Orthogonal signal correction-partial least squares method for simultaneous spectrophotometric determination of cypermethrin and tetramethrin

The simultaneous determination of cypermethrin and tetramethrin mixtures by using spectrophotometric method is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares (PLS) regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction (OSC) is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for partial least squares calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 200-350 nm range for 25 different mixtures of cypermethrin and tetramethrin. Calibration matrices were containing 0.1-12.9 and 0.1-13.8 microg mL(-1) for cypermethrin and tetramethrin, respectively. The RMSEP for cypermethrin and tetramethrin with OSC and without OSC were 0.0884, 0.0614 and 0.2915, 0.2309, respectively. This procedure allows the simultaneous determination of cypermethrin and tetramethrin in synthetic and real samples good reliability of the determination was proved.     

Spectrophotometric simultaneous determination of manganese(II) and iron(II) in pharmaceutical by orthogonal signal correction-partial least squares

The simultaneous determination of manganese(II) and iron(II) mixtures by using spectrophotometric methods is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares (PLS), it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction (OSC) is a preprocessing technique used to remove the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for partial least squares calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 450-600 nm range for 21 different mixtures of manganese(II) and iron(II). Calibration matrices were containing 0.05-1.2 and 0.1-2.3 microg mL(-1) Mn(II) and Fe(II), respectively. The RMSEP for manganese(II) and iron(II) with OSC and without OSC were 0.0316, 0.0291, and 0.0907, 0.115, respectively. This procedure allows the simultaneous determination of manganese(II) and iron(II) in synthetic and real matrix samples with good reliability of the determination.     

Simultaneous spectrophotometric determination of mercury and palladium with Thio-Michler's Ketone using partial least squares regression and orthogonal signal correction

A simple, novel and sensitive spectrophotometric method was described for simultaneous determination of mercury and palladium. The method is based on the complex formation of mercury and palladium with Thio-Michler's Ketone (TMK) at pH 3.5. All factors affecting on the sensitivity were optimized and the linear dynamic range for determination of mercury and palladium found. The simultaneous determination of mercury and palladium mixtures by using spectrophotometric method is a difficult problem, due to spectral interferences. By multivariate calibration methods such as partial least squares (PLS), it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction (OSC) is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for PLS calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 360-660 nm range for 25 different mixtures of mercury and palladium. Calibration matrices were containing 0.025-1.60 and 0.05-0.50 microg mL(-1) of mercury and palladium, respectively. The RMSEP for mercury and palladium with OSC and without OSC were 0.013, 0.006 and 0.048, 0.030, respectively. This procedure allows the simultaneous determination of mercury and palladium in synthetic and real matrix samples good reliability of the determination.     

Simultaneous spectrophotometric determination of cobalt,copper and nickel using 1-（2-thiazolylazo）-2-naphthol by chemometrics methods

The simultaneous determination of cobalt, copper and nickel using 1-（2-thiazolylazo）-2-naphthol （first figure of this article） by spectrophotometric method is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares （PLS） regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction （OSC） is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for PLS calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 550-750-nm range for 21 different mixtures of cobalt, copper and nickel. Calibration matrices were formed from samples containing 0.05-1.05, 0.05-1.30 and 0.05-0.80 μg·mL^-1 for cobalt, copper and nickel, respectively. The root mean square error of prediction （RMSEP） for cobalt, copper and nickel with OSC and without OSC were 0.007, 0.008, 0.011 and 0.031,0.037, 0.032 μg· mL^-1, respectively. This procedure allows the simultaneous determination of cobalt, copper and nickel in synthetic and real samples and good reliability of the determination was proved.     

Influence of temperature on thermodynamics of ethers + xylenes

The densities and ultrasonic velocity of the binary mixtures methyl tert-butyl ether (MTBE) or ethyl tert-butyl ether (ETBE) + (o-xylene, m-xylene and p-xylene) at the range 288.15–323.15 K and atmospheric pressure, have been measured over the whole concentration range. The experimental excess volumes and deviation of isentropic compressibilities data have been analyzed. The experimental values have been studied in terms of different theoretical models. The gathered data improve open literature related to gasoline additives, as the comparison has proved, and help to understand the ether effect into aromatic environment in terms of steric hindrance and oxygen group polar potency.     

