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PubMed2005

High benzene selectivity of mesoporous silicate for BTX gas sensing microfluidic devices.

The gas selectivities of highly ordered mesoporous silicates and commercially-obtained porous silicates with respect to benzene, toluene and xylene were studied. After studying the porosities, pore uniformities, and surface silanol structures of the silicates and their relationships to gas selectivity in detail, we found that we could achieve high benzene selectivity by controlling the micropore size (less than 1 nm). Concluding that mesoporous silicate has a suitable micropore size and structure for benzene selectivity, we also observed that mesoporous silicate SBA-16 exhibited a high (>6) benzene selectivity from toluene and xylene even in a pseudo-atmospheric environment. A benzene detection limit of about 100 ppb was achieved by introducing SBA-16 into a microfluidic device originally developed for the separate detection of benzene, toluene, and xylene gases.

Air Pollutants, Occupational↗

PubMed2002

Bioactivity of plasma sprayed dicalcium silicate coatings.

Dicalcium silicate coatings on titanium alloys substrates were prepared by plasma spraying and immersed in simulated body fluids for a period of time to investigate the nucleation and growth of apatite on the surface of the coatings. Surface structural changes of the specimens were analyzed by XRD and IR technologies. SEM and EDS were used to observe surface morphologies and determine the composition of dicalcium silicate coatings before and after immersion in simulated body fluid. The plasma sprayed dicalcium silicate coating was bonding tightly to the substrate. The coating was mainly composed of beta-Ca2SiO4 and glassy phase. A dense carbonate-containing hydroxyapatite (CHA) layer was formed on the surface of the plasma sprayed dicalcium silicate coating soaked in SBF solution for 2 days. In addition, a silica-rich layer was also observed between CHA layer and coatings. With an increase in the immersion time, the CHA layer gradually became thicker. The results obtained indicated that the plasma sprayed dicalcium silicate coating possesses excellent bioactivity.

Apatites↗

PubMed2003

A highly crystalline layered silicate with three-dimensionally microporous layers.

Layered silicates with three-dimensional microporosity within the layers have the potential to enable new applications in catalysis, adsorption and ion-exchange. Until now no such materials have been reported. However, here we present the synthesis and structure of AMH-3, a silicate with three-dimensionally microporous layers, obtained in high purity and crystallinity. AMH-3 is composed of silicate layers containing eight-membered rings in all three principal crystal directions, and spaced by strontium cations, sodium cations and water molecules. Because of its three-dimensional pore structure, acid and thermal stability, this layered material could find applications in polymer-silicate composites for membrane applications, for synthesis of combined microporous-mesoporous materials, and for the formation of new zeolites and microporous films. Its existence also opens new possibilities for the synthesis of other layered silicates with multidimensional microporous framework layers.

Cations↗

PubMed2000

Expression of silicatein and collagen genes in the marine sponge Suberites domuncula is controlled by silicate and myotrophin.

The major skeletal elements in the (Porifera) sponges, are spicules formed from inorganic material. The spicules in the Demospongiae class are composed of hydrated, amorphous silica. Recently an enzyme, silicatein, which polymerizes alkoxide substrates to silica was described from the sponge Tethya aurantia. In the present study the cDNA encoding silicatein was isolated from the sponge Suberites domuncula. The deduced polypeptide comprises 331 amino acids and has a calculated size of Mr 36 306. This cDNA was used as a probe to study the potential role of silicate on the expression of the silicatein gene. For these studies, primmorphs, a special form of aggregates composed of proliferating cells, have been used. It was found that after increasing the concentration of soluble silicate in the seawater medium from around 1 microM to approximately 60 microM, this gene is strongly upregulated. Without additional silicate only a very weak expression could be measured. Because silica as well as collagen are required for the formation of spicules, the expression of the gene encoding collagen was measured in parallel. It was also found that the level of transcripts for collagen strongly increases in the presence of 60 microM soluble silicate. In addition, it is demonstrated that the expression of collagen is also upregulated in those primmorphs which were treated with recombinant myotrophin obtained from the same sponge. Myotrophin, however, had no effect on the expression of silicatein. From these data we conclude that silicate influences the expression of the enzyme silicatein and also the expression of collagen, (via the mediator myotrophin).

Amino Acid Sequence↗

PubMed1996

Surface chemistry and biological pathogenicity of silicates: an X-ray photoelectron spectroscopic study.

