Dual contactless conductivity and amperometric detection on hybrid PDMS/glass electrophoresis microchips

A new approach for the integration of dual contactless conductivity and amperometric detection with an electrophoresis microchip system is presented. The PDMS layer with the embedded channels was reversibly sealed to a thin glass substrate (400 mu m), on top of which a palladium electrode had been previously fabricated enabling end-channel amperometric detection. The thin glass substrate served also as a physical wall between the separation channel and the sensing copper electrodes for contactless conductivity detection. The latter were not integrated in the microfluidic device, but fabricated on an independent plastic substrate allowing a simpler and more cost-effective fabrication of the chip. PDMS/glass chips with merely contactless conductivity detection were first characterized in terms of sensitivity, efficiency and reproducibility. The separation efficiency of this system was found to be similar or slightly superior to other systems reported in the literature. The simultaneous determination of ionic and electroactive species was illustrated by the separation of peroxynitrite degradation products, i.e. NO(3)(-) (non-electroactive) and NO(2)(-) (electroactive), using hybrid PDMS/glass chips with dual contactless conductivity and amperometric detection. While both ions were detected by contactless conductivity detection with good efficiency, NO(2)(-) was also simultaneously detected amperometrically with a significant enhancement in sensitivity compared to contactless conductivity detection.

Functional specialization of Eucalyptus fine roots: contrasting potential uptake rates for nitrogen, potassium and calcium tracers at varying soil depths

1. Little is known about the role of deep roots in the nutrition of forest trees and their ability to provide a safety-net service taking up nutrients leached from the topsoil. 2. To address this issue, we studied the potential uptake of N, K and Ca by Eucalyptus grandis trees (6 years of age - 25 m mean height), in Brazil, as a function of soil depth, texture and water content. We injected NO(3)(-)- (15)N, Rb(+) (analogue of K(+)) and Sr(2+) (analogue of Ca(2+)) tracers simultaneously in a solution through plastic tubes at 10, 50, 150 and 300 cm in depth in a sandy and a clayey Ferralsol soil. A complete randomized design was set up with three replicates of paired trees per injection depth and soil type. Recently expanded leaves were sampled at various times after tracer injection in the summer, and the experiment was repeated in the winter. Soil water contents were continuously monitored at the different depths in the two soils. 3. Determination of foliar Rb and Sr concentrations and (15)N atom % made it possible to estimate the relative uptake potential (RUP) of tracer injections from the four soil depths and the specific RUP (SRUP), defined as RUP, per unit of fine root length density in the corresponding soil layer. 4. The highest tracer uptake rates were found in the topsoil, but contrasting RUP distributions were observed for the three tracers. Whilst the RUP was higher for NO(3)(-)- (15)N than for Rb(+) and Sr(2+) in the upper 50 cm of soil, the highest SRUP values for Sr(2+) and Rb(+) were found at a depth of 300 cm in the sandy soil, as well as in the clayey soil when gravitational solutions reached that depth. 5. Our results suggest that the fine roots of E. grandis trees exhibit contrasting potential uptake rates with depth depending on the nutrient. This functional specialization of roots might contribute to the high growth rates of E. grandis trees, efficiently providing the large amounts of nutrients required throughout the development of these fast-growing plantations.

Laser-induced breakdown spectroscopy and chemometrics for classification of toys relying on toxic elements

Quality control of toys for avoiding children exposure to potentially toxic elements is of utmost relevance and it is a common requirement in national and/or international norms for health and safety reasons. Laser-induced breakdown spectroscopy (LIBS) was recently evaluated at authors` laboratory for direct analysis of plastic toys and one of the main difficulties for the determination of Cd. Cr and Pb was the variety of mixtures and types of polymers. As most norms rely on migration (lixiviation) protocols, chemometric classification models from LIBS spectra were tested for sampling toys that present potential risk of Cd, Cr and Pb contamination. The classification models were generated from the emission spectra of 51 polymeric toys and by using Partial Least Squares - Discriminant Analysis (PLS-DA), Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN). The classification models and validations were carried out with 40 and 11 test samples, respectively. Best results were obtained when KNN was used, with corrected predictions varying from 95% for Cd to 100% for Cr and Pb. (C) 2011 Elsevier B.V. All rights reserved.

