High-quality boron nitride nanoribbons : unzipping during nanotube synthesis

Zipper examined: High-quality boron nitride nanoribbons (BNNRs) can be produced directly during nanotube synthesis without post-treatment. These BNNRs are typically several micrometers long and tens of nanometers wide. Near-edge X-ray absorption fine structure investigations indicated that the BNNRs are of high chemical purity and crystallinity.

Reconstituting the invisible out of structure and repetition: a walk through diary V3.2.

This presentation will discuss the production of an interactive personal diary constructed in digital form as an interactive CD-Rom: Diary V 3.2. This diary was conceived as a digital version of the family photo album of the artist's nuclear family, which unfortunately disintegrated during 4 years of the diary's making. As a result Diary V 3.2 became more a documentation of the mood and state of mind of the maker than the family it began to focus on. It acted more as a trace or a remnant of mood, an artifact of loss. This was communicated not so much through narrative but ideas of loss and erasure. Another layer to this work concerns the migration of images, technique from the old analogue technology to the new digital technology which can act as a replay of the migrant experience.

Investigations into the analytical applications and fundamental chemistry of the chemiluminescent reactions of Tris(2,2'-bipyridyl)ruthenium(III) with certain Papaver Somniferum alkaloids and other related compounds

The reaction of tris(2,2’-bipyridyl)ruthenium(III) (Ru(bipy) ₃³⁺) with various analytes to generate chemiluminescence has been well documented. This investigation sought to undertake a chemiluminometic study of the reactions of Ru(bipy) ₃³⁺ with selected Papaver Somniferum alkaloids and specifically synthesised phenethylamines. The investigation, based on a kinetic study, primarily addressed the effect of varying reaction conditions (pH) on Ru(bipy) ₃³⁺ chemiluminescence production. To monitor these reactions, a batch chemiluminometer was specifically designed, fabricated and automated to conduct an extensive study on the selected compounds of interest. The instrumentation incorporated a custom built reaction cell and comprised an ‘on-line’ sample preparation system with which calibration standards could be automatically prepared. The instrumentation provided both time-independent (peak area) and time-dependent (kinetic profile) information. A novel approach to the stabilisation of Ru(bipy) ₃³⁺ as a chemiluminescencent reagent was also investigated and a recirculating system was employed with the batch chemiluminometer to provide a stable supply of Ru(bipy) ₃³⁺. Codeine, thebaine and 6-methoxy-codeine were the Papaver Somniferum alkaloids selected for this study and several N-methylated and N,N-dimethylated phenethylamines and methoxy-substituted phenetheylamines were also synthesised to investigate the affect of pH on the chemiluminescence emission efficiency. The versatility of the batch chemiluminometer facilitated the kinetic study of numerous analytes over a broad pH range. The exemplary performance of the chemiluminometer as an analytical instrument, was demonstrated by the calibration functions, based on peak area data, which exhibited excellent linearity and sensitivity. The estimated detection limits (3s) for the selected alkaloids were in the range 2 x 10^-9 M to 7 x 10^-9 at pH 5.0 and above, which compared favourably to detection limits for the same compounds determined using FIA. Relative standard deviations (n=5) for peak areas ranged between 1% to 5% with a mean of 3.1% for all calibration standards above 2.5 x 10^-8 M. Correlation between concentration and peak area, irrespective of pH and analyte was excellent, with all but two calibration functions having r-squared values greater than 0.990. The analytical figures of merit exemplified the precision and robustness of the reagent delivery and ‘on-line’ sample preparation, as well as the sensitivity of the system. The employment of the chemiluminometer for the measurement of total chemiluminescence emission (peak area) was in itself a feasible analytical technique, which generated highly reproducible and consistent data. Excellent analytical figures of merit, based on peak area, were similarly achieved for the phenethylamines. The effects of analyte structure on chemiluminescence activity was also investigated for the alkaloids and the phenethylamines. Subtle structural variations between the three alkaloids resulted in either a moderately reduced or enhanced total emission that was two or three fold difference only. A significant difference in reaction kinetics was observed between thebaine and codeine/6-methoxy-codeine, which was dependent upon pH. The time-dependent data, namely the observed rate constants for the initial rise in intensity and for the subsequent decay rate, were obtained by fitting a mathematical function (based on the postulated reaction mechanism) to the raw data. The determination of these rate constants for chemiluminescence reactions highlighted the feasibility for utilising such measurements for quantitative analytical applications. The kinetic data were used to discriminate between analyte responses in order to determine the concentrations of individual analytes in a binary mixture. A preliminary, multi-component investigation performed on a binary mixture of codeine and 6-methoxy-codeine (1:1) successfully determined the concentrations of these individual components using such rate constant measurements. Consequently, variations in kinetics resulted in a significant difference between the relative chemiluminescence response based on peak area measurements and the relative response base on peak height measurements obtained using FIA. With regards to the observed reactivity of secondary amines and tertiary amines, chemiluminescence peak area determinations confirmed the vital role of pH on reaction efficiency, which was governed by structural features and kinetics. The tertiary amines investigated generally produced a greater emission under acidic conditions than the corresponding secondary amines. However, the measured chemiluminescence responses were highly dependent upon pH, with similar peak areas obtained for both amine groups under slightly alkaline conditions.

