Concept: Silicic acid
Diatoms, the major contributors of the global biogenic silica cycle in modern oceans, account for about 40% of global marine primary productivity. They are an important component of the biological pump in the ocean, and their assemblage can be used as useful climate proxies; it is therefore critical to better understand the changes induced by environmental pH on their physiology, silicification capability and morphology. Here, we show that external pH influences cell growth of the ubiquitous diatom Thalassiosira weissflogii, and modifies intracellular silicic acid and biogenic silica contents per cell. Measurements at the single-cell level reveal that extracellular pH modifications lead to intracellular acidosis. To further understand how variations of the acid-base balance affect silicon metabolism and theca formation, we developed novel imaging techniques to measure the dynamics of valve formation. We demonstrate that the kinetics of valve morphogenesis, at least in the early stages, depends on pH. Analytical modeling results suggest that acidic conditions alter the dynamics of the expansion of the vesicles within which silica polymerization occurs, and probably its internal pH. Morphological analysis of valve patterns reveals that acidification also reduces the dimension of the nanometric pores present on the valves, and concurrently overall valve porosity. Variations in the valve silica network seem to be more correlated to the dynamics and the regulation of the morphogenesis process than the silicon incorporation rate. These multiparametric analyses from single-cell to cell-population levels demonstrate that several higher-level processes are sensitive to the acid-base balance in diatoms, and its regulation is a key factor for the control of pattern formation and silicon metabolism.
Frustules, the silica shells of diatoms, have unique porous architectures with good mechanical strength. In recent years, biologists have learned more about the mechanism of biosilica shells formation; meanwhile, physicists have revealed their optical and microfluidic properties, and chemists have identified ways to modify them into various materials while maintaining their hierarchical structures. These efforts have provided more opportunities to use biosilica structures in microsystems and other commercial products. This review focuses on the preparation of biosilica structures and their applications, especially in the development of microdevices. We discuss existing methods of extracting biosilica from diatomite and diatoms, introduce methods of separating biosilica structures by shape and sizes, and summarize recent studies on diatom-based devices used for biosensing, drug delivery, and energy applications. In addition, we introduce some new findings on diatoms, such as the elastic deformable characteristics of biosilica structures, and offer perspectives on planting diatom biosilica in microsystems.
We present a novel manufacture route for silica-titania photocatalysts using the diatom microalga Pinnularia sp. Diatoms self-assemble into porous silica cell walls, called frustules, with periodic micro-, meso- and macroscale features. This unique hierarchical porous structure of the diatom frustule is used as a biotemplate to incorporate titania by a sol-gel methodology. Important material characteristics of the modified diatom frustules under study are morphology, crystallinity, surface area, pore size and optical properties. The produced biosilica-titania material is evaluated towards photocatalytic activity for NO(x) abatement under UV radiation. This research is the first step to obtain sustainable, well-immobilised silica-titania photocatalysts using diatoms.
Silicon (Si) is the most abundant element present in the Earth’s crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4), as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K), the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel), silica gel (amorphous silicon dioxide), and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4) in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation)-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.
Magnesiothermic reduction can directly convert SiO2 into Si nanostructures. Despite intense efforts, efficient fabrication of highly nanoporous silicon by Mg still remains a significant challenge due to the exothermic reaction nature. By employing table salt (NaCl) as a heat scavenger for the magnesiothermic reduction, we demonstrate an effective route to convert diatom (SiO2) and SiO2/GeO2 into nanoporous Si and Si/Ge composite, respectively. Fusion of NaCl during the reaction consumes a large amount of heat that otherwise collapses the nano-porosity of products and agglomerates silicon domains into large crystals. Our methodology is potentially competitive for a practical production of nanoporous Si-based materials.
Orthosilicic acid (Si(OH)4) and its small condensation compounds are among the most important silicon compounds but have never been isolated, due to their instability. These compounds would be highly useful building blocks for advanced materials if they became available at high purity. Here we show a simple procedure to selectively synthesize orthosilicic acid and its dimer, cyclic trimer and tetramer in organic solvents. Isolation of orthosilicic acid, the dimer and the cyclic tetramer as hydrogen-bonded crystals with tetrabutylammonium halides and the cyclic trimer as solvent-containing crystals is also described. The solid-state structures of these compounds are unambiguously clarified by single crystal X-ray and neutron diffraction studies. The usefulness of orthosilicic acid and its oligomers prepared by the new procedure is demonstrated by the synthesis of functionalized oligosiloxanes.Orthosilicic acid is essential to many natural and synthetic materials but notoriously difficult to isolate, limiting its use in materials synthesis. Here, the authors successfully synthesize and stabilize orthosilicic acid and its oligomers, making available a new family of building blocks for silicon oxide-based materials.
Diatoms are highly abundant unicellular algae that often dominate pelagic as well as benthic primary production in the oceans and inland waters. Being strictly dependent on silica to build their biomineralized cell walls, marine diatoms precipitate 240 × 10(12) mol Si per year, which makes them the major sink in the global Si cycle. Dissolved silicic acid (dSi) availability frequently limits diatom productivity and influences species composition of communities. We show that benthic diatoms selectively perceive and behaviourally react to gradients of dSi. Cell speed increases under dSi-limited conditions in a chemokinetic response and, if gradients of this resource are present, increased directionality of cell movement promotes chemotaxis. The ability to exploit local and short-lived dSi hotspots using a specific search behaviour likely contributes to micro-scale patch dynamics in biofilm communities. On a global scale this behaviour might affect sediment-water dSi fluxes and biogeochemical cycling.
Recent advances in nanophotonic light-trapping technologies offer promising solutions in developing high-efficiency thin-film solar cells. However, the cost-effective scalable manufacturing of those rationally designed nanophotonic structures remains a critical challenge. In contrast, diatoms, the most common type of phytoplankton found in nature, may offer a very attractive solution. Diatoms exhibit high solar energy harvesting efficiency due to their frustules (i.e., hard porous cell wall made of silica) possessing remarkable hierarchical micro-/nano-scaled features optimized for the photosynthetic process through millions of years of evolution. Here we report numerical and experimental studies to investigate the light-trapping characteristic of diatom frustule. Rigorous coupled wave analysis (RCWA) and finite-difference time-domain (FDTD) methods are employed to investigate the light-trapping characteristics of the diatom frustules. In simulation, placing the diatom frustules on the surface of the light-absorption materials is found to strongly enhance the optical absorption over the visible spectrum. The absorption spectra are also measured experimentally and the results are in good agreement with numerical simulations.
Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica-biopolymer hybrids are a promising alternative. A one-pot process to monolithic, superinsulating pectin-silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed “neck-free” nanoscale network structure with thicker struts. Such a design is superior to “neck-limited”, classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica-biopolymer nanocomposite aerogels.
Today’s Sargasso Sea is nutrient starved, except for episodic upwelling events caused by wind-driven winter mixing and eddies. Enhanced diatom opal burial in Sargasso Sea sediments indicates that silicic acid, a limiting nutrient today, may have been more available in subsurface waters during Heinrich Stadials, millennial-scale climate perturbations of the last glacial and deglaciation. Here we use the geochemistry of opal-forming organisms from different water depths to demonstrate changes in silicic acid supply and utilization during the most recent Heinrich Stadial. We suggest that during the early phase (17.5-18 ka), wind-driven upwelling replenished silicic acid to the subsurface, resulting in low Si utilization. By 17 ka, stratification reduced the surface silicic acid supply leading to increased Si utilization efficiency. This abrupt shift in Si cycling would have contributed to high regional carbon export efficiency during the recent Heinrich Stadial, despite being a period of increasing atmospheric CO2.