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PubMed2005

Properties of the silica layer during the formation of MCM-41 studied by EPR of a silica-bound spin probe.

The properties of the silica layer during the formation of the mesoporous material MCM-41 were investigated by electron paramagnetic resonance (EPR) experiments carried out on a specifically designed, organo(trialkoxy)silane spin probe, SL1SiEt. Minute amounts of the spin probe were co-condensed with the silica source, tetraethyl orthosilicate (TEOS), in the synthesis of MCM-41 with cetyltrimethylammonium bromide (CTAB) under basic conditions. The mobility and location of the spin probe were followed in the CTAB micellar solution before the reaction, in the reaction mixture and in the final ordered material. It was found that the EPR spectra of hydrolyzed SL1SiEt throughout the room temperature part of the reaction are characteristic of a fast tumbling species, indicating that the silica is highly fluid prior to drying. After filtering, a slow motion type spectrum was observed, showing that the spin-label experiences considerable motional hindrance. The liquidlike behavior could be restored upon stirring the material in water. When the reaction is performed with a hydrothermal stage, the spectrum of SL1SiEt in the final product is the same as that of the room temperature synthesized material, but the addition of water did not restore the high mobility, due to a higher degree of silica cross-linking. The location of SL1SiEt throughout the formation process was obtained from electron spin-echo envelope modulation (ESEEM) measurements on MCM-41 prepared with CTAB deuterated either at the N-methyl or the alpha position and in a reaction carried out in D2O. Comparing the deuterium modulation depth, k(2H), induced by CTAB-alpha-d2, CTAB-d9, or D2O in CTAB micellar solutions of a number of reference spin probes with those of SL1SiEt revealed that the hydrolyzed SL1SiEt is located near the polar heads of the surfactant in the absence of base and TEOS. This supports the postulation of charge matching at the interface as a driving force for the formation of the mesostructure. Similar experiments carried out on reaction mixtures containing SL1SiEt showed a decrease of k(2H) from CTAB-alpha-d2 and CTAB-d9 compared to the micellar solution, exhibiting practically no time dependence. This indicates that the spin probe is pulled away from the micelle-water interface into the loosely linked, forming silica network. After drying, the modulation depth induced by CTAB-alpha-d2 and CTAB-d9 increases, showing that, once the water is removed, the silica walls contract around the micelles, pushing the silica-linked spin probe into the organic phase within the mesopores.

Electron Spin Resonance Spectroscopy↗
PubMed2005

Surfactant removal and silica condensation during the photochemical calcination of thin film silica mesophases.

The evolution of photochemical surfactant removal and silica condensation from organically templated thin film silica nanocomposites with mesoscopic ordering has been probed using a combined application of Fourier transform infrared (FT-IR) spectroscopy and single wavelength ellipsometry. Thin films of silica nanocomposites were prepared by a previously reported evaporation-induced self-assembly process. Specifically, oxidized silicon and gold substrates were withdrawn at 25 mm/min from a subcritical micelle concentration solution containing an ethylene oxide surfactant as a structure-directing agent and tetraethyl orthosilicate as a silica precursor. Real-time grazing incidence difference FT-IR spectra of the nanocomposite films on gold taken during exposure to short-wavelength ultraviolet light (184-257 nm) show that surfactant removal and silica condensation occur gradually and concomitantly. Surfactant removal and silica reconstructions were found to be nearly complete after 90 min of exposure. Further, a transient feature was observed in the FT-IR spectra around 1713 cm(-1) during the UV exposure process and was assigned to a carbonyl (C=O) stretching mode absorption, reflecting the transient formation of a partially oxidized surfactant intermediate. From these data we propose a stepwise model for surfactant removal from the nanocomposite films. Ellipsometrically determined index of refraction values collected as a function of UV exposure are also shown to support such a stepwise mechanism of surfactant removal from the ordered nanocomposite silica thin film mesophases studied here.

Carbon↗
PubMed2006

New route to synthesize highly active nanocrystalline sulfated titania-silica: synergic effects between sulfate species and silica in enhancing the photocatalysis efficiency.

