Concept: Silicon dioxide
Although amorphous silica is used in food products, cosmetics and paints and as vector for drug delivery, data on its potential health hazard are limited. The aim of this study was to investigate the cytotoxic and genotoxic potential of silica particles of different sizes (250 and 500nm) and structures (dense and mesoporous). Dense silica (DS) spheres were prepared by sol-gel synthesis, mesoporous silica particles (MCM-41) were prepared using hexadecyltrimethyl ammonium bromide as a structure-directing agent and tetraethylorthosilicate as silica source. Particles were accurately characterised by dynamic light scattering, nitrogen adsorption, X-ray diffraction and field emission scanning electron microscopy. Murine macrophages (RAW264.7) and human epithelial lung (A549) cell lines were selected for investigation. Genotoxicity was evaluated by Comet assay and micronucleus test. Cytotoxicity was tested by the trypan blue method. Cells were treated with 0, 5, 10, 20, 40 and 80 µg/cm(2) of different silica powders for 4 and 24 h. The intracellular localisation of silica was investigated by transmission electron microscopy. Amorphous particles penetrated into the cells, being compartmentalised within endocytic vacuoles. DS and MCM-41 particles induced cytotoxic and genotoxic effects in A549 and RAW264.7 although to different extent in the two cell lines. A549 were resistant in terms of cell viability, but showed a generalised induction of DNA strand breaks. RAW264.7 were susceptible to amorphous silica exposure, exhibiting both cytotoxic and genotoxic responses as DNA strand breaks and chromosomal alterations. The cytotoxic response of RAW264.7 was particularly relevant after MCM-41 exposure. The genotoxicity of amorphous silica highlights the need for a proper assessment of its potential hazard for human health.
The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO2, Ni2P/SiO2, and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO2 and especially Ni2P/SiO2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni2P/SiO2, the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.
Inositol-stabilized arginine silicate (ASI; Nitrosigine(®)) has been validated to increase levels of arginine, silicon and nitric oxide production. To evaluate potential enhancement of mental focus and clarity, ASI (1500 mg/day) was tested in two double-blind placebo-controlled crossover (DBPC-X) studies using the Trail Making Test (TMT, Parts A and B). In the two studies, healthy males took ASI for 14 and 3 days, respectively. In the first study, after 14 days of dosing, TMT B time decreased significantly from baseline (28% improvement, p = 0.045). In the second study evaluating shorter-term effects, TMT B time decreased significantly compared to placebo (33% improvement, p = 0.024) in a 10-min period. After 3 days of dosing, TMT B time significantly decreased from baseline scores (35% improvement, p < 0.001). These findings show that ASI significantly improved the ability to perform complex cognitive tests requiring mental flexibility, processing speed and executive functioning.
- Proceedings of the National Academy of Sciences of the United States of America
- Published over 4 years ago
Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.
The Mg-Si-O system is the major Earth and rocky planet-forming system. Here, through quantum variable-composition evolutionary structure explorations, we have discovered several unexpected stable binary and ternary compounds in the Mg-Si-O system. Besides the well-known SiO2 phases, we have found two extraordinary silicon oxides, SiO3 and SiO, which become stable at pressures above 0.51 TPa and 1.89 TPa, respectively. In the Mg-O system, we have found one new compound, MgO3, which becomes stable at 0.89 TPa. We find that not only the (MgO)x·(SiO2)y compounds, but also two (MgO3)x·(SiO3)y compounds, MgSi3O12 and MgSiO6, have stability fields above 2.41 TPa and 2.95 TPa, respectively. The highly oxidized MgSi3O12 can form in deep mantles of mega-Earths with masses above 20 M⊕ (M⊕:Earth’s mass). Furthermore, the dissociation pathways of pPv-MgSiO3 are also clarified, and found to be different at low and high temperatures. The low-temperature pathway is MgSiO3 ⇒ Mg2SiO4 + MgSi2O5 ⇒ SiO2 + Mg2SiO4 ⇒ MgO + SiO2, while the high-temperature pathway is MgSiO3 ⇒ Mg2SiO4 + MgSi2O5 ⇒ MgO + MgSi2O5 ⇒ MgO + SiO2. Present results are relevant for models of the internal structure of giant exoplanets, and for understanding the high-pressure behavior of materials.
