Chiral separation performance of micrometer‐sized monodispersed silica spheres with high protein loading

Micrometer‐sized monodispersed silica spheres (～360 μm) with high loading of bovine serum albumin (BSA) (～450 mg/g) were prepared as an adsorbent for large‐scale chiral separation. The new adsorbent was characterized with scanning electron microscopy (SEM), nitrogen adsorption‐desorption isotherms, the mercury intrusion method, infrared spectroscopic analysis, and elementary analysis. The extent of chiral separation was tested with rac‐tryptophan (rac‐Trp) and rac‐phenylalanine (rac‐Phe) as solutes. The results showed that the absorbent exhibited a high surface area, large pore volume, and bimodal macromesoporous structures, enabling fast mass transfer and high separation efficiency. A fast adsorption rate, reaching equilibrium in less than 6 min, and a high degree of chiral separation, with the enantiomer excess (e.e.) value reaching as high as 100% in the first 10 min, was observed in a small (5 cm in height, 0.46 cm in internal diameter) packed column that could be regenerated with a pH 5.0 HAc‐NaAc buffer. The results show that monodispersed silica spheres with a high BSA loading have great potential for applications in large‐scale chiral separation processes. Chirality, 2009. © 2008 Wiley‐Liss, Inc.     

Limitations of the Colloidal Silica Method in Mapping the Endothelial Plasma Membrane Proteome of the Mouse Heart

The endothelial cell (EC) membrane is an important interface, which plays a crucial role in signal transduction. Our aim was to selectively purify luminal EC membrane proteins from the coronary vasculature of the isolated perfused mouse heart and analyze its composition with mass spectrometry (MS). To specifically label coronary ECs in the intact heart, the colloidal silica method was applied, which is based on the binding of positively charged colloidal silica to the surface of EC membranes. Transmission electron microscopy revealed the specific labeling of ECs of macro and microvessels. Two different methods of tissue homogenization (Teflon pestle and ultra blade) together with density centrifugation were used for membrane protein enrichment. Enrichment and purity was controlled by Western blot analysis using the EC-specific protein caveolin 1 and various intracellular marker proteins. The ultra blade method resulted in a tenfold enrichment of caveolin 1, while there was negligible contamination as judged by Western blot. However, protein yield was low and required pooling of ten hearts for MS. When enriched endothelial membrane proteins were digested with trypsin and analyzed by LC-MS, a total of 56 proteins could be identified, of which only 12 were membrane proteins. We conclude that coronary endothelial membranes can be conveniently labeled with colloidal silica. However, due to the ionic nature of interaction of colloidal silica with the EC membrane the shear rate required for cardiac homogenization resulted in a substantial loss of specificity. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Adsorption of the PtII Anticancer Drug Carboplatin by Mesoporous Silica

MCM‐41, a mesoporous silica nanomaterial with a high surface area for adsorption of small molecules, is a potential new type of delivery vehicle for therapeutic and diagnostic agents. In this report, we show that MCM‐41 adsorbs the front‐line anticancer drug carboplatin, [Pt(CBDCA‐O,O′)(NH₃)₂] (CBDCA=cyclobutane‐1,1‐dicarboxylate; 1 ), which is used to treat ovarian, lung, and other types of cancer. UV/Visible difference absorption spectroscopy shows that MCM‐41 adsorbs 1.8±0.2% of its own weight of carboplatin after a 24 h exposure to 26.9 mM drug in H₂O. The pseudo‐first‐order rate constant for adsorption of carboplatin by MCM‐41, measured using [¹H,¹⁵N] heteronuclear single quantum coherence (HSQC) NMR, and ¹⁵N‐labeled carboplatin is k₁=2.92±2.17×10^?6 s^?1 at ca. 25°.     

