Michal Daszykowski

University of Silesia in Katowice · Institute of Chemistry

Visualization of a data set structure is one of the most challenging goals in data mining. Often, chemical data sets are multidimensional, and therefore visualization of their structure is not directly possible. To overcome this problem, the original data is compressed to the few new features by using projection techniques, preserving the original...

In this article, we present a new type of inexpensive multi-illumination source chamber. The innovation makes use of a smartphone camera which possesses the ability of capturing multiple images. Its performance was compared to a commercially available densitometer. Similar devices and suitable strategies for data analysis will help to solve diverse...

This study illustrates the successful application of near-infrared reflectance spectroscopy extended with chemometric modeling to profile Cd, Cu, Pb, Ni, Cr, Zn, Mn, and Fe in cultivated and fertilized Haplic Luvisol soils. The partial least-squares regression (PLSR) models were built to predict the elements present in the soil samples at very low...

The alignment of instrumental signals, such as chromatograms, is regarded as an important step before applying multivariate chemometric techniques for data analysis. Nowadays, many alignment techniques are available and they differ in achieving their goal. They can correct peak shifts in a set of chromatograms with differing degrees of success. Alm...

The study aimed to develop a cost-effective and rapid approach for monitoring eleven crucial parameters that describe the health of cultivated Haplic Luvisol soils. To achieve this, the diffuse reflectance spectra in the NIR spectral region, between 1100 and 2500 nm, were registered, and partial least-squares (PLS) models to predict the concentrati...

Evaporation is the phase transition process that plays a significant role in many spheres of life and science. Volatilization of hazardous materials, pesticides, petroleum spills, etc., impacts the environment and biosphere. Predicting evaporation fluxes under specific environmental conditions is challenging from theoretical and empirical points of...

This study illustrates at‐line application of hyperspectral imaging in the visible range for quality control of large‐scale offset printing. In particular, the measurement stability of a competitive device is assessed and compared to traditional handheld and desktop spectrophotometers. The performance of the commercially available instruments was a...

This study demonstrates the rapid and cost-effective possibility of quantifying adulterant amounts (corn flour or corn starch) in ground and dried garlic samples. Prepared mixtures with different concentrations of selected adulterant were effectively characterized using Fourier-transform near-infrared reflectance spectra (FT-NIR), and multivariate...

We do not know whether recycling will save us from environmental disaster. We believe, however, that segregating trash makes sense. From an early age, our children learn to link the colors of containers with various types of waste. Plastic bags, plastic bottles, metal caps, aluminum cans and milk cartons end up in yellow containers and bags every d...

This study examines the potential of near-infrared hyperspectral imaging for assessing the size of polymer particles in model fractions based on the scattering phenomena. Different fractions of ground polymers, either methacrylate or polypropylene, were characterized by near-infrared spectra collected between 900 and 1700 nm. The possibility to est...

Publikacja z okazji nadania Pani Jolancie Wadowskiej-Król godności Doktora Honoris Causa Uniwersytetu Śląskiego w Katowicach.

This article discusses the possibility of exploratory data analysis of samples described by second-order chromatographic data affected by peak shifts. In particular, the potential of the kernel Gram matrix representation as an alternative to the necessary and time-consuming alignment step is evaluated. It was demonstrated through several simulation...

In this study, we examine the chemical stability of two disazo dyes, namely Solvent Red 19 and 23 (SR 19 and SR 23), under simulated conditions. Both dyes are considered to be chemically stable under normal exploitation conditions and therefore, are used extensively as excise duty components that enable a rapid visual verification of the tax levels...

Already learned at school, planar chromatography summarizes sample results as illustrative image (fingerprints) understood intuitively. The list of globally urgent analyses is long to check the quality of especially food, dietary supplements, nutraceuticals, pharmaceuticals, environmental samples etc. An analytical public domain open source tool co...

Fiscal markers are chemical compounds with unique properties added to diesel oil to label the intended purpose of its usage and indicate expected tax level. In this study, we analyzed chemical changes in model systems with one of two red disazo dyes, the so-called Solvent Red 19 and 164 (concentration of dye equal to 4.6 mg·dm-3), dissolved in hept...

