Simultaneous determination of propanol and butanol by a fluorometric enzymatic method based on the intrinsic fluorescence of the enzyme

The application of the intrinsic fluorescence of alcohol dehydrogenase (ADH) for the simultaneous determination of propanol and butanol was investigated by using only one kinetic run. An absolute calibration method (based on a mathematical model derived from the enzymatic reaction) and a multivariate calibration method (partial least squares regression, PLSR) were tested for this purpose. Both methods were applied to synthetic samples of both alcohols with good results. Received: 17 September 1998 / Revised: 21 December 1998 / Accepted: 28 December 1998     

Advanced pulse calibration techniques for the quantitative analysis of TG–FTIR data

Two different pulse calibration techniques to estimate the total quantities of evolved gaseous substances formed in thermogravimetric (TG)–FTIR runs were compared and assessed. A gas-pulse calibration method was based on the use of a specific device able of sending a known quantity of a gaseous compound of interest to the FTIR analyzer. A second calibration method was based on the vaporization in the TG analyzer of liquid solutions of the compound of interest. Data obtained by these techniques were compared to those from conventional concentration-based calibration. The results confirmed the reliability of pulse calibration techniques to obtain quantitative data on evolved gaseous products in TG–FTIR applications. Moreover, both the gas-pulse and the vaporization-based calibration techniques proved to have several advantages with respect to conventional techniques. Among these are the need of a more limited number of standards and no need for online gas dilution systems.     

Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods

In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and – for the first time – by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3σ-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly threefold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.     

Comparison of near-infrared and mid-infrared spectroscopy for the determination of distillation property of kerosene

Near-infrared (NIR) and mid-infrared (MIR) spectroscopy have been compared and evaluated for the determination of the distillation property of kerosene with the use of partial least squares (PLS) regression. Since kerosene is a complex mixture of similar hydrocarbons, both spectroscopic methods will be best evaluated with this complex sample matrix. PLS calibration models for each percent recovery temperature have been developed by using both NIR and MIR spectra without spectral pretreatment. Both methods have shown good correlation with the corresponding reference method, however NIR provided better calibration performance over MIR. To rationalize the improved calibration performance of NIR, spectra of the same kerosene sample were continuously collected and the corresponding spectral reproducibility was evaluated. The greater spectral reproducibility including signal-to-noise ratio of NIR led to the improved calibration performance, even though MIR spectroscopy provided more qualitative spectral information. The reproducibility of measurement, signal-to-noise ratio, and richness of qualitative information should be simultaneously considered for proper selection of a spectroscopic method for quantitative analysis.     

The computational methods in the development of a novel multianalyte calibration technique for potentiometric integrated sensors systems

In recent years, integration and miniaturization of ion-selective electrodes (ISEs) have brought many benefits resulting in the possibility of simultaneous determination of the ions concentration in small volume samples. One of the key problems related to the preparation of potentiometric integrated sensors systems (PISSs) is a calibration procedure due to the necessity to calibrate each particular sensor separately. The main aim of the research was to develop a novel calibration method for PISSs fabricated with the use of an all-solid-state technology, which has been compared with other types of sensor calibration technique. The proposed algorithm concerns the method of calibration solutions composition determination for miniature ion-selective sensors before measuring in biological samples especially human saliva samples. This article also compares the parameters of ion-selective sensors for two types of PISSs, including ISEs based on gold (Au) and glassy carbon (GC) electrodes. In addition, a series of measurements was performed using PISS with Au-ISEs in samples of human saliva, which were preceded by different types of sensor calibration and compared with the results obtained with the clinical analyzer. Moreover, the effect of the viscosity of calibration solutions on the ISE parameters and the lifetime of the sensors were investigated.

     

Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods

In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and--for the first time--by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3sigma-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly three-fold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.     

The properties of calibration errors in the analysis of reduced sulfur compounds by the combination of a loop injection system and gas chromatography with pulsed flame photometric detection

In order to evaluate the extent of analytical biases involved in the GC calibration, we conducted a series of experiments to examine the calibration methods of trace gas components. For the purpose of this comparative study, gaseous standards of reduced sulfur compounds (RSC) including hydrogen sulfide (H₂S), methanethiol (CH₃SH), dimethyl sulfide (DMS), carbon disulfide (CS₂), and dimethyl disulfide (DMDS) were calibrated by the combination of a GC/PFPD technique and a loop-injection method. In the course of this study, two different types of calibration methods were tested and compared: incremental-injection of a given standard with the fixed standard concentration (FSC) versus injection of multiple standards (with different concentrations) at the fixed standard volume (FSV). In the case of the FSV calibration, a notable increase in the GC sensitivity is apparent with decreasing loop size (or injection volume). For instance, the calibration slope for RSC obtained using a 10 μl loop system was approximately three times higher than that for a 250 μl one. However, the results obtained by the FSC method exhibit much poorer sensitivity than its counterpart with slight differences in their sensitivities across different standard concentrations (due to such factors as the matrix effect from varying injection volumes). Thus, the overall results of this study confirm that the detailed characterization of the selected calibration method (e.g., the use of FSV approach relative to FSC) is of primary significance to perform an accurate quantification of trace gases.     

