Search

Hydrogen peroxide (H 2 O 2 ) is an abundant molecule associated with biological functions and reacts with natural enzymes, such as catalase. Even though direct H 2 O 2 measurement can be used to diagnose pathological conditions, such as infection and inflammation, H 2 O 2 quantification further enables the detection of disease biomarkers in enzyme-linked assays (e.g., ELISA) in which enzymatic reactions may generate or consume H 2 O 2 . Such a quantification is often measured optically with organic dyes in biological media that suffer, however, from poor stability. Currently, the optical H 2 O 2 biosensing without organic-dyes in biological media and at low, submicromolar, concentrations has yet to be achieved. Herein, we rationally design biomimetic artificial enzymes based on antioxidant CeO 2 nanoparticles that become luminescent upon their Eu 3+ doping. We vary systematically their diameter from 4 to 16 nm and study their catalase-mimetic antioxidant activity, manifested as catalytic H 2 O 2 decomposition in aqueous solutions, revealing a strong nanoparticle surface area dependency. The interaction with H 2 O 2 influences distinctly the particle luminescence rendering them highly sensitive H 2 O 2 biosensors down to 0.15 μM (5.2 ppb) in solutions for biological assays. Our results link two, so far, unrelated research domains, the CeO 2 nanoparticle antioxidant activity and luminescence by rare-earth doping. When these enzyme-mimetic nanoparticles are coupled with alcohol oxidase, biosensing can be extended to ethanol exemplifying how their detection potential can be broadened to additional biologically relevant metabolites. The enzyme-mimetic nanomaterial developed here could serve as a starting point of sophisticated in vitro assays toward the highly sensitive detection of disease biomarkers.

We report a new kind of long-range ordered binary superlattices comprising atomically defined inorganic clusters and colloidally synthesized nanocrystals. In a model system, we combined surfactant-encapsulated, nearly spherical giant polyoxometalate clusters containing 2.9 nm polyoxomolybdate or 2.5 nm polyoxovanadomolybdate cores with monodisperse colloidal semiconductor nanocrystals (PbS, CdSe, PbS/CdS; 4-11 nm). The results are rationalized on the basis of dense packing principles of sterically stabilized particles with predominantly hard-spherelike interparticle interactions. By varying the size-ratios and relative concentrations of constituents, we obtained known thermodynamically stable binary packings of hard-spheres such as NaCl, AlB2, and NaZn13 lattices and also CaCu5-type lattice and aperiodic quasicrystals with 12-fold symmetry. These results suggest that other kinds of cluster materials such as fullerenes and magic-sized metallic and semiconductor clusters can also be integrated into supramolecular assemblies with nanocrystals. Furthermore, synergistic effects are expected from the combination of redox and catalytic properties of polyoxometalates with excitonic and plasmonic properties of inorganic nanocrystals.

More than 100 million tonnes of municipal solid waste are incinerated worldwide every year. However, little is known about the fate of nanomaterials during incineration, even though the presence of engineered nanoparticles in waste is expected to grow. Here, we show that cerium oxide nanoparticles introduced into a full-scale waste incineration plant bind loosely to solid residues from the combustion process and can be efficiently removed from flue gas using current filter technology. The nanoparticles were introduced either directly onto the waste before incineration or into the gas stream exiting the furnace of an incinerator that processes 200,000 tonnes of waste per year. Nanoparticles that attached to the surface of the solid residues did not become a fixed part of the residues and did not demonstrate any physical or chemical changes. Our observations show that although it is possible to incinerate waste without releasing nanoparticles into the atmosphere, the residues to which they bind eventually end up in landfills or recovered raw materials, confirming that there is a clear environmental need to develop degradable nanoparticles.

The controlled production of ZnO nanoparticles within an amorphous silica matrix is achieved using a new methodology consisting of four stages. First, precursor zinc glycerolate nanoparticles are produced within reversed micelles of glycerol in heptane stabilized by the surfactant Aerosol-OT (bis-ethylhexyl sodium sulfosuccinate, AOT). The surface of these nanoparticles is then modified by exchanging AOT with bis-trimethoxysilyl-ethane (BTME). The surface-modified nanoparticles are copolymerized with tetramethoxysilane (TMOS) to provide a composite silica material, in which the nanoparticles are apparently dissolved, producing a uniform distribution of zinc in the silica matrix. Finally, the conversion of zinc to ZnO is achieved by heating the material at 700 degrees C, leading to a uniform dispersion of very small (<10 nm) ZnO particles within the amorphous matrix. The fluorescence spectrum of the ZnO particles within the matrix is blue-shifted, as expected from the strong quantum confinement achieved. The properties of the system at all stages in this synthetic process are monitored using TEM, XRD, fluorescence and FT-IR spectroscopy. Glycerol forms complexes with many metal ions, so the present procedure may be generalized to provide uniform distributions of metal ions and subsequently metal oxide nanoparticles in amorphous silica.

The crystallization of PbS in aqueous solutions containing the surfactant sodium dodecyl sulfate (SDS) and hydrophilic polymers resulted in a novel type of metastable nanotubes, the walls of which consist of layers of ordered PbS nanoparticles, apparently separated by layers of surfactant molecules. Information on the mechanism of formation of these structures was obtained by focusing on the roles of the polymer, and of the insoluble lead dodecyl sulfate (Pb(DS)2) present in the system. TEM investigations of the early stages of crystallization revealed the coexistence of PbS and Pb(DS)2 precipitates, the latter being surprisingly important for nanotube formation, and allowed to follow the evolution of layered structures from combination of the two types of crystals. Six different hydrophilic polymers have been used, which interact with SDS with varying strengths. Surprisingly, and in contrast to previous hypotheses, layered nanostructures were observed in all polymer solutions, regardless of the strength of polymer-surfactant interactions. This indicates that, although the presence of a polymer is necessary, polymer-SDS interactions are not a driving force for the formation of the layered structures and nanotubes. On the contrary, the interactions between the polymer chains and the growing particles appear to be of the utmost importance. Results presented here can be interpreted in terms of two alternative mechanisms for layered nanostructure and nanotube formation.