Controlled synthesis of poly(neopentyl p-styrene sulfonate) via reversible addition-fragmentation chain transfer polymerisation

The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using RAFT polymerisation has been studied. Selected experimental conditions led to the production of PNSS with variable molecular weights and low dispersities (D{stroke}≤1.50). The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using reversible addition-fragmentation chain transfer polymerisation has been studied under a wide range of experimental conditions. PNSS can be used as an organic-soluble, thermally labile precursor for industrially valuable poly(p-styrene sulfonate), widely employed in technologies such as ionic exchange membranes and organic electronics. The suitability of two different chain transfer agents, three solvents, three different monomer concentrations and two different temperatures for the polymerisation of neopentyl p-styrene sulfonate is discussed in terms of the kinetics of the process and characteristics of the final polymer. Production of PNSS with systematically variable molecular weights and low dispersities (D{stroke} ≤1.50 in all cases) has been achieved using 2-azidoethyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate in anisole at 75°C, with an initial monomer concentration of 4.0molL-1. Finally, a poly(neopentyl p-styrene sulfonate)-b-polybutadiene-b-poly(neopentyl p-styrene sulfonate) (PNSS-b-PBD-b-PNSS) triblock copolymer has been synthesised via azide-alkyne click chemistry. Moreover, subsequent thermolysis of the PNSS moieties generated poly(p-styrene sulfonate) end blocks. This strategy allows the fabrication of amphiphilic copolymer films from single organic solvents without the need for post-deposition chemical treatment.

A sensing mechanism for the detection of carbon nanotubes using selective photoluminescent probes based on ionic complexes with organic dyes

The multifunctional properties of carbon nanotubes (CNTs) make them a powerful platform for unprecedented innovations in a variety of practical applications. As a result of the surging growth of nanotechnology, nanotubes present a potential problem as an environmental pollutant, and as such, an efficient method for their rapid detection must be established. Here, we propose a novel type of ionic sensor complex for detecting CNTs – an organic dye that responds sensitively and selectively to CNTs with a photoluminescent signal. The complexes are formed through Coulomb attractions between dye molecules with uncompensated charges and CNTs covered with an ionic surfactant in water. We demonstrate that the photoluminescent excitation of the dye can be transferred to the nanotubes, resulting in selective and strong amplification (up to a factor of 6) of the light emission from the excitonic levels of CNTs in the near-infrared spectral range, as experimentally observed via excitation-emission photoluminescence (PL) mapping. The chirality of the nanotubes and the type of ionic surfactant used to disperse the nanotubes both strongly affect the amplification; thus, the complexation provides sensing selectivity towards specific CNTs. Additionally, neither similar uncharged dyes nor CNTs covered with neutral surfactant form such complexes. As model organic molecules, we use a family of polymethine dyes with an easily tailorable molecular structure and, consequently, tunable absorbance and PL characteristics. This provides us with a versatile tool for the controllable photonic and electronic engineering of an efficient probe for CNT detection.

Forecasting exchange rates with linear and nonlinear models

In this paper, the exchange rate forecasting performance of neural network models are evaluated against the random walk, autoregressive moving average and generalised autoregressive conditional heteroskedasticity models. There are no guidelines available that can be used to choose the parameters of neural network models and therefore, the parameters are chosen according to what the researcher considers to be the best. Such an approach, however,implies that the risk of making bad decisions is extremely high, which could explain why in many studies, neural network models do not consistently perform better than their time series counterparts. In this paper, through extensive experimentation, the level of subjectivity in building neural network models is considerably reduced and therefore giving them a better chance of Forecasting exchange rates with linear and nonlinear models 415 performing well. The results show that in general, neural network models perform better than the traditionally used time series models in forecasting exchange rates.