Simultaneous spectrophotometric determination of nitroaniline isomers after cloud point extraction by using least-squares support vector machines

Cloud point extraction has been used for the preconcentration of m-nitroaniline, o-nitroaniline and p-nitroaniline and later simultaneous spectrophotometric determination using polyethylene glycol tert-octylphenyl ether (Triton X-100) as surfactant. The resolution of a ternary mixture of the nitroaniline isomers (after extraction by cloud point) by the application of least-squares support vector machines (LS-SVM) was performed. The chemical parameters affecting the separation phase and detection process were studied and optimized. Under the optimum experimental conditions (i.e. pH 7.0, Triton X-100=0.6%, equilibrium time 20 min and cloud point 75 degrees C), calibration graphs were linear in the range of 0.2-20.0, 0.1-15.0 and 0.1-17.0 microg ml(-1) with detection limits of 0.08, 0.05 and 0.06 microg ml(-1) for m-nitroaniline, o-nitroaniline and p-nitroaniline, respectively. The experimental calibration matrix was designed with 21 mixtures of these chemicals. The concentrations were varied between calibration graphs concentrations of nitroaniline isomers. The root mean square error of prediction (RMSEP) for m-nitroaniline, o-nitroaniline and p-nitroaniline were 0.0146, 0.0308 and 0.0304, respectively. This procedure allows the simultaneous determination of nitroaniline isomers in synthetic and real matrix samples good reliability of the determination was proved.     

The effect of temperature on the solubility of benzoic acid derivatives in water

Using a laser monitoring observation technique, solubilities of o-nitro-benzoic acid, p-hydro-benzoic acid, p-methyl-benzoic acid and m-methyl-benzoic acid in water have been measured in the temperature range 290.15–323.15 K. The experimental data are regressed with the Wilson equation and the λH equation. The experimental results show that solubilities of these compounds in the range of 10⁻⁴–10⁻⁵ mole fraction in water, increase significantly with temperature. Except for o-nitro-benzoic acid, the solubility data are described adequately with the Wilson equation. The λH equation gives good agreement with all experimental data. The results indicate that the molecular structure and interactions affect the solubilities significantly.     

Excess molar volumes and enthalpies for the binary systems propyl propanoate + o-xylene, m-xylene, and p-xylene at 298.15 K

This paper reports excess molar enthalpies, H_m^E, and excess molar volumes, V_m^E, of the binary systems {propyl propanoate + o-xylene}, {propyl propanoate + m-xylene} and {propyl propanoate + p-xylene} at the temperature 298.15 K and atmospheric pressure, over the whole composition range. V_m^E was calculated from the experimental measurement of the corresponding densities, while H_m^E was measured directly. The excess magnitudes were correlated to a Redlich-Kister type equation. Finally, we will discuss the results of the three mixtures studied here and by comparison with other binary systems containing propyl propanoate and a benzene-based compound previously published.     

Synthesis and characterization of dinuclear p-, m- and o-xylyl bridged complexes of molybdenum and tungsten. The crystal structures of μ-p-xylyl- bis(η-pentamethyl-cyclopentadienyltri- carbonylmolybdenum) and μ-m-xylyl-bis(η- pentamethylcyclopentadienyltricarbonyltungsten)

The reactions of η⁵-Cp^*M(CO)₃Na (M = Mo, W) with ,′-p-, m- and o-dichloro-xylenes yielded p-, m- and o-xylyl bridged dinuclear complexes of η⁵-Cp^*M(CO)₃ in high yields. All of such new complexes are stable to air and water, even stable in dilute acids and bases.     

Kinetic spectrophotometric determination of trace amounts of palladium by whole kinetic curve and a fixed time method using resazurine sulfide reaction

The univariate and multivariate calibration methods were applied for the determination of trace amounts of palladium based on the catalytic effect on the reaction between resazurine and sulfide. The decrease in absorbance of resazurine at 602 nm over a fixed time is proportional to the concentration of palladium over the range of 10.0-160.0 ng mL(-1). The calibration matrix for partial least squares (PLS) regression was designed with 14 samples. Orthogonal signal correction (OSC) is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for PLS calibration without loss of prediction ability using spectrophotometric method. The root mean square error of prediction (RMSEP) for palladium determination with fixed-time, PLS and OSC-PLS were 3.71, 2.84 and 0.68, respectively. This procedure allows the determination of palladium in synthetic and real samples with good reliability of the determination.     

