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PubMed1999

Adsorption Mechanism of Conventional and Dimeric Cationic Surfactants on Silica Surface: Effect of the State of the Surface.

The aim of this study was to investigate the effect of the state of the silica surface and of the surfactant molecular structure on the adsorption of cationic surfactants onto silica. Thus, the adsorption of DTAB (dodecyltrimethylammonium bromide) and of the dimeric surfactant 12-2-12 (ethanediyl-1,2-bis(dodecyldimethylammonium bromide)) on raw silica (SiNa) and on HCl-washed silica (SiH) has been investigated under "free" system conditions. The amount of surfactant adsorbed (adsorption isotherm), the sodium ion and bromide ion concentrations and the pH in the equilibrated supernatant, and the silica particle electrophoretic mobility have been measured along the isotherms. The adsorption mechanisms of the two surfactants on the raw and washed silica are qualitatively similar. Nevertheless, important quantitative differences are observed which are all due to (i) the larger number of surface sites present at the surface of SiNa with respect to SiH and (ii) the larger ionic strength of the supernatant in SiNa/surfactant systems with respect to SiH/surfactant systems, due to the much larger amount of sodium ions released by SiNa upon surfactant binding. Thus, the amounts of surfactant adsorbed at the point of zero charge and at saturation of the silica particles, of sodium ions released by the surface and the decrease of critical micelle concentration (cmc) in the supernatant with respect to pure water are all larger for the raw silica than for the treated silica. For the four silica/surfactant systems investigated, the first adsorption step corresponds to the adsorption of individual surfactant ions on the negative sites of the silica surface. It is driven by electrostatic interactions and strongly dependent on the number of surface sites and ionic strength associated to the released ions. At the end of the first adsorption step, which is clearly seen with SiH/surfactant systems, the second adsorption step starts. This step is driven by hydrophobic interaction between surfactant alkyl chains and results in the formation of surface aggregates. The surfactant adsorption on the surface is shown to continue even after the cmc in the supernatant is reached. Copyright 1999 Academic Press.

Journal Article↗
PubMed1986

Silica containing primary hydroxyl groups for high-performance affinity chromatography.

Primary hydroxyl groups were incorporated into silica by a four-step reaction procedure which includes modification of the silica surface with gamma-glycidoxypropyltrimethoxysilane, leading to an epoxide silica; hydrolysis with acid to yield a diol silica; oxidation of the diol silica with periodate to yield a silica resin with aldehyde functions; and reduction with sodium borohydride to obtain the primary hydroxyl-containing silica. The hydroxyl groups were activated with chloroformates or carbodiimidazole. Proteins were coupled under mild conditions in high yield to these activated silica resins. Columns containing these newly developed silica derivatives were used for the fast and efficient purification of antibodies on antigen-containing silica, as well as for the purification of trypsin on a trypsin inhibitor column (or vice-versa). The effect of pressure on association and dissociation of the affinity complex is discussed.

Antibodies↗
PubMed1992

Enzymatic syntheses of DNA-silicas using DNA polymerase.

Oligothymidylic acids couple to an activated ester silica (N-hydroxysuccinimidyl-silica) only when they contain an added aminoalkyl group. Heteropolymeric oligomers containing other nucleotide bases were shown to also couple by way of the nucleotide base (adenine, cytosine, or guanine); however, when a heteropolymeric oligonucleotide also contains a 5'-aminoalkyl moiety, coupling by way of the latter is the favored reaction. When duplex hybrids of oligonucleotides are formed, the nucleotide bases are protected from chemical coupling. Coupling by way of nucleotide bases would be detrimental to some chromatography experiments. On the basis of these observations, two different procedures were developed to produce DNA-silicas in which a single strand of the DNA is coupled by only its 5'-terminus. In the first of these, the polymerase chain reaction was used with a 5'-aminoalkyl primer to make a duplex DNA with one strand containing the 5'-aminoalkyl group and the duplex DNA is then coupled to the activated ester silica. This yielded a silica containing about 0.17 nmol of a 242-mer per gram silica which bound only probes specific for the coupled strand. In the other procedure, a template DNA strand was poly(A) tailed and hybridized to (dT)18-silica. DNA polymerase I (Klenow large fragments) was then used to copy the template-specified sequence directly onto the 3'-terminus of the (dT)18. This procedure yielded about 1.2 to 2.7 nmol DNA copied/g of silica of a specific 21-mer sequence. The DNA-silica produced selectively hybridized only with complementary sequences and not with DNA lacking that sequence. Either of these procedures thus produces DNA-silicas from heteropolymeric DNA sequences with a predetermined, specific 5'-terminal site of attachment.