In this study, differences in the chemical compositions of rebated excise duty diesel oil samples that were caused by fuel laundering were investigated. Two possible laundering pathways were simulated using either reduction or adsorption agents in model samples that were spiked with Solvent Yellow 124 and Solvent Red 19. The samples were characteri...

The objective of our study was to evaluate the advantages of the proposed validation framework for a rigorous one-class classifier that operates on the large sets of multivariate pixels that are obtained using the hyperspectral imaging technique that are considered to be individual samples. The performance of the validation strategy was evaluated e...

This chapter focuses on the exploratory analysis of metabolomic data. The goal of data exploration is to uncover any possible differences in sampling procedures, to examine the between- or within-laboratory variations in the measurement processes, to understand the issues that are associated with the appropriateness of the selected experimental des...

Chemometric methods permit the construction of classifiers that effectively assist in monitoring safety, quality and authenticity of meat based on the near-infrared (NIR) spectral fingerprints. Discriminant techniques are often considered in multivariate quality control. However, when the authenticity of meat products is the primary concern, they o...

Today, the chemical labeling of various products (so-called tagging) is very important. It assists in the prevention and/or detection of diverse forms of counterfeiting. Because mineral oils are used on a large scale and are important for local and worldwide economies, they are protected against possible counterfeiting by spiking them with overt (v...

Uniform subset selection using the Duplex algorithm. [1] R.D. Snee, Technometrics 19 (1977) 415-428 [2] M. Daszykowski, B. Walczak, D.L. Massart, Representative subset selection, Analytica Chimica Acta, 468 (2002) 91-103

In EU countries, diesel oil is spiked with chemical substances to indicate tax level and designate its further usage. In Poland, diesel oil designated for regular transport contains Solvent Yellow 124 (a marker compound) and Solvent Red 19 or 164 (a red dye). Even though these substances are considered to be stable, there are many illegal attempts...

Basic PLS algorithm (NIPALS) programmed according to reference: B.G.M. Vandeginste, D.L. Massart, L.M.C. Buydens, S. de Jong, P.J. Lewi, J. Smeyers-Verbeke, Handbook of Chemometrics and Qualimetrics, Part B, Elsevier, Amsterdam, 1998, p. 336

This review article provides readers with a number of actual case studies dealing with verifying the authenticity of selected medicines supported by different chemometric approaches. In particular, a general data processing workflow is discussed with the major emphasis on the most frequently selected instrumental techniques to characterize drug sam...

Performs vector quantization using the Neural Gas algorithm [1] Martinetz M., Berkovich S., Schulten K.,”Neural-gas” network for vector quantization and its application to time series prediction, IEEE Trans. Neural Networks 4 (1993) 558-569. [2] M. Daszykowski, B. Walczak, D.L. Massart, On the optimal partitioning of data with K-means, Growing K-me...

Counterfeit medicines are a global threat to public health. High amounts enter the European market, which is why characterization of these products is a very important issue. In this study, a high-performance liquid chromatography–photodiode array (HPLC-PDA) and high-performance liquid chromatography–mass spectrometry (HPLC-MS) method were develope...

Matlab code for the ’duplex’ algorithm - uniform selection of model and test sets [1] R.D. Snee, Validation of regression models: methods and examples, Technometrics 19 (1977) 415-428. [2] M. Daszykowski, B. Walczak, D.L. Massart, Representative subset selection, Analytica Chimica Acta 468 (2002) 91-103.

In this study we discuss an attempt to build an expert system that can support decision making by analytical chemists regarding the presence of tributyltin (TBT) in inland Polish water samples in detail. It is possible to conclude with at least a 0.93 probability that a sample is free of TBT using the expert system that was constructed (if a sample...

Public health is threatened worldwide by counterfeit medicines. Their quality, safety and efficacy cannot be guaranteed since no quality control is performed during and/or after the manufacturing process. Characterization of these products is a very important topic. During this study a High Performance Liquid Chromatography-Photodiode Array (HPLC-P...

The performance of the recently proposed excitation-emission fluorescence method was compared to the method using infrared measurements for the evaluation of the antioxidant properties of intact samples and extracts that had been obtained from tomato pastes. The oxygen radical absorbance capacity assay (ORAC) was applied in order to estimate the an...

