Photometric procedure for quantitative analysis of Aflatoxin B1 in peanuts by thin-layer chromatography using charge coupled device detector

A photometric procedure was developed for determination of aflatoxin B1 in peanuts by TLC-CCD technique. The quantification and detection limit were 1.2 μg kg-1 and 0.4 ng per spot, respectively, with mean recovery of 98%. The CCD camera is sufficiently sensitive to detect small changes in spots fluorescence intensity and the results for performance confirmed the efficiency of the method. Another important property of CCD detector is its linearity for a wide range of luminous stimulus determined by analysis of five-point calibration curves using the intensity of AFB1 fluorescence versus AFB1 concentration (0.8 to 4.8 ng per spot). The method was applied to the analysis of thirty nine peanut samples and aflatoxin B1 levels ranged from 16 to 115 μg kg-1. The TLC-CCD and the photometric procedure developed in this study demonstrated to be a simple and efficient tool for quantitative analyses of AFB1 in peanut samples.

Development and validation of a dissolution test with reversed-phase liquid chromatography analysis for rupatadine in tablet dosage forms

A dissolution test for in vitro evaluation of tablet dosage forms containing 10 mg of rupatadine was developed and validated by RP-LC. A discriminatory dissolution method was established using apparatus paddle at a stirring rate of 50 rpm with 900 mL of deaerated 0.01 M hydrochloric acid. The proposed method was validated yielding acceptable results for the parameters evaluated, and was applied for the quality control analysis of rupatadine tablets, and to evaluate the formulation during an accelerated stability study. Moreover, quantitative analyses were also performed, to compare the applicability of the RP-LC and the LC-MS/MS methods.

Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C) are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

Characterization of the antibiotic doripenem using physicochemical methods: chromatography, spectrophotometry, spectroscopy and thermal analysis

Doripenem was characterized through physicochemical and spectroscopic techniques, as well as thermal analysis. TLC (Rf = 0.62) and HPLC (rt = 7.4 min) were found to be adequate to identify the drug. UV and infrared spectra showed similar profile between doripenem bulk and standard. The ¹H and 13C NMR analysis revealed chemical shifts that allowed identifying the drug. Thermal analysis demonstrated three steps with mass loss, at 128, 178 and 276 ºC. The work was successfully applied to qualitative analysis of doripenem, showing the reported methods can be used for physicochemical characterization of doripenem

Liquid-phase microextraction for simultaneous chromatographic analysis of three antidepressant drugs in plasma

A method using Liquid Phase Microextraction for simultaneous detection of citalopram (CIT), paroxetine (PAR) and fluoxetine (FLU), using venlafaxine as internal standard, in plasma by high performance liquid chromatography with fluorescence detection was developed. The linearity was evaluated between 5.0 and 500 ng mL-1 (r > 0.99) and the limit of quantification was 2.0, 3.0 and 5.0 ng mL-1 for CIT, PAR and FLU, respectively. Therefore, it can be applied to therapeutic drug monitoring, pharmacokinetics or bioavailability studies and its advantages are that it necessary relatively inexpensive equipment and sample preparation techniques.

A quantitative validated method using liquid chromatography and chemometric analysis for evaluation of raw material oF Maytenus ilicifolia (Schrad.) Planch., Celastraceae

The hydroalcoholic extracts prepared from standard leaves of Maytenus ilicifolia and commercial samples of espinheira-santa were evaluated qualitatively (fingerprinting) and quantitatively. In this paper, fingerprinting chromatogram coupled with Principal Component Analysis (PCA) is described for the metabolomic analysis of standard and commercial espinheira-santa samples. The epicatechin standard was used as an external standard for the development and validation of a quantitative method for the analysis in herbal medicines using a photo diode array detector. This method has been applied for quantification of epicatechin in commercialized herbal medicines sold as espinheira-santa in Brazil and in the standard sample of M. ilicifolia.

Simultaneous analysis of saturated and unsaturated fatty acids present in pequi fruits by capillary electrophoresis

In the current study, an alternative method has been proposed for simultaneous analysis of palmitic, stearic, oleic, linoleic, and linolenic acids by capillary zone electrophoresis (CZE) using indirect detection. The background electrolyte (BGE) used for the analysis of these fatty acids (FAs) consisted of 15.0 mmol L−1 NaH2PO4/Na2HPO4 at pH 6.86, 4.0 mmol L−1 SDBS, 8.3 mmol L−1 Brij 35, 45% v/v acetonitrile (can), and 2.1% n-octanol. The FAs quantification of FAs was performed using a response factor approach, which provided a high analytical throughput for the real sample. The CZE method, which was applied successfully for the analysis of pequi pulp, has advantages such as short analysis time, absence of lipid fraction extraction and derivatization steps, and no significant difference in the 95% confidence intervals for FA quantification results, compared to the gas chromatography official method (AOCS Ce 1h-05).