Base Sequence↗
PubMed2006

Enzyme-encapsulated silica monolayers for rapid functionalization of a gold surface.

We report a simple and rapid method for the deposition of amorphous silica onto a gold surface. The method is based on the ability of lysozyme to mediate the formation of silica nanoparticles. A monolayer of lysozyme is deposited via non-specific binding to gold. The lysozyme then mediates the self-assembled formation of a silica monolayer. The silica formation described herein occurs on a surface plasmon resonance (SPR) gold surface and is characterized by SPR spectroscopy. The silica layer significantly increases the surface area compared to the gold substrate and is directly compatible with a detection system. The maximum surface concentration of lysozyme was found to be a monolayer of 2.6 ng/mm(2) which allowed the deposition of a silica layer of a further 2 ng/mm(2). For additional surface functionalization, the silica was also demonstrated to be a suitable matrix for immobilization of biomolecules. The encapsulation of organophosphate hydrolase (OPH) was demonstrated as a model system. The silica forms at ambient conditions in a reaction that allows the encapsulation of enzymes directly during silica formation. OPH was successfully encapsulated within the silica particles and a detection limit for the substrate, paraoxon, using the surface-encapsulated enzyme was found to be 20 microM.

Aryldialkylphosphatase↗
PubMed2000

Epidemiological evidence on the carcinogenicity of silica: factors in scientific judgement.

In view of the extended debate and differing opinions on whether crystalline silica is a human carcinogen, we have reviewed a selection of epidemiological reports, to identify the areas of uncertainty and disagreement. We have chosen to examine the papers which in a recent review were considered to provide the least confounded examinations of an association between silica exposure and cancer risk. We also refer to a study of the mortality of coalminers very recently reported by ourselves and colleagues. We find that parts of the evidence are coherent but there are contradictions. On examination this resolves mostly into differences between types of studies. The three types of epidemiological study included are: (i) exposure-response studies, the most powerful for the confirmation of a relationship between a specific exposure and a health effect; (ii) descriptive studies in which incidence of disease in an exposed population is compared with that in a reference population; and (iii) studies of incidence of disease in subjects on silicosis case-registers. Descriptive studies frequently though not invariably suggest an excess lung cancer risk in silica-exposed workers compared with the general population, but exposure-response studies consistently fail to confirm that the cause is exposure to quartz. A single exposure-response study of cristobalite suggests a positive relation. Both sets of evidence have weaknesses. There are uncertainties on whether the excess risks in the descriptive studies are related to silica exposure or to lifestyle, including smoking habits. There are doubts on whether the exposure estimates in some of the exposure-response studies were sufficiently reliable to detect a small risk or weak association, though they are unlikely to have missed a strong effect. Studies of subjects on silicosis case registers consistently show an excess of lung cancer, but it is not clear to what extent these increased risks represent a direct effect of silica exposure, a secondary effect of the silicosis, preferential inclusion of subjects suffering from the effects of smoking, or bias in diagnostic accuracy. This not unnaturally leads to differences in opinion, exacerbated by variations in the strength of proof required by different experts. The main scientific uncertainties in the evidence are: 1. Whether, in the descriptive studies, the excess lung cancer rates in silica-exposed workers are explicable in terms of smoking habits, socio-economic class differences and inappropriate comparison populations. Better smoking information and more carefully chosen comparison populations are needed; 2. Whether the exposure-response studies could have missed a real relationship between silica exposure and lung cancer, if one exists. Many of the exposure-response studies were conducted with great care, but weaknesses, in the available data on which the exposure estimations were based, could have caused a real relationship of lung cancer and silica exposure to be missed. These studies were sufficiently powerful to demonstrate relationships of silica exposure with silicosis and silico-tuberculosis, so it is unlikely that they would have missed any but a small risk, or weak relationship, for lung cancer. Our own recent study of coalminers used uniquely detailed and reliable exposure data, and failed to demonstrate convincingly an increased risk. This negative finding, though, applies only to a dust in which the proportion of quartz in the dust is usually less than 10%. Exposure-response studies are needed, with high quality exposure estimates, in populations exposed to respirable dust of which crystalline silica comprises more than 10%; 3. Whether the excess cancer risks in subjects on silicosis registers are the result of selection and diagnostic bias. Given these difficulties, case-register studies may not be capable of giving a reliable answer to the central question, though they have been useful in pointing to the possibility of a can

