931 resultados para Heterogeneous Catalysis


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Consider the problem of assigning real-time tasks on a heterogeneous multiprocessor platform comprising two different types of processors — such a platform is referred to as two-type platform. We present two linearithmic timecomplexity algorithms, SA and SA-P, each providing the follow- ing guarantee. For a given two-type platform and a given task set, if there exists a feasible task-to-processor-type assignment such that tasks can be scheduled to meet deadlines by allowing them to migrate only between processors of the same type, then (i) using SA, it is guaranteed to find such a feasible task-to- processor-type assignment where the same restriction on task migration applies but given a platform in which processors are 1+α/2 times faster and (ii) SA-P succeeds in finding 2 a feasible task-to-processor assignment where tasks are not allowed to migrate between processors but given a platform in which processors are 1+α/times faster, where 0<α≤1. The parameter α is a property of the task set — it is the maximum utilization of any task which is less than or equal to 1.

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A significant number of process control and factory automation systems use PROFIBUS as the underlying fieldbus communication network. The process of properly setting up a PROFIBUS network is not a straightforward task. In fact, a number of network parameters must be set for guaranteeing the required levels of timeliness and dependability. Engineering PROFIBUS networks is even more subtle when the network includes various physical segments exhibiting heterogeneous specifications, such as bus speed or frame formats, just to mention a few. In this paper we provide underlying theory and a methodology to guarantee the proper operation of such type of heterogeneous PROFIBUS networks. We additionally show how the methodology can be applied to the practical case of PROFIBUS networks containing simultaneously DP (Decentralised Periphery) and PA (Process Automation) segments, two of the most used commercial-off-the-shelf (COTS) PROFIBUS solutions. The importance of the findings is however not limited to this case. The proposed methodology can be generalised to cover other heterogeneous infrastructures. Hybrid wired/wireless solutions are just an example for which an enormous eagerness exists.

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The scarcity and diversity of resources among the devices of heterogeneous computing environments may affect their ability to perform services with specific Quality of Service constraints, particularly in dynamic distributed environments where the characteristics of the computational load cannot always be predicted in advance. Our work addresses this problem by allowing resource constrained devices to cooperate with more powerful neighbour nodes, opportunistically taking advantage of global distributed resources and processing power. Rather than assuming that the dynamic configuration of this cooperative service executes until it computes its optimal output, the paper proposes an anytime approach that has the ability to tradeoff deliberation time for the quality of the solution. Extensive simulations demonstrate that the proposed anytime algorithms are able to quickly find a good initial solution and effectively optimise the rate at which the quality of the current solution improves at each iteration, with an overhead that can be considered negligible.

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Consider the problem of assigning implicit-deadline sporadic tasks on a heterogeneous multiprocessor platform comprising two different types of processors—such a platform is referred to as two-type platform. We present two low degree polynomial time-complexity algorithms, SA and SA-P, each providing the following guarantee. For a given two-type platform and a task set, if there exists a task assignment such that tasks can be scheduled to meet deadlines by allowing them to migrate only between processors of the same type (intra-migrative), then (i) using SA, it is guaranteed to find such an assignment where the same restriction on task migration applies but given a platform in which processors are 1+α/2 times faster and (ii) SA-P succeeds in finding a task assignment where tasks are not allowed to migrate between processors (non-migrative) but given a platform in which processors are 1+α times faster. The parameter 0<α≤1 is a property of the task set; it is the maximum of all the task utilizations that are no greater than 1. We evaluate average-case performance of both the algorithms by generating task sets randomly and measuring how much faster processors the algorithms need (which is upper bounded by 1+α/2 for SA and 1+α for SA-P) in order to output a feasible task assignment (intra-migrative for SA and non-migrative for SA-P). In our evaluations, for the vast majority of task sets, these algorithms require significantly smaller processor speedup than indicated by their theoretical bounds. Finally, we consider a special case where no task utilization in the given task set can exceed one and for this case, we (re-)prove the performance guarantees of SA and SA-P. We show, for both of the algorithms, that changing the adversary from intra-migrative to a more powerful one, namely fully-migrative, in which tasks can migrate between processors of any type, does not deteriorate the performance guarantees. For this special case, we compare the average-case performance of SA-P and a state-of-the-art algorithm by generating task sets randomly. In our evaluations, SA-P outperforms the state-of-the-art by requiring much smaller processor speedup and by running orders of magnitude faster.

