Nonlinear signal transformations:path to capacity above the linear AWGN Shannon limit

We present a methodology for simultaneous optimization of modulation format and regenerative transformations in nonlinear communication channels. We derived analytically the maximum regenerative Shannon capacity, towards which any regenerative channel tends at high SNR and large number of regenerators.

A static traffic assignment model combined with an artificial neural network delay model

As traffic congestion continues to worsen in large urban areas, solutions are urgently sought. However, transportation planning models, which estimate traffic volumes on transportation network links, are often unable to realistically consider travel time delays at intersections. Introducing signal controls in models often result in significant and unstable changes in network attributes, which, in turn, leads to instability of models. Ignoring the effect of delays at intersections makes the model output inaccurate and unable to predict travel time. To represent traffic conditions in a network more accurately, planning models should be capable of arriving at a network solution based on travel costs that are consistent with the intersection delays due to signal controls. This research attempts to achieve this goal by optimizing signal controls and estimating intersection delays accordingly, which are then used in traffic assignment. Simultaneous optimization of traffic routing and signal controls has not been accomplished in real-world applications of traffic assignment. To this end, a delay model dealing with five major types of intersections has been developed using artificial neural networks (ANNs). An ANN architecture consists of interconnecting artificial neurons. The architecture may either be used to gain an understanding of biological neural networks, or for solving artificial intelligence problems without necessarily creating a model of a real biological system. The ANN delay model has been trained using extensive simulations based on TRANSYT-7F signal optimizations. The delay estimates by the ANN delay model have percentage root-mean-squared errors (%RMSE) that are less than 25.6%, which is satisfactory for planning purposes. Larger prediction errors are typically associated with severely oversaturated conditions. A combined system has also been developed that includes the artificial neural network (ANN) delay estimating model and a user-equilibrium (UE) traffic assignment model. The combined system employs the Frank-Wolfe method to achieve a convergent solution. Because the ANN delay model provides no derivatives of the delay function, a Mesh Adaptive Direct Search (MADS) method is applied to assist in and expedite the iterative process of the Frank-Wolfe method. The performance of the combined system confirms that the convergence of the solution is achieved, although the global optimum may not be guaranteed.

A Static Traffic Assignment Model Combined with an Artificial Neural Network Delay Model

As traffic congestion continues to worsen in large urban areas, solutions are urgently sought. However, transportation planning models, which estimate traffic volumes on transportation network links, are often unable to realistically consider travel time delays at intersections. Introducing signal controls in models often result in significant and unstable changes in network attributes, which, in turn, leads to instability of models. Ignoring the effect of delays at intersections makes the model output inaccurate and unable to predict travel time. To represent traffic conditions in a network more accurately, planning models should be capable of arriving at a network solution based on travel costs that are consistent with the intersection delays due to signal controls. This research attempts to achieve this goal by optimizing signal controls and estimating intersection delays accordingly, which are then used in traffic assignment. Simultaneous optimization of traffic routing and signal controls has not been accomplished in real-world applications of traffic assignment. To this end, a delay model dealing with five major types of intersections has been developed using artificial neural networks (ANNs). An ANN architecture consists of interconnecting artificial neurons. The architecture may either be used to gain an understanding of biological neural networks, or for solving artificial intelligence problems without necessarily creating a model of a real biological system. The ANN delay model has been trained using extensive simulations based on TRANSYT-7F signal optimizations. The delay estimates by the ANN delay model have percentage root-mean-squared errors (%RMSE) that are less than 25.6%, which is satisfactory for planning purposes. Larger prediction errors are typically associated with severely oversaturated conditions. A combined system has also been developed that includes the artificial neural network (ANN) delay estimating model and a user-equilibrium (UE) traffic assignment model. The combined system employs the Frank-Wolfe method to achieve a convergent solution. Because the ANN delay model provides no derivatives of the delay function, a Mesh Adaptive Direct Search (MADS) method is applied to assist in and expedite the iterative process of the Frank-Wolfe method. The performance of the combined system confirms that the convergence of the solution is achieved, although the global optimum may not be guaranteed.

Sintonia automática de controladores PID: uma abordagem neuro - genética

Dissertação de dout. em Electrónica e Computação, Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2004

Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+) n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes.

