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PubMed2001

Photodegradation of SiO2-coated CdS nanoparticles within silica gels.

A comparative study of the photodegradation of CdS nanoparticles coated with silica shells dispersed in water and embedded in two silica gels with different pore size is presented. Although encapsulation of the quantum dots in a silica shell previously was proven to provide a basically permanent protection against light-induced surface oxidation (photodegradation), this protection is not always maintained when the coated particles are incorporated within different silica gels. Degradation of the CdS occurs when the coated particles are incorporated within silica gels with an open structure, which suggests that the shells somehow crack due to tension in the gel structure. This behavior is analyzed by absorption and luminescence spectroscopies, electron microscopy, and nitrogen sorption.

Cadmium Compounds↗
PubMed1992

In vitro studies of the efficacy of reversed phase silica gel as a sorbent for hemo- and plasmaperfusion.

The clearance capacities of reversed phase silica gel, widely used in analytical chemistry, were studied in vitro. The plasma clearances of amitriptyline, quinidine, digoxin, digitoxin, methaqualone, phenobarbital and phenytoin were determined at typical toxic plasma levels. Between 88.8 and 99.5% of the drugs were eliminated from plasma by reversed phase silica gel, which compares favorably with amberlite XAD-4 and coated activated charcoal. The biocompatibility of reversed phase silica gel was also evaluated in vitro. Thrombocytopenia and leukopenia were noted while coagulation parameters, electrolytes, acid-base balance, glucose, urea, creatinine, uric acid, total protein, albumin, bilirubin, cholesterol and triglycerides were not significantly affected. Preliminary results in vitro support the high clearance capacity of reversed phase silica gel and suggest a biocompatibility similar to that of other sorbents currently in use. Further investigation of the clearance capacities and biocompatibility of reversed phase silica gel seems justified.

Biocompatible Materials↗
PubMed1998

Surveillance of respirable crystalline silica dust using OSHA compliance data (1979-1995).

BACKGROUND: The objective of this work was to estimate the percentage of workers by industry that are exposed to defined concentrations of respirable crystalline silica dust. METHODS: An algorithm was used to estimate the percentage of total workers exposed to crystalline silica in 1993 at concentrations of at least 1, 2, 5, and 10 times the National Institute for Occupational Safety and Health (NIOSH) Recommended Exposure Limit (REL) of 0.05 mg/m3. Respirable crystalline silica air sampling data from regulatory compliance inspections performed by the Occupational Safety and Health Administration (OSHA), for the years 1979-1995, and recorded in the Integrated Management Information System (IMIS) were used to estimate exposures. Therefore, this work does not include industries such as mining and agriculture that are not covered by OSHA. The estimates are stratified by Standard Industrial Classification (SIC) codes. RESULTS: This work found that some of the highest respirable crystalline silica dust concentrations occurred in construction (masonry, heavy construction, and painting), iron and steel foundries (casting), and in metal services (sandblasting, grinding, or buffing of metal parts). It was found that 1.8% (13,800 workers) of the workers in SIC 174--Masonry, Stonework, Tile Setting, and Plastering--were exposed to at least 10 times the NIOSH REL. For SIC 162--Heavy Construction, Except Highway and Street Construction--this number is 1.3% (6,300 workers). SIC 172--Painting and Paper Hanging--which includes construction workers involved in sandblasting was found to have 1.9% (3,000 workers) exposed to at least 10 times the NIOSH REL. The industry that was found to have the highest percentage of workers (6%) exposed to at least the NIOSH REL was the cut stone and stone products industry. CONCLUSION: Not enough is being done to control exposure to respirable crystalline silica. Engineering controls should be instituted in the industries indicated by this work.

Algorithms↗
PubMed1986

Effects of silica on lung collagen.

