980 resultados para ASYMMETRIC MICHAEL REACTIONS
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The octameric nucleosomal core-histone complex, (H2A)2-(H2B)2-(H3)2-(H4)2, isolated from rat liver, undergoes dissociation during gel exclusion chromatography as a result of dilution occurring in the columns. The elution pattern at pH 7.0 and 4°C showed a sharp leading peak containing all four histones but predominantly H3 and H4, and a trailing peak containing equal amounts of histones H2A and H2B. As column length was increased the area under the leading peak decreased and that under the trailing peak increased. In addition the relative positions of the two peaks varied with column length. From an analysis of the data on increase in elution volume of the leading peak in relation to column length an apparent molecular weight of 86 000 was calculated for the undissociated molecule. Its apparent molecular weight, histone composition and pattern of further dissociation in relation to column length suggest that this species is the hexamer, (H2A-H2B)-(H3)2-(H4)2. At pH 7.0 and 4°C the dissociation of the core complex appears to be as follows: (H2A)2-(H2B)2-(H3)2-(H4)2 → (H2A-H2B) + (H2A-H2B)-(H3)2-(H4)2 → 2(H2A-H2B) + (H3)2-(H4)2 This dissociation was accelerated by an increase in temperature or decrease in pH and was accompanied by marked conformational changes as judged by circular dichroism measurements.
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A change-over from SN2(P) to SN1(P) mechanism is established for the chlorine replacement reactions of halogenocyclophosphazenes; this mechanistic change-over helps in rationalising the diverse findings reported for this class of reactions.
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The educational reform, launched in Finland in 2008, concerns the implementation of the Special Education Strategy (Opetusministeriö 2007) under an improvement initiative called Kelpo. One of the main proposed alterations of the Strategy relates to the support system of comprehensive school pupils. The existed two-level model (general and special support) is to be altered by the new three-level model (general, intensified and special support). There are 233 municipalities involved nationwide in the Kelpo initiative, each of which has a municipal coordinator as a national delegate. The Centre for Educational Assessment [the Centre] at the University of Helsinki, led by Professor Jarkko Hautamäki, carries out the developmental assessment of the initiative’s developmental process. As a part of that assessment the Centre interviewed 151 municipal coordinators in November 2008. This thesis considers the Kelpo initiative from Michael Fullan’s change theory’s aspect. The aim is to identify the change theoretical factors in the speech of the municipal coordinators interviewed by the Centre, and to constitute a view of what the crucial factors in the reform implementation process are. The appearance of the change theoretical factors, in the coordinators’ speech, and the meaning of these appearances are being considered from the change process point of view. The Centre collected the data by interviewing the municipal coordinators (n=151) in small groups of 4-11 people. The interview method was based on Vesala and Rantanen’s (2007) qualitative attitude survey method which was adapted and evolved for the Centre’s developmental assessment by Hilasvuori. The method of the analysis was a qualitative theory-based content analysis, processed using the Atlas.ti software. The theoretical frame of reference was grounded on Fullan’s change theory and the analysis was based on three change theoretical categories: implementation, cooperation and perspectives in the change process. The analysis of the interview data revealed spoken expressions in the coordinators’ speech which were either positively or negatively related to the theoretical categories. On the grounds of these change theoretical relations the existence of the change process was observed. The crucial factors of reform implementation were found, and the conclusion is that the encounter of the new reform-based and already existing strategies in school produces interface challenges. These challenges are particularly confronted in the context of the implementation of the new three-level support model. The interface challenges are classified as follows: conceptual, method-based, action-based and belief-based challenges. Keywords: reform, implementation, change process, Michael Fullan, Kelpo, intensified support, special support
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The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate,kI, are obtained by solving the associated first passage time problems. Both the average rate constant, kI, and the numerically calculated long-time rate constant, kL, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.
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A perturbation treatment was developed for the comparative study of the abstraction of hydrogen from methane by formaldehyde and thioformaldehyde in their nπ* and ππ* states. Both in-plane and perpendicularplane reactions are considered. Results are qualitative but reveal clearly the prominent distinguishing features of these two photochemical processes in agreement with the experimental observations.
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Son of Adolf and Maria Leschnitzer
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Abstract is not available.
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Recently, Tang et al. (Acta Mater. 56 (2008) 5818) published a paper explaining room temperature growth of the phases in the Au/Sn system. In their analysis, they considered Au as the only mobile species for all the product phases, and Sn as virtually immobile. It is shown here that this analysis is not correct, since Sn has a higher diffusion rate through the AuSn4 phase. On the other hand, the mobilities of species in the AuSn2 phase are as yet unknown.
