A study of robustness with multivariate calibration. Application to the polarographic determination of benzaldehyde

A procedure to evaluate the robustness of an analytical method when there are changes in some experimental variables, when using multivariate calibration, is proposed. The procedure consists of analysing the root mean square error of prediction (RMSEP) as a response to a Plackett–Burman experimental design, through which the influence of several experimental factors on the prediction capability of the multivariate partial least squares (PLS) models built is studied. Two different ways of analysing the experimental design response are considered: establishing the residual variance with replicates and using Lenth's method. The proposed methodology has been applied to estimate the robustness of the polarographic determination of benzaldehyde when PLS calibration is used.     

Analytic first and second derivatives of the energy in the fragment molecular orbital method combined with molecular mechanics

Analytic first and second derivatives of the energy are developed for the fragment molecular orbital method interfaced with molecular mechanics in the electrostatic embedding scheme at the level of Hartree-Fock and density functional theory. The importance of the orbital response terms is demonstrated. The role of electrostatic embedding upon molecular vibrations is analyzed, comparing force field and quantum mechanical treatments for an ionic liquid and a solvated protein. The method is applied for 100 protein conformations sampled in molecular dynamics (MD) to take into account the complexity of a flexible protein structure in solution, and a good agreement with experimental data is obtained: Frequencies from an experimental infrared (IR) spectrum are reproduced within 17 cm⁻¹ .     

Modélisation des temps de réponse des capteurs chimiques

Modelling consists of considering the response and recovery times of a sensor to the target chemical species, as the sum of an ‘intrinsic’ response/recovery time, independent of the experimental conditions, and of an ‘extrinsic’ one, linked to the volume of the measurement cell and to the fluid flow. The experimental response/recovery times being almost always dominated by the extrinsic part, a dissymmetry between the response and recovery signals is observed for sensors whose response is not linear with the concentration of the target chemical species.     

Response characteristics of the glucose-sensitive field-effect transistor. Computer simulation of the effect of gluconolactonase coimmobilization in a glucose oxidase membrane

The bienzyme system consisting of glucose oxidase and gluconolactonase was investigated using a conventional diffusion-kinetics model for an enzyme-modified field-effect transistor (FET) to clarify the effect of gluconolactonase coimmobilization in a glucose oxidase membrane on the steady-state response amplitude of a glucose sensor based on a FET. The model includes spontaneous and enzymatic hydrolysis reactions of d-glucono-δ-lactone and it elucidated the following experimental results: a glucose sensor with a membrane (about 1 μm in thickness) coimmobilizing these enzymes showed a sufficient response amplitude, whereas without coimmobilization of gluconolactonase no detectable response was observed up to 3 mM glucose; and the response amplitude depended strongly on the amount of lactonase in the membrane. The model also predicted an optimum enzyme ratio for coimmobilization in a membrane.     

Characterization of the flame photometric detector in the sulphur mode

Summary The effect of experimental conditions such as gas flow rates, detector and column temperatures on sulphur response are discussed. It is concluded that the response of the flame photometric detector is affected by the O/H ratio and the total gas flow. Column temperature has an important influence upon S₂ emission. It is shown that the sulphur response of the FPD is dependent on the compound containing the sulphur.     

Optimizing analytical methods using sequential response surface methodology. Application to the pararosaniline determination of formaldehyde

Sequential response surface methodology is a general procedure to re-optimize common analytical methods on the basis of the application of the response surface methodology and of a new approach to the steepest ascent method. This procedure, which is easy to apply, consists of estimating an analytical function relating the response with the experimental parameters by means of a second-degree polynomial. Thus, a 2nd order design covering the total experimental domain is used and when a maximum is obtained, the characteristics of the response surface are confirmed using a new design, which is obtained contracting the first one. In the proposed methodology, Box-Behnken designs are used because they offer advantages in comparison with second order designs more frequently used in the steepest ascent method (central composite designs), i.e. fewer experiments are needed, they are more efficient, they can be moved through the experimental domain and they can even be easily contracted or expanded.     

Optimizing analytical methods using sequential response surface methodology. Application to the pararosaniline determination of formaldehyde

Sequential response surface methodology is a general procedure to re-optimize common analytical methods on the basis of the application of the response surface methodology and of a new approach to the steepest ascent method. This procedure, which is easy to apply, consists of estimating an analytical function relating the response with the experimental parameters by means of a second-degree polynomial. Thus, a 2nd order design covering the total experimental domain is used and when a maximum is obtained, the characteristics of the response surface are confirmed using a new design, which is obtained contracting the first one. In the proposed methodology, Box-Behnken designs are used because they offer advantages in comparison with second order designs more frequently used in the steepest ascent method (central composite designs), i.e. fewer experiments are needed, they are more efficient, they can be moved through the experimental domain and they can even be easily contracted or expanded.     

