Porphyrins with metal, metalloid or phosphorus atoms directly bonded to the carbon periphery

Organometallic porphyrins with a metal, metalloid or phosphorus fragment directly attached to their carbon framework emerged for the first time in 1976, and these macrocycles have been intensively investigated in the past decade. The present review summarises for the first time all reported examples as well as applications of these systems.

PDMS spreading morphological patterns on substrates of different hydrophilicity in air vacuum and water

In paper has been to investigate the morphological patterns and kinetics of PDMS spreading on silicon wafer using combination of techniques like ellipsometry, atomic force microscope (AFM), scanning electron microscope (SEM) and optical microscopy. A macroscopic silicone oil drops as well as PDMS water based emulsions were studied after deposition on a flat surface of silicon wafer in air, water and vacuum. our own measurements using an imaging ellipsometer, which also clearly shows the presence of a precursor film. The diffusion constant of this film, measured with a 60 000 cS PDMS sample spreading on a hydrophilic silicon wafer, is Df = 1.4  10-11 m2/s. Regardless of their size, density and method of deposition, droplets on both types of wafer (hydrophilic and hydrophobic) flatten out over a period of many hours, up to 3 days. During this process neighbouring droplets may coalesce, but there is strong evidence that some of the PDMS from the droplets migrates into a thin, continuous film that covers the surface in between droplets. The thin film appears to be ubiquitous if there has been any deposition of PDMS. However, this statement needs further verification. One question is whether the film forms immediately after forced drying, or whether in some or all cases it only forms by spreading from isolated droplets as they slowly flatten out.

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Air evacuation in war : the role of RAAF nurses undertaking air evacuation of casualties between 1943-1953

Air transportation of Australian casualties in World War II was initially carried out in air ambulances with an accompanying male medical orderly. By late 1943 with the war effort concentrated in the Pacific, Allied military authorities realised that air transport was needed to move the increasing numbers of casualties over longer distances. The Royal Australian Air Force (RAAF) became responsible for air evacuation of Australian casualties and established a formal medical air evacuation system with trained flight teams early in 1944. Specialised Medical Air Evacuation Transport Units (MAETUs) were established whose sole responsibility was undertaking air evacuations of Australian casualties from the forward operational areas back to definitive medical care. Flight teams consisting of a RAAF nursing sister (registered nurse) and a medical orderly carried out the escort duties. These personnel had been specially trained in Australia for their role. Post-WWII, the RAAF Nursing Service was demobilised with a limited number of nurses being retained for the Interim Air Force. Subsequently, those nurses were offered commissions in the Permanent Air Force. Some of the nurses who remained were air evacuation trained and carried out air evacuations both in Australia and as part of the British Commonwealth Occupation Force in Japan. With the outbreak of the Korean War in June 1950, Australia became responsible for the air evacuation of British Commonwealth casualties from Korea to Japan. With a re-organisation of the Australian forces as part of the British Commonwealth forces, RAAF nurses were posted to undertake air evacuation from Korea and back to Australia from Iwakuni, Japan. By 1952, a specialised casualty staging section was established in Seoul and staffed by RAAF nurses from Iwakuni on a rotation basis. The development of the Australian air evacuation system and the role of the flight nurses are not well documented for the period 1943-1953. The aims of this research are three fold and include documenting the origins and development of the air evacuation system from 1943-1953; analysing and documenting the RAAF nurse’s role and exploring whether any influences or lessons remain valid today. A traditional historical methodology of narrative and then analysis was used to inform the flight nurse’s role within the totality of the social system. Evidence was based on primary data sources mainly held in Defence files, the Australian War Memorial or the National Archives of Australia. Interviews with 12 ex-RAAF nurses from both WWII and the Korean War were conducted to provide information where there were gaps in the primary data and to enable exploration of the flight nurses’ role and their contributions in war of the air evacuation of casualties. Finally, this thesis highlights two lessons that remain valid today. The first is that interoperability of air evacuation systems with other nations is a force multiplier when resources are scarce or limited. Second, the pre-flight assessment of patients was essential and ensured that there were no deaths in-flight.

Air vehicle simulator : An application for a cable array robot

The development of autonomous air vehicles can be an expensive research pursuit. To alleviate some of the financial burden of this process, we have constructed a system consisting of four winches each attached to a central pod (the simulated air vehicle) via cables - a cable-array robot. The system is capable of precisely controlling the three dimensional position of the pod allowing effective testing of sensing and control strategies before experimentation on a free-flying vehicle. In this paper, we present a brief overview of the system and provide a practical control strategy for such a system. ©2005 IEEE.

Selective growth of carbon nanotubes on bare silicon : MWNT sinthesys on patterned substrates without predeposition of metal catalyst

Carbon nanotubes (CNTs) are expected to become the ideal constituent of many technologes, in particular for future generation electronics. This considerable interest is due to their unique electrical and mechanical properties. They show indeed super-high current-carrying capacity, ballistic electron transport and good field-emission properties. Then, these superior features make CNTs the most promising building blocks for electronic devices, as organic solar cells and organic light emitting devices (OLED). By using Focused Ion Beam (FIB) patterning it is possible to a obtain a high control on position, relative distances and diameter of CNTs. The present work shows how to grow three-dimensional architecture made of vertical-aligned CNTs directly on silicon. Thanks to the higher activity of a pre-patterned surface the synthesis process results very quick, cheap and simple. Such large area growths of CNTs could be used in preliminary test for application as electrodes for organic solar cells.