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Consider the problem of scheduling a task set τ of implicit-deadline sporadic tasks to meet all deadlines on a t-type heterogeneous multiprocessor platform where tasks may access multiple shared resources. The multiprocessor platform has m k processors of type-k, where k∈{1,2,…,t}. The execution time of a task depends on the type of processor on which it executes. The set of shared resources is denoted by R. For each task τ i , there is a resource set R i ⊆R such that for each job of τ i , during one phase of its execution, the job requests to hold the resource set R i exclusively with the interpretation that (i) the job makes a single request to hold all the resources in the resource set R i and (ii) at all times, when a job of τ i holds R i , no other job holds any resource in R i . Each job of task τ i may request the resource set R i at most once during its execution. A job is allowed to migrate when it requests a resource set and when it releases the resource set but a job is not allowed to migrate at other times. Our goal is to design a scheduling algorithm for this problem and prove its performance. We propose an algorithm, LP-EE-vpr, which offers the guarantee that if an implicit-deadline sporadic task set is schedulable on a t-type heterogeneous multiprocessor platform by an optimal scheduling algorithm that allows a job to migrate only when it requests or releases a resource set, then our algorithm also meets the deadlines with the same restriction on job migration, if given processors 4×(1+MAXP×⌈|P|×MAXPmin{m1,m2,…,mt}⌉) times as fast. (Here MAXP and |P| are computed based on the resource sets that tasks request.) For the special case that each task requests at most one resource, the bound of LP-EE-vpr collapses to 4×(1+⌈|R|min{m1,m2,…,mt}⌉). To the best of our knowledge, LP-EE-vpr is the first algorithm with proven performance guarantee for real-time scheduling of sporadic tasks with resource sharing on t-type heterogeneous multiprocessors.

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Heterogeneous multicore platforms are becoming an interesting alternative for embedded computing systems with limited power supply as they can execute specific tasks in an efficient manner. Nonetheless, one of the main challenges of such platforms consists of optimising the energy consumption in the presence of temporal constraints. This paper addresses the problem of task-to-core allocation onto heterogeneous multicore platforms such that the overall energy consumption of the system is minimised. To this end, we propose a two-phase approach that considers both dynamic and leakage energy consumption: (i) the first phase allocates tasks to the cores such that the dynamic energy consumption is reduced; (ii) the second phase refines the allocation performed in the first phase in order to achieve better sleep states by trading off the dynamic energy consumption with the reduction in leakage energy consumption. This hybrid approach considers core frequency set-points, tasks energy consumption and sleep states of the cores to reduce the energy consumption of the system. Major value has been placed on a realistic power model which increases the practical relevance of the proposed approach. Finally, extensive simulations have been carried out to demonstrate the effectiveness of the proposed algorithm. In the best-case, savings up to 18% of energy are reached over the first fit algorithm, which has shown, in previous works, to perform better than other bin-packing heuristics for the target heterogeneous multicore platform.

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This article deals with a real-life waste collection routing problem. To efficiently plan waste collection, large municipalities may be partitioned into convenient sectors and only then can routing problems be solved in each sector. Three diverse situations are described, resulting in three different new models. In the first situation, there is a single point of waste disposal from where the vehicles depart and to where they return. The vehicle fleet comprises three types of collection vehicles. In the second, the garage does not match any of the points of disposal. The vehicle is unique and the points of disposal (landfills or transfer stations) may have limitations in terms of the number of visits per day. In the third situation, disposal points are multiple (they do not coincide with the garage), they are limited in the number of visits, and the fleet is composed of two types of vehicles. Computational results based not only on instances adapted from the literature but also on real cases are presented and analyzed. In particular, the results also show the effectiveness of combining sectorization and routing to solve waste collection problems.

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Unraveling the effect of selection vs. drift on the evolution of quantitative traits is commonly achieved by one of two methods. Either one contrasts population differentiation estimates for genetic markers and quantitative traits (the Q(st)-F(st) contrast) or multivariate methods are used to study the covariance between sets of traits. In particular, many studies have focused on the genetic variance-covariance matrix (the G matrix). However, both drift and selection can cause changes in G. To understand their joint effects, we recently combined the two methods into a single test (accompanying article by Martin et al.), which we apply here to a network of 16 natural populations of the freshwater snail Galba truncatula. Using this new neutrality test, extended to hierarchical population structures, we studied the multivariate equivalent of the Q(st)-F(st) contrast for several life-history traits of G. truncatula. We found strong evidence of selection acting on multivariate phenotypes. Selection was homogeneous among populations within each habitat and heterogeneous between habitats. We found that the G matrices were relatively stable within each habitat, with proportionality between the among-populations (D) and the within-populations (G) covariance matrices. The effect of habitat heterogeneity is to break this proportionality because of selection for habitat-dependent optima. Individual-based simulations mimicking our empirical system confirmed that these patterns are expected under the selective regime inferred. We show that homogenizing selection can mimic some effect of drift on the G matrix (G and D almost proportional), but that incorporating information from molecular markers (multivariate Q(st)-F(st)) allows disentangling the two effects.

