120 resultados para ULTRAFAST INTERNAL-CONVERSION

em Queensland University of Technology - ePrints Archive


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The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

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The impact of service direction, service training and staff behaviours on perceptions of service delivery are examined. The impact of managerial behaviour in the form of internal market orientation (IMO) on the attitudes of frontline staff towards the firm and its consequent influence on their customer oriented behaviours is also examined. Frontline service staff working in the consumer transport industry were surveyed to provide subjective data about the constructs of interest in this study, and the data were analysed using structural equations modelling employing partial least squares estimation. The data indicate significant relationships between internal market orientation (IMO), the attitudes of the employees to the firm and their consequent behaviour towards customers. Customer orientation, service direction and service training are all identified as antecedents to high levels of service delivery. The study contributes to marketing theory by providing quantitative evidence to support assumptions that internal marketing has an impact on services success. For marketing practitioners, the research findings offer additional information about the management, training and motivation of service staff towards service excellence.

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Internal marketing has been discussed in the management and academic literature for over three decades, yet it remains ill defined and poorly operationalized. This paper responds to calls for research to develop a single clear understanding of the construct, for the development of a suitable instrument to measure it, and for empirical evidence of its impact. Existing, divergent conceptualization of internal marketing are explored, and a new, multidimensional construct, describing the managerial behaviors associated with internal marketing is developed, and termed internal market orientation (IMO). IMO represents the adaptation of market orientation to the context of employer-employee exchanges in the internal market. The paper describes the development of a valid and reliable measure of IMO in a retail services context. Five dimensions of IMO are identified and confirmed. These are 1) formal written information generation, 2) formal face-to-face information generation, 3) informal information generation, 4) communication and dissemination of information, and 5) responding to this internal market information. The impact of IMO on important organizational factors is also explored. Results indicate positive consequences for customer satisfaction, relative competitive position, staff attitudes, staff retention and staff compliance.

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The role of internal marketing in developing organisational competencies is identified as a key area for continued research (Rafiq and Ahmed, 2003). One competence of particular interest to marketers is market orientation. This paper examines the impact of internal marketing, operationalised as a set of internal market orientated behaviours (IMO) on market orientation (MO), and consequently organisational performance, and provides the first quantitative evidence to support the long held assumption that internal marketing has an impact on marketing success. Data from UK retail managers were analysed using structural equations modelling employing LISREL software. These data indicate significant relationships between internal market orientation, employee motivation and external marketing success (market orientation, financial performance and customer satisfaction). Our results also support previous findings indicating a positive impact of external market orientation on customer satisfaction and financial performance. For marketing practitioners, the role of internal market orientation is developing marketing strategies is discussed.

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The research on project learning has recognised the significance of knowledge transfer in project based organisations (PBOs). Effective knowledge transfer across projects avoids reinventions, enhances knowledge creation and saves lots of time that is crucial in project environment. In order to facilitate knowledge transfer, many PBOs have invested lots of financial and human resources to implement IT-based knowledge repository. However, some empirical studies found that employees would rather turn for knowledge to colleagues despite their ready access to IT-based knowledge repository. Therefore, it is apparent that social networks play a pivotal role in the knowledge transfer across projects. Some scholars attempt to explore the effect of network structure on knowledge transfer and performance, however, focused only on egocentric networks and the groups’ internal social networks. It has been found that the project’s external social network is also critical, in that the team members can not handle critical situations and accomplish the projects on time without the assistance and knowledge from external sources. To date, the influence of the structure of a project team’s internal and external social networks on project performance, and the interrelation between both networks are barely known. In order to obtain such knowledge, this paper explores the interrelation between the structure of a project team’s internal and external social networks, and their effect on the project team’s performance. Data is gathered through survey questionnaire distributed online to respondents. Collected data is analysed applying social network analysis (SNA) tools and SPSS. The theoretical contribution of this paper is the knowledge of the interrelation between the structure of a project team’s internal and external social networks and their influence on the project team’s performance. The practical contribution lies in the guideline to be proposed for constructing the structure of project team’s internal and external social networks.

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Extended spectrum β-lactamases or ESBLs, which are derived from non-ESBL precursors by point mutation of β-lactamase genes (bla), are spreading rapidly all over the world and have caused considerable problems in the treatment of infections caused by bacteria which harbour them. The mechanism of this resistance is not fully understood and a better understanding of these mechanisms might significantly impact on choosing proper diagnostic and treatment strategies. Previous work on SHV β-lactamase gene, blaSHV, has shown that only Klebsiella pneumoniae strains which contain plasmid-borne blaSHV are able to mutate to phenotypically ESBL-positive strains and there was also evidence of an increase in blaSHV copy number. Therefore, it was hypothesised that although specific point mutation is essential for acquisition of ESBL activity, it is not yet enough, and blaSHV copy number amplification is also essential for an ESBL-positive phenotype, with homologous recombination being the likely mechanism of blaSHV copy number expansion. In this study, we investigated the mutation rate of non-ESBL expressing K. pneumoniae isolates to an ESBL-positive status by using the MSS-maximum likelihood method. Our data showed that blaSHV mutation rate of a non-ESBL expressing isolate is lower than the mutation rate of the other single base changes on the chromosome, even with a plasmid-borne blaSHV gene. On the other hand, mutation rate from a low MIC ESBL-positive (≤ 8 µg/mL for cefotaxime) to high MIC ESBL-positive (≥16 µg/mL for cefotaxime) is very high. This is because only gene copy number increase is needed which is probably mediated by homologous recombination that typically takes place at a much higher frequencies than point mutations. Using a subinhibitory concentration of novobiocin, as a homologous recombination inhibitor, revealed that this is the case.