In the countries of the European Community, diesel fuel samples are spiked with Solvent Yellow 124 and either Solvent Red 19 or Solvent Red 164. Their presence at a given concentration indicates the specific tax rate and determines the usage of fuel. The removal of these so-called excise duty components, which is known as fuel "laundering", is an i...

The aim of this work was to develop a general framework for the validation of discriminant models based on the Monte Carlo approach that is used in the context of authenticity studies based on chromatographic impurity profiles. The performance of the validation approach was applied to evaluate the usefulness of the diagnostic logic rule obtained fr...

A novel and rapid approach to screening antioxidant content is proposed. Its usefulness is illustrated for coffee and peppermint extracts. The antioxidant properties of extracts were predicted from their excitation-emission fluorescence matrices using the partial least squares and the N-way partial least squares regression. The total antioxidant ca...

Models to predict the total antioxidant capacity (TAC) of rooibos tea infusions from their chromatographic fingerprints and peak table data (content of individual phenolic compounds), obtained using HPLC with diode array detection, were developed in order to identify potential antioxidant markers. Peak table data included the content of 12 compound...

Data clustering plays an important role in the exploratory analysis of analytical data, and the use of clustering methods has been acknowledged in different fields of science. In this paper, principles of data clustering are presented with a direct focus on clustering of analytical data. The role of the clustering process in the analytical workflow...

The fluorescent fingerprints of diesel oil samples were investigated in order to develop a fast and cost-effective method to facilitate the discrimination of rebated tax diesel fuel from oil that is illegally processed by the sorption process. In the experiment oil samples were spiked with a fiscal marker (Solvent Yellow 124) and a dye (Solvent Red...

In this chapter, foundations of robust statistics are introduced, including classic and robust estimators as well as their statistical properties (breakdown point, efficiency, influence function and equivariance property). Then, some robust methods that have gained popularity in recent years are presented. The major benefit of using robust methods...

An artificial polypeptide receptor (APR) library was created by using the self-organization of N-lipidated peptides attached to cellulose via m-aminophenylamino-1,3,5-triazine. The response of the library was probed using a series of novel H3 receptor ligands. Since no guidelines on how to design an APRs selective vs. certain receptor types exist,...

Differences in tax levels for diesel oil stimulate the illegal removal of characteristic diazo compounds purposely added to designate its possible usage. In order to reduce the losses in the national income, there is a strong need to develop a sensitive and cost-effective analytical procedure for the detection of this illegal action. In this study,...

The aim of our study was to highlight the benefits of robust calibration in the context of process control. Two properties were monitored — the color and ash content of sugar samples. It was shown for the data being studied that robust models, constructed using the partial robust M-regression technique, have a better fit to the majority of the data...

In this paper, dissimilarity partial least squares, which deals with non-linear modeling problems, is discussed. It is based on the classic partial least squares approach, where the dissimilarity matrix representing dissimilarities among data objects replaces explanatory variables. This enables the construction of a global model able to adjust to l...

The aim of this work was to propose a quick and cost-effective procedure, which could help to identify the types of fat (rapeseed, a mixture of rapeseed and soybean, and lard oils) added to feed used for raising pigs. For this purpose, liver samples were examined and their near-infrared reflectance spectra served as data for the construction of cla...

Most of the counterfeit medicines are manufactured in non good manufacturing practices (GMP) conditions by uncontrolled or street laboratories. Their chemical composition and purity of raw materials may, therefore, change in the course of time. The public health problem of counterfeit drugs is mostly due to this qualitative and quantitative variabi...

In this article several approaches for the exploratory analysis of two-dimensional chromatographic signals (fingerprints) are presented. Their usefulness is illustrated on experimental chromatographic data obtained from high performance liquid chromatography using the photodiode-array detector (HPLC-DAD). Among the methods discussed are principal c...

Analysis of proteomic data, presented in form of 2D gel electropherograms, is still a real challenge and requires further improvements. Three main problems in data analysis are associated with (1) ‘software-induced variance’ (due to the different methods of data pre-processing or their different input parameters), (2) univariate significance analys...

A large progress in the development of robust methods as an efficient tool for processing of data contaminated with outlying objects has been made over the last years. Outliers in the QSAR studies are usually the result of an improper calculation of some molecular descriptors and/or experimental error in determining the property to be modelled. The...

