Evaluation of a highly sensitive amperometric biosensor with low cholinesterase charge immobilized on a chemically modified carbon paste electrode for trace determination of carbamates in fruit, vegetable and water samples

A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.

THERMAL-DECOMPOSITION OF THE HYDRATED BASIC CARBONATES OF LANTHANIDES AND YTTRIUM IN CO2 ATMOSPHERE

The hydrated basis carbonates of lanthanides and yttrium were prepared by precipitation from homogeneous solution via the hydrolysis of urea, without the addition of an auxiliary anion. Thermogravimetry, derivative thermogravimetry (TG-DTG), and differential thermal analysis (DTA) have been used in the study of these compounds in CO2 atmosphere. The results lead to the composition and thermal stability of the studied compounds, and also to a comparative study with reported results in air atmosphere.

ITERATIVE NUMERICAL-SOLUTION OF SCATTERING PROBLEMS

An iterative Neumann series method, employing a real auxiliary scattering integral equation, is used to calculate scattering lengths and phase shifts for the atomic Yukawa and exponential potentials. For these potentials the original Neumann series diverges. The present iterative method yields results that are far better, in convergence, stability and precision, than other momentum space methods. Accurate result is obtained in both cases with an estimated error of about 1 in 10(10) after some 8-10 iterations.

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.

ASSESSMENT of POLYATOMIC INTERFERENCES ELIMINATION USING A COLLISION REACTION INTERFACE (CRI) FOR INORGANIC ANALYSIS of FUEL ETHANOL BY ICP-QMS

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

Direct analysis of biodiesel microemulsions using an inductively coupled plasma mass spectrometry

An analytical procedure for direct introduction of biodiesel samples into an inductively coupled plasma mass spectrometer (ICP-MS) by using microemulsion for sample preparation was developed here. Cadmium, Co, Cu, Mn, Ni, Pb, Ti, and Zn were determined in biodiesel microemulsified samples prepared from different oleaginous sources (African palm, castor beans, palm, soybeans and an unknown oleaginous). Microemulsions were prepared using 0.25 mL Triton X-100, 0.25 mL 20% v v(-1) HNO(3), 0.50 mL biodiesel sample and 4.0 mL n-propanol. Argon-oxygen mixture was added to the plasma as auxiliary gas for correcting matrix effects caused by the high carbon load due to biodiesel microemulsions. The oxygen gas flow rate was set in 37.5 mL min(-1). The accuracy of the developed procedure was evaluated by applying addition-recovery experiments for biodiesel samples from different sources. Recoveries varied from 76.5 to 116.2% for all analytes but Zn in castor beans biodiesel sample (65.0 to 76.2%). Recoveries lower than 86.6% were obtained for palm biodiesel sample, probably due to matrix effects. Detection limits calculated by using oxygen in the composition of the auxiliary gas added to the plasma were higher than those calculated without using it, probably due to the highest formation of oxides. Despite oxides formation, best analytical performance was reached by using oxygen as auxiliary gas and by proper correction of transport interferences. The developed procedure based on microemulsion formation was suitable for direct introduction of biodiesel samples in ICP-MS. (C) 2010 Elsevier B.V. All rights reserved.

TWO DECOMPOSITION APPROACHES APPLIED TO THE MULTI-AREA OPTIMAL REACTIVE POWER FLOW PROBLEM

This paper applies two methods of mathematical decomposition to carry out an optimal reactive power flow (ORPF) in a coordinated decentralized way in the context of an interconnected multi-area power system. The first method is based on an augmented Lagrangian approach using the auxiliary problem principle (APP). The second method uses a decomposition technique based on the Karush-Kuhn-Tucker (KKT) first-order optimality conditions. The viability of each method to be used in the decomposition of multi-area ORPF is studied and the corresponding mathematical models are presented. The IEEE RTS-96, the IEEE 118-bus test systems and a 9-bus didactic system are used in order to show the operation and effectiveness of the decomposition methods.

Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

Thermal decomposition of the hydrated basic carbonates of lanthanides and yttrium in CO2 atmosphere

The hydrated basis carbonates of lanthanides and yttrium were prepared by precipitation from homogeneous solution via the hydrolysis of urea, without the addition of an auxiliary anion. Thermogravimetry, derivative thermogravimetry (TG-DTG), and differential thermal analysis (DTA) have been used in the study of these compounds in CO2 atmosphere. The results lead to the composition and thermal stability of the studied compounds, and also to a comparative study with reported results in air atmosphere. © 1993.

High-performance gel filtration patterns of venoms from three species of wasps of the genus Polybia (hymenoptera, vespidae).

The profiles of high-performance gel filtration of venoms from Polybia paulista, Polybia ignobilis and Polybia occidentalis occidentalis showed 13 peaks distributed among the three species. These profiles presented similarities that permitted the chromatographic characterization of the genus Polybia and differences that permitted the identification of each species studied. Thus, the comparative analysis of chromatographic profiles of high-performance gel filtration of venoms may be used as an auxiliary tool in taxonomic studies of Polybia wasps.

