A fast and reliable route integrating calibration and analysis protocols for water-soluble vitamin determination on microchip-electrochemistry platforms

A novel analytical route to determine water-soluble vitamins (B group and C) using single channel microchip-electrochemistry platforms is presented. The electrochemical detection protocol was carefully optimized, and it was shown that it was crucial to use 1 M nitric acid in the detector compartment to detect folic acid. A phosphate buffer (pH 6, 10 mM) and a separation voltage of 2 kV gave the complete separation of vitamins in less than 130 s, with good reproducibility (RSDs less than 10%) and accuracy (error less than 9%). In addition, a methodological innovation integrating calibration and analysis of water-soluble vitamins on the chip is also proposed. The strategy consisted in sequentially using both reservoirs (named calibration and analysis reservoirs) as well as a calibration factor (defined as signal/concentration of analyte). The analytical route required 350 s in the overall protocol (employing 130 s in calibration plus 130 s in analysis), an improvement over the times used in both conventional and microchip protocols.     

Electron doping versus antisite defects: Structural and magnetic properties of Sr2−xLaxCrMoO6 and Sr2−xLaxCr1+x/2Mo1−x/2O6 perovskites

This study reports the synthesis, structure and magnetic properties of Sr_2?xLa_xCrMoO₆ and Sr_2?xLa_xCr_1+x/2Mo_1?x/2O₆ samples. Although both series exhibit similar crystal structures, Sr_2?xLa_xCrMoO₆ samples present an effective electron doping revealed by a significant expansion of the unit cell with increasing x. In Sr_2?xLa_xCr_1+x/2Mo_1?x/2O₆ samples instead, the Cr-excess leads to a non electron doped system. Both series show a large amount of antisite defects whose number increases as La-content increases. Neutron diffraction patterns reveal the existence of long-range magnetic ordering for all samples but the magnetic peaks are very broad for Sr₂CrMoO₆ indicating a short coherence length of the magnetic ordering. This coherence length is increased upon replacing Sr by La. In both systems there is a clear increase of the magnetic transition temperature with increasing the La-content. The samples show ferromagnetic contributions at low temperature as deduced from the magnetic hysteresis loops typical of hard ferromagnetic materials. However, magnetic saturation is not achieved even at 5 T and the magnetic moment at this field is small. The ac magnetic susceptibility reveals the existence of several anomalies suggesting that these compounds are magnetically inhomogeneous. This is probably due to the presence of the large amount of structural defects not homogenously distributed.     

MALDI TOF‐TOF characterization of a light stabilizer polymer contaminant from polypropylene or polyethylene plastic test tubes

Disposable plasticware such as plastic test tubes are routinely used in all proteomics laboratories. Additives in polymers are used to protect them against oxygen or ultraviolet (UV) light degradation. Hindered amine light stabilizers (HALSs) are of utmost importance in modern polyolefin (polypropylene, polyethylene) stabilization. In this article, we demonstrate that the manufacturing polymeric agent: poly‐(N‐β‐hydroxyethyl‐2,2,6,6‐tetramethyl‐4‐hydroxy‐piperidinyl succinate), known as Tinuvin‐622 or Lowilite 62, from the HALS family, leaches from laboratory polypropylene or polyethylene plastic test tubes into the standard solvents for sample preparation. The analysis of these polluted samples by matrix‐assisted laser desorption/ionisation‐time of flight (MALDI‐TOF) mass spectrometry, in the positive mode, shows highly contaminated mass spectra, due to the high sensitivity of this technique. These contaminants have mass range and mass defect similar to those of peptides arising from the digestion of a protein in a conventional proteomics study. Therefore, they can be really harmful for proteomics studies, leading to misattributions, preventing any protein identification. In this article, an MS and MS/MS fingerprint of this pollutant is given and some pieces of advice to avoid it are proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

Lorentz Spaces Of Vector-Valued Measures

Given a non-atomic, finite and complete measure space (,,µ)and a Banach space X, the modulus of continuity for a vectormeasure F is defined as the function _F(t) = sup_µ(E)t |F|(E)and the space V^p,q(X) of vector measures such that t^–1/p'_F(t) L^q((0,µ()],dt/t) is introduced. It is shown thatV^p,q(X) contains isometrically L^p,q(X) and that L^p,q(X) = V^p,q(X)if and only if X has the Radon–Nikodym property. It isalso proved that V^p,q(X) coincides with the space of cone absolutelysumming operators from L^p',q^' into X and the duality V^p,q(X^*)=(Lp^',q^'(X))^*where 1/p+1/p^'= 1/q+1/q^' = 1. Finally, V^p,q(X) is identifiedwith the interpolation space obtained by the real method (V¹(X),V(X))_1/p^',q. Spaces where the variation of F is replaced bythe semivariation are also considered.     