Silica entry and accumulation in standing trees in a hot-spring environment: cellular pathways,rapid pace and fossilization potential

Silicification is the most important process of fossilization resulting in the preservation of internal tissues in plants, thereby providing essential information on the anatomy, life history, and evolution of land plants. However, fundamental knowledge of silica uptake, precipitation, and contribution to in situ plant fossilization is limited. To identify the cellular pathway of aqueous silica and subsequent fluid–wood interaction processes, we investigated upright standing young trees of lodgepole pine (Pinus contorta) in the hot-spring environment of Cistern Spring, Yellowstone National Park, USA. Our multi-method analytical approach using x-ray diffraction, Raman spectroscopy, scanning electron microscopy, and electron probe microanalyses shows that the surficial and internally co-precipitated silica–halite–gypsum assemblage traces the flow of silica-rich fluid and documents fluid retention after short-term hot-spring water immersion and evaporation. Element distribution maps reveal systematic 2D and 3D differences between silica quantities deposited in earlywood and latewood. The distribution of inorganic impurities in cell walls traces the anatomical structure of the wood and indicates rapid migration of homogeneous fluid into the waterlogged organic substrate. Our results show that the preferential pathway of silica-rich fluid into the above-ground wood was through the decorticated periphery which took place during a short-term flooding, ranging from days to weeks, of hot-spring fluid. In conclusion, the fluid retention capability in cellular pore space controls the in situ silicification process. The silicification of trees in growth position is a rapid process in which the in vivo transport of silica-rich fluid upward through the secondary xylem plays an insignificant role.     

INTERACTIVE EFFECTS OF COPPER AND SILICIC ACID ON RESTING SPORE FORMATION AND VIABILITY IN A MARINE DIATOM1

The toxic effects of copper on resting spore formation and viability in the marine diatom Chaetoceros protuberans Lauder were determined both with and without silicic acid added to the medium. With silicic acid available, partial inhibition of resting spore formation occurred only at the highest cupric ion activity (pCu 8.6), while the percentage of cells forming spores at pCu's 10.2 and 11.3 was nearly the same as in the controls. Without silicic acid added to the medium, sporulation was completely inhibited at pCu 8.6 and greatly inhibited at pCu 10.2. At pCu 11.3 and in the controls, the rate of spore formation was less than 50%. The results indicate that the inhibition of resting spore formation by copper is related to the concentration of silicic acid available to cells of C. protuberans. This is consistent with previous studies which show that copper toxicity during vegetative growth involves interference with silicification in diatoms and is a function of the silicic acid concentration of the medium. Viable resting spores of C. protuberans were still present in cultures following exposure to elevated copper concentrations during a 100-day incubation period. This indicates that resting spores can serve to enhance diatom survival in areas polluted by heavy metals.     

Water-in-oil emulsions that improve the storage and delivery of the biolarvacide <Emphasis Type="Italic">Lagenidium giganteum</Emphasis>

Lagenidium giganteum is an effective biological control agent for mosquitoes with limited use due to poor survival and contamination during storage. Invert (water-in-oil) emulsions using crop oils were investigated for formulating L. giganteum mycelium for improved shelf life and delivery. Cells formulated in a water-in-oil (W/O) emulsion were just as effective against larvae as those formulated in aqueous suspension. Cells formulated in the W/O emulsion and cell suspension settled during storage and formed clumps, which significantly reduced the efficacy of formulations. Hydrophobic silica nanoparticles were added to the W/O emulsion formulation for oil thickening. The addition of silica significantly reduced cell sedimentation and improved storage; thickened W/O emulsions with an initial cell density of 3900 CFU/mg applied at 0.5 mg/cm² were greater than 95% effective at infecting mosquitoes after 12 weeks of storage at room temperature. Cell density reduction during storage was represented using first-order kinetics. Surface treatment of silica nanoparticles and oil refinement both had a significant effect on the first-order rate constant; as the hydrophobicity of the silica increased and level of oil refinement decreased, the rate constant increased. The percentage of water in the W/O emulsion and type of refined crop oil had no significant effect on the first-order rate constant. Cells formulated in the thickened W/O emulsion were less likely to settle when applied to water compared to cells in aqueous suspension, suggesting better cell distribution in an aqueous environment could be achieved when cells are applied in a W/O emulsion.     

