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The development of novel organocatalytic and transition-metal catalysed methodologies for amide bond formation
Get PDFWith the formation of amide bonds being one of the most widely performed reactions within organic chemistry, highly efficient and atom economical approaches enabling the transformation are desired. Traditional methodologies, in which a stoichiometric coupling reagent is utilised, although efficient, have several inherent drawbacks hindering their general applicability, including stoichiometric by-product formation, low atom economy and poor cost effectiveness. Therefore, the development of atom economical catalytic approaches to facilitate the facile synthesis of amide bonds would successfully address the aforementioned outstanding issues.Building upon previous research performed within the Jamieson group, one such approach is the trifluoroethanol-catalysed amidation of unactivated ester derivatives. However, in the initial studies, the general applicability of this methodology was limited by the incompatibility of acyclic secondary amines under the reaction manifold, and additionally, stereoerosion when the use of α-stereogenic ester substrates was examined. Further optimisation of the progenitor conditions successfully addressed these limitations, allowing the synthesis of a diverse range of acyclic tertiary amides and chiral secondary amides, with the latter synthesised in good to excellent levels of stereoretention (Scheme 1.1). Additionally, a multicomponent approach enabling the formation of secondary amides fromepoxides, amines and unactivated esters, mediated by the organobase BEMP, has also been developed. The use of a multicomponent process, employing only catalytic quantities of base, limits by-product formation, thereby resulting in a highly atom efficient amide bond forming method (Scheme 1.2). This approach has also been further adapted to enable the synthesis of corresponding oxazolidinone moieties. The use of transition-metal catalysis has also been employed to facilitate amide bond formation. Utilising silanoate-derived imidate salt species, synthesised from the corresponding nitriles as amide surrogates, a Buchwald-Hartwig amidation methodology has been developed, enabling the synthesis of secondary amides (Scheme 1.3). Investigations into the use of these species in other amide bond forming transformations have also been carried out.With the formation of amide bonds being one of the most widely performed reactions within organic chemistry, highly efficient and atom economical approaches enabling the transformation are desired. Traditional methodologies, in which a stoichiometric coupling reagent is utilised, although efficient, have several inherent drawbacks hindering their general applicability, including stoichiometric by-product formation, low atom economy and poor cost effectiveness. Therefore, the development of atom economical catalytic approaches to facilitate the facile synthesis of amide bonds would successfully address the aforementioned outstanding issues.Building upon previous research performed within the Jamieson group, one such approach is the trifluoroethanol-catalysed amidation of unactivated ester derivatives. However, in the initial studies, the general applicability of this methodology was limited by the incompatibility of acyclic secondary amines under the reaction manifold, and additionally, stereoerosion when the use of α-stereogenic ester substrates was examined. Further optimisation of the progenitor conditions successfully addressed these limitations, allowing the synthesis of a diverse range of acyclic tertiary amides and chiral secondary amides, with the latter synthesised in good to excellent levels of stereoretention (Scheme 1.1). Additionally, a multicomponent approach enabling the formation of secondary amides fromepoxides, amines and unactivated esters, mediated by the organobase BEMP, has also been developed. The use of a multicomponent process, employing only catalytic quantities of base, limits by-product formation, thereby resulting in a highly atom efficient amide bond forming method (Scheme 1.2). This approach has also been further adapted to enable the synthesis of corresponding oxazolidinone moieties. The use of transition-metal catalysis has also been employed to facilitate amide bond formation. Utilising silanoate-derived imidate salt species, synthesised from the corresponding nitriles as amide surrogates, a Buchwald-Hartwig amidation methodology has been developed, enabling the synthesis of secondary amides (Scheme 1.3). Investigations into the use of these species in other amide bond forming transformations have also been carried out
High dimensional uncertainty propagation for hypersonic flows and entry propagation
Get PDFTo solve complex design problems, engineers cannot avoid to take into account the involved uncertainties. This is important for the analysis and design of hypersonic objects and vehicles, which have to operate in extreme conditions.;In this work, two approaches for a high dimensional uncertainty quantification (UQ) are developed. The first approach performs a single-fidelity non-intrusive forward UQ, while the second one performs a multi fidelity UQ, as an extension of the first approach. Both methods are focused on real engineering problems and, therefore, appropriate heuristics are included to achieve an optimal trade-off between accuracy and computational costs.;In the first approach, the stochastic domain is decomposed into domains of lower dimensionality, and, then, each domain is handled separately. This is possible due to the application of the HDMR, which is here derived in a new way. This new derivation allowed to deduce important conclusions about the high dimensional modelling, which are used in the prediction scheme.;This novel approach for the selection of the higher order interaction effects drastically reduce the required number of samples. In order to have optimally distributed samples for the problem of interest, the adaptive sampling scheme is introduced. Moreover, the multi-surrogate approach is introduced in order to improve the robustness of the method. The single-fidelity approach is tested on a debris re-entry case and the method is validated with respect to the MC simulation method.;In the second approach, the multi-fidelity approach has been developed.In order to have the optimal combination of the low fidelity models, the power ratio approach is introduced. To correct the low fidelity model, the classical additive correction, adapted to work within the HDMR approach, is used. The multi-fidelity approach has been tested on the GOCE re-entry case, where the performed tests demonstrate the potentialities of the method.To solve complex design problems, engineers cannot avoid to take into account the involved uncertainties. This is important for the analysis and design of hypersonic objects and vehicles, which have to operate in extreme conditions.;In this work, two approaches for a high dimensional uncertainty quantification (UQ) are developed. The first approach performs a single-fidelity non-intrusive forward UQ, while the second one performs a multi fidelity UQ, as an extension of the