Carcinogens↗
PubMed1997

Separation of enantiomers on a chiral stationary phase based on ovoglycoprotein. I. Influences of the pore size of base silica materials and bound protein amounts on chiral resolution.

The influences of the pore size of base silica gels and the bound amounts of ovoglycoprotein (OGCHI) on the chiral resolution of racemates have been investigated. To the 12-, 20- and 30-nm pore size silica gels, aminopropyl groups were introduced, activated with N,N'-disuccinimidyl carbonate and then reacted with OGCHI followed by blocking with D-glucosamine. For the OGCHI material prepared with the same pore size silica gel, a linear correlation was obtained between the capacity factor or each enantiomer and the amount of bound OGCHI. Enantioselectivity and resolution obtained with the reaction of 40 mg OGCHI per 1 g silica gel were lower than those obtained with the reaction of 80, 160 and 320 mg OGCHI, when the same pore size silica gel was used. This is due to the superfluous achiral interaction with base silica gels and/or spacers because of low protein coverage. With regard to comparison of the pore sizes of silica gel, the OGCHI materials prepared with the 12-nm pore size silica gel gave the largest capacity factor, and the highest enantioselectivity and/or resolution for the racemates tested, when the same amount of OGCHI was reacted. Thus, the OGCHI materials were prepared with the reaction of 80 mg OGCHI per 1 g silica gel having a 12-nm pore size followed by blocking with D-glucosamine. By diminishing the superfluous achiral interaction with base silica materials and/or spacers, much more efficient OGCHI materials should be obtainable.

Chemical Phenomena↗
PubMed2002

[Characteristics of lung cancer in patients exposed to silica at work. A comparison of exposed and non-exposed individuals].

INTRODUCTION: In 1977 silica was listed as a group 1 carcinogen (demonstrated in humans) by the International Agency for Research on Cancer. However, conflicting results from various studies have kept debate alive as to its carcinogenic capacity. The interest of this debate lies in the large number of workers exposed to silica. OBJECTIVE: To analyze the differential characteristics of lung cancer among silica exposed and silica non-exposed individuals, to identify indirectly a possible carcinogenic effect of silica. METHODS: For all males with a diagnosis of lung cancer over a period of 22 consecutive months at the National Silicosis Institute (Oviedo, Spain), we recorded work history, age, smoking habits, spirometry, the presence of pneumoconiosis and histology. RESULTS: Comparing the results for silica exposed and non-exposed individuals, we found significant differences for age (63.7 8.8 and 66.7 8.6 y, respectively; p < 0.05), smoking (44.1 22.4 and 48.9 22.3 packs/year; p < 0.05) and a Tiffeneau index under 70% (in 78% of exposed vs. 55% of non-exposed patients; p < 0.05). No significant differences in histology, signs and symptoms or radiographs were observed between the two groups. In the multifactorial analysis in function of age of onset, exposure to silica continued to be an independent predictor. CONCLUSION: Our results show that the clinical and radiological signs and histology of patients exposed or non-exposed to silica did not differ. However, lung cancer appears earlier among individuals with work-related exposure to silica and lower rates of tobacco smoking, suggesting some carcinogenic effect for silica.

Aged↗
PubMed2004

A sol-gel method using acetic anhydride in the presence of cholesterol in organic solution media: preparation of silicas that recognize steroid hormones.