A FACTORIAL DESIGN APPLIED TO THE STUDY OF CHROMIUM TOXICITY ON THE GLUTATHIONE LEVELS OF Brachiaria brizantha AND Brachiaria ruziziensis SEEDLINGS

Chromium toxicity affects redox reactions within plant cells, generating detrimental reactive oxygen species. Glutathione is an antioxidant peptide and also a substrate for the production of phytochelatins, which are chelating peptides reported to mitigate Cr3+ toxicity in plants. In this study, Brachiaria brizantha (B. brizantha) and Brachiaria ruziziensis (B. ruziziensis) seedlings were evaluated for physiological responses and glutathione production following the addition of zero or 5 mg L-1 Cr3+ to the nutrient solution. Glutathione levels were determined by colorimetric analysis at 412 nm using 5,5'-dithio-bis(2-nitrobenzoic acid) as a chromophore reagent and recovery with glutathione reductase (with evaluations at days 10 and 20 of continuous growth). The assessments were carried out in a completely randomized design with 2 authentic replications, and arranged in a 23 factorial. Cr3+ caused an average increase of 0.76 mg g-1 in the initial glutathione content. However, by day 20 there was an average reduction of 3.63 mg g-1. Chromium-affected physiological detrimental responses, albeit detected in both species, were less-pronounced in B. ruziziensis, along with a much higher level of glutathione. This study indicates that B. ruziziensis has a greater tolerance for chromium toxicity than B. brizantha, and that glutathione is likely to be involved in the mitigation of chromium stress in B. ruziziensis.

Comparison Structure Analysis

This study presents an automatic, computer-aided analytical method called Comparison Structure Analysis (CSA), which can be applied to different dimensions of music. The aim of CSA is first and foremost practical: to produce dynamic and understandable representations of musical properties by evaluating the prevalence of a chosen musical data structure through a musical piece. Such a comparison structure may refer to a mathematical vector, a set, a matrix or another type of data structure and even a combination of data structures. CSA depends on an abstract systematic segmentation that allows for a statistical or mathematical survey of the data. To choose a comparison structure is to tune the apparatus to be sensitive to an exclusive set of musical properties. CSA settles somewhere between traditional music analysis and computer aided music information retrieval (MIR). Theoretically defined musical entities, such as pitch-class sets, set-classes and particular rhythm patterns are detected in compositions using pattern extraction and pattern comparison algorithms that are typical within the field of MIR. In principle, the idea of comparison structure analysis can be applied to any time-series type data and, in the music analytical context, to polyphonic as well as homophonic music. Tonal trends, set-class similarities, invertible counterpoints, voice-leading similarities, short-term modulations, rhythmic similarities and multiparametric changes in musical texture were studied. Since CSA allows for a highly accurate classification of compositions, its methods may be applicable to symbolic music information retrieval as well. The strength of CSA relies especially on the possibility to make comparisons between the observations concerning different musical parameters and to combine it with statistical and perhaps other music analytical methods. The results of CSA are dependent on the competence of the similarity measure. New similarity measures for tonal stability, rhythmic and set-class similarity measurements were proposed. The most advanced results were attained by employing the automated function generation – comparable with the so-called genetic programming – to search for an optimal model for set-class similarity measurements. However, the results of CSA seem to agree strongly, independent of the type of similarity function employed in the analysis.

Parallel-Operating Three-Phase Voltage Source Inverters – Circulating CurrentModeling, Analysis and Mitigation

The maximum realizable power throughput of power electronic converters may be limited or constrained by technical or economical considerations. One solution to this problemis to connect several power converter units in parallel. The parallel connection can be used to increase the current carrying capacity of the overall system beyond the ratings of individual power converter units. Thus, it is possible to use several lower-power converter units, produced in large quantities, as building blocks to construct high-power converters in a modular manner. High-power converters realized by using parallel connection are needed for example in multimegawatt wind power generation systems. Parallel connection of power converter units is also required in emerging applications such as photovoltaic and fuel cell power conversion. The parallel operation of power converter units is not, however, problem free. This is because parallel-operating units are subject to overcurrent stresses, which are caused by unequal load current sharing or currents that flow between the units. Commonly, the term ’circulatingcurrent’ is used to describe both the unequal load current sharing and the currents flowing between the units. Circulating currents, again, are caused by component tolerances and asynchronous operation of the parallel units. Parallel-operating units are also subject to stresses caused by unequal thermal stress distribution. Both of these problemscan, nevertheless, be handled with a proper circulating current control. To design an effective circulating current control system, we need information about circulating current dynamics. The dynamics of the circulating currents can be investigated by developing appropriate mathematical models. In this dissertation, circulating current models aredeveloped for two different types of parallel two-level three-phase inverter configurations. Themodels, which are developed for an arbitrary number of parallel units, provide a framework for analyzing circulating current generation mechanisms and developing circulating current control systems. In addition to developing circulating current models, modulation of parallel inverters is considered. It is illustrated that depending on the parallel inverter configuration and the modulation method applied, common-mode circulating currents may be excited as a consequence of the differential-mode circulating current control. To prevent the common-mode circulating currents that are caused by the modulation, a dual modulator method is introduced. The dual modulator basically consists of two independently operating modulators, the outputs of which eventually constitute the switching commands of the inverter. The two independently operating modulators are referred to as primary and secondary modulators. In its intended usage, the same voltage vector is fed to the primary modulators of each parallel unit, and the inputs of the secondary modulators are obtained from the circulating current controllers. To ensure that voltage commands obtained from the circulating current controllers are realizable, it must be guaranteed that the inverter is not driven into saturation by the primary modulator. The inverter saturation can be prevented by limiting the inputs of the primary and secondary modulators. Because of this, also a limitation algorithm is proposed. The operation of both the proposed dual modulator and the limitation algorithm is verified experimentally.

