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.

Determination of sodium oxalate in Bayer liquor using flow-analysis incorporating an anion exchange column and tris(2,2`-bipyridyl)ruthenium(II) chemiluminescence detection

Semi-automated flow injection instrumentation, incorporating a small anion exchange column coupled with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bipy)₃²⁺) chemiluminescence detection, was configured and utilised to develop rapid methodology for the determination of sodium oxalate in Bayer liquors. The elimination of both negative and positive interferences from aluminium(III) and, as yet, unknown concomitant organic species, respectively are discussed. The robustness of the methodology was considerably enhanced by using the temporally stable form of the chemiluminescence reagent, tris(2,2′-bipyridyl)ruthenium(III) perchlorate in dry acetonitrile. Real Bayer process samples were analysed and the results obtained compared well with those performed using standard methods within industrial laboratories.

Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2’-bipyridyl)ruthenium(II) chemiluminescence

For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2′-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 × 10⁻⁷ M and 9 × 10⁻⁹ M for tris(2,2′-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4′-methyl-2,2′-bipyridine)bis(2,2′-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 × 10⁻⁷ M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 × 10⁻¹⁰ M using SIA.

Plant bioactive determinations using flow analysis, chromatography with chemiluminescence detection

The development of rapid analytical methodologies for the determination of plant bioactives including antioxidants, amino acids and opium alkaloids was investigated using novel flow analysis and liquid chromatographic techniques. These methodologies were applied to the wine, food and pharmaceutical industries.

Determination of sodium oxalate in Bayer process liquors using flow analysis with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection

The research was a detailed investigation into a challenging analytical chemistry problem for the alumina industry. The successful outcomes were derived through innovative reagent chemistry and novel instrumental development. The resultant methodology and instrumentation deployed on this most demanding sample matrix is more robust, reliable and less expensive than anything currently used in this industry worldwide.

An extended multivariate autoregressive framework for EEG-based information flow analysis of a brain network

Recently effective connectivity studies have gained significant attention among the neuroscience community as Electroencephalography (EEG) data with a high time resolution can give us a wider understanding of the information flow within the brain. Among other tools used in effective connectivity analysis Granger Causality (GC) has found a prominent place. The GC analysis, based on strictly causal multivariate autoregressive (MVAR) models does not account for the instantaneous interactions among the sources. If instantaneous interactions are present, GC based on strictly causal MVAR will lead to erroneous conclusions on the underlying information flow. Thus, the work presented in this paper applies an extended MVAR (eMVAR) model that accounts for the zero lag interactions. We propose a constrained adaptive Kalman filter (CAKF) approach for the eMVAR model identification and demonstrate that this approach performs better than the short time windowing-based adaptive estimation when applied to information flow analysis.

The relationship between labour market conditions and welfare receipt in Australia: A stock-flow analysis

Understanding the determinants of changes in welfare caseloads is an important, but little studied, topic in Australia. This paper evaluates the role of labour market conditions in explaining the changes in the Australian welfare caseload since the late 1990s. The paper employs a stock-flow approach to better control for persistence in welfare receipt and includes different specifications to deal with measurement error in labour market data. The results suggest that the labour market is an important determinant of movements on and off welfare, accounting for the majority of the caseload decline during 1997-2005. The results also highlight the importance of robustness checks when data are measured with error.

Application of extended multivariate modeling for information flow analysis of event related responses

Event related potential (ERP) analysis is one of the most widely used methods in cognitive neuroscience research to study the physiological correlates of sensory, perceptual and cognitive activity associated with processing information. To this end information flow or dynamic effective connectivity analysis is a vital technique to understand the higher cognitive processing under different events. In this paper we present a Granger causality (GC)-based connectivity estimation applied to ERP data analysis. In contrast to the generally used strictly causal multivariate autoregressive model, we use an extended multivariate autoregressive model (eMVAR) which also accounts for any instantaneous interaction among variables under consideration. The experimental data used in the paper is based on a single subject data set for erroneous button press response from a two-back with feedback continuous performance task (CPT). In order to demonstrate the feasibility of application of eMVAR models in source space connectivity studies, we use cortical source time series data estimated using blind source separation or independent component analysis (ICA) for this data set.

