and tungstate anions on the adsorption of molybdate onto goethite.

The mobility of Mo in soils and sediments depends on several factors including soil mineralogy and the presence of other oxyanions that compete with Mo for the adsorbent's retention sites. Batch experiments addressing Mo adsorption onto goethite were conducted with phosphate, sulfate, silicate, and tungstate as competing anions in order to produce competitive two anions adsorption envelopes, as well as competitive two anions adsorption isotherms. Tungstate and phosphate appear to be the strongest competitors of Mo for the adsorption sites of goethite, whereas little competitive effects were observed in the case of silicate and sulfate. Mo adsorption isotherm from a phosphate solution was similar to the one from a tungstate solution. The charge distribution multi-site complexation (CD-MUSIC) model was used to predict competitive adsorption between MoO(4)(2-) and other anions (i.e., phosphate, sulfate, silicate and tungstate) using model parameters obtained from the fitting of single ion adsorption envelopes. CD-MUSIC results strongly agree with the experimental adsorption envelopes of molybdate over the pH range from 3.5 to 10. Furthermore, CD-MUSIC prediction of the molybdate adsorption isotherm show a satisfactory fit of the experimental results. Modeling results suggest that the diprotonated monodentate complexes, FeOW(OH)(5)(-0.5) and FeOMo(OH)(5)(-0.5), were respectively the dominant complexes of adsorbed W and Mo on goethite 110 faces at low pH. The model suggests that Mo and W are retained mainly by the formation of monodentate complexes on the goethite surface. Our results indicate that surface complexation modeling may have applications in predicting competitive adsorption in more complex systems containing multiple competing ions.

Adsorption↗

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants.

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.

Calcium↗

Evaluation of cyclonic ash, commercial Na-silicates, lime and phosphoric acid for metal immobilisation purposes in contaminated soils in Flanders (Belgium).

In order to reduce the health risks associated with historically enriched metal smelting sites in Flanders (Belgium), the capacities of a non-beringite cyclonic ash and commercial Na-silicates to fix metals and create conditions to restore vegetation cover were evaluated and compared to lime and H(3)PO(4). All tested amendments reduced Ca(NO(3))(2)-extractable soil metal concentrations and reduced metal uptake in Agrostis capillaris seedlings. Sodium released by Na-silicates was possibly toxic to bean plants while an isotopic dilution technique revealed that metals were only weakly sorbed by silicates (i.e. reversible sorption). Cyclonic ash appeared more efficient than lime in both reducing oxidative stress in beans and Zn, Cu and Pb uptake in grasses. The metal fixing mechanism for both amendments appeared similar (i.e. irreversible fixation at constant pH), in contrast to H(3)PO(4) where at least part of the immobilised Cd was irreversibly fixed across a range of pH.

Adsorption↗

Selective adsorption of nonionic surfactant on hexagonal mesoporous silicates (HMSs) in the presence of ionic dyes.

Selective adsorption of alkylphenol polyethoxylates (APnEOs) from synthetic textile wastewater was investigated using hexagonal mesoporous silicates (HMSs). HMSs are synthetic silicate that have uniform mesopores, large surface areas and uniform surface functional groups. Five different types of HMSs were synthesized by surfactant-templating methods, and three of them were grafted with organic surface functional groups, i.e., n-octyldimethyl-, 3-aminopropyltriethoxy-, and 3-mercaptopropyl-groups. Titanium-substituted HMS was also made in the same way as HMS. Adsorption capacities and selectivities of these HMSs for APnEOs were investigated in batch adsorption experiments either in single-solute APnEO solutions or in mixed solutions with ionic dyes. Triton X-100 was used as a model APnEO and either Basic Yellow 1 or Acid Blue 45 was used as cationic or anionic dyes, respectively. All the HMSs except 3-aminopropyltriethoxy-grafted HMS had higher adsorption capacities of Triton X-100 than powdered activated carbon. HMS and Ti-HMS had the highest BET surface areas and mesopore volumes measured by the nitrogen adsorption method, and thereby the highest adsorption capacities for Triton X-100. Surface charge was the most important attractive force between HMSs and dyes. FT-IR spectra proved that hydrophilic HMSs adsorbed both Basic Yellow 1 and Acid Blue 45 by hydrogen bonding. Acid-base titration experiments revealed that all the HMSs except 3-aminopropyltriethoxy-grafted HMS were negatively charged at neutral pH, whereas PAC and 3-aminopropyltriethoxy-grafted HMS were positively charged. Due to negative surface charge, the anionic dye (Acid Blue 45) was not adsorbed on the four HMSs, which proves high selectivities of these HMSs for Triton X-100 over Acid Blue 45. On the contrary, a small amount of cationic dye (Basic Yellow 1) was adsorbed on all HMSs, but 3-aminopropyltriethoxy-grafted HMS showed the lowest adsorption capacity for Basic Yellow 1 due to positive surface charge. Unlike other silicate adsorbents, no surface solubilization was observed for all HMSs.

