984 resultados para ARENE OXIDATION-PRODUCT
Resumo:
Many websites offer the opportunity for customers to rate items and then use customers' ratings to generate items reputation, which can be used later by other users for decision making purposes. The aggregated value of the ratings per item represents the reputation of this item. The accuracy of the reputation scores is important as it is used to rank items. Most of the aggregation methods didn't consider the frequency of distinct ratings and they didn't test how accurate their reputation scores over different datasets with different sparsity. In this work we propose a new aggregation method which can be described as a weighted average, where weights are generated using the normal distribution. The evaluation result shows that the proposed method outperforms state-of-the-art methods over different sparsity datasets.
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Cytochrome P450 (P450) enzymes are involved in the oxidations of numerous steroids, eicosanoids, alkaloids, and other endogenous substrates. These enzymes are also the major ones involved in the oxidation of potential toxicants and carcinogens such as those encountered among pollutants, solvents, and pesticides, as well as many natural products. A proper understanding of the basic mechanisms by which the P450 enzymes oxidize such compounds is important in developing rational strategies for the evaluation of the risks of these compounds.
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Aflatoxin B1, a potently carcinogenic fungal metabolite, is converted to the biologically active form by chemical oxidation using dimethyldioxirane and enzymatically by cytochrome P450 mixed-function oxidases. Both processes give rise to mixtures of the exo- and endo-8,9-epoxides. Methanolysis studies reveal exclusive trans opening of both epoxides under neutral conditions in CH3OH and CH3OH/H2O mixtures; an SN2 mechanism is postulated. Under acidic conditions, the exo isomer gives mixtures of trans and cis solvolysis products, suggesting that the reaction is, at least in part, SN1; the endo isomer gives only the trans product. The exo isomer reacts with DNA by attack of the nitrogen atom at the 7 position of guanine on C8 of the epoxide to give the trans adduct; the endo epoxide fails to form an adduct at this or any other site in DNA. The exo isomer is strongly mutagenic in a base-pair reversion assay employing Salmonella typhimurium; the endo isomer is essentially nonmutagenic. Aflatoxin B1 and its derivatives intercalate in DNA. These results are consistent with a mechanism in which intercalation of the exo epoxide optimally orients the epoxide for an SN2 reaction with guanine but intercalation of the endo isomer places the epoxide in an orientation which precludes reaction. Thus, while the exo epoxide is a potent mutagen, the endo epoxide fails to react with DNA.
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Dihalomethanes can produce liver tumors in mice but not in rats, and concern exists about the risk of these compounds to humans. Glutathione (GSH) conjugation of dihalomethanes has been considered to be a critical event in the bioactivation process, and risk assessment is based upon this premise; however, there is little experimental support for this view or information about the basis of genotoxicity. A plasmid vector containing rat GSH S-transferase 5-5 was transfected into the Salmonella typhimurium tester strain TA1535, which then produced active enzyme. The transfected bacteria produced base-pair revertants in the presence of ethylene dihalides or dihalomethanes, in the order CH2Br2 > CH2BrCl > CH2Cl2. However, revertants were not seen when cells were exposed to GSH, CH2Br2, and an amount of purified GSH S-transferase 5-5 (20-fold excess in amount of that expressed within the cells). HCHO, which is an end product of the reaction of GSH with dihalomethanes, also did not produce mutations. S-(1-Acetoxymethyl)GSH was prepared as an analog of the putative S-(1-halomethyl)GSH reactive intermediates. This analog did not produce revertants, consistent with the view that activation of dihalomethanes must occur within the bacteria to cause genetic damage, presenting a model to be considered in studies with mammalian cells. S-(1-Acetoxymethyl)GSH reacted with 2′-deoxyguanosine to yield a major adduct, identified as S-[1-(N2-deoxyguanosinyl)methyl]GSH. Demonstration of the activation of dihalomethanes by this mammalian GSH S-transferase theta class enzyme should be of use in evaluating the risk of these chemicals, particularly in light of reports of the polymorphic expression of a similar activity in humans.
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The travel and tourism industry has come to rely heavily on information and communication technologies to facilitate relations with consumers. Compiling consumer data profiles has become easier and it is widely thought that consumers place great importance on how that data is handled by firms. Lack of trust may cause consumers to have privacy concerns and may, in turn, have an adverse impact on consumers’ willingness to purchase online. Three specific aspects of privacy that have received attention from researchers are unauthorized use of secondary data, invasion of privacy, and errors. A survey study was undertaken to examine the effects of these factors on both prior purchase of travel products via the Internet and future purchase probability. Surprisingly, no significant relationships were found to indicate that such privacy concerns affect online purchase behavior within the travel industry. Implications for managers are discussed.
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Strategic capability development refers to the renewal of the organisational capabilities which are sources of competitive advantage. The aim of this paper is to examine how strategic capability and competitive advantage build up over time. Recent literature points to the integration of dynamic capability and ambidexterity perspectives in explaining organisational capability development. Literature analysis reveals the role of knowledge integration and product innovation in integrating dynamic capability and ambidexterity. However, little attention has yet been paid to knowledge integration within innovation projects as a context for capability development. Accordingly, this paper aims to develop a conceptual framework for strategic capability development focusing on the role of knowledge integration within product innovation projects. This framework contributes to identifying and emphasising the role of micro processes in capability renewal which in turn enhances our understanding of strategic capability development.