We extend our electron spectroscopy for chemical analysis studies of the chemistry of silicates to provide direct surface chemical information on the interactions involved in silicate-induced lung and tissue pathology. A total of five fibrous and non-fibrous silicate minerals, primarily amphiboles, have been studied: anthophyllite, tremolite, cummingtonite, hornblende and actinolite. We have followed the 'inlattice' surface chemistry of these materials and monitored features such as the simultaneous presence of four- and six-coordinate (with respect to oxygen) structural aluminium, and the presence of iron in the M4 octahedral positions. In vitro experiments involving contact of the silicate with cultured murine Ehrlich cells have identified modifications in the surface chemistry of Al, Mg and Fe in the silicates and changes in cellular iron content.

Animals↗

PubMed1993

Mechanism of silicate binding to the bacterial cell wall in Bacillus subtilis.

To investigate the chemical mechanism of silicate binding to the surface of Bacillus subtilis, we chemically modified cell wall carboxylates to reverse their charge by the addition of an ethylenediamine ligand. For up to 9 weeks, mixtures of Si, Al-Fe-Si, and Al-Fe-Si plus toxic heavy metals were reacted with these cells for comparison with control cells and abiotic solutions. In general, more Si and less metal were bound to the chemically modified surfaces, thereby showing the importance of an electropositive charge in cell walls for fine-grain silicate mineral development. The predominant reaction for this development was the initial silicate-to-amine complexation in the peptidoglycan of ethylenediamine-modified and control cell walls, although metal ion bridging between electronegative sites and silicate had an additive effect. The binding of silicate to these bacterial surfaces can thus be described as outer sphere complex formation because it occurs through electrostatic interaction.

Adsorption↗

PubMed1997

Electron microscopic microanalysis of bronchoalveolar lavage: a way to identify exposure to silica and silicate dust.

OBJECTIVES: The diagnostic implications of finding non-fibrous inorganic particles in bronchoalveolar lavage (BAL) fluid has not been fully assessed. The aim of this study has been to measure the silica and non-fibrous silicates in BAL fluid from populations with different exposures to inorganic dust, and to find whether such measurement is useful for diagnostic purposes. MATERIALS AND METHODS: BAL samples from 19 subjects with only environmental exposure to inorganic dust (group A, mean (SD) age 50.7 (15.2)), 23 subjects with normal chest x ray films exposed to silica or silicates at work (group B, mean (SD) age 52.0 (12.4)), and 15 subjects with a previous diagnosis of silicosis (group C, mean (SD) age 68.0 (6.5)) were studied. Absolute and relative cell counts were found, and the samples were prepared for microanalysis by electron microscopy (EM). Firstly, semiquantitative x ray microanalysis was performed to find the level of silicon (Si) (peak/background Si) and this was followed by microanalysis of individual particles by EM. Variables related to the level of Si detected were assessed with multivariate analysis. RESULTS: Detected levels were higher in group B (2.09, 95% confidence interval (95% CI) 1.56 to 2.82) and C (1.50, 95% CI 1.07 to 2.12) than in group A (0.87, 95% CI 0.66 to 1.16) (P < 0.05, Dunett t test). A first multivariate analysis showed that exposure to silica or silicates was the only determinant of the level of Si expressed as log peak/background Si, when adjusted for age, sex, smoking habit, and cell count. A second multivariate analysis with microanalysis of individual particles as an independent variable showed the silica count to be the main predictor of detected concentration of Si. Silica and non-aluminium silicates together explain 55.5% (R2) of the variation in detected levels of Si. CONCLUSIONS: Detected levels of Si in BAL fluid depend on silica count and are higher in subjects with exposure to inorganic dust at work, but will not discriminate between exposed subjects with and without silicosis. Because semiquantitative x ray microanalysis does not accurately define exposure to non-silica inorganic particles, this measurement must be followed by EM microanalysis of individual particles in most cases, especially when exposure to silicates or metal dust is suspected.

Adult↗

PubMed1992

Role of surface complexed iron in oxidant generation and lung inflammation induced by silicates.