Metacarpophalangeal pattern profile in Marfan syndrome and Marfan-like patients

Marfan syndrome (MFS) is an autosomal dominant trait due to mutations in the fibrillin gene (FBN1). The MFS expressivity is variable, and its diagnosis relies completely on clinical criteria. Atypical cases and Marfan- like (marfanoid) clinical presentations are commonly found. The metacarpophalangeal pattern profile (MCPP), a radiological method in which the 19 tubular hand bones are assessed, has been used in the diagnosis of various syndromes. To investigate whether the MCPP was adequate to discriminate between MFS and Marfan-like subjects, we studied 38 patients who were referred to our service because they had an MFS diagnosis, diagnostic hypothesis, or differential diagnosis or had arachnodactyly with dolichostenomelia. Two groups were formed: 1) MFS: 21 patients with a mean age of 18.3 (10.8 S.D.) years and 2) Marfan-like syndromes: 16 patients who did not meet the current criteria, with a mean age of 14.6 (4.6 S.D.) years. The MCPP was performed in each case following the classical technique, and a characteristic mean profile was obtained for group I (MFS), with Z scores ranging from 0.69 to 2.73 (1.80 ± 0.50; mean ± S.D.). In group I, three cases had no correlation with the typical MFS pattern. In group II, three cases had an MFS pattern. The correlation with the mean MCPP of MFS permitted the differential diagnosis of MFS and marfanoid syndromes with 86% sensitivity, 81% specificity, and 86% positive and 81% negative predictive values. The results suggest that MCPP can be used effectively as an auxiliary tool in the nosology of these conditions and, because there is no change in MCPP with age, can be helpful in early diagnosis.

Design of the main racetrack microtron accelerator end magnets of the Institute of Physics of University of São Paulo

This work deals with the design of the Institute of Physics of the University of São Paulo (IFUSP) main racetrack microtron accelerator end magnets. This is the last stage of acceleration, comprised of an accelerating section (1.04 m) and two end magnets (0.1585 T), in which a 5.10 MeV beam, produced by a racetrack microtron booster has its energy raised up to 31.15 MeV after 28 accelerations. POISSON code was used to give the final configuration that includes auxiliary pole pieces (clamps) and auxiliary homogenizing gaps. The clamps create a reverse fringe field region and avoid the vertical defocusing and the horizontal displacement of the beam produced by extended fringe fields; PTRACE code was used to perform the trajectory calculations in the fringe field region. The auxiliary homogenizing gaps improve the field uniformity as they create a magnetic shower that provides uniformity of ±0.3%, before the introduction of the correcting coils that will be attached to the pole faces. This method of correction, used in the IFUSP racetrack microtron booster magnets, enabled uniformity of ±0.001% in an average field of 0.1 T and will also be employed for these end magnets. © 1999 The American Physical Society.

New approach of induction machine drive using an adaptive digital PID controller with gain planning based on artificial neural networks

The present work introduces a new strategy of induction machines speed adjustment using an adaptive PID (Proportional Integral Derivative) digital controller with gain planning based on the artificial neural networks. This digital controller uses an auxiliary variable to determine the ideal induction machine operating conditions and to establish the closed loop gain of the system. The auxiliary variable value can be estimated from the information stored in a general-purpose artificial neural network based on CMAC (Cerebellar Model Articulation Controller).

Necessary conditions of optimality for vector-valued impulsive control problems

A vector-valued impulsive control problem is considered whose dynamics, defined by a differential inclusion, are such that the vector fields associated with the singular term do not satisfy the so-called Frobenius condition. A concept of robust solution based on a new reparametrization procedure is adopted in order to derive necessary conditions of optimality. These conditions are obtained by taking a limit of those for an appropriate sequence of auxiliary standard optimal control problems approximating the original one. An example to illustrate the nature of the new optimality conditions is provided. © 2000 Elsevier Science B.V. All rights reserved.

Renormalization of the ladder light-front Bethe-Salpeter equation in the Yukawa model

The reduction of the two-fermion Bethe-Salpeter equation in the framework of light-front dynamics is studied for the Yukawa model. It yields auxiliary three-dimensional quantities for the transition matrix and the bound state. The arising effective interaction can be perturbatively expanded in powers of the coupling constant gs allowing a defined number of boson exchanges; it is divergent and needs renormalization; it also includes the instantaneous term of the Dirac propagator. One possible solution of the renormalization problem of the boson exchanges is shown to be provided by expanding the effective interaction beyond single boson exchange. The effective interaction in ladder approximation up to order g4 s is discussed in detail. It is shown that the effective interaction naturally yields the box counterterm required to be introduced ad hoc previously. The covariant results of the Bethe-Salpeter equation can be recovered from the corresponding auxiliary three-dimensional quantities.