Flow-injection spectrophotometric determination of cyanate in bioremediation processes by use of immobilised inducible cyanase

A new flow injection (FI) method for photometric monitoring of cyanate in bioremediation processes using immobilised native cyanase is described. The method is based on the catalytic reaction between cyanate and bicarbonate to produce ammonia and carbon dioxide in the presence of an inducible native cyanase, immobilised in a reactor packed with glass beads. Two degrees of purification of the biocatalyst were used-heated cell-free extract and purified extract of cyanase from Pseudomonas pseudoalcaligenes CECT 5344. The ammonia produced by the enzymatic reaction is finally monitored photometrically at 700 nm using a modification of the conventional Berthelot method. The method furnishes different calibration curves depending on the degree of purification of the cyanase, with linear ranges between 1.23 and 616.50 micromol L(-1) ( r(2)=0.9979, n=7) and between 1.07 and 308.25 micro mol L(-1) ( r(2)= 0.9992, n=7) for the heated cell-free extract and the purified cyanase extract, respectively. No statistically significant differences between the samples were found in the precision study evaluated at two cyanate concentration levels using one-way analysis of variance. A sampling frequency of 15 h(-1) was achieved. The method was used to monitor cyanate consumption in a cyanate bioremediation tank inoculated with Pseudomonas pseudoalcaligenes CECT 5344 strain. The correlation between cyanate degradation and ammonia production was tested using a conventional method. Finally, the method was applied to different samples collected from the bioremediation tank using the standard addition method; recoveries between 85.9 and 97.4% were obtained.     

The H-point and generalized H-point standard additions methods for flow injection procedures

This paper establishes the fundamentals of the H-point standard additions method (HPSAM) and generalized H-point standard additions method (GHPSAM) in the flow injection technique. Two kinds of analytical signals can be employed, FIA peaks and spectra. Different analytical problems have been studied: determinations of one analyte in the presence or absence of matrix effect when different blank features are present, and determination of two analytes in the presence of blank bias error affecting the development of one of them. The determination of chloride with mercury thiocyanate which presents a matrix effect, and the determinations of calcium and/or magnesium with arsenazo III are examined. The methods were compared with conventional data treatment and proved able to isolate the analyte signal from the global one, thus providing accurate and precise results in the determination of the above mentioned species in bottled waters. No additional experimental work is needed to apply the methods.     

Evaluation of Accuracy of Electrochemical Isoflavonoid Index for the Determination of Total Isoflavones in Soy Samples

The accuracy of a novel electroanalytical route to determine total isoflavones using a secondary standard from Drug Master File (SW/1211/03) as metrological reference with well‐known traceability and its applicability using representative soy samples is demonstrated. Calibration protocols were used i) for choosing a suitable isoflavone standard to determine the total isoflavone content, ii) to evaluate matrix effects and, iii) to evaluate the overall reliability and performance of the method in analytical operations, extraction and analysis. The inherent electroactivity of both, aglycones and glycoside structures and the similar analytical sensitivity exhibited by the prominent soy isoflavones was relevant to determine the total amount with reliability in terms of accuracy (E<10%) and precision (RSDs<7%) in soy samples. In consequence, the introduction of the term isoflavonoid index as the total amount of isoflavones obtained when they are amperometrically monitorized at +1.0 V as a particular case of the electrochemical index concept is proposed.     

A fractional-step method for the incompressible Navier–Stokes equations related to a predictor–multicorrector algorithm

An implicit fractional-step method for the numerical solution of the time-dependent incompressible Navier–Stokes equations in primitive variables is studied in this paper. The method, which is first-order-accurate in the time step, is shown to converge to an exact solution of the equations. By adequately splitting the viscous term, it allows the enforcement of full Dirichlet boundary conditions on the velocity in all substeps of the scheme, unlike standard projection methods. The consideration of this method was actually motivated by the study of a well-known predictor–multicorrector algorithm, when this is applied to the incompressible Navier–Stokes equations. A new derivation of the algorithm in a general setting is provided, showing in what sense it can also be understood as a fractional-step method; this justifies, in particular, why the original boundary conditions of the problem can be enforced in this algorithm. Two different finite element interpolations are considered for the space discretization, and numerical results obtained with them for standard benchmark cases are presented. © 1998 John Wiley & Sons, Ltd.