DOSY NMR studies of chemical exchange behavior of poly(2-hydroxyethyl methacrylate)

PFG-NMR was used to study the chemical exchange of linear PHEMA having a range of molecular weights with water in DMSO containing varying quantities of water. The aim was to investigate the use of PFG-NMR to study chemical exchange between a polymer with exchangeable protons and a small fast diffusing molecule to provide insight into the conformation adopted by a polymer in solution. The experimental data were simulated closely for the two-site exchange case using the Bloch equations modified for chemical exchange and diffusion. The exchange rate could be used to detect changes in polymer conformation resulting from changes in the solvent. PHEMA of MW 10 000 showed significant time-dependent changes in exchange rate, resulting from preferential solvation of the OH sites by water, and subsequent conformational changes which altered accessibility of the OH sites to water. This behavior was not observed for larger MW PHEMA, which adopted a stable conformation immediately. Large changes in the exchange rate were not reflected in changes to the hydrodynamic radius, suggesting that a minimal overall change in the chain dimensions occurred. DMSO was found to be a poor solvent for PHEMA, which adopts a compact conformation in DMSO. This work has demonstrated that PFG-NMR is a sensitive method for detecting subtle changes in polymer conformation in polymers with exchangeable protons.

Analytical electron microscopy of proton exchange membrane fuel cells

Microtome sections of proton exchange membrane cells produce a wide range of information ranging from macroscopic distribution of components through specimens in which the detailed distribution of catalyst particles can be observed. Using modern data management practices it is possible to combine information at different scales and correlate processing and performance data. Analytical electron microscopy reveals the compositional variations across used cells at the electrolyte/electrode interface. In particular analytical techniques indicate that sulphur concentrations are likely to diminish at the interface Nafion/anode interface. © 2006 Elsevier B.V. All rights reserved.

Constructing internationally comparable real income aggregates by combining sparse benchmark data with annual national accounts data: A state-space approach

The importance of availability of comparable real income aggregates and their components to applied economic research is highlighted by the popularity of the Penn World Tables. Any methodology designed to achieve such a task requires the combination of data from several sources. The first is purchasing power parities (PPP) data available from the International Comparisons Project roughly every five years since the 1970s. The second is national level data on a range of variables that explain the behaviour of the ratio of PPP to market exchange rates. The final source of data is the national accounts publications of different countries which include estimates of gross domestic product and various price deflators. In this paper we present a method to construct a consistent panel of comparable real incomes by specifying the problem in state-space form. We present our completed work as well as briefly indicate our work in progress.

A multilevel analysis of team climate and interpersonal exchange relationships at work

This study advances research on interpersonal exchange relationships by integrating social exchange, workplace friendship and climate research to develop a multilevel model. Data were collected from 215 manager-employee dyads working within 36 teams. At the individual level, LMX was positively associated with TMX and workplace friendship. Further, workplace friendship was positively related to TMX, and mediated the LMX-TMX relationship. At the team level, HLM results demonstrated that the relationship between LMX and workplace friendship was moderated by affective climate. Findings suggest that high-quality LMX relationships are associated with enhanced employees' perceptions of workplace friendship when affective group climate was strong.

Leader-member exchange in a Chinese context:antecedents, outcomes and mediating role of psychological empowerment

This study examines organizational antecedents of LMX and the mediating influence of empowerment on the relationships between LMX and the work outcomes of job satisfaction, task performance and psychological withdrawal behavior. Data were obtained from employees of a listed Chinese company in Guangdong Province, People's Republic of China. The results revealed that: (a) supervisor control of rewards and work unit climate were related to LMX and (b) empowerment fully mediated the relationship between LMX and the work outcomes as hypothesized.

Exchange fairness and employee performance:An examination of the relationship between organizational politics and procedural justice

Data obtained from a manufacturing firm and a newspaper firm in India were used to examine the relationship between organizational politics and procedural justice in three separate studies. Study 1 constructively replicated research on the distinctiveness of the two constructs. Confirmatory factor analyses in which data from the manufacturing firm served as the development sample and data from the newspaper firm served as the validation sample demonstrated the distinctiveness of organizational politics and procedural justice. Study 2 examined the antecedents of the two constructs using data from the manufacturing firm. Structural equation modeling (SEM) results revealed formalization and participation in decision making to be positively related to procedural justice but negatively related to organizational politics. Further, authority hierarchy and spatial distance were positively related to organizational politics but unrelated to procedural justice. Study 3 examined the consequences of the two constructs in terms of task and contextual performance using data from the newspaper firm. Results of SEM analysis revealed procedural justice but not organizational politics to be related to task performance and the contextual performance dimensions of interpersonal facilitation and job dedication. © 2004 Elsevier Inc. All rights reserved.

