162 resultados para Hierarchical analytical process


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In the Hammersley-Aldous-Diaconis process, infinitely many particles sit in R and at most one particle is allowed at each position. A particle at x, whose nearest neighbor to the right is at y, jumps at rate y - x to a position uniformly distributed in the interval (x, y). The basic coupling between trajectories with different initial configuration induces a process with different classes of particles. We show that the invariant measures for the two-class process can be obtained as follows. First, a stationary M/M/1 queue is constructed as a function of two homogeneous Poisson processes, the arrivals with rate, and the (attempted) services with rate rho > lambda Then put first class particles at the instants of departures (effective services) and second class particles at the instants of unused services. The procedure is generalized for the n-class case by using n - 1 queues in tandem with n - 1 priority types of customers. A multi-line process is introduced; it consists of a coupling (different from Liggett's basic coupling), having as invariant measure the product of Poisson processes. The definition of the multi-line process involves the dual points of the space-time Poisson process used in the graphical construction of the reversed process. The coupled process is a transformation of the multi-line process and its invariant measure is the transformation described above of the product measure.

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This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

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Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

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The exploitation of aqueous biphasic extraction is proposed for the first time in flow analysis This extraction strategy stands out for being environmentally attractive since it is based in the utilization of two immiscible phases that are intrinsically aqueous The organic solvents of the traditional liquid-liquid extractions ale no longer used, being replaced by non-toxic, non-flammable and non-volatile ones. A single interface flow analysis (SIFA) system was implemented to carry out the extraction process due to its favourable operational characteristics that include the high automation level and simplicity of operation, the establishment of a dynamic interface where the mass transfer occurred between the two immiscible aqueous phases, and the versatile control over the extraction process namely the extraction time The application selected to demonstrate the feasibility of SIFA to perform this aqueous biphasic extraction was the pre-concentration of lead. After extraction, lead reacted with 8-hydroxyquinoline-5-sulfonic acid and the resulting product was determined by a fluorimetric detector included in the flow manifold. Therefore, the SIFA single interface was used both as extraction (enrichment) and reaction interface. (C) 2010 Elsevier B.V All rights reserved.

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Phosphoric acid is generally obtained from an aqueous process starting with the reaction between phosphate rock and sulphuric acid. Due to their chemical similarity, uranium is usually associated with phosphate rock which during chemical processing is partitioned to phosphoric acid. Uranium determination in this matrix is a very important task because of its ingestion it could lead to radiological impact on the population. Therefore, a procedure was developed using an initial precipitation with calcium hydroxide and evaporation, followed by instrumental neutron activation analysis (INAA). The procedure was applied to analyse fourteen uranium enriched phosphoric acid samples.

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A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macronutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic, A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 mu s integration time gate, 1.1 mu s delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem. (C) 2009 Elsevier B.V. All rights reserved.

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In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

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A single reaction interface flow analysis (SIFA) system for the monitoring of mannitol in pharmaceutical formulations and human urine is presented. The developed approach takes advantage of the mannitol scavenger aptitude to inhibit the chemiluminescent reaction between luminol and myoglobin in the absence of H(2)O(2). The SIFA system facilitated the fully automation of the developed methodology, allowing the in-line reproducible handling of chemical species with a very short lifetime as is the case of the hydroxyl radical generated in the abovementioned luminol/myoglobin reaction. The proposed methodology allowed the determination of mannitol concentrations between 25 mmol L(-1) and 1 mol L(-1), with good precision (R.S.D. < 4.7%, n = 3) and a sampling frequency of about 60 h(-1). The procedure was applied to the determination of mannitol in pharmaceuticals and in human urine samples Without any pretreatment process. The results obtained for pharmaceutical formulations were statistically comparable to those provided by the reference method (R.D. < 4.6%); recoveries values obtained in the analysis of spiked urine samples (between 94.9 and 105.3% of the added amount) were also satisfactory. (C) 2008 Elsevier B.V. All rights reserved.

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An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20-200 mg L(-1), described by the equation S = -0.0767 + 0.00438C (mg L(-1)), r = 0.999. The detection limit was estimated as 3 mg L(-1) at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7-16 mg L(-1), described by the equation S = -0.865 + 0.132C (mg L(-1)), r = 0.999. The detection limit was estimated as 150 mu g L(-1) at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level. (C) 2008 Elsevier B.V All rights reserved.

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Salbutamol is a bronchodilator whose use is restricted due to its anabolic effects. A flow-based procedure for salbutamol determination based on the inhibition of chemiluminescence of the luminol/hypochlorite system was developed. A flow cell constructed with a liquid-core waveguide was employed to constrain the emitted radiation, minimizing losses during transport to detector. Linear response was observed within 2.5 x 10(-6) and 1.0 x 10(-5) mol L-1 with a detection limit estimated as 1 x 10(-7) mol L-1 at the 99.7% confidence level. The coefficient of variation (n = 20), sampling rate, and luminol consumption per determination were estimated as 2.8%, 164 determinations h(-1), and 50 mu g, respectively. Results for pharmaceutical samples were in agreement with those obtained by reference procedures at the 95% confidence level.

