999 resultados para 540 Chimica e scienze connesse
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Linear unmixing decomposes a hyperspectral image into a collection of reflectance spectra of the materials present in the scene, called endmember signatures, and the corresponding abundance fractions at each pixel in a spatial area of interest. This paper introduces a new unmixing method, called Dependent Component Analysis (DECA), which overcomes the limitations of unmixing methods based on Independent Component Analysis (ICA) and on geometrical properties of hyperspectral data. DECA models the abundance fractions as mixtures of Dirichlet densities, thus enforcing the constraints on abundance fractions imposed by the acquisition process, namely non-negativity and constant sum. The mixing matrix is inferred by a generalized expectation-maximization (GEM) type algorithm. The performance of the method is illustrated using simulated and real data.
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Chpater in Book Proceedings with Peer Review Second Iberian Conference, IbPRIA 2005, Estoril, Portugal, June 7-9, 2005, Proceedings, Part II
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Chapter in Book Proceedings with Peer Review First Iberian Conference, IbPRIA 2003, Puerto de Andratx, Mallorca, Spain, JUne 4-6, 2003. Proceedings
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Chapter in Book Proceedings with Peer Review First Iberian Conference, IbPRIA 2003, Puerto de Andratx, Mallorca, Spain, JUne 4-6, 2003. Proceedings
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The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation–extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%). The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 µm polyacrylate fiber for a 60 min headspace extraction at 40ºC with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g−1 of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g−1 of extract), borneol (3.0 mg g−1 of extract) and bornyl acetate (3.9 mg g−1 of extract) were identified in the SDE extracts obtained from the fresh plant material.
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Two chromatographic methods, gas chromatography with flow ionization detection (GC–FID) and liquid chromatography with ultraviolet detection (LC–UV), were used to determine furfuryl alcohol in several kinds of foundry resins, after application of an optimised extraction procedure. The GC method developed gave feasibility that did not depend on resin kind. Analysis by LC was suitable just for furanic resins. The presence of interference in the phenolic resins did not allow an appropriate quantification by LC. Both methods gave accurate and precise results. Recoveries were >94%; relative standard deviations were ≤7 and ≤0.3%, respectively for GC and LC methods. Good relative deviations between the two methods were found (≤3%).
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The electrochemical behaviour of propanil and related N-substituted amides (acetanilide and N,N-diphenylacetamide) was studied by cyclic and square wave voltammetry using a glassy carbon electrode. Propanil has been found to have chemical stability under the established analytical conditions and showed an oxidation peak at +1.27V versus Ag/AgCl at pH 7.5. N,N-diphenylacetamide has a higher oxidation potential than the other compounds of +1.49V versus Ag/AgCl. Acetanilide oxidation occurred at a potential similar to that of propanil, +1.24V versus Ag/AgCl. These results are in agreement with the substitution pattern of the nitrogen atom of the amide. A degradation product of propanil, 3,4-dichloroaniline (DCA), was also studied, and showed an oxidation peak at +0.66V versus Ag/AgCl. A simple and specific quantitative electroanalytical method is described for the analysis of propanil in commercial products that contain propanil as the active ingredient, used in the treatment of rice crops in Portugal.
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Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.
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Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.
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In this paper we survey the most relevant results for the prioritybased schedulability analysis of real-time tasks, both for the fixed and dynamic priority assignment schemes. We give emphasis to the worst-case response time analysis in non-preemptive contexts, which is fundamental for the communication schedulability analysis. We define an architecture to support priority-based scheduling of messages at the application process level of a specific fieldbus communication network, the PROFIBUS. The proposed architecture improves the worst-case messages’ response time, overcoming the limitation of the first-come-first-served (FCFS) PROFIBUS queue implementations.
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Inorganica Chimica Acta 356 (2003) 215-221
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Consider the problem of scheduling sporadically-arriving tasks with implicit deadlines using Earliest-Deadline-First (EDF) on a single processor. The system may undergo changes in its operational modes and therefore the characteristics of the task set may change at run-time. We consider a well-established previously published mode-change protocol and we show that if every mode utilizes at most 50% of the processing capacity then all deadlines are met. We also show that there exists a task set that misses a deadline although the utilization exceeds 50% by just an arbitrarily small amount. Finally, we present, for a relevant special case, an exact schedulability test for EDF with mode change.
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Consider the problem of scheduling real-time tasks on a multiprocessor with the goal of meeting deadlines. Tasks arrive sporadically and have implicit deadlines, that is, the deadline of a task is equal to its minimum inter-arrival time. Consider this problem to be solved with global static-priority scheduling. We present a priority-assignment scheme with the property that if at most 38% of the processing capacity is requested then all deadlines are met.
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Traditional Real-Time Operating Systems (RTOS) are not designed to accommodate application specific requirements. They address a general case and the application must co-exist with any limitations imposed by such design. For modern real-time applications this limits the quality of services offered to the end-user. Research in this field has shown that it is possible to develop dynamic systems where adaptation is the key for success. However, adaptation requires full knowledge of the system state. To overcome this we propose a framework to gather data, and interact with the operating system, extending the traditional POSIX trace model with a partial reflective model. Such combination still preserves the trace mechanism semantics while creating a powerful platform to develop new dynamic systems, with little impact in the system and avoiding complex changes in the kernel source code.
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The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.