Direct and simultaneous spectrofluorometric determination of naproxen and salicylate in human serum assisted by chemometric analysis

A direct method for the simultaneous determination of naproxen and salicylate in human serum is reported, based on a combination of spectrofluorometric measurements with two multivariate calibration techniques: partial least-squares (PLS-1) and the novel net analyte preprocessing (NAP). The method is rapid, selective and sensitive, and is based on the measurement of the fluorescence spectra of NH₃ alkalinized whole human sera at the excitation wavelength of 315 nm. It can be applied within the ranges of concentrations 50-200 ng ml⁻¹ for naproxen and 100-300 ng ml⁻¹ for salicylate. The employed chemometric techniques have been compared on the basis of the statistical indicators for calibration and validation. Reproducibility and interference studies in abnormal sera have also been carried out.     

Optically clear simulataneous interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and epoxy. II. Kinetic study

Simultaneous interpenetrating polymer networks (SINs) based on diglycidyl ether of bis-phenol A (DGEBA) and poly(ethylene glycol) diacrylate (PEGDA) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using benzoyl peroxide (BPO) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 45, 55, 63, and 70°C. Concentration changes for both the epoxide and C?C bond were monitored with FTIR. A rate expression for DGEBA cure kinetics was established with a model reaction of phenyl glycidyl ether (PGE) and benzylamine. Experimental results revealed that lower rate constants and higher activation energy for the SIN were found, compared with those for the constituent DGEBA and PEGDA network formation. A model of network interlock was proposed to account for this phenomenon. During simultaneous cure of DGEBA and PEGDA, the interlock (mutual entanglement) between DGEBA and PEGDA networks provided a sterically hindered environment, which subsequently increased the activation energy and reduced cure rates for both DGEBA and PEGDA. © 1993 John Wiley & Sons, Inc.     

The determination of adsorbable organically bound halogens (AOX) in soil: interlaboratory comparisons and reference materials

The interlaboratory variability in the quantification of adsorbable organically bound halogens (AOX) in industrially contaminated soil is presented. Three consecutive rounds of a proficiency testing scheme, in which between 88 and 119 routine laboratories participated, yielded relative reproducibility standard deviations between 7 and 20% at AOX contents between 10.9 and 268 mg kg⁻¹. Nineteen laboratories with established proficiency were invited to participate in the certification of the AOX content in three soil reference materials meant for the internal quality control in analytical laboratories. The certified values are (1349 ± 59) mg kg⁻¹, (80 ± 7) mg kg⁻¹ and (102 ± 8) mg kg⁻¹, respectively.     

Insights into the Retention Mechanisms on Perfluorohexylpropylsiloxane-Bonded (Fluophase-RP) and Octadecylsiloxane-Bonded (Betasil C18) Stationary Phases Based on the Same Silica Substrate in RP-LC

The solvation parameter model is used to elucidate the retention mechanism on a perfluorohexylpropylsiloxane-bonded (Fluophase RP) and octadecylsiloxane-bonded (Betasil C18) stationary phases based on the same silica substrate with acetonitrile–water and methanol–water mobile phase compositions. Dewetting affects the retention properties of Fluophase RP at mobile phase compositions containing less than 20% (v/v) acetonitrile or 40% (v/v) methanol. It results in a loss of retention due to an unfavorable change in the phase ratio as well as changes in specific intermolecular interactions. Steric repulsion reduces retention of bulky solutes on fully solvated Betasil C18 with methanol–water (but not acetonitrile–water) mobile phase compositions but is not important for Fluophase RP. The retention of weak bases is affected by ion-exchange interactions on Fluophase RP with acetonitrile–water, and to a lesser extent, methanol-water mobile phases but these are weak at best for Betasil C18. The system constants of the solvation parameter model and retention factor scatter plots are used to compare selectivity differences for Fluophase RP, Betasil C18 and a perfluorophenylpropylsiloxane-bonded silica stationary phase Discovery HS F5 for conditions where incomplete solvation, steric repulsion and ion-exchange do not significantly contribute to the retention mechanism. Lower retention on Fluophase RP results from weaker dispersion and/or higher cohesion moderated to different extents by polar interactions since solvated Fluophase RP is a stronger hydrogen-bond acid and more dipolar/polarizable than Betasil C18. Retention factors for acetonitrile–water mobile phases are highly correlated for Fluophase RP and Betasil C18 except for compounds with a large excess molar refraction and weak hydrogen-bonding capability. Selectivity differences are more significant for methanol–water mobile phases. Retention factors on Fluophase RP are strongly correlated with those on Discovery HSF5 for acetonitrile–water mobile phases while methanol–water mobile phases retention on Fluophase RP is a poor predictor of the retention order on Discovery HS F5.     