Simultaneous spectrophotometric determination of Sn(II) and Sn(IV) by mean centering of ratio kinetic profiles and partial least squares methods

Two spectrophotometric methods are described for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) in water samples and fruit juice samples, without prior separation steps, using the mean centering of ratio kinetic profiles and partial least squares (PLS) methods. The methods are based on the difference in the rate of the reactions of Sn(II) and Sn(IV) with pyrocatechol violet at pH 4.0. The methods allow rapid and accurate determination of Sn(II) and Sn(IV). The analytical characteristics of the methods for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) were calculated. The results showed that the methods were capable to simultaneous determination of 0.1–1.80 mg L⁻¹ each of cations. The proposed methods were successfully applied to the simultaneous determination of Sn(II) and Sn(IV)in an orange juice sample.     

Resonance Raman study of the solvation of p-nitroaniline in supercritical water

Resonance Raman spectra of p-nitroaniline (pNA) have been measured in various states of water. The relative intensities of two bands assigned to the NO₂ stretching mode show a large temperature dependence along the 30.4 MPa isobar between ambient temperature and 669 K. Along the supercritical isotherm at 668.5 K, the higher frequency band shifts by 8 cm⁻¹ over the accessible density range (0.3–1.7ρ_c). We also performed density-functional calculations of the Raman spectra of water clusters of pNA. The calculated changes in electronic structure and Raman spectra with cluster size are used to rationalize these experimental observations.     

人工神经网络紫外光度法同时测定甲基苯甲醛的三种同分异构体及其与偏最小二乘法的比较

同分异构体的同时测定一直是分析化学领域的热点和难点问题,本文将化学计量学中的多元校正方法,如偏最小二乘法和人工神经网络法与紫外分光光度法相结合,同时测定了紫外吸收光谱严重重叠的甲基苯甲醛的三种同分异构体混合体系中各组分的含量。确定了测定的最佳波长范围为230～304 nm;测得48个混合标样的吸光度值用于建立模型,其中,邻、间、对甲基苯甲醛的浓度范围分别为6.0～15.0、7.0～16.0和8.0～19.0 μg·mL-1。7个模拟样品作为监测集用于检验所建立模型的预测性能。本文还讨论了三种组分浓度比例对所建立模型预测性能的影响并确定了可以准确测定的浓度比例范围。所建立的方法用于模拟样品的测定,其回收率在84.00%与109.60%之间。与偏最小二乘法的测定结果比较,经成对t检验表明,两种方法对邻、间甲基苯甲醛测定结果无显著性差异;而对甲基苯甲醛的测定,人工神经网络法的测定结果优于偏最小二乘法。     

Genetic Algorithm Applied to Selection of Wavelength in Partial Least Squares for Simultaneous Spectrophotometric Determination of Nitrophenol Isomers

Abstract

Ternary mixtures of nitrophenol isomers have been simultaneously determined in synthetic and real matrix by application of genetic algorithm and partial least squares model. All factors affecting the sensitivity were optimized and the linear dynamic range for determination of nitrophenol isomers found. The simultaneous determination of nitrophenol mixtures by using spectrophotometric methods is a difficult problem, due to spectral interferences. The partial least squares modeling was used for the multivariate calibration of the spectrophotometric data. A genetic algorithm is a suitable method for selecting wavelength for PLS calibration of mixtures with almost identical spectra without loss prediction capacity. The experimental calibration matrix was designed by measuring the absorbance over the range 300–520 nm for 21 samples of 1–20 µg mL^?1, 1–20 µg mL^?1, and 1–10 µg mL^?1 of m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol, respectively. The root mean square error of prediction for m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol with genetic algorithms and without genetic algorithms were 0.3732, 0.5997, 0.3181 and 0.7309, 0.9961, 1.0055, respectively. The proposed method was successfully applied for the determination of m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol in synthetic and water samples.     

Simultaneous spectrophotometric determination of ethinylestradiol and levonorgestrel by partial least squares and principal component regression multivariate calibration

Two spectrophotometric methods for the determination of Ethinylestradiol (ETE) and Levonorgestrel (LEV) by using the multivariate calibration technique of partial least square (PLS) and principal component regression (PCR) are presented. In this study the PLS and PCR are successfully applied to quantify both hormones using the information contained in the absorption spectra of appropriate solutions. In order to do this, a calibration set of standard samples composed of different mixtures of both compounds has been designed. The results found by application of the PLS and PCR methods to the simultaneous determination of mixtures, containing 4–11 μg ml⁻¹ of ETE and 2–23 μg ml⁻¹ of LEV, are reported. Five different oral contraceptives were analyzed and the results were very similar to that obtained by a reference liquid Chromatographic method.     

