Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Biocompatible in-tube solid phase microextraction coupled with liquid chromatography-fluorescence detection for determination of interferon alpha in plasma samples

The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN alpha(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN alpha(2a) analyses in plasma sample were carried out within 25 min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0 MIU mL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN alpha(2a) in plasma samples for therapeutic drug monitoring. (C) 2010 Elsevier B.V. All rights reserved.

Fluoxetine and norfluoxetine analysis by direct injection of human plasma in a column switching liquid chromatographic system

A column switching LC method is presented for the analysis of fluoxetine (FLU) and norfluoxetine (NFLU) by direct injection of human plasma using a lab-made restricted access media (RAM) column. A RAM-BSA-octadecyl silica (C-18) column (40 min x 4.6 mm, 10 mu m) is evaluated in both backflush and foreflush elution modes and coupled with a C-18 lab-made (50 mm x 4.6 mm, 3 pm) analytical column in order to perform online sample preparation. Direct injection of 100 mu L, of plasma samples is possible with the developed approach. In addition, reduction of sample handling is obtained when compared with traditional liquid-liquid extraction (LLE) and SPE. The total analysis time is around 20 min. A LOQ of 15 ng/mL is achieved in a concentration range of 15-500 ng/mL, allowing the therapeutic drug monitoring of clinical samples. The precision values achieved are lower than 15% for all the evaluated points with adequate recovery and accuracy. Furthermore, no matrix interferences are found in the analysis and the proposed method shows to be an adequate alternative for analysis of FLU in plasma.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Thermoeconomic analysis of an evaporative desiccant air conditioning system

In this paper, a thermoeconomic analysis method based on the first and second law of thermodynamics and applied to an evaporative cooling system coupled to an adsorption dehumidifier, is presented. The main objective is the use of a method called exergetic manufacturing cost (EMC) applied to a system that operates in three different conditions to minimize the operation costs. Basic parameters are the RIP ratio (reactivation air/process air) and the reactivation air temperature. Results of this work show that the minimum reactivation temperature and the minimum RIP ratio corresponds to the smaller EMC. This result can be corroborated through an energetic analysis. It is noted that this case is also the one corresponding to smaller energy loss. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Analysis of the Coupled Stretching-Bending Problem of Stiffened Plates by a BEM Formulation Based on Reissner's Hypothesis

In this work, the plate bending formulation of the boundary element method - BEM, based on the Reissner's hypothesis, is extended to the analysis of plates reinforced by beams taking into account the membrane effects. The formulation is derived by assuming a zoned body where each sub-region defines a beam or a slab and all of them are represented by a chosen reference surface. Equilibrium and compatibility conditions are automatically imposed by the integral equations, which treat this composed structure as a single body. In order to reduce the number of degrees of freedom, the problem values defined on the interfaces are written in terms of their values on the beam axis. Initially are derived separated equations for the bending and stretching problems, but in the final system of equations the two problems are coupled and can not be treated separately. Finally are presented some numerical examples whose analytical results are known to show the accuracy of the proposed model.

Force system evaluation of symmetrical beta-titanium T-loop springs preactivated by curvature and concentrated bends

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of thyroid hormone T3 on Myosin-Va expression in the central nervous system

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Female reproductive system of the sugarcane spittlebug Mahanarva fimbriolata (Auchenorrhyncha): Vitellogenesis dynamics and protein quantification