The limits of open innovation:openness and (quasi-)markets in the organization of innovation

Recent studies have stressed the importance of ‘open innovation’ as a means of enhancing innovation performance. The essence of the open innovation model is to take advantage of external as well as internal knowledge sources in developing and commercialising innovation, so avoiding an excessively narrow internal focus in a key area of corporate activity. Although the external aspect of open innovation is often stressed, another key aspect involves maximising the flow of ideas and knowledge from different sources within the firm, for example through knowledge sharing via the use of cross-functional teams. A fully open innovation approach would therefore combine both aspects i.e. cross-functional teams with boundary-spanning knowledge linkages. This suggests that there should be complementarities between the use cross-functional teams with boundary-spanning knowledge linkages i.e. the returns to implementing open innovation in one innovation activity is should be greater if open innovation is already in place in another innovation activity. However, our findings – based on a large sample of UK and German manufacturing plants – do not support this view. Our results suggest that in practice the benefits envisaged in the open innovation model are not generally achievable by the majority of plants, and that instead the adoption of open innovation across the whole innovation process is likely to reduce innovation outputs. Our results provide some guidance on the type of activities where the adoption of a market-based governance structure such as open innovation may be most valuable. This is likely to be in innovation activities where search is deterministic, activities are separable, and where the required level of knowledge sharing is correspondingly moderate – in other words those activities which are more routinized. For this type of activity market-based governance mechanisms (i.e. open innovation) may well be more efficient than hierarchical governance structures. For other innovation activities where outcomes are more uncertain and unpredictable and the risks of knowledge exchange hazards are greater, quasi-market based governance structures such as open innovation are likely to be subject to rapidly diminishing returns in terms of innovation outputs.

Design and development of a time of flight fast scattering spectrometer : a quantitative surface analysis technique and a new approach towards the experimental investigation of the surface particle interactions

A new surface analysis technique has been developed which has a number of benefits compared to conventional Low Energy Ion Scattering Spectrometry (LEISS). A major potential advantage arising from the absence of charge exchange complications is the possibility of quantification. The instrumentation that has been developed also offers the possibility of unique studies concerning the interaction between low energy ions and atoms and solid surfaces. From these studies it may also be possible, in principle, to generate sensitivity factors to quantify LEISS data. The instrumentation, which is referred to as a Time-of-Flight Fast Atom Scattering Spectrometer has been developed to investigate these conjecture in practice. The development, involved a number of modifications to an existing instrument, and allowed samples to be bombarded with a monoenergetic pulsed beam of either atoms or ions, and provided the capability to analyse the spectra of scattered atoms and ions separately. Further to this a system was designed and constructed to allow incident, exit and azimuthal angles of the particle beam to be varied independently. The key development was that of a pulsed, and mass filtered atom source; which was developed by a cyclic process of design, modelling and experimentation. Although it was possible to demonstrate the unique capabilities of the instrument, problems relating to surface contamination prevented the measurement of the neutralisation probabilities. However, these problems appear to be technical rather than scientific in nature, and could be readily resolved given the appropriate resources. Experimental spectra obtained from a number of samples demonstrate some fundamental differences between the scattered ion and neutral spectra. For practical non-ordered surfaces the ToF spectra are more complex than their LEISS counterparts. This is particularly true for helium scattering where it appears, in the absence of detailed computer simulation, that quantitative analysis is limited to ordered surfaces. Despite this limitation the ToFFASS instrument opens the way for quantitative analysis of the 'true' surface region to a wider range of surface materials.

Transformational-transactional leadership and upward influence:the role of Relative Leader-Member Exchanges (RLMX) and Perceived Organizational Support (POS)

By utilizing the resource theory of social exchange (Foa & Foa, 1974), we attempted to cast light on the dynamics of the relationship between transformational-transactional leadership and employees' upward influence tactics. Using data collected in two time points (N=200, 1. year apart), we found perceptions of transformational leadership (Time 1) to be positively related to the use of soft and rational upward influence tactics (Time 2) whereas transactional leadership (Time 1) was positively related to the use of soft and hard upward influence tactics (Time 2). We also found support for a 3-way interaction between transformational-transactional leadership, relative Leader Member Exchanges (RLMX) and Perceived Organizational Support (POS) on employees' upward influence tactics. Specifically, in resource-constrained conditions (low RLMX and low POS), employees were likely to use soft tactics to influence a manager they perceived as transformational to a greater extent than in resource-munificent conditions. They were also likely to employ higher levels of soft and hard tactics to influence a transactional manager in resource-constrained rather than in resource-munificent conditions. © 2012 Elsevier Inc.