A single intratracheal injection of 50 mg crystalline silica (quartz) into rats produces silicosis. This animal model may be used to study collagen metabolism during the early, middle, and late phases of lung injury, corresponding respectively to the stages of lung injury, development of discrete granulomas, and development of mature silicotic nodules. The early phase is characterized by a rapid increase in the rate of synthesis of lung collagen (within one week of instillation) and increased deposition of excess lung collagen (significant increases within two weeks of instillation). Later phases are characterized by a continuing increase in deposition of excess lung collagen for at least one year after instillation. Silica-induced fibrosis is unique among all the animal models (and in most human fibrotic diseases) thus far examined, in that the excess collagen deposited in the lung contains normal ratios of the two major collagen types of the lung: types I and III. This collagen is nonetheless biochemically different from normal lung collagen. There are reproducible and characteristic differences in the intermolecular cross-links of the collagen in lungs from rats injected with silica. Within one month of silica instillation (the earliest time point examined thus far), an increased hydroxylysine content of collagen can be appreciated. The reducible dysfunctional cross-links are also more likely to be derived from hydroxylysine (i.e. the ratio of dihydroxylated to monohydroxylated cross-links increases). Within four months of silica instillation (and increasingly thereafter), increased amounts of the mature trifunctional cross-link hydroxypyridinium (derived from three residues of hydroxylysine) can also be appreciated, seemingly paralleling the evolution of mature silicotic nodules in these lungs. These changes in cross-linking of lung collagen seem to be common to all the animal models of pulmonary fibrosis examined, and are also consistent with changes occurring in human fibrotic lungs. Preliminary observations suggest that the locus of cross-linking remains the same: hydroxylysine replaces lysine in the primary structure of a specific collagen alpha chain to form the altered cross-links. Thus, there may be molecular markers for the collagen of fibrosis in diseased lungs.

Animals↗
PubMed2003

Monitoring of DNA damage in foundry and pottery workers exposed to silica by the alkaline comet assay.

BACKGROUND: Workers in foundry and pottery are exposed to a mixture of chemicals and silica, which is suspected to cause genetic alterations. METHODS: To investigate the potential hazard associated with the occupational exposure to silica, DNA damage in the peripheral lymphocytes of 30 foundry and 22 pottery workers were examined by the alkaline single-cell gel electrophoresis or Comet Assay, and compared to 52 healthy subjects with no history of occupational silica or chemical exposure. RESULTS: The DNA damage observed in the lymphocytes of both foundry and pottery workers was significantly higher than that in their controls. Cigarette smoking was also related to DNA damage since the DNA damage observed in smoking silica-exposed workers compared with the non-smoking workers was significantly higher. CONCLUSIONS: Occupational exposure of silica from foundry and pottery workplaces has been associated with the increased DNA damage and smoking which represents an additional risk factor and must be avoided.

Adolescent↗
PubMed1995

Silica exposure and autoimmune diseases.

There have long been case reports linking silica exposure to a variety of autoimmune diseases (systemic sclerosis, rheumatoid arthritis, lupus, chronic renal disease). Evidence of this association in larger epidemiologic studies has been increasing in the last decade. We summarize this evidence here, and present some plausible mechanisms which have been discussed in the literature. The link between silica exposure and autoimmune disease may have been missed in cohort mortality studies because autoimmune diseases are rarely underlying causes of death. Similarly, case-control studies of autoimmune diseases have often failed to consider occupational exposure to silica. Further research is needed in occupationally exposed populations to verify this association. The link between respirable silica exposure and autoimmune disease may have some bearing on the possible association between silicone breast implants and autoimmune disease, although the nature of the silica involved is quite different in the two situations.

Autoimmune Diseases↗
PubMed2003

Creation of double silica nanotubes by using crown-appended cholesterol nanotubes.

