Desenvolvimento e validação de método analítico para determinação de teor de ácido gálico e catequina no fitoterápico sanativo® por cromatografia líquida de alta eficiência

The herbal medicine Sanativo® is produced by the Pernambucano Laboratory since 1888 with indications of healing and hemostasis. It is composed of a fluid extract about Piptadenia colubrina, Schinus terebinthifolius, Cereus peruvianus and Physalis angulata. Among the plants in their composition, S. terebinthifolius and P. colubrina have in common phenolic compounds which are assigned most of its pharmacological effects. The tannins, gallic acid and catechin were selected as markers for quality control. The aim of this study was the development and validation of analytical method by HPLC/UV/DAD for the separation and simultaneous quantification of gallic acid (GAC) and catechin (CTQ) in Sanativo®. The chromatographic system was to stationary phase, C-18 RP column, 4,6 x 150 mm (5 mm) under a temperature of 35 ° C, detection at 270 and 210 nm. The mobile phase consisted of 0.05% trifluoroacetic acid and methanol in the proportions 88:12 (v/v), a flow rate of 1 ml/min. The analytical method presented a retention factor of 0.30 and 1.36, tail factor of 1.8 and 1.63 for gallic acid and catechin, respectively, resolution of 18.2, and theoretical plates above 2000. The method validation parameters met the requirements of Resolution n º 899 of May 29, 2003, ANVISA. The correlation coefficient of linear regression analysis for GAC and CTQ from the standard solution was 0.9958 and 0.9973 and when performed from the Sanativo® 0.9973 and 0.9936, the matrix does not interfere in the range 70 to 110 %. The limits of detection and quantification for GAC and CQT were 3.25 and 0.863, and 9.57 and 2.55 mg/mL, respectively. The markers, GAC and CQT, showed repetibility (coefficient of variation of 0.94 % and 2.36 %) and satisfactory recovery (100.02 ± 1.11 % and 101.32 ± 1.36 %). The method has been characterized selective and robust quantification of GAC and CTQ in the Sanativo® and was considered validated

Desenvolvimento e validação de método analítico para determinação de WE010, WE014 e WE017

The synthetic guanylhydrazones WE010 (3,5-di-tert-butil-4-hidroxibenzaldehyde-guanylhydrazone), WE014 (4-bifenilcarboxialdehydeguanylhydrazone) and WE017 (3,4-diclorobenzaldehydeguanylhydrazone) showed high cytotoxic activity in terms of percentage inhibition of cancer cells growth. However, further progress in the development of these drug candidates requires precise and convenient methods for their qualitative and quantitative analyses. The aim of this study was to develop and validate High Performance Liquid Chromatography with diode-array detection (HPLC-DAD) and Ultra Fast Liquid Chromatography with diode-array detection (UFLC-DAD) methods suitable for as simultaneous as isolated determination of studied guanylhydrazones, based on the optimization of chromatographic parameters and obtaining reduced detection times. The chromatographic analyses of analytes by HPLC were performed on C18 ACE analytical column (150 mm x 4.6 mm), with a particle size of 5.0 μm. Among all the conditions assayed, the best results of separation were obtained with a mixture of methanol:water (60:40, v/v) as the mobile phase at a flow rate 1.5mL/min and pH of 3.5 adjusted at acetic acid. The UFLC method was developed by experimetal desing techniques in order to find optimal chromatographic analytical conditions, which were achieved on XR-ODS analytical column (50 mm x 3.0 mm), with a particle size of 2,2 μm, maintained at 25 ºC. The mobile phase was consisted of methanol:water (65:35, v/v) with 0.1% triethylamine (TEA) and pH of 3.5 adjusted at acetic acid, at a flow rate 0.5 mL/min. The procedure were validated following evaluating parameters such as specificity, linearity, limits of detection (LD) and quantification (LQ), precision, accuracy and robustness, giving results within the acceptable range. Although the UFLC method shows better sensitivity (lower values of LD and LQ), robustness (lower rates of relative standard deviation) and minimize spending time and solvent, both developed methods were adequately applied to the analysis of guanylhydrazones molecules, may be used in routine of quality control laboratories. Keywords: guanylhydrazones, HPLC/DAD, UFLC/DAD, validation of analitical method