Spectrophotometric determination of terfenadine in pharmaceutical preparations by charge-transfer reactions

A simple, rapid and accurate method for the spectrophotometric determination of terfenadine has been developed. The proposed method based on the charge-transfer reactions of terfenadine, as n-electron donor, with 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, p-CLA) as π-acceptors to give highly colored complexes. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the highest sensitivity. Beer's law is obeyed over the concentration ranges of 3–72, 3–96, 12–168 and 24–240 μg mL⁻¹ terfenadine using TCNQ, TCNE, DDQ and p-CLA, respectively, with correlation coefficients 0.9999, 0.9974, 0.9997 and 0.9979 and detection limits 0.3, 0.4, 2.6 and 12.3 μg mL⁻¹, for the reagents in the same order. DDQ and p-CLA react spontaneously with terfenadine to give colored complexes that can be applied for the flow injection analysis of terfenadine in the concentration ranges 2.4–120 and 24–240 μg with correlation coefficients 0.9990 and 0.9985 and detection limits 0.8 and 2.7 μg for DDQ and p-CLA, respectively, in addition to the high sampling through output of 40 sample h⁻¹.     

Boiling points for five binary systems of sulfolane with aromatic hydrocarbons at 101.33 kPa

Boiling points have been determined at 101.33 kPa for the binary mixtures of sulfolane+o-xylene, sulfolane+m-xylene, sulfolane+p-xylene, sulfolane+ethylbenzene and sulfolane+1,2,4-trimethylbenzene. Calculations of the non-ideality of the vapor phase were made with the second virial coefficients evaluated from the Hayden–O’Connell method. The binary parameters for five activity coefficient models (Margules, van Laar, Wilson, NRTL and UNIQUAC) have been fitted with the experimental boiling points measured in this work. A comparison of model performances has been carried out using the criterion of the average absolute deviations in boiling point. The activity coefficient of the component in the liquid phase is discussed based on the UNIFAC model with the consideration of the dipole–dipole interactions.     

Laser-induced fluorescence, dispersed fluorescence and lifetime measurements of jet-cooled chloro-substituted benzyl radicals

We measured the laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled -, o- and m-chlorobenzyl radicals after they were generated by the 193 nm photolysis of the corresponding parent molecules. The vibronically resolved spectra were obtained to analyze their D₁–D₀ transitions. The fluorescence lifetimes of -, o-, m- and p-chlorobenzyls in the zeroth vibrational levels of the D₁ states were measured to estimate the oscillator strengths of a series of benzyl derivatives. It was found that the -substitution is inefficient to break the ‘accidental forbiddenness' of the D₁–D₀ transition of benzyl, while the ring-substitution enhances the oscillator strength by 50%.     

A Partial Least-Squares Multivariate Calibration Method for the Simultaneous Spectrophotometric Determination of Spironolactone,Canrenone and Hydrochlorothiazide

Abstract

An application of a partial least squares calibration method for the simultaneous spectrophotometric determination of spironolactone, canrenone and hydrochlorothiazide is suggested. The use of the PLS for the multicomponent spectrophotometric determination is demonstrated on the analysis of several synthetic mixtures. It was shown that is possible to resolve complex mixtures of     

Absorption and velocity of ultrasonic waves in thiophene, o-, p-xylenes and their mixtures

The results of acoustic measurements of velocity and absorption in three pure liquids: thiophene, p-and m-xylenes and their mixtures are presented. The experiments for the mixtures of thiophene were carried out by Eggers' method at frequencies 0.3–5 MHz, and for pure liquids by the pulse method in the frequency range 10 MHz–10 GHz, all at 293.15 K except for thiophene (at 281 and 333 K).

The absorption in thiophene shows that all vibrational degrees of freedom take part in the observed relaxation, caused by the Kneser processes. This process can be described as a vibrational relaxation with one relaxation time. Absorption in the mixtures decreased when increasing the amount of xylenes, as predicted by theory of gases, thus suggesting that the absorption is probably due to the same phenomenon as in gases.