Inhalation of silicates induces a variety of lung diseases in humans. The molecular mechanism(s) by which these dusts cause disease is not known. Because several naturally occurring mineral oxides have large amounts of transition metal ions on their surfaces, we tested the hypothesis that surface complexation of iron may be an important determinant of their ability to induce disease. Silica, crocidolite, kaolinite, and talc complexed considerable concentrations of Fe3+ onto their surfaces from both in vitro and in vivo sources. The potential biological importance of iron complexation was assessed by examining the relationship between surface [Fe3+] and the ability of silicates to mediate oxidative degradation of deoxyribose in vitro, induce a respiratory burst and elicit leukotriene B4 (LTB4) release by alveolar macrophages (AM) in vitro, and cause acute alveolitis after intratracheal insufflation. For these studies, three varieties of silicate dusts were used: iron-loaded, wetted (unmodified), and deferoxamine-treated to remove Fe3+. The ability of silicates to catalyze oxidant generation in an ascorbate/H2O2 system in vitro, to trigger respiratory burst activity and LTB4 release by AM, and to induce acute lung inflammation in the rat all increased with surface complexed Fe3+. The results of these studies suggest that surface complexation of iron may be an important determinant in the pathogenesis of disease after silicate exposure.

Adsorption↗

PubMed1989

The effect of silicic acid on calcium phosphate precipitation.

So that a possible involvement in the mineralization of dental plaque could be investigated, the effects of silicic acid on calcium phosphate precipitation were assessed in vitro. By measuring the decrease in Ca2+ concentration (by means of ion-selective electrodes), we determined both spontaneous precipitation and seeded crystal growth from solutions that contained 1 mmol/L calcium, 7.5 mmol/L phosphate, 50 mmol/L Hepes pH 7.2, and various amounts of silicic acid. Polymerized silicic acid, but not its monomer, was found both to cause a 60% reduction in the lag period that precedes spontaneous precipitation and to enhance the growth rate of seeded hydroxyapatite crystals. Silica suspensions showed effects similar to those of polysilicic acid. In all cases, the precipitated material was found to be hydroxyapatite. Whereas seeded brushite crystals grew slowly without silicic acid, hydroxyapatite was the only mineral detected after crystal growth in the presence of silicic acid. Apparently, polysilicic acid acted as a substrate for hydroxyapatite nucleation, inducing secondary nuclei on both hydroxyapatite and brushite crystals. The finding that polysilicic acid could overcome part of the inhibitory effect of a phosphoprotein on calcium phosphate precipitation gave additional support for the idea that polysilicic acid and silica may promote the formation of dental calculus.

Calcium Phosphates↗

PubMedDate not supplied

Kinetics of chromate adsorption on goethite in the presence of sorbed silicic acid.

The adsorption of chromate on mineral surfaces has received much attention due to its toxicity in natural systems. Spectroscopic studies have demonstrated that chromate forms inner-sphere complexes on variable-charge surfaces. However, in natural systems chromate has been observed to be fairly mobile, which has been explained by the presence of naturally occurring ligands competing with chromate for mineral surface sites. Silicic acid is a ubiquitous ligand in soil and water environments and also sorbs strongly to variable-charge surfaces. Yet little research has examined its influence on chromate adsorption to variable-charge surfaces such as goethite. This study examined the influence of silicic acid (0.10 and 1.0 mM) on the adsorption kinetics of chromate (0.05 and 0.10 mM) on goethite over a range of common soil pH values (4, 6, and 8). The rate and total quantity of chromate adsorption decreased in all the experiments except at a pH value of 4 and a chromate concentration of 0.05 mM. The inhibition of chromate adsorption ranged from 3.1% (pH = 4, Si = 0.10 mM, chromate = 0.10 mM) to 83.3% (pH = 8, Si = 1.0 mM, chromate = 0.05 mM). The rate of chromate adsorption decreased with an increase in pH and silicic acid concentration. This was attributed to a reduction in the surface potential of goethite on silicic acid adsorption as well as a competition for surface sites. The presence of naturally occurring ligands such as silicic acid may be responsible for the enhanced mobility of chromate in natural systems and demonstrates the importance of competitive adsorption for evaluating the mobility of trace elements.

Adsorption↗

PubMed1976

[Bacterial accumulation on silicate and composite materials].

It was shown in a previous study that more plaque accumulates on composite filling materials than on silicate cement and amalgam. The purpose of the present investigation was to compare the accumulation of Streptococcus mutans on silicate cement and on composite material by scanning electron microscopy. Whether the adhesion was dependent on the presence of sucrose was also tested. Round disks, 6 mm in diameter, were made from the two materials. The disks were submerged in media with and without sucrose and inoculated with S. mutans OMZ 176. The disks were removed after 1 or 30 minutes, rinsed in saline and prepared for SEM. Along the diameter of each disk pictures were taken at similar intervals. From a total of 48 pictures from each material 18 pictures were selected at random and the number of microorganisms counted. The results indicated that bacteria initially adhered to both silicate and composite in about the same number. The presence of sucrose did not influence the initial adsorption. After 30 minutes bacteria were scarcely found on silicate, whereas large clumps of bacteria were attached to the composite. Sucrose increased bacterial accumulation on composites but did not affect the adherence to silicate cement.