A simple and efficient approach has been set up for fabricating highly active sulfated titania-silica (SO(4)(2-)/TiO(2)-SiO(2)): Ti(SO(4))(2) was hydrolyzed in the presence of silica, making it possible to sulfate titania and form titania-silica mixed oxide in one step. This study was focused on investigating the roles of sulfate species and silica in improving the physicochemical properties and photoactivity of SO(4)(2-)/TiO(2)-SiO(2) through comparison with sulfated titania (SO(4)(2-)/TiO(2)) and sulfate-free catalysts (TiO(2) and TiO(2)-SiO(2)). Various characterization methods, including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and surface photovoltage spectroscopy (SPS), were employed to test these materials. The results revealed that for SO(4)(2-)/TiO(2) and TiO(2)-SiO(2) the sole presence of either sulfate species or silica imposes negative effects on the photocatalysis behavior of titania, leading them to have negligible photoactivities. On the contrary, in the case of SO(4)(2-)/TiO(2)-SiO(2), sulfate species and silica were proved to act in a cooperative manner; therefore, the following enhanced structure and surface properties of SO(4)(2-)/TiO(2)-SiO(2) were obtained: (i) relatively well-crystallized and smaller-size (15.4 nm) anatase-phase titania was formed upon 500 degrees C calcination without forming rutile phase and (ii) the formation of active surface sulfate species promotes the separation of photoinduced electron-hole pairs and therefore accelerates the photocatalysis reaction. Therefore, its photoactivity is enhanced as a result of the favorable synergic effects between sulfate species and silica due to their simultaneous presence.

Journal Article↗
PubMed2005

Investigation of the core-shell interface in gold@silica nanoparticles: a silica imprinting approach.

The nature of the self-assembled core-shell interface in gold@silica nanoparticles synthesized via a 3-aminopropyltrimethoxysilane (APTMS) route is investigated using materials synthesis as a sensitive tool for elucidating interfacial composition and organization. Our approach involves condensation of the gold@silica nanoparticles within a silica framework for synthesis of a composite gold-silica material containing approximately 30 wt % gold. This material contains one of the highest gold loadings reported, but maintains gold core isolation as ascertained via a single surface plasmon resonance absorption band frequency corresponding to that of gold nanoparticles in dilute aqueous solution. The immobilized gold cores are subsequently etched using cyanide anion for the synthesis of templated porosity, which corresponds to the space that was occupied by the gold. Characterization of immobilized amines is performed using probe molecule binding experiments, which demonstrate a lack of accessible amines after gold removal. Solid-state 13C CPMAS NMR spectroscopy on these materials demonstrates that the amount of amine immobilization must be less than 10% of the expected yield, assuming that all of the APTMS becomes bound to the gold nanoparticle template. These results require a core-shell interface in the gold@silica nanoparticles that is predominantly occupied by inorganic silicate species, such as Si-O-Si and Si-OH, rather than primary amines. Such a result is likely a consequence of the weak interaction between primary amines and gold in aqueous solution. Our method for investigating the core-shell interface of gold@silica nanoparticles is generalizable for other interfacial structures and enables the synthesis of bulk imprinted silica using colloidal templates.

Journal Article↗
PubMed2005

Variability of biological effects of silicas: different degrees of activation of the fifth component of complement by amorphous silicas.

A biogenic and a pyrogenic amorphous silica were incubated in normal human plasma and compared on a per unit surface basis for their ability to split C5 molecules and yield small C5a peptides. Since C5a peptides induce selective chemotactic attraction of polymorphonuclear leukocytes (PMN), measurement of PMN-induced chemotaxis was used as an index of C5 activation. Though to a lesser extent than the crystalline forms, amorphous silicas can promote the cleavage of C5 protein and generation of C5a-like fragment. The biogenic silica, which differs from the pyrogenic variety in particle shape, level of contaminants, and degree of surface hydrophilicity, besides specific surface, induced a greater response. Both silicas activated C5 through a process which seems to involve multiple events similar to those induced by crystalline silica. C5 molecules are adsorbed and hydroxyl radicals are generated through Haber Weiss cycles catalyzed by the redox-active iron present at the particle surface either as trace impurities or chelated from plasma by silanol groups. In turn, these radicals convert native C5 to an oxidized C5-like form C5(H2O2). Finally, C5(H2O2) is cleaved by protease enzymatic action of plasma kallikrein activated by the same silica dusts, yielding a product, C5a(H2O2), having the same functional characteristic as C5a.