Avaliação de um método de cromatografia em fase gasosa head space e estudo da estabilidade do etanol em amostras de sangue

The ethanol is the most overused psychoactive drug over the world; this fact makes it one of the main substances required in toxicological exams nowadays. The development of an analytical method, adaptation or implementation of a method known, involves a process of validation that estimates its efficiency in the laboratory routine and credibility of the method. The stability is defined as the ability of the sample of material to keep the initial value of a quantitative measure for a defined period within specific limits when stored under defined conditions. This study aimed to evaluate the method of Gas chromatography and study the stability of ethanol in blood samples, considering the variables time and temperature of storage, and the presence of preservative and, with that check if the conditions of conservation and storage used in this study maintain the quality of the sample and preserve the originally amount of analyte present. Blood samples were collected from 10 volunteers to evaluate the method and to study the stability of ethanol. For the evaluation of the method, part of the samples was added to known concentrations of ethanol. In the study of stability, the other side of the pool of blood was placed in two containers: one containing the preservative sodium fluoride 1% and the anticoagulant heparin and the other only heparin, was added ethanol at a concentration of 0.6 g/L, fractionated in two bottles, one being stored at 4ºC (refrigerator) and another at -20ºC (freezer), the tests were performed on the same day (time zero) and after 1, 3, 7, 14, 30 and 60 days of storage. The assessment found the difference in results during storage in relation to time zero. It used the technique of headspace associated with gas chromatography with the FID and capillary column with stationary phase of polyethylene. The best analysis of chromatographic conditions were: temperature of 50ºC (column), 150ºC (jet) and 250ºC (detector), with retention time for ethanol from 9.107 ± 0.026 and the tercbutanol (internal standard) of 8.170 ± 0.081 minutes, the ethanol being separated properly from acetaldehyde, acetone, methanol and 2-propanol, which are potential interfering in the determination of ethanol. The technique showed linearity in the concentration range of 0.01 and 3.2 g/L (0.8051 x + y = 0.6196; r2 = 0.999). The calibration curve showed the following equation of the line: y = x 0.7542 + 0.6545, with a linear correlation coefficient equal to 0.996. The average recovery was 100.2%, the coefficients of variation of accuracy and inter intra test showed values of up to 7.3%, the limit of detection and quantification was 0.01 g/L and showed coefficient of variation within the allowed. The analytical method evaluated in this study proved to be fast, efficient and practical, given the objective of this work satisfactorily. The study of stability has less than 20% difference in the response obtained under the conditions of storage and stipulated period, compared with the response obtained at time zero and at the significance level of 5%, no statistical difference in the concentration of ethanol was observed between analysis. The results reinforce the reliability of the method of gas chromatography and blood samples in search of ethanol, either in the toxicological, forensic, social or clinic

Modelo 2,5D de predição de propagação para ambientes interiores utilizando o método do traçado de raios

A 2.5D ray-tracing propagation model is proposed to predict radio loss in indoor environment. Specifically, we opted for the Shooting and Bouncing Rays (SBR) method, together with the Geometrieal Theory of Diffrartion (GTD). Besides the line-of-sight propagation (LOS), we consider that the radio waves may experience reflection, refraction, and diffraction (NLOS). In the Shooting and Bouncing Rays (SBR) method, the transmitter antenna launches a bundle of rays that may or may not reach the receiver. Considering the transmitting antenna as a point, the rays will start to launch from this position and can reach the receiver either directly or after reflections, refractions, diffractions, or even after any combination of the previous effects. To model the environment, a database is built to record geometrical characteristics and information on the constituent materials of the scenario. The database works independently of the simulation program, allowing robustness and flexibility to model other seenarios. Each propagation mechanism is treated separately. In line-of-sight propagation, the main contribution to the received signal comes from the direct ray, while reflected, refracted, and diffracted signal dominate when the line-of-sight is blocked. For this case, the transmitted signal reaches the receiver through more than one path, resulting in a multipath fading. The transmitting channel of a mobile system is simulated by moving either the transmitter or the receiver around the environment. The validity of the method is verified through simulations and measurements. The computed path losses are compared with the measured values at 1.8 GHz ftequency. The results were obtained for the main corridor and room classes adjacent to it. A reasonable agreement is observed. The numerical predictions are also compared with published data at 900 MHz and 2.44 GHz frequencies showing good convergence