New crown-appended cholesterol-based organogelators 1-3, which have one or two cholesterol skeletons as a chiral aggregate-forming site, two amino groups as an acidic proton binding site, and one crown moiety as a cation binding site, were synthesized, and the gelation ability was evaluated in organic solvents. These gelators could gelatinize several organic solvents under 1.0 wt %, indicating that 1-3 act as a versatile gelator of various organic solvents. We observed CD spectra of the acetic acid or propionic acid gels of 1-3 to characterize the aggregation mode in the organogel system. In the CD spectrum of the acetic acid gel 1, the positive sign for the first Cotton effect indicates that the dipole moments of azobenzene chromophores tend to orient into the clockwise direction. On the other hand, propionic acid gels 2 and 3, bearing only one cholesterol, moiety exhibit a negative sign for the first Cotton effect, strongly suggesting that the dipole moments of the azobenzene chromophores orient into the anticlockwise direction. The TEM images of the 1+acetic acid gel resulted in the helical ribbon and tubular structures. Sol-gel polycondensation of tetraethoxysilane (TEOS) was carried out with 1-3 as templates in the gel phase. The silica obtained from the 1+acetic acid gel showed the helical ribbon with 200-1700 nm width and the tubular structure of the silica with constant about 560 nm outer diameter. As far as can be recognized, all the helicity possesses a right-handed helical motif. Since the exciton coupling band of the organogel also shows P (right-handed) helicity, we consider that a microscopic helicity is reflected by a macroscopic helicity. On the other hand, the tubular structure of the silica obtained from the organogels 2 and 3 is somewhat different from that prepared from the organogel 1. The careful examination of SEM and TEM pictures revealed that the tube wall of the silica features a roll-paper-like multilayer structure. Thus, this paper demonstrates successful and rare examples for precise transcription of gel superstructures into inorganic silica materials.

Cholesterol↗
PubMed2004

High-temperature synthesis of stable ordered mesoporous silica materials by using fluorocarbon-hydrocarbon surfactant mixtures.

Highly ordered hexagonal mesoporous silica materials (JLU-20) with uniform pore sizes have been successfully synthesized at high temperature (150-220 degrees C) by using fluorocarbon-hydrocarbon surfactant mixtures. The fluorocarbon-hydrocarbon surfactant mixtures combine the advantages of both stable fluorocarbon surfactants and ordered hydrocarbon surfactants, giving ordered and stable mixed micelles at high temperature (150-220 degrees C). Mesoporous JLU-20 shows extraordinary stability towards hydrothermal treatment (100 % steam at 800 degrees C for 2 h or boiling water for 80 h), thermal treatment (calcination at 1000 degrees C for 4 h), and toward mechanical treatment (compressed at 740 MPa). Transmission electron microscopy images of JLU-20 show well-ordered hexagonal arrays of mesopores with one-dimensional (1D) channels and further confirm that JLU-20 has a two-dimensional (2D) hexagonal (P6 mm) mesostructure. 29Si HR MAS NMR spectra of as-synthesized JLU-20 shows that JLU-20 is primarily made up of fully condensed Q4 silica units (delta=-112 ppm) with a small contribution from incompletely cross-linked Q3 (delta=-102 ppm) as deduced from the very high Q4/Q3 ratio of 6.5, indicating that the mesoporous walls of JLU-20 are fully condensed. Such unique structural features should be directly attributed to the high-temperature synthesis, which is responsible for the observed high thermal, hydrothermal, and mechanical stability of the mesoporous silica materials with well-ordered hexagonal symmetry. Furthermore, the concept of "high-temperature synthesis" is successfully extended to the preparation of three-dimensional (3D) cubic mesoporous silica materials by the assistance of a fluorocarbon surfactant as a co-template. The obtained material, designated JLU-21, has a well-ordered cubic Im3m mesostructure with fully condensed pore walls and shows unusually high hydrothermal stability, as compared with conventional cubic mesoporous silica materials such as SBA-16.

Journal Article↗
PubMed2006

Silica self-assembly and synthesis of microporous and mesoporous silicates.