Adsorption↗

Dissolution of silicic acid from dusts of kaolin, mica and talc and its relation to their hemolytic activity. -- an in vitro study.

Hemolysis induced by native kaolin dust was found to run parallel to the amount of silicic acid dissolved from it. Native mica and talc dusts were hemolytic only to a small extent and the silicic acid dissolution from these dusts was also smaller in comparison to that of native kaolin. The proportionality between hemolysis and the amount of dissolved silicic acid was not consistently observed in the case of acid, alkali and water treated kaolin, mica and talc dusts.

Animals↗

Determination of silicate in water by ion exclusion chromatography with conductivity detection.

A novel method for the direct determination of silicate in water by ion exclusion chromatography with conductivity detection is reported. The method is simple and sensitive with good precision. The calibration graph was linear from 0.1000 micromol l(-1) to 1000.0 micromol l(-1) for silicate with a correlation coefficient of 0.997 (n=6). The detection limit was 0.02 micromol l(-1). The method was successfully applied to the determination of silicate in mineral water, tap water, distilled water and seawater. The recovery was from 93 to 104% and the relative standard deviation was in the range of 1.1 to 4.4%.

Calibration↗

The influence of environmental variability on silicate exchange rates between sediment and water in a shallow-water coastal ecosystem, the Seto Inland Sea, Japan.

Silicate regeneration was determined in a shallow-water coastal ecosystem (Shido Bay, the Seto Inland Sea, Japan) during 1999-2000. The present study was carried out directly by core incubation and by determining gradients of dissolved silicate (DSi) in the pore water. Incubated fluxes ranged from 25.5 to 132.6 mgSim(-2)d(-1), and were 1.6-21.6 times greater than diffusive fluxes (5.4-43.3 mgSim(-2)d(-1)). The disparity between fluxes measured by core incubation and modeling pore water indicated that other physical, chemical or biological processes, in addition to diffusion of DSi from below, contribute to DSi fluxes measured during the incubation of undisturbed cores. A regression analysis revealed that water temperature and salinity explained 24% and 23%, respectively, of season to season variability in incubated fluxes. Microphytobenthos was responsible for 37% of the variability in measured rate of DSi fluxes, with greatly reducing DSi release rates due to their own DSi demand. Moreover, the inverse relationship between the DSi fluxes and biogenic silica (Bio-Si) concentrations in the surface sediment, suggested that about 41% of the variability in the DSi fluxes were explained by Bio-Si concentrations in the surface sediment. As a result, Shido Bay showed silicate regeneration of incubated cores to be a consequence of Bio-Si dissolution depending on microphytobenthos, temperature and salinity, while diffusive fluxes appeared to be limited by DSi in the pore water. An annual average of DSi flux (68.7+/-32.9 mgSim(-2)d(-1)) from the sediments to the water column corresponds to 38% of DSi, required for primary production by phytoplankton in Shido Bay.

Ecosystem↗

Bonelike apatite coating on organic polymers: novel nucleation process using sodium silicate solution.

A bonelike apatite layer was formed on organic polymers when sodium silicate was used as a catalyst for the apatite nucleation, and modified simulated body fluid was used as a medium for the apatite growth. The apatite-forming ability was the highest when the SiO2 concentration and SiO2/Na2O mole ratio of the sodium silicate solution were above 2.0 M and 1.0-1.5, respectively. It is assumed that particular silicate oligomers with structures such as dimer, linear trimer and cyclic tetramer contribute to the apatite nucleation the most. The apatite layer was formed not only on limited surfaces but also on the whole surfaces of fine PET fibers constituting a fabric. This method is expected to enable the bonelike apatite coating on various kinds of materials with complex shapes.

Apatites↗

Kinetics of uptake and elimination of silicic acid by a human subject: a novel application of 32Si and accelerator mass spectrometry.

Silicon is possibly important in human physiology in protecting against the toxic effects of aluminium, but the kinetics of uptake and excretion of silicic acid, the bioavailable form, are not well characterised. We have used 32Si as a tracer in a human uptake experiment to determine a gastrointestinal uptake factor for silicic acid, and to elucidate the kinetics of renal elimination. Urine collections were made for extending intervals from 2 to 12 h over 2 days following ingestion by a single human subject of a neutral silicic acid solution containing tracer levels of 32Si (t1/2 approximately 150 y). Silicon was isolated as SiO2 and the 32Si content determined by accelerator mass spectrometry (AMS), using a gas-filled magnet technique to eliminate a prolific isobaric interference from 32S. Silicon uptake appears to have been essentially complete within 2 h of ingestion. Elimination occurred by two simultaneous first-order processes with half-lives of 2.7 and 11.3 h, representing around 90% and 10%, respectively, of the total output. The rapidly eliminated 32Si was probably retained in the extracellular fluid volume, whilst the slower component may represent intracellular uptake and release. Elimination of absorbed 32Si was essentially complete after 48 h and was equivalent to 36% of the ingested dose. This establishes only a lower limit for gastrointestinal absorption as, although there was no evidence for longer term retention of additional 32Si, the possibility could not be excluded by these results.