Utilization of a Time Domain Simulator in the Technical and Economic Analysis of a Wind Turbine Electric Drive Train

The amount of installed wind power has been growing exponentially during the past ten years. As wind turbines have become a significant source of electrical energy, the interactions between the turbines and the electric power network need to be studied more thoroughly than before. Especially, the behavior of the turbines in fault situations is of prime importance; simply disconnecting all wind turbines from the network during a voltage drop is no longer acceptable, since this would contribute to a total network collapse. These requirements have been a contributor to the increased role of simulations in the study and design of the electric drive train of a wind turbine. When planning a wind power investment, the selection of the site and the turbine are crucial for the economic feasibility of the installation. Economic feasibility, on the other hand, is the factor that determines whether or not investment in wind power will continue, contributing to green electricity production and reduction of emissions. In the selection of the installation site and the turbine (siting and site matching), the properties of the electric drive train of the planned turbine have so far been generally not been taken into account. Additionally, although the loss minimization of some of the individual components of the drive train has been studied, the drive train as a whole has received less attention. Furthermore, as a wind turbine will typically operate at a power level lower than the nominal most of the time, efficiency analysis in the nominal operating point is not sufficient. This doctoral dissertation attempts to combine the two aforementioned areas of interest by studying the applicability of time domain simulations in the analysis of the economicfeasibility of a wind turbine. The utilization of a general-purpose time domain simulator, otherwise applied to the study of network interactions and control systems, in the economic analysis of the wind energy conversion system is studied. The main benefits of the simulation-based method over traditional methods based on analytic calculation of losses include the ability to reuse and recombine existing models, the ability to analyze interactions between the components and subsystems in the electric drive train (something which is impossible when considering different subsystems as independent blocks, as is commonly done in theanalytical calculation of efficiencies), the ability to analyze in a rather straightforward manner the effect of selections other than physical components, for example control algorithms, and the ability to verify assumptions of the effects of a particular design change on the efficiency of the whole system. Based on the work, it can be concluded that differences between two configurations can be seen in the economic performance with only minor modifications to the simulation models used in the network interaction and control method study. This eliminates the need ofdeveloping analytic expressions for losses and enables the study of the system as a whole instead of modeling it as series connection of independent blocks with no lossinterdependencies. Three example cases (site matching, component selection, control principle selection) are provided to illustrate the usage of the approach and analyze its performance.

Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

Flow injection visible diffuse reflectance quantitative analysis of total sulfur in biodiesel, in plant leaves and in natural waters

Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of total sulfur in the form of sulfate, precipitated in the form of barium sulfate, is presented. The method was applied to biodiesel, to plant leaves and to natural waters analysis. The analytical signal (S) correlates linearly with sulfate concentration (C) between 20 and 120 ppm, through the equation S=-1.138+0.0934 C (r = 0.9993). The experimentally observed limit of detection is about 10 ppm. The mean R.S.D. is about 3.0 %. Real samples containing sulfate were analyzed and the results obtained by the FI and by the reference batch turbidimetric method using the statistical Student's t-test and F-test were compared.

Flow-batch analyser for preparation of calibration standard mixtures in simultaneous multicomponent spectrometric analysis

The application of multivariate calibration techniques to multicomponent analysis by UV-VIS molecular absorption spectrometry is a powerful tool for simultaneous determination of several chemical species. However, when this methodology is accomplished manually, it is slow and laborious, consumes high amounts of reagents and samples, is susceptible to contaminations and presents a high operational cost. To overcome these drawbacks, a flow-batch analyser is proposed in this work. This analyser was developed for automatic preparation of standard calibration and test (or validation) mixtures. It was applied to the simultaneous determination of Cu2+, Mn2+ and Zn2+ in polyvitaminic and polymineral pharmaceutical formulations, using 4-(2-piridilazo) resorcinol as reagent and a UV-VIS spectrophotometer with a photodiode array detector. The results obtained with the proposed system are in good agreement with those obtained by flame atomic absorption spectrometry, which was employed as reference method. With the proposed analyser, the preparation of calibration and test mixtures can be accomplished about four hours, while the manual procedure requires at least two days. Moreover, it consumes smaller amounts of reagents and samples than the manual procedure. After the preparation of calibration and test mixtures, 60 samples h-1 can be carried out with the proposed flow-batch analyser.

A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.