Silica structure in the spicules of the sponge <Emphasis Type="Italic">Suberites domuncula</Emphasis>

Accumulation of silica in marine organisms such as diatoms and sponges has been widely reported. The proteins depositing silica in these organisms have been identified and its structure has also been described. The ultrastructure of silica has not been studied in detail, however. Herein we describe the structure of silica in the spicules of the sponge Suberites domuncula. Peroxide treatment was performed to remove the organic compounds, thereby enabling a better study of the silica. Methods used for the study included scanning and transmission electron microscopy. Electron diffraction enabled structural comparison with silica glass at the atomic level. Small-angle X-ray scattering (SAXS) of the spicules was also conducted and structure correlation between these methods attempted. At a lower magnification, spicule needles with a smooth outer surface were visible. Diffraction results suggested a network-like structure in the spicules. Silica particles of 3 nm diameter could be measured by SAXS.     

Evaluation of phenyldimethylethoxysilane treated high-performance thin-layer chromatographic plates. Application to analysis of flavonoids inScutellariae radix

Summary The retention and selectivity of flavonoids (baicalin, baicalein, wogonin, oroxylin A) inScutellariae radix have been studies by high-performance thin-layer chromatography on phenyldimethylethoxysilane-treated silica plates. The silica plates treated with phenyl groups were used for physical and chemical analysis. From elemental carbon analysis, the maximum number of bonded phenyl surface groups per gram was calculated to be 0.467×10²¹ (Oginal silica plate: Merck Art. 15109, Silica gel 100 F₂₅₄). With methanol-1/15 M phosphate buffer (pH 6.2) mixtures as mobile phase, baicalin, baicalein, wogonin, and oroxylin A inScutellariae radix were separated. It has been shown that phenyl-treated plates are more suitable for selective separation of baicalin, baicalein, wogonin, and oroxylin A than octadecyl-treated plates.     

Silicification and biosilicification

Biosilicification takes place at or very close pH 7.0 and under ambient conditions of temperature and pressure in vivo. The silicic acid transporters and the proteins facilitating biosilicification in diatoms have been identified. Silica synthesis under mild conditions in vitro has been demonstrated using synthetic polymers with control over the resulting silica morphology. The results presented herein show that the silica synthesis in vitro is not specific to particular enzymes/polypeptides due to their particular chemical structure and activity but that many other synthetic macromolecules are also capable of facilitating silica formation at neutral pH. We also report the synthesis of organic-inorganic hybrid materials that have potential in optoelectronic applications.     

Structural and analytical studies of silica accumulations in <Emphasis Type="Italic">Equisetum hyemale</Emphasis>

Horsetail (Equisetum spp.) is known as one of the strongest accumulators of silicon among higher terrestrial plants. We use the combination of position-resolved analytical techniques, namely microtomography, energy-dispersive X-Ray elemental mapping, Raman microscopy, as well as small-angle and wide-angle scattering of X-rays, to study the type, distribution and nanostructure of silica in the internodes of Equisetum hyemale. The predominant silicification pattern is a thin continuous layer on the entire outer epidermis with the highest density in particular knob regions of the long epidermal cells. The knob tips contain up to 33 wt% silicon in the form of pure hydrated amorphous silica, while the silica content is lower in the inner part of the knobs and on the continuous layer. In contrast to the knob tips, the silica in these regions lacks silanol groups and is proposed to be in close association with polysaccharides. No mentionable amount of crystalline silica is detected by wide-angle X-ray scattering. The small-angle X-ray scattering data are consistent with the presence of colloidal, sheet-like silica agglomerates with a thickness of about 2 nm. From these results we conclude that there are at least two distinct forms of silica in E. hyemale which may have different functions. The close association of silica with cell wall polymers suggests that they may act as a polymeric template that controls the shape and size of the colloidal silica particles similar to many other biominerals and mineralised tissues. We propose that owing to its specific distribution in E. hyemale, a protective role and possibly also an important biomechanical role are among the most likely functions of silica in these plants. Figure 3D rendering of X-ray microtomography data from a dry Equisetum hyemale stalk. The red colour indicates high X-ray absorption values due to local silica accumulations     

Fabrication of carbon/silica hybrid materials using cationic polymerization and the sol-gel process

Silica particles with different morphology have been functionalized with carbon shells by different synthetic procedures. In the key step, the bare silica particles are functionalized by a specific cationic surface polymerization with furfuryl alcohol (FA). The polyfurfuryl alcohol (PFA)/silica hybrid particles have been also post-functionalized with maleic anhydride (MSA) by a Diels Alder reaction. Simultaneously occuring cationic polymerization of FA and sol-gel process with TEOS has been used for producing interpenetrating carbon-silica hybrid materials. The thermal transformation of the PFA component on silica into the carbon phase has been carried out under argon atmosphere in a temperature range from 700°C to 900°C. The influence of the former morphology of the silica on the homogenity of the resulting carbon layer is shown by zetapotential measurements and electron microscopic investigations.     

