21 resultados para kinetic undercooling

em Deakin Research Online - Australia


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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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In a photocatalytic reduction process when products formed are not effectively desorbed, they could hinder the diffusion of intermediates on the surface of the catalyst, as well as increase the chance of collisions among the products, resulting photo-oxidation in a reserve reaction on the surface. This paper analyses a simple kinetic model incorporating the coupled effect of the adsorptive photocatalytic reduction and oxidation. The development is based on Langmuir–Hinshelwood mechanism to model the formation rates of hydrogen and methane through photocatalytic reduction of carbon dioxide with water vapour. Experimental data obtained from literatures have achieved a very good fit. Such model could aid as a tool for related areas of studies. A comparative study using the model developed, showed that product concentration in term of ppm would be an effective measurement of product yields through photocatalytic reduction of carbon dioxide with water vapour.

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Use of hydrogen as a temporary alloying element in titanium alloys is an attractive approach to improve the mechanical properties of the materials, enhance processability and thereby reduce manufacturing costs. In this paper, the hydrogen diffusion process and the phase transformation both between titanium particles and in titanium sheets were computationally simulated to analyze the mechanism of hydrogen diffusion in different phases (α-Ti, β-Ti and TiHx). With the simulation based on the thermodynamics and kinetics, quantitative behaviors of the hydrogen diffusion and the phase transformation were analyzed. The simulation results provide an insight into the diffusion process and improve the fundamental understanding of the mechanism of diffusion and phase transformation.

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Use of hydrogen as a temporary alloying element in Ti alloys is an attractive approach to improve the mechanical properties of the materials, enhance processability and thereby reduce manufacturing costs. In this paper, the hydrogen diffusion process and the phase transformation both between Ti particles and in Ti sheets were simulated to analyze the mechanism of hydrogen diffusion in different phases (α-Ti, β-Ti and TiHx). With the simulation based on the kinetics and thermodynamics, quantitative behaviors of the hydrogen diffusion and the phase transformation were analyzed. The simulation results provide an insight into the diffusion process and improve the fundamental understanding of the mechanism of diffusion and phase transformation.

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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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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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This study investigated the effectiveness of action observation (AO) on facilitating learning of the power clean technique (kinematics) compared with traditional strength coaching methods and whether improvements in performance (kinetics) were associated with an improvement in lifting technique. Fifteen subjects (age, 20.9 ± 2.3 years) with no experience in performing the power clean exercise attended 12 training and testing sessions over a 4-week period. Subjects were assigned to 2 matched groups, based on preintervention power clean performance and performed 3 sets of 5 repetitions of the power clean exercise at each training session. Subjects in the traditional coaching group (TC; n = 7) received the standard coaching feedback (verbal cues and physical practice), whereas subjects in the AO group (n = 8) received similar verbal coaching cues and physical practice but also observed a video of a skilled model before performing each set. Kinematic data were collected from video recordings of subjects who were fitted with joint center markings during testing, whereas kinetic data were collected from a weightlifting analyzer attached to the barbell. Subjects were tested before intervention, at the end of weeks 2 and 3, and at after intervention at the end of week 4. Faster improvements (3%) were observed in power clean technique with AO-facilitated learning in the first week and performance improvements (mean peak power of the subject's 15 repetitions) over time were significant (p < 0.001). In addition, performance improvement was significantly associated (R = 0.215) with technique improvements. In conclusion, AO combined with verbal coaching and physical practice of the power clean exercise resulted in significantly faster technique improvements and improvement in performance compared with traditional coaching methods.

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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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Activated carbon (AC) developed from loofah sponge with phosphoric acid activation was applied to absorb cefalexin (CEX) in aqueous solution. AC was characterized by N2 adsorption–desorption isotherms and Fourier transform infrared spectroscopy (FTIR). Factors influencing the adsorption process were investigated. The equilibrium adsorption isotherms and kinetics of CEX were also studied. The results showed that AC prepared from loofah sponge had rough surface and abundant pores. The determination results of specific surface area (810.12 m2/g) and average pore size (5.28 nm) suggested the high adsorption capability. At low concentration, the AC could adsorb about 95% of CEX. The adsorption effect was independent of the temperature and pH. The maximum adsorption amount of CEX was about 55.11 mg/g at 308 K. The equilibrium data agreed well with Freundlich isotherm equation (R2 = 0.9957) at 308 K, which indicated multilayer adsorption. FTIR analysis suggested the existence of phosphorus-containing functional groups, C–O bond, and C=C bond on the surface of AC of which the peak intensity of AC after adsorption was slightly lower after adsorption, indicating that the AC surface groups interacted with or were covered by the CEX species.