Monitoramento em tempo real de processos fermentativos por espectroscopia no infravermelho próximo (NIRS)

A chemical process optimization and control is strongly correlated with the quantity of information can be obtained from the system. In biotechnological processes, where the transforming agent is a cell, many variables can interfere in the process, leading to changes in the microorganism metabolism and affecting the quantity and quality of final product. Therefore, the continuously monitoring of the variables that interfere in the bioprocess, is crucial to be able to act on certain variables of the system, keeping it under desirable operational conditions and control. In general, during a fermentation process, the analysis of important parameters such as substrate, product and cells concentration, is done off-line, requiring sampling, pretreatment and analytical procedures. Therefore, this steps require a significant run time and the use of high purity chemical reagents to be done. In order to implement a real time monitoring system for a benchtop bioreactor, these study was conducted in two steps: (i) The development of a software that presents a communication interface between bioreactor and computer based on data acquisition and process variables data recording, that are pH, temperature, dissolved oxygen, level, foam level, agitation frequency and the input setpoints of the operational parameters of the bioreactor control unit; (ii) The development of an analytical method using near-infrared spectroscopy (NIRS) in order to enable substrate, products and cells concentration monitoring during a fermentation process for ethanol production using the yeast Saccharomyces cerevisiae. Three fermentation runs were conducted (F1, F2 and F3) that were monitored by NIRS and subsequent sampling for analytical characterization. The data obtained were used for calibration and validation, where pre-treatments combined or not with smoothing filters were applied to spectrum data. The most satisfactory results were obtained when the calibration models were constructed from real samples of culture medium removed from the fermentation assays F1, F2 and F3, showing that the analytical method based on NIRS can be used as a fast and effective method to quantify cells, substrate and products concentration what enables the implementation of insitu real time monitoring of fermentation processes

Hidrocarbonetos alifáticos em sedimentos de fundo do estuário do Rio Potengi, grande Natal (RN): implicações ambientais

The Potengi river estuary is located in the region of Natal (RN, Brazil), comprising a population of approximately 1,000,000 inhabitants. Besides the dominant urban presence, the estuary has fragments of mangrove forest. The objective of this study is to determine the aliphatic hydrocarbons found in the bottom sediments of this estuary, identifying their levels, distribution and their possible origins through the diagnostic rates, indexes and results comparisons with the local anthropic and natural characteristics. The samples were obtained according to a plan that allowed sampling of the estuary up to 12 km upstream from it as mounth. 36 stations were selected, grouped into 12 cross sections through the course of the river and spaced on average by 1 km. Each section consisted of three stations: the right margin, the deepest point and the left margin. The hydrocarbon n-alkanes from C10 to C36, the isoprenoids pristane and phytane, the unresolved complex mixture (UCM) and the total resolved hydrocarbons were analyzed by gas chromatography. N-alkanes, pristane, phytane and UCM were detected only at some stations. In the other, the concentration was below the detection limit defined by the analytical method (0.1 mg / kg), preventing them from being analyzed to determine the origin of the material found. By using different parameters, the results show that the estuary receives both the input of petrogenic hydrocarbons, but also of biogenic hydrocarbons, featuring a mixture of sources and relatively impacted portions. Based on the characteristics and activities found in the region, it is possible to affirm that petrogenic sources related to oil products enter the estuary via urban runoff or boats traffic, boat washing and fueling. Turning to the biogenic source, the predominant origin was terrestrial, characterized by vascular plants, indicating contribution of mangrove vegetation. It was evident the presence of, at specific points in the estuary, hydrocarbon pollution, and, therefore is recommended the adoption of actions aimed at interrupting or, at least, mitigating the sources potentially capable of damp petrogenic hydrocarbons in the estuary studied.