The role of eicoapentaenoic acid in cancer cahexia

Cachexia is a wasting syndrome often associated with malignancy, characterised by alterations in host metabolism and significant catabolism of host adipose tissue and skeletal muscle. The MAC16 murine adenocarcinoma is profoundly cachexigenic, inducing host weight-loss at relatively small tumour burden without the induction of anorexia. A 4DkDa factor capable of inducing lipolysis in vitro via an activation of adenylate cyclase (AC) has been isolated from the MAC16 tumour, and the urine of cachectic cancer patients, using a series of ion exchange and gel exclusion chromatography procedures. This lipid-mobilising factor (LMF) has been demonstrated to stimulate lipolysis in adipocytes dose-dependently via a signal transduction pathway involving, possibly, β3-adrenoceptors. Oral administration of the n-3 polyunsaturated fatty acid (PUFA) eicosapentaenoic acid (EPA) attenuated the progression of cachexia, but not the production of LMF, in MAC16 tumour-bearing mice, and was significantly incorporated into plasma phospholipids, skeletal muscle and adipose tissue. EPA supplemented cancer patients also demonstrated significantly increased plasma EPA concentrations. Decreased plasma membrane AC activity in response to LMF was observed in adipocytes isolated from mice receiving EPA. Incubation in vitro of adipocytes, or plasma membranes, with PUFAs significantly altered membrane fatty acid composition and attenuated the induction of both lipolysis, and AC activity, by LMF. The inhibitory actions of EPA, but not docosahexaenoic acid, are probably the consequence of an interaction with guanine nucleotide binding proteins (G-proteins). Progression of the cachectic state induced an up-regulation of adipocyte membrane expression of stimulatory G-proteins, allied with a concomitant down-regulation of inhibitory G-proteins, thus facilitating the catabolic actions of LMF, implying some tumour-mediated effect. A reversal of such alterations was observed upon oral administration of EPA, suggesting that the primary mechanism of action of this fatty acid is an inhibition of the end organ effects of LMF.

The pore system and engineering properties of hardened cement paste

The work described in this thesis is an attempt to elucidate the relationships between the pore system and a number of engineering properties of hardened cement paste, particularly tensile strength and resistances to carbonation and ionic penetration. By examining aspects such as the rate of carbonisation, the pore size distribution, the concentration of ions in the pore solution and the phase composition of cement pastes, relationships between the pore system (pores and pore solution) and the resistance to carbonation were investigated. The study was carried out in two parts. First, cement pastes with different pore systems were compared, whilst secondly comparisons were made between the pore systems of cement pastes with different degrees of carbonation. Relationships between the pore structure and ionic penetration were studied by comparing kinetic data relating to the diffusion of various ions in cement pastes with different pore systems. Diffusion coefficients and activation energies for the diffusion process of Cl- and Na+ ions in carbonated and non-carbonated cement pastes were determined by a quasi-steady state technique. The effect of the geometry of pores on ionic diffusion was studied by comparing the mechanisms of ionic diffusion for ions with different radii. In order to investigate the possible relationship between tensile strength and macroporosity, cement paste specimens with cross sectional areas less than 1mm2 were produced so that the chance of a macropore existing within them was low. The tensile strengths of such specimens were then compared with those of larger specimens.

Ionic and molecular diffusion in cementitious materials

The work described in this thesis is an attempt to provide improved understanding of the effects of several factors affecting diffusion in hydrated cement pastes and to aid the prediction of ionic diffusion processes in cement-based materials. Effect of pore structure on diffusion was examined by means of comparative diffusion studies of quaternary ammonium ions with different ionic radii. Diffusivities of these ions in hydrated pastes of ordinary portland cement with or without addition of fly ash were determined by a quasi-steady state technique. The restriction of the pore geometry on diffusion was evaluated from the change of diffusivity in response to the change of ionic radius. The pastes were prepared at three water-cement ratios, 0.35, 0.50 and 0.65. Attempts were made to study the effect of surface charge or the electrochemical double layer at the pore/solution interface on ionic diffusion. An approach was to evaluate the zeta potentials of hydrated cement pastes through streaming potential measurements. Another approach was the comparative studies of the diffusion kinetics of chloride and dissolved oxygen in hydrated pastes of ordinary portland cement with addition of 0 and 20% fly ash. An electrochemical technique for the determination of oxygen diffusivity was also developed. Non-steady state diffusion of sodium potassium, chloride and hydroxyl ions in hydrated ordinary portland cement paste of water-cement ratio 0.5 was studied with the aid of computer-modelling. The kinetics of both diffusion and ionic binding were considered for the characterization of the concentration profiles by Fick's first and second laws. The effect of the electrostatic interactions between ions on the overall diffusion rates was also considered. A general model concerning the prediction of ionic diffusion processes in cement-based materials has been proposed.