Computational investigations on periodic trends in Group 14 chemistry

Describes the use of computer-aided molecular modelling to investigate trends in the chemistry of the Group 14 elements, namely carbon, silicon, germanium, tin and lead. The chemical behaviour of two classes of molecules containing Group 14 elements was related to trends in the fundamental properties of these elements.

Framework investigations for harmonizing global taxation of internet commerce

Identifies and evaluates contemporary global approaches to taxation in internet commerce. Adapts the principles of evidence-based medicine to develop a working model for evidence-based taxation. A collaborative extranet structure is used to validate the axioms underpinning the critical success factors for a modern knowledge management solution.

Structure and transport properties in an N,N-substituted pyrrolidinium tetrafluoroborate plastic crystal system

The structure and transport of N-propyl-N-methylpyrrolidinium tetrafluoroborate (P₁₃BF₄) has been investigated over a wide temperature range in consequence to exhibiting properties suitable for potential solid-state superionic electrolyte applications. Prior to melting, the organic salt, P₁₃BF₄, transforms into a plastic crystal phase. Intrinsic conductivity in this solid, phase I (45–65 °C), is comparable to that in the melt (_~10⁻³ S cm⁻¹). Ionic motion and transport properties were investigated by ¹H and ¹¹B nuclear magnetic resonance (NMR) spectroscopy. Pressure-induced plastic flow in this system may accommodate volume changes in device application and to this extent, X-ray diffraction (XRD) has been used. Scanning electron microscopy (SEM) revealed complex surface morphology and lattice imperfections associated with the strong orientational disorder of the plastic state.

An nmr investigation of ionic structure and mobility in plasticized solid polymer electrolytes

²³Na and ¹⁹F nuclear magnetic resonance spectroscopy is used to investigate the effect of plasticizer addition on ionic structure and mobility in a urethane crosslinked polyether solid polymer electrolyte. The incorporation of dimethyl formamide and propylene carbonate plasticizers in a sodium triflate/polyether system results in an upfield chemical shift for the ²³Na resonance consistent with decreased anion-cation association and increased cation-plasticizer interactions. The ¹⁹F resonances appears less susceptible to changes in chemical environment with only minor chemical shift changes recorded. Spin lattice relaxation measurements for the ¹⁹F nucleus are also reported. Two minima are observed in the relaxation measurements consistent with both an inter and intramolecular relaxation mechanism.

Structural characterization of conducting polypyrrole using 13C cross-polarization/magic-angle spinning solid-state nuclear magnetic resonance spectroscopy

¹³C nuclear magnetic resonance (n.m.r.) has been used to study polypyrrole and N-substituted polypyrrole in the solid state. The extent of oxidation appears to be counterion-dependent; in particular, the quinoid structure appears favoured in the films prepared with dodecyl sulfate. Resonances associated with the quinoid unit are lost upon reduction of the polypyrrole film, which supports the idea that the quinoid structure is associated with the oxidized form of polypyrrole. N-substituted polypyrroles have a more distinct resonance at 110 ppm, which is linked to lower degrees of oxidation or charge delocalization in these systems. The decrease in conductivity of polypyrrole upon thermal ageing in air is associated with both the loss of counterion (‘thermal dedoping’) and the decomposition of the quinoid structure in the polymer backbone. There is no indication of carbonyl formation in the solid-state n.m.r. spectra obtained in the present study.

Quantifying rubber degradation using NMR

Ageing can lead to the degradation of the tensile properties of natural rubber. The ageing process causes changes in the polymer segmental motion as well as the chemical structure, both of which can be monitored using nuclear magnetic resonance (NMR) spectroscopy. This work demonstrates that NMR can quantify rubber degradation due to ageing, and also that relatively simple NMR equipment can be used. This simpler equipment can be made portable and so could give a simple and fast indication of the condition of rubber in service. The 1H NMR transverse relaxation time, T2, and the 13C NMR spectrum using cross polarization and magic angle spinning (CP MAS) for samples taken at various levels of a degraded natural rubber liner were compared. These experiments showed that, as the level of degradation increased, the 1H NMR transverse relaxation time decreased. The 13C spectra showed considerable peak broadening, indicative of decreased mobility with increased level of degradation as well as the presence of degradation products. Further investigations using lower powered NMR equipment to measure the 1H NMR transverse relaxation times of two different series of natural rubbers were also performed. This work has shown that this simpler method is also sensitive to structural and mechanical property changes in the rubber. This method of monitoring rubber degradation could lead to the non-destructive use of NMR to determine the condition of a part in service.

