Independent component analysis (ICA) algorithms for improved spectral deconvolution of overlapped signals in 1H NMR analysis: application to foods and related products

The major challenge facing NMR spectroscopic mixture analysis is the overlapping of signals and the arising impossibility to easily recover the structures for identification of the individual components and to integrate separated signals for quantification. In this paper, various independent component analysis (ICA) algorithms [mutual information least dependent component analysis (MILCA); stochastic non‐negative ICA (SNICA); joint approximate diagonalization of eigenmatrices (JADE); and robust, accurate, direct ICA algorithm (RADICAL)] as well as deconvolution methods [simple‐to‐use‐interactive self‐modeling mixture analysis (SIMPLISMA) and multivariate curve resolution‐alternating least squares (MCR‐ALS)] are applied for simultaneous ¹H NMR spectroscopic determination of organic substances in complex mixtures. Among others, we studied constituents of the following matrices: honey, soft drinks, and liquids used in electronic cigarettes. Good quality spectral resolution of up to eight‐component mixtures was achieved (correlation coefficients between resolved and experimental spectra were not less than 0.90). In general, the relative errors in the recovered concentrations were below 12%. SIMPLISMA and MILCA algorithms were found to be preferable for NMR spectra deconvolution and showed similar performance. The proposed method was used for analysis of authentic samples. The resolved ICA concentrations match well with the results of reference gas chromatography–mass spectrometry as well as the MCR‐ALS algorithm used for comparison. ICA deconvolution considerably improves the application range of direct NMR spectroscopy for analysis of complex mixtures. Copyright © 2014 John Wiley & Sons, Ltd.     

Estimation of the main characteristics of reagents of the diphenylamine series using quantum chemistry and chemometrical methods

The possibility of using quantum chemistry and chemometrical methods for the a priori estimation of the major analytical characteristics of analytical reagents has been demonstrated by the example of compounds of the diphenylamine series. The employed methods for the estimation of the characteristics of compounds are simple and rapid and are equal to the known experimental approaches in terms of precision.     

Phase diagram of an iodine-potassium iodide-water-ethanol system at 25°C

Phase equilibriums are studied in the isothermal-isobaric sections of the phase diagram of a fourcomponent iodine-potassium iodide-water-ethanol system at 25°C and atmospheric pressure. The compositions of the solvent at which it exhibits the greatest ability to dissolve iodine are established. It is shown that in all the investigated sections, there is three-phase eutonic equilibrium with potassium iodide and crystalline iodine as the solid phases. It is revealed that in the sections containing 30 and 50% of ethanol, potassium iodide serves as the salting in agent for crystalline iodine, due to the formation of polyiodide complexes of various composition in the studied system.     

Enhancement of second harmonic generation efficiency: Cs(I)-doped tris(thiourea)zinc(II) sulphate crystals

The effect of dopant cesium (Cs(I)) over a concentration range from 1 to 10 mol% on the growth process, morphology, thermal and optical properties of tri(thiourea)zinc(II) sulfate (ZTS) single crystals grown by slow evaporation solution growth technique has been investigated. Incorporation of Cs(I) into the crystal lattice was well confirmed by energy dispersive X-ray spectroscopy (EDS). The lattice parameters of the as-grown crystals were obtained by single crystal X-ray diffraction analysis. The reduction in the intensities observed in powder X-ray diffraction patterns of doped specimen and slight shifts in vibrational frequencies in fourier transform infrared spectra (FT-IR) indicate the lattice stress as a result of doping. Thermal studies reveal the purity of the material and no decomposition is observed up to the melting point. High transmittance is observed in the visible region and the cut-off λ is ～280 nm. The surface morphology of the as-grown specimens was studied by scanning electron microscopy (SEM). The second harmonic generation (SHG) efficiency of the host crystal is enhanced greatly in the presence of high concentrations of the dopant.     

