Alan Man Ching Ng

Toxicity of Metal Oxide Nanoparticles: Mechanisms, Characterization, and Avoiding Experimental Artefacts

Metal oxide nanomaterials are widely used in practical applications and represent a class of nanomaterials with the highest global annual production. Many of those, such as TiO2 and ZnO, are generally considered non-toxic due to the lack of toxicity of the bulk material. However, these materials typically exhibit toxicity to bacteria and fungi, and there have been emerging concerns about their ecotoxicity effects. The understanding of the toxicity mechanisms is incomplete, with different studies often reporting contradictory results. The relationship between the material properties and toxicity appears to be complex and diifficult to understand, which is partly due to incomplete characterization of the nanomaterial, and possibly due to experimental artefacts in the characterization of the nanomaterial and/or its interactions with living organisms. This review discusses the comprehensive characterization of metal oxide nanomaterials and the mechanisms of their toxicity.

Mechanisms of Antibacterial Activity of MgO: Non‐ROS Mediated Toxicity of MgO Nanoparticles Towards Escherichia coli

The toxicity of metal oxide nanomaterials and their antimicrobial activity is attracting increasing attention. Among these materials, MgO is particularly interesting as a low cost, environmentally-friendly material. The toxicity of MgO, similar to other metal oxide nanomaterials, is commonly attributed to the production of reactive oxygen species (ROS). We investigated the toxicity of three different MgO nanoparticle samples, and clearly demonstrated robust toxicity towards Escherichia coli bacterial cells in the absence of ROS production for two MgO nanoparticle samples. Proteomics data also clearly demonstrate the absence of oxidative stress and indicate that the primary mechanism of cell death is related to the cell membrane damage, which does not appear to be due to lipid peroxidation.

Strategies for improving the efficiency of semiconductor metal oxide photocatalysis

Photocatalysis is of significant interest for a wide range of applications related to energy and environment, such as pollutant degradation and hydrogen production. We will provide a review of the relationship between photocatalyst properties and its photocatalytic performance, as well as the strategies for the enhancement of photocatalytic activity, in particular under solar/ambient/visible illumination. Common applications of photocatalysts will then be reviewed, and we will summarize existing problems and areas requiring further improvements.

Effect of ZnO Nanoparticle Properties on Dye-Sensitized Solar Cell Performance

We have investigated the effect of ZnO nanoparticle properties on the dye-sensitized solar cell performance. Nanoparticles with different sizes and optical properties were considered. We found that there is a complex relationship between native defects, dye adsorption, charge transport and solar cell performance. The presence of a high concentration of nonradiative defects was found to be detrimental to photovoltaic performance, whereas for radiative defects, samples displaying orange-red defect emission exhibited better performance compared to samples with green defect emission (when the samples had similar emission intensities). Detailed discussion of the nanoparticle properties and their relationship with dye adsorption, electron injection, electron lifetime, electron transport time, and solar cell performance is given.

ZnO nanorod/GaN light-emitting diodes: The origin of yellow and violet emission bands under reverse and forward bias

ZnO nanorods have been prepared by electrodeposition under identical conditions on various p-GaN-based thin film structures. The devices exhibited lighting up under both forward and reverse biases, but the turn-on voltage and the emission color were strongly dependent on the p-GaN-based structure used. The origin of different luminescence peaks under forward and reverse bias has been studied by comparing the devices with and without ZnO and by photoluminescence and cathodoluminescence spectroscopy. We found that both yellow-orange emission under reverse bias and violet emission under forward bias, which are commonly attributed to ZnO, actually originate from the p-GaN substrate and/or surface/interface defects. While the absolute brightness of devices without InGaN multiple quantum wells was low, high brightness with luminance exceeding 10 000 cd/m2 and tunable emission (from orange at 2.1 V to blue at 2.7 V, with nearly white emission with Commission internationale de l’eclairage (CIE) coordinates (0.30,...

