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The chemical behavior of silica in water in saline area; comparison for region and evaporation process.

The chemical behavior of silica in the water samples from Death Valley were examined by the speciation of silica and the measurements of the silica and alkaline and alkaline earth cation contents to compare with those from the arid area in Xinjiang, Northwest China. Basically, the chemical behavior of silica in spring water samples from Death Valley coherent with those in Xinjiang, Northwest China. And the observed chemical species of silica with alkaline and alkaline earth cations in spring water samples in Death Valley were in good agreement with those in Xinjiang, Northwest China. However, some of the silica behavior observed in water samples in Death Valley was distinct from those observed in Xinjiang, Northwest China. It is considered that some of the water samples in Death Valley were subject to evaporation process.

Calcium↗

Overexpression of cyclin D1-CDK4 in silica-induced transformed cells is due to activation of ERKs, JNKs/AP-1 pathway.

Silica has been known to be a factor inducing acute injury and chronic pulmonary fibrosis. Silica has also been listed as a human carcinogen in 1996 by International Agency for Research on Cancer (IARC). However, the molecular mechanisms involved its pathologic effects are not well understood. In these studies, we found that exposure of human embryonic lung fibroblasts (HELF) to crystalline silica could cause increases in activation of extracellular signal-regulated kinases (ERKs), p38K, and c-Jun NH2-terminal amino kinases (JNKs), and HELF transformation. Interestingly, silica-induced transformation of HELF (S-HELF) led to increases in activated levels of ERKs and p46 of JNKs, and decrease in p38K activation, and no effect on activation of p54 of JNKs, as compared with those in parental HELF. Further studies showed that there are differential effects of ERKs, JNKs and p38K, as well as their downstream transcription factor AP-1, in regulation of expression of cyclin D1 and CDK4 and cell cycle alternations induced by silica. Cyclin D1 and CDK4 were increased in S-HELF as compared with those in HELF. Inhibition of ERKs activation by AG126, JNK by SP600125, and AP-1 by curcumin could reduced the induction of cyclin D1 and CDK4. There is no significant difference for cell cycle distribution between groups. These results demonstrate that ERKs and JNKs, but not p38K is responsible for induction of cyclin D1 and CDK4 in S-HELF, suggesting that overexpression of cyclin D1 and CDK4 caused by silica is mediated by ERK, JNK/AP-1signaling pathway.

Blotting, Western↗

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution.

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.

Adsorption↗

Complement facilitates macrophage phagocytosis of inhaled iron particles but has little effect in mediating silica-induced lung inflammatory and clearance responses.

Complement-mediated mechanisms are known to play a role in pulmonary inflammation and clearance responses to some types of inhaled particles. The present studies were undertaken to investigate the role of complement in mediating pulmonary inflammation and/or phagocytosis as a function of particle clearance in rats exposed to silica or carbonyl iron (CI) particles. Both particle types were shown to be weak activators of serum complement in vitro. In these studies, normal and complement-depressed (CVF-treated) rats were exposed to aerosols of CI or silica particles for 6 hr at 100 mg/m3. Following exposure, alveolar fluids and cells from sham and dust-exposed animals were recovered by bronchoalveolar lavage (BAL) at several time periods postexposure and measured for a variety of biochemical and cellular indices. In addition, pulmonary macrophages were cultured and studied for morphology and phagocytosis. Our results showed that CI exposure did not produce cellular or biochemical indices of pulmonary inflammation, either in normal or complement-depleted rats. However, fewer phagocytic macrophages were recovered from the lungs of CVF-treated, CI-exposed rats than from normal exposed animals. In contrast, silica inhalation produced a sustained PMN inflammatory response in the lungs of exposed rats, measured up through 1 month postexposure, along with significant increases in BAL fluid levels of LDH, protein, and alkaline phosphatase (P less than 0.05) and deficits in pulmonary macrophage phagocytic functions. Cobra venom factor (CVF) treatment prior to exposure in rats had no significant effect upon the silica-induced parameters, suggesting that complement may not play an important role in the acute pulmonary response to silica. The results indicate that complement may play a role in mediating CI-related macrophage clearance responses but has little effect upon sustained silica-induced pulmonary inflammatory parameters.