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Product Ecosystem theory is an emerging theory that shows that disruptive “game changing” innovation is only possible when the entire ecosystem is considered. When environmental variables change faster than products or services can adapt, disruptive innovation is required to keep pace. This has many parallels with natural ecosystems where species that cannot keep up with changes to the environment will struggle or become extinct. In this case the environment is the city, the environmental pressures are pollution and congestion, the product is the car and the product ecosystem is comprised of roads, bridges, traffic lights, legislation, refuelling facilities etc. Each one of these components is the responsibility of a different organisation and so any change that affects the whole ecosystem requires a transdisciplinary approach. As a simple example, cars that communicate wirelessly with traffic lights are only of value if wireless-enabled traffic lights exist and vice versa. Cars that drive themselves are technically possible but legislation in most places doesn’t allow their use. According to innovation theory, incremental innovation tends to chase ever diminishing returns and becomes increasingly unable to tackle the “big issues.” Eventually “game changing” disruptive innovation comes along and solves the “big issues” and/or provides new opportunities. Seen through this lens, the environmental pressures of urban traffic congestion and pollution are the “big issues.” It can be argued that the design of cars and the other components of the product ecosystem follow an incremental innovation approach. That is why the “big issues” remain unresolved. This paper explores the problems of pollution and congestion in urban environments from a Product Ecosystem perspective. From this a strategy will be proposed for a transdisciplinary approach to develop and implement solutions.
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This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two single bondSH groups and the other single bondSH group is pointing away from the electrode surface. The free single bondSH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN)6]4−/3− was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (ks) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 × 10−3 cm s−1. The oxidation peak of AA at Au/HDT/AuNPs electrode was highly stable upon repeated potential cycling. Linear calibration plot was obtained for AA over the concentration range of 1–110 μM with a correlation coefficient of 0.9950. The detection limit of AA was found to be 1 μM. The common physiological interferents such as glucose, oxalate ions and urea do not show any interference within the detection limit of AA. The selectivity of the AuNPs modified electrode was illustrated by the determination of AA in the presence of uric acid.
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Identifying product families has been considered as an effective way to accommodate the increasing product varieties across the diverse market niches. In this paper, we propose a novel framework to identifying product families by using a similarity measure for a common product design data BOM (Bill of Materials) based on data mining techniques such as frequent mining and clus-tering. For calculating the similarity between BOMs, a novel Extended Augmented Adjacency Matrix (EAAM) representation is introduced that consists of information not only of the content and topology but also of the fre-quent structural dependency among the various parts of a product design. These EAAM representations of BOMs are compared to calculate the similarity between products and used as a clustering input to group the product fami-lies. When applied on a real-life manufacturing data, the proposed framework outperforms a current baseline that uses orthogonal Procrustes for grouping product families.
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Purpose – There is limited evidence on how differences in economic environments affect the demand for and supply of auditing. Research on audit pricing has mainly focused on large client markets in developed economies; in contrast, the purpose of this paper is to focus on the small client segment in the emerging economy of Thailand which offers a choice between auditors of two different qualities. Design/methodology/approach – This paper is based on a random stratified sample of small clients in Thailand qualifying for audit exemption. The final sample consists of 1,950 firm-year observations for 2002-2006. Findings – The authors find evidence of product differentiation in the small client market, suggesting that small firms view certified public accountants as superior and pay a premium for their services. The authors also find that audit fees have a positive significant association with leverage, metropolitan location and client size. Audit risk and audit opinion are not, however, significantly associated with audit fees. Furthermore, the authors find no evidence that clients whose financial year ends in the auditors’ busy period pay significantly higher audit fees, and auditors engage in low-balling on initial engagements to attract audit clients. Research limitations/implications – The research shows the importance of exploring actual decisions regarding audit practice and audit pricing in different institutional and organizational settings. Originality/value – The paper extends the literature from developed economies and large/listed market setting to the emerging economy and small client market setting. As far as the authors are aware, this is the first paper to examine audit pricing in the small client market in an emerging economy.
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In December 2013, settlement was reached between approximately 100 Australian and New Zealand Thalidomide victims and the company which had acted as the Australian distributor of the infamous drug, thus putting to rest the possibility of litigation. Around the same time, Thalidomide victims in the United Kingdom (UK) launched a similar bid for compensation against the manufacturer and distributor. It is clear that despite a lengthy amount of time having passed ever since the thalidomide disaster commenced in 1962, the controversy over compensation continues. Indeed, the author of Medicinal Product Liability and Regulation (published before the announcement of the British legal claim), Professor Goldberg, notes that claims for resulting birth defects continue to emerge right into the present day. His prescient insight into the contemporary relevance of compensation for pharmaceutical injuries thus makes Medicinal Product Liability and Regulation a very relevant addition to the small body of scholarship that is available on this rather specific and complex issue.
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Aligned with the decline of Marshalian view of industry as constituting homogeneous set of firms, the new perspective is emerging by concentrating more on dynamics of sectors as the building block of industrial changes. Based on new assumptions, much of the action in terms of strategy, technology, and knowledge development does not happen either among firms within a stable industry, or through the growth or decline of certain sectors compared to others. Instead, the action happens in terms of the definition, redefinition, drawing, and redrawing of the very nature of these sectors. Technology does not progress and develop within a sector; rather it shapes (and is shaped by) the encompassing architecture of multiple sectors.
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Under the legacy of neoliberalism, it is important to consider how the indigenous people, in this case of Australia, are to advance, develop and achieve some approximation of parity with broader societies in terms of health, educational outcomes and economic participation. In this paper, we explore the relationships between welfare dependency, individualism, responsibility, rights, liberty and the role of the state in the provision of Government-funded programmes of sport to Indigenous communities. We consider whether such programmes are a product of ‘white guilt’ and therefore encourage dependency and weaken the capacity for independence within communities and individuals, or whether programmes to increase rates of participation in sport are better viewed as good investments to bring about changes in physical activity as (albeit a small) part of a broader social policy aimed at reducing the gaps between Indigenous and non-Indigenous Australians in health, education and employment.