Square-wave adsorptive-stripping voltammetric detection in the quality control of fluoxetine

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with square-wave adsorptive-stripping voltammetric detection (FIA-SWAdSV) were developed for the determination of fluoxetine (FXT). The methods were based on the reduction of FXT at a mercury drop electrode at -1.2 V versus Ag/AgCl, in a phosphate buffer of pH 12.0, and on the possibility of accumulating the compound at the electrode surface. The SWAdSV method was successfully applied in the quantification of FXT in pharmaceutical products, human serum samples, and in drug dissolution studies. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was possible to quantify FXT in several pharmaceutical products using FIA-SWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs.

Voltammetric quantification of fluoxetine: application to quality control and quality assurance processes

The oxidative behaviour of fluoxetine was studied at a glassy carbon electrode in various buffer systems and at different pH using cyclic, differential pulse and square wave voltammetry. A new square wave voltammetric method suitable for the quality control of fluoxetine in commercial formulations has been developed using a borate pH 9 buffer solution as supporting electrolyte. Under optimized conditions, a linear response was obtained in the range 10 to 16 μM with a detection limit of 1.0 μM. Validation parameters such as sensitivity, precision and accuracy were evaluated. The proposed method was successfully applied to the determination of fluoxetine in pharmaceutical formulations. The results were statistically compared with those obtained by the reference high-performance liquid chromatographic method. No significant differences were found between the methods.

Practical Quality Control: Comparision of Methods on the Quantification of Stationary Phases in Paper and Thin-Layer Chromatographic Systems

Introduction: Paper and thin layer chromatography methods are frequently used in Classic Nuclear Medicine for the determination of radiochemical purity (RCP) on radiopharmaceutical preparations. An aliquot of the radiopharmaceutical to be tested is spotted at the origin of a chromatographic strip (stationary phase), which in turn is placed in a chromatographic chamber in order to separate and quantify radiochemical species present in the radiopharmaceutical preparation. There are several methods for the RCP measurement, based on the use of equipment as dose calibrators, well scintillation counters, radiochromatografic scanners and gamma cameras. The purpose of this study was to compare these quantification methods for the determination of RCP. Material and Methods: 99mTc-Tetrofosmin and 99mTc-HDP are the radiopharmaceuticals chosen to serve as the basis for this study. For the determination of RCP of 99mTc-Tetrofosmin we used ITLC-SG (2.5 x 10 cm) and 2-butanone (99mTc-tetrofosmin Rf = 0.55, 99mTcO4- Rf = 1.0, other labeled impurities 99mTc-RH RF = 0.0). For the determination of RCP of 99mTc-HDP, Whatman 31ET and acetone was used (99mTc-HDP Rf = 0.0, 99mTcO4- Rf = 1.0, other labeled impurities RF = 0.0). After the development of the solvent front, the strips were allowed to dry and then imaged on the gamma camera (256x256 matrix; zoom 2; LEHR parallel-hole collimator; 5-minute image) and on the radiochromatogram scanner. Then, strips were cut in Rf 0.8 in the case of 99mTc-tetrofosmin and Rf 0.5 in the case of 99mTc-HDP. The resultant pieces were smashed in an assay tube (to minimize the effect of counting geometry) and counted in the dose calibrator and in the well scintillation counter (during 1 minute). The RCP was calculated using the formula: % 99mTc-Complex = [(99mTc-Complex) / (Total amount of 99mTc-labeled species)] x 100. Statistical analysis was done using the test of hypotheses for the difference between means in independent samples. Results:The gamma camera based method demonstrated higher operator-dependency (especially concerning the drawing of the ROIs) and the measures obtained using the dose calibrator are very sensitive to the amount of activity spotted in the chromatographic strip, so the use of a minimum of 3.7 MBq activity is essential to minimize quantification errors. Radiochromatographic scanner and well scintillation counter showed concordant results and demonstrated the higher level of precision. Conclusions: Radiochromatographic scanners and well scintillation counters based methods demonstrate to be the most accurate and less operator-dependant methods.

Modelling and Control of Freeway Traffic

This paper presents the most recent developments of the Simulator of Intelligent Transportation Systems (SITS). The SITS is based on a microscopic simulation approach to reproduce real traffic conditions in an urban or non-urban network. In order to analyse the quality of the microscopic traffic simulator SITS a benchmark test was performed. A dynamical analysis of several traffic phenomena, applying a new modelling formalism based on the embedding of statistics and Laplace transform, is then addressed. The paper presents also a new traffic control concept applied to a freeway traffic system.