Administration, Inhalation↗

Relationship of silica and bacillus Calmette-Guerin exposures to humoral and cellular immune functions.

The consequences of silica preexposures were studied on subsequent bacillus Calmette-Guerin (BCG) pulmonary infections. Silica had a variable effect on colonization by BCG depending on organ and number of BCG treatments. Silica preexposures resulted in increased numbers of free alveolar cells subsequent to BCG infections, with an initially rapid increase of neutrophils. Both silica and two BCG treatments were capable of decreasing the animals' splenic response to stimulations with Escherichia coli aerosols, and BCG greatly enhanced antibody-dependent cell-mediated cytotoxicity in silica preexposed mice. 5'-Nucleotidase activity was depressed by both silica and BCG in pulmonary washout cells indicating that inhalation of these substances may have a stimulating effect on the alveolar macrophages.

Animal Diseases↗

Coated silica supports for high-performance affinity chromatography of proteins.

Polymer-coated silica supports are potentially good stationary phases for high-performance affinity chromatographic separations of proteins. Silica beads have been coated with a polysaccharide (dextran or agarose), substituted by a calculated amount of positively charged diethylaminoethyl functions in order to neutralize the negatively charged silanol groups of silica and to facilitate the formation of a hydrophilic polymeric layer on the inorganic surface. The silica-based supports were prepared in two steps. First, the silica was impregnated with a solution of diethylaminoethylated polymer, and then the coating polymer was crosslinked in order to avoid leakage of the polymeric layer. The supports present minimal non-specific interactions with proteins, as tested by high-performance size-exclusion chromatography. These coated silica supports were coupled with active ligands, such as protein A, concanavalin A and heparin, by conventional coupling methods. The resulting affinity stationary phases were tested by the elution of proteins in order to study their performance in high-performance affinity chromatography.

Antithrombin III↗

Comparison of bonded, polymeric and silica columns for chromatography of some penicillins.

The retention of ampicillin, amoxicillin, and penicillin G was determined on ODS and cyanopropyl (CN)-bonded to silica, on an all-organic polymeric reversed-phase column (styrene-divinylbenzene) and on bare silica. Solvents tested were 0.01 M H3PO4 (pH 1.6)-acetonitrile and 0.002 M KH2PO4 (pH 4.6)-acetonitrile in the proportions 100:0 to 10:90. Retention with 0.002 M KH2PO4 was weaker than with 0.01 M H3PO4 at all proportions of acetonitrile on all packings. With 0.01 M H3PO4, retention of penicillins on the polymeric column decreased rapidly from 100 to 50% aqueous phase and remained low to 10% aqueous phase. On the ODS bonded column, retention was similar, except that retention of the aminopenicillins, amoxicillin and ampicillin increased at less than 30% aqueous phase. On the CN-bonded column, results were similar to those on the ODS column, except that the aminopenicillins were less strongly retained when using 100% 0.01 M H3PO4. On the bare silica, penicillin G was poorly retained at all proportions of acetonitrile, while retention of aminopenicillins increased rapidly at less than 50% 0.01 M H3PO4. Retention of aminopenicillins at less than 50% 0.01 M H3PO4 was parallel on bonded and bare silica but weaker on the bonded silica. A bonded organic layer weakened but did not prevent binding of amines to silica.

Acetonitriles↗

Size-exclusion chromatography of low-molecular-mass polymers using mesoporous silica.

In this study, the mesoporous silicas APMS-30 and MCM-41 were compared to a commercial silica, Nucleosil, in size-exclusion chromatography (SEC). Polystyrenes of various molecular masses (M) were passed through HPLC columns of the silicas (each column contained a single type of silica) and retention times were plotted as a function of log M for each type of silica. Linear fits to the data were used to identify regions of total exclusion, size exclusion, and total permeation in each of the three plots. Due to their small pore sizes, APMS-30 and MCM-41 (pore radii: 14.5 and 17.0 A from N2 physisorption, respectively) did not exhibit a total permeation region even at M= 104 g mol(-1) (styrene monomer), while Nucleosil (pore radius: 57.9 A) showed total permeation at M=644 g mol(-1). These results indicate that mesoporous silica is better than Nucleosil in SEC of polymers with low M, making it useful in a variety of SEC applications including the determination of M for small molecules such as oligomers and oligopeptides. Interestingly, calculation of the radius of gyration, Rg, of the largest polymer that still exhibits a size-exclusion effect proved to be a reasonable method of determining the pore diameters of each material, with estimated Rg = 8.9, 11.5, and 63.5 A for APMS-30, MCM-41, and Nucleosil, respectively.