first approach. Both methods are focused on real engineering problems and, therefore, appropriate heuristics are included to achieve an optimal trade-off between accuracy and computational costs.;In the first approach, the stochastic domain is decomposed into domains of lower dimensionality, and, then, each domain is handled separately. This is possible due to the application of the HDMR, which is here derived in a new way. This new derivation allowed to deduce important conclusions about the high dimensional modelling, which are used in the prediction scheme.;This novel approach for the selection of the higher order interaction effects drastically reduce the required number of samples. In order to have optimally distributed samples for the problem of interest, the adaptive sampling scheme is introduced. Moreover, the multi-surrogate approach is introduced in order to improve the robustness of the method. The single-fidelity approach is tested on a debris re-entry case and the method is validated with respect to the MC simulation method.;In the second approach, the multi-fidelity approach has been developed.In order to have the optimal combination of the low fidelity models, the power ratio approach is introduced. To correct the low fidelity model, the classical additive correction, adapted to work within the HDMR approach, is used. The multi-fidelity approach has been tested on the GOCE re-entry case, where the performed tests demonstrate the potentialities of the method
The effect of corporate social responsibility on firm's foreign direct investement
Get PDFStrathclyde theses - ask staff. Thesis no. : T15078This thesis examines the relation between corporate social responsibility and firm's foreign direct investment decisions. Three empirical chapters focusing on the different aspects of the relation are investigated. I begin the analysis by examining whether there is a positive relation between corporate social responsibility and firm's overall foreign direct investment propensity. I find that corporate social responsibility can help firms to overcome the liability of foreignness, thus increase their likelihood of undertaking foreign direct investment. The thesis then focuses on the influence of corporate social responsibility on multinational enterprises' foreign investment location and entry mode choices. I find that multinational enterprises with high corporate social responsibility performance have higher likelihood to invest in a developed rather than a developing country, and to choose a full rather than a partial control entry method. I further find that the relation above are affected by the level of liability of foreignness multinational enterprises encountered and the institutional qualities of the host country. The final part of the empirical analysis examines whether corporate social responsibility can create value for shareholders around the foreign direct investment announcements. I find a neutral relation between corporate social responsibility and firm's three day, five day, and 11 day cumulative abnormal returns, thus in general corporate social responsibility cannot create value for shareholders in the short term. However, I identify several occasions where a positive relation exists. That is when the investment is in developing countries, or through a partial control entry method, or the investing firm encounters a high level of liability of foreignness. This thesis contributes both to academic literature and practice by examining the various impact of corporate social responsibility on firm's foreign investment decisions. Evidence is provided on the important role corporate social responsibility plays on firm's foreign investment decision making process.This thesis examines the relation between corporate social responsibility and firm's foreign direct investment decisions. Three empirical chapters focusing on the different aspects of the relation are investigated. I begin the analysis by examining whether there is a positive relation between corporate social responsibility and firm's overall foreign direct investment propensity. I find that corporate social responsibility can help firms to overcome the liability of foreignness, thus increase their likelihood of undertaking foreign direct investment. The thesis then focuses on the influence of corporate social responsibility on multinational enterprises' foreign investment location and entry mode choices. I find that multinational enterprises with high corporate social responsibility performance have higher likelihood to invest in a developed rather than a developing country, and to choose a full rather than a partial control entry method. I further find that the relation above are affected by the level of liability of foreignness multinational enterprises encountered and the institutional qualities of the host country. The final part of the empirical analysis examines whether corporate social responsibility can create value for shareholders around the foreign direct investment announcements. I find a neutral relation between corporate social responsibility and firm's three day, five day, and 11 day cumulative abnormal returns, thus in general corporate social responsibility cannot create value for shareholders in the short term. However, I identify several occasions where a positive relation exists. That is when the investment is in developing countries, or through a partial control entry method, or the investing firm encounters a high level of liability of foreignness. This thesis contributes both to academic literature and practice by examining the various impact of corporate social responsibility on firm's foreign investment decisions. Evidence is provided on the important role corporate social responsibility plays on firm's foreign investment decision making process
Enhanced weather modelling for dynamic line rating
Get PDFConventional approaches to dynamic line rating (DLR) forecasting provide single point estimates with no indication of the distribution of possible errors. Furthermore, most research related to DLR forecasting deals only with continuous or steady-state ratings while less attention has been given to short-term or transient-state ratings.;This thesis describes (a) weather-based models to estimate probabilistic forecasts of steady-state DLRs for up to three 10-minutes time steps ahead for a particular span and a complete overhead line (OHL) and also (b) a fast-computational weather-based approach to probabilistic forecasting of transient-state DLRs for a particular span for time horizons of 10, 20 and 30 minutes. The percentiles of DLR forecasts can be used by a system operator within a chosen risk policy informed by the probability of a rating being exceeded.;The thesis first develops time series forecasting models for different weather variables that impact on line rating (i.e. air temperature, wind speed, wind direction and solar radiation) at weather stations that are installed along the route of 132kV OHLs in North Wales. Predictive centres of weather variables are modelled as a sum of residuals predicted by a suitable auto-regressive process and temporal trends fitted by Fourier series.;Conditional heteroscedasticity of the predictive distribution is modelled as a