The microstructure of silica in basic aqueous solutions containing organic cations and prepared from monomeric precursors is reviewed and interpreted within the context of classical ideas of self-assembly of molecular aggregates. The solution properties can be understood by using the pseudo-phase separation approach coupled to the acid-base chemistry of silanol groups and the Poisson-Boltzmann equation. The silica nanoparticles frequently observed in these systems have a core-shell structure with silica in the core and the organic cations at the shell. Individual particles are observed when the forces between particles are repulsive-as is the case for small cations such as tetramethylammonium or tetrapropylammonium-and extended structures such as M41S materials are formed when the forces are attractive--as is the case for surfactants such as cetyltrimethylammonium. These ideas are useful to understand the evolution of zeolite synthesis gels from nucleation to crystal growth. Although at room temperature the silica and the organic cations are segregated, upon heating the organic cations are embedded within the particles. This transformation signals the onset of structure direction whereby the size and geometry of the organic cation induce changes in the structure of silica that may lead to zeolite nuclei.

Journal Article↗
PubMed2003

Estimation and comparison of zeta-potentials of silica-based anion-exchange type porous particles for capillary electrochromatography from electrophoretic and electroosmotic mobility.

Mobilities of different chromatographic particles obtained from two electrokinetic methods were determined and compared. The particles were all based on porous silica, between 3 and 15 microm diameter, and were either native, or derivatized. As intermediate of chemical modification 3-mercaptopropyl-modified silica particles (TP-silica) are obtained. These particles were finally transformed into weakly basic anion exchangers with O-9-(tert-butylcarbamoyl)quinine (tBuCQN) as chiral selector. The electrophoretic mobility of the particles was determined from their migration velocity in an electric field using microelectrophoresis. Electrokinetic chromatography with a capillary column packed with the same particles was used to measure the electroosmotic flow generated. All measurements were carried out in background electrolytes of equal ionic strength (10(-2) mol/L), at pH varying between 3.5 and 9.5. From these data a rough estimation of the zeta-potential was made, taking Helmholtz-Smoluchowski conditions into consideration. With both methods the zeta-potential of the native silica particles is negative throughout, and its value increases with pH. The weakly basic tBuCQN particles have positive zeta-potentials at pH lower than about 7.5, but exhibit a negative zeta-potential above this pH, indicating the dominating effect of residual silanol groups at the silica surface. The zeta-potential for these anion-exchange particles ranged between +30 and -40 mV. The zeta-potentials derived with electrophoresis and electroosmosis agree, showing the adequacy of the approach, although many limitations must be taken into account in the treatment of the electrokinetic phenomena in such porous systems. These restrictions in interpreting mobility and zeta-potential were discussed.

Anion Exchange Resins↗
PubMed1994

The role of hydrated silica, titania, and alumina in inducing apatite on implants.

Pure soluble silica prepared by a sol-gel method induced bone-like hydroxyapatite formation onto its surface when the silica was immersed in a simulated body fluid (SBF), whereas silica glass and quartz did not. This finding directly supports the hypothesis that hydrated silica plays an important role in biologically active hydroxyapatite formation on the surfaces of bioactive glasses and glass-ceramics, which leads to bone-bonding. Gel-derived titania is also a hydroxyapatite inducer because of its abundant TiOH groups. These results provide further insight into the unique osseointegration of titanium and its alloys. It is suspected that gel-derived titania develops an apatite layer by taking calcium and phosphate from the body fluid, thus producing bone-bonding. Although sufficient AlOH groups may remain in the alumina gel, they do not serve to initiate apatite generation when immersed in SBF. This phenomenon explains the fact that an intermediate fibrous tissue is usually found to separate the alumina implant from bone. One may infer that both abundant OH groups and negatively charged surfaces of gel-derived silica and titania are important for hydroxyapatite induction. material which possesses and/or develops both a negatively charged surface and abundant OH groups in a physiologically-related fluid is most likely to be an efficient apatite inducer. Such materials are suitable candidates to serve as bone-bonding biomaterials.

Aluminum Oxide↗
PubMed1995

In vivo calcium phosphate formation induced by sol-gel-prepared silica.