Calibration↗

Capillary electrochromatography with a silica column with a dynamically modified cationic surfactant.

A novel mode of capillary electrochromatography (CEC), called dynamically modified silica-capillary electrochromatography, is described in this paper. The column packed with bare silica was dynamically modified with long chain quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), which was added into the mobile phase. CTAB ions were adsorbed onto the surface of bare silica, and the resulted hydrophobic layer on the silica gel was used as the stationary phase. Using the dynamically modified silica column, neutral solutes were separated by CEC. The highest number of theoretical plates obtained was about 71,500/m and the relative standard deviations for t0 and capacity factor of toluene were 4.7% and 4.9% for 20 consecutive runs, respectively. The separation mechanism of neutral solutes and the influence of mobile phase composition on the separation was investigated. The separation of nitrogen-containing solutes was carried out with this mode and the peak tailing of basic solute was effectively eliminated because the adsorption of basic solute on silica was blocked by the preferred adsorption of CTAB.

Cations↗

Silica nanobottles templated from functional polymer spheres.

Nanosized hollow silica spheres with holes in the wall (denoted as silica nanobottles) have been successfully prepared by assembly of functional polymer nanospheres with tetraethoxysilane (TEOS) through hydrothermal methods, coupled with removal of the core by programmed calcination. The functional polymer nanospheres were obtained by emulsifier-free emulsion copolymerization of styrene and (ar-vinylbenzyl) trimethylammoium chloride. The silica nanobottle sample was characterized by thermogravimetric analysis (TG), differential thermal analysis (DTA), transmission electron microscopy (TEM), and nitrogen adsorption techniques. The above characterizations confirm that the silica nanobottles have holes of about 8 nm in the wall and this unique structural feature might be useful for their encapsulation. Furthermore, characterization by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV-visible absorption (UV-vis) showed that the luminescent material Eu(TTA)(3)(TPPO)(2) could be effectively encapsulated in silica nanobottles. This reveals that silica nanobottles have potential applications for nanotechniques.

Journal Article↗

Phosphate measurement in natural waters: two examples of analytical problems associated with silica interference using phosphomolybdic acid methodologies

Assessment of phosphate species for bicarbonate-bearing lowland rivers of the Thames valley, England and acidic Welsh upland streams (the Plynlimon area, mid-Wales) reveal problems of silica interference when employing standard automated 'phosphomolybdic acid' colorimetric methodologies. The interference occurs under a combination of two conditions: (1) when the reagents and samples are heated to speed up the rate of formation of phosphomolybdic acid; and (2) when the strength of a sulfuric acid reagent is too low. While this paper alerts researchers to potential analytical problems with silica interference within phosphomolybdic acid methodologies to determine soluble reactive phosphorus (SRP) concentrations, it cannot detail whether or not there is a general problem. This lack of specificity occurs because there are a variety of phosphomolybdic acid methodologies available which vary in their reagent recipes and it is not clear which methods will or will not suffer from silica interference. Changing the sulfuric acid reagent strength by a factor of two overcame the problem, in this case, with regards to the determination of soluble reactive phosphorus. However, even here, the method may not be applicable to very high alkalinity waters owing to their potential for reducing the acidity of the analyte. With regard to total dissolved phosphorus (TDP) and total phosphorus (TP) measurements, the importance of undertaking the analysis under ambient conditions is clearly shown. There are many small variants on standard phosphomolybdate methods for determining SRP, TDP and TP in use and it is not always clear which methods will or will not show silica interference for particular water types. It is therefore recommended that individual laboratories check their methodologies for silica interference using phosphate-free solutions with similar silica and alkalinity ranges for the waters being assayed.