Silicas were prepared by a sol-gel method from tetraethoxysilane and acetic anhydride in the presence of cholesterol in organic solution media. Some silicas had higher pore volumes than silicas obtained in the absence of cholesterol. The adsorption abilities by these silicas were compared using various compounds in benzene solution. Although no clear difference among their adsorptions of cholesterol was observed, progesterone and other analogous steroid hormones were well adsorbed by silicas prepared in the presence of cholesterol, especially, prepared with n-heptane as an additional solvent. This silica adsorbed steroid hormones more selectively than other analogous compounds such as bisphenol A and hexestrol. On the other hand, a silica prepared by the usual aqueous sol-gel method with cholesterol had no clear adsorption selectivity to steroid hormones. Furthermore, no selective adsorption of steroid hormones was observed in the case of a common silica gel for column chromatography. This unique property of adsorption observed in silicas prepared using acetic anhydride in the presence of cholesterol is likely to be induced by the imprinting effect of the steroid skeleton part of cholesterol in silica matrix.

Acetic Anhydrides↗
PubMed2006

Silica-shelled single quantum dot micelles as imaging probes with dual or multimodality.

The present study describes a stabilization of single quantum dot (QD) micelles by a "hydrophobic" silica precursor and an extension of a silica layer to form a silica shell around the micelle using "amphiphilic" and "hydrophilic" silica precursors. The obtained product consists of approximately 92% single nanocrystals (CdSe, CdSe/ZnS, or CdSe/ZnSe/ZnS QDs) into the silica micelles, coated with a silica shell. The thickness of the silica shell varies, starting from 3-4 nm. Increasing the shell thickness increases the photoluminescence characteristics of QDs in an aqueous solution. The silica-shelled single CdSe/ZnS QD micelles possess a comparatively high quantum yield in an aqueous solution, a controlled small size, sharp photoluminescence spectra (fwhm approximately 30 nm), an absence of aggregation, and a high transparency. The surface of the nanoparticles is amino-functionalized and ready for conjugation. A comparatively good biocompatibility is demonstrated. The nanoparticles show ability for intracellular delivery and are noncytotoxic during long-term incubation with viable cells in the absence of light exposure, which makes them appropriate for cell tracing and drug delivery. The presence of the hydrophobic layer between the QD and silica-shell ensures an incorporation of other hydrophobic molecules with interesting properties (e.g., hydrophobic paramagnetic substances, hydrophobic photosensitizers, membrane stabilizers, lipid-soluble antioxidants or prooxidants, other hydrophobic organic dyes, etc.) in the close proximity of the nanocrystal. Thus, it is possible to combine the characteristics of hybrid materials with the priority of small size. The silica-shelled single QD micelles are considered as a basis for fabrication of novel hybrid nanomaterials for industrial and life science applications, for example, nanobioprobes with dual modality for simultaneous application in different imaging techniques (e.g., fluorescent imaging and functional magnetic resonance imaging).

Contrast Media↗
PubMed2001

A fluorescence spectroscopic study of phenanthrene sorption on porous silica.

Fluorescence spectroscopic characteristics of sorbed phenanthrene in porous silica provide information about its chemical state such as monomer vs dimer or higher aggregates, as well as a basis for high sensitivity detection. In this study, the chemical state and distribution of phenanthrene sorbed in two types of porous silica particles, mesoporous silica (365 microns particle diameter, 150 A average pore diameter) and microporous silica (custom synthethized, 1 micron particle diameter, 20 A pore diameter), is determined by fluorescence spectroscopy, fluorescence lifetime measurements, and scanning two-photon excitation fluorescence profiling. From the characteristic fluorescence emission spectra, it is found that at loading levels of < or = 4.7 mg/g (phenanthrene/silica) phenanthrene exists as monomers in both meso- and microporous silica particles for phenanthrene loaded from super critical CO2 (SCF). Two-photon excitation fluorescence intensity distribution profiles indicate that for the mesoporous silica particles phenanthrene is adsorbed throughout the entire silica particle. Introduction of water into phenanthrene-loaded mesoporous silica particles causes instantaneous conversion of phenanthrene from monomer to crystalline form at phenantherene loading levels > or = 4.7 micrograms/g due to hydration of the silica surface. In this process, sorption of water molecules expels phenanthrene from the surface sorption sites and causes localized phenanthrene concentration beyond its solubility limit, resulting in crystallization. In comparison this fast conversion is not observed for phenanthrene-loaded microporous silica particles that show extremely slow conversion even for phenanthrene loading levels as high as 4.7 mg/g. This difference is interpreted as reflecting hindered diffusion of phenanthrene in the nearly monodispersed micropores with pore sizes close to the molecular diameter of phenanthrene.

