Chemometrics-assisted spectrophotometric method for simultaneous determination of vitamins in complex mixtures

An advanced independent component analysis algorithm (MILCA) is applied for simultaneous chemometric determination of fat- and water-soluble vitamins in complex mixtures. The analysis is based on the decomposition of spectra of multicomponent mixtures in the UV region. The key features of the proposed method are simplicity, accuracy, and reliability. Comparisons between the new algorithm and other established methods (MCR-ALS, SIMPLISMA, other ICA techniques) were made. Our results indicate that in most cases, MILCA is comparable or even outperforms other chemometrics methods taken for comparisons. The influence of different factors (abundance of components, noise, step of spectral scan, and scan speed) on decomposition performance has been investigated. The optimal conditions for spectroscopic registration have been identified. The proposed method was used for analysis of model mixtures and real objects (multivitamin drugs, food additives, and energy drinks). The resolved concentrations match well with the declared amounts and the results of reference methods.     

UV-Vis spectroscopic and chemometric study on the aggregation of ionic dyes in water

The monomer-dimer equilibrium in several ionic dyes (Methylene Blue, Acridine Orange, Nile Blue A, Neutral Red, Rhodamine 6G and Safranine O) has been investigated by means of UV-Vis spectroscopy. The data have been processed by a recently developed method for quantitative analysis of undefined mixtures, based on simultaneous resolution of the overlapping bands in the whole set of absorption spectra. In the cases of Acridine Orange a second chemometric approach has been used as a reference. It is based on a decomposition of the recorded spectra into a product of target and projection matrices using non iterative partial least squares (NIPALS). The matrices are then rotated to give the correct concentrations, spectral profiles of the components and the equilibrium constant. The dimeric constants determined by the two methods were in excellent agreement, evidencing the accuracy of the analysis. From the calculated dimeric constant and monomer and dimer spectra, the structures of the dimeric forms of the studied dyes are estimated.     

Standardless multicomponent qNMR analysis of compounds with overlapped resonances based on the combination of ICA and PULCON

A fast and reliable nuclear magnetic resonance (NMR) method for quantitative analysis of targeted compounds with overlapped signals in complex mixtures has been established. The method is based on the combination of chemometric treatment for spectra deconvolution and the PULCON principle (pulse length based concentration determination) for quantification. Independent component analysis (ICA) (mutual information least dependent component analysis (MILCA) algorithm) was applied for spectra deconvolution in up to six component mixtures with known composition. The resolved matrices (independent components, ICs and ICA scores) were used for identification of analytes, calculating their relative concentrations and absolute integral intensity of selected resonances. The absolute analyte concentrations in multicomponent mixtures and authentic samples were then calculated using the PULCON principle. Instead of conventional application of absolute integral intensity in case of undisturbed signals, the multiplication of resolved IC absolute integral and its relative concentration in the mixture for each component was used. Correction factors that are required for quantification and are unique for each analyte were also estimated. The proposed method was applied for analysis of up to five components in lemon and orange juice samples with recoveries between 90% and 111%. The total duration of analysis is approximately 45 min including measurements, spectra decomposition and quantification. The results demonstrated that the proposed method is a promising tool for rapid simultaneous quantification of up to six components in case of spectral overlap and the absence of reference materials. Copyright © 2015 John Wiley & Sons, Ltd.     

FT-IR studies of molecular interactions in formamide–methanol mixtures

FT-IR spectra of formamide (FA)–methanol (MeOH) mixtures have been measured by ATR technique. Factor analysis applied to the spectra has shown two kinds of intermolecular complexes differing in a manner of polarization of component molecules. The composition of the complexes changes monotonically with the composition of the mixtures. The spectra in the CO stretching region have been analyzed separately using both: the factor analysis and the difference spectra method. Four different environments of carbonyl group of formamide has been revealed over the whole range of the mixture composition. The mean number of formamide molecules disturbed by one methanol molecule via carbonyl group in the formamide-rich region has been found as equal to 1.5. Presumable structures for the molecular complexes have been proposed to explain the results of the analyses.     

Decomposition of multicomponent mass spectra using Bayesian probability theory

We present a method for the decomposition of the mass spectra of mixed gases using Bayesian probability theory. The method works without any calibration measurement and therefore applies also to the analysis of spectra containing unstable species. For the example of mixtures of three different hydrocarbon gases the algorithm provides concentrations and cracking coefficients of each mixture component and also their confidence intervals. The amount of information needed to obtain reliable results and its relation to the accuracy of our analysis are discussed.     

