A simple simultaneous flow injection method based on phosphomolybdenum chemistry for nitrate and nitrite determinations in water and fish samples

A direct spectrophotometric flow injection method for the simultaneous determination of nitrite and nitrate has been developed. The method is based on the oxidation of a phosphomolybdenum blue complex by the addition of nitrite and the decrease in absorbance of the blue complex is monitored at 820 nm. The injected sample is split into two segments. One of the streams was directly reacted with the above reagent and detected as nitrite. The other stream was passed through a copperised cadmium reductor column where reduction of nitrate to nitrite occurs, and the sample was then mixed with the reagent and passed through the cell of the spectrophotometer to be detected as nitrite plus nitrate. The conditions for the flow injection manifold parameters were optimised by experimental design and the concentration of nitrite and nitrate was determined in the linear range from 0.05 to 1.15 mug ml(-1) nitrite and 0.06 to 1.6 mug ml(-1) nitrate with a detection limit of 0.01 mug ml(-1) for nitrite and 0.025 mug ml(-1) for nitrate. The method is suitable for the simultaneous determination of nitrite and nitrate in fish and water samples with a sampling rate of 25+/-2 sample per hour.     

Chromatographic analysis of tryptophan metabolites

The kynurenine pathway generates multiple tryptophan metabolites called collectively kynurenines and leads to formation of the enzyme cofactor nicotinamide adenine dinucleotide. The first step in this pathway is tryptophan degradation, initiated by the rate‐limiting enzymes indoleamine 2,3‐dioxygenase, or tryptophan 2,3‐dioxygenase, depending on the tissue. The balanced kynurenine metabolism, which has been a subject of multiple studies in last decades, plays an important role in several physiological and pathological conditions such as infections, autoimmunity, neurological disorders, cancer, cataracts, as well as pregnancy. Understanding the regulation of tryptophan depletion provide novel diagnostic and treatment opportunities, however it requires reliable methods for quantification of kynurenines in biological samples with complex composition (body fluids, tissues, or cells). Trace concentrations, interference of sample components, and instability of some tryptophan metabolites need to be addressed using analytical methods. The novel separation approaches and optimized extraction protocols help to overcome difficulties in analyzing kynurenines within the complex tissue material. Recent developments in chromatography coupled with mass spectrometry provide new opportunity for quantification of tryptophan and its degradation products in various biological samples. In this review, we present current accomplishments in the chromatographic methodologies proposed for detection of tryptophan metabolites and provide a guide for choosing the optimal approach.     

Poly(vinylalcohol)/poly(ethyleneglycol)/poly(ethyleneimine) blend membranes - structure and CO2 facilitated transport

Poly(vinylalcohol) (PVA)/poly(ethyleneimine) (PEI)/poly(ethyleneglycol) (PEG) blend membranes were prepared by solution casting followed by solvent evaporation. The effects of the blend polymer composition on the membrane structure and CO₂/N₂ permeation characteristics were investigated. IR spectroscopy evidenced strong hydrogen bonding interactions between amorphous PVA and PEI, and weaker interactions between PVA and PEG. DSC studies showed that PVA crystallization was partially inhibited by the interactions between amorphous PVA and PEI blend, in which PEG separated into nodules. The CO₂ permeability decreased with an increase in CO₂ partial pressure in feed gas, while the N₂ permeability remained constant. This result indicated that only CO₂ was transported by the facilitated transport mechanism. The CO₂ and N₂ permeabilities increased monotonically with the PEI content in the blend membranes, whereas the ideal selectivity of CO₂ to N₂ transport showed a maximum. When CO₂ is humidified, its permeability through the blend membranes is much higher than that of dry CO₂, but the change in permeability due to the presence of humidity is reversible.     

New algorithm for computing the Hermite interpolation polynomial

Let x ₀, x ₁,? , x _n , be a set of n + 1 distinct real numbers (i.e., x _i ≠ x _j , for i ≠ j) and y _{i, k} , for i = 0,1,? , n, and k = 0 ,1 ,? , n _i , with n _i ≥ 1, be given of real numbers, we know that there exists a unique polynomial p _{N ? 1}(x) of degree N ? 1 where \(N={\sum }_{i=0}^{n}(n_{i}+1)\), such that \(p_{N-1}^{(k)}(x_{i})=y_{i,k}\), for i = 0,1,? , n and k = 0,1,? , n _i . P _N?1(x) is the Hermite interpolation polynomial for the set {(x _i , y _{i, k} ), i = 0,1,? , n, k = 0,1,? , n _i }. The polynomial p _N?1(x) can be computed by using the Lagrange polynomials. This paper presents a new method for computing Hermite interpolation polynomials, for a particular case n _i = 1. We will reformulate the Hermite interpolation polynomial problem and give a new algorithm for giving the solution of this problem, the Matrix Recursive Polynomial Interpolation Algorithm (MRPIA). Some properties of this algorithm will be studied and some examples will also be given.     