Iron oxide/gold core/shell nanomagnetic probes and CdS biolabels for amplified electrochemical immunosensing of Salmonella typhimurium

There is an imminent need for rapid methods to detect and determine pathogenic bacteria in food products as alternatives to the laborious and time-consuming culture procedures. In this work, an electrochemical immunoassay using iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-Salmonella antibodies was developed. The chemical synthesis and functionalization of magnetic and gold-coated magnetic nanoparticles is reported. Fe@Au nanoparticles were functionalized with different self-assembled monolayers and characterized using ultraviolet-visible spectrometry, transmission electron microscopy, and voltammetric techniques. The determination of Salmonella typhimurium, on screen-printed carbon electrodes, was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals. The calibration curve was established between 1×101 and 1×106 cells/mL and the limit of detection was 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1 h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.

Flow injection electrochemical determination of apomorphine

Few analytical methods are currently available for determination of apomorphine, the active substance of a new oral formulation used in the treatment of erectile dysfunction. In this way a flow injection electrochemical method (FIA-EC) was developed for its quantification and applied to pharmaceutical dosage forms. Based in previous findings regarding the stability of apomorphine in borate buffer and after optimization of several analytical parameters a single channel flow injection manifold was set up that enables the determination of this drug over the concentration range of 3 to 16 µmol L-1 with a detection limit of 0.5 µmol L-1 at a sampling rateof 90 h-1. The simplicity and rapidity of the FIA-EC method used, its reproducibility and sensitivity make it suitable for quality control of pharmaceutical preparations of apomorphine intended for clinical use and research.

Electrochemical determination of dihydrocodeine in pharmaceuticals

Two analytical methods for the quality control of dihydrocodeine in commercial pharmaceutical formulations have been developed and compared with reference methods: a square wave voltammetric (SWV) method and a flow injection analysis system with electrochemical detection (FIA-EC). The electrochemical methods proposed were successfully applied to the determination of dihydrocodeine in pharmaceutical tablets and in oral solutions. These methods do not require any pretreatment of the samples, the formulation only being dissolved in a suitable electrolyte. Validation of the methods showed it to be precise, accurate and linear over the concentration range of analysis. The automatic procedure based on a flow injection analysis manifold allows a sampling rate of 115 determinations per hour.

Influence of wearing an unstable shoe construction on compensatory control of posture

This study investigated the influence of wearing unstable shoe construction (WUS) on compensatory postural adjustments (CPA) associated with external perturbations. Thirty-two subjects stood on a force platform resisting an anterior-posterior horizontal force applied to a pelvic belt via a cable, which was suddenly released. They stood under two conditions: barefoot and WUS. The electromyographic (EMG) activity of gastrocnemius medialis, tibialis anterior, rectus femoris, biceps femoris, rectus abdominis, and erector spinae muscles and the center of pressure (CoP) displacement were acquired to study CPA. The EMG signal was used to assess individual muscle activity and latency, antagonist co-activation and reciprocal activation at joint and muscle group levels. Compared to barefoot, WUS led to: (1) increased gastrocnemius medialis activity, (2) increased total agonist activity, (3) decreased antagonist co-activation at the ankle joint and muscle group levels, (4) increased reciprocal activation at the ankle joint and muscle group levels, and (5) decrease in all muscle latencies. No differences were observed in CoP displacement between conditions. These findings demonstrate that WUS led to a reorganization of the postural control system associated to improved performance of some components of postural control responses.

Influence of long-term wearing of unstable shoes on compensatory control of posture: An electromyography-based analysis