Trust as a mediator of the relationship between organizational justice and work outcomes:test of a social exchange model

Data obtained from full-time employees of a public sector organization in India were used to test a social exchange model of employee work attitudes and behaviors. LISREL results revealed that whereas the three organizational justice dimensions (distributive, procedural and interactional) were related to trust in organization only interactional justice was related to trust in supervisor. The results further revealed that relative to the hypothesized fully mediated model a partially mediated model better fitted the data. Trust in organization partially mediated the relationship between distributive and procedural justice and the work attitudes of job satisfaction, turnover intentions, and organizational commitment but fully mediated the relationship between interactional justice and these work attitudes. In contrast, trust in supervisor fully mediated the relationship between interactional justice and the work behaviors of task performance and the individually- and organizationally-oriented dimensions of citizenship behavior.

On the use of likert-type scales in multilevel data:Influence on aggregate variables

In multilevel analyses, problems may arise when using Likert-type scales at the lowest level of analysis. Specifically, increases in variance should lead to greater censoring for the groups whose true scores fall at either end of the distribution. The current study used simulation methods to examine the influence of single-item Likert-type scale usage on ICC(1), ICC(2), and group-level correlations. Results revealed substantial underestimation of ICC(1) when using Likert-type scales with common response formats (e.g., 5 points). ICC(2) and group-level correlations were also underestimated, but to a lesser extent. Finally, the magnitude of underestimation was driven in large part to an interaction between Likert-type scale usage and the amounts of within- and between-group variance. © Sage Publications.

Model specification and forecasting foreign exchange rates with vector autoregressions

This study examines the forecasting accuracy of alternative vector autoregressive models each in a seven-variable system that comprises in turn of daily, weekly and monthly foreign exchange (FX) spot rates. The vector autoregressions (VARs) are in non-stationary, stationary and error-correction forms and are estimated using OLS. The imposition of Bayesian priors in the OLS estimations also allowed us to obtain another set of results. We find that there is some tendency for the Bayesian estimation method to generate superior forecast measures relatively to the OLS method. This result holds whether or not the data sets contain outliers. Also, the best forecasts under the non-stationary specification outperformed those of the stationary and error-correction specifications, particularly at long forecast horizons, while the best forecasts under the stationary and error-correction specifications are generally similar. The findings for the OLS forecasts are consistent with recent simulation results. The predictive ability of the VARs is very weak.

The sensitivity of US banks' stock returns to interest and exchange rate changes

Purpose – The purpose of this paper is to investigate the impact of foreign exchange and interest rate changes on US banks’ stock returns. Design/methodology/approach – The approach employs an EGARCH model to account for the ARCH effects in daily returns. Most prior studies have used standard OLS estimation methods with the result that the presence of ARCH effects would have affected estimation efficiency. For comparative purposes, the standard OLS estimation method is also used to measure sensitivity. Findings – The findings are as follows: under the conditional t-distributional assumption, the EGARCH model generated a much better fit to the data although the goodness-of-fit of the model is not entirely satisfactory; the market index return accounts for most of the variation in stock returns at both the individual bank and portfolio levels; and the degree of sensitivity of the stock returns to interest rate and FX rate changes is not very pronounced despite the use of high frequency data. Earlier results had indicated that daily data provided greater evidence of exposure sensitivity. Practical implications – Assuming that banks do not hedge perfectly, these findings have important financial implications as they suggest that the hedging policies of the banks are not reflected in their stock prices. Alternatively, it is possible that different GARCH-type models might be more appropriate when modelling high frequency returns. Originality/value – The paper contributes to existing knowledge in the area by showing that ARCH effects do impact on measures of sensitivity.

What's in a handshake? Exploring business-to-business relational exchange

Despite its importance in the development of competitive advantage, attempts to unify diverse classifications of business-to-business relational exchange (B2B RE) have been largely unsuccessful. We used 18 semi-structured, in-depth interviews with managers from a range of industries to explore the B2B RE construct. Analysis of the data revealed that B2B RE comprises five key dimensions. These are communication, understanding, commitment, trust and power symmetry. The research identifies the importance of personal interaction in business relationships and provides additional insights into the importance of affective commitment. In addition we uncover a number of negative consequences of affective commitment, which have been previously unexplored. This research contributes to the domain of B2B research by synthesising and advancing knowledge in this area to provide a new conceptual framework of B2B RE and directions for future research.

Trade balance and real exchange rate:new evidence from Mauritius-UK trade

In this study we investigate whether there exists a relationship between the exchange rate and the trade balance using bilateral data for the Mauritius/UK trade. We also investigate whether following depreciation or a devaluation the trade balance initially worsens due to contractual agreements and subsequently improves when new contracts for international trade are signed. Using a variety of econometric techniques we are able to establish that there exists a long-run relationship between the trade balance and the real exchange rate. The existence of such a relationship signifies that the authorities would be able to use the exchange rate to steer the trade balance. We also find following a depreciation or devaluation the trade balance initially worsens due to contractual agreements but the trade balance subsequently improves when new contracts are signed. This signifies that if the authorities want to devalue their currency to improve the trade balance, the desired effect does not occur immediately but it occurs with a lag, in this particular case after approximately a year.