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A method for isotopic determination of silicon by mass spectrometry in plants and soils labeled with Si-30 is reported. The development of this method is for use with studies involving the physiological process of absorption, transport, and redistribution of Si in the soil-plant system by use of the stable isotope Si-30 as a tracer. The procedure leads to SiF4 formation, and the isotopic determination of Si was based on the measurements of the (SiF3+)-Si-28, (SiF3+)-Si-29, and (SiF3+)-Si-30 signals. Relative standard deviation of Si-30 abundance measurements (n = 6) were lower than 0.1%, and the detection limit was 0.5 mg Si (dry mass).

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The study and understanding of alterations taking place during the micropropagation process can provide valuable information about this technology. The objective of this work was to evaluate the anatomical modifications in leaves of micropropagated banana (Musa spp.) plants during their adaptation to ex vitro conditions. Aseptic axillary shoots of `Preciosa` cultivar (AAAB) were rooted for 24 days in MS medium containing NAA (1mg.l(-1)) and agar (6g.l(-1)), and acclimatized for 120 days. The treatments consisted of leaves at different stages of development: T1 - leaves from plants at the end of in vitro rooting phase, T2 persistent leaves from plants after 30 days of acclimatization, T3 - new leaves from plants after 30 days of acclimatization (transition leaves). T4 - transition leaves from plants after 60 days, T5 - new leaves from plants after 60 days of acclimatization, and T6 - new leaves from plants after 120 days of acclimatization. A higher degree of differentiation and, thereby, better adaptation took place in leaves from leaf primordial differentiated in ex vitro conditions. The acclimatization phase is crucial for a greater thickness and differentiation of spongy and palisade parenchyma, and to correct the modifications of plants developed in vitro. The study of leaf anatomy provides a better understanding of alterations occurring in micropropagated banana plants.

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Here we present a system of coupled phase oscillators with nearest neighbors coupling, which we study for different boundary conditions. We concentrate at the transition to the total synchronization. We are able to develop exact solutions for the value of the coupling parameter when the system becomes completely synchronized, for the case of periodic boundary conditions as well as for a chain with fixed ends. We compare the results with those calculated numerically.

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Under physiological conditions, elderly people present memory deficit associated with neuronal loss. This pattern is also associated with Alzheimer`s disease but, in this case, in a dramatically intensified level. Kinin receptors have been involved in neurodegeneration and increase of amyloid-beta concentration, associated with Alzheimer`s disease (AD). Considering these findings, this work evaluated the role of kinin receptors in memory consolidation during the aging process. Male C57BI/6 (wt), knock-out B1 (koB1) or B2 (koB2) mice (3, 6, 12 and 18-month-old - mo; n = 10 per group) were submitted to an acquisition session, reinforcement to learning (24 h later: test 1) and final test (7 days later: test 2), in an active avoidance apparatus, to evaluate memory. Conditioned avoidance responses (CAR, % of 50 trials) were registered. In acquisition sessions, similar CAR were obtained among age matched animals from all strains. However, a significant decrease in CAR was observed throughout the aging process (3mo: 8.8 +/- 2.3%; 6mo: 4.1 +/- 0.6%; 12mo: 2.2 +/- 0.6%, 18mo: 3.6 +/- 0.6%, P < 0.01), indicating a reduction in the learning process. In test 1, as expected, memory retention increased significantly (P < 0.05) in all 3- and 6-month-old animals as well as in 12-month-old-wt and 12-month-old-koB1 (P < 0.01), compared to the training session. However, 12-month-old-koB2 and all 18-month-old animals did not show an increase in memory retention. In test 2, 3- and 6-month-old wt and koB1 mice of all ages showed a significant improvement in memory (P < 0.05) compared to test 1. However, 12-month-old wt and koB2 mice of all ages showed no difference in memory retention. We suggest that, during the aging process, the B1 receptor could be involved in neurodegeneration and memory loss. Nevertheless, the B2 receptor is apparently acting as a neuroprotective factor. (C) 2009 Elsevier Ltd. All rights reserved.

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Samples from the weathering mantle containing crandallite of three Brazilian phosphate deposits, Tapira, Catalo, and Juqui, were characterized, calcined, and agronomically evaluated. The calcination process increased total phosphorus (P) and neutral ammonium citrate soluble (NAC) P contents of all samples. The NAC solubility of original Tapira, Catalo, and Juqui was about 5% of total P, whereas for calcined samples it was 54, 16, and 53%, respectively. In a greenhouse study, rates of P were applied at 0, 10, 20, 40, 80, and 120mg P kg(-1) from the calcined materials and MCP (monocalcium phosphate) to an Ultisol cropped with upland and flooded rice for 65 days. The results showed that the calcined P samples increased dry-matter yield and P uptake with increasing rates of P applied for both crops. Tapira and Juqui were more effective for flooded than for upland rice. The calculated values of relative agronomic effectiveness of Tapira, Catalo, and Juqui with respect to MCP were 57, 48, and 53% in dry-matter yield for upland rice and 64, 50, and 69% for flooded rice, respectively.