linear function of recent changes in residuals within one hour for air temperature and wind speed or concentration of wind direction observations within the most recent two hours. A technique of minimum continuous ranked probability score estimation is employed to determine predictive distributions of the measured weather variables.;Then the thesis uses Monte Carlo simulation to generate a large number of random weather samples from the modelled predictive distributions which are paired to have rank correlations similar to those among their recent observations. The probabilistic steady-state DLR forecasts for a particular span in proximity to a weather station are estimated from the random weather samples combined with a maximum allowable conductor temperature using a thermal model of the conductors (i.e. a steady-state heat balance equation).;For a complete OHL, possible weather predictions at each span are inferred from random weather samples at stations by using suitable spatial interpolation models; the steady-state DLR forecast of the OHL is then identified as the minimum DLR among all spans for each generated scenario.;Using an enhanced analytical method which evolves from a non-steady-state heat balance equation to track the transient-state conductor temperature, the transient-state DLR forecast for a particular span is calculated as that which increases the conductor temperature from an initial value to the maximum allowable limit for a particular future time period (i.e. in this study, 10, 20 and 30 minutes) under each set of random weather samples.;The calibration of probabilistic DLR forecasts estimated from independent or correlated random weather samples are then examined to determine which approaches are most suited to estimation of DLRs at the lower end of a predictive distribution consistent with a system operator's risk policy. The potential use of DLR forecasting is then evaluated through estimating the degree to which wind generation curtailment for various assumed installed capacities at a wind farm that is connected to the 132kV network in North Wales can be alleviated through using the lower percentiles of steady-state DLR forecasts in place of the SLRs for each 132kV OHL.Conventional approaches to dynamic line rating (DLR) forecasting provide single point estimates with no indication of the distribution of possible errors. Furthermore, most research related to DLR forecasting deals only with continuous or steady-state ratings while less attention has been given to short-term or transient-state ratings.;This thesis describes (a) weather-based models to estimate probabilistic forecasts of steady-state DLRs for up to three 10-minutes time steps ahead for a particular span and a complete overhead line (OHL) and also (b) a fast-computational weather-based approach to probabilistic forecasting of transient-state DLRs for a particular span for time horizons of 10, 20 and 30 minutes. The percentiles of DLR forecasts can be used by a system operator within a chosen risk policy informed by the probability of a rating being exceeded.;The thesis first develops time series forecasting models for different weather variables that impact on line rating (i.e. air temperature, wind speed, wind direction and solar radiation) at weather stations that are installed along the route of 132kV OHLs in North Wales. Predictive centres of weather variables are modelled as a sum of residuals predicted by a suitable auto-regressive process and temporal trends fitted by Fourier series.;Conditional heteroscedasticity of the predictive distribution is modelled as a linear function of recent changes in residuals within one hour for air temperature and wind speed or concentration of wind direction observations within the most recent two hours. A technique of minimum continuous ranked probability score estimation is employed to determine predictive distributions of the measured weather variables.;Then the thesis uses Monte Carlo simulation to generate a large number of random weather samples from the modelled predictive distributions which are paired to have rank correlations similar to those among their recent observations. The probabilistic steady-state DLR forecasts for a particular span in proximity to a weather station are estimated from the random weather samples combined with a maximum allowable conductor temperature using a thermal model of the conductors (i.e. a steady-state heat balance equation).;For a complete OHL, possible weather predictions at each span are inferred from random weather samples at stations by using suitable spatial interpolation models; the steady-state DLR forecast of the OHL is then identified as the minimum DLR among all spans for each generated scenario.;Using an enhanced analytical method which evolves from a non-steady-state heat balance equation to track the transient-state conductor temperature, the transient-state DLR forecast for a particular span is calculated as that which increases the conductor temperature from an initial value to the maximum allowable limit for a particular future time period (i.e. in this study, 10, 20 and 30 minutes) under each set of random weather samples.;The calibration of probabilistic DLR forecasts estimated from independent or correlated random weather samples are then examined to determine which approaches are most suited to estimation of DLRs at the lower end of a predictive distribution consistent with a system operator's risk policy. The potential use of DLR forecasting is then evaluated through estimating the degree to which wind generation curtailment for various assumed installed capacities at a wind farm that is connected to the 132kV network in North Wales can be alleviated through using the lower percentiles of steady-state DLR forecasts in place of the SLRs for each 132kV OHL
The development of a real-time wave energy device control algorithm based on artificial neural network
Get PDFThis thesis is aimed at proposing an artificial intelligence controller to maximize the energy absorption of wave energy converter (WEC) in practical application. The controller maximizes the energy absorption by locking and releasing the WEC alternately, and such control is known as the latching control. The model predictive control strategy is used to implement real-time control. Since the control inputs are future wave forces, the controller is a non-causal system. An artificial neural network is developed and trained by the machine learning algorithm to predict the short-term wave forces.Firstly, the state-space dynamic model is developed to simulate the kinetic motion of the WEC in sea waves. Compared with traditional convolution dynamic model, the state-space representation extremely enhances the computation efficiency. Moreover, the state-space model is represented by a differential formula so that it is more convenient to implement the control algorithm. The state-space model is acquired based on the so-called system identification, which transforms the frequency-domain hydrodynamic coefficients of the WEC into a set of state vectors. A Rankine source boundary element method code is developed to calculate the hydrodynamic coefficients. By separating the entire fluid boundary into a set of elements and