Adhesiveness↗

PubMed1976

Silicic acid chromatographic separation of polychlorinated biphenyls and pesticides: some contaminants and limitations.

The Armour and Burke method for separating polychlorinated biphenyls (PCBs) from pesticides involves the use of silicic acid. However, we detected di-2-ethylhexyl phthalate, PCBs, and other impurities as interfering contaminants in several batches of silicic acid. The presence of H2SO4 in some batches of silicic acid is inferred. The acid may be responsible for the production of contaminants which interfere in gas-liquid chromatographic analyses. Contaminants in silicic acid are reduced by extracting the adsorbent with solvent, and/or partitioning the concentrated pesticide fraction with 1N NaOH. These purification procedures provide separations relatively free of impurities, but result in reduced adsorbent activity. PCB-pesticide separations are reproducible only within a given batch lot of silicic acid because of the varying adsorbent characteristics of each lot. Alternative adsorbents should be explored for most PCB-pesticide separations.

Chromatography, Gas↗

PubMedDate not supplied

The mitochondrial activation of silicate and its role in silicosis, black lung disease and lung cancer.

Silicate substitutes for phosphate in the transitory uncoupling of rat liver mitochondria induced by hydrazine when beta-hydroxy-butyrate is the substrate. Uncoupling is blocked by rutamycin. Just as in the case when phosphate is combined with hydrazine, ATP, ADP, PPi, and Mg++ protect against hydrazine when silicate is combined with hydrazine. A high level of ADP in the absence of added phosphate, but in the presence of silicate, induces a pseudo state three of the mitochondria. Silicate, like sulfate and arsenate which have been reported previously, is activated by the enzymes which mediate oxidative phosphorylation. These results serve to explain a role for silicate in silicosis, black lung disease, and cancer. In addition, since there is suggestive evidence in the literature that lung tissue solubilizes asbestos fibers, these results not only expand the confluence between oxidative phosphorylation and chemical carcinogenesis but are correlated with the synergistic carcinogenicity of asbestos and smoking observed by epidemiologists.

Adenosine Diphosphate↗

PubMed1980

Silicates: non-specific adsorbents in purification of water from viruses.

Amorphous silicates having small particles with large surface area, were found to have high non-specific adsorption capacity. Escherichia coli T4 bacteriophage was used as a model in this research. Investigations have shown an adsorption capacity of up to 99% on different tested commercially available silicates. Optimal conditions for the adsorption of T4 bacteriophage on various silicates were determined. Amorphous silicates may be used in purification of water from viral contaminants. A silicate-containing model unit for filtration by adsorption of viruses is described.

Adsorption↗

PubMed1986

Biocompatibility of silicates for medical use.

Implantation of commercial silicate glasses in soft or hard tissue will produce a thick non-adherent capsule consisting of scar tissue. However, special compositions of bioactive silicate glasses and crystallized glass-ceramics bond to bone and soft tissue without such a capsule. Bonding is via ion exchange and formation of active surface layers which incorporate collagen and bone mineral. These bioactive silicates have been studied in vivo and in vitro and the cellular response appears to depend on total cell surface nectin concentrations as well as on specific nectins and cellular proteins which may be silicon-sensitive. Simple amino acids polymerize and adhere strongly and randomly to binding sites on the bioactive surfaces, in contrast to their epitaxial behaviour on crystalline quartz. Toxicity tests in vivo and in vitro on powders and on solid forms show no adverse effects associated with bioactive silicates, in contrast with the marked toxicity of crystalline quartz. The bioactivity of the bioactive silicates may be destroyed by addition of small quantities of multivalent ions. The bioactive materials are currently in clinical use and being tested preclinically for a variety of surgical and dental applications.

Animals↗

PubMed2002

Characterization of silicate monomer with sodium, calcium and strontium but not with lithium and magnesium ions by fast atom bombardment mass spectrometry.