Journal Article↗

Silica fragments from millet bran in mucosa surrounding oesophageal tumours in patients in northern China.

Millet bran is a component of the diet in the area of highest oesophageal cancer incidence in northern China. Millet bran was found to contain up to 20% by weight of silica; some of this silica occurs as friable sheets or sharply-pointed fibres. These types of silica in millet bran are the most likely source of an unusual contamination with fragments of silica found in the oesophageal mucosa surrounding tumours in patients in northern China. A group of mucosal samples analysed together contained over 5,000 particles/g (100 parts per million by weight), ten times as many as were found in tissue from normal controls taken at necropsy in London. The modal diameter was 10 microgram (1-70 microgram). The particles were in the body of the mucosa and were not simply a surface contaminant. Silica fragments and fibres of similar size originating from other plant species occur in the diet in the two other regions of greatest incidence of oesophageal cancer, the Transkei and Iran. If such fragments enter the mucosa, they must cause some degree of trauma, and they may also be able to stimulate proliferation by providing anchorage. These findings suggest the possibility that silica particles might be involved in the aetiology of oesophageal cancer.

Adult↗

Model studies of the precipitation of silica in the presence of aluminium; implications for biology and industry.

The unique chemical affinity between the oxides of silicon and aluminium has been cited as a potential route for the amelioration of the detrimental effects of aluminium in the environment and in biological systems. A greater understanding of silicon-aluminium interactions may assist in this endeavour and also provide a means of overcoming silica fouling problems encountered by industry which are exacerbated by the presence of aluminium. It is also conceivable that this increased knowledge may demonstrate a positive use for aluminium in the processing of the silicon dioxide phase. In this study we report the effect of aluminium ions, derived from aluminium chloride, on silicic acid species obtained from potassium catecholato complexes of silicon at circumneutral pH at the molar ratios 1000Si:Al, 100Si:Al and 50Si:Al. Silica and low levels of aluminium-rich silica materials were formed with Si:Al ratios of about 3.5:1 comparable with the element ratios detected in senile plaques and aluminium-rich scale. A kinetic study showed that aluminium in the reaction medium slowed down the rate of formation of one of the silica species formed early in the condensation process, e.g. trimers, but increased the rate at which silicic acid was removed from sub 1 nm diameter particles. The materials precipitated in the presence of aluminium were composed of smaller particles and aggregates with smaller pores (Si100:Al and Si50:Al systems) or larger pores (Si1000:Al) compared to the control. The nature of the interactions responsible for these differences is discussed. The effects described here demonstrate the ability of silica and aluminium to interact under conditions such as those found in biological systems. That silica reacts with aluminium in the presence of catechol supports the protective role assigned to silicon.

Aluminum↗

Silica and glomerulonephritis: case report and review of the literature.

A 54-year-old foundry worker with extensive silica exposure, but no pulmonary disease, developed the nephrotic syndrome and renal failure over a 3-month period. Renal biopsy demonstrated a proliferative glomerulonephritis; energy dispersive x-ray analysis detected silicon within the renal tubules. Measurements of respirable silica at the foundry revealed levels up to 2.5 times the current occupational standard. Similar glomerular disease has been reported in silica-exposed animals and workers with silicosis. This case suggests that clinicians should include silica exposure in the differential diagnosis of unexplained diffuse proliferative glomerulonephritis, renal disease may occur without clinically evident pulmonary disease in silica exposure, and silica-induced glomerulonephritis warrants further clinical and epidemiologic research.

Glomerulonephritis↗

Mechanism of silica-induced ROS generation in Rat2 fibroblast cells.