Tardigrades are microscopic animals that survive a remarkable array of stresses, including desiccation. How tardigrades survive desiccation has remained a mystery for more than 250 years. Trehalose, a disaccharide essential for several organisms to survive drying, is detected at low levels or not at all in some tardigrade species, indicating that tardigrades possess potentially novel mechanisms for surviving desiccation. Here we show that tardigrade-specific intrinsically disordered proteins (TDPs) are essential for desiccation tolerance. TDP genes are constitutively expressed at high levels or induced during desiccation in multiple tardigrade species. TDPs are required for tardigrade desiccation tolerance, and these genes are sufficient to increase desiccation tolerance when expressed in heterologous systems. TDPs form non-crystalline amorphous solids (vitrify) upon desiccation, and this vitrified state mirrors their protective capabilities. Our study identifies TDPs as functional mediators of tardigrade desiccation tolerance, expanding our knowledge of the roles and diversity of disordered proteins involved in stress tolerance.
In various shocked meteorites, low-pressure silica polymorph α-cristobalite is commonly found in close spatial relation with the densest known SiO2 polymorph seifertite, which is stable above ∼80 GPa. We demonstrate that under hydrostatic pressure α-cristobalite remains untransformed up to at least 15 GPa. In quasi-hydrostatic experiments, above 11 GPa cristobalite X-I forms-a monoclinic polymorph built out of silicon octahedra; the phase is not quenchable and back-transforms to α-cristobalite on decompression. There are no other known silica polymorphs, which transform to an octahedra-based structure at such low pressures upon compression at room temperature. Further compression in non-hydrostatic conditions of cristobalite X-I eventually leads to the formation of quenchable seifertite-like phase. Our results demonstrate that the presence of α-cristobalite in shocked meteorites or rocks does not exclude that materials experienced high pressure, nor is the presence of seifertite necessarily indicative of extremely high peak shock pressures.
Oxide-based two-terminal resistive random access memory (RRAM) is considered one of the most promising candidates for next-generation nonvolatile memory. We introduce here a new RRAM memory structure employing a nanoporous (NP) silicon oxide (SiOx) material which enables unipolar switching through its internal vertical-nanogap. Through the control of the stochastic filament formation at low voltage, the NP SiOx memory exhibited extremely low electroforming voltage (~ 1.6 V) and outstanding performance metrics. These include multi-bit storage ability (up to 9-bits), high ON-OFF ratio (up to 10(7) A), long high-temperature lifetime (≥ 10(4) s at 100 °C), excellent cycling endurance (≥ 10(5)), sub-50 ns switching speeds, and low power consumption (~ 6 x 10(-5) W/bit). Also provided is room temperature processability for versatile fabrication without any compliance current being needed during electroforming or switching operations. Taken together, these metrics in NP SiOx RRAM provide a route toward easily accessed nonvolatile memory applications.
We report the new development of fire extinguishing agents employing the latest technology of fighting and preventing fires. The in situ technology of fighting fires and explosions involves using large-scale ultrafast-gelated foams, which possess new properties and unique characteristics, in particular, exceptional thermal stability, mechanical durability and full biocompatibility. We provide a detailed description of the physico-chemical processes of silica foam formation at the molecular level and functional comparison with current fire extinguishing and fighting agents. The new method allows to produce controllable gelation silica hybrid foams in the range from 2 to 30 seconds up to 100 Pa·s viscosity. Chemical structure and hierarchical morphology obtained by SEM and TEM images develop thermal insulation capabilities of the foams, reaching a specific heat value of more than 2.5 kJ/(kg·°С). The produced foam consists of organized silica nanoparticles as determined by XPS and X-Ray diffraction analysis with a narrow particle size distribution of about 10-20 nm. As a result of fire extinguishing tests, it is shown that the extinguishing efficiency exhibited by silica-based sol-gel foams is almost 50 times higher than that for ordinary water and 15 times better than that for state-of-the-art firefighting agent AFFF(aqueous film forming foam). The biodegradation index determined by the time of the induction period was only 3 days, while even for conventional foaming agents this index is several times higher.
Novel NH(2)-functionalized cellulose acetate (CA)/silica composite nanofibrous membranes were successfully prepared by sol-gel combined with electrospinning technology. Tetraethoxysilane (TEOS) as a silica source, CA as precursor and 3-ureidopropyltriethoxysilane as a coupling agent were used in membrane preparation. The membrane’s chemical and morphological structures were investigated by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), element analyzer, Fourier-transform infrared spectroscopy (FTIR) and N(2) adsorption-desorption isotherms. The composite nanofibrous membranes exhibited high surface area and porosity. The membranes were used for Cr(VI) ion removal from aqueous solution through static and dynamic experiments. The adsorption behavior of Cr(VI) can be well described by the Langmuir adsorption model, and the maximum adsorption capacity for Cr(VI) is estimated to be 19.46 mg/g. The membrane can be conveniently regenerated by alkalization. Thus the composite membrane prepared from biodegradable raw material has potential applications in the field of water treatment.