distributing the Rankine source across the elements uniformly, the velocity potential of the fluid is determined.;The latching control, a kind of phase control, maximizes the energy absorption by tuning the velocity phase and making it in phase with the wave excitation forces. The tuning of velocity phase is fulfilled by locking the WEC at some time instants following the control command. The Pontryagin's maximum principle is applied to derive the control command, which maximizes the energy absorption over a time horizon [ti, ti+p]. By receding the time horizon forward step by step, the control command is updated at each time instant and thereby the control is implemented in a real-time manner. It is the basic idea of the model predictive control. Since the derived control command just maximizes the energy absorption over the time horizon [ti,ti+p] rather than the entire interval [0, T], the model predictive control is a sub-optimal control strategy.The inputs to a non-causal wave energy controller are future wave forces, and it is what prevents the practical application of wave energy control. An artificial neural network is developed to predict the short-term wave forces. Unlike traditional deterministic forecasting approach, which is based on a specific model defined by the users, the neural network forecasts the future wave forces by learning from examples itself since even the users don't know anything about the prediction model. In another word, the neural network is a data-driven prediction approach. The developed neural network is trained by a set of examples using the machine learning algorithm.;With the artificial neural network, the real-time smart controller is incorporated into a heaving-point absorber to maximize the energy absorption. It is shown that the energy absorption is indeed increased substantially even if the wave forces are predicted. It indicates that the real-time controller is applicable in the real practice. Besides, the effects of prediction duration and prediction deviation on the control performance are also investigated. Long prediction duration enhances the control efficiency whereas the energy absorption is reduced with the presence of prediction deviation. Since the deviation accumulates with the prediction duration, a moderate prediction duration is thus recommended.The multi-stable mechanism of the WEC is also investigated in this thesis. A non-linear PTO (power take-off) system with two oblique springs is proposed. The PTO system is either monostable or bistable depending on the initial configuration of the oblique springs. Correspondingly, a single-well potential or a double-well potential is identified. The behaviors of the WEC show considerable discrepancies in the two modes. At the monostable mode, the WEC responds to the waves in a linear manner. The energy absorption and bandwidth are hardly varied compared with a linear WEC. Comparatively, the WEC operates with a distinguished mechanism at the bistable mode. Two types of floater responses are identified. The energy capture is significantly increased although the bandwidth is narrowed at the same time. The enhancement of energy absorption is mainly attributed to the tuning of the velocity phase, which occurs when the floater moves around the two potential wells.This thesis is aimed at proposing an artificial intelligence controller to maximize the energy absorption of wave energy converter (WEC) in practical application. The controller maximizes the energy absorption by locking and releasing the WEC alternately, and such control is known as the latching control. The model predictive control strategy is used to implement real-time control. Since the control inputs are future wave forces, the controller is a non-causal system. An artificial neural network is developed and trained by the machine learning algorithm to predict the short-term wave forces.Firstly, the state-space dynamic model is developed to simulate the kinetic motion of the WEC in sea waves. Compared with traditional convolution dynamic model, the state-space representation extremely enhances the computation efficiency. Moreover, the state-space model is represented by a differential formula so that it is more convenient to implement the control algorithm. The state-space model is acquired based on the so-called system identification, which transforms the frequency-domain hydrodynamic coefficients of the WEC into a set of state vectors. A Rankine source boundary element method code is developed to calculate the hydrodynamic coefficients. By separating the entire fluid boundary into a set of elements and distributing the Rankine source across the elements uniformly, the velocity potential of the fluid is determined.;The latching control, a kind of phase control, maximizes the energy absorption by tuning the velocity phase and making it in phase with the wave excitation forces. The tuning of velocity phase is fulfilled by locking the WEC at some time instants following the control command. The Pontryagin's maximum principle is applied to derive the control command, which maximizes the energy absorption over a time horizon [ti, ti+p]. By receding the time horizon forward step by step, the control command is updated at each time instant and thereby the control is implemented in a real-time manner. It is the basic idea of the model predictive control. Since the derived control command just maximizes the energy absorption over the time horizon [ti,ti+p] rather than the entire interval [0, T], the model predictive control is a sub-optimal control strategy.The inputs to a non-causal wave energy controller are future wave forces, and it is what prevents the practical application of wave energy control. An artificial neural network is developed to predict the short-term wave forces. Unlike traditional deterministic forecasting approach, which is based on a specific model defined by the users, the neural network forecasts the future wave forces by learning from examples itself since even the users don't know anything about the prediction model. In another word, the neural network is a data-driven prediction approach. The developed neural network is trained by a set of examples using the machine learning algorithm.;With the artificial neural network, the real-time smart controller is incorporated into a heaving-point absorber to maximize the energy absorption. It is shown that the energy absorption is indeed increased substantially even if the wave forces are predicted. It indicates that the real-time controller is applicable in the real practice. Besides, the effects of prediction duration and prediction deviation on the control performance are also investigated. Long prediction duration enhances the control efficiency whereas the energy absorption is reduced with the presence of prediction deviation. Since the deviation accumulates with the prediction duration, a moderate prediction duration is thus recommended.The multi-stable mechanism of the WEC is also investigated in this thesis. A non-linear PTO (power take-off) system with two oblique springs is proposed. The PTO system is either monostable or bistable depending on the initial configuration of the oblique springs. Correspondingly, a single-well potential or a double-well potential is identified. The behaviors of the WEC show considerable discrepancies in the two modes. At the monostable mode, the WEC responds to the waves in a linear manner. The energy absorption and bandwidth are hardly varied compared with a linear WEC. Comparatively, the WEC operates with a distinguished mechanism at the bistable mode. Two types of floater responses are identified. The energy capture is significantly increased although the bandwidth is narrowed at the same time. The enhancement of energy absorption is mainly attributed to the tuning of the velocity phase, which occurs when the floater moves around the two potential wells