Dysautonomia due to reduced cholinergic neurotransmission causes cardiac remodeling and heart failure

Overwhelming evidence supports the importance of the sympathetic nervous system in heart failure. In contrast, much less is known about the role of failing cholinergic neurotransmission in cardiac disease. By using a unique genetically modified mouse line with reduced expression of the vesicular acetylcholine transporter (VAChT) and consequently decreased release of acetylcholine, we investigated the consequences of altered cholinergic tone for cardiac function. M-mode echocardiography, hemodynamic experiments, analysis of isolated perfused hearts, and measurements of cardiomyocyte contraction indicated that VAChT mutant mice have decreased left ventricle function associated with altered calcium handling. Gene expression was analyzed by quantitative reverse transcriptase PCR and Western blotting, and the results indicated that VAChT mutant mice have profound cardiac remodeling and reactivation of the fetal gene program. This phenotype was attributable to reduced cholinergic tone, since administration of the cholinesterase inhibitor pyridostigmine for 2 weeks reversed the cardiac phenotype in mutant mice. Our findings provide direct evidence that decreased cholinergic neurotransmission and underlying autonomic imbalance cause plastic alterations that contribute to heart dysfunction.

ECAP of Fe. Experiments and simulations of the in-elbow textures

The study of deformation properties of low carbon steels is of particular interest because of their many technological applications. Obtaining fine grained Fe based materials can be approached by one of the several available Severe Plastic Deformation (SPD) techniques. The current paper shows experimental data and simulations of the deformation process of iron samples by Equal Channel Angular Extrusion (ECAE). The samples were extruded in a 120 degrees channel die either by one or a few passes. The heterogeneity and local development of the deformation on the elbow of the channel has been studied by X-ray measuring and simulation of the texture evolution. The Self Consistent models used for simulation allowed the calculation of the spin of the main texture components which agreed pretty well with the experiments.

Failure analysis of low velocity impact on thin composite laminates: Experimental and numerical approaches

The dynamic behavior of composite laminates is very complex because there are many concurrent phenomena during composite laminate failure under impact load. Fiber breakage, delaminations, matrix cracking, plastic deformations due to contact and large displacements are some effects which should be considered when a structure made from composite material is impacted by a foreign object. Thus, an investigation of the low velocity impact on laminated composite thin disks of epoxy resin reinforced by carbon fiber is presented. The influence of stacking sequence and energy impact was investigated using load-time histories, displacement-time histories and energy-time histories as well as images from NDE. Indentation tests results were compared to dynamic results, verifying the inertia effects when thin composite laminate was impacted by foreign object with low velocity. Finite element analysis (FEA) was developed, using Hill`s model and material models implemented by UMAT (User Material Subroutine) into software ABAQUS (TM), in order to simulate the failure mechanisms under indentation tests. (C) 2007 Elsevier Ltd. All rights reserved.

A boundary element formulation for analysis of elastoplastic plates with geometrical nonlinearity

In this paper a new boundary element method formulation for elastoplastic analysis of plates with geometrical nonlinearities is presented. The von Mises criterion with linear isotropic hardening is considered to evaluate the plastic zone. Large deflections are assumed but within the context of small strain. To derive the boundary integral equations the von Karman`s hypothesis is taken into account. An initial stress field is applied to correct the true stresses according to the adopted criterion. Isoparametric linear elements are used to approximate the boundary unknown values while triangular internal cells with linear shape function are adopted to evaluate the domain value influences. The nonlinear system of equations is solved by using an implicit scheme together with the consistent tangent operator derived along the paper. Numerical examples are presented to demonstrate the accuracy and the validity of the proposed formulation.

