Characterisation and processing of amorphous binary mixtures with low glass transition temperature

The number of drug substances in formulation development in the pharmaceutical industry is increasing. Some of these are amorphous drugs and have glass transition below ambient temperature, and thus they are usually difficult to formulate and handle. One reason for this is the reduced viscosity, related to the stickiness of the drug, that makes them complicated to handle in unit operations. Thus, the aim in this thesis was to develop a new processing method for a sticky amorphous model material. Furthermore, model materials were characterised before and after formulation, using several characterisation methods, to understand more precisely the prerequisites for physical stability of amorphous state against crystallisation. The model materials used were monoclinic paracetamol and citric acid anhydrate. Amorphous materials were prepared by melt quenching or by ethanol evaporation methods. The melt blends were found to have slightly higher viscosity than the ethanol evaporated materials. However, melt produced materials crystallised more easily upon consecutive shearing than ethanol evaporated materials. The only material that did not crystallise during shearing was a 50/50 (w/w, %) blend regardless of the preparation method and it was physically stable at least two years in dry conditions. Shearing at varying temperatures was established to measure the physical stability of amorphous materials in processing and storage conditions. The actual physical stability of the blends was better than the pure amorphous materials at ambient temperature. Molecular mobility was not related to the physical stability of the amorphous blends, observed as crystallisation. Molecular mobility of the 50/50 blend derived from a spectral linewidth as a function of temperature using solid state NMR correlated better with the molecular mobility derived from a rheometer than that of differential scanning calorimetry data. Based on the results obtained, the effect of molecular interactions, thermodynamic driving force and miscibility of the blends are discussed as the key factors to stabilise the blends. The stickiness was found to be affected glass transition and viscosity. Ultrasound extrusion and cutting were successfully tested to increase the processability of sticky material. Furthermore, it was found to be possible to process the physically stable 50/50 blend in a supercooled liquid state instead of a glassy state. The method was not found to accelerate the crystallisation. This may open up new possibilities to process amorphous materials that are otherwise impossible to manufacture into solid dosage forms.

Using APSIM-soiltemp to simulate soil temperature in the podding zone of peanut

Measurement or accurate simulation of soil temperature is important for improved understanding and management of peanuts (Arachis hypogaea L.), due to their geocarpic habit. A module of the Agricultural Production Systems Simulator Model (APSIM), APSIM-soiltemp, which uses input of ambient temperature, rainfall and solar radiation in conjunction with other APSIM modules, was evaluated for its ability to simulate surface 5 cm soil temperature in 35 peanut on-farm trials conducted between 2001 and 2005 in the Burnett region (25°36'S to 26°41'S, 151°39'E to 151°53'E). Soil temperature simulated by the APSIM-soiltemp module, from 30 days after sowing until maturity, closely matched the measured values (R2 ≥ 0.80)in the first three seasons (2001-04). However, a slightly poorer relationship (R2 = 0.55) between the observed and the simulated temperatures was observed in 2004-05, when the crop was severely water stressed. Nevertheless, over all the four seasons, which were characterised by a range of ambient temperature, leaf area index, radiation and soil water, each of which was found to have significant effects on soil temperature, a close 1:1 relationship (R2 = 0.85) between measured and simulated soil temperatures was observed. Therefore, the pod zone soil temperature simulated by the module can be generally relied on in place of measured input of soil temperature in APSIM applications, such as quantifying climatic risk of aflatoxin accumulation.

Variability in exposure to ambient ultrafine particles in urban schools: Comparative assessment between Australia and Spain

Ambient ultrafine particle number concentrations (PNC) have inhomogeneous spatio-temporal distributions and depend on a number of different urban factors, including background conditions and distant sources. This paper quantitatively compares exposure to ambient ultrafine particles at urban schools in two cities in developed countries, with high insolation climatic conditions, namely Brisbane (Australia) and Barcelona (Spain). The analysis used comprehensive indoor and outdoor air quality measurements at 25 schools in Brisbane and 39 schools in Barcelona. PNC modes were analysed with respect to ambient temperature, land use and urban characteristics, combined with the measured elemental carbon concentrations, NOx (Brisbane) and NO2 (Barcelona). The trends and modes of the quantified weekday average daily cycles of ambient PNC exhibited significant differences between the two cities. PNC increases were observed during traffic rush hours in both cases. However, the mid-day peak was dominant in Brisbane schools and had the highest contribution to total PNC for both indoors and outdoors. In Barcelona, the contribution from traffic was highest for ambient PNC, while the mid-day peak had a slightly higher contribution for indoor concentrations. Analysis of the relationships between PNC and land use characteristics in Barcelona schools showed a moderate correlation with the percentage of road network area and an anti-correlation with the percentage of green area. No statistically significant correlations were found for Brisbane. Overall, despite many similarities between the two cities, school-based exposure patterns were different. The main source of ambient PNC at schools was shown to be traffic in Barcelona and mid-day new particle formation in Brisbane. The mid-day PNC peak in Brisbane could have been driven by the combined effect of background and meteorological conditions, as well as other local/distant sources. The results have implications for urban development, especially in terms of air quality mitigation and management at schools.