Developing strategies and equipment for continuous isolation of active pharmaceutical ingredients (APIs) by filtration, washing and drying
Get PDFIn pharmaceutical sector, compounds forming the drug and especially the activep harmaceutical ingredients (API's) are required to be pure, in accordance with the regulatory authorities' rules. The isolation stage is used to remove the impure liquid phase and to remove surface impurities from the crystalline product. Physico-chemical properties of crystals formed during the crystallization process and the solvents selected for the crystallization process influence the performance and the efficacy of isolation. Lots of effort was made in the last few decades to understand how to improve the crystallization stage. Relatively less effort has been made to understand the chemo-physical and process characteristics affecting the properties of the final isolated product. As consequence, the isolation stage can be responsible for extended API manufacturing time, the consumption of high quantities of materials and solvents and sometimes the requirement for isolated product post-processing to overcome variation of crystallized material properties caused by isolation.The aim of this thesis is to understand from a microscopic to a macroscopic point of view how the physic-chemical properties of the crystallized material and the washing solvents used in combination with the filtration, washing and drying approaches used can influence the final isolated product characteristics. To broaden the field, an alternative analytical technique for pharmaceutical field, TOF-SIMS, allows investigating the surface/subsurface of crystal to localize adsorption of related impurities to help to design isolation strategy and solvent selection. A major objective of this work is to reduce API manufacturing time in the R&D stage, to minimize chemical, especially solvent consumption, and to maximize the isolation knowledge gathered to design an optimal isolation process. The work also addresses the development of an analytical workflows/procedures to characterize materials during each step of the isolation. The final component was the development of a lab/small scale isolation prototype unit for API's development, which was developed during this work.In pharmaceutical sector, compounds forming the drug and especially the activep harmaceutical ingredients (API's) are required to be pure, in accordance with the regulatory authorities' rules. The isolation stage is used to remove the impure liquid phase and to remove surface impurities from the crystalline product. Physico-chemical properties of crystals formed during the crystallization process and the solvents selected for the crystallization process influence the performance and the efficacy of isolation. Lots of effort was made in the last few decades to understand how to improve the crystallization stage. Relatively less effort has been made to understand the chemo-physical and process characteristics affecting the properties of the final isolated product. As consequence, the isolation stage can be responsible for extended API manufacturing time, the consumption of high quantities of materials and solvents and sometimes the requirement for isolated product post-processing to overcome variation of crystallized material properties caused by isolation.The aim of this thesis is to understand from a microscopic to a macroscopic point of view how the physic-chemical properties of the crystallized material and the washing solvents used in combination with the filtration, washing and drying approaches used can influence the final isolated product characteristics. To broaden the field, an alternative analytical technique for pharmaceutical field, TOF-SIMS, allows investigating the surface/subsurface of crystal to localize adsorption of related impurities to help to design isolation strategy and solvent selection. A major objective of this work is to reduce API manufacturing time in the R&D stage, to minimize chemical, especially solvent consumption, and to maximize the isolation knowledge gathered to design an optimal isolation process. The work also addresses the development of an analytical workflows/procedures to characterize materials during each step of the isolation. The final component was the development of a lab/small scale isolation prototype unit for API's development, which was developed during this work
The role of social capital and entrepreneurial orientation in innovation capability
Get PDFMany researchers and practitioners believe that innovation is a key business process. It is also the competitive advantage in supporting organisational capability. This competitive advantage distinguishes the company to become unique and different from the others. It directs the company to be a success in the fluctuation of a dynamic market. To reach the competitive advantage, the company should manage the innovation capability. However, it is not easy to manage innovation capability. It needs the good configuration of resource and innovation capability. Many previous studies focused on tangible resources such as machine, technology, and financial can enable innovation. Then, the researchers realised that intangible resources have more advantages such as more valuable, unique, difficult to be imitated, and thus it can support competitive advantage. The mixed result from previous studies explains that intangible resource in the context of SME's could be the driver or hinder of innovation capability inspired the researcher to identify what kind of intangible resource could affect innovation capability and how does it affect innovation capability. Some gaps attained from literature review sections such as (1) the limited study focused more in effect between intellectual capital and innovation capability in developing country; and (2) the limited study was investigating the additional of mediating variable in bolstering innovation capability. In this case, the researcher found the advantage of entrepreneurial orientation (risk-taking, proactiveness, and openness) as the organisational behaviour which can support innovation capability. Based on the gaps found, the researcher builds the conceptual model upon the theory of resource-based view and innovation management literature. This study fills this gap by conducting an empirical study in the context of ICT-SMEs in developing country, i.e., Indonesia. This research tests the hypothesis based on the empirical study which collected the primary data, i.e., 297 respondents from 132 Information and Communication Technology of