17 resultados para kinetic resolution of activated cyclopropanes

em Deakin Research Online - Australia


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The addition of an adjuvant to a pesticide usually occurs in a mix-tank, before spray application to the crop. Their interaction is potentially crucial to overall efficacy but has received little attention from a physical-chemical perspective. Study was undertaken by laser diffraction, Raman spectroscopy, and small-angle X-ray scattering to resolve these physical processes. It was shown that migration of the pesticide into the adjuvant droplet occurred in all cases studied. The level of transfer was dependent upon adjuvant level, adjuvant solubility, and surfactant level. For suspension pesticides, dissolution of crystallites within the droplet occurred to a degree limited by solubility. The results directly demonstrate the transfer of the pesticide into the adjuvant carrier. This indicates that for emulsion-based pesticides, application to the target is likely as a homogeneously mixed droplet, whereas for suspension pesticides, solubility may limit transfer and dissolution, leading to heterogeneity in the applied particles.

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Excess copper is effluxed from mammalian cells by the Menkes or Wilson P-type ATPases (MNK and WND, respectively). MNK and WND have six metal binding sites (MBSs) containing a CXXC motif within their N-terminal cytoplasmic region. Evidence suggests that copper is delivered to the ATPases by Atox1, one of three cytoplasmic copper chaperones. Attempts to monitor a direct Atox1-MNK interaction and to determine kinetic parameters have not been successful. Here we investigated interactions of Atox1 with wild-type and mutated pairs of the MBSs of MNK using two different methods: yeast two-hybrid analysis and real-time surface plasmon resonance (SPR). A copper-dependent interaction of Atox1 with the MBSs of MNK was observed by both approaches. Cys to Ser mutations of conserved CXXC motifs affected the binding of Atox1 underlining the essentiality of Cys residues for the copper-induced interaction. Although the yeast two-hybrid assay failed to show an interaction of Atox1 with MBS5/6, SPR analysis clearly demonstrated a copper-dependent binding with all six MBSs highlighting the power and sensitivity of SPR as compared with other, more indirect methods like the yeast two-hybrid system. Binding constants for copper-dependent chaperone-MBS interactions were determined to be 10–5-10–6 M for all the MBSs representing relatively low affinity binding events. The interaction of Atox1 with pairs of the MBSs was non-cooperative. Therefore, a functional difference of the MBSs in the MNK N terminus cannot be attributed to cooperativity effects or varying affinities of the copper chaperone Atox1 with the MBSs.

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Time-resolved extinction spectroscopy is employed to study the reaction kinetics in the shape-conversion reaction involving halide ions (including Cl-, Br- and I-) etching (sculpturing) silver nanoplates. A series of time-resolved extinction spectra are obtained during the in situ etching process and the evolution of surface plasmon resonance (SPR) of the silver nanoparticles is analyzed. Spectral analysis indicates that the conversion of nanoprisms starts simultaneously with the emergence of nanodisks when the halide ions are added. The etching rate of different halide ions is evaluated through the in-plane dipole resonance peak intensity of silver nanoplates vs. the reaction time (dI/dt). The relationship between the etching rate and the halide ion concentration shows that the halide ion etching reaction can be considered as a pseudo-first-order reaction. The effect of different halide ions on the shape-conversion of silver nanoplates is compared in detail. The activation energy of the etching reaction is calculated, which indicates that the etching ability of different halide ions is on the order of Cl - < I- < Br-.

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Numerous authors have expressed concerns that the introduction of the Personally Controlled Electronic Health Record (PCEHR) will lead to an escalation of disputes. Some disputes will concern the accuracy of the record whereas others will arise simply due to greater access to health care records. Online dispute resolution (ODR) programs have been successfully applied to cost-effectively help disputants resolve commercial, insurance and other legal disputes, and can also facilitate the resolution of health care related disputes. However, we expect that health differs from other application domains in ODR because of the emotional engagement patients have with their health and those of loved ones. In this study we will be looking at whether the success of an online negotiation is related to how people recognise and manage emotions, and in particular, their Emotional intelligence score.

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Super-resolution is a method of post-processing image enhancement that increases the spatial resolution of video or images. Existing super-resolution techniques apply only to images captured of a planar scene. This paper aims to extend super-resolution concepts from the 2D domain to the 3D domain, drawing on ideas from both superresolution and multi-view geometry, two fields of research that until now have predominantly been studied in isolation. 2D super-resolution methods are not without their complexities and limitations. However, once multiple views of a scene are considered within a super-resolution framework, a new range of issues arise that must also be resolved. For example, when input images of a scene with variation in depth are considered, it is no longer clear how and where the images should be registered. This paper describes the use of sparse 3D reconstruction in order to ‘register’ the input images, which are then transferred to a novel image plane and combined to increase the perceived detail in the scene. Experimental results using real images captured from generally positioned input cameras are presented.