Modelos matemáticos para estimativa do consumo máximo de oxigênio pela ventilometria de esforço em indivíduos saudáveis

The relation between metabolic demand and maximal oxygen consumption during exercise have been investigated in different areas of knowledge. In the health field, the determination of maximal oxygen consumption (VO2max) is considered a method to classify the level of physical fitness or the risk of cardiocirculatory diseases. The accuracy to obtain data provides a better evaluation of functional responses and allows a reduction in the error margin at the moment of risk classification, as well as, at the moment of determination of aerobic exercise work load. In Brasil, the use of respirometry associated to ergometric test became an opition in the cardiorespiratory evaluation. This equipment allows predictions concerning the oxyredutase process, making it possible to identify physiological responses to physical effort as the respiratory threshold. This thesis focused in the development of mathematical models developed by multiple regression validated by the stepwise method, aiming to predict the VO2max based on respiratory responses to physical effort. The sample was composed of a ramdom sample of 181 healthy individuals, men and women, that were randomized to two groups: regression group and cross validation group (GV). The voluntiars were submitted to a incremental treadmill test; objetiving to determinate of the second respiratory threshold (LVII) and the Peak VO2max. Using the método forward addition method 11 models of VO2max prediction in trendmill were developded. No significative differences were found between the VO2max meansured and the predicted by models when they were compared using ANOVA One-Way and the Post Hoc test of Turkey. We concluded that the developed mathematical models allow a prediction of the VO2max of healthy young individuals based on the LVII

Alcoolemia em vítimas fatais de acidentes de trânsito no Rio Grande do Norte empregando cromatografia em fase gasosa - head space

Alcohol is one of the few psychotropic drugs that their consumption has admitted legally and sometimes encouraged by the society. Studies show alcohol as the highest consumption of drugs among young people and society in general, probably because of its availability and easy access. The abuse causes public health problems, which was closely related to the violence, socioeconomic problems and the high number of automobile accidents. Transit is one of the main sectors affected by the effects of alcohol, observing a high incidence in the studies. About half of automobile accidents occurs after the consumption of alcoholic beverage, and the vast majority of cases related to high concentrations of alcohol in the bloodstream. The relationship of drunk with traffic accidents is in fact evident everywhere in the world, including Brazil, where studies have shown a high relationship between alcohol consumption and traffic accidents. This study determined the alcohol in fatal victims of traffic accidents in the state of Rio Grande do Norte and established the profile of this population compared with those found in Brazil and other countries. Samples of blood of ethanol added to fulfillment of the standardization of chromatographic conditions and procedures for the analysis, being employed in the determination of alcohol in blood samples of 277 victims of traffic accidents, collected at the Institute of Scientific Technical Police of Rio Grande do North (ITEP) in the year 2007. The blood alcohol level was determined in these samples correlated with the sex, age and marital status of the victim and the location, day of week and month when the accident occurred, is doing a statistical analysis and outlining a profile of the victims of an accident at transit in the state of Rio Grande do Norte. The parameters of standardization studied ensured the quality of the analytical method and, consequently, to obtain reliable laboratory results. Being given the best temperature for injector (150 ºC), detector (250 ºC) and column (50 ºC) with a flow of gas in the column of 2mL/minutos and analysis of time of 12 minutes. The method was linear in the range of 0.01 to 3.2 g / L (r2 = 0.9989) with average recovery of 100.2% and precision with coefficient of variation less than 15%. The analysis carried out on victims of fatal road traffic accidents, ethanol detected in the blood in 66.43% of the victims and these, 96% showed concentration ≥ 0.2 g / L, 87.73% of victims were male, while 12.27% female. The younger age group (1535 years) was the most involved (52,35%) and most single (55.60%). The accidents occurred with greater prevalence in the day on Monday (27%) followed by Sunday (24,19%) and Saturday (15,52%) and it was found that the prevalence of injuries varied between the different months of the year, and in February (14.4%) and April (10.47%) the months that had a higher number of accidents, however this oscillation showed no statistically significant difference. Also no significant difference was observed between the tracks of concentration found in men and women. The standardized method showed to be efficient, given satisfactorily to the goals of this work, and the high levels of alcohol found in victims of fatal road traffic accidents are consistent with several studies of literature, and the profile of the victim also supported by presenting in its most young adults, male and single

Educação corporativa para Micro e Pequenas empresas: aplicação do MADEC em empresas do setor supermercadista