Multivariate autoregressive-based neuronal network flow analysis for in-vitro recorded bursts

Neuroscientific studies of in vitro neuron cell cultures has attracted paramount attention to investigate the behaviour of neuronal networks in response to different environmental conditions and external stimuli such as drugs, optical and electrical stimulations. Microelec trodearray (MEA) technology has been widely adopted as a tool for this investigation. In this work, we present a new approach to estimate interconnectivity of neural spikes using multivariate autoregressive (MVAR) analysis and Partial Directed Coherence (PDC). The proposed approach has the potential to discover hidden intra-burst causal connectivity patterns and to help understand the spatiotemporal communication patterns within bursts, pre and post stimulations.

Real-time traffic flow statistical analysis based on network-constrained moving object trajectories

In this paper, we propose a novel traffic flow analysis method, Network-constrained Moving Objects Database based Traffic Flow Statistical Analysis (NMOD-TFSA) model. By sampling and analyzing the spatial-temporal trajectories of network constrained moving objects, NMOD-TFSA can get the real-time traffic conditions of the transportation network. The experimental results show that, compared with the floating-car methods which are widely used in current traffic flow analyzing systems, NMOD-TFSA provides an improved performance in terms of communication costs and statistical accuracy.

Monitoring urea levels during haemodialysis with a pulsed-flow chemiluminescence analyser

We have developed a rapid and robust method for the determination of urea in spent haemodialysis fluid as a measure of the efficiency of haemodialysis treatments. A novel flow analysis instrument (which generates a pulsed solution flow) was coupled with a chemiluminescence detection system, based on the oxidation of urea with hypobromite. The ‘pulsed-flow chemiluminescence analyser’ exhibited high precision (1.6% relative standard deviation (R.S.D.) for a 1×10−5 M urea standard, n=10) and good limit of detection (9×10−7 M, S/N=3) as a result of the rapid and reproducible mixing of small volumes of reagent and sample at the point of detection. The proposed chemiluminescence technique and an established urease-based laboratory procedure were compared, and showed a very similar trend for the change in urea concentration during a typical haemodialysis treatment. The relative chemiluminescence response from the oxidation of species with similar structure has revealed the inherent selectivity of the light producing pathway, but a positive interference was obtained from protein when this technique was applied to the determination of urea in serum samples. Arginine was identified as the predominant source of this interference.

Improvements to separation and detection for forensic analysis of illicit substances

This article gives an overview of our recent research into separation and detection of analytes of forensic interest. This work has been carried out in collaboration with local forensic service providers and is based on our previous studies of chemiluminescence detection, flow analysis and capillary electrophoresis as applied to process analytical chemistry for the pharmaceutical industry. Chemiluminescence has the potential to provide low limits of detection in combination with high selectivity, while capillary electrophoresis allows for rapid, highly efficient separations. Examples of recent forensic applications are presented and future directions are discussed.

Chemiluminescence: liquid-phase

Article Outline
• Introduction
• Acidic Potassium Permanganate
• Acridinium Esters
• Diaryl Oxalates and Oxamides
• Dioxetanes
• Hypohalites
• Luminol and Its Analogs
• Tris(2,2′-bipyridyl)ruthenium(II)
• Practical Considerations
• HPLC and Flow Analysis
• Capillary Electrophoresis
• Enzyme Reaction Products
• Immunoassay and DNA Assays
• Further Reading

Chemiluminescence detection of opium poppy (papaver somniferum) alkaloids

A review with 98 references. The determination of the opium poppy (Papaver somniferum) alkaloids and their semi-synthetic derivatives has important applications in industrial process monitoring, clinical analysis and forensic science. Liquid-phase chemiluminescence reagents such as tris(2,2′-bipyridyl)ruthenium(II) and acidic potassium permanganate exhibit remarkable sensitivity and complementary selectivity for many P. somniferum alkaloids, which has been exploited in the development of a range of analytical procedures using flow analysis, high-performance liquid chromatography, capillary electrophoresis and microfluidic instrumentation.