Evaluation of micellar liquid chromatography and capillary zone electrophoresis for dope control in sport

Micellar liquid chromatography (MLC) and capillary zone electrophoresis (CZE) have been evaluated for the analysis of twelve banned drugs in sport including diuretics and -blockers. In MLC, a sodium dodecylsulphate aqueous solution has been used as mobile phase using an octadecylsilica column. In CZE, a pH 8 buffer solution and a silica capillary have been employed. Parameters of retention and efficiency have been compared. Limits of detection with UV detection at 254 nm and relative standard deviations for atenolol, furosemide, nadolol, spironolactone and triamterene were established and compared in both techniques. Examples of direct urine injection into the separation systems are presented. Drugs overlapping in MLC are well resolved in CZE, while the opposite is true for a limited number of drugs. Some interferences from urine may arise in CZE. The selectivity of analysis would be greatly enhanced by using both techniques, which require only filtration as pre-treatment.     

Optimality of a Threshold Policy in theM/M/ queue with repeated vacations

Consider anM/M/1 queueing system with server vacations where the server is turned off as soon as the queue gets empty. We assume that the vacation durations form a sequence of i.i.d. random variables with exponential distribution. At the end of a vacation period, the server may either be turned on if the queue is non empty or take another vacation. The following costs are incurred: a holding cost ofh per unit of time and per customer in the system and a fixed cost of each time the server is turned on. We show that there exists a threshold policy that minimizes the long-run average cost criterion. The approach we use was first proposed in Blanc et al. (1990) and enables us to determine explicitly the optimal threshold and the optimal long-run average cost in terms of the model parameters.     

Measurement scheduling for recursive team estimation

We consider a decentralized LQG measurement scheduling problem in which every measurement is costly, no communication between observers is permitted, and the observers' estimation errors are coupled quadratically. This setup, motivated by considerations from organization theory, models measurement scheduling problems in which cost, bandwidth, or security constraints necessitate that estimates be decentralized, although their errors are coupled. We show that, unlike the centralized case, in the decentralized case the problem of optimizing the time integral of the measurement cost and the quadratic estimation error is fundamentally stochastic, and we characterize the -optimal open-loop schedules as chattering solutions of a deterministic Lagrange optimal control problem. Using a numerical example, we describe also how this deterministic optimal control problem can be solved by nonlinear programming.This research was supported in part by ARPA Grant N00174-91-C-0116 and NSF Grant NCR-92-04419.     

Langevin dynamic simulation of hysteresis in a field-swept Landau potential

Numerical simulations are done of Langevin dynamics for a uniform-orderparameter, field-swept Landau model,= –|a/2|m ²+|b/4|m ⁴–mh(t) , to study hysteresis effects. The field is swept at a constant rateh(t)=h(0)+ht. The stochastic jump values of the field {h_J from an initially prepared metastable minimumm(0) are recorded, on passage to a global minimum m(). The results are: (a) The mean jump¯h _J(h) increases (hysteresis loop widens) with h, confirming a previous theoretical criterion based on rate competition between field-sweep and inverse mean first-passage time (FPT); (b) The broad jump distribution(h _J,h) is related to intrinsically large FPT fluctuations ( ²–²)/ ² O(1), and can be quantitatively understood. Possible experimental tests of the ideas are indicated.     

High throughput continuous titration based on a flow ratiometry controlled with feedback-based variable triangular waves and subsequent fixed triangular waves

We propose a new approach for high-throughput continuous titration based on a flow ratiometry. The method was applied to potentiometric titrations of acids and bases. A base solution, the flow rate F_B of which was varied in response to controller output voltage V_c, was merged with an acid solution under constant total (acid + base) flow rate. Downstream, the pH of the mixed solution was measured with a flow-through glass electrode. Initially, V_c, and thus F_B was increased linearly. At the instant the equivalence point (EP) was sensed, the ramp direction of V_c was reversed from upward to downward. The direction was reversed to upward when EP was sensed again. Such the feedback-based operation gives a triangular waveform of V_c, because there is a delay corresponding mainly to the transit time of merged solutions to reach the sensor. The value of V_c that gives EP composition, V_E, was estimated by averaging the most recent maximum and minimum values of V_c. Next, fixed triangular waves of V_c was used to control F_B. The amplitude and the scan rate of the waves were fixed narrower and faster, respectively, than those in the feedback-based operation in order to improve the throughput rate. The EP can be located as long as the scan range covers V_E. These automated processes limited the titration to just the narrow range around EP, and thus realized extremely high throughput rate of maximally 17.6 titrations per minute (=3.4 s per titration) at R.S.D. = 0.35%.     