Aprotinin↗
PubMed2003

Effect of silica sand on activation energy for diffusion of sodium ions in montmorillonite and silica sand mixture.

The effect of silica sand on the diffusion of sodium ions in mixtures of montmorillonite and silica sand was studied by measuring the apparent diffusion coefficients, activation energies for diffusion, and the basal spacing of the mixed samples. These diffusion experiments suggest that the apparent diffusion coefficients of sodium ions in the mixed samples were almost the same as those of pure montmorillonite samples having the same partial dry densities of montmorillonite. The activation energy dependence for diffusion of sodium ions on the partial dry density was different between the mixed samples and the pure montmorillonite samples. The activation energy increased by adding silica sand at the partial dry density of 1.0 Mg m(-3), and decreased by adding silica sand at the partial dry densities higher than 1.2 Mg m(-3). A change in the XRD profile was observed after adding silica sand at the partial dry density of 1.6 Mg m(-3). Here, a three-water-layer hydrate state of montmorillonite was found in the mixed sample whereas only a two-water-layer hydrate state was observed in the pure montmorillonite sample. These experimental results suggest that silica sand changed the montmorillonite microstructure in the mixed samples, which then altered the sodium-ion diffusion process.

Bentonite↗
PubMed1996

Apatite formation on silica gel in simulated body fluid: its dependence on structures of silica gels prepared in different media.

It has been shown that the prerequisite for glasses and glass-ceramics to bond to living bone is the formation of a layer of biologically active bonelike apatite on their surfaces. The hydrated silica formed on the surfaces of glasses and glass-ceramics plays an important role in nucleating the apatite. In the present study, the structure of the hydrated silica responsible for the apatite nucleation was investigated in an accellular simulated body fluid with ion concentrations nearly equal to those of human blood plasma. Three kinds of porous silica gels were prepared by hydrolysis and polycondensation of tetraethoxysilane in pure water or in aqueous solution containing polyethylene glycol or polyacrylic acid. The silica gels prepared in aqueous solution containing polyethylene glycol or polyacrylic acid had micron-size interconnected pores, whereas the gel prepared in pure water did not. All the gels contained a large volume of nanometer-size pores, almost the same amounts of silanol groups and D2 defect, and showed a high dissolution rate of the silica. Despite this, only the gel prepared in the solution containing polyethylene glycol formed the apatite on its surface in the simulated body fluid. This indicates that only a certain type of structural unit of the silanol group is responsible for the apatite nucleation.

Acrylates↗
PubMed1999

Microwave Dielectric Relaxation of Bound Water to Silica, Alumina, and Silica-Alumina Gel Suspensions.

By the use of a time domain reflectomery method, dielectric measurements were carried out on silica, alumina, and silica-alumina gel suspensions (five types with composition varying between 0.3 < Si/Al atomic ratio <0.8) in the frequency range of 100 kHz to 20 GHz. For all the gels, a relaxation peak due to bound water was observed. This peak locates at around 1-10 MHz, indicating that the peak is a decade or 10 decades lower than those of biological polymers such as an aqueous DNA solution. The silica and alumina gels have a different bound water structure, judging from the fact that the peaks are different in their locations and shapes between the two gels. The silica-alumina gels exhibit two different peaks other than the peak of bulk water. The sum of the relaxation strength on the two peaks is proportional to the monolayer capacity obtained from water vapor isotherms. The shape of the one peak holds that of the silica gel, whereas the other retains that of alumina gel, and furthermore the ratio of the relaxation strength on the former peak to that on the latter depends on Si/Al atomic ratio. It is suggested that both peaks are caused by the orientation of bound water molecules. Copyright 1999 Academic Press.

Journal Article↗
PubMed2005

Fast HPLC for quality control of Harpagophytum procumbens by using a monolithic silica column: method transfer from conventional particle-based silica column.