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Knowledge of the spatial distribution of hydraulic conductivity (K) within an aquifer is critical for reliable predictions of solute transport and the development of effective groundwater management and/or remediation strategies. While core analyses and hydraulic logging can provide highly detailed information, such information is inherently localized around boreholes that tend to be sparsely distributed throughout the aquifer volume. Conversely, larger-scale hydraulic experiments like pumping and tracer tests provide relatively low-resolution estimates of K in the investigated subsurface region. As a result, traditional hydrogeological measurement techniques contain a gap in terms of spatial resolution and coverage, and they are often alone inadequate for characterizing heterogeneous aquifers. Geophysical methods have the potential to bridge this gap. The recent increased interest in the application of geophysical methods to hydrogeological problems is clearly evidenced by the formation and rapid growth of the domain of hydrogeophysics over the past decade (e.g., Rubin and Hubbard, 2005).

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Cuscuta spp. are holoparasitic plants that can simultaneously parasitise several host plants. It has been suggested that Cuscuta has evolved a foraging strategy based on a positive relationship between preuptake investment and subsequent reward on different host species. Here we establish reliable parasite size measures and show that parasitism on individuals of different host species alters the biomass of C. campestris but that within host species size and age also contributes to the heterogeneous resource landscape. We then performed two additional experiments to test whether C. campestris achieves greater resource acquisition by parasitising two host species rather than one and whether C. campestris forages in communities of hosts offering different rewards (a choice experiment). There was no evidence in either experiment for direct benefits of a mixed host diet. Cuscuta campestris foraged by parasitising the most rewarding hosts the fastest and then investing the most on them. We conclude that our data present strong evidence for foraging in the parasitic plant C. campestris.

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The work to be presented herein illustrates several important facts. First, the synthesis of BIBOL (19), a 1,4-diol derived from the monoterpene camphor has allowed us to demonstrate that oxidative dimerizations of enolates can, and do proceed with nearly complete diastereoselectivity under kinetically controlled conditions. The yield of BIBOL is now 50% on average, with a 10% yield of a second diastereomer, which is likely the result of a non-kinetic hydride reduction, thereby affording the epimeric alcohol, 20, coupled on the exo face of camphor. This implies the production of 60% of a single coupling diastereomer. No other diastereomers from the reduction were observed. The utility of BEBOL has been illustrated in early asymmetric additions of diethylzinc to aryl aldehydes, with e.e.'s as high as 25-30%. '^' To further the oxidative coupling work, the same methodology which gave rise to BIBOL was applied to the chiral pool ketone, menthone. Interestingly, this gave an excellent yield of the a-halohydrin (31), which is the result of a chlorination of menthone. This result clearly indicates the high stereoselectivity of the process regardless of the outcome, and has illustrated an interesting dichotomy between camphor and menthone. The utility of the chlorination product as a precursor other chiral ligands is currently being investigated. > ' Finally, a new series of 1,3-diols as well as a new aminoalcohol have successfully been synthesized from highly diastereoselective aldol/mannich reactions. Early studies have indicated their potential in asymmetric catalysis, while employing pi-stack interactions as a means of controlling enantioselective aldol reactions.

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ZnF2, CdF2, and CUF2 have been adsorbed onto the surface of montmorillonite K10, and the infrared and 19F, 27 AI, and 29Si MAS NMR spectra of the reagents over a range of loadings have been obtained. CUF2 was observed to attack the Si02 layer and form the complex CuSiF6, Zn F2 tends to attack the aluminium oxide layer, in which Zn isomorphously replaces AI, and forms AIF3 and AIF4 - complexes. All the spectroscopic evidence ruled out the formation of any AI-F and/or Si-F free species as CdF2 is adsorbed on the surface of montmorillonite K10. The reactivity of MF2-K10 reagents towards Friedel-Crafts benzylation of benzene with benzyl chloride varied from one reagent to another. ZnF2-K10 was observed to be the most reactive and CUF2 was the least reactive.

