967 resultados para photochemical reaction mechanisms


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The introduction of Eragrostis curvula (African Lovegrass, herafter Lovegrass) for pasture improvement across Australia has not been successful. Instead Lovegrass, a C4 perennial grass originating from Southern African, has proven unpalatable to stock and to have low nutritional value if stocks do eat it. It has spread prolifically along roadsides, stream banks, conservation areas and pastures. Because control efforts have not been effective, our aim was to determine the putative mechanisms responsible for the dominance of Lovegrass, specifically disturbance (selective grazing) and competition.

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The structures of the compounds from the reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with 4-chloroaniline [rac-N-(4-chlorophenyl)-2-carboxycycloclohexane-1-carboxamide] (1), 4-bromoaniline [2-(4-bromophenyl)-perhydroisoindolyl-1,3-dione] (2) and 3-hydroxy-4-carboxyaniline (5-aminosalicylic acid) [2-(3-hydroxy-4-carboxyphenyl)-perhydroisoindolyl-1,3-dione] (3) have been determined at 200 K. Crystals of the open-chain amide carboxylic acid 1 are orthorhombic, space group Pbcn, with unit cell dimensions a = 20.1753(10), b = 8.6267(4), c = 15.9940(9) Å, and Z = 8. Compounds 2 and 3 are cyclic imides, with 1 monoclinic having space group P21 and cell dimensions a = 11.5321(3), b = 6.7095(2), c = 17.2040(5) Å, β = 102.527(3)o. Compound 3 is orthorhombic with cell dimensions a = 6.4642(3), b = 12.8196(5), c = 16.4197(7) Å. Molecules of 1 form hydrogen-bonded cyclic dimers which are extended into a two-dimensional layered structure through amide-group associations: 3 forms into one-dimensional zigzag chains through carboxylic acid…imide O-atom hydrogen bonds, while compound 2 is essentially unassociated. With both cyclic imides 2 and 3, disorder is found which involves the presence of partial enantiomeric replacement of the cis-cyclohexane-1,2-substituted ring systems.

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This paper studies traffic hysteresis arising in traffic oscillations from a behavioral perspective. It is found that the occurrence and type of traffic hysteresis is closely correlated with driver behavior when experiencing traffic oscillations and with the time driver reaction begins relative to the starting deceleration wave. Statistical results suggest that driver behavior is different depending on its position along the oscillation. This suggests that different car-following models should be used inside the different stages of an oscillation in order to replicate realistic congestion features.

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In this article, we consider the Eldar model [3] from embryology in which a bone morphogenic protein, a short gastrulation protein, and their compound react and diffuse. We carry out a perturbation analysis in the limit of small diffusivity of the bone morphogenic protein. This analysis establishes conditions under which some elementary results of [3] are valid.

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Our understanding of the mechanisms of action of GH and its receptor, the GHR, has advanced significantly in the last decade and has provided some important surprises. It is now clear that the GH-GHR axis activates a number of inter-related signalling pathways, not all of which are dependent on the intracellular tyrosine kinase, JAK2 as originally postulated. JAK2-independent pathways, mediated via the Src family kinases, together with a number of negative regulators of GH signalling and emerging cross-talk mechanisms with other growth factor receptors, provide a complex array of mechanisms that are capable of fine-tuning responses to GH in a cell context dependent manner. Additionally, it is also now clear that GH and the GHR can translocate to the nucleus of target cells and initiate, as yet not well defined, nuclear responses. Continued emphasis on elucidation of these complex mechanisms is critical to provide further insights into the diverse physiological and pathophysiological effects of GH.

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Secure communications in wireless sensor networks operating under adversarial conditions require providing pairwise (symmetric) keys to sensor nodes. In large scale deployment scenarios, there is no prior knowledge of post deployment network configuration since nodes may be randomly scattered over a hostile territory. Thus, shared keys must be distributed before deployment to provide each node a key-chain. For large sensor networks it is infeasible to store a unique key for all other nodes in the key-chain of a sensor node. Consequently, for secure communication either two nodes have a key in common in their key-chains and they have a wireless link between them, or there is a path, called key-path, among these two nodes where each pair of neighboring nodes on this path have a key in common. Length of the key-path is the key factor for efficiency of the design. This paper presents novel deterministic and hybrid approaches based on Combinatorial Design for deciding how many and which keys to assign to each key-chain before the sensor network deployment. In particular, Balanced Incomplete Block Designs (BIBD) and Generalized Quadrangles (GQ) are mapped to obtain efficient key distribution schemes. Performance and security properties of the proposed schemes are studied both analytically and computationally. Comparison to related work shows that the combinatorial approach produces better connectivity with smaller key-chain sizes.