Small and Medium Entreprises (ICT-SME) in Indonesia. In addition, this research analyses the primary data by using statistical analyses, i.e., Confirmatory Factor Analysis (CFA), Exploratory Factor Analysis (EFA) and Structural Equation Modelling (SEM). The findings indicate that human capital could improve radical as well as incremental innovation capability whereas social capital could reduce radical as well as incremental innovation capability. When SMEs have entrepreneurial orientation, their human capital will enhance their radical and incremental innovation. On the other hand, SMEs' entrepreneurial orientation with openness in working with others reduces the relationship between social capital and radical/incremental innovation capability. The differences in the findings may be because of the influence of national culture. Since the culture can interpret the behavioural preference of individual or team in the organisation such as entrepreneurial behaviour (Hayton et al., 2002), the researcher evaluates the pros and cons among the findings by using Hofstede Model.Many researchers and practitioners believe that innovation is a key business process. It is also the competitive advantage in supporting organisational capability. This competitive advantage distinguishes the company to become unique and different from the others. It directs the company to be a success in the fluctuation of a dynamic market. To reach the competitive advantage, the company should manage the innovation capability. However, it is not easy to manage innovation capability. It needs the good configuration of resource and innovation capability. Many previous studies focused on tangible resources such as machine, technology, and financial can enable innovation. Then, the researchers realised that intangible resources have more advantages such as more valuable, unique, difficult to be imitated, and thus it can support competitive advantage. The mixed result from previous studies explains that intangible resource in the context of SME's could be the driver or hinder of innovation capability inspired the researcher to identify what kind of intangible resource could affect innovation capability and how does it affect innovation capability. Some gaps attained from literature review sections such as (1) the limited study focused more in effect between intellectual capital and innovation capability in developing country; and (2) the limited study was investigating the additional of mediating variable in bolstering innovation capability. In this case, the researcher found the advantage of entrepreneurial orientation (risk-taking, proactiveness, and openness) as the organisational behaviour which can support innovation capability. Based on the gaps found, the researcher builds the conceptual model upon the theory of resource-based view and innovation management literature. This study fills this gap by conducting an empirical study in the context of ICT-SMEs in developing country, i.e., Indonesia. This research tests the hypothesis based on the empirical study which collected the primary data, i.e., 297 respondents from 132 Information and Communication Technology of Small and Medium Entreprises (ICT-SME) in Indonesia. In addition, this research analyses the primary data by using statistical analyses, i.e., Confirmatory Factor Analysis (CFA), Exploratory Factor Analysis (EFA) and Structural Equation Modelling (SEM). The findings indicate that human capital could improve radical as well as incremental innovation capability whereas social capital could reduce radical as well as incremental innovation capability. When SMEs have entrepreneurial orientation, their human capital will enhance their radical and incremental innovation. On the other hand, SMEs' entrepreneurial orientation with openness in working with others reduces the relationship between social capital and radical/incremental innovation capability. The differences in the findings may be because of the influence of national culture. Since the culture can interpret the behavioural preference of individual or team in the organisation such as entrepreneurial behaviour (Hayton et al., 2002), the researcher evaluates the pros and cons among the findings by using Hofstede Model
Advance work : art and advertising in Buffalo Bill's Wild West
Get PDFThis analysis of the visual record of Buffalo's Bill Wild West posters in the United States provides the first scholarly interpretation focused on the commercial print production and related cultural impact of the show on American and international audiences, and is divided into two sections: Inventing Buffalo Bill's Wild West, and Visualizing Buffalo Bill's Wild West. Part One interprets the history of the art, advertising, and commercial prints developed for the Wild West. Part Two includes overview and analysis of the visual culture of the Wild West for U.S. tours, the importance of the Strobridge Lithographing Co. and the city of Cincinnati as a commercial printing hub, and the Wild West diplomacy and international perspectives of the program following the successful 1893 season.;The evolution of the art and advertising of Buffalo Bill's Wild West is linked to the highly publicized life of William F. Cody, and his exposure to the art and landscape of the American West. Chapters in each part of this study consistently incorporate elements of Cody's life, his interest in American art, and his friendships with successful artists. Chapter One, The Art of Buffalo Bill's Wild West, William F. Cody, and the American West, presents a biography of Cody within that context: his celebrated life and times, and the art of the American West that influenced him.;Chapter Two, Advertising the Wild West: Cody and Cooke, introduces the professional relationships crucial to Cody's success as a performer and entrepreneur leading the Wild West team, including the impact of general publicity agent Louis E. Cooke on Cody's artistic and business decisions over several decades. Chapter Three, The Wild West Company and Commercial Printers, establishes significant advances in lithographic printing following the American Civil War, introducing the printing firms contracted with the show, and the artists and photographers instrumental in advancing the art of the Wild West.;Chapter Four, The Visual Culture of the Wild West in the United States, defines the history of the three most prominent printing companies in the development of color lithographic posters for the Wild West-A. Hoen & Co., of Baltimore, MD; Courier Lithographic Co., of Buffalo, NY, and Enquirer Job Printing Co., of Cincinnati, OH-and the unique poster art developed through the relationships between Cody, the owners, and artists at the companies. Chapter Five, The Strobridge Lithographing Company and Cincinnati Show Printers, explores the prominence of the city of Cincinnati on American lithography and Strobridge and Enquirer as leaders in circus and traveling show poster production, including those for the Wild West.;Chapter Six, Wild West Diplomacy and Going Global, expands on the changes in the Wild West with the introduction of the Congress of Rough Riders of the World, and considers Cody's ongoing role in promoting international peace and diplomacy amid