Synthesis of polystyrene/SiO2 composite microparticles by dispersion polymerization in supercritical fluid

A novel synthetic route to prepare polystyrene/SiO₂ composite microparticles in supercritical carbon dioxide (scCO₂) is presented. Silica particles with the size of 130 nm which were surface-modified with 3-(trimethoxysilyl) propyl methacrylate were used as seeds in the dispersion polymerization of styrene in the presence of a polymeric stabilizer, poly(1,1-dihydroheptafluorobutyl methacrylate-co-diisopropylaminoethyl methacrylate) to produce dry composite particles. The transmission electron microscopy analysis revealed that the composite microspheres contained several silica particles.     

Study of the organic carbon content of silica gel carbonised by pyrolysis of alcohols

Silica gel partially carbonised by pyrolysis of a mixture of C₇ aliphatic and aromatic alcohols at 773 K for 6 h was studied by means of transmission electron microscopy, temperature-programmed desorption (TPD), reaction gas chromatography, and quantum chemical methods. Pyrolysis of n-heptanol and benzyl alcohol at the silica gel surface results in formation of the carbon deposit (globules of 100–500 nm on the outer surfaces of silica gel and smaller carbon particles distributes on the external and internal surfaces of the oxide matrix) and grafted different organic compounds, which begin to desorb at relatively low temperatures (350–500 K) and activation energies of ≈70–120 kJ mol⁻¹. These compounds are not entirely removed from the surface on washing in solvents and subsequent drying at 470 K, as they can be packed in the pyrocarbon deposit between graphene sheets or in silica gel pores partially filled or blocked by pyrocarbon. Some of these compounds have also the second high-temperature TPD maximum at T close to the temperature of alcohol pyrolysis.     

Preparation of silica/perfluoroalkyl methacrylate polymer inorganic/organic particles in supercritical carbon dioxide

Silica/perfluoroalkyl methacrylate polymer (PHDFDMA) particles were prepared using various types of silica by polymerization in supercritical carbon dioxide. There are three steps in the fabrication of inorganic/organic hybrid composites: silane treatment, polymerization, and soxhlet extraction. After these steps, we observed the morphology of silica/PHDFDMA particles using field emission scanning electron microscope and transmission electron microscope. From these analyses, we can confirm that the silica/PHDFDMA core/shell particles were obtained when we used Ludox and silica gel as a silica template. On the other hand, core/shell particles were not formed when using fused silica and precipitated silica. In addition, to confirm the amount of polymer on silica, we performed an analysis using thermogravimetric analysis and electron probe micro-analyzer. In this case, PHDFDMA was approximately 20 wt.% on the silica gel and 40 wt.% on the Ludox, respectively. When using fused silica and precipitated silica as a template, amount of PHDFDMA on silica was maximum 5 wt.% and over 40 wt.%, respectively. From these results, to obtain enough PHDFDMA encapsulated silica particle, colloidal silica, Ludox is the best template in four different types of silica.     

Encapsulation of Inorganic Particles by Dispersion Polymerization in Polar Media: 2. Effect of Silica Size and Concentration on the Morphology of Silica–Polystyrene Composite Particles

Following a previous work (Bourgeat-Lami, E., and Lang, J.,J. Colloid Interface Sci.197, 293 (1998)), encapsulation of silica beads has been achieved by dispersion polymerization of styrene in an aqueous ethanol medium using poly(N-vinyl pyrrolidone) as stabilizer. Silica beads, prepared according to the Stöber method, were coated prior to polymerization by grafting 3-(trimethoxysilyl)propyl methacrylate onto the surface. A great number of silica beads per composite particle were previously found using beads that had diameters between 49 and 120 nm. In the present work, larger silica beads with diameters between 191 and 629 nm are investigated. We demonstrate by transmission electron microscopy that, consequently, only a small number of silica beads are contained in the composite particles. By counting the composite particles containing precisely zero, one, two, three, four, and more than four silica beads, it clearly appears that the encapsulation of only one silica bead can be obtained simply by increasing the size of the beads. Under our experimental conditions, the optimal bead diameter for achieving composite particles containing only one silica bead turns out to be around 450 nm. We show that increasing the silica bead size above this value results in an increased number of composite particles without silica beads. In contrast, the number of composite particles with two, three, four, or more than four silica beads increases with decreasing silica bead size. In addition to the above variations in composition of the composite particles, changes in particle shapes were also observed as a function of the size of the silica beads and the styrene concentration in the polymerization medium. Hypotheses concerning these variations are presented.     