Box-Behnken design for the optimization of an enantioselective method for the simultaneous analysis of propranolol and 4-hydroxypropranolol by CE

An experimental design optimization (Box-Behnken design, BBD) was used to develop a CE method for the simultaneous resolution of propranolol (Prop) and 4-hydroxypropranolol enantiomers and acetaminophen (internal standard). The method was optimized using an uncoated fused silica capillary, carboxymethyl-beta-cyclodextrin (CM-beta-CD) as chiral selector and triethylamine/phosphoric acid buffer in alkaline conditions. A BBD for four factors was selected to observe the effects of buffer electrolyte concentration, pH, CM-beta-CD concentration and voltage on separation responses. Each factor was studied at three levels: high, central and low, and three center points were added. The buffer electrolyte concentration ranged from 25 to 75 mM, the pH ranged from 8 to 9, the CM-beta-CD concentration ranged from 3.5 to 4.5%w/v, and the applied run voltage ranged from 14 to 20 W. The responses evaluated were resolution and migration time for the last peak. The obtained responses were processed by Minitab (R) to evaluate the significance of the effects and to find the optimum analysis conditions. The best results were obtained using 4%w/v CM-beta-CD in 25 mM triethylamine/H(3)PO(4) buffer at pH 9 as running electrolyte and 17 kV of voltage. Resolution values of 1.98 and 1.95 were obtained for Prop and 4-hydroxypropranolol enantiomers, respectively. The total analysis time was around of 15 min. The BBD showed to be an adequate design for the development of a CE method, resulting in a rapid and efficient optimization of the pH and concentration of the buffer, cyclodextrin concentration and applied voltage.

Optimization of a HPLC procedure for simultaneous determination of cisplatin and the complex cis,cis,trans-diamminedichlorodihydroxoplatinum(IV) in aqueous solutions

A RP-HPLC procedure for the simultaneous determination of cisplatin and the complex cis,cis,trans-diamminedichlorodihydroxo-platinum(IV), was development. The developed procedure was validated in terms of linearity, accuracy, precision, limits of detection (LOD), limits of quantification (LOQ) and specificity. The limits of detection (LOD) were 0.47 x 10-4 and 0.53 x 10-4 mol L-1 and the limits of quantification (LOQ) were 1.57 x 10-4 and 1.75 x 10-4 mol L-1, for cisplatin and cis,cis,trans-diamminedichlorodihydroxopla-tinum(IV), respectively. The average recoveries of cisplatin and cis,cis,trans-diamminedichlorodihydroxoplatinum(IV) was 100.6% ± 1.4 and 101.2% ± 1.1, respectively. Intermediate (inter-day) precision, repeatability and specificity of the procedure for hydrolysis products of cisplatin were studied. The results of the study showed that the proposed RP-HPLC procedure is simple, rapid, precise, accurate and specific.

Multivariant optimization, validation, and application of capillary electrophoresis for simultaneous determination of polyphenols and phenolic acids in Brazilian wines

A method for the simultaneous determination of the stilbene resveratrol, four phenolic acids (syringic, coumaric, caffeic, and gallic acids), and five flavonoids (catechin, rutin, kaempferol, myricetin, and quercetin) in wine by CE was developed and validated. The CE electrolyte composition and instrumental conditions were optimized using 2(7-3) factorial design and response surface analysis, showing sodium tetraborate, MeOH, and their interaction as the most influential variables. The optimal electrophoretic conditions, minimizing the chromatographic resolution statistic values, consisted of 17 mmol/L sodium tetraborate with 20% methanol as electrolyte, constant voltage of 25 kV, hydrodynamic injection at 50 mbar for 3 s, and temperature of 25 degrees C. The R(2) values for linearity varied from 0.994 to 0.999; LOD and LOQ were 0.1 to 0.3 mg/L and 0.4 to 0.8 mg/L, respectively. The RSDs for migration time and peak area obtained from ten consecutive injections were less than 2% and recoveries varied from 97 to 102%. The method was applied to 23 samples of inexpensive Brazilian wines, showing wide compositional variation.

Simultaneous material and structural optimization by multiscale topology optimization

Acknowledgments The authors acknowledge the support from Engineering and Physical Sciences Research Council, grant number EP/M002322/1. The authors would also like to thank Numerical Analysis Group at the Rutherford Appleton Laboratory for their FORTRAN HSL packages (HSL, a collection of Fortran codes for large-scale scientific computation. See http://www.hsl.rl.ac.uk/).

Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their determination by inductively coupled plasma optic emission spectrometry

A procedure for simultaneous separation/preconcentration of copper. zinc, cadmium, and nickel in water samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with 4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and preconcentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-I 14). The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and incubation time were optimized and their respective values were 5, 0.6 mmol L(-1). 0.3 mL, 0.15% (w/v), 50 degrees C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.) between 1.3% and 2.6% (n = 9). The concentration factors with and without dilution of the surfactant-rich phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0. and 6.3 mu g L(-1), respectively. The accuracy of the procedure was evaluated through recovery experiments on aqueous samples. (C) 2009 Published by Elsevier B.V.