America's emerging imperial role in the world.;Numerous artists, photographers, and lithographers collaborated to create the dynamic and effective imagery for Cody and the Wild West between 1883 and 1913. Newly accessible digital and archival collections provide new opportunities for the analysis and documentation of the art created to advance the celebrity of "Buffalo Bill" and foster the national and international success of the Wild West. The artwork conveyed a carefully crafted and sometimes nuanced version of how the West was won, in which Cody, himself, was always central.;The surviving posters and photographs, programs, newspaper accounts, personal correspondence and expense records, confirm the process and intent behind the Wild West advertising phenomenon that fixed the performers and performances into the national memory and American history.This analysis of the visual record of Buffalo's Bill Wild West posters in the United States provides the first scholarly interpretation focused on the commercial print production and related cultural impact of the show on American and international audiences, and is divided into two sections: Inventing Buffalo Bill's Wild West, and Visualizing Buffalo Bill's Wild West. Part One interprets the history of the art, advertising, and commercial prints developed for the Wild West. Part Two includes overview and analysis of the visual culture of the Wild West for U.S. tours, the importance of the Strobridge Lithographing Co. and the city of Cincinnati as a commercial printing hub, and the Wild West diplomacy and international perspectives of the program following the successful 1893 season.;The evolution of the art and advertising of Buffalo Bill's Wild West is linked to the highly publicized life of William F. Cody, and his exposure to the art and landscape of the American West. Chapters in each part of this study consistently incorporate elements of Cody's life, his interest in American art, and his friendships with successful artists. Chapter One, The Art of Buffalo Bill's Wild West, William F. Cody, and the American West, presents a biography of Cody within that context: his celebrated life and times, and the art of the American West that influenced him.;Chapter Two, Advertising the Wild West: Cody and Cooke, introduces the professional relationships crucial to Cody's success as a performer and entrepreneur leading the Wild West team, including the impact of general publicity agent Louis E. Cooke on Cody's artistic and business decisions over several decades. Chapter Three, The Wild West Company and Commercial Printers, establishes significant advances in lithographic printing following the American Civil War, introducing the printing firms contracted with the show, and the artists and photographers instrumental in advancing the art of the Wild West.;Chapter Four, The Visual Culture of the Wild West in the United States, defines the history of the three most prominent printing companies in the development of color lithographic posters for the Wild West-A. Hoen & Co., of Baltimore, MD; Courier Lithographic Co., of Buffalo, NY, and Enquirer Job Printing Co., of Cincinnati, OH-and the unique poster art developed through the relationships between Cody, the owners, and artists at the companies. Chapter Five, The Strobridge Lithographing Company and Cincinnati Show Printers, explores the prominence of the city of Cincinnati on American lithography and Strobridge and Enquirer as leaders in circus and traveling show poster production, including those for the Wild West.;Chapter Six, Wild West Diplomacy and Going Global, expands on the changes in the Wild West with the introduction of the Congress of Rough Riders of the World, and considers Cody's ongoing role in promoting international peace and diplomacy amid America's emerging imperial role in the world.;Numerous artists, photographers, and lithographers collaborated to create the dynamic and effective imagery for Cody and the Wild West between 1883 and 1913. Newly accessible digital and archival collections provide new opportunities for the analysis and documentation of the art created to advance the celebrity of "Buffalo Bill" and foster the national and international success of the Wild West. The artwork conveyed a carefully crafted and sometimes nuanced version of how the West was won, in which Cody, himself, was always central.;The surviving posters and photographs, programs, newspaper accounts, personal correspondence and expense records, confirm the process and intent behind the Wild West advertising phenomenon that fixed the performers and performances into the national memory and American history
An experimental and computational investigation of transition metal-free reactions
Get PDFThis thesis was previously restricted to Strathclyde users only until 26th October 2023.Over recent decades transition metal-catalysed cross-coupling has been developed significantly, opening up new areas of reactivity in both an academic and industrial environment. However, over recent years transition metal-free coupling reactions of haloarenes to arenes, proceeding by the Base-promoted Homolytic Aromatic Substitution (BHAS) mechanism have been widely reported in the literature. These reactions work well when initiated by organic electron donors that are formed in situ from organic additives of various types. The work in this thesis builds on previous work carried out within the Murphy group and other groups working in this field.;Scheme 1 - BHAS mechanism proposed by Studer and Curran as responsible for transition metal-free cross coupling reactions. [Graphic Item];The work in this thesis looks at transition metal-free reactions in two forms; firstly looking at new additives that could form electron donors to initiate the BHAS mechanism and secondly, looking at where coupling reactions are occurring when there is no electron donor present. The final aspect of this thesis looks at exploring observations seen in experiments with haloarenes and potassium hydride.;The first set of work was looking at a series of additives that were designed to form electron-rich alkenes, a common feature of electron donors, under basic conditions. These were studied both computationally and experimentally and this work showed these can work together effectively in studying electron donors.;Scheme 2 - Additives used in Chapter 4 produced high yields of coupled products. [Graphic Item];While these reactions proceed in good yield when there is an electron donor present in the reaction, when there is no electron donor a measurable amount of cross coupling still occurs. A plausible mechanism, shown in scheme 3, has been proposed for the initiation of the BHAS pathway. This thesis shows that biradicals, generated in Bergman cyclisations and hexadehydro-Diels-Alder reactions, can indeed act as a source of initiation for this pathway. This thesis now shows that additives that afford arenediyls, provide independent initiation of the coupling reactions for this substrate in the absence of electron donors, supporting a similar capability for benzyne generated by base-dependent means.;Scheme 3 - Proposed benzyne initiation of the BHAS cycle. [Graphic Item];In reactions performed by other members of the Murphy group