Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

On a generalized Laguerre operational matrix of fractional integration

A new operationalmatrix of fractional integration of arbitrary order for generalized Laguerre polynomials is derived.The fractional integration is described in the Riemann-Liouville sense.This operational matrix is applied together with generalized Laguerre tau method for solving general linearmultitermfractional differential equations (FDEs).Themethod has the advantage of obtaining the solution in terms of the generalized Laguerre parameter. In addition, only a small dimension of generalized Laguerre operational matrix is needed to obtain a satisfactory result. Illustrative examples reveal that the proposedmethod is very effective and convenient for linear multiterm FDEs on a semi-infinite interval.

Optimal scheduling of a renewable micro-grid in an isolated load area using mixed-integer linear programming

In the energy management of the isolated operation of small power system, the economic scheduling of the generation units is a crucial problem. Applying right timing can maximize the performance of the supply. The optimal operation of a wind turbine, a solar unit, a fuel cell and a storage battery is searched by a mixed-integer linear programming implemented in General Algebraic Modeling Systems (GAMS). A Virtual Power Producer (VPP) can optimal operate the generation units, assured the good functioning of equipment, including the maintenance, operation cost and the generation measurement and control. A central control at system allows a VPP to manage the optimal generation and their load control. The application of methodology to a real case study in Budapest Tech, demonstrates the effectiveness of this method to solve the optimal isolated dispatch of the DC micro-grid renewable energy park. The problem has been converged in 0.09 s and 30 iterations.

Ancillary services dispatch using linear programming and genetic algorithm approaches

Electricity market players operating in a liberalized environment requires access to an adequate decision support tool, allowing them to consider all the business opportunities and take strategic decisions. Ancillary services represent a good negotiation opportunity that must be considered by market players. For this, decision support tools must include ancillary market simulation. This paper proposes two different methods (Linear Programming and Genetic Algorithm approaches) for ancillary services dispatch. The methodologies are implemented in MASCEM, a multi-agent based electricity market simulator. A test case concerning the dispatch of Regulation Down, Regulation Up, Spinning Reserve and Non-Spinning Reserve services is included in this paper.

Safety high accuracy Context-Aware Matrix (CAM) making based on X.509 proxy certificate

Human Computer Interaction (HCl) is to interaction between computers and each person. And context-aware (CA) is very important one of HCI composition. In particular, if there are sequential or continuous tasks between users and devices, among users, and among devices etc, it is important to decide the next action using right CA. And to take perfect decision we have to get together all CA into a structure. We define that structure is Context-Aware Matrix (CAM) in this article. However to make exact decision is too hard for some problems like low accuracy, overhead and bad context by attacker etc. Many researcher has been studying to solve these problems. Moreover, still it has weak point HCI using in safety. In this Article, we propose CAM making include best selecting Server in each area. As a result, moving users could be taken the best way.

Inexact restoration approaches to solve mathematical program with complementarity constraints

Mathematical Program with Complementarity Constraints (MPCC) finds applica- tion in many fields. As the complementarity constraints fail the standard Linear In- dependence Constraint Qualification (LICQ) or the Mangasarian-Fromovitz constraint qualification (MFCQ), at any feasible point, the nonlinear programming theory may not be directly applied to MPCC. However, the MPCC can be reformulated as NLP problem and solved by nonlinear programming techniques. One of them, the Inexact Restoration (IR) approach, performs two independent phases in each iteration - the feasibility and the optimality phases. This work presents two versions of an IR algorithm to solve MPCC. In the feasibility phase two strategies were implemented, depending on the constraints features. One gives more importance to the complementarity constraints, while the other considers the priority of equality and inequality constraints neglecting the complementarity ones. The optimality phase uses the same approach for both algorithm versions. The algorithms were implemented in MATLAB and the test problems are from MACMPEC collection.

Interlaboratory validation of an environmental monitoring method for trace analysis of endocrine disrupting compounds

Environmental pollution continues to be an emerging study field, as there are thousands of anthropogenic compounds mixed in the environment whose possible mechanisms of toxicity and physiological outcomes are of great concern. Developing methods to access and prioritize the screening of these compounds at trace levels in order to support regulatory efforts is, therefore, very important. A methodology based on solid phase extraction followed by derivatization and gas chromatography-mass spectrometry analysis was developed for the assessment of four endocrine disrupting compounds (EDCs) in water matrices: bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol. The study was performed, simultaneously, by two different laboratories in order to evaluate the robustness of the method and to increase the quality control over its application in routine analysis. Validation was done according to the International Conference on Harmonisation recommendations and other international guidelines with specifications for the GC-MS methodology. Matrix-induced chromatographic response enhancement was avoided by using matrix-standard calibration solutions and heteroscedasticity has been overtaken by a weighted least squares linear regression model application. Consistent evaluation of key analytical parameters such as extraction efficiency, sensitivity, specificity, linearity, limits of detection and quantification, precision, accuracy and robustness was done in accordance with standards established for acceptance. Finally, the application of the optimized method in the assessment of the selected analytes in environmental samples suggested that it is an expedite methodology for routine analysis of EDC residues in water matrices.

Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

Actuador linear para teste de teclas na indústria automóvel

As indústrias de componentes e acessórios automóveis são um elo fundamental no processo produtivo da indústria automóvel. Neste leque industrial encontra-se a Preh Portugal, Lda, como empresa fornecedora de componentes electrónicos, mais concretamente, painéis de controlo de climatização. Os painéis fornecidos pela Preh aos seus clientes encontram-se sujeitos a rigorosos testes de qualidade e funcionalidade. Neste sentido o teste funcional das teclas surge, relacionando o curso da tecla em função de uma força actuante. Esta relação está comprometida com uma curva característica padrão para o tipo de tecla. Para além destes compromissos, também é necessário que a tecla feche e abra o seu contacto eléctrico. Esta tese foca-se no desenvolvimento do teste de teclas, apresentando uma alteração ao sistema actual com a introdução de um sistema embebido, no intuito de flexibilizar o sistema de teste e reduzindo custos. O sistema embebido pretende dar capacidade de processamento ao teste e, desta forma, substituir o actual computador como elemento de processamento. A solução implementada consistiu numa mudança estrutural, através da inclusão do sistema embebido entre o computador e o sistema de deslocamento. Passando o foco central do processo de teste a residir no sistema embebido, este tem de estabelecer comunicações com os restantes elementos intervenientes no teste. Estabelece comunicações série RS-232 com o sistema de deslocamento (leitura do curso e força na tecla), Ethernet com o computador (comandos, parâmetros e resultados) e CAN com o painel de controlo de climatização (fecho/abertura do contacto eléctrico). A concretização deste projecto resultou numa nova estrutura e aplicação, a qual é facilmente integrada na linha de produção com as vantagens de ser menos onerosa e mais flexível, conforme o pretendido.

Sulfadiazine-potentiometric sensors for flow and batch determinations of sulfadiazine in drugs and biological fluids

New PVC membrane electrodes for the determination of sulfadiazine (SDZ) are presented. The electrodes are fabricated with conventional and tubular configurations with a graphite-based electrical contact, and no internal reference solution. The selective membranes consist of bis(triphenylphosphoranilidene)ammonium·SDZ (electrode A), tetraoctylammonium bromide (electrode B), or iron(II)-phthalocyanine (FePC) (electrode C) electroactive materials dispersed in a PVC matrix of o-nitrophenyl octyl ether (o-NPOE) plasticizer. The sensors A, B, and C displayed linear responses over the concentration ranges 1.0*10-2 – 1.0*10–5, 1.0*10–2 – 7.5*10–6, and 3.2*10–2 – 7.0* 10–6 mol l–1 (detection limits of 1.09, 2.04 and 0.87 mg ml–1) with anionic slopes of –57.3 ± 0.1, –46.7 ± 0.5, and –65.1 ± 0.2 mV decade–1, respectively. No effect from pH was observed within 4.0 – 5.5, 4.8 – 10, and 4.5 – 8, respectively, and good selectivity was found. The sensors were applied to the analysis of pharmaceuticals and biological fluids in steady state and in flow conditions.

Biomimetic norfloxacin sensors made of molecularly-imprinted materials for potentiometric transduction

A biomimetic sensor for norfloxacin is presented that is based on host-guest interactions and potentiometric transduction. The artificial host was imprinted into polymers made from methacrylic acid and/or 2-vinyl pyridine. The resulting particles were entrapped in a plasticized poly(vinyl chloride) (PVC) matrix. The sensors exhibit near-Nernstian response in steady state evaluations, and detection limits range from 0.40 to 1.0 μgmL−1, respectively, and are independent of pH values at between 2 and 6, and 8 and 11, respectively. Good selectivity was observed over several potential interferents. In flowing media, the sensors exhibit fast response, a sensitivity of 68.2 mV per decade, a linear range from 79 μM to 2.5 mM, a detection limit of 20 μgmL−1, and a stable baseline. The sensors were successfully applied to field monitoring of norfloxacin in fish samples, biological samples, and pharmaceutical products

Molecularly-imprinted materials for potentiometric transduction: application to the antibiotic enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mVΔlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL 1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (47 mV/Dlog([ENR]/ M), wide linear range (1.0×10-5–1.0×10-3 M), low detection limit (0.9 µg mL-1), and a stable baseline for a 5×10-2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Economic, environmental and mixed objective functions in non-linear process optimization using simulated annealing and tabu search

Screening of topologies developed by hierarchical heuristic procedures can be carried out by comparing their optimal performance. In this work we will be exploiting mono-objective process optimization using two algorithms, simulated annealing and tabu search, and four different objective functions: two of the net present value type, one of them including environmental costs and two of the global potential impact type. The hydrodealkylation of toluene to produce benzene was used as case study, considering five topologies with different complexities mainly obtained by including or not liquid recycling and heat integration. The performance of the algorithms together with the objective functions was observed, analyzed and discussed from various perspectives: average deviation of results for each algorithm, capacity for producing high purity product, screening of topologies, objective functions robustness in screening of topologies, trade-offs between economic and environmental type objective functions and variability of optimum solutions.

Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline

A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host–guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42–63 mV/decade and 2.5–31.3 µg/mL, respectively. Sensors were independent from the pH of test solutions within 2–5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0×10−5 to 1.0×10−2 mol/L), low detection limit (19.8 µg/mL), and a stable baseline for a 5×10−3M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

Effects of international diffusion of a general purpose technology on wage inequality

This paper studies the effects of the diffusion of a General Purpose Technology (GPT) that spreads first within the developed North country of its origin, and then to a developing South country. In the developed general equilibrium growth model, each final good can be produced by one of two technologies. Each technology is characterized by a specific labor complemented by a specific set of intermediate goods, which are enhanced periodically by Schumpeterian R&D activities. When quality reaches a threshold level, a GPT arises in one of the technologies and spreads first to the other technology within the North. Then, it propagates to the South, following a similar sequence. Since diffusion is not even, neither intra- nor inter-country, the GPT produces successive changes in the direction of technological knowledge and in inter- and intra-country wage inequality. Through this mechanism the different observed paths of wage inequality can be accommodated.