Implantation with plugs made of a porous sol-gel-prepared silica into the femurs of goats demonstrated that a calcium phosphate was formed both on the silica plugs and within the pores inside the silica plugs 12 weeks postoperatively. This observation indicates that a highly hydrated silica surface is effectively catalytic for calcium phosphate nucleation. Calcification can be triggered in physiologic solution under stimulation of the silica gel. A high level of silicon in the uncalcified osteoid region of young bone is thus thought to provide a number of SiOH groups for initiating calcium phosphate formation. Our results provide some information about the mechanism of calcium phosphate mineralization in higher animals. We believe that heterogeneous nucleation of apatite can be induced from metastable calcium phosphate solutions including physiologic fluids on those specific surfaces of materials, where there are abundant acidic OH groups.

Animals↗
PubMed2006

Drug entrapment in silica microspheres through a single step sol-gel process and in vitro release behavior.

A single step sol-gel process was used to precipitate silica microspheres containing ibuprofen or naproxen for controlled drug delivery applications. The drug release behavior from these systems was analyzed in vitro. Pure ibuprofen and naproxen exhibited linear release with time, while sol-gel silica entrapped drugs were released with a logarithmic time dependence starting with an initial burst effect followed by a gradual decrease. Microscopic analysis combined with gravimety and infrared spectroscopy indicated that some of the drug is entrapped as large crystals attached to silica microspheres while the rest is encapsulated inside the microspheres. Drug-loaded silica microspheres with no open porosity and with a narrow particle size distribution were obtained. Both erosion of the microspheres and diffusion through them contributed to drug release. Sol-gel precipitation of silica microspheres is a promising method for drug entrapment and controlled release.

Anti-Inflammatory Agents, Non-Steroidal↗
PubMed1987

Nonresident macrophages in peripheral nerve of rat: effect of silica on migration, myelin phagocytosis, and apolipoprotein E expression during Wallerian degeneration.

The selective toxicity of silica quartz dust to macrophages was used to assess the role of these cells in Wallerian degeneration and nerve repair. Left sciatic nerves of adult Wistar rats were crushed and one group of animals received repetitive intraperitoneal injections of silica (200 mg two times per week starting 1 day prior to injury), whereas the control group received saline. Unexpectedly, silica treatment did not impair the initial invasion of (hematogenous) macrophages into the degenerating distal nerve stump as revealed by histological and immunocytochemical methods. However, 4 weeks after the lesion three specific events in Wallerian degeneration were significantly inhibited in silica-treated animals: 1) inhibition of phagocytosis and degradation of myelin, 2) delay in disappearance of nonresident macrophages from regenerating nerve, 3) reduction of synthesis and/or secretion of apolipoprotein E in resting macrophages. On the other hand, axonal regrowth and remyelination were not affected by silica. These in situ experiments support and extend previous studies suggesting specific functions for nonresident macrophages in Wallerian degeneration of peripheral nerve.

Animals↗
PubMed2006

Two-dimensional and serial column reversed-phase separation of phenolic antioxidants on octadecyl-, polyethyleneglycol-, and pentafluorophenylpropyl-silica columns.

The separation selectivity of octadecyl-silica (C18) and of bonded pentafluorophenylpropyl-silica (F5) and PEG-silica columns was compared for natural phenolic antioxidants. The separation selectivities for phenolic antioxidants on C18 and F5 columns are strongly correlated, but low selectivity correlation indicating strong differences in the retention mechanism was observed between the C18 and PEG columns. Hence, the combination of a C18 and a PEG column is useful for separation of phenolic antioxidants that are not fully separated on single columns. Two-dimensional comprehensive liquid chromatography using a short PEG-silica column in the first dimension and a conventional C18-silica in the second dimension has the advantage of on-column focusing of the fractions transferred onto the C18 column in the second dimension, as a weaker mobile phase is used in the first dimension than in the second dimension. However, a stop-flow set-up in the first dimension system is necessary after the transfer of each fraction to the second dimension. Peak capacity is considerably larger but the separation time is much longer than with serially coupled PEG and C18 columns, which were employed for separation of beer and hop extract samples in connection with coulometric detection.

