The increasing use of silver (Ag) and titanium dioxide (TiO2) nanoparticles (NPs) in consumer products and their inevitable seepage into the environment prompted us to investigate their potential toxicity to a fish cell line (BF-2) and zebrafish embryos under dark and Simulated Solar Light (SSL) exposure conditions. Using high throughput screening (HTS) platforms, we showed that the oxidative stress-dependent cytotoxicity and embryonic toxicity of NPs were significantly increased upon exposure to SSL. While, the toxicity of TiO2 NPs under SSL exposure could be explained by hydroxyl radical generation, the enhanced toxicity of Ag NPs under SSL exposure was due to surface oxidation and physicochemical modification of Ag NPs and shedding of Ag+, leading to an increased bioavailability of silver. Our observations that solar light could induce physicochemical transformation of TiO2 and Ag NPs and enhance their toxic potential emphasizes the need for conducting future toxicity studies under environmentally relevant exposure conditions to guide decision making on the safe handling of NPs.

The dithiolene ligand transfer reaction between Ni(S2C2Ph2)2 (1) and CpMo(CO)3Cl (2; Cp = eta-C5H5) affords the neutral paramagnetic molybdenum bis(dithiolene) complex CpM(S2C2Ph2)2 (3), which has been structurally characterized. As found in other d1 complexes of this type, one dithiolene ligand is planar while the other is significantly folded toward the Cp ligand. An unexpected second product of the reaction is the unusual trinuclear species Ni[Mo(S2C2Ph2)2Cp]2 (4), which in the solid state contains three different dithiolene bonding modes (terminal, bridging, and semi-bridging) in the same molecule. Complex 4 can also be synthesized by displacement of the diene ligands in Ni(cod)2 with 2 equiv of 3. In contrast, the reaction of nickelocene with 3 proceeds by displacement of the Cp ligands in a stepwise manner to give initially the dinuclear species NiMo(mu-S2C2Ph2)2Cp2 5, which then reacts further with 3 to produce 4.

While the wide-spectrum antimicrobial properties and stability of silver nanomaterials have been copiously utilized in many medical and consumer products, we found that Methicillin Resistant Staphylococcus aureus (MRSA) is less susceptible to silver in comparison to Methicillin Sensitive Staphylococcus aureus (MSSA). Pre-exposure of MRSA to sub-lethal concentrations of AgNO3 caused 2.5-fold increase in LD50 of silver suggesting an inducible resistance mechanism. Studies involving gene expression profiling and efflux pump blockers showed the induction of P-type efflux pumps (Cop A, Cop Z and Nor B) as the principle mechanism conferring silver resistance in MRSA. Chlorpromazine—an efflux pump blocker increased sensitivity of MRSA to silver. Leveraging on these observations, silver resistance in MRSA was circumvented by enhancing the bioavailability of silver by cationic functioning of silver nanoparticles or by co-delivering silver together with chlorpromazine. Atomic Force Microscopy showed that poly-ethylene imine (PEI) functionalized silver nanoparticles adhere to bacterial cells which was found to increase the bioavailability, membrane rupture and cell death. The strategy of co-delivery of AgNO3 and chlorpromazine using chitosan-functionalized wormhole silica nanoparticles caused 12 log reduction in bacterial count which was 1000 times higher than bacterial reduction by AgNO3 alone. In short, these studies showed that circumventing antimicrobial resistance in pathogenic bacteria is possible by designed silver nanotechnology.

A novel wicking material using nanostructured titania grown on high aspect ratio titanium micropillars is demonstrated. High aspect ratio titanium micropillars were micromachined from bulk titanium sheets. Nanostructured titania was then grown on the surface of titanium micropillars by oxidation in aqueous hydrogen peroxide solution followed by thermal annealing. The nanostructured titania formed has an open porous structure with a nanoscale pore diameter and wall thickness. X-ray diffraction and pole figure studies indicate the formation of anatase phase of titania and the absence of a preferred orientation in the porous film. The hybrid nanostructured titania on titanium micropillars has excellent hydrophilic properties with a water capillary speed comparable to or exceeding that of conventional wick materials commonly used in heat pipes for the thermal management of electronic devices.

Alternating polyelectrolyte deposition is a promising route to the low-cost fabrication of electroluminescent devices based on semiconductor nanoparticles, but optimization and exploitation demand a deeper understanding of the fabrication mechanism, which has not hitherto been scrutinized in detail. Nanoparticle–polymer composites were assembled by repeated alternate exposures of a substrate to polyanionic thioglycolate-coated CdTe nanoparticles and the organic polycation polydiallyldimethylammonium while monitoring the process kinetics in situ using optical waveguide lightmode spectroscopy, which enabled detailed structural information to be obtained with good time resolution. This complements the previously reported device characterization. Two hitherto unnoticed features were observed: (i) apparently spontaneous acceleration of addition of semiconductor nanoparticles after a certain quantity has already been deposited and (ii) during subsequent exposure to the organic polycation, an appreciable proportion of the immediately previously deposited nanoparticles is removed. Analysis of the evolution of the optogeometrical parameters of the assembly revealed that during the initial slow addition the nanoparticles enter nanopores in the immediately previously deposited polymer. The deposition régime then switches abruptly to the formation of an adlayer of the nanoparticles. These are initially deposited in considerable excess, which is removable by simple dilution of the system. Further nanoparticle removal takes place during the following phase of polycation deposition via a process of particle scavenging by the polycation molecules. Changes in film refractive index during these various processes show that the predominantly columnar (rather than laminar) molecular arrangement established for polyelectrolyte-only films is maintained in the hybrid polymer–particle films, although the filling of the polyelectrolyte pores makes the film more isotropic.