Effects of initial geometric imperfections on dynamic behavior of rectangular plates

The present work deals with the influence of initial geometric imperfections on the dynamic behavior of simply supported rectangular plates subjected to the action of periodic in-plane forces. The nonlinear large-deflection plate theory used in this analysis corresponds to the dynamic analog of von Karman's theory. The temporal response is analyzed by the first-order generalized asymptotic method. The solution for the temporal equations of motion takes into account the possibility of existence of simultaneous forced and parametric vibrations. The results indicate that the presence of initial imperfections may significantly raise the resonance frequencies, cause the plate to exhibit a soft spring behavior and improve slightly the stability of the plate by reducing the area of its instability zones. Furthermore, the presence of initial imperfections induces forced vibrations which interact with parametric vibrations in order to generate a competitive hesitation phenomenon in the transition zone.     

New look-ahead Lanczos-type algorithms for linear systems

Summary. A breakdown (due to a division by zero) can arise in the algorithms for implementing Lanczos' method because of the non-existence of some formal orthogonal polynomials or because the recurrence relationship used is not appropriate. Such a breakdown can be avoided by jumping over the polynomials involved. This strategy was already used in some algorithms such as the MRZ and its variants. In this paper, we propose new implementations of the recurrence relations of these algorithms which only need the storage of a fixed number of vectors, independent of the length of the jump. These new algorithms are based on Horner's rule and on a different way for computing the coefficients of the recurrence relationships. Moreover, these new algorithms seem to be more stable than the old ones and they provide better numerical results. Numerical examples and comparisons with other algorithms will be given. Received September 2, 1997 / Revised version received July 24, 1998     

Identification of phenyl-N-methylcarbamates and their transformation products in Tunisian surface water by solid-phase extraction liquid chromatography-tandem mass spectrometry

Liquid chromatography-pneumatically assisted electrospray mass spectrometry with both negative and positive ionization has been used for the determination of carbamates pesticides and their transformation products in Tunisian surface water. Eight pesticides and four of their hydrolysis products were covered in this study.Optimization of electrospray inlet conditions is described as well as results from investigations of the linearity of the detector response. Conditions for tandem mass spectrometry (MS-MS) detection of characteristic daughter ions formed by collision induced dissociation (CID) of the parent ion are described. Detection limits using MS in the selected ion monitoring (SIM) mode were generally in the order of 0.5 μg L⁻¹ or below. A principle of analysis is proposed based on triple quadrupole MS as a method for quantitative determination followed by verification of positive findings by CID-MS-MS. Application of the method for detecting carbamates residues in surface water is demonstrated.     

New convergence results on the global GMRES method for diagonalizable matrices

In the present paper, we give some new convergence results of the global GMRES method for multiple linear systems. In the case where the coefficient matrix A is diagonalizable, we derive new upper bounds for the Frobenius norm of the residual. We also consider the case of normal matrices and we propose new expressions for the norm of the residual.     

Flow-injection methylene blue-based spectrophotometric method for the determination of peroxide values in edible oils

A flow-injection method for measuring the peroxide value (PV, mequiv. O₂ kg⁻¹) in edible oils is described. The technique is based on spectrophotometric monitoring at 660 nm of methylene blue (MB), generated from leucomethylene blue (LMB) oxidation with peroxides present in oil samples. After being optimized, the method was validated in terms of linearity, precision sensitivity and recovery.Linear calibration graph was obtained in the range 0.1-5 mequiv. O₂ kg⁻¹, with a detection limit (S/N  =  3) of 0.014 mequiv. O₂ kg⁻¹. The precision of the method (R.S.D., n = 9) for within and between-days is better than 1.5% and 2.2%, respectively at 0.4 mequiv. O₂ kg⁻¹. The method was applied successfully to the determination of PV in six edible oil samples, and compared to the classical official method. Using the linear regression test, Student's t-test and variance ratio F-test, there was no significant difference between the compared methods. The proposed method is accurate, simple, cheap and could be used to control edible oil rancidity with a high sample throughputs (30 samples h⁻¹).