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In the present study, copper-bearing low carbon steels were produced by direct strip casting (DSC) method on a pilot scale. The effects of copper on mechanical, microstructural, and recrystallization behavior were investigated. As-cast microstructure mainly consists of polygonal ferrite and Widmanstatten ferrite. The increase in Cu increases the amount of Widmanstatten ferrite and induces the formation of bainite in the as-cast condition. It was found that copper increases strength and hardness by solid solution strengthening, grain refinement, and precipitation hardening and the increment is significant above 1% Cu in as-cast condition. Six different compositions were selected for recrystallization study. All the samples were cold rolled to 70% reduction and annealed at three different temperatures, 600, 650, and 700°C for various times. Recrystallization responses were strongly dependent on initial microstructure and Cu content and the effect is dramatic between 1 and 2% Cu. Recrystallization time and temperature were found to be increased with increase in copper content.

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Super-resolution is an image enhancement method that increases the resolution of images and video. Previously this technique could only be applied to 2D scenes. The super-resolution algorithm developed in this thesis creates high-resolution views of 3-dimensional scenes, using low-resolution images captured from varying, unknown positions.

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Plastic yielding in magnesium alloys frequently involves the initiation of both slip and twinning events. A proper understanding of the phenomenon at the grain level requires knowledge of how these two mechanisms progress and interact over both time and space and what the local resolved stresses are. To date, simultaneous collection of such information has not been achievable. To address this shortfall, we have developed a modified Laue based in situ micro X-ray diffraction technique with an unprecedented combination of time and spatial resolution. A ten-fold reduction in data collection times is realized by the refinement of rapid polychromatic Laue "single-shot" mapping. From single Laue patterns, we extract grain depth information, detect onset of yielding and achieve 2 × 10-4 lattice strain resolution. The technique is employed to examine yielding and twinning in a magnesium grain embedded ∼200 μm below the sample surface. We examine 13 time steps and reveal the following behaviour: initial onset of basal slip, subsequent onset of twinning, development of further accommodation slip and evolution of twin shape and size; along with the corresponding values of local resolved shear stresses. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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Fibers growing, branching, and bundling are essential for the development of crystalline fiber networks of molecular gels. In this work, for two typical crystalline fiber networks, i.e. the network of spherulitic domains and the interconnected fibers network, related kinetic information is obtained using dynamic rheological measurements and analysis in terms of the Avrami theory. In combination with microstructure characterizations, we establish the correlation of the Avrami derived kinetic parameter not only with the nucleation nature and growth dimensionality of fibers and branches, but also with the fiber bundles induced by fiber-fiber interactions. Our study highlights the advantage of simple dynamic rheological measurements over other spectroscopic methods used in previous studies for providing more kinetic information on fiber-fiber interactions, enabling the Avrami analyses to extract distinct kinetic features not only for fibers growing and branching, but also for bundling in the creation of strong interconnected fibers networks. This work may be helpful for the implementation of precise kinetic control of crystalline fiber network formations for achieving desirable microstructures and rheological properties for advanced applications of gel materials. This journal is © the Partner Organisations 2014.

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The effects of copper on as-cast structure, recrystallization and precipitation kinetics of strip cast low carbon steel were investigated. As-cast microstructure mainly consists of polygonal ferrite and Widmanstatten ferrite. Recrystallization responses were strongly dependent on initial microstructure and Cu content. Precipitation strengthening was observed in high copper content alloys.

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We report observations of the microstructure of 7 pulsars at 102 MHz with a time resolution of up to 1 μs. We have detected fine pulse structure with a μs time-scale for all seven pulsars. We observe that interstellar scattering does not broaden the μs time-scale pulsar microstructure, and find structure of a time-scale much shorter than the interstellar scatter broadening. In addition to the previously known structure with time-scale τμ of tens of μs, we have detected structures with characteristic time-scale of a few μs, nearly equal to the reciprocal of the analysis bandwidth. This suggests that even shorter micropulses may exist.
Micropulses usually cluster in groups, each of duration tens to hundreds of μs, which may be identified as microstructure observed previously with smaller time resolution.
In addition to the previously known quasi-periodicity of hundreds of milliseconds, we reveal a structures with characteristic period of tens of μs. We observe structures with short quasi-periodicity to have a limited bandwidth. The characteristic period Pμ of these structures in PSR B0950+08 does not have a common value for different frequency regions in the same single pulse.
Scattering was revealed as a train of quasi-periodic micropulses with an exponentially damped envelope. The scatter-broadening and decorrelation bandwidth were measured. We report two time-scales of decorrelation bandwidth of pulsar PSR B0950+08 and propose two branches of Δνd(ν) dependence.
The dispersion measure of PSR B0950+08 as DM= 2.9686 ± 0.0001 pc cm−3 has been determined.