Determination of paraquat and diquat: LC-MS method optimization and validation.

2016

Computational study of the step size parameter of the subgradient optimization method

The subgradient optimization method is a simple and flexible linear programming iterative algorithm. It is much simpler than Newton's method and can be applied to a wider variety of problems. It also converges when the objective function is non-differentiable. Since an efficient algorithm will not only produce a good solution but also take less computing time, we always prefer a simpler algorithm with high quality. In this study a series of step size parameters in the subgradient equation is studied. The performance is compared for a general piecewise function and a specific p-median problem. We examine how the quality of solution changes by setting five forms of step size parameter.

Allocating reforestation areas for sediment flow minimization: an integer programming formulation and a heuristic solution method

Policy and decision makers dealing with environmental conservation and land use planning often require identifying potential sites for contributing to minimize sediment flow reaching riverbeds. This is the case of reforestation initiatives, which can have sediment flow minimization among their objectives. This paper proposes an Integer Programming (IP) formulation and a Heuristic solution method for selecting a predefined number of locations to be reforested in order to minimize sediment load at a given outlet in a watershed. Although the core structure of both methods can be applied for different sorts of flow, the formulations are targeted to minimization of sediment delivery. The proposed approaches make use of a Single Flow Direction (SFD) raster map covering the watershed in order to construct a tree structure so that the outlet cell corresponds to the root node in the tree. The results obtained with both approaches are in agreement with expert assessments of erosion levels, slopes and distances to the riverbeds, which in turn allows concluding that this approach is suitable for minimizing sediment flow. Since the results obtained with the IP formulation are the same as the ones obtained with the Heuristic approach, an optimality proof is included in the present work. Taking into consideration that the heuristic requires much less computation time, this solution method is more suitable to be applied in large sized problems.

Doehlert Design-desirability Function Multi-criteria Optimal Separation Of 17 Phenolic Compounds From Extra-virgin Olive Oil By Capillary Zone Electrophoresis.

In Brazil, the consumption of extra-virgin olive oil (EVOO) is increasing annually, but there are no experimental studies concerning the phenolic compound contents of commercial EVOO. The aim of this work was to optimise the separation of 17 phenolic compounds already detected in EVOO. A Doehlert matrix experimental design was used, evaluating the effects of pH and electrolyte concentration. Resolution, runtime and migration time relative standard deviation values were evaluated. Derringer's desirability function was used to simultaneously optimise all 37 responses. The 17 peaks were separated in 19min using a fused-silica capillary (50μm internal diameter, 72cm of effective length) with an extended light path and 101.3mmolL(-1) of boric acid electrolyte (pH 9.15, 30kV). The method was validated and applied to 15 EVOO samples found in Brazilian supermarkets.

Integració de tècniques per a la comprovació eficient de restriccions d'integritat en la generació de programari per entorns web

Estudi elaborat a partir d’una estada al Politecnico de Milano, Itàlia, entre gener i juny del 2006. Un dels principals objectius de l’Enginyeria del Programari és automatitzar el màxim possible el procés de desenvolupament del programari, reduint costos mitjançant la generació automàtica del programari a partir de la seva especificació. Per assolir-ho, entre altres, cal resoldre el problema de la comprovació eficient de restriccions, que són una part fonamental de l’especificació del programari. Aquest és precisament l’àmbit en què s’està desenvolupant una tesi que presentarà un mètode que poden integrar totes les eines generadores de codi per tal d’assolir una implementació eficient de les restriccions d’integritat. En l’actual fase del projecte s’ha treballat per validar el mètode de la tesi, optimitzant-lo pel cas específic de les aplicacions web i estendre’l per poder tractar també aplicacions basades en workflows. Pel que fa a l’optimització del mètode per aplicacions web, s’han definit una sèrie de paràmetres que permeten configurar la implementació del mètode tenint en compte les necessitats específiques de rendiment de cada aplicació web en particular. Respecte als workflows (cada cop més populars i que s’usen com a definició d’alt nivell per a les aplicacions a desenvolupar) s’ha estudiat quins són els tipus de restriccions que impliquen i com després es pot aplicar el mètode de la tesi sobre aquestes restriccions per tal de generar de forma eficient també les aplicacions basades en workflows.