Reactive oxygen species (ROS) play an important role in cell signaling pathway. Previously, we found that silica induced immediate ROS generation and sequential cellular responses such as kinase activation in Rat2 cells as well as an increase of intracellular calcium concentration in A549 cells. However, the detailed mechanism underlying the immediate ROS generation induced by silica in fibroblast cells remains to be elucidated. Therefore, in the present study, we investigated the mechanism of ROS generation by silica within Rat2 fibroblast cells by examining the effects of a diverse group of inhibitors for the enzymes related with signal transduction events. Inhibitors for protein tyrosine kinase (PTK), phospholipase C (PLC), protein kinase C (PKC) and calmodulin (CaM) kinase II effectively suppressed ROS generation in silica-stimulated Rat2 cells, whereas those for protein kinase A and phospholipase A(2) did not. Diphenyleneiodonium chloride (DPI), an inhibitor for NADPH oxidase was also found to be effective in inhibiting silica-induced ROS generation. These results suggest that PTK, PLC, PKC, CaM kinase II, and NADPH oxidase are all involved in signal transduction pathways for ROS generation in silica-stimulated Rat2 cells.

Animals↗

Silica induces nuclear factor-kappaB activation through TAK1 and NIK in Rat2 cell line.

Silica has been known to be a factor in acute cell injury and chronic pulmonary fibrosis. In Rat2 fibroblasts, silica induced the activation of nuclear factor-kappa B (NF-kappaB), which plays a crucial role in regulating the expression of many genes involved in the subsequent inflammatory response. In addition, we observed that transforming growth factor-beta activated kinase 1 (TAK1) and NF-kappaB-inducing kinase (NIK) were involved in silica-mediated NF-kappaB activation in Rat2 cells. The dominant negative mutant forms of TAK1 and NIK inhibited the silica-induced NF-kappaB activation in Rat2 cells. Furthermore, we demonstrated that endogenous TAK1 is phosphorylated in silica-stimulated Rat2 cells. These results indicate that TAK1 functions as a critical mediator in the silica-induced signaling pathway.

Animals↗

Protein phosphorylation in alveolar macrophages after stimulation with heavy metal-coated silica particles.

The aim of our study was to determine agonist- and time-dependent phosphorylation of distinct proteins in bovine alveolar macrophages after activation with quartz dusts and heavy metal-coated silica particles. Silica particles were coated with vanadium oxide or cadmium oxide. Separation of proteins was achieved by one-dimensional and optimized horizontal two-dimensional polyacrylamide gel electrophoresis. Protein phosphorylation was either determined by [32P] labeling and subsequent autoradiography or Western blotting using monoclonal antibodies against phosphotyrosine. One of the phosphorylated proteins was identified as the heat shock protein HSP-27. Stimulation with cadmium oxide-coated silica particles and PMA led to a significant increase of phosphorylated HSP-27. Additionally cadmium oxide-coated silica particles induced tyrosine phosphorylation of six main proteins. Stimulation with vanadium oxide-coated silica particles drastically increased the amount of tyrosine phosphorylated proteins while this effect was not observed with uncoated silica particles.

Animals↗

Effect of silica on the genetic regulation of antibody responsiveness.

The high (H) and low (L) antibody responder lines of mice produced by selective breeding are characterized by different modifications in immunocompetent cell potentialities, according to the immunization procedure used for the selection process. In selections I and II, the difference in antibody responsiveness between H and L lines was clearly shown to depend mainly on macrophage function: the more rapid catabolism of antigens in L mice was the main cause of the low antibody production. In contrast, up to now, no difference has been observed between H and L mice of selections III and IV in terms of the macrophage accessory role. The administration of silica particles has a well known impairment effect on macrophage activity. Therefore, the effect of silica injection on the kinetics of antibody responses to selection antigens was compared in H and L mice of the four selections. Silica was given either intravenously or locally in one hind footpad 6 or 24 h before immunization by the same route. Silica treatment consistently improved antibody responsiveness in the L mice of selections I and II, but had no effect in the L mice of selections III and IV. The antibody responses of the H lines of the four selections were not substantially modified by silica injections. Therefore, the silica treatment reduced the interline difference in antibody responses in selections I and II only, by interfering with the expression of the genetic modification of macrophage activity. However, a similar effect was not obtained with other substances known to affect macrophages, including dextran sulphate or carrageenan. The results reported here are in agreement with the above-mentioned statement that the genetic modification of macrophage function plays a major role in the interline difference in selections I and II and is not involved in selections III and IV.

Animals↗