1000 resultados para Analytical Chemistry


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Amperometric biosensors based on surface modifications of electrodes are described. Cobalt porphyrins modified on glassy carbon and carbon fiber electrodes can greatly decrease the overpotential and increase the sensitivity of detection due to EC electroc

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In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so-called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright (C) 2010 John Wiley & Sons, Ltd.

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Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

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This collection of seventy-five publications represents the authors contribution to spectroscopy, separation science and flow analysis. Of particular note are the fundamental investigations into chemiluminescence and the innovative strategies for its utilisation as a sensitive and selective means of detection for several important and challenging problems in analytical chemistry.

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This study monitored concentration changes in the major constituents of wine during its production, through the development of new and innovative methodologies for a range of analytical instrumentation. Chemometrics (statistical analysis) was employed to enhance data interpretation, which provided insight into the reactions occurring between the key chemical species present.

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The measurement of nitrogen dioxide at the parts-perbillion level is described. The experimental arrangement consists of two optical fibers placed on opposite sides of and in contact with a liquid film (14-57 μL in volume) supported on a U-shaped wire guide and two tubular conduits (one of which constitutes the means for the delivery of the liquid), light from a green (555 nm) light-emitting diode enters the liquid film, composed of Griess-Saltzman reagent. The transmitted light is measured by a referenced photodetection arrangement. Sample gas flows past the droplet at a low flow rate (typically 0.10-0.25 L/min). The response is proportional to the sampling period and the analyte concentration. The limit of detection for this nonoptimized arrangement is estimated to be <10 ppb by volume for a 5 min sample. Some unusual characteristics are observed. The initial absorbance, when most of the analyte/reaction product is still near the surface, is higher than that when the content of the droplet is fully mixed. The signal depends on the sample flow rate in a nonmonotonic fashion, first increasing and then decreasing with increasing sampling rate; the specific chemistry involved in the collection and determination of NO2 may be responsible.

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Potentiometric, amperometric and conductometric electrochemical sensors have found a number of interesting applications in the areas of environmental, industrial, and clinical analyses. This review presents a general overview of the three main types of electrochemical sensors, describing fundamental aspects, developments and their contribution to the area of analytical chemistry, relating relevant aspects of the development of electrochemical sensors in Brazil.

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CHEMICAL AND PHYSICAL FACTORS INFLUENCING LEAD AND COPPER CONTAMINATION IN DRINKING WATER: APPROACH FOR A CASE STUDY IN ANALYTICAL CHEMISTRY. Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirao Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

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This thesis is based on five papers addressing variance reduction in different ways. The papers have in common that they all present new numerical methods. Paper I investigates quantitative structure-retention relationships from an image processing perspective, using an artificial neural network to preprocess three-dimensional structural descriptions of the studied steroid molecules. Paper II presents a new method for computing free energies. Free energy is the quantity that determines chemical equilibria and partition coefficients. The proposed method may be used for estimating, e.g., chromatographic retention without performing experiments. Two papers (III and IV) deal with correcting deviations from bilinearity by so-called peak alignment. Bilinearity is a theoretical assumption about the distribution of instrumental data that is often violated by measured data. Deviations from bilinearity lead to increased variance, both in the data and in inferences from the data, unless invariance to the deviations is built into the model, e.g., by the use of the method proposed in paper III and extended in paper IV. Paper V addresses a generic problem in classification; namely, how to measure the goodness of different data representations, so that the best classifier may be constructed. Variance reduction is one of the pillars on which analytical chemistry rests. This thesis considers two aspects on variance reduction: before and after experiments are performed. Before experimenting, theoretical predictions of experimental outcomes may be used to direct which experiments to perform, and how to perform them (papers I and II). After experiments are performed, the variance of inferences from the measured data are affected by the method of data analysis (papers III-V).