Absorption↗
PubMed2003

Investigation of the inhibitory effect of silica on the degradation of 1,1,1-trichloroethane by granular iron.

Although iron-based permeable reactive barriers are gaining importance for treating groundwater contaminants, little is currently known about the effect of cosolutes on barrier longevity. Because of their corrosion inhibiting properties, dissolved silica species are of particular concern. This research investigates the effect of silica on the reduction of 1,1,1-trichloroethane by granular iron as a function of added silica concentration, pH, and duration of iron exposure to dissolved silica. Batch studies reveal that, at pH 8.5 and above, added silica concentrations as low as 0.17 mM cause a 30% reduction in the reactivity of iron. At higher silica concentrations, reactivity decreases by 65-75%. The inhibitory effect is greater at higher pH: 0.83 mM silica has no apparent adverse effect at pH 7.5, but leads to a 46% decrease in reaction rate at pH 8 and 90% at pH 9. This corresponds to observed trends in silica adsorption onto iron, which is low at pH 7.3 but increases at higher pH. Extending the duration of iron exposure to silica solutions also leads to a more pronounced inhibitory effect. This is in good agreement with the increase in silica coverage on the iron surface as revealed by X-ray photoelectron spectroscopy.

Corrosion↗
PubMed2004

Synthesis of monodisperse high-aspect-ratio colloidal silicon and silica rods.

We describe the synthesis and the physical properties of suspensions of colloidal silicon and silica rodlike particles. In addition to pure silicon and pure silica rods, we have also synthesized silicon rods with a silica shell and silica rods with a fluorescent silica layer. Pre-patterned p-type (100) silicon wafers were electrochemically etched in electrolyte solutions containing hydrogen fluoride. By the current density being varied while etching, macropores were etched with controllable modulated pore diameters. These silicon structures were transformed into rods with indentations 5.5 mum apart and with lengths up to 100 mum using iterative oxidation in air and dissolution of the silica by HF. Complete oxidation of these rods was also achieved. Sonication of the modulated rods resulted in monodisperse particles of 5.5 mum length and 300 nm width. A high yield of 10(12) particles, or more, is possible with this method. At high concentrations, these particles show nematic ordering in charge-stabilized suspensions. The oxidized silica outer layer of the silicon rods makes the further growth of silica in solution or on a wafer possible. This allows for control of the particles' interaction potential. Labeling with a fluorescent dye and index matching of the complete silica rods enable the study of concentrated dispersions quantitatively, on a single particle level, with confocal microscopy. Because of their high refractive index in the near-IR, the nematic phases of rods with a silica core are also interesting for photonic applications.

Colloids↗
PubMed2005

Micropore to macropore structure-designed silicas with regulated condensation of silicic acid nanoparticles.

A new preparation method for porous silica particles was developed using activated silica sols which are called nano-silica solutions in this paper. Several kinds of organic and inorganic acids are employed to neutralize diluted sodium silicate solutions to form the nano-silica solutions: formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, dl-malic acid, citric acid, and tricarballylic acid as carboxylic acids, and sulfuric acid and hydrochloric acid as inorganic acids. The effect of salts in the nano-silica solution is also studied. The products were investigated using a field emission scanning electron microscope, an X-ray diffractometer, the nitrogen adsorption technique, and a mercury porosimeter. Microporous silicas were produced when carboxylic acids were applied; the formation of micropores was influenced by the pH of the nano-silica solutions and molecular sizes of the carboxylic acids. Addition of a salt in a citric acid solution increased the mesopore volume. Macropores were formed when inorganic acids including salts were applied; the salt nanoparticles which were crystallized in silica spheres acted as templates. The anion types and salt concentrations in the nano-silica solutions affected the aggregation condition of silica nanoparticles, following the Schulze-Hardy rule.

Journal Article↗
PubMed1999

Freshly fractured crystalline silica induces activator protein-1 activation through ERKs and p38 MAPK.