GENERALIZED FINITE ELEMENT METHOD FOR NONLINEAR THREE-DIMENSIONAL ANALYSIS OF SOLIDS

The Generalized Finite Element Method (GFEM) is employed in this paper for the numerical analysis of three-dimensional solids tinder nonlinear behavior. A brief summary of the GFEM as well as a description of the formulation of the hexahedral element based oil the proposed enrichment strategy are initially presented. Next, in order to introduce the nonlinear analysis of solids, two constitutive models are briefly reviewed: Lemaitre`s model, in which damage and plasticity are coupled, and Mazars`s damage model suitable for concrete tinder increased loading. Both models are employed in the framework of a nonlocal approach to ensure solution objectivity. In the numerical analyses carried out, a selective enrichment of approximation at regions of concern in the domain (mainly those with high strain and damage gradients) is exploited. Such a possibility makes the three-dimensional analysis less expensive and practicable since re-meshing resources, characteristic of h-adaptivity, can be minimized. Moreover, a combination of three-dimensional analysis and the selective enrichment presents a valuable good tool for a better description of both damage and plastic strain scatterings.

Leak detection by inverse transient analysis in an experimental PVC pipe system

Leakage reduction in water supply systems and distribution networks has been an increasingly important issue in the water industry since leaks and ruptures result in major physical and economic losses. Hydraulic transient solvers can be used in the system operational diagnosis, namely for leak detection purposes, due to their capability to describe the dynamic behaviour of the systems and to provide substantial amounts of data. In this research work, the association of hydraulic transient analysis with an optimisation model, through inverse transient analysis (ITA), has been used for leak detection and its location in an experimental facility containing PVC pipes. Observed transient pressure data have been used for testing ITA. A key factor for the success of the leak detection technique used is the accurate calibration of the transient solver, namely adequate boundary conditions and the description of energy dissipation effects since PVC pipes are characterised by a viscoelastic mechanical response. Results have shown that leaks were located with an accuracy between 4-15% of the total length of the pipeline, depending on the discretisation of the system model.

A novel aerobic-anoxic biological filter for nitrogen removal from UASB effluent using biogas compounds as electron donors for denitrification

The performance of a new trickling filter (TF) configuration composed of an upper compartment for nitrification and a lower compartment for denitrification of effluent from a UASB reactor treating domestic sewage was evaluated. The TF was packed with new plastic material characterized by its durability and high percentage of void spaces. The feasibility of using the reduced compounds present in the biogas produced by a UASB reactor as electron donor for denitrification was also evaluated. Efficient nitrification and denitrification was achieved for the mean hydraulic (5.6 m(3) m(-2) d(-1)) organic (0.26 kg COD m(-3) d(-1)) and ammonia-N (0.08 kg m(-3) d(-1)) loading rates applied, resulting in ammonia-N removal ranging from 60 to 74%. The final effluent presented ammonia-N lower than 13 mg L(-1). Despite the presence of dissolved oxygen (DO) in the denitrification compartment, its performance was considered quite satisfactory and final nitrate concentrations were lower than 10 mg L(-1). The results indicate that methane was the main electron donor used for denitrification. Additionally, denitrification can probably be improved by avoiding high DO concentration in the denitrification compartment and by enhancing biogas transfer in the anoxic zone.

Kinetic studies of urban solid residues and leachate from sanitary landfill

Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc. The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn-Wall-Ozawa method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban`s samples, but not for leachate`s sample. The occurred difference can be attributed to the constituents present in leachate.

Microstructural characteristics and corrosion behavior of a super duplex stainless steel casting

The machining of super duplex stainless steel castings is usually complicated by the difficulty involved in maintaining the dimensional tolerances required for given applications. Internal stresses originating from the solidification process and from subsequent heat treatments reach levels that exceed the material`s yield strength, promoting plastic strain. Stress relief heat treatments at 520 degrees C for 2 h are an interesting option to solve this problem, but because these materials present a thermodynamically metastable condition, a few precautions should be taken. The main objective of this work was to demonstrate that, after solution annealing at 1130 degrees C and water quenching, stress relief at 520 degrees C for 2 h did not alter the duplex microstructure or impair the pitting corrosion resistance of ASTM A890/A890M Grade 6A steel. This finding was confirmed by microstructural characterization techniques, including light optical and scanning electron microscopy, and X-ray diffraction. Corrosion potential measurements in synthetic sea water containing 20,000 ppm of chloride ions were also conducted at three temperatures: 5 degrees C, 25 degrees C and 60 degrees C. (c) 2008 Elsevier Inc. All rights reserved.