Purpose: This study investigated the influence of long-term wearing of unstable shoes (WUS) on compensatory postural adjustments (CPA) to an external perturbation. Methods: Participants were divided into two groups: one wore unstable shoes while the other wore conventional shoes for 8 weeks. The ground reaction force signal was used to calculate the anterior– posterior (AP) displacement of the centre of pressure (CoP) and the electromyographic signal of gastrocnemius medialis (GM), tibialis anterior (TA), rectus femoris (RF) and biceps femoris (BF) muscles was used to assess individual muscle activity, antagonist co-activation and reciprocal activation at the joint (TA/GM and RF/(BF + GM) pairs) and muscle group levels (ventral (TA + RF)/dorsal (GM + BF) pair) within time intervals typical for CPA. The electromyographic signal was also used to assess muscle latency. The variables described were evaluated before and after the 8-week period while wearing the unstable shoes and barefoot. Results: Long-term WUS led to: an increase of BF activity in both conditions (barefoot and wearing the unstable shoes); a decrease of GM activity; an increase of antagonist co-activation and a decrease of reciprocal activation level at the TA/GM and ventral/dorsal pairs in the unstable shoe condition. Additionally, WUS led to a decrease in CoP displacement. However, no differences were observed in muscle onset and offset. Conclusion: Results suggest that the prolonged use of unstable shoes leads to increased ankle and muscle groups’ antagonist co-activation levels and higher performance by the postural control system.

Application of continuous wavelet transform to the analysis of the modulus of the fractional Fourier transform bands for resolving two component mixture

In this paper, the fractional Fourier transform (FrFT) is applied to the spectral bands of two component mixture containing oxfendazole and oxyclozanide to provide the multicomponent quantitative prediction of the related substances. With this aim in mind, the modulus of FrFT spectral bands are processed by the continuous Mexican Hat family of wavelets, being denoted by MEXH-CWT-MOFrFT. Four modulus sets are obtained for the parameter a of the FrFT going from 0.6 up to 0.9 in order to compare their effects upon the spectral and quantitative resolutions. Four linear regression plots for each substance were obtained by measuring the MEXH-CWT-MOFrFT amplitudes in the application of the MEXH family to the modulus of the FrFT. This new combined powerful tool is validated by analyzing the artificial samples of the related drugs, and it is applied to the quality control of the commercial veterinary samples.

Hybrid adaptive control of a dragonfly model

Dragonflies show unique and superior flight performances than most of other insect species and birds. They are equipped with two pairs of independently controlled wings granting an unmatchable flying performance and robustness. In this paper, it is presented an adaptive scheme controlling a nonlinear model inspired in a dragonfly-like robot. It is proposed a hybrid adaptive (HA) law for adjusting the parameters analyzing the tracking error. At the current stage of the project it is considered essential the development of computational simulation models based in the dynamics to test whether strategies or algorithms of control, parts of the system (such as different wing configurations, tail) as well as the complete system. The performance analysis proves the superiority of the HA law over the direct adaptive (DA) method in terms of faster and improved tracking and parameter convergence.

Control of baker’s yeast fermentation: PID and fuzzy algorithms

A MATLAB/SIMULINK-based simulator was employed for studies concerning the control of baker’s yeast fed-batch fermentation. Four control algorithms were implemented and compared: the classical PID control, two discrete versions- modified velocity and position algorithms, and a fuzzy law. The simulation package was seen to be an efficient tool for the simulation and tests of control strategies of the nonlinear process.

Using attractor dynamics to generate decentralized motion control of two mobile robots transporting a long object in coordination

Dynamical systems theory is used here as a theoretical language and tool to design a distributed control architecture for a team of two mobile robots that must transport a long object and simultaneously avoid obstacles. In this approach the level of modeling is at the level of behaviors. A “dynamics” of behavior is defined over a state space of behavioral variables (heading direction and path velocity). The environment is also modeled in these terms by representing task constraints as attractors (i.e. asymptotically stable states) or reppelers (i.e. unstable states) of behavioral dynamics. For each robot attractors and repellers are combined into a vector field that governs the behavior. The resulting dynamical systems that generate the behavior of the robots may be nonlinear. By design the systems are tuned so that the behavioral variables are always very close to one attractor. Thus the behavior of each robot is controled by a time series of asymptotically stable states. Computer simulations support the validity of our dynamic model architectures.

Modeling and control of a dragonfly-like robot

Dragonflies demonstrate unique and superior flight performances than most of the other insect species and birds. They are equipped with two pairs of independently controlled wings granting an unmatchable flying performance and robustness. In this paper, the dynamics of a dragonfly-inspired robot is studied. The system performance is analyzed in terms of time response and robustness. The development of computational simulation based on the dynamics of the robotic dragonfly allows the test of different control algorithms. We study different movements, the dynamics, and the level of dexterity in wing motion of the dragonfly. The results are positive for the construction of flying platforms that effectively mimic the kinematics and dynamics of dragonflies and potentially exhibit superior flight performance than existing flying platforms.