Administration, Oral↗

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate.

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.

Calcium Compounds↗

Near-infrared spectroscopy investigation of the water confined in tricalcium silicate pastes.

Near-infrared (NIR) spectroscopy has been employed to investigate the evolution of the vibrational spectrum of water entrapped in a tricalcium silicate paste. The overall free water, which decreases as a function of time due to the formation of the hydrated phases (portlandite, Ca(OH)(2), and hydrated calcium silicate, C-S-H) during the hydration reaction, is quantified by the decrease in the area of the NIR band at about 5000 cm(-1). The coexistence of two types of water in the hydrated phases (a "surface-interacting water" (type I) and a "bulklike water" (type II)) during the hydration is obtained by the analysis of the band at about 7000 cm(-1). The deconvolution of this band allows the quantification of the two water types. As the reaction advances, part of the "bulklike water" is converted to "surface-interacting water" in direct agreement with the C-S-H surface development. Finally, the Ca(OH)(2) formation can be concurrently monitored by NIR through the increase of a very sharp peak at 7083 cm(-1). Near-infrared spectroscopy allows determination in a very simple way of the most important features of the tricalcium silicate setting process.

Calcium Compounds↗

Biomimetic formation of silica thin films by surface-initiated polymerization of 2-(dimethylamino)ethyl methacrylate and silicic acid.

Biosilicification in diatoms is achieved by specific interactions between silaffins, composed of polypeptides and long-chain polyamines, and silicic acid derivatives. The polycondensation of silicic acids is reported to be catalyzed by the long-chain polyamines that mainly contain tertiary N-methylpropyleneimine moieties. In this report, we utilized a tertiary amine-containing polymer, poly(2-(dimethylamino)ethyl methacrylate) (poly(DMAEMA)), as a surface-grafted, biomimetic counterpart of the long-chain polyamines in silaffins and demonstrated that the surface-initiated polycondensation of silicic acids, leading to the formation of silica thin films, proceeded smoothly on surfaces presenting poly(DMAEMA), where poly(DMAEMA) was grown from gold surfaces by surface-initiated, atom transfer radical polymerization. The formed silica film was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy.

Gold↗

Identification of multiple structural species in silicate glasses by 29Si NMR.

Knowledge of the structure of silicate glasses is one key to understanding their chemical and physical properties, as well as those of the high-temperature liquids from which they form. Because first-neighbour ordering into SiO4 tetrahedra is well known, much of the recent discussion about glass structure has concerned intermediate-range order. One of the most fundamental questions that can be posed is the distribution of silicate tetrahedra with n bridging oxygens (shared between two tetrahedra), labelled as 'Qn' (0 less than or equal to n less than or equal to 4). This distribution is probably important in determining the properties of melts and glasses, but considerable controversy exists concerning the identification and quantification of such species. Here I present new evidence from 29Si NMR (nuclear magnetic resonance) spectroscopy that clearly resolves one significant part of this dispute: at least in sodium silicate glasses, a variety of species is present that is greater than that required by composition alone.

Glass↗

Simultaneous determination of phosphate and silicate in waste water by sequential injection analysis.

A sequential injection analysis system for the simultaneous determination of phosphate and silicate in waste water is proposed. The method is based on the formation of yellow vanadomolybdophosphate and molybdosilicate, respectively, in addition to the use of large sample volumes. The mutual interference between both analytes was eliminated by selection of the appropriate acidity and by sample segmentation with oxalic acid. The calibration graph for phosphate and silicate is linear up to 12 mg l-1 P and 30 mg l-1 Si, respectively. The detection limits are 0.2 mg l-1 P and 0.9 mg l-1 Si. The method provides a throughput of 23 samples h-1 with a relative standard deviation < 1.4% for phosphate and < 4% for silicate. The method was found to be suitable for the determination of these species in waste water samples.

Evaluation Studies as Topic↗

Ultrastructural effects of silicic acid on primary lung fibroblasts in tissue culture.

Transmission and scanning electron microscopic examination of primary lung fibroblasts exposed in tissue culture to polymeric silicic acid (PSA) revealed profound cellular changes in the cell surface membranes, resulting in rapid endocytosis of affected membranes and formation of multivesicular bodies. Exposure to monomeric silicic acid did not appear to exhibit any immediate adverse effects. Appearance of numerous cytoplasmic vacuoles within 1 h of PSA exposure was easily visible by light microscopy. Electron microscopy revealed that PSA exposure caused formation of an 'osmiophilic' cell surface membrane. Numerous osmiophilic cytoplasmic blebs on the surface and subsequent endocytotic vesicles appeared to collapse and aggregate into multivesicular bodies. This study provides ultrastructural evidence of the direct interaction between lung fibroblasts and polymeric silicic acid, which has a dramatic effect the surface membrane, its subsequent internalization and cytoplasmic processing. This interaction could be one of the key steps in the damaging effects of silica containing dust.

Animals↗