Efficient and accurate experimental design for enzyme kinetics: Bayesian studies reveal a systematic approach

In areas such as drug development, clinical diagnosis and biotechnology research, acquiring details about the kinetic parameters of enzymes is crucial. The correct design of an experiment is critical to collecting data suitable for analysis, modelling and deriving the correct information. As classical design methods are not targeted to the more complex kinetics being frequently studied, attention is needed to estimate parameters of such models with low variance. We demonstrate that a Bayesian approach (the use of prior knowledge) can produce major gains quantifiable in terms of information, productivity and accuracy of each experiment. Developing the use of Bayesian Utility functions, we have used a systematic method to identify the optimum experimental designs for a number of kinetic model data sets. This has enabled the identification of trends between kinetic model types, sets of design rules and the key conclusion that such designs should be based on some prior knowledge of K-M and/or the kinetic model. We suggest an optimal and iterative method for selecting features of the design such as the substrate range, number of measurements and choice of intermediate points. The final design collects data suitable for accurate modelling and analysis and minimises the error in the parameters estimated. (C) 2003 Elsevier Science B.V. All rights reserved.

Oxidation of oleic acid at the air-water interface and its potential effects on cloud critical supersaturations

The oxidation of organic films on cloud condensation nuclei has the potential to affect climate and precipitation events. In this work we present a study of the oxidation of a monolayer of deuterated oleic acid (cis-9-octadecenoic acid) at the air-water interface by ozone to determine if oxidation removes the organic film or replaces it with a product film. A range of different aqueous sub-phases were studied. The surface excess of deuterated material was followed by neutron reflection whilst the surface pressure was followed using a Wilhelmy plate. The neutron reflection data reveal that approximately half the organic material remains at the air-water interface following the oxidation of oleic acid by ozone, thus cleavage of the double bond by ozone creates one surface active species and one species that partitions to the bulk (or gas) phase. The most probable products, produced with a yield of similar to(87 +/- 14)%, are nonanoic acid, which remains at the interface, and azelaic acid (nonanedioic acid), which dissolves into the bulk solution. We also report a surface bimolecular rate constant for the reaction between ozone and oleic acid of (7.3 +/- 0.9) x 10(-11) cm(2) molecule s(-1). The rate constant and product yield are not affected by the solution sub-phase. An uptake coefficient of ozone on the oleic acid monolayer of similar to 4 x 10(-6) is estimated from our results. A simple Kohler analysis demonstrates that the oxidation of oleic acid by ozone on an atmospheric aerosol will lower the critical supersaturation needed for cloud droplet formation. We calculate an atmospheric chemical lifetime of oleic acid of 1.3 hours, significantly longer than laboratory studies on pure oleic acid particles suggest, but more consistent with field studies reporting oleic acid present in aged atmospheric aerosol.

Copper(II) complexes of tetradentate N2S2 donor sets: synthesis, crystal structure characterization and reactivity

Two mononuclear and one dinuclear copper(II) complexes, containing neutral tetradentate NSSN type ligands, of formulation [Cu-II(L-1)Cl]ClO4 (1), [Cu-II(L-2)Cl]ClO4 (2) and [Cu-2(II)(L-3)(2)Cl-2](ClO4)(2) (3) were synthesized and isolated in pure form [where L-1 = 1,2-bis(2-pyridylmethylthio)ethane, L-2 = 1,3-bis(2-pyridylmethylthio)propane and L-3 = 1,4-bis(2-pyridylmethylthio)butane]. All these green colored copper(II) complexes were characterized by physicochemical and spectroscopic methods. The dinuclear copper(II) complex 3 changed to a colorless dinuclear copper(I) species of formula [Cu-2(1)(L-3)(2)](ClO4)(2),0.5H(2)O (4) in dimethylformamide even in the presence of air at ambient temperature, while complexes I and 2 showed no change under similar conditions. The solid-state structures of complexes 1, 2 and 4 were established by X-ray crystallography. The geometry about the copper in complexes 1 and 2 is trigonal bipyramidal whereas the coordination environment about the copper(I) in dinuclear complex 4 is distorted tetrahedral. (C) 2008 Elsevier Ltd. All rights reserved.