Analysis of spectral data by complementary methods. Inspection of the molecular complex in N,N-dimethylformamide-methanol mixtures

FT-IR spectra of N,N-dimethylformamide (DMF)-methanol (MeOH) mixtures have been measured in the range of 4000-950 cm(-1). The data have been analyzed using the difference spectra method and factor analysis. The usefulness of the methods for recognizing the hydrogen bonds in the mixtures has been critically examined. It has been shown that 1:1 intermolecular complex existing in the whole range of the mixture composition is modified by interactions with environment. The structure of different forms of the complex depending on the solvent composition has been shown. Weak CH...O hydrogen bonds have been postulated for explanation of the spectra.     

Multi‐component analysis: blind extraction of pure components mass spectra using sparse component analysis

The paper presents sparse component analysis (SCA)‐based blind decomposition of the mixtures of mass spectra into pure components, wherein the number of mixtures is less than number of pure components. Standard solutions of the related blind source separation (BSS) problem that are published in the open literature require the number of mixtures to be greater than or equal to the unknown number of pure components. Specifically, we have demonstrated experimentally the capability of the SCA to blindly extract five pure components mass spectra from two mixtures only. Two approaches to SCA are tested: the first one based on ?₁ norm minimization implemented through linear programming and the second one implemented through multilayer hierarchical alternating least square nonnegative matrix factorization with sparseness constraints imposed on pure components spectra. In contrast to many existing blind decomposition methods no a priori information about the number of pure components is required. It is estimated from the mixtures using robust data clustering algorithm together with pure components concentration matrix. Proposed methodology can be implemented as a part of software packages used for the analysis of mass spectra and identification of chemical compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Fourier transform Raman spectral measurements of powdered quaternary mixtures of organic compounds: Exceptional pure component spectral reconstruction using band-target entropy minimization (BTEM)

Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures.     

含未知干扰物体系的多元光度分析的化学计量学算法

基于投影矩阵算法和最小熵概念,本文提出了处理含部份未知成份体系的定性定量分析新方法。将此法应用于金属离子及多环芳烃混合物体系测定,获得了满意的结果。     

Mean centering of ratio spectra as a new spectrophotometric method for the analysis of binary and ternary mixtures

In this paper a new and very simple method was developed for the simultaneous determination of binary and ternary mixtures, without prior separation steps. This method is based on the mean centering of ratio spectra. The mathematical explanation of the procedure is illustrated. After modeling procedure, the method has been successfully applied to the simultaneous analysis of binary mixtures of mefnamic acid and paracetamol and ternary mixtures of acetylsalysilic acid, ascorbic acid and paracetamol. The analytical characteristics of the method such as detection limit, accuracy, precision, relative standard deviation (R.S.D.) and relative standard error (R.S.E.) was calculated. The results showed that the proposed method is simple, rapid, accurate and precise method for analysis of binary and ternary mixtures.     

Standardless spectrochemical analysis and direct simulations of time-resolved vibronic spectra of polyatomic molecules, isomers and mixtures

The efficient method for calculation of dynamical time-resolved vibronic spectra of polyatomic molecules is proposed. It allows to perform direct real-time computer simulations of such spectra for models of complex compounds, isomers and multicomponent mixtures with quantum beats and non-radiative vibrational relaxation taken into account. The examples of calculated spectra show the ways of how to search and select optimal experimental conditions and retrieve the most informative data for solution of inverse spectral problems in different situations. The new method of standardless analysis based on time-resolved vibronic spectroscopy has been developed and its main ideas are presented here. This method is able to solve quantitative and qualitative spectrochemical problems for individual substances and multicomponent mixtures (even for species with similar optical properties) with the use of experimentally measured relative intensities of dynamical spectra only. The algorithms of how to perform analysis in various experimental conditions are proposed.     

Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol–water binary solvents processed by parallel factor analysis

A new spectrophotometric method for the determination of nicotine in mixtures without pre-separation has been proposed. Nicotine could react with 2,4-dinitrophenol through a charge-transfer reaction to form a colored complex. The second-order data from the visible absorption spectra of the complex in a series of ethanol–water binary solvents with various water volume fractions could be expressed as the combination of two bilinear data matrices. With the bilinear model, the second-order spectra data of mixtures containing nicotine and other interferents could be analysed by using second-order calibration algorithms, and the determination of nicotine in the mixtures could be achieved. The algorithm used here was parallel factor analysis. The method has been successfully used to determine nicotine in tobacco samples with satisfactory results.     

