Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

ESR STUDY OF CUCL2 ADSORBED ON A CHEMICALLY-MODIFIED SILICA-GEL SURFACE WITH BENZIMIDAZOLE MOLECULE

The ESR spectrum of CuCl2 adsorbed onto a silica gel surface chemically modified with the benzimidazole molecule showed that the surface complex has an octahedral symmetry with tetragonal distortion. The measured ESR parameters were g(parallel to) = 2.287, g(perpendicular to) = 2.062, A(parallel to) = 153 G and superhyperfine splitting A(N) = 15 G. The fit of the theoretical expressions to the experimental data was very reasonable. The effective spin orbit coupling constant for Cu2+ was reduced from its normal free ion value of lambda = -828 cm(-1) by as much as 30%. This reduction of lambda is normal in the solid state and in frozen solution complexes.

The element-free Galerkin method applied to the study of fully developed magnetohydrodynamic duct flows

In this paper, the meshless method is introduced to magnetohydrodynamics. A numerical scheme based on the element-free Galerkin method is used to solve the laminar steady-state two-dimensional fully developed magnetohydrodynamic flow in a rectangular duct. Accurate and convergent solutions are achieved for low to moderately high Hartmann numbers.

Surface effects on moving vortices in superconducting stripes

Size and surface dynamical effects are investigated in thin superconducting stripes with variable width. We perform numerical simulations of the vortex dynamics, with the inclusion of the surface confining potential and a random distribution of pinning centers. To fully characterize the vortex flow, we calculate the differential resistance, the transverse diffusion coefficient, the structure factor and the intensity of the Bragg peaks, as functions of the transport force. We found that surface effects induce a premature ordering of the flux line lattice, and the system displays plastic and smectic behavior only in a very narrow range of forces. (c) 2007 Elsevier B.V. All rights reserved.

Flow-through cell based on an array of gold microelectrodes obtained from modified integrated circuit chips

The construction of a flow-through cell incorporating an array of gold microelectrodes is described and its application to flow injection analysis with amperometric detection is presented, Simple modification of almost any conventional integrated circuit chip, used as an inexpensive source of pre-assembled gold micro-wires, leads to the rapid and successful preparation of arrays of 8-48 elements, the polymeric encapsulation material from the top face of the chip is removed by abrasion until the gold micro-mires (used to interconnect the silicon circuit to the external contact pins of the chip) are disrupted and their transversal (elliptical) sections become exposed. Once polished, the flat and smooth top surface of the gold microelectrode-array chip (MEAC) is provided with a spacer and fitted under pressure against an acrylic block with the reference and auxiliary electrodes, to form the electrochemical (thin-layer) flow cell, while the contact pins are plugged into a standard IC socket, This design ensures autonomous electric contact with each electrode and allows fast dismantling for polishing or substitution, the performance of flow cells with MEACs was investigated utilizing the technique of reverse pulse amperometry without oxygen removal, A method was established for the determination of the copper concentration in sugar cane spirit, regulated by law for beverages, Samples from industrial producers and small-scale (alembic) brewers were compared, With a 24 MEAC, a detection limit of 30 mu g I-l of copper (4.7 x 10(-7) mol l(-1) of Cu-II for 100 mu l injections) was calculated, Routine operation was established at a frequency of 60-90 determinations per hour, Intercomparison with atomic absorption spectrometric determinations resulted in excellent agreement.

Molecular engineering strategies to control photo-induced birefringence and surface-relief gratings on layer-by-layer films from an azopolymer

The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

A Chloro-Bridged Linear Chain Imine-Copper(II) Complex and Its Application as an Enzyme-Free Amperometric Biosensor for Hydrogen Peroxide

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

The influence of fermentation time and the presence of salts in the rheology of the fermentation broth of a polysaccharide-producing bacteria free of soil

Rheological studies were carried out in the fermentation broth of a polysaccharide-producing microorganism free of soil. This microorganism was designated 4B. The bacteria 4B was inoculated in the fermentation broth, which consisted of a carbon source and mineral salts, and it was incubated in a rotating agitator at 30 degreesC for 72 h at 210 rpm. A rheometer of concentric cylinders equipped with a thermostatic bath was used and the readings were taken at 25 degreesC. A study was made of the influence of the fermentation time and the readings were made after 24, 48 and 72 h of incubation, using, separately, sucrose and glucose as carbon sources. The influence of the salt concentrations was determined in each carbon source; the salts used were NaCl, KCl and CaCl2 in the concentrations of 0.4%, 1.0%, 2.0% and 3.0%. It was observed that the fermentation broth behaves as a non-Newtonian fluid and it presents pseudoplastic behaviour. Calculations were made of the flow behaviour index (n) and the consistency index (k) of the samples after 24, 48 and 72 h of fermentation, and it was observed that the 72 h sample presented higher k and consequently higher apparent viscosity. of the carbon sources used, the sucrose presented higher viscous broths after 24 and 48 h, and the glucose after 72 h of fermentation. With relation to the effect of the addition of salts, the CaCl2 presented a higher influence on the viscosity of the fermentation broths. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