This study searches to supply an existing gap in the empirical research about the performance of controllers of Micron and Small Companies (MSCs) in the context of corporative education (EC) through the Method of Support of Decision in Corporative Education (MSDCE). In the context of MCSs, this is a pioneering work, for other works related to this thematic searched in literature are limited to conjecture the possibility of its implantation via cooperation between companies; moreover, they do not apply any type of diagnosis method or viability. The object of study is an association of supermarkets of the city of Natal/RN, composed by 16 stores, of what 14 had been searched. The main objective of this work was to apply the first stage of the MSDCE and to verify the possibility of implanting the Corporative Education in the searched MSCs. As a result, it was obtained the profile of the companies and the validation of the above-mentioned Method. The phase of diagnosis conceived through the implantation of the first stage occurred through visits to the stores, interviews, application of questionnaires and place observation. The first stage - strategical analysis for professional education - was divided in two phases: analysis of the current corporative situation and available identification of the involved difficulties and resources. The implantation of the first stage of the MSDCE in the Association of Supermarkets Parceiros da Economia demanded a mapping of abilities and demonstrated how the education management works, the main difficulties and limitations of the MCSs of the supermerket branch of Natal/RN. Beyond the technological aspects, it was verified that cultural and educational aspects need to be worked to reach efficiency in the process of implantation of a corporative education program

Desenvolvimento de um modelo computacional para a ampliação do atendimento do Programa de Acessibilidade Especial Porta a Porta - PRAE

Worldwide, the demand for transportation services for persons with disabilities, the elderly, and persons with reduced mobility have increased in recent years. The population is aging, governments need to adapt to this reality, and this fact could mean business opportunities for companies. Within this context is inserted the Programa de Acessibilidade Especial porta a porta PRAE, a door to door public transportation service from the city of Natal-RN in Brazil. The research presented in this dissertation seeks to develop a programming model which can assist the process of decision making of managers of the shuttle. To that end, it was created an algorithm based on methods of generating approximate solutions known as heuristics. The purpose of the model is to increase the number of people served by the PRAE, given the available fleet, generating optimized schedules routes. The PRAE is a problem of vehicle routing and scheduling of dial-a-ride - DARP, the most complex type among the routing problems. The validation of the method of resolution was made by comparing the results derived by the model and the currently programming method. It is expected that the model is able to increase the current capacity of the service requests of transport

Dinâmica Estocástica e Cosmologia: alguns resultados analíticos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Efeitos interfaciais em heteroestruturas quânticas nô-abruptas: GaAs/ALxGa1-xAs

Um minuncioso estudo das propriedades de confinamento em heterostructuras bidimensionais(poços quânticos) GaAs/AlxGa1_xAs, com interfaces graduais é realizado. Um modelo teórico que represente bem a variação da fração molar do alumínio nas interfaces, resultante do aparecimento de micro-rugosidades e ilhas durante os processos de crescimento e recozimento pós-crescimento da amostra, é elaborado. Vários perfis desta fração molar de alumínio nas interfaces são considerados. Soluções analíticas da equação de Schrodinger, na aproximação da massa efetiva constatne nas interfaces, resultando em equações transcendentais, que possibilitam a obtenção dos níveis de energia dos portadores, decorrentes do seu confinamento quântico, são apresentadas. Energias de ligação e de confinamento de excitons 2D, utilizando-se um método analítico e numerérico e a aproximação do potencial efetivo, são também calculadas. Resultados numéricos para os níveis de energia dos portadores e para as energias de ligação e de confinamento dos excitons 2D, em poços quânticos GaAs/Al0.35Ga0.65As não-abruptos, sem e com a presença de campo elétrico aplicado para vários perfis interfaciais da fração de molar, são mostrados. Para a obtenção desses resultados, faz-se uso do método dos degraus múltiplos e da técnica da matriz de transferência, e adota-se, como operador de energia cinética, o de Ben-Daniel e Duque para uma massa efetiva dependente da posição. Conclui-se que um modelo que leva em conta a existência de interfaces não-abruptas e seus diversos perfis é indispensável para uma melhor descrição das propriedades opto-eletrônicas de poços quânticos GaAs/AlxGa1-xAs, enquanto que a aproximação das interfaces abruptas apresenta-se bastante limitada