The transcription factor activator protein-1 (AP-1) reportedly plays an important role in the induction of neoplastic transformation and multiple genes involved in cell proliferation, differentiation, and inflammation. To investigate the mechanisms of silica-induced carcinogenesis, AP-1-luciferase reporter transgenic mice were used as an in vivo model, whereas the JB6 mouse epidermal cell line and a rat lung epithelial cell line were employed as in vitro models to study the effects of silica at the molecular level. Freshly fractured silica caused an 8-fold increase in AP-1 activity in JB6 cells and a 2.5-fold increase in rat lung epithelial cells. The induction of AP-1 activity in cultured cell lines was time- and dose-dependent. Intratracheal administration of silica was also able to induce AP-1 transactivation in transgenic mice. AP-1 activation was first observed at 2 days after silica administration and reached its maximum at 3 days post-exposure of the mice to silica. The signal transduction pathways for AP-1 activation were also investigated using these cell lines. The results demonstrate that freshly fractured silica stimulates mitogen-activated protein kinase (MAPK) family members, as determined by the phosphorylation of p38 MAPK and extracellular signal-regulated protein kinases (ERKs). Inhibition of ERKs with PD98059 or of p38 with SB203580 significantly inhibited silica-induced AP-1 activation. These findings demonstrate for the first time that freshly fractured silica induces AP-1 activation, which may be mediated through p38 MAPK and ERK pathways. Unraveling the complex mechanisms associated with these events may provide insights into the initiation and progression of silica-induced carcinogenesis.

Animals↗
PubMed1996

Characteristics of the acute-phase pulmonary response to silica in rats.

Exposure to silica, a cytotoxic and fibrogenic mineral dust, has been demonstrated to cause pulmonary inflammation and damage to the lung tissue. In contrast to the long-term consequences, little information exists on the sequence of inflammatory/damaging events occurring acutely after exposure to silica. The purpose of this study was to determine the minimum time after the administration of silica that the inflammatory/damage response is detectable and the temporal relationship of these processes. Male Fischer 344 rats were dosed intratracheally with silica (2.5 or 10 mg/100 g body weight) or saline vehicle. At 2 and 4 h after instillation, both cellular (total cell count and neutrophil count) and biochemical (total protein, albumin, and beta-glucuronidase and lactate dehydrogenase activities) parameters of inflammation and damage were evaluated in the bronchoalveolar lavage fluid. At 2 h, total protein levels were elevated at both silica doses, but all other parameters were unchanged; however, 4 h after silica exposure all parameters were elevated over those of the saline control. In a further attempt to characterize the inflammatory/damage processes, luminol-dependent chemiluminescence (LDCL) was performed on aliquots of chopped lung. At 2 h after silica instillation, phorbol myristate acetate-stimulated lung tissue from silica-treated rats had no increase in light production when compared to controls, whereas after 4 h there were significant increases in LDCL activity in both dose groups when compared to controls. The addition of superoxide dismutase (SOD) decreased LDCL activity of the 2.5 mg/100 g group by 59% (2 h) and 66% (4 h), and of the 10 mg/100 g group by 49% (2 h) and 73% (4 h). Alternatively, the addition of N-omega-nitro-L-arginine methyl ester (L-NAME), an inhibitor of nitric oxide synthase, decreased the 2.5 mg/100 g group by 52% (2 h) and 60% (4 h). The 10 mg/100 g group was decreased by 67% (2 h), but only exhibited a 12% reduction at 4 h. SOD and L-NAME also inhibited the background LDCL in saline-treated rats. These reductions in LDCL activity indicate that reactive oxygen and nitrogen species play a role in the acute phase pulmonary response from silica. The results of this study indicate that the initial stages of damage begin to appear by 2 h, but damage and inflammation are definitive by 4 h after administration of silica in rats.

Albumins↗
PubMed2002

Silica-induced generation of extracellular factor(s) increases reactive oxygen species in human bronchial epithelial cells.