A linguistic study of interview and conversation

The present thesis focuses on the overall structure of the language of two types of Speech Exchange Systems (SES) : Interview (INT) and Conversation (CON). The linguistic structure of INT and CON are quantitatively investigated on three different but interrelated levels of analysis : Lexis, Syntax and Information Structure. The corpus of data 1n vest1gated for the project consists of eight sessions of pairs of conversants in carefully planned interviews followed by unplanned, surreptitiously recorded conversational encounters of the same pairs of speakers. The data comprise a total of approximately 15.200 words of INT talk and of about 19.200 words in CON. Taking account of the debatable assumption that the language of SES might be complex on certain linguistic levels (e.g. syntax) (Halliday 1979) and might be simple on others (e.g. lexis) in comparison to written discourse, the thesis sets out to investigate this complexity using a statistical approach to the computation of the structures recurrent in the language of INT and CON. The findings indicate clearly the presence of linguistic complexity in both types. They also show the language of INT to be slightly more syntactically and lexically complex than that of CON. Lexical density seems to be relatively high in both types of spoken discourse. The language of INT seems to be more complex than that of CON on the level of information structure too. This is manifested in the greater use of Inferable and other linguistically complex entities of discourse. Halliday's suggestion that the language of SES is syntactically complex is confirmed but not the one that the more casual the conversation is the more syntactically complex it becomes. The results of the analysis point to the general conclusion that the linguistic complexity of types of SES is not only in the high recurrence of syntactic structures, but also in the combination of these features with each other and with other linguistic and extralinguistic features. The linguistic analysis of the language of SES can be useful in understanding and pinpointing the intricacies of spoken discourse in general and will help discourse analysts and applied linguists in exploiting it both for theoretical and pedagogical purposes.

Kindness is the parent of kindness: reciprocity in the UK call centre workplace

This research developed, proposed and tested an integrated psychological process to performance model. The model utilized the overarching theory of social exchange to incorporate the climate perceptions and affective reactions of 3,012 employees across 88 UK call centres. In the pursuit of parsimony, a review of the applied psychology literature gave rise to a model where the path between global service climate and contextual performance was fully mediated by, first, perceived organizational support, second, job satisfaction and third, affective commitment. The resulting integrated and parsimonious model was tested via SEM and the mediation hypotheses were tested via a series of nested competing models. A moderate fit and partial, rather than full, mediation were reported. Nested Competing Model 4 proved to be the most parsimonious and to have the best fit. It is important to recognise, however, that Nested Competing Model 4 is not intended to be the most comprehensive model (which would include all significant paths), but a more practically useful one (i.e. parsimonious), that focuses on the main relationships.

Ionic and neutral hydrogels for dermal and ophthalmic applications

This thesis is concerned with the use of ionic and neutral hydrogels in dermal and ocular applications with particular reference to controlled release applications. The work consists of three interconnected themes.The first area of study is the use of skin adhesive bioelectrode hydrogels as ground plate electrodes for ophthalmic iontophoresis applications. The work provides a basis of understanding the relative contributions made by ionic monomers (such as sodium s-(acrylamide)-2-methyl propane sulphonate and acrylic acid-bis-(3-sulfopropyl-ester, potassium salt) and neutral monomers (such as acryloymorpholine, N,N-dimethylacrylamide and N-vinyl pyrrolidone) to adhesion, rheology and impedance of bioelectrode gels. The general advantage of neutral monomers, which have been used to successfully replace ionic monomers, is that they enable more effective control of independent anion and cation species (for example potassium chloride and sodium chloride) unlike ionic monomers where polymerisation produces an immobile polyanion thus limiting cation mobility. Secondly, release from a completely neutral hydrogel under the influence of mechanical shaking was studied for the case of crosslinked polyvinyl alcohol (PVA) containing low concentration of linear soluble PVA in a contact lens application. The soluble PVA was observed to be eluting by reptation from the lens matrix due to the mechanical action of the eyelid. This process was studied in an in vitro model, which in this research was used as a basis for developing a lens made with enhanced release polymer. The third area of work is related to the factors that control drug release (in particular non-steroidal anti-inflammatory drugs) from a hydrogel matrix. This links both electrotherapy applications, such as transcutaneous electrical nerve stimulation, in which the passive diffusion from the gel could be used in conjunction with enhanced transmission across the dermal surface with passive diffusion from a contact lens matrix and the development of therapeutic contact lenses.