Change in construction: a critical perspective

Change within the construction sector has been a central concern of governments and a select few private-sector clients for a considerable time. The discourse of change emanating from organizations concerned with reform in the construction sector reflects these ongoing concerns for change in the sector. The underlying assumptions of the content of change and appropriate change mechanisms in the UK are critically examined and challenged. In particular, the limitations of measurement and best practice are explored. The allegiance to approaches based on measurement and best practice is acontextual, unreflective and insufficient in providing wholly reliable explanations for the relationship between practice and performance. Claims for the use of measurement and best practice by the reform movement must therefore be understood to have limitations and their use approached with caution. The emphasis on best practice is also understood to direct attention away from understanding the legitimacy of current practice and change within the UK construction sector. An agenda for change in the UK construction sector will need to engage with and be more reflective of current managerial practice and past change initiatives. Contextual approaches such as structuration theory offer a way in which to underpin a research framework that could support the reform movement in setting such an agenda.

Competitiveness in construction: a critical review of research

Since its popularization in the 1980s, competitiveness has received close attention from practitioners and researchers across a wide range of industries. In the construction sector, many works on competitiveness have also been published. So far, however, there seems to be no comprehensive review to summarize and critique existing research on competitiveness in construction. This research, therefore, reviews the extant literature from four aspects: concept of competitiveness, competitiveness research at the construction industry level, competitiveness research at the firm level, and competitiveness research at the project level. The review presents the state-of-the-art development of competitiveness research in construction, identifies the research gaps, and proposes new directions for further studies. Further research is recommended to validate previous studies in construction practices, identify the mechanisms that encourage mutual enhancement of competitiveness at different levels, and how to achieve its sustainability by embracing new management and/or economics techniques.

The futures of construction: A critical review of construction future studies

Anticipating the future is increasingly being seen as a useful way to align, direct and improve current organizational strategy. Several such 'future studies' have been produced which envision various construction industry scenarios which result from technological and socio-economic trends and influences. Thirteen construction-related future studies are critically reviewed. Most studies fail to address the complexities and uncertainties of both the present and the future, and fail to explore the connections between global, local, construction-specific and more widespread factors. The methodological approaches used in these studies do not generate any significantly different advice or recommendations for the industry than those emerging from the much larger canon of non-future oriented construction research. As such, these reports are less about the future than the present. If future studies are to make a worthwhile contribution to construction, it is critical that they develop our appreciation of the practical ability of stakeholders to influence some aspects of the future and not others, and an awareness of the competing agendas and the relative benefits and disadvantages of specific futures within the construction sector. Only then can future studies provide insights and help in preparing for the opportunities and threats the future may bring.

Critical success factors for competitiveness of contractors: A China study

Gaining or maintaining a “contractor's” competitive advantage is not easy as it is determined by a large number of factors. Identification of critical success factors (CSFs) allows one to reduce the vast number of factors to some manageable few but vital ones. Based on the CSFs, contractors' limited resources such as money and manpower can be allocated and aligned appropriately for yielding a maximum outcome of overall competitiveness. This paper describes the CSFs identified from a survey study carried out in Mainland China. The ranking analysis of the survey results shows that 35 factors are rated as critical for determining the competitiveness of a contractor. Factor analysis reveals that the 35 CSFs identified can be grouped into eight clusters, namely, project management skills, organization structure, resources, competitive strategy, relationships, bidding, marketing, and technology. The CSFs in this study provide a vehicle for guiding a contractor in managing its resources in order to improve competitive advantage. The study also provides insights into the management of competitiveness for contractors that are operating in the particular context of the Chinese construction industry.

Critical reliability issues for building services systems

This paper addresses two critical issues associated with reliability and maintenance of building services systems. The first is the ratio of operating and/or maintenance costs to initial costs for building services systems. It is an important parameter for life cycle costing and maintenance policy development. The second is the proportion of items among building services systems that need preventive maintenance. In this paper, we estimate the ratios based on a cost dataset. It suggests that correctly estimating the ratio be important but using a constant ratio in life cycle costing may result in wrong decisions. It also estimates the proportion of preventive maintenance for building services systems on the basis of the distribution of failure patterns.