Freeze-drying of ovalbumin loaded mesoporous silica nanoparticle vaccine formulation increases antigen stability under ambient conditions

Amino functionalised mesoporous silica nanoparticles (AM-41) have been identified as a promising vaccine delivery material. The capacity of AM-41 to stabilise vaccine components at ambient temperature (23–27 °C) was determined by adsorbing the model antigen ovalbumin (OVA) to AM-41 particles (OVA-41). The OVA-41 was successfully freeze-dried using the excipients 5% trehalose and 1% PEG8000. Both the immunological activity of OVA and the nanoparticle structure were maintained following two months storage at ambient temperature. The results of immunisation studies in mice with reconstituted OVA-41 demonstrated the induction of humoral and cell-meditated immune responses. The capacity of AM-41 particles to facilitate ambient storage of vaccine components without loss of immunological potency will underpin the further development of this promising vaccine delivery platform.

Survival of Hendra Virus in the Environment: Modelling the Effect of Temperature

Hendra virus (HeV), a highly pathogenic zoonotic paramyxovirus recently emerged from bats, is a major concern to the horse industry in Australia. Previous research has shown that higher temperatures led to lower virus survival rates in the laboratory. We develop a model of survival of HeV in the environment as influenced by temperature. We used 20 years of daily temperature at six locations spanning the geographic range of reported HeV incidents to simulate the temporal and spatial impacts of temperature on HeV survival. At any location, simulated virus survival was greater in winter than in summer, and in any month of the year, survival was higher in higher latitudes. At any location, year-to-year variation in virus survival 24 h post-excretion was substantial and was as large as the difference between locations. Survival was higher in microhabitats with lower than ambient temperature, and when environmental exposure was shorter. The within-year pattern of virus survival mirrored the cumulative within-year occurrence of reported HeV cases, although there were no overall differences in survival in HeV case years and non-case years. The model examines the effect of temperature in isolation; actual virus survivability will reflect the effect of additional environmental factors

Virtual Special Issue: “The impact of temperature on human health: new insights”

Ambient temperature is one of the basic parameters characterising human comfort: are we too hot, too cold, or just right? The impact of temperature goes beyond comfort: inadequate temperature and temperature variations have consequences on human health, as the increasing numbers of studies have demonstrated. The topic is of particular significance at the times when climate change shifts the traditional – as we know them- temperature zones, and brings much wider temperature variations. For these reasons the impact of temperature on health has been one of the most popular topics among the articles submitted and published in Science of the Total Environment over the last few years. This Virtual Special Issue compiles 18 articles published in our journal on this topic since 2012. It is worth briefly summarizing the rich scientific insights brought by these articles, as well as broader considerations, particularly those extending to management, discussed by the authors of the articles.

Oscillatory flow and temperature fields in an open tube with temperature difference across the ends

The oscillating flow and temperature field in an open tube subjected to cryogenic temperature at the cold end and ambient temperature at the hot end is studied numerically. The flow is driven by a time-wise sinusoidally varying pressure at the cold end. The conjugate problem takes into account the interaction of oscillatory flow with the heat conduction in the tube wall. The full set of compressible flow equations with axisymmetry assumption are solved with a pressure correction algorithm. Parametric studies are conducted with frequencies of 5-15 Hz, with one end maintained at 100 K and other end at 300 K. The flow and temperature distributions and the cooldown characteristics are obtained. The frequency and pressure amplitude have negligible effect on the time averaged Nusselt number. Pressure amplitude is an important factor determining the enthalpy flow through the solid wall. The frequency of operation has considerable effect on penetration of temperature into the tube. The density variation has strong influence on property profiles during cooldown. The present study is expected to be of interest in applications such as pulse tube refrigerators and other cryocoolers, where oscillatory flows occur in open tubes. (C) 2011 Elsevier Ltd. All rights reserved.

Low temperature crystallographic data on Kevlar 49 fibres

Using X-ray diffraction data, the behaviour of Kevlar 49 fibres at low temperatures, up to -100degreesC, has been analysed. During cooling, the basal plane of the monoclinic unit cell shrinks whereas the c- (unique, chain axis) length is not significantly affected. In contrast, in the return heating cycle to ambient temperature, the basal plane expands and contraction occurs along the chain direction. The unit cell registers a reduction in volume in both the cooling and heating cycles. Conspicuously, after a cycle of cooling and heating, the unit cell does not return to its initial volume. (C) 2003 Kluwer Academic Publishers.