Fast atom bombardment mass spectrometry (FABMS) was applied to the direct detection of silica species dissolved in LiCl, NaCl, MgCl(2), CaCl(2) and SrCl(2) solutions in order to investigate its dissolution process in solution. Several species of dissolved silicate complexes in the solution were directly detected by FABMS. The peak intensities of [SiO(2)(OH)(2)Na](-), [SiO(3)(OH)Ca](-) and [SiO(3)(OH)Sr](-) increased with increasing concentrations of NaCl, CaCl(2) and SrCl(2), whereas the peak intensities of [SiO(2)(OH)(2)Li](-) and [SiO(3)(OH)Mg](-) did not increase with increasing concentrations of LiCl and MgCl(2). These results indicte that silicate and cation bind in the solution not after but before ionization. The isotope pattern of Sr(2+) confirmed the existence of the silicate-Sr complex not only with increase of the concentration of silica but also the mass numbers of Sr. The silicate complexes formed with Na(+), Ca(2+) and Sr(2+) showed high stability in chloride solution. This is in good accordance with the fact that Na(+), Ca(2+) and Sr(2+) accelerate the dissolution of silica to form complexes during solution equilibrium. Considering that the stability constant was examined and reported in other papers, this new findings that Mg(2+) does not form a complex with silicic acid (Si(OH)(4)) is very important.

Journal Article↗

PubMed2005

Physical chemistry of nanostructured molecular sieves by the study of phase diagrams: the case of the cetyltrimethylammonium bromide-tetramethylammonium silicate-water system.

A phase diagram for the system cetyltrimethylammonium bromide (CTAB)/tetramethylammonium silicate (TMASi)/water has been constructed in order to better understand the interactions between these precursors of the MCM-41 mesoporous molecular sieves. Three different CTAB concentration regions were analyzed: the dilute and semidilute regions, where simple surfactant species, such as monomers and spherical and nonspherical CTAB micelles, are found, and the concentrated region, involving liquid-crystalline phases. In the dilute and semidilute regions, the formation of a white nanostructured solid, having a hexagonal array similar to that found in MCM-41 materials, was observed. Precipitation of this solid requires some degree of surfactant monomer aggregation, which is favored by the presence of silicate anions. If micelles have already been formed, the material can be obtained at any CTAB concentration above a threshold concentration of silicate anions. These facts suggest that silicate anions have an important role in changing the aggregation and/or the shape of the surfactant aggregates. In the concentrated region, precipitation of the solid was not observed, but the presence of the silicate anions alter the characteristics of the liquid-crystalline phase formed by the surfactant. The system shows very complex and rich behavior and its investigation may be very useful in understanding the processes of nanostructured solid formation.

Journal Article↗

PubMed2003

29Si chemical shift anisotropies in calcium silicates from high-field 29Si MAS NMR spectroscopy.

29Si chemical shift anisotropy (CSA) data have been determined from (29)Si MAS NMR spectra recorded at 14.1 T for a number of synthetic calcium silicates and calcium silicate hydrates. These are beta- and gamma-Ca(2)SiO(4), Ca(3)SiO(4)Cl(2), alpha-dicalcium silicate hydrate (alpha-Ca(2)(SiO(3)OH)OH), rankinite (Ca(3)Si(2)O(7)), cuspidine (Ca(4)Si(2)O(7)F(2)), wollastonite (beta-Ca(3)Si(3)O(9)), pseudowollastonite (alpha-Ca(3)Si(3)O(9)), scawtite (Ca(7)(Si(6)O(18))CO(3).2H(2)O), hillebrandite (Ca(2)SiO(3)(OH)(2)), and xonotlite (Ca(6)Si(6)O(17)(OH)(2)). The (29)Si MAS NMR spectra of rankinite and wollastonite clearly resolve manifolds of spinning sidebands from two and three Si sites, respectively, allowing the CSA parameters to be obtained with high precision for each site. For the (29)Si Q(1) sites in rankinite and cuspidine, the CSA asymmetry parameters (eta(sigma) approximately 0.6) contrast the general expectation that sorosilicates should possess small eta(sigma) values as a result of the nearly axially symmetric environments of the SiO(4) tetrahedra. The (29)Si CSA parameters provide an improved insight into the electronic and geometric environments for the SiO(4) tetrahedra as compared to the values solely for the isotropic chemical shift. It is shown that the shift anisotropy (delta(sigma)) and the CSA asymmetry parameter (eta(sigma)) allow a clear distinction of the different types of condensation of SiO(4) tetrahedra in calcium silicates. This relationship may in general be valid for neso-, soro-, and inosilicates. The CSA data determined in this work may form a valuable basis for (29)Si MAS NMR studies of the structures for tobermorites and calcium silicate hydrate phases resulting from hydration of Portland cements.

Journal Article↗