Simultaneous saccharification and ethanol fermentation of oxalic acid pretreated corncob assessed with response surface methodology

Response surface methodology was used to evaluate optimal time, temperature and oxalic acid concentration for simultaneous saccharification and fermentation (SSF) of corncob particles by Pichia stipitis CBS 6054. Fifteen different conditions for pretreatment were examined in a 2(3) full factorial design with six axial points. Temperatures ranged from 132 to 180 degrees C, time from 10 to 90 min and oxalic acid loadings from 0.01 to 0.038 g/g solids. Separate maxima were found for enzymatic saccharification and hemicellulose fermentation, respectively, with the condition for maximum saccharification being significantly more severe. Ethanol production was affected by reaction temperature more than by oxalic acid and reaction time over the ranges examined. The effect of reaction temperature was significant at a 95% confidence level in its effect on ethanol production. Oxalic acid and reaction time were statistically significant at the 90% level. The highest ethanol concentration (20 g/l) was obtained after 48 h with an ethanol volumetric production rate of 0.42 g ethanol l(-1) h(-1). The ethanol yield after SSF with P. stipitis was significantly higher than predicted by sequential saccharification and fermentation of substrate pretreated under the same condition. This was attributed to the secretion of beta-glucosidase by P. stipitis. During SSF, free extracellular beta-glucosidase activity was 1.30 pNPG U/g with P. stipitis, while saccharification without the yeast was 0.66 pNPG U/g. Published by Elsevier Ltd.

Integral Piezoactuator System with Optimum Placement of Functionally Graded Material - A Topology Optimization Paradigm

Piezoactuators consist of compliant mechanisms actuated by two or more piezoceramic devices. During the assembling process, such flexible structures are usually bonded to the piezoceramics. The thin bonding layer(s) between the compliant mechanism and the piezoceramic may induce undesirable behavior, including unusual interfacial nonlinearities. This constitutes a drawback of piezoelectric actuators and, in some applications, such as those associated to vibration control and structural health monitoring (e. g., aircraft industry), their use may become either unfeasible or at least limited. A possible solution to this standing problem can be achieved through the functionally graded material concept and consists of developing `integral piezoactuators`, that is those with no bonding layer(s) and whose performance can be improved by tailoring their structural topology and material gradation. Thus, a topology optimization formulation is developed, which allows simultaneous distribution of void and functionally graded piezoelectric materials (including both piezo and non-piezoelectric materials) in the design domain in order to achieve certain specified actuation movements. Two concurrent design problems are considered, that is the optimum design of the piezoceramic property gradation, and the design of the functionally graded structural topology. Two-dimensional piezoactuator designs are investigated because the applications of interest consist of planar devices. Moreover, material gradation is considered in only one direction in order to account for manufacturability issues. To broaden the range of such devices in the field of smart structures, the design of integral Moonie-type functionally graded piezoactuators is provided according to specified performance requirements.

Simultaneous analysis of parabens in cosmetic products by stir bar sorptive extraction and liquid chromatography

A sensitive and precise stir bar sorptive extraction (SBSE) combined with LC (SBSE/LC) analysis is described for simultaneous determination of methyl, ethyl, propyl, and butyl parabens in commercial cosmetic products in agreement with the European Union Cosmetics Directive 76/768/EEC. Important factors in the optimization of SB SE efficiency are discussed, such as time and temperature of extraction, pH, and ionic strength of the sample, matrix effects, and liquid desorption conditions by different modes (magnetic stirring, ultrasonic). The LOQs of the SBSE/LC method ranged from 30 to 200 ng/mg, with linear response over a dynamic range, from the LOQ to 2.5 mu g/mg, with a coefficient of determination higher than 0.993. The interday precision of the SBSE/LC method presented a coefficient of variation lower than 5%. The effectiveness of the proposed method was proven for analysis of commercial cosmetic products such as body creams, antiperspirant creams, and sunscreens.

Three-dimensional electrical impedance, tomography: A topology optimization approach

Electrical impedance tomography is a technique to estimate the impedance distribution within a domain, based on measurements on its boundary. In other words, given the mathematical model of the domain, its geometry and boundary conditions, a nonlinear inverse problem of estimating the electric impedance distribution can be solved. Several impedance estimation algorithms have been proposed to solve this problem. In this paper, we present a three-dimensional algorithm, based on the topology optimization method, as an alternative. A sequence of linear programming problems, allowing for constraints, is solved utilizing this method. In each iteration, the finite element method provides the electric potential field within the model of the domain. An electrode model is also proposed (thus, increasing the accuracy of the finite element results). The algorithm is tested using numerically simulated data and also experimental data, and absolute resistivity values are obtained. These results, corresponding to phantoms with two different conductive materials, exhibit relatively well-defined boundaries between them, and show that this is a practical and potentially useful technique to be applied to monitor lung aeration, including the possibility of imaging a pneumothorax.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.