The present study aimed describing the ovaries of the sugarcane spittlebug Mahanarva fimbriolata which are meroistic telotrophic with nurse cells and oocytes located in the tropharium. SEM revealed paired ovaries located dorsolaterally around the intestine, and oocytes exhibiting shapes ranging from round (less developed) to elliptic (more developed), suggesting a simultaneous, although, asynchronous development. Based on histological data we classified the oocytes in stages from I to V. Stage I oocytes exhibit follicular epithelium with cubic and/or prismatic cells, fine cytoplasmic granules. Stage II oocytes present intercellular spaces in the follicular epithelium due to the incorporation of yolk elements from the hemolymph. Small granules are present in the periphery of oocytes while larger granules are observed in the center. Stage III oocytes are larger and intercellular spaces in the follicular epithelium are evident, as well as the interface between follicular epithelium and oocyte. Yolk granules of different sizes are present in the cytoplasm. During this stage, chorion deposition initiates. Stage IV oocytes exhibit squamous follicular cells and larger intercellular spaces when compared to those observed in the previous stage. The oocyte cytoplasm present granular and viscous yolk, the latter is the result of the breakdown of granules. Stage V oocytes exhibit a follicular epithelium almost completely degenerated, smaller quantities of granular yolk and large amounts of viscous yolk. Based on our findings we established the sequence of yolk deposition in M. fimbriolata oocyte as follows: proteins and lipids, which are first produced by endogenous processes in stages I and II oocytes. Exogenous incorporation begins in stage III. In stages I and II oocytes, lipids are also produced by follicular epithelial cells. The third element to be deposited is polysaccharides, mainly found as complexes. Therefore, the yolk present in the oocytes of this species consists of glycolipoproteins. Molecular weights of proteins present in M. fimbriolata oocytes ranged from 10 to 92 KDa, differently from vitellogenin, the most common protein present in insect oocytes, weighing approximately 180 KDa. (c) 2006 Elsevier Ltd. All rights reserved.

Photoeletrolytic system applied to remazol red brilliant degradation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On exact boundary controllability for linearly coupled wave equations

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Solitons in tunnel-coupled repulsive and attractive condensates

We study solitons in the condensate trapped in a double-well potential with far-separated wells, when the s-wave scattering length has different signs in the two parts of the condensate. By employing the coupled-mode approximation it is shown that there are unusual stable bright solitons in the condensate, with the larger share of atoms being gathered in the repulsive part. Such unusual solitons derive their stability from the quantum tunneling and correspond to the strong coupling between the parts of the condensate. The ground state of the system, however, corresponds to weak coupling between the condensate parts, with the larger share of atoms being gathered in the attractive part of the condensate.

Dressed (renormalized) coordinates in a nonlinear system

In previous publications, the concepts of dressed coordinates and dressed states have been introduced in the context of a harmonic oscillator linearly coupled to an infinity set of other harmonic oscillators. In this paper, we show how to generalize such dressed coordinates and. states to a nonlinear version of the mentioned system. Also, we clarify some misunderstandings about the concept of dressed coordinates. Indeed, now we: prefer to call them renormalized coordinates to emphasize the analogy with the renormalized fields in quantum field theory.

Stable periodic waves in coupled Kuramoto-Sivashinsky-Korteweg-de Vries equations

Periodic waves are investigated in a system composed of a Kuramoto-Sivashinsky-Korteweg-de Vries (KS-KdV) equation linearly coupled to an extra linear dissipative one. The model describes, e.g., a two-layer liquid film flowing down an inclined plane. It has been recently shown that the system supports stable solitary pulses. We demonstrate that a perturbation analysis, based on the balance equation for the net field momentum, predicts the existence of stable cnoidal waves (CnWs) in the same system. It is found that the mean value u(0) of the wave field u in the main subsystem, but not the mean value of the extra field, affects the stability of the periodic waves. Three different areas can be distinguished inside the stability region in the parameter plane (L, u(0)), where L is the wave's period. In these areas, stable are, respectively, CnWs with positive velocity, constant solutions, and CnWs with negative velocity. Multistability, i.e., the coexistence of several attractors, including the waves with several maxima per period, appears at large value of L. The analytical predictions are completely confirmed by direct simulations. Stable waves are also found numerically in the limit of vanishing dispersion, when the KS-KdV equation goes over into the KS one.

The Faddeev-Jackiw approach and the conformal affine sl(2) Toda model coupled to the matter field

The conformal affine sl(2) Toda model coupled to the matter field is treated as a constrained system in the context of Faddeev-Jackiw and the (constrained) symplectic schemes. We recover from this theory either the sine-Gordon or the massive Thirring model, through a process of Hamiltonian reduction, considering the equivalence of the Noether and topological currrents as a constraint and gauge fixing the conformal symmetry. (C) 2000 Academic Press.