Nanoscale control of the polymerization of silicon and oxygen determines the structures and properties of a wide range of siloxane-based materials, including glasses, ceramics, mesoporous molecular sieves and catalysts, elastomers, resins, insulators, optical coatings, and photoluminescent polymers. In contrast to anthropogenic and geological syntheses of these materials that require extremes of temperature, pressure, or pH, living systems produce a remarkable diversity of nanostructured silicates at ambient temperatures and pressures and at near-neutral pH. We show here that the protein filaments and their constituent subunits comprising the axial cores of silica spicules in a marine sponge chemically and spatially direct the polymerization of silica and silicone polymer networks from the corresponding alkoxide substrates in vitro, under conditions in which such syntheses otherwise require either an acid or base catalyst. Homology of the principal protein to the well known enzyme cathepsin L points to a possible reaction mechanism that is supported by recent site-directed mutagenesis experiments. The catalytic activity of the ''silicatein'' (silica protein) molecule suggests new routes to the synthesis of silicon-based materials.Silicon, the second most abundant element in the earth's crust, interacts with living systems by mechanisms that have remained poorly understood (1-6). Evidence suggests that silicon is essential for normal growth and biological function in a diversity of plant, animal, and microbial systems (2); silicon compounds have been shown to modulate these activities (1, 2), but the molecular mechanisms of these effects have proved elusive. Studies of marine organisms that produce relatively large masses of silicified structures (3) show the underlying molecular and genetic mechanisms by which living systems process silicon. Hildebrand et al. (7) recently characterized the cDNAs coding for a family of silicon transporters in diatoms and showed that the transporters are likely transmembrane proteins. We have found that the marine sponge Tethya aurantia produces copious silica spicules (1-2 mm in length and 30 m in diameter) that constitute 75% of the dry weight of the organism and that each of these spicules contains a central axial filament of protein (1-2 mm in length and 2 m in diameter) consisting of three very similar subunits that we have named silicateins (for silica proteins; ref. 8). Characterization of silicatein ␣ (the subunit comprising nearly 70% of the mass of the filaments) and its cloned cDNA indicated that it is homologous to members of the cathepsin L subfamily of the papain family of proteolytic enzymes (8).We show here that, at neutral pH, the silicatein filaments and their constituent subunits catalyze the in vitro polymerization of silica and silsesquioxanes from tetraethoxysilane and organically modified silicon triethoxides, respectively. These substrates were chosen because of their stability at neutral pH and the similarity of their chemical reactivity to that of...

Quorum sensing (QS) signalling has been extensively studied in single species populations. However, the ecological role of QS in complex, multi-species communities, particularly in the context of community assembly, has neither been experimentally explored nor theoretically addressed. Here, we performed a long-term bioreactor ecology study to address the links between QS, organization and composition of complex microbial communities. The conversion of floccular biomass to highly structured granules was found to be non-random, but strongly and positively correlated with N-acyl-homoserine-lactone (AHL)-mediated QS. Specific AHLs were elevated up to 100-fold and were strongly associated with the initiation of granulation. Similarly, the levels of particular AHLs decreased markedly during the granular disintegration phase. Metadata analysis indicated that granulation was accompanied by changes in extracellular polymeric substance (EPS) production and AHL add-back studies also resulted in increased EPS synthesis. In contrast to the commonly reported nanomolar to micromolar signal concentrations in pure culture laboratory systems, QS signalling in the granulation ecosystem occurred at picomolar to nanomolar concentrations of AHLs. Given that low concentrations of AHLs quantified in this study were sufficient to activate AHL bioreporters in situ in complex granular communities, AHL mediated QS may be a common feature in many natural and engineered ecosystems, where it coordinates community behaviour.

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Silicatein is an enzyme isolated from the biosilica produced by the marine demosponge, Tethya aurantia. Once isolated from the sponge, silicatein can be used in vitro to catalyze the hydrolysis and direct polycondensation of a wide variety of alkoxide, ionic, and organometallic precursors to the corresponding chalcogens at standard temperature and pressure and neutral pH. On the basis of these results, an array of small molecules that mimic the unique physiochemical environment found in the enzyme active site was investigated for catalytic activity in the formation of silica from silicon alkoxides at neutral pH. The most successful of these biomimetic catalysts (cysteamine) was used to encapsulate firefly luciferase, green and blue fluorescent proteins (GFP, BFP), and Escherichia coli cells expressing GFP in silica matrixes. The benign conditions required for the catalysis of synthesis of these silica composites does not impair the activities of the encapsulated enzyme, fluorescent proteins, or live cells as shown by fluorescence measurements. In conjunction with microcontact printing, this biomimetically catalyzed encapsulation method has been used to produce patterned functional arrays of silica nanoparticulate composite materials.

Nitrite has generally been recognized as an inhibitor of N2O reduction during denitrification. This inhibitory effect is investigated under various pH conditions using a denitrifying-enhanced biological phosphorus removal (EBPR) sludge. The degree of inhibition was observed to correlate much more strongly with the free nitrous acid (FNA) concentration than with the nitrite concentration, suggesting that FNA, rather than nitrite, is likely the true inhibitor on N2O reduction. Fifty percent inhibition was observed at an FNA concentration of 0.0007-0.001 mg HNO2-N/L (equivalent to approximately 3-4 mg NO2(-) -N/L at pH 7), while complete inhibition occurred when the FNA concentration was greater than 0.004 mg HNO2-N/L. The results also suggest that the inhibition on N2O reduction was not due to the electron competition between N2O and NO2- reductases. The inhibition was found to be reversible, with the rate of recovery independent of the duration of the inhibition, but dependent on the concentration of FNAthe biomass was exposed to during the inhibition period. A higher FNA concentration caused slower recovery.

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Metal vanadium phosphates (MVP), particularly Li3V2(PO4)3 (LVP) and Na3V2(PO4)3 (NVP), are regarded as the next-generation cathode materials in lithium/sodium ion batteries. These materials possess desirable properties such as high stability, theoretical capacity, and operating voltages. Yet, low electrical/ionic conductivities of LVP and NVP have limited their applications in demanding devices such as electric vehicles. In this work, a novel synthesis route for the preparation of LVP/NVP micro/mesoporous 3D foams via assembly of elastin-like polypeptides is demonstrated. The as-synthesized MVP 3D foams consist of microporous networks of mesoporous nanofibers, where the surfaces of individual fibers are covered with MVP nanocrystallites. TEM images further reveal that LVP/NVP nanoparticles are about 100-200 nm in diameter, with each particle enveloped by a 5 nm thick carbon shell. The MVP 3D foams prepared in this work exhibit ultrafast rate capabilities (79 mA h g(-1) at 100C and 66 mA h g(-1) at 200C for LVP 3D foams; 73 mA h g(-1) at 100C and 51 mA h g(-1) at 200C for NVP 3D foams) and excellent cycle performance (almost 100% performance retention after 1000 cycles at 100C); their properties are far superior compared to current state-of-the-art active materials.

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