Rapid dissolution procedure for base-metals-bearing complex materials for quality control assessment

A less labour-intensive method, involving a mixture of 1.0 g MnO₂ + 20 mL HCl (11), is proposed for decomposing seven ores and six metallurgical products for accurate and precise estimation of copper, lead, zinc, cobalt and nickel for quality control assessment. Twentyone international reference materials were also analysed. Results of regression analyses are presented and intermethod comparison studies reveal that the probability of results being different compared with a reference method was less than 1%. Sample decomposition is straightforward and the method has been found to be very simple, rapid and easily adaptable, as it involves no separation of the analyte from the matrix elements.     

Quality assurance and statistical control

In scientific research laboratories it is rarely possible to use quality assurance schemes, developed for large-scale analysis. Instead methods have been developed to control the quality of modest numbers of analytical results by relying on statistical control: Analysis of precision serves to detect analytical errors by comparing thea priori precision of the analytical results with the actual variability observed among replicates or duplicates. The method relies on the chi-square distribution to detect excess variability and is quite sensitive even for 5–10 results. Interference control serves to detect analytical bias by comparing results obtained by two different analytical methods, each relying on a different detection principle and therefore exhibiting different influence from matrix elements; only 5–10 sets of results are required to establish whether a regression line passes through the origo. Calibration control is an essential link in the traceability of results. Only one or two samples of pure solid or aqueous standards with accurately known content need to be analyzed. Verification is carried out by analyzing certified reference materials from BCR, NIST, or others; their limited accuracy of 5–10% make them less suitable for calibration purposes.     

High solids content emulsion terpolymerization of vinyl acetate,methyl methacrylate and butyl acrylate. II. Open loop composition control

A method for the calculation of the optimal monomer addition policies for polymer composition control in emulsion terpolymerization is developed. The method is applied to reactors with and without limited heat removal capacity. A mathematical model that incorporates the main features of the vinyl acetate/methyl methacrylate/butyl acrylate high solids content emulsion terpolymerization system allows the calculation of the composition of the initial charge of the reactor and the time-dependent monomer addition rates required. © 1994 John Wiley & Sons, Inc.     

Evaluation of the limit of performance of an analytical method based on a statistical calculation of its critical concentrations according to ISO standard 11843: Application to routine control of banned veterinary drug residues in food according to European Decision 657/2002/EC

Traceability of the measurement of analytical parameters capable of evaluating the performance of methods is an important concept for the assessment of quality for the routine control, especially for residue monitoring of non-authorized medicinal substances in food from animal origin. The European Decision no. 657/2002/EC recommends to calculate two statistical limits, CCα and CCβ, which allow to evaluate the critical concentrations above which the method reliably distinguish and quantify a substance taking into account the variability of the method and the statistical risk to take a wrong decision. The calculation, which can be derived from the ISO standard no. 11843 is applied on a routine basis. An example displays a very simple way for evaluating the performance of an LC-MSMS method which has been validated a few years ago and is qualified onto a Micromass Quattro LCZ tandem mass spectrometer to monitor and confirm the nitrofuran metabolite residues in food from animal origin. Community Reference Laboratory for Antimicrobial Veterinary Drug Residue Control in Food from Animal Origin     

A discrete method of optimal control based upon the cell state space concept

A discrete method of optimal control is proposed in this paper. The continuum state space of a system is discretized into a cell state space, and the cost function is discretized in a similar manner. Assuming intervalwise constant controls and using a finite set of admissible control levels (u) and a finite set of admissible time intervals (), the motion of the system under all possible interval controls (u, ) can then be expressed in terms of a family of cell-to-cell mappings. The proposed method extracts the optimal control results from these mappings by a systematic search, culminating in the construction of a discrete optimal control table.The possibility of expressing the optimal control results in the form of a control table seems to give this method a means to make systems real-time controllable.Dedicated to G. LeitmannThe material is based upon work supported by the National Science Foundation under Grant No. MEA-82-17471. The author is also indebted to Professor G. Leitmann for his many helpful comments.