Simultaneous Differential Pulse Adsorptive Stripping Determination of Imipramine and Its Metabolite Desipramine by the PLS‐1 Multivariate Method

A method, using stripping differential pulse voltammetry, for the simultaneous determination of Imipramine and its metabolite Desipramine is reported. Both compounds produce, at glassy carbon electrode, an electrochemical signal due to an adsorptive‐oxidative process. The voltammograms show a very high overlap degree between IM and DE peaks. The multivariate calibration method PLS‐1 was employed for the simultaneous determination of both compounds. An experimental design together with the response surface methodology has been used to find the optimum experimental conditions. The developed procedure has been utilized in the analysis of fortified human serum samples with good recovery values for each analyte.     

Quantification of the sensitivity increase of a micro-high-performance liquid chromatography-electrospray ionization mass spectrometry system with decreasing column diameter

This study details the sensitivity achieved with capillary columns when used with a micro-HPLC-electrospray ionization MS system. It is comprised of two sections, the first is the comparative study of three columns, one of narrow-bore diameter and two of capillary diameter. The second section compares three columns of decreasing diameter in the capillary scale. All the experiments achieved enhanced sensitivity using capillary columns. The increase in the experimental MS response ranged from -20% to +20% compared to the UV experimental response when decreasing the internal diameter of the columns used. When comparing the experimental MS response to the maximum theoretical UV response achievable, the increase in response ranged from 40 to 50%.     

Chemometric Methods for the Study of Toxic Metals on the Growth of Plants: Use of Experimental Design and Response Surface Methodology

Abstract

Chemometrics is a recent discipline concerned, principally, with the application of mathematics and statistics to laboratory systems. One way in which the chemometrician can aid the environmental analytical chemist is via planned experimental designs. In this paper the importance of experimental design is illustrated and the main considerations prior to experimentation, namely, degrees of freedom, analytical errors, coding and modelling, are outlined. This is exemplified by a study of the influence of potentially toxic heavy metals on the growth of barley seedlings. Undesigned univariate experiments suggest that Tl is probably more toxic than Cd. A three factor central composite design is reported, to study the relative toxicities of Tl, Cd and Pb and also of Tl, Fe and Zn. The paper exemplifies how much information can be obtained from the resultant experimental response data. Multilinear regression can be employed to produce a quadratic model: this can be interpreted graphically by reconstructed univariate response curves and 3-dimensional response surfaces. Analysis of variance is a statistical method for computing how well the model has been fitted, taking into account analytical errors. With the aid of modern graphical computing, a variety of confidence intervals can be displayed for both univariate and bivariate responses. The usefulness of the design can be visualised by displaying leverage over and outside the experimental region. Finally future trends in multivariate response methodology are discussed.     

Effect of the Wavelength of the Laser Beam on the Response of an Evaporative Light Scattering Detector

Abstract

The effects of the wavelength of the laser beam on the response of an evaporative light scattering detector (ELSD) are discussed. Data characterizing the response of the detector and its dependence on the sample size have been collected for six solutes, using a pulsed dye laser as light source. The experimental results suggest that there is little influence of the wavelength on the intensity of the scattered light. On the other hand, the noise decreases in proportion to the wavelength of the incident light beam. Thus, the detection limit (at constant value of the signal to noise ratio) decreases with decreasing wavelengths. The performance of the ELSD improves when a short wavelength is used.     

The application of experimental design to the robustness testing of a method for the determination of drug-related impurities by capillary electrophoresis

Summary Robustness testing of capillary electrophoresis methods is an important part of method validation. Appropriate use of experimental designs can be employed in this robustness testing. In this study experimental designs were used in the assessment of a capillary electrophoresis method used to determine drug related impurities. Initially a fractional factorial screening design was used to identify the critical parameters which were found to be pH and voltage. A central composite design was then performed to evaluate the response surfaces for pH and voltage which showed operation at the optimum pH and voltage values.     

