Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Including nonequilibrium interface kinetics in a continuum model for melting nanoscaled particles

The melting temperature of a nanoscaled particle is known to decrease as the curvature of the solid-melt interface increases. This relationship is most often modelled by a Gibbs--Thomson law, with the decrease in melting temperature proposed to be a product of the curvature of the solid-melt interface and the surface tension. Such a law must break down for sufficiently small particles, since the curvature becomes singular in the limit that the particle radius vanishes. Furthermore, the use of this law as a boundary condition for a Stefan-type continuum model is problematic because it leads to a physically unrealistic form of mathematical blow-up at a finite particle radius. By numerical simulation, we show that the inclusion of nonequilibrium interface kinetics in the Gibbs--Thomson law regularises the continuum model, so that the mathematical blow up is suppressed. As a result, the solution continues until complete melting, and the corresponding melting temperature remains finite for all time. The results of the adjusted model are consistent with experimental findings of abrupt melting of nanoscaled particles. This small-particle regime appears to be closely related to the problem of melting a superheated particle.

Polymer-mediated synthesis of γ-Fe2O3 nano-particles

Nano-particles of γ-Fe2O3 were synthesized by reacting polyethylene oxide–FeCl3 complex with NH4OH. These were characterized by X-ray diffraction (XRD), scanning electron miscroscopy (SEM), selected area electron diffraction (SAED) and transmision electron microscopy (TEM). The average particle size was found to be 10 nm, as determined from the line broadening of the main XRD peak. The crystalline phase was a spinel-type tetragonal structure, which was confirmed from the electron diffraction pattern. The zero field cooled magnetization of samples with varying γ-Fe2O3 content as a function of temperature was measured using a vibrating sample magnetometer. The magnetization curves show a peak at low temperature (15 K) corresponding to the blocking temperature TB. The value of TB was found to decrease with decreasing particle size. The magnetization measurements with respect to field at 5 and 170 K confirmed the transition from superparamagnetic to spin-glass state at TB, as evidenced from the remanence and hysteresis. These results can be explained on the basis of Néel's theory of superparamagnetism as applied to nano-particles.

Investigations of ultrafine particles emitted by ships and other transport modes in the port of Brisbane

This research measured particle and gaseous emissions from ships and trains operating within the Port of Brisbane, and explored their influence on ambient air composition at a downwind suburban measurement site. The ship and train emission factor investigations resulted in the development of novel measurement techniques which permit the quantification of particle and gaseous emission factors using samples collected from post-emission exhaust plumes. The urban influence investigation phase of the project produced a new approach to identifying influences from ship emissions.

Molecular camouflage : making use of protecting groups to control the self-assembly of inorganic janus particles onto metal–chalcogenide nanotubes by Pearson Hardness

Hard and soft: Binding of inorganic Pt@Fe3O4 Janus particles to WS2 nanotubes through their Pt or Fe3O4 domains is governed by the difference in Pearson hardness: the soft Pt block has a higher sulfur affinity than the harder magnetite face; thus the binding proceeds preferentially through the Pt face. This binding preference can be reversed by masking the Pt face with an organic protecting group.

Stefan problems for melting nanoscaled particles

Under certain conditions, the mathematical models governing the melting of nano-sized particles predict unphysical results, which suggests these models are incomplete. This thesis studies the addition of different physical effects to these models, using analytic and numerical techniques to obtain realistic and meaningful results. In particular, the mathematical "blow-up" of solutions to ill-posed Stefan problems is examined, and the regularisation of this blow-up via kinetic undercooling. Other effects such as surface tension, density change and size-dependent latent heat of fusion are also analysed.

Charged particles and cluster ions produced during cooking activities

Previous studies showed that a significant number of the particles present in indoor air are generated by cooking activities, and measured particle concentrations and exposures have been used to estimate the related human dose. The dose evaluation can be affected by the particle charge level which is usually not considered in particle deposition models. To this purpose, in this paper we show, for the very first time, the electric charge of particles generated during cooking activities and thus extending the interest on particle charging characterization to indoor micro-environments, so far essentially focused on outdoors. Particle number, together with positive and negative cluster ion concentrations, was monitored using a condensation particle counter and two air ion counters, respectively, during different cooking events. Positively-charged particle distribution fractions during gas combustion, bacon grilling, and eggplant grilling events were measured by two Scanning Mobility Particle Sizer spectrometers, used with and without a neutralizer. Finally, a Tandem Differential Mobility Analyzer was used to measure the charge specific particle distributions of bacon and eggplant grilling experiments, selecting particles of 30, 50, 80 and 100 nm in mobility diameter. The total fraction of positively-charged particles was 4.0%, 7.9%, and 5.6% for gas combustion, bacon grilling, and eggplant grilling events, respectively, then lower than other typical outdoor combustion-generated particles.