Advantages of PARAFAC calibration in the determination of malachite green and its metabolite in fish by liquid chromatography-tandem mass spectrometry

This paper reports the properties and advantages of the three-way calibration models based on parallel factor analysis (PARAFAC) in the simultaneous determination of malachite green (MG) and its metabolite (leucomalachite green, LMG) in trout. A recently method proposed by community reference laboratory AFSSA-LERMVD (Fougères, France) has been used. The method is based on liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) in multiple reaction monitoring (MRM) mode. The validation of the method has been carried out taking into account the Decision 2002/657/EC. The figures of merit for PARAFAC and univariate calibration models of six non-consecutive days analyzed during a month were evaluated. With the samples of the first 3 days, calibration models were built and the fish fortification samples of the other days were predicted. Decision limits (CCalpha, alpha=0.01), detection capabilities (CCbeta, beta=0.05) and mean relative errors in absolute value (in calibration and with test samples) obtained with PARAFAC calibrations were more homogeneous than the ones obtained with the univariate calibrations, especially in LMG. These figures of merit were in the range of 0.2-0.83 microg kg(-1) (CCbeta) and 0.2-0.49 microg kg(-1) (CCalpha), whereas mean relative errors in absolute value were in the range of 1.1-7.4% in calibration and 3-12% in test samples for MG and LMG with PARAFAC calibrations. The PARAFAC calibrations allow detecting the test samples which are not similar to the calibration samples and in this way their wrong quantification is avoided.     

An indirect GPC calibration method for the low-molecular-weight region

A new gel permeation chromatography indirect calibration method is proposed for a polymer for which samples of known molecular weight and narrow molecular weight distribution are not available. This method is based on conversion of an experimentally obtained calibration curve for another polymer (polymer standard) through the universal calibration concept but using a new intrinsic viscosity-molecular weight relation. This indirect calibration curve is proposed especially for the low-molecular-weight region, where the method based on the Mark-Houwink-Sakurada equation gives erroneous results.     

The effect of cold trap adsorbents on the gas chromatographic analysis of ambient VOCs under Peltier cooling conditions

In this work, the relative analytical performance of the GC-based detection method was investigated with a major focus on cold trap (CT) adsorbent materials against four aromatic volatile organic compounds (VOCs) (e. g., benzene, toluene, xylene, and styrene). A series of calibration experiments were hence conducted under cryofocusing conditions formed by the Peltier cooling system in a thermal desorber (TD) unit. During the course of this study, comparative calibration datasets were acquired for each of the three CT types: (i) CT (I) = Carbopack B + Carbopack C, (ii) CT (II) = Carbopack B + Carboxen 1000, and (iii) CT (III) = Tenax TA. All calibration datasets were obtained under subambient temperature (-10 degrees C) conditions controlled by the Peltier cooling system. The reliability of the calibration data was also assessed in an ancillary experiment with the aid of the modified injection through a thermal desorber (MITD) method. The results demonstrated that the GC detection properties of different VOCs were not altered significantly between different CT applications under Peltier conditions, although relative sensitivity could be distinguished moderately depending on the CT type.     

Review on the thickness measurement of ultrathin oxide films by mutual calibration method

Mutual calibration was suggested as a method to determine the absolute thickness of ultrathin oxide films. It was motivated from the large offset values in the reported thicknesses in the Consultative Committee for Amount of Substance (CCQM) pilot study P-38 for the thickness measurement of SiO₂ films on Si(100) and Si(111) substrates in 2004. Large offset values from 0.5 to 1.0 nm were reported in the thicknesses by ellipsometry, X-ray reflectometry (XRR), medium-energy ion scattering spectrometry (MEIS), Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), and transmission electron microscopy (TEM). However, the offset value for the thicknesses by X-ray photoelectron spectroscopy (XPS) was close to zero (−0.013 nm). From these results, the mutual calibration method was reported for the thickness measurement of SiO₂ films on Si(100) by combination of TEM and XPS. The mutual calibration method has been applied for the thickness measurements of hetero oxide films such as Al₂O₃ and HfO₂. Recently, the effect of surface contamination was reported to be critical to the thickness measurement of HfO₂ films by XPS. On the other hand, MEIS was proved to be a powerful zero offset method which is not affected by the surface contamination. As a result, the reference thicknesses in the CCQM pilot study P-190 for the thickness measurement of HfO₂ films on Si(100) substrate were determined by mutual calibration method from the average XRR data and MEIS analysis. Conclusively, the thicknesses of ultrathin oxide films can be traceably certified by mutual calibration method and most thickness measurement methods can be calibrated from the certified thicknesses.     