Development of asymmetric rolling for the better control over structure and mechanical properties in IF steel

In the present study, the effects of kinematic and geometric asymmetries in rolling during multi-pass processing of IF steel are examined. The theoretical investigation by final element simulations and experimental investigations by means of electron-backscatter diffraction analysis and tensile tests suggest that asymmetric rolling increases the total imposed strain compared to symmetric rolling, and largely re-distributes the strain components due to additional shear. This enhances the intensity of grain refinement, strengthens and tilts crystallographic orientations, and increases mechanical strength. The effect is highest in the asymmetric rolling with differential roll diameters.

Data gathered during investigations into the ecofriendly production of bamboo fibres having UV-screening and antibacterial properties

This dataset comprises morphological image-based data of the cross and longitudinal sections of the powder particles and fibres of the bamboo plant, gathered using the Scanning Electron Microscope (SED). The morophology of the treated and untreated samples was compared before and after several chemical treatments. The diameter of the fibre and porous structure was measured, giving an indication of particle size.

Multilocus phylogeography of Australian teals (Anas spp.) : a case study of the relationship between vagility and genetic structure

Biogeographic barriers potentially restrict gene flow but variation in dispersal or vagility can influence the effectiveness of these barriers among different species and produce characteristic patterns of population genetic structure. The objective of this study was to investigate interspecific and intraspecific genetic structure in two closely related species that differ in several life-history characteristics. The grey teal Anas gracilis is geographically widespread throughout Australia with a distribution that crosses several recognized biogeographic barriers. This species has high vagility as its extensive movements track broad-scale patterns in rainfall. In contrast, the closely related chestnut teal A. castanea is endemic to the mesic southeastern and southwestern regions of Australia and is more sedentary. We hypothesized that these differences in life-history characteristics would result in more pronounced population structuring in the chestnut teal. We sequenced five nuclear loci (nuDNA) for 49 grey teal and 23 chestnut teal and compared results to published mitochondrial DNA (mtDNA) sequences. We used analysis of molecular variance to examine population structure, and applied coalescent based approaches to estimate demographic parameters. As predicted, chestnut teal were more strongly structured at both mtDNA and nuDNA (ΦST= 0.163 and 0.054, respectively) than were grey teal (ΦST < 0.0001 for both sets of loci). Surprisingly, a greater proportion of the total genetic variation was partitioned among populations within species (ΦSC= 0.014 and 0.047 for nuDNA and mtDNA, respectively) than between the two species (ΦCT < 0.0001 for both loci). The ‘Isolation with Migration’ coalescent model suggested a late Pleistocene divergence between the taxa, but remarkably, a deeper divergence between the southeastern and southwestern populations of chestnut teal. We conclude that dispersal potential played a prominent role in the structuring of populations within these species and that divergent selection associated with ecology and life history traits likely contributed to rapid and recent speciation in this pair.

Limited population structure, genetic drift and bottlenecks characterise an endangered bird species in a dynamic, fire-prone ecosystem

Fire is a major disturbance process in many ecosystems world-wide, resulting in spatially and temporally dynamic landscapes. For populations occupying such environments, fire-induced landscape change is likely to influence population processes, and genetic patterns and structure among populations. The Mallee Emu-wren Stipiturus mallee is an endangered passerine whose global distribution is confined to fire-prone, semi-arid mallee shrublands in south-eastern Australia. This species, with poor capacity for dispersal, has undergone a precipitous reduction in distribution and numbers in recent decades. We used genetic analyses of 11 length-variable, nuclear loci to examine population structure and processes within this species, across its global range. Populations of the Mallee Emu-wren exhibited a low to moderate level of genetic diversity, and evidence of bottlenecks and genetic drift. Bayesian clustering methods revealed weak genetic population structure across the species' range. The direct effects of large fires, together with associated changes in the spatial and temporal patterns of suitable habitat, have the potential to cause population bottlenecks, serial local extinctions and subsequent recolonisation, all of which may interact to erode and homogenise genetic diversity in this species. Movement among temporally and spatially shifting habitat, appears to maintain long-term genetic connectivity. A plausible explanation for the observed genetic patterns is that, following extensive fires, recolonisation exceeds in-situ survival as the primary driver of population recovery in this species. These findings suggest that dynamic, fire-dominated landscapes can drive genetic homogenisation of populations of species with low-mobility and specialised habitat that otherwise would be expected to show strongly structured populations. Such effects must be considered when formulating management actions to conserve species in fire-prone systems.