Thermo-Reversible Sol-Gel Transition of Surface Modified Titanium Poly Oxo Building Blocks

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

The minimum quantity of lubricant (MQL) technique in the surface grinding of steel

This research aimed to analyze the viability of the minimum quantity of lubricant (MQL) technique towards different methods of lubri-refrigeration in surface grinding of steel, considering process quality, wheel life and the viability of using cutting fluids The proposal methods were the conventional (abundant fluid flow), the minimum quantity lubrication (MQL) and the optimized method with Webster nozzle (rounded) This analysis was carried out in equal machining conditions, through the assessment of variables such as grinding force, surface roughness, G ratio (volume of removed material/volume of wheel wear), and microhardness The results showed the possibility of improvement of the grinding process Besides, there is the opportunity for production of high quality workpieces with lower costs The MQL technique showed efficiency in machining with lower depths of cut The optimized method with Webster nozzle applies the fluid in a rational way, without considerable waste Hence, the results show that industry can rationalize and optimize the application of cutting fluids, avoiding inappropriate disposal, inadequate use and consequently environment pollution

Sensitive Affimer and Antibody Based Impedimetric Label-Free Assays for C-Reactive Protein

C-reactive protein (CRP) is an acute phase protein whose levels are increased in many disorders. Levels greater than 3 mu g/mL serum have hitherto been considered to indicate pathology, but there is increasing interest in assessments between 0.1 and 10 mu g/mL, which have been found to correlate with severity of risk for cardiovascular disease. We report herein the generation of both antibody and Affimer based impedance immunoassays for CRP that are substantially more sensitive than clinically utilized immunonephelometry and immunoturbidity assessments. Significant in this study is not only the use of a constrained peptide to detect a clinically important target but also that derived electrochemical impedance assays can be highly sensitive even with probes whose relatively weak (mu M) affinities are not amenable to target detection by surface plasmon resonance (SPR). Key to this finding is acknowledging that receptive surfaces of comparatively low initial steric bulk and charge transfer resistance are especially primed to be highly responsive to target binding in electroanalytical assays of this type.

Size, electrophoretic mobility, and ion dissociation of vesicles prepared with synthetic amphiphiles

Vesicles prepared with synthetic amphiphiles (dioctadecyldimethylammonium bromide and chloride, dihexadecyl phosphate and its sodium salt) were obtained by sonication, ethanol injections, and chloroform injections. The hydrodynamic diameter of vesicles (Dh), estimated from the diffusivity measured by quasielastic light scattering, ranged from 230 to 3000 Å. The electrophoretic mobility (Um) was measured by free-flow electrophoresis. The zeta potential (ζ) and the degree of counterion dissociation (α) of the vesicles were calculated from Um and conductivity data, α decreased with increasing Dh of the vesicles, probably due to the decreasing headgroup area and the increasing counterion association needed to relax the surface electrostatic potential. The electrophoretic mobility was also calculated (Uc) according to an impenetrable, nonconducting sphere model with a spherically symmetric charge distribution approximation. Within the limits of the experimental error(s) of the (different) methods employed and the assumptions made in the calculations, the fact that the Um/Uc ratio ranged from 1.3 to 7.5 was considered to be a good agreement between the calculated and the experimental values. © 1990 American Chemical Society.

Electromyographic study of the trapezius muscle in free movements of the shoulder

The objective of this study is to analyze the simultaneity of the actions of the three portions of the trapezius (superior portion = TS; middle portion = TM and inferior portion = TI) in elevation, lowering, retraction and protraction of the shoulders. The electromyographic tests were carried out in 20 volunteers using a 4-channel TECA TE 2-7 electromyograph and surface and single coaxial needle electrodes. The electromyographs, obtained with the two types of electrodes, show that in elevation and lowering of the shoulders, TS and TM present increasing and decreasing activity, respectively, from the beginning until the end of these movements. In retraction of the shoulders, TM and TI present increasing activity from the beginning to the end of the movement. In protraction, TS, TM and TI do not show any activity.

Pre-concentration of Cd(II), Cr(III), Cu(II) and Ni(II) on a column packed with free carboxymethylcellulose (CMCH)

Carboxymethylcellulose packed in to a glass column was used to pre-concentrate metallic cations from aqueous solutions. The pre-concentrated metal cations are directly eluted from the column using 5.0 mL of 1.0 mol L -1 hydrochloric acid. The optimum pre-concentration conditions are given (glass column, 16 cm length, 0.80 cm i.d., stationary phase height of 12 cm, flow-rate, 1.5 mL min -1). The recuperation efficiency achieved is greater than 95%, while the enrichment factor is 10 for 50 mL of solution (0.50 mg L -1 each).