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Key distribution is one of the most challenging security issues in wireless sensor networks where sensor nodes are randomly scattered over a hostile territory. In such a sensor deployment scenario, there will be no prior knowledge of post deployment configuration. For security solutions requiring pairwise keys, it is impossible to decide how to distribute key pairs to sensor nodes before the deployment. Existing approaches to this problem are to assign more than one key, namely a key-chain, to each node. Key-chains are randomly drawn from a key-pool. Either two neighboring nodes have a key in common in their key-chains, or there is a path, called key-path, among these two nodes where each pair of neighboring nodes on this path has a key in common. Problem in such a solution is to decide on the key-chain size and key-pool size so that every pair of nodes can establish a session key directly or through a path with high probability. The size of the key-path is the key factor for the efficiency of the design. This paper presents novel, deterministic and hybrid approaches based on Combinatorial Design for key distribution. In particular, several block design techniques are considered for generating the key-chains and the key-pools.

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The structure and composition of reaction products between Bi-Sr-Ca-Cu-oxide (BSCCO) thick films and alumina substrates have been characterized using a combination of electron diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry (EDX). Sr and Ca are found to be the most reactive cations with alumina. Sr4Al6O12SO4 is formed between the alumina substrates and BSCCO thick films prepared from paste with composition close to Bi-2212 (and Bi-2212 + 10 wt.% Ag). For paste with composition close to Bi(Pb)-2223 + 20 wt.% Ag, a new phase with f.c.c. structure, lattice parameter about a = 24.5 A and approximate composition Al3Sr2CaBi2CuOx has been identified in the interface region. Understanding and control of these reactions is essential for growth of high quality BSCCO thick films on alumina. (C) 1997 Elsevier Science S.A.

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In this paper we give an overview of some very recent work, as well as presenting a new approach, on the stochastic simulation of multi-scaled systems involving chemical reactions. In many biological systems (such as genetic regulation and cellular dynamics) there is a mix between small numbers of key regulatory proteins, and medium and large numbers of molecules. In addition, it is important to be able to follow the trajectories of individual molecules by taking proper account of the randomness inherent in such a system. We describe different types of simulation techniques (including the stochastic simulation algorithm, Poisson Runge-Kutta methods and the balanced Euler method) for treating simulations in the three different reaction regimes: slow, medium and fast. We then review some recent techniques on the treatment of coupled slow and fast reactions for stochastic chemical kinetics and present a new approach which couples the three regimes mentioned above. We then apply this approach to a biologically inspired problem involving the expression and activity of LacZ and LacY proteins in E coli, and conclude with a discussion on the significance of this work. (C) 2004 Elsevier Ltd. All rights reserved.

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Secure communications between large number of sensor nodes that are randomly scattered over a hostile territory, necessitate efficient key distribution schemes. However, due to limited resources at sensor nodes such schemes cannot be based on post deployment computations. Instead, pairwise (symmetric) keys are required to be pre-distributed by assigning a list of keys, (a.k.a. key-chain), to each sensor node. If a pair of nodes does not have a common key after deployment then they must find a key-path with secured links. The objective is to minimize the keychain size while (i) maximizing pairwise key sharing probability and resilience, and (ii) minimizing average key-path length. This paper presents a deterministic key distribution scheme based on Expander Graphs. It shows how to map the parameters (e.g., degree, expansion, and diameter) of a Ramanujan Expander Graph to the desired properties of a key distribution scheme for a physical network topology.