The applicability of a monolithic C18-bonded silica column for the rapid HPLC separation of ingredients in medicinal plants and their phytopharmaceutical preparations has been evaluated in the author's laboratory. In this presentation, an existing method for the determination of the iridoid glycoside harpagoside in Harpagophytum procumbens (Devil's Claw) was successfully transferred from a conventional particle-based C18 silica column to a monolithic silica column. The very high porosity of the stationary phase allows chromatography with a much lower backpressure than on conventional columns. Therefore, the flow rate could be easily increased from 0.8 mL/min (particle-based column) to 5 mL/min (monolithic column) and the run-time reduced from 30 to 5 min (that is a reduction about 85% !), without losing any chromatographic resolution of the compound of interest. The amount of harpagoside was measured with the original method on a conventional particle-based silica column and on the adapted method on a monolithic silica column. The statistical mean t-test showed no significant differences of the variances and the means indicating that the fast HPLC method is an acceptable alternative. The shorter analysis time makes the method very valuable for commercial quality control of Harpagophytum extracts and its pharmaceutical preparations.

Chromatography, High Pressure Liquid↗
PubMed2005

Stability of mixtures of charged silica, silica-alumina, and magnetite colloids.

We report experiments on the stability of aqueous mixtures of charged colloidal magnetite and charged silica and silica covered with alumina particles of similar size. First, positively charged magnetite dispersions were mixed with negatively charged silica dispersions at pH 4, at different volume ratios and low colloid volume fractions, producing mixtures which were stable over a period of weeks despite the expected electrostatic attraction between the oppositely charged particles. When magnetite particles were mixed with positively charged silica covered with alumina at pH 4 under exactly the same conditions, some of the systems separated to form a magnetite sediment. When the volume fraction of the initial dispersions was increased, the behavior of the mixtures was the opposite: positive magnetite/negative silica mixtures were unstable at intermediate volume ratios. The unexpected behavior of the mixtures was investigated by means of electrophoretic mobility, initial susceptibility, and dynamic light scattering measurements as well as sedimentation experiments.

Aluminum Oxide↗
PubMed2006

Control of silica shell thickness and microporosity of titania-silica core-shell type nanoparticles to depress the photocatalytic activity of titania.

Titania is of potential interest as an ultraviolet (UV) radiation blocking material in personal care products because of its excellent UV light absorption properties. Its high photocatalytic activity, however, facilitates the generation of reactive oxygen species, which can oxidize and degrade other ingredients during its formulation, raising safety concerns. Dense coating of titania nanoparticles with a silica layer could help in depression of their photocatalytic activity by disturbing the formation of radicals produced by the reaction of oxygen and/or water with the electron-hole pair. Depression of the high photocatalytic activity of titania necessitates that the silica shell has to be thick, with minimum microporosity. Coating parameters were optimized to attain greater amounts of precipitated silica and thicker shells with lower microporosity, which in turn resulted in great depression of photocatalytic activity. Silica-coated titania nanoparticles were characterized by TEM, XPS, FT-IR, EDX, and microporosity measurements. The photocatalytic activity was evaluated for the coated powder to investigate the efficiency of the silica coating as well.

Journal Article↗
PubMed2003

Possible role of ubiquitin in silica biomineralization in diatoms: identification of a homologue with high silica affinity.

In diatom silicon biomineralization peptides are believed to play a role in silica precipitation and the consequent structure direction of the cell wall. Characterization of such peptides should reveal the nature of this organic-inorganic interaction, knowledge that may eventually well be used to expand the existing range of artificial silicas ("biomimicking"). Biochemical studies on Navicula pelliculosa revealed a set of proteins, which have a high affinity for a solid silica matrix; some were only eluted from the matrix when SDS-denaturation was applied. One of the proteins with an affinity for silica, about 8.5 kDa, is shown to be a homologue of ubiquitin on the basis of its N-terminal amino acid sequence; ubiquitin itself is a highly conserved 8.6 kDa protein that is involved in protein degradation. This finding is in line with a model of silica biomineralization in diatoms that implies the removal of templating polypeptides when pores in the growing cell wall develop. Western blotting with specific anti-ubiquitin antibodies confirmed cross-reactivity. Immunocytochemical localization of ubiquitin indicates that it is present along the diatom cell wall and inside pores during different stages of valve formation.