Antioxidants↗
PubMed1986

Modulation of fibroblast activity by normal and silica-exposed alveolar macrophages.

Silica-induced pulmonary fibrosis is thought to involve fibroblast stimulation by a product of alveolar macrophages (AM) but various cell culture systems have given conflicting results. Macrophage-fibroblast interactions are now studied using an homologous system in which supernatants of rat AM after incubation with silica, are tested on fibroblasts isolated from the same animals to assess the effects on cell proliferation and collagen production. Fibroblast growth varied with initial seeding density and changes induced by AM supernatants varied depending on the proliferative rate. Normal AM supernatants inhibited [3H]-thymidine incorporation into fibroblasts, especially in more rapidly dividing cells. Supernatants of silica-treated AMs also inhibited division of rapidly growing fibroblasts, whereas the same material stimulated growth of slowly dividing cells. Collagen synthesis increased with the length of time that fibroblasts were confluent and was inhibited by control AM supernatants. Silica-treated AM supernatants increased collagen production by fibroblasts confluent for 3 days, whereas the same supernatants inhibited collagen synthesis by cells confluent for at least 8 days. The observation that a factor derived from silica-exposed AM first stimulates them inhibits fibrogenesis, indicates a modulation of the normal macrophage-fibroblast control system. This suggests that other factors may be required in vivo to shift this cellular balance towards the fibrotic process.

Animals↗
PubMed2006

Selective binding and enrichment for low-molecular weight biomarker molecules in human plasma after exposure to nanoporous silica particles.

The present manuscript describes a biomarker capturing strategy based on nanoporous silica particles. The method is shown to enrich the yield of species in the low-molecular weight proteome (LMWP), allowing detection of small peptides in the low-nanomolar range. Plasma samples were exposed to the silica particles, and the captured molecular species were profiled using MALDI-TOF. Mass spectra of the silica-treated human plasma samples showed a significant enrichment in MALDI-TOF protein profiles in the LMWP. Preliminary results indicated good level of reproducibility in plasma profiles with CVs on peak heights ranging from 6.3 to 14.7%. The MALDI-TOF signature changed significantly when the characteristics of the nanoporous silica were altered. The facile sample pretreatment before MS analysis, coupled to the potential for tailoring the surface properties of silica supports, hold promise for improving the recovery of low-abundance serum biomarkers.

Biomarkers↗
PubMed2007

Boosting silica levels in wheat leaves reduces grazing by rabbits.

Systemic application of sodium silicate can significantly enhance the levels of leaf silica in winter wheat (Triticum aestivum L. cv. Mercia), suggesting that this material could reduce the palatability of plants to vertebrate herbivores (e.g. rabbits, Oryctolagus cuniculus L.). A bioassay was developed using hydroponically grown wheat plants. Plants treated with sodium silicate were significantly more resistant to grazing by wild rabbits than untreated plants, with severe, potentially lethal feeding damage being reduced by over 50%. Further studies were carried out to develop more practical techniques for boosting silica levels in plants using silicon-rich 'fertilisers' including calcium silicate and calcium silicate slag (CSS). Silica levels were elevated in the plant 1.9-2.8 times over the control through the application of various silicon materials, in line with those of the hydroponic treatment. Encouragingly, levels of silica were elevated even in young wheat plants, which are most vulnerable to rabbit damage, and in a range of wheat varieties. The use of CSS is particularly promising because of its lower cost in comparison with calcium silicate, and it has a proven track record in slag fertilisation of rice and sugar cane crops. At the optimum CSS application rate of 3 g silicon L(-1) soil, wheat silica levels were approximately doubled, with no detrimental impacts on long-term growth or yield.

Animals↗