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Synthetic amphiphiles have been employed for the investigation of diverse topics, e.g. membrane mimetics, drug delivery, ion sensing and even in certain separation processes. Metal-complexing amphiphiles comprise an interesting class of compounds possessing multiple utilities. Upon solubilization in water they form metallomicelles. For achieving specific catalysis of a variety of reactions, metallomicelles were utilized by applying the principles of coordination chemistry and self-organizing systems. Because of their certain similarities with the natural enzymes, metallomicelles were synthesized as catalysts for many reactions. In particular the metallomicelles play a catalytic role in reactions involving the hydrolysis of activated carboxylate esters, phosphate esters and amides at ambient conditions near neutral pH. Apart from the hydrolysis reactions, these were exploited to play pertinent role as Lewis acid catalysts in cycloaddition reactions, and in other reactions such as phenolic oxidation in presence of hydrogen peroxide. In this review we emphasize with the help of assorted examples, the design, synthesis of metal-complexing amphiphiles and their aggregation behavior leading to catalytic hydrolysis reactions in aqueous media.
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We consider the asymmetric distributed source coding problem, where the recipient interactively communicates with N correlated informants to gather their data. We are mainly interested in minimizing the worst-case number of informant bits required for successful data-gathering at recipient, but we are also concerned with minimizing the number of rounds as well as the number of recipient bits. We provide two algorithms, one that optimally minimizes the number of informant bits and other that trades-off the number of informant bits to efficiently reduce the number of rounds and number of recipient bits.
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Analytical solutions are presented for the effectiveness factor of a zeroth-order reaction with volume change and nonuniform catalyst activity profile in slab, cylinder and spherical pellets. The possibility of shape normalization is considered for a variety of activity profiles and pellet shapes. When the catalyst activity at the external surface of the pellet is non-zero, shape normalization is obtained, which makes the asymptotic behavior of the effectiveness factor identical for small and large values of Thiele modulus, however, the normalization can lead to significant errors, particularly for the case of activity profiles decreasing towards the outer surface of the catalyst.
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The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, and its geminal bis-t-butylamino- and diphenyl derivatives, with ethylenediamine and ethanolamine are reported. In each case, both chlorine atoms attached to the same phosphorus atoms are replaced, giving rise to spirocyclic derivatives. A small quantity of a bis spirocyclic derivative, N3P3(NHCH2CH2O)2Cl2, is also obtained; this compound occurs in both cis and trans forms. Attempts to prepare fully substituted tris spirocyclic derivatives have been unsuccessful and only resinous materials were obtained. The 1H and 31P n.m.r. spectra of the products are discussed.
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Owing to the structural flexibility, uncomplicated processing and manufacturing capabilities, plasma polymers are the subject of active academic as well as industrial research. Polymer thin films prepared from non-synthetic monomers combine desirable optical and physical properties with biocompatibility and environmental sustainability. However, the ultimate expediency and implementation of such materials will dependent on the stability of these properties under varied environmental conditions. Polyterpenol thin films were manufactured at different deposition powers. Under ambient conditions, the bulk of ageing occurred within first 150h after deposition and was attributed to oxidation and volumetric relaxation. Films observed for further 12 months showed no significant changes in thickness or refractive index. Thermal degradation behaviour indicated thermal stability increased for the films manufactured at higher RF powers. Annealing the films to 405°C resulted in full degradation, with retention between 0.29 and 0.99%, indicating films' potential as sacrificial material.
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Purpose A fundamental aspect of hierarchical loyalty programs is that some consumers get rewards that others do not. Despite the widespread use of such programs, academics have long debated whether these benefits are outweighed by the potential negative impact of the differential treatment of customers. This study extends our understanding, examining the impact of message framing on consumers’ reactions to hierarchical loyalty structures. Design/methodology/approach Three online studies were conducted. Study 1 uses advertisements to manipulate the message frame’s emphasis (benefits vs. status). Study 2 manipulates consumers’ frame of thought by directing their attention to either changes in benefits or status. Finally, Study 3 uses the proposed framework to reconcile contradictory findings from past research. Findings Low-frequency customers who do not expect to qualify for a superior customer tier tend to reject hierarchical programs when thinking about status. In contrast, when these customers think about concrete rewards, loyalty program messages produce no negative reactions. High-frequency customers are positively affected by communication regardless of the type of benefits framed. Research limitations/implications All studies were done online potentially limiting the external validity of the results. Nevertheless, the impact of message framing on perceptions about the loyalty program seems to be quite robust across different studies and manipulations. Practical implications When communicating with low-frequency customers managers should avoid promising status; customers should instead be motivated based on concrete rewards. High-frequency customers are indifferent to alternative emphasis of communication frames. Originality/value Marketing academics have acknowledged the importance of being able to reward top customers without demotivating light and moderate users. Our research is the first to provide a solution to this issue.