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The focus of knowledge management (KM) in the construction industry is moving towards capability building for value creation. The study reported by this paper is motivated by recent assertions about the genesis and evolution of knowledge management capability (KMC) in the strategic management field. It attempts to shed light on the governance of learning mechanisms that develop KMC within the context of construction firms. A questionnaire survey was administered to a sample of construction contractors operating in the very dynamic Hong Kong market to elicit opinions on the learning mechanisms and business outcomes of targeted firms. On the basis of a total of 149 usable responses, structural equation modeling (SEM) analysis identified relationships among knowledge-governance mechanisms, knowledge processes, and business performance, thereby supporting the existence of strategic learning loops. The study findings provide evidence from the construction context for capability assertions that knowledge-governance mechanisms and processes form learning mechanisms that carry out strategic learning to create value, effect performance outcomes, and ultimately drive the evolution of KMC. The findings imply that it is feasible for managing construction firms to govern learning mechanisms through managing the capability-based holistic KM system, thereby reconfiguring KMC to match needs in the dynamic market environment over time.

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Concepts used in this chapter include: Thermoregulation:- Thermoregulation refers to the body’s sophisticated, multi-system regulation of core body temperature. This hierarchical system extends from highly thermo-sensitive neurons in the preoptic region of the brain proximate to the rostral hypothalamus, down to the brain stem and spinal cord. Coupled with receptors in the skin and spine, both central and peripheral information on body temperature is integrated to inform and activate the homeostatic mechanisms which maintain our core temperature at 37oC1. Hyperthermia:- An imbalance between the metabolic and external heat accumulated in the body and the loss of heat from the body2. Exertional heat stroke:- A disorder of excessive heat production coupled with insufficient heat dissipation which occurs in un-acclimated individuals who are engaging in over-exertion in hot and humid conditions. This phenomenon includes central nervous system dysfunction and critical dysfunction to all organ systems including renal, cardiovascular, musculoskeletal and hepatic functions. Non-exertional heat stroke:- In contrast to exertional heatstroke as a consequence of high heat production during strenuous exercise, non-exertional heatstroke results from prolonged exposure to high ambient temperature. The elderly, those with chronic health conditions and children are particularly susceptible.3 Rhabdomylosis:- An acute, sometimes fatal disease characterised by destruction of skeletal muscle. In exertional heat stroke, rhabdomylosis occurs in the context of strenuous exercise when mechanical and/or metabolic stress damages the skeletal muscle, causing elevated serum creatine kinease. Associated with this is the potential development of hyperkalemia, myoglobinuria and renal failure. Malignant hyperthermia:- Malignant hyperthermia is “an inherited subclinical myopathy characterised by a hypermetabolic reaction during anaesthesia. The reaction is related to skeletal muscle calcium dysregulation triggered by volatile inhaled anaesthetics and/or succinylcholine.”4 Presentation includes skeletal muscle rigidity, mixed metabolic and respiratory acidosis, tachycardia, hyperpyrexia, rhabdomylosis, hyperkalaemia, elevated serum creatine kinease, multi-organ failure, disseminated intravascular coagulation and death.5

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Catalytic decomposition is a very attractive way to convert tar components into H2, CO and other useful chemicals. The performance of Fe3Ni8/PG (palygorskite, PG) reduced in hydrogen at different temperatures for the catalytic decomposition of benzene has been assessed. Benzene was used as the model biomass tar. The effects of calcination atmosphere, temperatures and benzene concentration on catalytic cracking of benzene were measured. The results of XRD (X-Ray Diffraction), TEM (Transmission Electron Microscope), TPR (Temperature Program Reduction), TPSR (Temperature Program Surface Reduction), TC (Total Carbon), the reactivity component and reaction mechanism over Fe3Ni8/PG for catalytic cracking of benzene are discussed. The results showed particles of awaruite (Fe, Ni) about 2–30 nm were found on the surface of palygorskite by TEM when the calcination temperature was 600 °C. Particles with size smaller than 30 nm were obtained on all prepared Fe3Ni8/PG catalysts as shown by XRD. The nanoparticles proved to be the reactive component for catalytic cracking of benzene and the increase of active particle size caused the decrease in the reactivity of Fe3Ni8/PG. Fe3Ni8/PG annealed in hydrogen at 600 °C was proved to have the best reactivity in experiments (45% hydrogen yield). High concentration benzene (448 g/m3) accelerated the formation of carbon deposition. However, iron oxide decreases carbon deposition and increases the stability of catalyst for catalytic cracking of benzene. The application of Fe3Ni8/PG catalysts was proved a very effective catalyst for the catalytic cracking of benzene.