involving haloarenes and KH, some interesting reaction products were observed. In this thesis these have been rationalised using computational studies.;Scheme 4 - This thesis proposes formation of 7.7 proceeds via the four-memberedtransition state calculated. [Graphic Item]Over recent decades transition metal-catalysed cross-coupling has been developed significantly, opening up new areas of reactivity in both an academic and industrial environment. However, over recent years transition metal-free coupling reactions of haloarenes to arenes, proceeding by the Base-promoted Homolytic Aromatic Substitution (BHAS) mechanism have been widely reported in the literature. These reactions work well when initiated by organic electron donors that are formed in situ from organic additives of various types. The work in this thesis builds on previous work carried out within the Murphy group and other groups working in this field.;Scheme 1 - BHAS mechanism proposed by Studer and Curran as responsible for transition metal-free cross coupling reactions. [Graphic Item];The work in this thesis looks at transition metal-free reactions in two forms; firstly looking at new additives that could form electron donors to initiate the BHAS mechanism and secondly, looking at where coupling reactions are occurring when there is no electron donor present. The final aspect of this thesis looks at exploring observations seen in experiments with haloarenes and potassium hydride.;The first set of work was looking at a series of additives that were designed to form electron-rich alkenes, a common feature of electron donors, under basic conditions. These were studied both computationally and experimentally and this work showed these can work together effectively in studying electron donors.;Scheme 2 - Additives used in Chapter 4 produced high yields of coupled products. [Graphic Item];While these reactions proceed in good yield when there is an electron donor present in the reaction, when there is no electron donor a measurable amount of cross coupling still occurs. A plausible mechanism, shown in scheme 3, has been proposed for the initiation of the BHAS pathway. This thesis shows that biradicals, generated in Bergman cyclisations and hexadehydro-Diels-Alder reactions, can indeed act as a source of initiation for this pathway. This thesis now shows that additives that afford arenediyls, provide independent initiation of the coupling reactions for this substrate in the absence of electron donors, supporting a similar capability for benzyne generated by base-dependent means.;Scheme 3 - Proposed benzyne initiation of the BHAS cycle. [Graphic Item];In reactions performed by other members of the Murphy group involving haloarenes and KH, some interesting reaction products were observed. In this thesis these have been rationalised using computational studies.;Scheme 4 - This thesis proposes formation of 7.7 proceeds via the four-memberedtransition state calculated. [Graphic Item
Characterisation and development of the incremental shear forming process for nickel-based aerospace structures
No full textThe increasing interest from the engineering community to manufacture near-net-shape components in order to improve the material utilisation and cost competitiveness at a product level as well as the product characteristics drives research towards a deeper understanding of cold forming technologies. The herein research investigated the shear forming process applied to 304L stainless steel and Inconel 718 and intended to facilitate an improved exploitation route of the technology into component applications by characterising it geometrically and metallurgically. First, the identification and impact of the key processing variables (KPVs) on the geometry and surface roughness of the component when applied to 304L stainless steel and Inconel 718 were studied through experimental work using a systematic approach and then compared to the literature (triangulation). A design of experiments approach was undertaken on an industrial scale machine and predictive numerical models were established by statistical analysis to allow optimisation of the process capabilities within component tolerances. The feeds and speeds were revealed to have a significant impact across the different thicknesses and geometries.Secondly, the microstructure and texture of 304L stainless steel and Inconel 718 post shear forming were studied using scanning electron microscopy coupled with electron back-scattered diffraction. Elongated grains following the roller path were observed as well as shear bands, which are characteristic of high local deformation.The grain size was found to be dependent on the cone angle and an increased hardness was noted. The primary mechanism of deformation was identified as simple shear. The statistical analysis of the texture of the Inconel 718 parts after a two-step aging treatment revealed a significant link between the torsion component B and the cone angle, initial thickness, and their interaction. The research and findings were considered in light of the current literature and recommendations and areas for future research were given.The increasing interest from the engineering community to manufacture near-net-shape components in order to improve the material utilisation and cost competitiveness at a product level as well as the product characteristics drives research towards a deeper understanding of cold forming technologies. The herein research investigated the shear forming process applied to 304L stainless steel and Inconel 718 and intended to facilitate an improved exploitation route of the technology into component applications by characterising it geometrically and metallurgically. First, the identification and impact of the key processing variables (KPVs) on the geometry and surface roughness of the component when applied to 304L stainless steel and Inconel 718 were studied through experimental work using a systematic approach and then compared to the literature (triangulation). A design of experiments approach was undertaken on an industrial scale machine and predictive numerical models were established by statistical analysis to allow optimisation of the process capabilities within component tolerances. The feeds and speeds were revealed to have a significant impact across the different thicknesses and geometries.Secondly, the microstructure and texture of 304L stainless steel and Inconel 718 post shear forming were studied using scanning electron microscopy coupled with electron back-scattered diffraction. Elongated grains following the roller path were observed as well as shear bands, which are characteristic of high local deformation.The grain size was found to be dependent on the cone angle and an increased hardness was noted. The primary mechanism of deformation was identified as simple shear. The statistical analysis of the texture of the Inconel 718 parts after a two-step aging treatment revealed a significant link between the torsion component B and the cone angle, initial thickness, and their interaction. The research and findings were considered in light of the current literature and recommendations and areas for future research were given
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