Heuristic charge assignment for deconvolution of electrospray ionization mass spectra

We propose a new algorithm for deconvolution of electrospray ionization mass spectra based on direct assignment of charge to the measured signal at each mass-to-charge ratio (m/z). We investigate two heuristics for charge assignment: the entropy-based heuristic is adapted from a deconvolution algorithm by Reinhold and Reinhold;10 the multiplicative-correlation heuristic is adapted from the multiplicative-correlation deconvolution algorithm of Hagen and Monnig.6 The entropy-based heuristic is insensitive to overestimates of z(max), the maximum ion charge. We test the deconvolution algorithm on two single-component samples: the measured spectrum of human beta-endorphin has two prominent and one very weak line whereas myoglobin has a well-developed quasi-gaussian envelope of 17 peaks. In both cases, the deconvolution algorithm gives a clean deconvoluted spectrum with one dominant peak and very few artefacts. The relative heights of the peaks due to the parent molecules in the deconvoluted spectrum of a mixture of two peptides, which are expected to ionize with equal efficiency, give an accurate measure of their relative concentration in the sample.     

Effect of linewidth on the phaseshifts in the scattering of weakly amplitude modulated light

When light which is weakly modulated in amplitude is scattered from a two-level system a phase-shift occurs. We have calculated this phase-shift for a Lorentzian lineshape, and find it depends strongly on linewidth. Expressions are given which would enable a realistic comparison between theory and experiment to be made.     

Coulometric determination of serum iron

The iron in 500 μl of serum is determined by a coulometric titration developed for ferroin. The titration step is preceded by chloroform extraction from a protein-free filtrate of serum iron as ferroin perchlorate. Evaporation of chloroform in the presence of an acetate buffer of pH 4.6 causes the ferroin perchlorate to back-extract into the aqueous layer. The ferroin is introduced into a titration cell and titrated with electrogenerated cerium(IV), a modified amperometric end-point detection system being used.     

Highly sensitive fluorescence detection system for microfluidic lab-on-a-chip

We demonstrate a compact, low cost and practical fluorescence detection system for lab-on-a-chip applications. The system comprises a commercially available InGaN light emitting diode (501 nm) as light source, an organic or silicon photodiode detector, absorptive dye coated colour filters and linear and reflective polarisers. An injection moulded polystyrene microfluidic chip is used as the platform for fluorescence immunoassays for cardiac markers myoglobin and CK-MB. The optical limit of detection (LOD) is measured using a TransFluoSphere? suspension at 5.6 × 10(4) beads μl(-1) which can be equated to ～3 nM fluorescein equivalent concentration. The LOD for the human plasma immunoassays is measured as 1.5 ng ml(-1) for both myoglobin and CK-MB.     

A non-parametric competing risks model for manpower planning

One of the most important variables for manpower planners is duration until a specified event occurs. This is frequently the completed length of service until leaving a job, but may also include such variables as length of service in a grade until promotion, or length of a spell of withdrawal from the labour force. In this paper we develop non-parametric maximum likelihood estimators for the survivor functions of length of stay in a grade until leaving for a number of different possible destinations. Since the data are statistically incomplete, including right censored and left truncated durations, as well as complete durations, we must modify the competing risks theory in the biostatistical literature to take such incompleteness into account. Right censored durations arise when the individual is still in the grade when data collection ceases and left truncated durations when the individual is already in service when data collection commences. The competing risks model is fitted to data for Northern Ireland nursing service and used to predict staff flows between grades. We may thus estimate future movements within the system and predict the future manpower stocks.     

The Steady-State Behaviour of a Manpower Planning Model in Which Class Corresponds to Length of Service

We consider a discrete time Markov population model in which class corresponds to length of service. For this particular system it is shown that the steady state distributions of class sizes are independently Poisson. The model is applied to eight firms for which the steady state tenure distribution is evaluated.     

Heuristic Methods for the Data Placement Problem

Databases require a management system which is capable of retrieving and storing information as efficiently as possible. The data placement problem is concerned with obtaining an optimal assignment of data tuples onto secondary storage devices. Such tuples have complicated interrelationships which make it difficult to find an exact solution to our problem in a realistic time.We therefore consider heuristic methods—three of which are discussed and compared — the ‘greedy’ graph-collapsing method, the probabilistic hill-climbing method of simulated annealing and a third ‘greedy’ heuristic, the random improvement method, which is a local search heuristic. Overall, the best performance is obtained from the graph-collapsing method for the less complicated situations, but for larger-scale problems with complex interrelationships between tuples the simulated annealing and random improvement algorithms give better results.     

Estimation for incomplete manpower data

Much attention has been paid to both non-parametric and parametric estimation for survival data with right censoring, particularly in the medical literature. In manpower planning the completed length of service until leaving is of great interest, and here also the data are right censored since people are still in service when data collection ends. However, it often occurs that the data are also left truncated since people are already in service at the beginning of data collection. These people have often been neglected both in estimation of the empirical distribution function and also in fitting particular parametric distributions. However, it is important to include them so as to use all the data, particularly when data are only present for a short period. The methods developed were applied to data for the completed length of service of both skilled and unskilled workers where the data were collected over a period of years. Using modified Kaplan-Meier estimation, applied to these data sets, empirical distribution functions were obtained. A number of parametric distributions were also fitted. The goodness of fit of these distributions as predictors of leavers and stayers over a given period was then tested using a chi-squared test.     

A multi-phase DES modelling framework for patient-centred care

We provide a framework for simulating the entire patient journey across different phases (such as diagnosis, treatment, rehabilitation and long-term care) and different sectors (such as GP, hospital, social and community services), with the aim of providing better understanding of such processes and facilitating evaluation of alternative clinical and care strategies. A phase-type modelling approach is used to promote better modelling and management of the specific elements of a patient pathway, using performance measures such as clinical outcomes, patient quality of life, and cost. The approach is illustrated using stroke disease. Approximately 5% of the United Kingdom National Health Service budget is spent treating stroke disease each year. There is an urgent need to assess whether existing services are cost-effective or new interventions could increase efficiency. This assessment can be made using models across primary and secondary care; in particular we evaluate the cost-effectiveness of thrombolysis (clot busting therapy), using discrete event simulation. Using our model, patient quality of life and the costs of thrombolysis are compared under different regimes. In addition, our simulation framework is used to illustrate the impact of internal discharge queues, which can develop while patients are awaiting placement. Probabilistic Sensitivity Analysis of the value parameters is also carried out.