Modeling foreign exchange rate pass-through using the exponential GARCH

In this chapter, the authors use an EGARCH-ECM to estimate the pass-through effects of Foreign Exchange (FX) rate changes and changes in producers' prices for 20 U.K. export sectors. The long-run adjustments of export prices to FX rate changes and changes in producers' prices are within the range of -1.02% (for the Textiles sector) and -17.22% (for the Meat sector). The contemporaneous Pricing-To-Market (PTM) coefficients are within the range of -72.84% (for the Fuels sector) and -8.05% (for the Textiles sector). Short-run FX rate pass-through is not complete even after several months. Rolling EGARCH-ECMs show that the short and long-run effects of changes in FX rate and producers' prices vary substantially, as do asymmetry and volatility estimates before equilibrium is achieved.

Ties that bind:understanding why and how diversity management relates to black and ethnic minority employees’ experience of organisational life

Despite much anecdotal and oftentimes empirical evidence that black and ethnic minority employees do not feel integrated into organisational life and the implications of this lack of integration for their career progression, there is a dearth of research on the nature of the relationship black and ethnic minority employees have with their employing organisations. Additionally, research examining the relationship between diversity management and work outcomes has returned mixed findings. Scholars have attributed this to the lack of an empirically validated measure of workforce diversity management. Accordingly, I sought to address these gaps in the extant literature in a two-part study grounded in social exchange theory. In Study 1, I developed and validated a measure of workforce diversity management practices. Data obtained from a sample of ethnic minority employees from a cross section of organisations provided support for the validity of the scale. In Study 2, I proposed and tested a social-exchange-based model of the relationship between black and ethnic minority employees’ and their employing organisations, as well as assessed the implications of this relationship for their work outcomes. Specifically, I hypothesised: (i) perception of support for diversity, perception of overall justice, and developmental experiences (indicators of integration into organisational life) as mediators of the relationship between diversity management and social exchange with organisation; (ii) the moderating influence of diversity climate on the relationship between diversity management and these indicators of integration; and (iii) the work outcomes of social exchange with organisation defined in terms of career satisfaction, turnover intention and strain. SEM results provide support for most of the hypothesised relationships. The findings of the study contribute to the literature on workforce diversity management in a number of ways. First, the development and validation of a diversity management practice scale constitutes a first step in resolving the difficulty in operationalising and measuring the diversity management construct. Second, it explicates how and why diversity management practices influence a social exchange relationship with an employing organisation, and the implications of this relationship for the work outcomes of black and ethnic minority employees. My study’s focus on employee work outcomes is an important corrective to the predominant focus on organisational-level outcomes of diversity management. Lastly, by focusing on ethno-racial diversity my research complements the extant research on such workforce diversity indicators as age and gender.

Bid-ask spread dynamics in foreign exchange markets

The aim of this paper is to examine the short term dynamics of foreign exchange rate spreads. Using a vector autoregressive model (VAR) we show that most of the variation in the spread comes from the long run dependencies between past and future spreads rather than being caused by changes in inventory, adverse selection, cost of carry or order processing costs. We apply the Integrated Cumulative Sum of Squares (ICSS) algorithm of Inclan and Tiao (1994) to discover how often spread volatility changes. We find that spread volatility shifts are relatively uncommon and shifts in one currency spread tend not to spillover to other currency spreads. © 2013.