How to overcome matrix effects in the determination of pesticides in fruit by HPLC-ESI-MS-MS

A high-performance liquid chromatographic method, with electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS-MS) for detection, has been developed for the determination of thiabendazole, carbendazime, and phenylurea pesticides in fruit matrices. During the validation process the method was tested for matrix effects, blanks, and the stability of the system. Considerable unspecific matrix effects in the ESI (+) process were detected by comparing standard calibration, and matrix calibration, although blank values were very low and the specific calibration functions showed only small standard deviations. This effect was overcome by using a more complex clean-up, i.e. an additional size-exclusion step.     

Comparison of different calibration approaches in the application of thermal desorption technique: A test on gaseous reduced sulfur compounds

In this study, the reliability of thermal desorbing technique was investigated using the gaseous standards of five reduced sulfur compounds (RSCs: hydrogen sulfide, methane thiol, dimethyl sulfide, carbon disulfide, and dimethyl disulfide). A series of calibration experiments for RSCs were performed using gas chromatography (GC) with pulsed flame photometric detector (PFPD) that is interfaced with a thermal desorber (TD) unit. These calibration data were evaluated by means of two contrasting concepts: fixed standard concentration method (FSC: variable volumetric injection of standard gases prepared at a given concentration) and fixed standard volume method (FSV: injection of multiple standards with varying concentrations at a given volume). When the results of both methods were compared, RSCs generally showed enhanced sensitivity with increasing concentration (FSC) and sample loading volume (FSV). This study highlights that TD-based calibration properties are practically undistinguishable between different sample transfer approaches (e.g., FSV and FSC). As a result, the calibration properties of RSCs derived by thermal desorption technique are greatly distinguished from those of direct injection into GC.     

校正变换矩阵法及其在多组分直接同时测定中的应用

将目标变换因子分析中自由浮动技术引入多元校准中，提出了一种新的多组分同时校准法———校正变换矩阵法。该法用于四组分氨基酸人工混合样品分析，结果令人满意，通过与传统目标变换因子分析法比较研究，表明该法用于组分光谱严重共线的波长范围时，其校准能力大大优于传统目标变换法。     

Comparison of calibration methods in quantitative diffuse reflectance infrared spectroscopy

Four different calibration methods were used for quantitative analysis of quartz and calcite in atmospheric aerosols by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS): (A) conventional calibration with one measurement on each standard (single calibration); (B) calibration with an internal standard; (C) calibration with parallel (n = 4) measurements on each standard (multiple calibration); (D) multiple calibration followed by reference reflectance correction. The accuracy and the precision of the methods were compared and it was found that by using method D the reliability of the conventional pellet preparation transmission technique can be achieved.     

Alternative calibration approaches to compensate the effect of co-extracted matrix components in liquid chromatography-electrospray ionisation tandem mass spectrometry analysis of pesticide residues in plant materials

The aim of this study was to evaluate the applicability of different calibration approaches in a multi- and single-residue analysis of modern pesticides in plant matrices using liquid chromatography-electrospray mass spectrometry (HPLC-ESI-MS). In the first set of experiments the determination of eight pesticides representing different groups of polar/unstable pesticides (carbamates, benzimidazoles, azoles, benzoylphenylurea) in apple samples was performed. The trueness and precision of data obtained by using: (i) external solvent standard calibration, (ii) external matrix-matched standard calibration and (iii) echo-peak internal standard calibration was compared. The last mentioned method is a novel technique providing the possibility to inject internal standard of the same identity as a target analyte, so that its retention time is close to the analyte from the sample. According to expectation, when using external standard solvent calibration the results were under- or overestimated due to suppression or enhancement of analyte's signal by matrix components. On the other hand with the use of matrix-matched calibration accurate data were obtained. With echo-peak technique accurate results comparable to those obtained by matrix calibration were obtained for six out of eight pesticides. In the second set of experiment we used the echo-peak technique to overcome the problem with the response instability in the analysis of chlormequat in pear concentrate samples. As an internal standard method the echo-peak technique provided the possibility of monitoring of signal decrease during the analytical sequence and to compensate this decrease by relating sample peak area relatively to this internal standard.     