Optimal mission path planning (MPP) for an air sampling unmanned aerial system

This paper presents advanced optimization techniques for Mission Path Planning (MPP) of a UAS fitted with a spore trap to detect and monitor spores and plant pathogens. The UAV MPP aims to optimise the mission path planning search and monitoring of spores and plant pathogens that may allow the agricultural sector to be more competitive and more reliable. The UAV will be fitted with an air sampling or spore trap to detect and monitor spores and plant pathogens in remote areas not accessible to current stationary monitor methods. The optimal paths are computed using a Multi-Objective Evolutionary Algorithms (MOEAs). Two types of multi-objective optimisers are compared; the MOEA Non-dominated Sorting Genetic Algorithms II (NSGA-II) and Hybrid Game are implemented to produce a set of optimal collision-free trajectories in three-dimensional environment. The trajectories on a three-dimension terrain, which are generated off-line, are collision-free and are represented by using Bézier spline curves from start position to target and then target to start position or different position with altitude constraints. The efficiency of the two optimization methods is compared in terms of computational cost and design quality. Numerical results show the benefits of coupling a Hybrid-Game strategy to a MOEA for MPP tasks. The reduction of numerical cost is an important point as the faster the algorithm converges the better the algorithms is for an off-line design and for future on-line decisions of the UAV.

A cable-array robot for air vehicle simulation

The development of autonomous air vehicles can be an expensive research pursuit. To alleviate some of the financial burden of this process, we have constructed a system consisting of four winches each attached to a central pod (the simulated air vehicle) via cables - a cable-array robot. The system is capable of precisely controlling the three dimensional position of the pod allowing effective testing of sensing and control strategies before experimentation on a free-flying vehicle. In this paper, we present a brief overview of the system and provide a practical control strategy for such a system.

An adaptive local meshfree updated Lagrangian approach for large deformation analysis of metal forming

The large deformation analysis is one of major challenges in numerical modelling and simulation of metal forming. Because no mesh is used, the meshfree methods show good potential for the large deformation analysis. In this paper, a local meshfree formulation, based on the local weak-forms and the updated Lagrangian (UL) approach, is developed for the large deformation analysis. To fully employ the advantages of meshfree methods, a simple and effective adaptive technique is proposed, and this procedure is much easier than the re-meshing in FEM. Numerical examples of large deformation analysis are presented to demonstrate the effectiveness of the newly developed nonlinear meshfree approach. It has been found that the developed meshfree technique provides a superior performance to the conventional FEM in dealing with large deformation problems for metal forming.

GIS-based mapping and statistical analysis of air pollution and mortality in Brisbane, Australia

In this thesis, the relationship between air pollution and human health has been investigated utilising Geographic Information System (GIS) as an analysis tool. The research focused on how vehicular air pollution affects human health. The main objective of this study was to analyse the spatial variability of pollutants, taking Brisbane City in Australia as a case study, by the identification of the areas of high concentration of air pollutants and their relationship with the numbers of death caused by air pollutants. A correlation test was performed to establish the relationship between air pollution, number of deaths from respiratory disease, and total distance travelled by road vehicles in Brisbane. GIS was utilized to investigate the spatial distribution of the air pollutants. The main finding of this research is the comparison between spatial and non-spatial analysis approaches, which indicated that correlation analysis and simple buffer analysis of GIS using the average levels of air pollutants from a single monitoring station or by group of few monitoring stations is a relatively simple method for assessing the health effects of air pollution. There was a significant positive correlation between variable under consideration, and the research shows a decreasing trend of concentration of nitrogen dioxide at the Eagle Farm and Springwood sites and an increasing trend at CBD site. Statistical analysis shows that there exists a positive relationship between the level of emission and number of deaths, though the impact is not uniform as certain sections of the population are more vulnerable to exposure. Further statistical tests found that the elderly people of over 75 years age and children between 0-15 years of age are the more vulnerable people exposed to air pollution. A non-spatial approach alone may be insufficient for an appropriate evaluation of the impact of air pollutant variables and their inter-relationships. It is important to evaluate the spatial features of air pollutants before modeling the air pollution-health relationships.

The relationship between particulate air pollution and emergency hospital visits for hypertension in Beijing, China

BACKGROUND: A number of epidemiological studies have examined the adverse effect of air pollution on mortality and morbidity. Also, several studies have investigated the associations between air pollution and specific-cause diseases including arrhythmia, myocardial infarction, and heart failure. However, little is known about the relationship between air pollution and the onset of hypertension. OBJECTIVE: To explore the risk effect of particulate matter air pollution on the emergency hospital visits (EHVs) for hypertension in Beijing, China. METHODS: We gathered data on daily EHVs for hypertension, fine particulate matter less than 2.5 microm in aerodynamic diameter (PM(2.5)), particulate matter less than 10 microm in aerodynamic diameter (PM(10)), sulfur dioxide, and nitrogen dioxide in Beijing, China during 2007. A time-stratified case-crossover design with distributed lag model was used to evaluate associations between ambient air pollutants and hypertension. Daily mean temperature and relative humidity were controlled in all models. RESULTS: There were 1,491 EHVs for hypertension during the study period. In single pollutant models, an increase in 10 microg/m(3) in PM(2.5) and PM(10) was associated with EHVs for hypertension with odds ratios (overall effect of five days) of 1.084 (95% confidence interval (CI): 1.028, 1.139) and 1.060% (95% CI: 1.020, 1.101), respectively. CONCLUSION: Elevated levels of ambient particulate matters are associated with an increase in EHVs for hypertension in Beijing, China.