Electrochemical determination of acetaminophen at a carbon electrode modified in the presence of β-cyclodextrin: role of the activated glassy carbon and the electropolymerised β-cyclodextrin

Acetaminophen is a well-known drug commonly used to provide pain relief, but it can also lead to acute liver failure at high concentrations. Therefore, there is considerable interest in monitoring its concentrations. Sensitive and selective acetaminophen electrochemical sensors were designed by cycling a glassy carbon electrode (GCE) to high potentials in the presence of β-CD in a phosphate electrolyte, or by simply activating the GCE electrode in the phosphate solution. Using cyclic voltammetry, adsorption-like voltammograms were recorded. The acetaminophen oxidation product, N-acetyl benzoquinone imine, was protected from hydrolysis, and this was attributed to the adsorption of acetaminophen at the modified GCE. The rate constants for the oxidation of acetaminophen were estimated as 4.3 × 10^–3 cm² s^–1 and 3.4 × 10^–3 cm² s^–1 for the β-CD-modified and -activated electrodes, respectively. Using differential pulse voltammetry, the limit of detection was calculated as 9.7 × 10^–8 M with a linear concentration range extending from 0.1 to 80 μM. Furthermore, good selectivity was achieved in the presence of caffeine, ascorbic acid and aspirin, enabling the determination of acetaminophen in a commercial tablet. Similar electrochemical data were obtained for both the β-CD-modified and activated GCE surfaces, suggesting that the enhanced detection of acetaminophen is connected mainly to the activation and oxidation of the GCE. Using SEM, EDX and FTIR, no evidence was obtained to indicate that the β-CD was electropolymerised at the GCE.

     

Bounds in Multistage Linear Stochastic Programming

Multistage stochastic programs, which involve sequences of decisions over time, are usually hard to solve in realistically sized problems. Providing bounds for optimal solution may help in evaluating whether it is worth the additional computations for the stochastic program vs. simplified approaches. In this paper we generalize measures from the two-stage case, based on different levels of available information, to the multistage stochastic programming problems. A set of theorems providing chains of inequalities among the new quantities are proved. Numerical results on a case study related to a simple transportation problem illustrate the described relationships.     

Testing the structure of multistage stochastic programs

A fixed topology of stages and/or a fixed branching scheme are common assumptions for applications and numerical solution of scenario based multistage stochastic programs. Using contamination technique to test this structure, we extend the results of Dupačová (Contamination for multistage stochastic programs. In: Hušková M, Janžura M (eds) Prague stochastics. Matfyzpress, Praha, pp 91–101, 2006a) to stochastic programs with multistage polyhedral risk objectives. The ideas are exemplified by bond portfolio management problems and complemented by illustrative numerical results.     

Monotonic bounds in multistage mixed-integer stochastic programming

Multistage stochastic programs bring computational complexity which may increase exponentially with the size of the scenario tree in real case problems. For this reason approximation techniques which replace the problem by a simpler one and provide lower and upper bounds to the optimal value are very useful. In this paper we provide monotonic lower and upper bounds for the optimal objective value of a multistage stochastic program. These results also apply to stochastic multistage mixed integer linear programs. Chains of inequalities among the new quantities are provided in relation to the optimal objective value, the wait-and-see solution and the expected result of using the expected value solution. The computational complexity of the proposed lower and upper bounds is discussed and an algorithmic procedure to use them is provided. Numerical results on a real case transportation problem are presented.     

A stochastic model for investments in different technologies for electricity production in the long period

We present a single stage stochastic mixed integer linear model for determining the optimal mix of different technologies for electricity generation, ranging from coal, nuclear and combined cycle gas turbine to hydroelectric, wind and photovoltaic, taking into account the existing plants, the cost of investment in new plants, maintenance costs, purchase and sale of ${CO}_2$ emission trading certificates and green certificates, in order to satisfy regulatory requirements. The power producer is assumed to be a price-taker. Stochasticity of future fuel prices, which affect the generation variable costs, is included in the model by means of a set of scenarios. The main contribution of the paper, beyond considering stochasticity in the future fuel prices, is the introduction of CVaR risk measure in the objective function in order to limit the possibility of low profits in bad scenarios with a fixed confidence level.     

Focused Microwave-Assisted Extraction and LC Determination of Ketoprofen in the Presence of Preservatives in a Pharmaceutical Cream Formulation

A simple and rapid open-vessel focused microwave-assisted extraction (FMAE) method followed by LC analysis was developed for the determination of ketoprofen lysine salt in the presence of methyl p-hydroxybenzoate and propyl p-hydroxybenzoate preservatives in topical cream. Extraction were performed in acetone/potassium dihydrogenphosphate (25 mM, pH 3.0) (70:30 v/v) by reaching a target temperature of 65 °C in a 10 min linear ramp. The chromatographic separation was performed on a Discovery RP-Amide C16 column (250 × 4.6 mm I.D., 5 μm particle size). The optimal mobile phase consisted of acetonitrile/potassium dihydrogen phosphate 25 mM adjusted to pH 3.0 with phosphoric acid (50:50 v/v). The complete analytical procedure was validated with regard to limit of quantification, linearity, precision and accuracy. The method was linear over the concentration range of 0.08–0.12 mg mL⁻¹; the relative standard deviations of intra- and inter-day assays were 1.9–2.3 and 1.8% respectively. The limit of quantification was 0.54 μg mL⁻¹. The proposed method shows many advantages as short extraction time, little solvent consumption without requiring further sample clean-up steps before liquid chromatographic analysis and is proposed for vast scale screening of cream dosage forms aimed to the detection of counterfeit and substandard drugs.

     

A stochastic model for the daily coordination of pumped storage hydro plants and wind power plants

We propose a stochastic model for the daily operation scheduling of a generation system including pumped storage hydro plants and wind power plants, where the uncertainty is represented by the hourly wind power production. In order to assess the value of the stochastic modeling, we discuss two case studies: in the former the scenario tree is built so as to include both low and high wind power production scenarios, in the latter the scenario tree is built on historical wind speed data covering a time span of one and a half year. The Value of the Stochastic Solution, computed by a modified new procedure, shows that in scenarios with low wind power production the stochastic solution allows the producer to obtain a profit which is greater than the one associated to the deterministic solution. In-sample stability of the optimal function values for increasing number of scenarios is reported.     

A leader-followers model of power transmission capacity expansion in a market driven environment

We introduce a model for analyzing the upgrade of the national transmission grid that explicitly accounts for responses given by the power producers in terms of generation unit expansion. The problem is modeled as a bilevel program with a mixed integer structure in both upper and lower level. The upper level is defined by the transmission company problem which has to decide on how to upgrade the network. The lower level models the reactions of both power producers, who take a decision on new facilities and power output, and Market Operator, which strikes a new balance between demand and supply, providing new Locational Marginal Prices. We illustrate our methodology by means of an example based on the Garver’s 6-bus Network.     

Bond portfolio management with repo contracts: the Italian case

In this paper we present a model for management of bond portfolio including financing and investment repo contracts. Different specifications are suggested in order to reduce the problem to a linear programming problem and to consider a self-financing portfolio. The models are tested on historical data assuming a technical time scale equal to the minimum length of the contracts in the portfolio. We also compared different operative strategies on a time horizon of one month. This revised version was published online in June 2006 with corrections to the Cover Date.