Extending the working calibration ranges of four hexachlorocyclohexane isomers in gas chromatography-electron capture detector by radial basis function neural network

A radial basis function neural network (RBFNN) method was developed for the first time to model the nonlinear calibration curves of four hexachlorocyclohexane (HCH) isomers, aiming to extend their working calibration ranges in gas chromatography-electron capture detector (GC-ECD). Other 14 methods, including seven parametric curve fitting methods, two nonparametric curve fitting methods, and five other artificial neural network (ANN) methods, were also developed and compared. Only the RBFNN method, with logarithm-transform and normalization operation on the calibration data, was able to model the nonlinear calibration curves of the four HCH isomers adequately. The RBFNN method accurately predicted the concentrations of HCH isomers within and out of the linear ranges in certified test samples. Furthermore, no significant difference (p > 0.05) was found between the results of HCH isomers concentrations in water samples calculated with RBFNN method and ordinary least squares (OLS) method (R² > 0.9990). Conclusively, the working calibration ranges of the four HCH isomers were extended from 0.08-60 ng/ml to 0.08-1000 ng/ml without sacrificing accuracy and precision by means of RBFNN. The outstanding nonlinear modeling capability of RBFNN, along with its universal applicability to various problems as a “soft” modeling method, should make the method an appealing alternative to traditional modeling methods in the calibration analyses of various systems besides the GC-ECD.     

Simultaneous determination of the colorants tartrazine, ponceau 4R and sunset yellow FCF in foodstuffs by solid phase spectrophotometry using partial least squares multivariate calibration

A method is proposed for the simultaneous determination of the colorants tartrazine (TT), sunset yellow FCF (SY) and ponceau 4R (PR) in foods. The colorants were fixed in Sephadex DEAE A-25 gel at pH 2.0 and then packed in a 1-mm silica cell. The spectra of the analytes fixed in the solid support were recorded between 400 and 800 nm against a blank and the partial least squares (PLS) multivariate calibration was used to obtain the results. The linear dynamic ranges of the calibration graphs were from 50.0 to 650.0 ng ml(-1) for the three colorants and these ranges were taking in account the optimisation of the calibration matrix using the PLS-1 algorithm. The experimental results showed that the optimum number of factors for the calibration matrix was four in all instances and the residual means standard deviation was 5.5267 for SY, 6.3878 for TT and 6.9816 for PR. The square of the correlation coefficients were 0.9977, 0.9978 and 0.9954 for SY, TT and PR respectively. The method was applied to the determination of the colorants in foods and results were compared with those obtained by means of HPLC as reference method. The results obtained can be considered as acceptable in most cases (eight of nine commercial samples). The relative standard deviations ranging between 0.5 and 10.8 for the commercial samples analysed.     

The maintenance of the second-order advantage: second-order calibration of excitation-emission matrix fluorescence for quantitative analysis of herbicide napropamide in various environmental samples

A rapid non-separative spectrofluorometric method based on the second-order calibration of excitation-emission matrix (EEM) fluorescence was proposed for the determination of napropamide (NAP) in soil, river sediment, and wastewater as well as river water samples. With 0.10 mol L⁻¹ sodium citrate-hydrochloric acid (HCl) buffer solution of pH 2.2, the system of NAP has a large increase in fluorescence intensity. To handle the intrinsic fluorescence interferences of environmental samples, the alternating penalty trilinear decomposition (APTLD) algorithm as an efficient second-order calibration method was employed. Satisfactory results have been achieved for NAP in complex environmental samples. The limit of detection obtained for NAP in soil, river sediment, wastewater and river water samples were 0.80, 0.24, 0.12, 0.071 ng mL⁻¹, respectively. Furthermore, in order to fully investigate the performance of second-order calibration method, we test the second-order calibration method using different calibration approaches including the single matrix model, the intra-day various matrices model and the global model based on the APTLD algorithm with nature environmental datasets. The results showed the second-order calibration methods also enable one or more analyte(s) of interest to be determined simultaneously in the samples with various types of matrices. The maintenance of second-order advantage has been demonstrated in simultaneous determinations of the analyte of interests in the environmental samples of various matrices.     

Study of binding of warfarin to serum albumins by high-performance liquid chromatography

The binding of warfarin to human serum albumin and bovine serum albumin, respectively, was studied by high-performance liquid chromatography (HPLC). Based upon the Hummel - Dreyer method, two techniques were developed: the internal calibration and the external calibration. The results obtained by the HPLC method and those obtained by the classical method (equilibrium dialysis) were compared. The external calibration method seems to be superior to others for its simplicity, speed and convenience.