Fatigue behaviour of friction stir welded AA2024-T3 alloy: longitudinal and transverse crack growth

The fatigue crack growth properties of friction stir welded joints of 2024-T3 aluminium alloy have been studied under constant load amplitude (increasing-Delta K), with special emphasis on the residual stress (inverse weight function) effects on longitudinal and transverse crack growth rate predictions (Glinka`s method). In general, welded joints were more resistant to longitudinally growing fatigue cracks than the parent material at threshold Delta K values, when beneficial thermal residual stresses decelerated crack growth rate, while the opposite behaviour was observed next to K-C instability, basically due to monotonic fracture modes intercepting fatigue crack growth in weld microstructures. As a result, fatigue crack growth rate (FCGR) predictions were conservative at lower propagation rates and non-conservative for faster cracks. Regarding transverse cracks, intense compressive residual stresses rendered welded plates more fatigue resistant than neat parent plate. However, once the crack tip entered the more brittle weld region substantial acceleration of FCGR occurred due to operative monotonic tensile modes of fracture, leading to non-conservative crack growth rate predictions next to K-C instability. At threshold Delta K values non-conservative predictions values resulted from residual stress relaxation. Improvements on predicted FCGR values were strongly dependent on how the progressive plastic relaxation of the residual stress field was considered.

Wavelet-Galerkin method for one-dimensional elastoplasticity and damage problems: Constitutive modeling and computational aspects

This work presents an analysis of the wavelet-Galerkin method for one-dimensional elastoplastic-damage problems. Time-stepping algorithm for non-linear dynamics is presented. Numerical treatment of the constitutive models is developed by the use of return-mapping algorithm. For spacial discretization we can use wavelet-Galerkin method instead of standard finite element method. This approach allows to locate singularities. The discrete formulation developed can be applied to the simulation of one-dimensional problems for elastic-plastic-damage models. (C) 2007 Elsevier Inc. All rights reserved.

Effects of elastic indenter deformation on spherical instrumented indentation tests: the reduced elastic modulus

Although the Hertz theory is not applicable in the analysis of the indentation of elastic-plastic materials, it is common practice to incorporate the concept of indenter/specimen combined modulus to consider indenter deformation. The appropriateness was assessed of the use of reduced modulus to incorporate the effect of indenter deformation in the analysis of the indentation with spherical indenters. The analysis based on finite element simulations considered four values of the ratio of the indented material elastic modulus to that of the diamond indenter, E/E(i) (0, 0.04, 0.19, 0.39), four values of the ratio of the elastic reduced modulus to the initial yield strength, E(r)/Y (0, 10, 20, 100), and two values of the ratio of the indenter radius to maximum total displacement, R/delta(max) (3, 10). Indenter deformation effects are better accounted for by the reduced modulus if the indented material behaves entirely elastically. In this case, identical load-displacement (P - delta) curves are obtained with rigid and elastic spherical indenters for the same elastic reduced modulus. Changes in the ratio E/E(i), from 0 to 0.39, resulted in variations lower than 5% for the load dimensionless functions, lower than 3% in the contact area, A(c), and lower than 5% in the ratio H/E(r). However, deformations of the elastic indenter made the actual radius of contact change, even in the indentation of elastic materials. Even though the load dimensionless functions showed only a little increase with the ratio E/E(i), the hardening coefficient and the yield strength could be slightly overestimated when algorithms based on rigid indenters are used. For the unloading curves, the ratio delta(e)/delta(max), where delta(e) is the point corresponding to zero load of a straight line with slope S from the point (P(max), delta(max)), varied less than 5% with the ratio E/E(i). Similarly, the relationship between reduced modulus and the unloading indentation curve, expressed by Sneddon`s equation, did not reveal the necessity of correction with the ratio E/E(i). The most affected parameter in the indentation curve, as a consequence of the indentation deformation, was the ratio between the residual indentation depth after complete unloading and the maximum indenter displacement, delta(r)/delta(max) (up to 26%), but this variation did not significantly decrease the capability to estimate hardness and elastic modulus based on the ratio of the residual indentation depth to maximum indentation depth, h(r)/h(max). In general, the results confirm the convenience of the use of the reduced modulus in the spherical instrumented indentation tests.