Silica Nanohybrid Membranes with High CO2 Affinity for Green Hydrogen Purification

An effective separation of CO₂ from H₂ can be achieved using currently known polyethylene oxide (PEO)‐based membranes at low temperatures but the CO₂ permeability is inadequate for commerical operations. For commercial‐scale CO₂/H₂ separation, CO₂ permeability of these membranes must be significantly enhanced without compromising CO₂/H₂ selectivity. We report here exceptional CO₂/H₂ separation properties of a nanohybrid membrane comprising polyethylene glycol methacrylate (PEGMA) grafts on an organic‐inorganic membrane (OIM) consisting of a low molecular weight polypropylene oxide (PPO)‐PEO‐PPO diamine and 3‐glycidyloxypropyltrimethoxysilane (GOTMS), an alkoxysilane. The CO₂ gas permeability of this nanohybrid membrane can reach 1990 Barrer with a CO₂/H₂ selectivity of 11 at 35 °C for a mixed gas mixture comprising 50% CO₂ ‐ 50% H₂ at 3.5 atm. The transformation of the inorganic silica phase from a well‐dispersed network of finely defined nanoparticles to rough porous clusters appears to be responsible for this OIM membrane exceeding the performance of other state‐of‐the‐art PEO‐based membranes.     

Comparison of solutes, nutrients, and bacteria inputs from two types of groundwater to the Rhône river during an artificial drought

Solute, nutrient and bacterial inputs to the River Rhône from the interstitial habitat of a gravel bar and the floodplain aquifer were investigated during an artificial drought. Eight springs were investigated: four groundwater-fed springs in the floodplain, located at the bottom of the bank; and four interstitial-fed springs located at the downstream end of a gravel bar. During this period, the inflows of groundwater to the river represented an average input of 0.77 mg l^–1 of nitrogen (of which 93.3% were nitrates), 0.0187 mg l^–1 of total phosphorus (of which 42.2% was orthophosphate), 3.56 mg l^–1 of silica, 2.315 ± 0.703 mg l^–1 of dissolved organic carbon (DOC, of which 47% was biodegradable) and 7.3 × 10⁴ ± 3.7 × 10⁴ bacteria per ml (of which 8.8% were active). Silica, DOC, biodegradable DOC, and bacteria concentrations displayed temporal variations during the study, which seem to be linked to the biological activity of the groundwater biofilm. There was a strong heterogeneity between the two types of groundwater that flow to the river: concentrations of calcium and alkalinity were higher in bank springs than in gravel bars springs. In these latters, sulfate, sodium, nitrogen, phosphorus were significantly higher.     

Diatom silicon biomineralization as an inspirational source of new approaches to silica production

The demand for new materials and products is still growing and the interest in naturally formed biopolymers and biominerals, such as chitin, calcium precipitates and silica is increasing. Photosynthesizing microalgae of the family Bacillariophyceae (diatoms) produce silica exoskeletons with a potential to be used in specific industrial or technological processes, they also are an excellent model in studies of silicon biomineralization. In contrast to geologically aged diatomaceous earth, the freshly prepared silica of cultured or harvested natural diatoms has been characterized insufficiently with respect to the properties (e.g. purity, specific surface area, porosity) required for technological and industrial application. In this contribution we summarize aspects of cellular processes that are involved in silicon biomineralization of diatoms and the current knowledge of the characterization of diatomaceous silica, following methods used for synthetically derived silica-based materials.     

Mesoporous Hybrid Electrolyte for Simultaneously Inhibiting Lithium Dendrites and Polysulfide Shuttle in Li–S Batteries

A bifunctional hybrid electrolyte composed of mesoporous silica nanosheets and liquid electrolyte is achieved for lithium–sulfur (Li–S) batteries. This hybrid electrolyte possesses abundant mesopores (2.8 nm), thin feature (20 µm), and high ionic conductivity (1.17 × 10^?1 mS cm^?1) as well as a low interfacial resistance with electrodes. Such unique features not only enable the efficient inhibition of the growth of lithium dendrites, but also significantly prevents polysulfide shuttling. Consequently, a Li–S battery with this hybrid electrolyte exhibits a relatively high reversible capacity and good capacity retention.