Exchange rate forecasting using a combined parametric and nonparametric self-organising modelling approach

Financial prediction has attracted a lot of interest due to the financial implications that the accurate prediction of financial markets can have. A variety of data driven modellingapproaches have been applied but their performance has produced mixed results. In this study we apply both parametric (neural networks with active neurons) and nonparametric (analog complexing) self-organisingmodelling methods for the daily prediction of the exchangerate market. We also propose acombinedapproach where the parametric and nonparametricself-organising methods are combined sequentially, exploiting the advantages of the individual methods with the aim of improving their performance. The combined method is found to produce promising results and to outperform the individual methods when tested with two exchangerates: the American Dollar and the Deutche Mark against the British Pound.

Packet voice/data in local broadcast networks

A local area network that can support both voice and data packets offers economic advantages due to the use of only a single network for both types of traffic, greater flexibility to changing user demands, and it also enables efficient use to be made of the transmission capacity. The latter aspect is very important in local broadcast networks where the capacity is a scarce resource, for example mobile radio. This research has examined two types of local broadcast network, these being the Ethernet-type bus local area network and a mobile radio network with a central base station. With such contention networks, medium access control (MAC) protocols are required to gain access to the channel. MAC protocols must provide efficient scheduling on the channel between the distributed population of stations who want to transmit. No access scheme can exceed the performance of a single server queue, due to the spatial distribution of the stations. Stations cannot in general form a queue without using part of the channel capacity to exchange protocol information. In this research, several medium access protocols have been examined and developed in order to increase the channel throughput compared to existing protocols. However, the established performance measures of average packet time delay and throughput cannot adequately characterise protocol performance for packet voice. Rather, the percentage of bits delivered within a given time bound becomes the relevant performance measure. Performance evaluation of the protocols has been examined using discrete event simulation and in some cases also by mathematical modelling. All the protocols use either implicit or explicit reservation schemes, with their efficiency dependent on the fact that many voice packets are generated periodically within a talkspurt. Two of the protocols are based on the existing 'Reservation Virtual Time CSMA/CD' protocol, which forms a distributed queue through implicit reservations. This protocol has been improved firstly by utilising two channels, a packet transmission channel and a packet contention channel. Packet contention is then performed in parallel with a packet transmission to increase throughput. The second protocol uses variable length packets to reduce the contention time between transmissions on a single channel. A third protocol developed, is based on contention for explicit reservations. Once a station has achieved a reservation, it maintains this effective queue position for the remainder of the talkspurt and transmits after it has sensed the transmission from the preceeding station within the queue. In the mobile radio environment, adaptions to the protocols were necessary in order that their operation was robust to signal fading. This was achieved through centralised control at a base station, unlike the local area network versions where the control was distributed at the stations. The results show an improvement in throughput compared to some previous protocols. Further work includes subjective testing to validate the protocols' effectiveness.

The magnetic exchange interactions in chromium chalcogenide spinels

The chromium chalcogenide spinels, MCr2X4 (M = Zn, Cd, Hg; X = O, S, Se), have been the subject of considerable interest in recent years. In each case the crystal structure is that of a normal spinel with the chromium ions exclusively occupying the octahedral (B) sites, so that when diamagnetic ions are located at the tetrahedral (A) sites the only magnetic interactions present are those between B-site ions. Despite such apparently simple circumstances a rich variety of magnetic behaviour is exhibited. For the oxides the ground state spin configurations are antiferromagnetic whilst for the selenides ferromagnetic interactions dominate and several authors have drawn attention to the fact that the nature of the dominant interaction is a function of the nearest neighbour chromium - chromium separation. However, at least two of the compounds exhibit spiral structures and it has been proved difficult to account for the various spin configurations within a unified theory of the magnetic interactions involved. More recently, the possibility of formulating a simplified interpretation of the magnetic interactions has been provided by the discovery that the crystal struture of spinels does not always conform to the centrosymmetrical symmetry Fd3m that has been conventionally assumed. The deviation from this symmetry is associated with small < 111> displacements of the octahedrally coordinated metal ions and the structures so obtained are more correctly referred to the non-centrosymmetrical space group F43m. In the present study, therefore, extensive X-ray diffraction data have been collected from four chromium chalcogenide specimens and used to refine the corresponding structural parameters assuming F43m symmetry and also with conventional symmetry. The diffracted intensities from three of the compounds concerned cannot be satisfactorily accounted for on the basis of conventional symmetry and new locations have been found for the chromium ions in these cases. It is shown, however, that these displacements in chromium positions only partially resolve the difficulties in interpreting the magnetic behaviour. A re-examination of the magnetic data from different authors indicates much greater uncertainty in their measurements than they had claimed. By taking this into consideration it is shown that a unified theory of magnetic behaviour for the chromium chalcogenide spinels is a real possibility.