Differential catalytic determination of iridium(IV) and rhodium(III) based on the oxidation of N-methyldiphenylamine-4-sulfonic acid

The kinetics of the oxidation of N-methyldiphenylamine-4-sulfonic acid with periodate ions was studied in weakly acidic solutions in the presence of iridium(IV), rhodium(III), and their mixtures. Oxidation rate constants were determined in the presence of individual catalysts and their mixtures. The synergetic effect of iridium(IV) and rhodium(III) on the rate of the indicator reaction was estimated; the range of catalyst ratios for the simultaneous determination of analytes was determined. The effect of some factors (oxidant nature and concentration, temperature, the ionic strength of solution, and interfering ions) on the rate of the indicator reaction in the presence of iridium(IV) and rhodium(III) mixtures was assessed. A procedure for the differential catalytic determination of iridium(IV) and rhodium(III) was proposed and tested in the analysis of artificial mixtures and a platinum concentrate of complex composition (KP-5).     

Investigations into the catalytic activity of rhodium(III) in red-ox reactions by capillary zone electrophoresis

Speciation of rhodium(III) in different acidic media has been studied by capillary zone electrophoresis (CZE). Depending on the nature of the acid, rhodium was shown to occur in the form of positive, neutral and/or negatively charged complexes. The relationship between the distribution of rhodium forms and its catalytic action on the oxidation of N-methyldiphenylamine-4-sulfonic acid by periodate ions has been investigated. It was found that only positively charged complexes of rhodium, such as those dominating in perchloric acid solutions, catalyzed a given reaction to form a colored oxidation product. The rate of the catalyzed reaction was optimized with respect to the pH, reagent and oxidant concentration levels, ionic strength, concentration of the catalyst, as well as the presence of interfering ions. The developed kinetic spectrophotometric method features rather high sensitivity (limit of determination 10 μg l⁻¹) and tolerance for most platinum metals and was applied to a complex industrial sample of a platinum concentrate.     

Standardless spectral analysis of independent mixture components: Experimental case studies

We applied recently proposed methods for mixture decomposition in statistically independent components (MILCA and SNICA) to solve practical problems in analytical spectroscopy. These methods aim at reconstructing the spectra of individual mixture components and their concentrations from linear mixtures. Here, they were applied to experimental standardless qualitative and quantitative analysis in UV and visible absorption spectroscopy. However, this family of methods can be coupled with almost any sort of spectroscopic measurements. The results are presented through a series of experimental case studies, including the analysis of major ecotoxicants, polyaromatic hydrocarbons.     

Physicochemical and Analytical Properties of Surfactant-Modified Redox Reagents of the Diphenylamine Series

The effect of the nature and concentration of aqueous solutions of surfactants (ions and micelles) on the spectrochemical, acid-base and redox properties of organic reagents of the diphenylamine series bearing different substituents in phenyl rings and at the bridging nitrogen atom was studied by potentiometric titration and absorption and photoluminescence spectroscopy. The surfactant micelle–reagent binding constants were determined, and the correlation between the binding constants and the above-mentioned properties was analyzed.     

Quantum hysteresis loops in microscopic system: The loop area as a dynamical parameter

The area enclosed by hysteresis loops in a periodically forced bistable microscopic system at zero-temperature is examined by using the time dependent Hellmann-Feynman theorem and the Fourier grid Hamiltonian recipe for solving time-dependent Schrödinger equation. Effects of non-zero temperatures are explored with reference to a symmetric double well potential. The barrier crossing or, relaxation rates are shown to correlate systematically with the area of the loop. The possible use of hysteresis loop area in designing field parameters for optimal control is suggested.     

Synthesis,growth, structure,spectral, thermal and first-order molecular hyperpolarizability of benzophenone-2-furoyl hydrazone single crystal

Single crystals of benzophenone-2-furoyl hydrazone are grown by slow evaporation solution growth technique from ethanol at room temperature. It belongs to monoclinic system with the space group P2₁/c and the cell parameters are, a = 6.1631(3) Å, b = 13.1397(8) Å, c = 18.0030(11) Å and V = 1457.72(14) Å³. NMR spectral studies reveal the structure and powder XRD indicates the crystallinity of the specimen. The characteristic functional groups present in the molecule are confirmed by Fourier transform infrared spectroscopy. The crystals are transparent in the visible region having a lower optical cut-off at ∼406 nm and the band gap energies are estimated by the application of Kubelka–Munk algorithm. Thermal analysis by TG/DTA indicates the stability of the material. The scanning electron microscopy studies reveal the surface morphology of the as-grown crystal. Theoretical calculations were performed using Hartree–Fock method with 6-31G(d,p) as the basis set for to derive the optimized geometry, dipole moment and first-order molecular hyperpolarizability (β) values.