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Catalase dismutes H20 2 to O2 and H20. In successive twoelectron reactions H20 2 induces both oxidation and reduction at the heme group. In the first step the protoheme prosthetic group of beef liver catalase forms compound I, in which the heme has been oxidized from Fe3+ to Fe4+=0 and a porphyrin radical has been created. Compound II is formed by the oneelectron reduction of comp I. It retains Fe4+=0 but lacks the porphyrin radical and is catalytically inert. Molecular structures are available for Escherichia coli Hydroperoxidase II, Micrococcus Iysodeiktus, Penicillium vitale and beef liver enzymes, which contain different hemes and heme pockets. In the present work, the pockets and substrate access channels of protoheme (beef liver & Micrococcus) and heme d (HPII of E. coli and Penicillium) catalases have been analysed using Quanta™ and CharmMTM molecular modeling packages on the Silicon Graphics Iris Indigo 2 computer. Experimental studies have been carried out with two catalases, HPII (and its mutants) and beef liver. Fluoride and formate' are inhibitors of both enzymes, and their binding is modulated by the heme and by distal residues N201 & H128. Both HPII and beef liver enzymes form compound I with H202 or peracetate. The reduction of beef liver enzyme compound I to II and the decay of compound II are accelerated by fluoride. The decay of compound II is also accelerated by formate, and this reagent acts as a 2-electron donor towards compound I of both enzymes. It is concluded that heme d enzymes (Penicillium and HPII of E. coli) are formed by autocatalytic transformation of protoheme in a modified pocket which contains a characteristic serine residue as well as a partially occluded heme channel. They are less active than protoheme enzymes but also do not form the inactive compound II species. Binding of peroxide as well as fluoride and formate is prevented by mutation of H128 and modulated by mutation of N201.

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The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

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The syntheses, catalytic reactivity and mechanistic investigations of novel Mo(IV) and Mo(VI) imido systems is presented. Attempts at preparing mixed bis(imido) Mo(IV) complexes of the type (RN)(R′N)Mo(PMe3)n (n = 2 or 3) derived from the mono(imido) complexes (RN)Mo(PMe3)3(X)2 (R = tBu (1) or Ar (2); X = Cl2 or HCl, Ar=2,6-iPr2C6H3) are also described. The addition of lithiated silylamides to 1 or 2 results in the unexpected formation of the C-H activated cyclometallated complexes (RN)Mo(PMe3)2(η2-CH2PMe2)(X) (R = Ar, X = H (3); R = tBu, X = Cl (4)). Complexes 3 and 4 were used in the activation of R′E-H bonds (E = Si, B, C, O, P; R′ = alkyl or aryl), which typically give products of addition across the M-C bond of the type (RN)Mo(PMe3)3(ER′)(X) (4). In the case of 2,6-dimethylphenol, subsequent heating of 4 (R = Ar, R′ = 2,6-Me2C6H3, E = O) to 50 °C results in C-H activation to give the cyclometallated complex (ArN)Mo(PMe3)3(κ2-O,C-OPh(Me)CH2) (5). An alternative approach was developed in synthesizing the mixed imido complex (ArN)(tBuN)Mo(PMe3)(η2-C2H4) (6) through EtMgBr reduction of (ArN)(tBuN)MoCl2(DME) in the presence of PMe3. Complex 6 reacts with various hydro- and chlorosilanes to give β-agostic silylamido complexes and in one case, when Me2SiHCl is the silane, leads to the silanimine complex (tBuN)Mo(η2-SiMe2-NAr)(Et)(η2-C2H4) (7). Mechanistic studies on the formation of the Mo(VI) tris(silyl) complex (tBuN)Mo(SiHPh)(H){(μ-NtBu)(SiHPh)}(PMe3)2 (8) were done from the addition of three equivalents of PhSiH3 to (tBuN)Mo(PMe3)(η2-C2H4), resulting in identification of β- and γ-agostic SiH…Mo intermediates. The reactivity of complex 8 towards ethylene and nitriles was studied. In both cases coupling of unsaturated substrates with the Mo-Si bond of the metalacycle was observed. In the case of nitriles, insertion into the 4-membered disilaazamolybdacycle results in complexes of the type (tBuN)Mo{(κ2-Si,C-SiHPh-NtBu-SiHPh-N=C(R)}(PMe3)2. Catalytic hydrosilylation of carbonyls mediated by the β-agostic silylamido complex (ArN)2Mo(η3-NtBu-SiMe2-H)(H) (9) was investigated. Stoichiometric reactions with organic substrates showed that catalysis with 9 does not proceed via the conventional insertion of substrate into the Mo-H bond.