Signaling Pathways Regulated by Silica Nanoparticles

Silica nanoparticles are a class of molecules commonly used in drug or gene delivery systems that either facilitate the delivery of therapeutics to specific drug targets or enable the efficient delivery of constructed gene products into biological systems. Some in vivo or in vitro studies have demonstrated the toxic effects of silica nanoparticles. Despite the availability of risk management tools in response to the growing use of synthetic silica in commercial products, the molecular mechanism of toxicity induced by silica nanoparticles is not well characterized. The purpose of this study was to elucidate the effects of silica nanoparticle exposure in three types of cells including human aortic endothelial cells, mouse-derived macrophages, and A549 non-small cell lung cancer cells using toxicogenomic analysis. The results indicated that among all three cell types, the TNF and MAPK signaling pathways were the common pathways upregulated by silica nanoparticles. These findings may provide insight into the effects of silica nanoparticle exposure in the human body and the possible mechanism of toxicity.     

Morphology and Texture of Silica Prepared by Sol–Gel Synthesis on the Surface of Fibrous Carbon Materials

Silica materials are synthesized by the sol–gel method including the deposition of tetraethoxysilane on various micro- and nanocarbon fibers. The use of nanofibrous carbon as a template makes it possible to prepare thermally stable mesoporous SiO₂ samples with unusually high surface areas (up to 1255 m²/g) and high porosity (up to 5.6 cm³/g). These silica materials and aerogels prepared by supercritical drying have comparable pore volumes. It is found by high-resolution electron microscopy that a thin-wall matrix permeated by channels is a prevailing structure of silica materials. When some catalytic fibrous carbons are used as templates, silica nanotubes can be prepared.     

Gravimetric determination of free carbon and silicon carbide in silica fume

Silica fume is formed as a by-product in the manufacture of silicon from quartzite. This paper describes an analytical method for the determination of free carbon and silicon carbide in silica fume. The silicon carbide was determined after removal of free carbon, amorphous silica, crystalline silica, graphite and silicon from the fume. The free carbon content was found to vary from 2 to 8% while the silicon carbide content ranged from 1 to 5%. X-ray diffraction, thermal analysis, scanning electron microscopy and Fourier Transform infrared spectroscopy were used to validate the steps used in the analytical procedure. The purpose of determining the free carbon and silicon carbide content of the fume is to help understand the efficiency of the reduction process and mechanism of the reaction.     

Mass spectrometry of condensed N-heterocycles: II—A novel ortho effect in the electron impact induced fragmentation of some C-(2-nitrophenyl)-azoles and -azoloazines

Heterocycles containing an integrated 2-nitrobenzaldehyde imine moiety produce ions of m/z 134 with high abundance under electron impact. As shown by kinetic energy release measurements these ions have the same structure in all the cases studied, identical to m/z 134 formed from the reference compound 2-nitrobenzoylpiperidide. The mechanism of formation of m/z 134 most probably involves isomerization of its precursor ion to give a spiro intermediate, from which m/z 134 arises either synchronously or after a second isomerization. Both alternatives formally represent an oxygen transfer from the nitro group to the imino carbon via a 5-membered transition state.     

Biomimetic silica formation: analysis of the phosphate-induced self-assembly of polyamines

The highly siliceous cell walls of diatoms are probably the most outstanding examples of nanostructured materials in nature. Previous in vitro experiments have shown that the biomolecules found in the cell walls of diatoms, namely polyamines and silaffins, are capable of catalysing the formation of silica nanospheres from silicic/oligosilicic acid solutions. In a previous publication, silica precipitation was found to be strictly correlated with a phosphate-induced microscopic phase separation of the polyamines. The present contribution further characterises the phase separation behaviour of polyamines in aqueous solutions. In particular, a pronounced pH-dependence of the average particle diameter is found. It is, furthermore, shown that the ability of phosphate ions to form polyamine aggregates in aqueous solutions cannot be a purely electrostatic effect. Instead, a defined hydrogen-bonded network stabilised by properly balanced electrostatic interactions should be considered. Finally, solid-state 31P NMR studies on phase-separated polyamines, synthetic silica precipitates, and diatom cell walls from the species Coscinodicus granii support the assumption of a phosphate-induced phase separation process taking place during cell wall formation.     

Detailed Structural Characterizations of SBA‐15 and MCM‐41 Mesoporous Silicas on a High‐Resolution Transmission Electron Microscope

Using high‐resolution transmission electronic micrograph (HR‐TEM) observation, one can clearly see the pore geometry of the MCM‐41 and SBA‐15 mesoporous silicas to determine that their pore shapes are hexagonal and round, respectively. With the perpendicular orientations of the nanochannels to the electron beam, parallel line images of the (100) and (110) repeating spacings were observed. In the SBA‐15 mesoporous silicas, there are byproducts of the granular silica and disordered mesostructures, attributed to the weak hydrogen interactions between Pluronic 123 blockcopolymer and the silica species. There are also many different and significant +π disclination defects in SBA‐15 and MCM‐41 surfactant‐silica composites. The SBA‐15 with a thicker silica wall is more stable under irradiation by high‐energy electron beams compared to MCM‐41, which has thinner wall thickness. Some carbon nanostructure impurities were found in some carbon films on the metal grids.     