Biomimetic Materials↗
PubMed2004

Mechanism of mesoporous silica formation. A time-resolved NMR and TEM study of silica-block copolymer aggregation.

The dynamics of the synthesis of a mesoporous silica material SBA-15 is followed using time-resolved in situ 1H NMR and transmission electron microscopy (TEM). Block copolymer-silica particles of two-dimensional hexagonal symmetry evolve from an initially micellar solution. The synthesis was carried out with the block copolymer Pluronic P123 (EO20-PO70-EO20) at 35 degrees C and using tetramethyl orthosilicate as the silica precursor. By using TEM, we can image different stages during the evolution of the synthesis. Flocs of spherical micelles held together by the polymerizing silica are observed prior to precipitation. With time, the structure of these flocs evolves and the transition from spherical to cylindrical hexagonally packed micelles can be monitored. The signal from the methyl protons of the PO part was recorded with 1H NMR. One observes a continuous increase in the signal width but with distinct changes in the spectral characteristics occurring in narrow time intervals. The spectral changes can be attributed to structural changes of the self-assembled aggregates. The 1H NMR and TEM studies reveal the same mechanism of formation. It is concluded that the aggregation is caused by a micelle-micelle attraction induced by oligomeric/polymeric silica that adsorbs to the EO palisade layer of the micelles and has the ability to bridge to another micelle. This adsorption also favors the formation of cylindrical aggregates relative to spherical micelles. The sequence of NMR and TEM observations can then be interpreted as the following sequence of events: (i) silicate adsorption on globular micelles possibly accompanied with some aggregate growth, (ii) the association of these globular micelles into flocs, (iii) the precipitation of these flocs, and (iv) micelle-micelle coalescence generating (semi)infinite cylinders that form the two-dimensional hexagonal packing.

Journal Article↗
PubMed1996

Heparin attenuates bleomycin but not silica-induced pulmonary fibrosis in mice: possible relationship with involvement of myofibroblasts in bleomycin, and fibroblasts in silica-induced fibrosis.

Pulmonary fibrosis was elicited in mice or rats by the intratracheal instillation of bleomycin or silica. Daily injections of heparin significantly reduced the collagen deposition in bleomycin, but not in silica, injected mice, as evaluated by the lung hydroxyproline content on day 15 after instillation. Heparin also reduced the bleomycin-induced morbidity and mortality. Study of the broncho-alveolar lavage fluid (BAL) detected no significant change in the number of leucocytes or the amount of protein in heparin treated mice. Histologies of bleomycin instilled mice suggested that heparin did reduce the alveolar remodelling but not the alveolitis, evidenced by leucocytic infiltration. As detected by electron microscopy (EM), bleomycin increased the number of leucocytes and platelets within the alveolar capillaries but this was not significant ly reduced by heparin. The phenotype of the interstitial cell involved in these two types of pulmonary fibrosis was investigated by immunohistochemistry and EM. While in bleomycin injected animals the interstitial cells had the phenotype of an actin (alpha-actin in the rat) and lipid containing interstitial cell, with a poorly developed RE, in silica injected animals in contrast, the interstitial cells were without cytoplasmic actin or lipid but with a markedly developed endoplasmic reticulum (ER). Thus bleomycin and silica induced the growth of two different types of interstitial cells, the myofibroblast and the regular fibroblast, which might be a reason why heparin selectively inhibits bleomycin but not silica-induced fibrosis.

Animals↗
PubMed2005

Mortality in the UK industrial silica sand industry: 1. Assessment of exposure to respirable crystalline silica.