铽芳香族羧酸配合物的热分解机理及动力学研究

本文采用TG-DTA-DTG等技术研究了铽羧酸配合物的热分解过程,通过对中间产物进行红外光谱、元素分析、确定了热分解机理。采用三种方法尝试求得了希土羧酸配合物热分解过程的活化能和焓变,发现并总结了其相变过程。     

Principal component and decomposition analysis of multicomponent mixtures of carcinogenic fluorophores

A series of binary and tertiary mixtures of polycyclic aromatic hydrocarbons is analyzed by using principal component and decomposition analysis of molecular fluorescence spectra. The results demonstrate the ability to determine the number and identity of species that are present. Failures caused by high correlation among spectra are considered.     

三线性直接分解法分析高维灰色体系

对于由多个两维测量数据组成的三维阵，本文提出一种新三线性直接分解方法。采用高维ＰＣＡ分解，从三维阵中直接提取抽象光谱和抽象浓度，再结合ＱＺ算法，唯一地确定混合物中各组分光谱的浓度。该方法可以排除其它未知组分的干扰，适用于高维灰色体系定性定量分析和多点校准。用模拟数据讨论了光谱分离度对该方法的影响，应用于混合维生素Ｂ１、Ｂ２和Ｂ６的荧光分析，求得的光谱和浓度与实验值吻合很好。     

Resolution of overlapped peaks in liquid chromatography by use of derivative spectrophotometry and multivariate analysis and its application in the determination of active components in insecticide formulations

Two procedures for the determination of active components in insecticide formulations have been devised. The first is based in the use of derivative spectra of the components obtained by a diode-array spectrophotomer around the maxima signal of the chromatographic peak. In the second method, mixtures are resolved by the partial least-squares (PLS) regression method from standard spectra of the pure components; spectra of the components were also registered around the maxima signal of the peak. Both procedures have been applied to the analysis of diverse mixtures of active components (piperonyl butoxide, neopynamine and fenitrothion) in insecticide formulations with satisfactory results.     

A graphical derivative approach to the photometric determination of lutetium and praseodymium in mixtures

The reaction of lanthanides with 1,4-dihydroxyanthraquinone has been examined and optimum conditions have been found for the separate spectrophotometric determination of Lu and Pr. A graphical method based on use of first and second derivative spectra has been developed for analysis of binary mixtures of the two, in concentration ratios from 1:5 to 5:1. Linear calibration curves were obtained between 1 and 10 mug/ml.     

Thermal-spectroscopic characterization of acetone peroxide and acetone peroxide mixtures with nitrocompounds

Triacetone triperoxide (TATP), also known as acetone peroxide, is a powerful homemade energetic compound, highly unstable and not detectable by traditional detection technologies. The calorimetric profiles of TATP mixtures with TNT, ammonium nitrate, and nitroguanidine were evaluated and compared to pure materials. Raman spectroscopy was used to identify possible interactions between mixture components that may arise on contact. Typical results show a shift of the TATP decomposition temperature to higher temperatures, as well as decomposition of the nitrocompound initiated by TATP decomposition. The vibrational spectra were used as spectroscopic signatures for these mixtures, which can be used to understand detection challenges and for the development of desensitization approaches.     

Spectral-chemometric and quantum-chemical study of the water-acetonitrile system

Association of molecules in the solution of acetonitrile and its binary mixtures with water has been studied using spectroscopy in the near-IR region (800–1100 nm) and the chemometric method of independent components implemented as a MILCA algorithm. The decomposition of the spectral curves of solutions has aimed to determine the number, structure, size, and stability of the associates in the wide concentration range (0–100%). The well-known MCR-ALS algorithm has been used to confirm the accuracy of the independent component analysis. Quantum-chemical computation has been performed for particles occurring in the solution. The results explain some abnormalities observed for water-acetonitrile solutions in reversephase chromatography.     

Analysis of multicomponent mass spectra applying Bayesian probability theory

In this paper we develop a method for the decomposition of mass spectra of gas mixtures, together with the relevant calibration measurements. The method is based on Bayesian probability theory. Given a set of spectra, the algorithm returns the relative concentrations and the associated margin of confidence for each component of the mixture. In addition to the concentrations, such a data set enables the derivation of improved values of the cracking coefficients of all contributing species, even for those components for which the set does not contain a calibration measurement. This latter feature also allows one to analyze mixtures that contain radicals in addition to stable molecules. As an example, we analyze and discuss the mass spectra obtained from the pyrolysis of azomethane, which contain the radical CH3 apart from nitrogen and C1- and C2-hydrocarbons.