Uma linguagem de modelagem da interação para auxiliar a comunicação designer-usuário

The development of interactive systems involves several professionals and the integration between them normally uses common artifacts, such as models, that drive the development process. In the model-driven development approach, the interaction model is an artifact that includes the most of the aspects related to what and how the user can do while he/she interacting with the system. Furthermore, the interactive model may be used to identify usability problems at design time. Therefore, the central problematic addressed by this thesis is twofold. In the first place, the interaction modeling, in a perspective that helps the designer to explicit to developer, who will implement the interface, the aspcts related to the interaction process. In the second place, the anticipated identification of usability problems, that aims to reduce the application final costs. To achieve these goals, this work presents (i) the ALaDIM language, that aims to help the designer on the conception, representation and validation of his interactive message models; (ii) the ALaDIM editor, which was built using the EMF (Eclipse Modeling Framework) and its standardized technologies by OMG (Object Management Group); and (iii) the ALaDIM inspection method, which allows the anticipated identification of usability problems using ALaDIM models. ALaDIM language and editor were respectively specified and implemented using the OMG standards and they can be used in MDA (Model Driven Architecture) activities. Beyond that, we evaluated both ALaDIM language and editor using a CDN (Cognitive Dimensions of Notations) analysis. Finally, this work reports an experiment that validated the ALaDIM inspection method

Geração de casos de teste a partir de especificações B

With the increasing complexity of software systems, there is also an increased concern about its faults. These faults can cause financial losses and even loss of life. Therefore, we propose in this paper the minimization of faults in software by using formally specified tests. The combination of testing and formal specifications is gaining strength in searches mainly through the MBT (Model-Based Testing). The development of software from formal specifications, when the whole process of refinement is done rigorously, ensures that what is specified in the application will be implemented. Thus, the implementation generated from these specifications would accurately depict what was specified. But not always the specification is refined to the level of implementation and code generation, and in these cases the tests generated from the specification tend to find fault. Additionally, the generation of so-called "invalid tests", ie tests that exercise the application scenarios that were not addressed in the specification, complements more significantly the formal development process. Therefore, this paper proposes a method for generating tests from B formal specifications. This method was structured in pseudo-code. The method is based on the systematization of the techniques of black box testing of boundary value analysis, equivalence partitioning, as well as the technique of orthogonal pairs. The method was applied to a B specification and B test machines that generate test cases independent of implementation language were generated. Aiming to validate the method, test cases were transformed manually in JUnit test cases and the application, created from the B specification and developed in Java, was tested. Faults were found with the execution of the JUnit test cases

Determinação de CD, PB, e TL em água produzida por HR-CS GF AAS após extração em ponto nuvem

Produced water is a major problem associated with the crude oil extraction activity. The monitoring of the levels of metals in the waste is constant and requires the use of sensitive analytical techniques. However, the determination of trace elements can often require a pre-concentration step. The objective of this study was to develop a simple and rapid analytical method for the extraction and pre-concentration based on extraction phenomenon cloud point for the determination of Cd, Pb and Tl in produced water samples by spectrometry of high resolution Absorption source continues and atomization graphite furnace. The Box Behnken design was used to obtain the optimal condition of extraction of analytes. The factors were evaluated: concentration of complexing agent (o,o-dietilditilfosfato ammonium, DDTP), the concentration of hydrochloric acid and concentration of surfactant (Triton X -114). The optimal condition obtained through extraction was: 0,6% m v-1 DDTP, HCl 0,3 mol L-1 and 0,2% m v-1 of Triton X - 114 for Pb; 0,7% m v-1 DDTP, HCl 0,8 mol L-1 and 0,2% m v-1 Triton X-114 for Cd. For Tl was evidenced that best extraction condition occurs with no DDTP, the extraction conditions were HCl 1,0 mol L-1 e 1,0% m v-1 de Triton X - 114. The limits of detection for the proposed method were 0,005 µg L-1 , 0,03 µg L-1 and 0,09 µg L-1 to Cd, Pb and Tl, Respectively. Enrichment factors Were greater than 10 times. The method was applied to the water produced in the Potiguar basin, and addition and recovery tests were performed, and values were between 81% and 120%. The precision was expressed with relative standard deviation (RSD) is less than 5%