Long cycle life of CoMn2O4 lithium ion battery anodes with high crystallinity

CoMn2O4 nanomaterials are prepared by a low temperature precipitation route employing metal acetates and NaOH. Structural changes, induced by different annealing temperatures, are comprehensively analyzed by X-ray powder diffraction and Raman spectroscopy. With rising annealing temperature the crystal lattice of CoMn2O4 undergoes changes ; AO4 tetrahedra expand due to thermally induced substitution of Co2+ by larger Mn2+ metal ions on the A-site of the spinel structure, while in contrast, BO6 octahedra shrink since the B-site becomes partially occupied by smaller Co3+ metal ions on account of the migrated Mn ions. CoMn2O4 particle sizes are easily fine-tuned by applying different annealing temperatures ; the particle size increases with increasing annealing temperature. During the battery operation, pulverization and reduction of particle sizes occurs regardless of the initial size of the particles, but the degree of division of the particles during the operation is dependent on the initial particle properties. Thus, contrary to the common assumption that nanostructuring of the anode material improves the battery performance, samples with the largest particle sizes exhibit excellent performance with a capacity retention of 104% after 1000 cycles (compared to the 2nd cycle).

Encapsulation of Perovskite Solar Cells for High Humidity Conditions.

We examined different encapsulation strategies for perovskite solar cells by testing the device stability under continuous illumination, elevated temperature (85 °C) and ambient humidity of 65 %. The effects of the use of different epoxies, protective layers and the presence of desiccant were investigated. The best stability (retention of ∼80 % of initial efficiency on average after 48 h) was obtained for devices protected by a SiO2 film and encapsulated with a UV-curable epoxy including a desiccant sheet. However, the stability of ZnO-based cells encapsulated by the same method was found to be inferior to that of TiO2 -based cells. Finally, outdoor performance tests were performed for TiO2 -based cells (30-90 % ambient humidity). All the stability tests were performed following the established international summit on organic photovoltaic stability (ISOS) protocols for organic solar cell testing (ISOS-L2 and ISOS-O1).

Indium tin oxide nanorod electrodes for polymer photovoltaics.

We have deposited indium tin oxide (ITO) nanorods on glass and glass/ITO substrates by DC sputtering and by e-beam deposition. The properties of the nanorods deposited by different methods and on different substrates have been investigated. The ITO nanorods were also used as an electrode in bulk heterojunction polymer solar cells. We found that the nanorod morphology and sheet resistance had a significant effect on the solar cell performance, with significant improvements in the efficiency compared to commercial ITO film substrates in all cases except for e-beam deposited nanorods on glass that had high sheet resistance. The best power conversion efficiency achieved was 3.2 % (for sputtered ITO nanorods on ITO), compared to 2.1 % for commercial ITO substrates.

Multifunctional Poly(N‐vinylcarbazole)‐Based Block Copolymers and their Nanofabrication and Photosensitizing Properties

The synthesis of poly(N-vinylcarbazole)-based block copolymers functionalized with rhenium diimine complexes or pendant terpyridine ligands is reported. The copolymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, and they exhibit interesting morphological properties as a result of the phase separation between different blocks. The rhenium complex polymer block may function as a photosensitizer, while the terpyridine-containing polymer block can be used as the template for nanofabrication by selective deposition of zinc complexes.

Toxicity of ZnO and TiO 2 to Escherichia coli cells

We performed a comprehensive investigation of the toxicity of ZnO and TiO2 nanoparticles using Escherichia coli as a model organism. Both materials are wide band gap n-type semiconductors and they can interact with lipopolysaccharide molecules present in the outer membrane of E. coli, as well as produce reactive oxygen species (ROS) under UV illumination. Despite the similarities in their properties, the response of the bacteria to the two nanomaterials was fundamentally different. When the ROS generation is observed, the toxicity of nanomaterial is commonly attributed to oxidative stress and cell membrane damage caused by lipid peroxidation. However, we found that significant toxicity does not necessarily correlate with up-regulation of ROS-related proteins. TiO2 exhibited significant antibacterial activity, but the protein expression profile of bacteria exposed to TiO2 was different compared to H2O2 and the ROS-related proteins were not strongly expressed. On the other hand, ZnO exhibited lower antibacterial activity compared to TiO2, and the bacterial response involved up-regulating ROS-related proteins similar to the bacterial response to the exposure to H2O2. Reasons for the observed differences in toxicity and bacterial response to the two metal oxides are discussed.