Flow analysis based on a pulsed flow of solution: theory, instrumentation and applications

The increased demands placed on solution propulsion by programmed flow systems, such as sequential injection analysis, lab-on-value technology, bead injection and multi-commutation, has highlighted the inability of many conventional pumps to generate a smooth, consistent flow. A number of researchers have examined ways to overcome the inadvertent, uncontrolled pulsation caused by the mechanical action of peristaltic pumps. In contrast, we have developed instruments that exploit the characteristics of a reproducible pulsed flow of solution. In this paper, we discuss our instrumental approaches and some applications that have benefited from the use of a reproducible pulsed flow rather than the traditional linear flow approach. To place our approach in the context of the continuously developing field of flow analysis, an overview of other programmed flow systems is also presented.

Multi-dimensional liquid chromatography and metabolomics, are two dimensions better than one?

 While data processing methods in metabolomic studies often work with 'n' number of dimensions, analytical techniques, with the notable exception of NMR, have mostly stuck only to one. Peak overlap continues to be a problem and there is an ever-present demand to maximize the number of metabolites that can be separated and identified in a single run. One method that might help to overcome these issues is multidimensional liquid chromatography, which uses two columns of different phases. A sequential collection of aliquots is made from the first column and reinjected onto a second, and the resulting data are then plotted in 2D or 3D space. The total peak capacity of such a system is the combined peak capacities of each column. The 'offline' version of this technique, using a fraction collector, was introduced over 30 years ago but with recent advances in instrumentation and software, particularly the 'online' approach using automated switching valves, has led to increasing interest in the technique. Both offline and online methods can be carried out as a comprehensive procedure, or via 'heart-cutting', in which only specific peaks are analysed in the second dimension. Past applications include proteomics, natural product chemistry, forensic science and pharmaceutical analysis. These successes are likely to be built on in the future as new column chemistries and bio-informatic approaches are developed. In this review an overview of the theory of twodimensional liquid chromatography is presented, its potential in the field of metabolomics is assessed and predictions for future research directions are made.

Longitudinal studies into science learning - methodological issues

The Gold Standard for education research promotes randomized controlled trials (RCTs) that can produce generalizable knowledge claims across similar problems and situations. Unfortunately, the Gold Standard does not fully recognize the need for developmental research to better understand the problem space, formulate theory and approaches to teaching and learning, and formulate and pursue associated research questions. This developmental research has been a precursor to the development of interventions together with the necessary instrumentation and technologies required to fully investigate these through the more formal evaluative processes imagined by the Gold Standard. This chapter focuses on longitudinal studies that cover a continuum from such developmental research to research that uses control-experimental features to evaluate interventions. These studies attend to a set of issues dealing with  developmental progressions and learning trajectories that require  investigation over an extended period of time. It will be argued that
these longitudinal studies of a variety of methodological types represent quality research in that rigorous design and implementation produce  evidence-based claims. The chapter examines the nature of the relationship between evidence and claims in these studies, to show the possibility of building in control features every bit as strong as those in classic Gold Standard designs. Further, it will be argued that, given the complexity of learning pathways, a simplistic interpretation of RCTs conducted over the shorter term can be misleading in terms of both internal and external validity claims.

Determination of rate constants using microelectrodes

An understanding of the rate and the mechanism of reaction is of fundamental importance in the many facets of chemistry. Electrochemical systems are further complicated by the heterogeneous boundary, between the solution and the electrode, that the electron passes through before any electrochemical reaction can take place. This thesis concerns the development of methods for analysing electrode kinetics. One part involves the further development of the Global Analysis procedure to include electrodes with a spherical geometry which are traditionally the most popular form of electrodes. Simulated data is analysed to ascertain the accuracy of the procedure and then the known artifacts of uncompensated solution resistance and charging current are added to the simulated data so that the effects can be observed. The experimental analysis of 2-methyl-2-nitropropane is undertaken and comparisons are made with the Marcus-Hush electrochemical theories concerning electrode kinetics. A related section explores procedures for the kinetic analysis of steady state voltammetric data obtained at microdisc electrodes. A method is proposed under the name of Normalised Steady State Voltammetry and is tested using data obtained from a Fast Quasi-Explicit Finite Difference simulation of diffusion to a microdisc electrode. In a second area of work using microelectrodes, the electrochemical behaviour of compounds of the general formula M(CO)3(η3 - P2P1) where M is either Cr, Mo or W and P2P' is bis(2-diphenylphosphinoethyl)phenylphosphine) is elucidated. The development of instrumentation and mathematical procedures relevant to the measurement and quantitation of these systems is also investigated. The tungsten compound represents the first examples where the 17-electronfac+ and mer+ isomers are of comparable stability.

Preliminary tools assisting collected building performance measurements

Investigating on-site building performance in architectural science is increasing. However, the simplest forms of measurement often lack any analytical support other than presentation on a time-series plot. Here, we present instrumentation and analytical tools to assist in reporting building performance. The intention is to explore formats for observing performance of buildings based on collected data. Sometimes data are presented directly, but more often, information is revealed by calculation. We introduce examples of tools pertaining to interior-exterior climatic comparisons, occupant comfort and thermal performance, such as weather data plotted against a neutral temperature so that adaptive model comfort tolerances can be illustrated. We plot the interior and exterior air condition on the ASHRAE psychrometric chart to understand conditioning requirements. Other tools calculate the ISO 7730 (Fanger) comfort model, and an adaptive model of comfort is provided for the interior measurements alongside an 80 – 90% comfort band. These tools add value to reporting data by displaying in several formats, so the researcher can observe and report quickly and clearly on the potential of various conditioning periods within a building.A case study is presented for a house in Darwin during the wet-season.