有序的介观尺寸生物SiO2针的合成

生物体利用生物矿化作用,在有机分子模板上协同合成有种间差异的生物SiO2材料。具有精确形态可控的固态SiO2结构是在蛋白和多糖生物分子诱导下,在水相、中性pH和室温等温和反应条件下形成的,然而,利用化学合成方法,使SiO2的前体分子聚合形成具有一定模式结构的SiO2则需要极端的pH值或表面活性剂诱导。在人工培养条件下施用硅酸钠(Na2SiO3)时,在芦荟植物叶刺内,以细胞壁为模板生物矿化合成微米尺寸有序SiO2材料。X-ray(EDX)能谱分析显示一根硅针中含有Si,O和C元素,表明Si(OH)4吸收进入植物体内后Si-OH与细胞壁多糖和糖蛋白上的羟基(OH)组分,通过界面分子识别、细胞水平调控和再加工作用,聚合形成了有序的无定形(电子衍射确定)SiO2针状结构体。     

Synthesis of Ordered Biosilica Materials

Biogenic silica with amazing diversity of nanostructure shells,fibers and granules in diatoms and sponges is mediated by proteins and polysaccharides and forms at ambient pressure and temperatures.Chemical synthetic methods,in contrast,have to rely on extreme pH and /or surfactants to induce the condensation of silica precurors into specific patterns.One kind of benign synthesis method through plant cell wall template-directed ordered biosilica materials under ambient conditions in intriguing in this context.Organized silica materials in intercellular spaces of epidermal cells of tall fescue leaves were synthesized through molecular recognition between Si-OH and polysaccharide-OH or glycoprotein-OH of main components of plant cell walls and cellular processing as well when Si(OEt)4 was supplied rather than monosilicic acid.The biosynthesis of structural silica in tall fescue plant was correlated with the Si species applied,reflecting the slower condensation from tetraethoxysilane (TEOS) and thus providing greater opportunities for structural control by the underlying matrix of cell walls.The composition was estimated by energy dispersive X-ray(EDX) spectra on a scanning electron microscope.All organized structures showed carbon,oxygen and silicon peaks,indication that their formations differ from natural siliceous process.     

增强掺Tb凝胶玻璃荧光性能的有机螯合体的选择

采用原位合成技术, 用溶胶凝胶法制备了稀土离子(Tb^3＋), β-二酮及协同体共掺的二氧化硅玻璃, 测量了它们发射光谱和红外光谱, 并进行了XRD, SEM和TG-DSC测试. 探讨各不同成分原位合成稀土有机配合物在二氧化硅玻璃中的发光性能及热处理温度对发光性能的影响. 结果表明, 在凝胶玻璃中掺入能级较匹配的β-二酮, 可以使稀土离子的荧光增强; 合适的协同体的引用也能使稀土离子的荧光增强. 这些结果为今后制备荧光较强的含Tb离子的SiO₂凝胶玻璃提供了一定的依据.     

Preparation of hollow silica microspheres with controlled shell thickness in supercritical fluids

This article presents a novel route to prepare hollow silica microspheres with well-defined wall thickness by using cross-linked polystyrene (PS) microspheres as templates with the assistance of supercritical carbon dioxide (SC-CO₂). In this approach, the cross-linked PS templates can be firstly prepared via emulsifier-free polymerization method by using ethylene glycol dimethacrylate or divinylbenzene as cross-linkers. Then, the silica shell from the sol–gel process of tetraethyl orthosilicate (TEOS) which was penetrated into the PS template with the assistance of SC-CO₂ was obtained. Finally, the hollow silica spheres were generated after calcinations at 600 °C for 4 h. The shell thickness of the hollow silica spheres could be finely tuned not only by adjusting the TEOS/PS ratio, which is the most frequently used method, but also by changing the pressure and aging time of the SC-CO₂ treatment. Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscope were used to characterize these hollow silica spheres.     

Electron-microscope investigation of polish sandomir silicas

Summary Silica was examined under the electron microscope —directly by transmission and indirectly in the form of carbon replicas — and the change in structure resulting from alkaline treatment was examined. It was found that the original silica has a larnellar structure with marked surface relief. After treatment with alkali and washing with water, its surface becomes covered with round particles about 100–200 A in size, a phenomenon which results from the hydrolysis of, alkali silicate and separation of colloidal silicon dioxide.