Elemental composition of ambient fine particles in urban schools : sources of children’s exposure

Currently, there is a limited understanding of the sources of ambient fine particles that contribute to the exposure of children at urban schools. Since the size and chemical composition of airborne particle are key parameters for determining the source as well as toxicity, PM1 particles (mass concentration of particles with an aerodynamic diameter less than 1 µm) were collected at 24 urban schools in Brisbane, Australia and their elemental composition determined. Based on the elemental composition four main sources were identified; secondary sulphates, biomass burning, vehicle and industrial emissions. The largest contributing source was industrial emissions and this was considered as the main source of trace elements in the PM1 that children were exposed to at school. PM1 concentrations at the schools were compared to the elemental composition of the PM2.5 particles (mass concentration of particles with an aerodynamic diameter less than 2.5 µm) from a previous study conducted at a suburban and roadside site in Brisbane. This comparison revealed that the more toxic heavy metals (V, Cr, Ni, Cu, Zn and Pb), mostly from vehicle and industrial emissions, were predominantly in the PM1 fraction. Thus, the results from this study points to PM1 as a potentially better particle size fraction for investigating the health effects of airborne particles.

Ultrafine Particles from Traffic Emissions and Children’s Health (UPTECH) in Brisbane, Queensland (Australia): Study design and implementation

Ultrafine particles are particles that are less than 0.1 micrometres (µm) in diameter. Due to their very small size they can penetrate deep into the lungs, and potentially cause more damage than larger particles. The Ultrafine Particles from Traffic Emissions and Children’s Health (UPTECH) study is the first Australian epidemiological study to assess the health effects of ultrafine particles on children’s health in general and peripheral airways in particular. The study is being conducted in Brisbane, Australia. Continuous indoor and outdoor air pollution monitoring was conducted within each of the twenty five participating school campuses to measure particulate matter, including in the ultrafine size range, and gases. Respiratory health effects were evaluated by conducting the following tests on participating children at each school: spirometry, forced oscillation technique (FOT) and multiple breath nitrogen washout test (MBNW) (to assess airway function), fraction of exhaled nitric oxide (FeNO, to assess airway inflammation), blood cotinine levels (to assess exposure to second-hand tobacco smoke), and serum C-reactive protein (CRP) levels (to measure systemic inflammation). A pilot study was conducted prior to commencing the main study to assess the feasibility and reliably of measurement of some of the clinical tests that have been proposed for the main study. Air pollutant exposure measurements were not included in the pilot study.

Sub-genomic RNA of defective interfering (D.I.) dengue viral particles is replicated in the same manner as full length genomes

The predicted secondary structure of sub-genomic RNA in dengue virus defective interfering (D.I.) particles from patients, or generated in vitro, resembled that of the 3′ and 5′ regions of wild type dengue virus (DENV) genomes. While these structures in the sub-genomic RNA were found to be essential for its replication, their nucleotide sequences were not, so long as any new sequences maintained wild type RNA secondary structure. These observations suggested that these sub-genomic fragments of RNA from dengue viruses were replicated in the same manner as the full length genomes of their wild type, “helper”, viruses and that they probably represent the smallest fragments of DENV RNA that can be replicated during a natural infection. While D.I. particles containing sub-genomic RNA are completely parasitic, the relationship between wild type and D.I. DENV may be symbiotic, with the D.I. particles enhancing the transmission of infectious DENV.

Production of biodegradable nano and micro particles via ultrasonic atomization for biopharmaceutical delivery

Biopharmaceuticals have been shown to have low delivery and transformation efficiencies. To over come this, larger doses are administered in order to obtain the desired response which may lead to toxicity and drug resistance. This paper reports upon a continuous particle production method utilizing surface acoustic wave atomization to reliably produce micro and nanoparticles with physical characteristics to facilitate the cellular uptake of biopharmaceuticals. By producing particles of an optimal size for cellular uptake, the efficacy and specificity of drug loaded nanoparticles will be increased. Better delivery methods will result in dosage reduction (hence lower costs per dose), reduced toxicity, and reduced problems associated with multidrug resistance due to over dosing.