Analysis of a sub-optimal scheme of drug dosage in the AIDS treatment

Here the results for CD4+T cells count and the viral load obtained from HIV sero-positive patients are compared with results from numerical simulations by computer. Also, the standard scheme of administration of drugs anti HIV (HAART schemes) which uses constant doses is compared with an alternative sub-optimal teatment scheme which uses variable drug dosage according to the evolution of a quantitative measure of the side effects. The quantitative analysis done here shows that it is possible to obtain, using the alternative scheme, the same performance of actual data but using variable dosage and having fewer side effects. Optimal control theory is used to solve and also to provide a prognosis related to the strategies for control of viraemia.

Mathematical optimisation techniques applied to power system operation and planning

Nowadays, power system operation becomes more complex because of the critical operating conditions resulting from the requirements of a market-driven operation. In this context, efficient methods for optimisation of power system operation and planning become critical to satisfy the operational (technical), financial and economic demands. Therefore, the detailed analysis of modern optimisation techniques as well as their application to the power system problems represent a relevant issue from the scientific and technological points of view. This paper presents a brief overview of the developments on modern mathematical optimisation methods applied to power system operation and planning. Copyright © 2007 Inderscience Enterprises Ltd.

Divergência genética de cultivares de cana-de-açúcar quanto à resistência a Diatraea saccharalis

The objective was to evaluate the genetic diversity of cultivars in sugar cane for resistance to D. saccharalis. The experiment was carried out in the laboratory in completely randomized design with 11 treatments (one control and 10 treatments) in ten replications. The replications were made from artificial diets (food and refood) made with dry steam crushed from sugar cane cultivars stems, except for one of them considered standard diet. The cultivars used were: RB867515, RB855453, RB855536, CTC 15, CTC 9, SP80-1842, SP79-1011, SP89-1115, SP81-3250 and SP87-365. In the evaluation biological characteristics of the insect considered were: larval development (days), larval viability (%), pupal development (days), pupal weight (g), pupal viability (%), period of hatched larvae to adults emergence (days), total viability (%) and adults longevity without food (days). The generalized Mahalanobis distance (D-2) for the cluster analysis by the method of average linkage between groups (UPGMA) and Tocher's method optimization was determined. Four and five groups were formed, respectively, by the method of average linkage between groups (UPGMA) and Tocher's method optimization. We concluded that the cultivar CTC 15 standed out as highly susceptible to D. saccharalis, while the cultivar SP87-365 behaved as moderately resistant by antibiosis to D. saccharalis.

Desenvolvimento de método por cromatografia líquida bidimensional abrange para documentação química de extratos vegetais e estudos metabolômicos

Pós-graduação em Química - IQ

Progress in Monitoring alcohol consumption and alcohhol abuse by phosphatidylethanol

For early diagnosis and therapy of alcohol-related disorders, alcohol biomarkers are highly valuable. Concerning specificity, indirect markers can be influenced by nonethanol-related factors, whereas direct markers are only formed after ethanol consumption. Sensitivity of the direct markers depends on cutoffs of analytical methods, material for analysis and plays an important role for their utilization in different fields of application. Until recently, the biomarker phosphatidylethanol has been used to differentiate between social drinking and alcohol abuse. After method optimization, the detection limit could be lowered and phosphatidylethanol became sensitive enough to even detect the consumption of low amounts of alcohol. This perspective gives a summary of most common alcohol biomarkers and summarizes new developments for monitoring alcohol consumption habits.