Pulsed plasma treatment of polluted gas using wet/low temperature corona reactors

pplication of pulsed plasma for gas cleaning is gaining prominence in recent years mainly from the energy consideration point of view. Normally, gas treatment is carried out, at or above room temperature, by a conventional dry type corona reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the exhaust/flue gas mixture. The authors report some interesting results of the treatment of such stable gases with pulsed plasma at very low ambient temperature. Also reported in the paper is an improvement in DeNO/DeNOx efficiency using unconventional wet-type reactors, designed and fabricated by the authors, operating at different ambient temperatures. Apart from laboratory tests on simulated gas mixtures, field tests were also carried out on the exhaust gas of a 8 kW diesel engine. Further, an attempt was made to test the feasibility of a helical wire as a corona electrode in place of the conventional straight wire electrode. A comparative analysis of the various tests is presented together with a note on the energy consideration

Non-Thermal Plasma Applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Pulsed plasma treatment of polluted gas using wet/low temperature corona reactors

Application of pulsed plasma for gas cleaning is gaining prominence in recent years mainly from the energy consideration point of view. Normally, gas treatment is carried out, at or above room temperature, by a conventional dry type corona reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the exhaust/flue gas mixture. The authors report some interesting results of the treatment of such stable gases with pulsed plasma at very low ambient temperature. Also reported in the paper is an improvement in DeNO/DeNOx efficiency using unconventional wet-type reactors, designed and fabricated by the authors, operating at different ambient temperatures. Apart from laboratory tests on simulated gas mixtures, field tests were also carried out on the exhaust gas of a 8 kW diesel engine. Further, an attempt was made to test the feasibility of a helical wire as a corona electrode in place of the conventional straight wire electrode. A comparative analysis of the various tests is presented together with a note on the energy consideration

Non-thermal plasma applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Increased time-dependent room temperature plasticity in metallic glass nanopillars and its size-dependency

Room temperature, uniaxial compression creep experiments were performed on micro-/nano-sized pillars (having diameters in the range of 250-2000 nm) of a Zr-based bulk metallic glass (BMG) to investigate the influence of sample size on the time-dependent plastic deformation behavior in amorphous alloys. Experimental results reveal that plastic deformation indeed occurs at ambient temperature and at stresses that are well below the nominal quasi-static yield stress. At a given stress, higher total strains accrue in the smaller specimens. In all cases, plastic deformation was found to be devoid of shear bands, i.e., it occurs in homogeneous manner. The stress exponent obtained from the slope of the linear relation between strain rate and applied stress also shows a strong size effect, which is rationalized in terms of the amount of free volume created during deformation and the surface-to-volume ratio of the pillar. (C) 2012 Elsevier Ltd. All rights reserved.

Mechanism to synthesize a `moving optical mark' at solid-ambient interface for the estimation of thermal diffusivity of solid

supporting unsteady heat flow with its ambient-humidity; invokes phase transformation of water-vapour molecule and synthesize a `moving optical-mark' at sample-ambient-interface. Under tailored condition, optical-mark exhibits a characteristic macro-scale translatory motion governed by thermal diffusivity of solid. For various step-temperature inputs via cooling, position-dependent velocities of moving optical-mark are measured at a fixed distance. A new approach is proposed. `Product of velocity of optical-mark and distance' versus `non-dimensional velocity' is plotted. The slope reveals thermal diffusivity of solid at ambient-temperature; preliminary results obtained for Quartz-glass is closely matching with literature. (C) 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Position-dependent velocity of an effective temperature point for the estimation of the thermal diffusivity of solids

A new approach is proposed to estimate the thermal diffusivity of optically transparent solids at ambient temperature based on the velocity of an effective temperature point (ETP), and by using a two-beam interferometer the proposed concept is corroborated. 1D unsteady heat flow via step-temperature excitation is interpreted as a `micro-scale rectilinear translatory motion' of an ETP. The velocity dependent function is extracted by revisiting the Fourier heat diffusion equation. The relationship between the velocity of the ETP with thermal diffusivity is modeled using a standard solution. Under optimized thermal excitation, the product of the `velocity of the ETP' and the distance is a new constitutive equation for the thermal diffusivity of the solid. The experimental approach involves the establishment of a 1D unsteady heat flow inside the sample through step-temperature excitation. In the moving isothermal surfaces, the ETP is identified using a two-beam interferometer. The arrival-time of the ETP to reach a fixed distance away from heat source is measured, and its velocity is calculated. The velocity of the ETP and a given distance is sufficient to estimate the thermal diffusivity of a solid. The proposed method is experimentally verified for BK7 glass samples and the measured results are found to match closely with the reported value.