AIMS: To develop a job-exposure matrix (JEM) from personal and static respirable crystalline silica (RCS) measurements in UK industrial silica sand workers. METHODS: A total of 2429 personal and 583 static RCS dust samples were collected using cyclone samplers at seven UK quarries between 1978 and 2000. These data were combined, and analysis of variance using general linear models was used to evaluate the effect of quarry, job, and year on RCS concentrations, and facilitate the creation of five quarry and three time categories with similar exposure levels by comparing the least-square GM RCS concentrations. RESULTS: The overall geometric mean (GM) RCS concentration was 0.09 mg/m3 (geometric standard deviation 3.9). Silica flour and dry job categories tended to have the highest RCS exposure and 13.3% of all samples exceeded the UK maximum exposure level of 0.3 mg/m3. RCS levels generally decreased over time. CONCLUSIONS: Data have been collected and used to develop a JEM for UK industrial silica sand workers between 1978 and 2000. Although there were some limitations in the data and certain assumptions were made, the use of available data to estimate exposure quantitatively is an improvement over the use of qualitative and surrogate measures of exposure. The continual collection of dust measurements in the industry is essential to facilitate the exploration of exposure-response relations that may exist between silica and silicosis, lung cancer, and other diseases.

Air Pollutants, Occupational↗
PubMed1995

Direct interaction between crystalline silica and DNA - a proposed model for silica carcinogenesis.

Crystalline silica in aqueous buffer produced oxygen radicals that mediated in vitro DNA (deoxyribonucleic acid) strand breakage. The oxidized DNA base, thymine glycol, was also produced. The hydroxyl radical, responsible for most DNA damage, has a reaction distance of about 15 Angstroms, requiring close contact of silica with DNA. Fourier transform infrared spectroscopy of incubations of quartz particles with DNA showed distinct alterations in both DNA and quartz spectra and therefore indicated extensive hydrogen bonding between surface silanol groups and the phosphate-sugar backbone of DNA. Electron microscopy and energy dispersive X-ray spectroscopy of alveolar epithelial cells in fetal rat lung, exposed to quartz in culture, showed localization of quartz particles in the nuclei and mitotic spindles. Direct interaction of crystalline silica with DNA may be important in silica carcinogenesis by anchoring DNA close to sites of free radical production on the silica surface, or by interfering with DNA replication, repair, or the mitotic process.

Animals↗
PubMed2005

Assembly of silica nanowires on silica aerogels for microphotonic devices.

We report on the assembly of low-loss silica nanowires into functional microphotonics devices on a low-index nondissipative silica aerogel substrate. Using this all-silica technique, we fabricated linear waveguides, waveguide bends, and branch couplers. The devices are significantly smaller than existing comparable devices and have low optical loss, indicating that the all-silica technique presented here has great potential for future applications in optical communication, optical sensing, and high-density optical integration.

Adsorption↗
PubMed2000

Sol-gel polycondensation in a cyclohexane-based organogel system in helical silica: creation of both right- and left-handed silica structures by helical organogel fibers.

Chiral amide- and urea-type organic gelators (1-6), based on cyclohexanediamine, have been prepared, and the superstructures of the organogels were evaluated by circular dichroism (CD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The CD spectrum of the amide-based organogel system 1+2 exhibited a negative sign for the first Cotton effect, indicating that the dipole moments in the gelator aggregate orient into an anticlockwise direction. In contrast, the system 3+4 has a positive sign for the first Cotton effect, indicating that they orient into a clockwise direction. In the mixture of urea- and amide-based organogels, CD spectra of 5+2 and 6+4 revealed negative and positive signs, respectively. The helical structure of the amide-based organogels 1+2 and 3+4 clearly showed left- and right-handed structures, respectively, by SEM. To transcribe the chiral, helical structures of the organogels into silica gel, the sol-gel polycondensation of tetraethoxysilane (TEOS) was carried out in acetonitrile or ethanol. Very surprisingly, the left- and right-handed structures of the silica can be created by transcription of left- and right-handed structures of the organogels 1+2 (R enantiomer) and 3+4 (S enantiomer), respectively. In addition, in the mixture systems of urea- and amide-based organogels, the right- and left-handed structures of the organogels 5+2 (R enantiomer) and 6+4 (S enantiomer) were precisely transcribed into the silica structure. The findings suggest that the sol-gel polycondensation proceeds along the surface of the helical structure of the organogels. We therefore believe that the sol-gel polycondensation by means of molecular assembly templates abundantly built in the organogel phase is a new strategy to create superstructured silica materials.

Journal Article↗