Desenvolvimento de método para determinação de espécies de mercúrio empregando MSPD e GC-MS

Neste trabalho é proposto pela primeira vez, o desenvolvimento e validação de um método analítico baseado no emprego da dispersão da matriz em fase sólida (MSPD) modificada, para extração das espécies CH3Hg+ e Hg2+ em amostras de peixe e determinação por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS). O método de extração utilizando a MSPD combina o rompimento da estrutura física da amostra, através da maceração e do uso de SiO2 como suporte sólido, com o método da extração ácida, utilizando uma solução de HCl 4,2 mol L-1 e NaCl 0,5 mol L-1. Para otimização da MSPD, foram avaliados parâmetros como massa de amostra, massa de suporte sólido, concentração de HCl, concentração de NaCl, tipo de suporte sólido e o tempo de agitação, com auxílio da metodologia de superfície de resposta. Além disso, a etapa de derivatização e a separação cromatográfica também foram otimizadas na determinação de CH3Hg+ e Hg2+ por GC-MS. O método mostrouse adequado para extração e determinação de espécies de mercúrio através da aplicação em materiais de referência certificados de fígado de peixe (DOLT-3) e músculo de peixe (DORM-2), apresentando boas concordâncias com os valores certificados e desvio padrão relativo inferior a 9,5%. Os limites de detecção foram de 0,06 e 0,12 µg g-1 para CH3Hg+ e Hg2+, respectivamente. Além disso, foi observado um significativo efeito de matriz e, por isso, a calibração foi feita com curvas preparadas com o extrato da MSPD. O método mostrou boa concordância na comparação entre a soma da concentração das espécies e a concentração de mercúrio total determinada por espectrometria de massas com plasma indutivamente acoplado com geração de vapor frio (CVG-ICP-MS), após digestão assistida por micro-ondas (MAD) em peixes do tipo atum (Thunnus thynnus), cação anjo (Squatina squatina) e cação viola (Rhinobatos blochii.).

Optimization and validation of a LIBS method for the determination of macro and micronutrients in sugar cane leaves

Laser induced breakdown spectrometry (LIBS) was applied for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Cu, Fe, Mn and Zn) in sugar cane leaves, which is one of the most economically important crops in Brazil. Operational conditions were previously optimized by a neuro-genetic approach, by using a laser Nd:YAG at 1064 nm with 110 mJ per pulse focused on a pellet surface prepared with ground plant samples. Emission intensities were measured after 2.0 mu s delay time, with 4.5 mu s integration time gate and 25 accumulated laser pulses. Measurements of LIBS spectra were based on triplicate and each replicate consisted of an average of ten spectra collected in different sites (craters) of the pellet. Quantitative determinations were carried out by using univariate calibration and chemometric methods, such as PLSR and iPLS. The calibration models were obtained by using 26 laboratory samples and the validation was carried out by using 15 test samples. For comparative purpose, these samples were also microwave-assisted digested and further analyzed by ICP OES. In general, most results obtained by LIBS did not differ significantly from ICP OES data by applying a t-test at 95% confidence level. Both LIBS multivariate and univariate calibration methods produced similar results, except for Fe where better results were achieved by the multivariate approach. Repeatability precision varied from 0.7 to 15% and 1.3 to 20% from measurements obtained by multivariate and univariate calibration, respectively. It is demonstrated that LIBS is a powerful tool for analysis of pellets of plant materials for determination of macro and micronutrients by choosing calibration and validation samples with similar matrix composition.

MULTIVARIATE STATISTICAL METHOD IN OPTIMIZATION OF PROTEIN EXTRACTION FROM SOYBEAN FLOUR WITH DAIRY WHEY

The aim objective of this project was to evaluate the protein extraction of soybean flour in dairy whey, by the multivariate statistical method with 2(3) experiments. Influence of three variables were considered: temperature, pH and percentage of sodium chloride against the process specific variable ( percentage of protein extraction). It was observed that, during the protein extraction against time and temperature, the treatments at 80 degrees C for 2h presented great values of total protein (5.99%). The increasing for the percentage of protein extraction was major according to the heating time. Therefore, the maximum point from the function that represents the protein extraction was analysed by factorial experiment 2(3). By the results, it was noted that all the variables were important to extraction. After the statistical analyses, was observed that the parameters as pH, temperature, and percentage of sodium chloride, did not sufficient for the extraction process, since did not possible to obtain the inflection point from mathematical function, however, by the other hand, the mathematical model was significant, as well as, predictive.