CALCULATING THE MOLECULAR INTERNAL ROTATING STERIC FACTOR OF POLYMERS BY THE RADIATION CROSSLINKING METHOD

In this paper, calculating the molecular internal rotating steric factor of polymers by the radiation crosslinking method is studied and a relationship between the molecular internal rotating steric factor (σ) and crosslinking parameter βis established~([1]) by taking account of the effect of polymer chain flexibility on βvalue, σvalue of polymer obtained by this method is in agreement with that given with other method.     

Parameter identification of thermophilic anaerobic degradation of valerate

The considered mathematical model of the decomposition of valerate presents three unknown kinetic parameters, two unknown stoichiometric coefficients, and three unknown initial concentrations for biomass. Applying a structural identifiability study, we concluded that it is necessary to perform simultaneous batch experiments with differenitial conditions for estimating these parameters. Four simultaneous batch experiments were conducted at 55°C, characterized by four different initial acetate concentrations. Product inhibition of valerate degradation by acetate was considered. Practical identification was done optimizing the sum of the multiple determination coefficients for all measured state viariables and for all experiments simultaneously. The estimated values of kinetic parameters and stoichiometric coefficients were characterized by the parameter correlation matrix, the confidence interval, and the student's t-test at 9% significance level with positive results except for the saturation constant, for which more eperiments for improving its identifiability should be conducted. In this article, we discussekinetic parameter estimation methods.     

Performance of quantitative analyses by liquid chromatography–electrospray ionisation tandem mass spectrometry: from external calibration to isotopomer-based exact matching

Liquid chromatography–tandem mass spectrometry (LC-MS/MS) is a versatile coupling system which combines both selectivity and sensitivity and certainty. Hence, it is generally considered as the most reliable technique to quantify chemical compounds in complex matrices. In the present paper, we evaluate the performance of LC-MS/MS methods for the quantification of 3-nitrotyrosine in human urine in order to point out its dependence on the design of the quantification method, and emphasize the role of matrix effects in the performance. We compare external and internal calibrations, isotope dilution and isotopomer-based exact matching. The role of both sample preparation and multiple transitions monitoring is particularly addressed.     

Precise bounds for the petersen time-varying real parameter uncertainty system stabilized via linear static controllers

Using a class of linear static controllers, we stabilize the Petersen open-loop two-dimensional linear system (Ref. 1), which consists of one time-varying uncertainty in the state matrixA and one timevarying uncertainty in the input matrixB. We show that the worst-case uncertainty strategy for the closed-loop system is a piecewise constant strategy of the angular state with three switches on the half-turn, –/2/2; it is unique with respect to a set of measure zero. Formulas are derived for the worst-case half-turn radius gainr _HT as a function of the parameters of the class of stabilizing linear static controllers. Using the class of scalar-quadratic Lyapunov functions, we show that a necessary and sufficient condition for the closed-loop system to be robustly stable against all time-varying admissible uncertainties is thatr _HT be less than unity. The bound on the time-varying real parameter uncertainties for the closed-loop system to be robustly stable is derived for the class of linear static feedback controllers. We obtain stabilizing linear static controllers such that the bound is as close to infinity as desired. The derived results are compared with numerical results obtained using commerical robust-control software.     

Parameter choice by discrepancy principles for ill-posed problems leading to optimal convergence rates

Schock (Ref. 1) considered a general a posteriori parameter choice strategy for the Tikhonov regularization of the ill-posed operator equationTx=y which provides nearly the optimal rate of convergence if the minimal-norm least-squares solution belongs to the range of the operator (T ^* T) ^v , o<v1. Recently, Nair (Ref. 2) improved the result of Schock and also provided the optimal rate ifv=1. In this note, we further improve the result and show in particular that the optimal rate can be achieved for 1/2v1.The final version of this work was written while M. T. Nair was a Visiting Fellow at the Centre for Mathematics and Its Applications, Australian National University, Canberra, Australia. The work of S. George was supported by a Senior Research Fellowship from CSIR, India.     

The strong coupling constant: Its theoretical derivation from a geometric approach to hadron structure

Since more than a decade, abi-scale, unified approach to strong and gravitational interactions has been proposed, that uses the geometrical methods of general relativity, and yielded results similar to strong gravity theory's. We fix our attention, in this note, on hadron structure, and show that also the strong interaction strength _S, ordinarily called the (perturbative) coupling-constant square, can be evaluated within our theory, and found to decrease (increase) as the distancer decreases (increases). This yields both the confinement of the hadron constituents (for large values ofr) and their asymptotic freedom (for small values ofr inside the hadron): in qualitative agreement with the experimental evidence. In other words, our approach leads us, on a purely theoretical ground, to a dependence of _S onr which had been previously found only on phenomenological and heuristic grounds. We expect the above agreement to be also quantitative, on the basis of a few checks performed in this paper, and of further work of ours on calculating meson mass spectra.