Chronic inflammation and production of DNA-damaging reactive oxygen species (ROS) may be involved in silica-induced lung cancer. Studies to date have largely focused on silica-induced production of ROS by lung phagocytes. In this study, we investigated the hypothesis that particulate silica (DQ12) can also induce elevations in intracellular ROS in a cancer-target cell type, i.e., human bronchial epithelial cells (BECs), via an indirect mechanism that involves ROS-inducing extracellular factor(s) that occur upon the interaction of silica with culture medium. The intracellular production of hydrogen peroxide (H(2)O(2)) in BECs was assessed by flow cytometry via monitoring dichlorofluorescein (DCF) fluorescence. Culture medium containing 10% human serum was incubated with silica particles in concentrations ranging from 10 to 50 microg/ml, and following incubation for 1 h and removal of the particles, the resulting supernatants were added to BECs. Silica-treated medium induced significant increases in intracellular H(2)O(2) after the medium had been treated with as little as 10 microg/ml of the particles. Further, the level of ROS increases in BECs in response to silica-treated medium was found to be virtually identical to that induced in cells that were directly treated with silica in suspension. Based on enzyme inhibitory studies, the mechanism for this increased generation of intracellular ROS appears to involve both mitochondrial respiration and a NAD(P)H oxidase-like system. Spectrofluorimetric experiments with the antioxidant enzymes superoxide dismutase and catalase showed that superoxide anions (O2*-) and H(2)O(2) are generated in silica-treated medium, but these ROS do not fully account for the induction of the intracellular ROS response. Iron, on the other hand, was found to be crucial to the process. Our collective results suggest silica-aqueous medium interactions can lead to the generation of factor(s) that induce the intracellular production of potentially DNA-damaging ROS in BECs in a manner that does not require direct particle-cell interactions.

Bronchi↗
PubMedDate not supplied

Silica-containing urinary calculi in dogs (1981-1993).

Silica-containing urinary calculi obtained from 773 dogs and submitted by veterinarians throughout the United States were analyzed by quantitative crystallographic analysis to determine mineral composition. Specimens were composed of either multiple mineral layers (535 specimens) or 1 mineral layer (238 specimens). Most multiple-layer calculi were composed of 80% or greater silica (300 of 535, 56%) or 20% to 79% silica (184 of 535, 34%) in any mineral layer. Most 1-layer calculi were composed of 100% silica (212 of 238, 89%). Most dogs forming silica-containing calculi were of male gender (679 of 773, 88%). Bacterial cultures of calculus or urine or both were performed on 49% (376 of 773) of the specimens, and bacterial growth was obtained from 37% (139 of 376) of samples cultured. The prevalence of calculus-associated urinary tract infection was 35% (113 of 321) in males and 47% (26 of 55) in females. The gender prevalence for infection with Staphylococcus species was 16% (51 of 321) in males and 33% (18 of 55) in females. The breed and gender of dogs that formed calculi (silica population) were compared with the hospital population (Veterinary Medical Teaching Hospital [VMTH] population) and with a population of calculus-forming dogs (Stonelab population) to determine risk factors for silica calculus formation. For all breeds compared, the ratio of males to females was higher in the silica population. The German Shepherd Dog and Old English Sheepdog were significantly overrepresented when the silica population was compared with either the VMTH population or the Stonelab population. We conclude that male German Shepherd Dogs and Old English Sheepdogs are at increased risk for formation of silica-containing urinary calculi.

Animals↗
PubMed1992

Relation between exposure to respirable silica dust and silicosis in a tungsten mine in China.

To estimate the quantitative relation between exposure to respirable silica dust and risk of an attack of silicosis, 1151 workers exposed to silica dust and employed from 1958 to 1987 in a tungsten mine in China were investigated. The results showed that the ratio of respirable silica dust concentration to total silica dust concentration was 0.529. Then, the total silica dust concentration in historical surveillance and monitoring data was converted to respirable silica dust concentration. The free silica content in respirable dust determined by x ray diffraction averaged 24.7%. Multiple logistic regression was used for the dichotomous dependent variables (presence or absence of silicosis). The independent variables in the multiple logistic regression with presence of silicosis as the dependent variable were age when first exposed, tuberculosis (presence or absence), and cumulative exposure to respirable silica dust. The partial regression coefficient of individual cumulative exposure was estimated as 0.079. It implied a positive association between exposure to respirable silica dust and risk of an attack of silicosis. The exposure limit for respirable silica dust was estimated as 0.24 mg/m3 under given conditions.

Dust↗