Description of the response of a fiber optic velocity sensor applied to capillary gas chromatography

This paper explores the response of a novel fiber optics sensor allowing real-time determination of the migration rate of vapor zones in capillary gas chromatography. The sensitivity is related to the gradient of the vapor zone distribution in the capillary and it is highest when vapor zones show steep variations in concentration. The expected linearity between the height of the velocity peaks and the response of a thermal conductivity detector is demonstrated experimentally. The sensor can be used to infer an approximate value of the analyte diffusion coefficient from the time response. Finally, the time evolution of the envelope of the optical signal is explained with experimental evidences.     

Packed Column SFC of Gas Oils. Part II: Experimental Design Optimization of the Group-Type Analysis using CO2-SF6 as the Mobile Phase

An optimization procedure is presented for group-type analysis of diesel fuel by supercritical fluid chromatography using packed silica column and a mixed mobile phase. A set of five responses, four values of resolution of a performance mixture and analysis time, was modeled using a Doehlert matrix for experimental design. Optimized experimental conditions for the five responses were obtained from a response surfaces optimization, taking into account various constraints on SF₆ content in mobile phase and analysis time. The predicted and experimental resolutions were in good agreement for the different optimized conditions and one of them was selected to for application to a given diesel fuel for comparison with the results obtained by SFC using pure CO₂ and by HPLC. The conditions found in this study provide an alternative method for the determination of mono-, di-, and polyaromatic compounds in middle distillates.     

Modelling and graphic interpretation of response surface in chemical analysis

The complicated effects of several factors on an analytical signal can be studied comprehensively only by an experimental design in which the additive and non-additive effects of these factors are included in one experimental run, with simultaneous variation of the values of all factors. From the law of mass action, it is shown that systems in which the analytical signal is produced by a species formed during a chemical reaction (i.e., for spectrophotometry) can be described by a model based on quasi-linear regressions with squares and products of variables. The regression coefficients can be evaluated by means of factorial designs at three levels. Interpretation of results in the case of two or three independent variables is simplified by using a graphic method in which the complex effects of factors on the dependent variable are represented as an empirical response surface. In the case of regression with three independent variables, the response surface is four-dimensional; its dimensionality is reduced to three by several three-dimensional representations. The shapes of the response surfaces described by the response functions and the adequacy of the models are discussed.     

Calibration of mass selective detector in non-target analysis of volatile organic compounds in the air

Volatile organic compounds (VOCs) play an important role in the chemistry of the atmosphere and in biogeochemistry. They contribute to the oxidative capacity of the atmosphere, particle and air pollutants, as well as to the production of greenhouse gases (for instance ozone). Among analytical techniques for their determination in the atmosphere gas chromatography coupled with mass spectrometry (GC-MS) offers several advantages. However, for an accurate quantification calibration with standard substances is necessary. A quantitative structure-property relationship (QSPR) model for the prediction of MS response factors was developed on basis of our experimental measurements for the quantification of ozone precursors present in the atmosphere. A linear correlation between chemical structures and response factors was established by using a 7-parameter MLR model. The average error in the prediction of response factors was calculated by cross-validation procedure and was below 20%, which is sufficient for the determination of VOCs in the air. The proposed procedure is time consuming so it is more suited for the quantification of tentatively identified organic compounds during the reprocessing of MS chromatograms in cases when the original sample is no longer available.     

Electrochemical Investigation of the Commercial Iron Sulfide Stick-Interaction with Complexing Ligands

The present work aims to examine iron sulfide for its interfacial properties in aqueous media containing different ionic/complexing agents. The primary experimental investigation is the potentiometric response of the commercial iron sulfide stick in various aqueous media supplemented by cyclic voltammetry and UV-visible and IR spectroscopy. The significance of employing the commercial iron sulfide stick is that it is quite stable under ordinary conditions and possesses appreciable conductivity for employing it as an electrode. Copyright 2001 Academic Press.     

Complex heat capacity measurements by TMDSC Part 1. Influence of non-linear thermal response

To treat data from temperature modulated differential scanning calorimetry (TMDSC) in terms of complex or reversing heat capacity one should know heat transfer and apparatus influences on experimental results. On the other hand one should pay attention that the response is linear because this is a prerequisite for data evaluation. The reason for non-linear thermal response is discussed and its influence on complex heat capacity determination is shown. The criterion for linear response is proposed. This allows to choose correct experimental conditions for any complex heat capacity measurements. In the case when these conditions cannot be fulfilled because of experimental restrictions one can estimate the influence of non-linear response on measured value of complex or reversing heat capacity.