A general framework for the automatic alignment of one-dimensional chromatographic signals is presented in this article. The alignment of signals was achieved by explicitly modeling the warping function. Its shape was estimated using a linear combination of several B-spline functions. The coefficients of the spline functions were found in the cours...

The primary focus of the European Union funded project entitled “Establishing a WINE Data Bank for analytical parameters for wines from Third Countries” (WINE-DB project, G6RD-CT-2001-00646-WINE-DB) was the discrimination of wine samples with respect to their geographical origin using only a few chemical parameters. Taking a step further, we have i...

Michał Daszykowski received his Ph.D. in 2003 from the University of Silesia (Katowice, Poland) for the thesis entitled ‘Exploration of multidimensional chemical data; methods of compression and visualization.’ Since 2003 he has been working at the Department of Chemometrics (Institute of Chemistry, the University of Silesia, Katowice, Poland) for...

Comparative analysis of twenty different sage (Salvia L.) species grown in Poland has been performed on the basis of two types of chromatographic fingerprints. For efficient preprocessing and comparison of these fingerprints, chemometric methods were used. The main emphasis was on preprocessing of herbal fingerprints and selecting a suitable prepro...

The development of a new drug substance is an expensive and time-consuming process. Therefore, the developers want to maximize the profit from the drug by patenting the concerned molecule as well as its synthesis pathway. In a later stage a faster or cheaper manufacturing process can be developed and patented. The aim of this study is to recognize...

Astrocytes are supportive cells, necessary for ensure optimal environment for neural cells functioning. They are involved in extracellular K+ level regulation and neurotransmitters removal. They are also dependent for myelination and synapses formation. They may make a contribution in signal propagation in the central nervous system, for example, t...

Analysis of two-dimensional (2D) electrophoretic images is a multi-step approach, enabling application of a variety of methods at different stages of data processing. The choice of these, as well as input parameters, leads to software-induced variations. Effective preprocessing methods, which do not require optimization of input parameters, are pot...

Recently, we have witnessed to a considerable growth of interest in characterization of chemical samples by their analytical signals obtained from the fingerprinting techniques [1]. Among different analytical techniques well-suited for the fingerprinting purposes, chromatographic methods have their special place, since they offer a possibility to s...

Analysis of proteomic data requires the alignment of 2D gel electropherograms. The Matlab ‘Image Processing Toolbox’ contains many interesting subroutines to deal with image processing. Among them there is a subroutine for manual markers selection. Attractive in many cases, it is time-consuming and error prone in the case of gel images, which conta...

Near-infrared reflectance spectroscopy (NIRS) is often applied when a rapid quantification of major components in feed is required. This technique is preferred over the other analytical techniques due to the relatively few requirements concerning sample preparations, high efficiency and low costs of the analysis. In this study, NIRS was used to con...

In this paper a broad overview of the retention behaviour of twenty flavonoids and their analogues in 74 TLC systems is reported. The compounds were chromatographed on different stationary phases (non-polar and polar-bonded stationary phases - wettable RP18W, silica, and aminopropyl-modified and diol-modified plates) developed with a variety of bin...

Hyphenated techniques such as capillary electrophoresis-mass spectrometry (CE-MS) or high-performance liquid chromatography with diode array detection (HPLC-DAD), etc., are known to produce a huge amount of data since each sample is characterized by a two-way data table. In this paper different ways of obtaining sample-related information from a se...

Because of the increasing problem of drug counterfeiting and the potential danger related as well as the economic losses involved, the pharmaceutical industry and the regulatory instances are interested in the development of anti-counterfeiting and patent protection methodologies. In this paper, the evaluation of measured isotopic ratios by means o...

In this paper a robust version of the partial least squares model (partial robust M-regression, PRM) was built to predict the total antioxidant capacity of green tea extracts. In order to construct a calibration model, chromatograms obtained by a fast high-performance liquid chromatographic method on a monolithic silica column were related with the...

Gel electrophoresis serves as a basic analytical tool in the proteomic studies. However, processing of gel electrophoretic images is still the main bottleneck of data analysis, and there is an increasing need for the fully automated approaches. The proposed start-to-end strategy of analyzing the gel images consists of chemometric tools, which allow...

In this paper an application of the uninformative variable elimination–partial least squares (UVE-PLS) method extended by the Monte Carlo approach for selection of possible biomarkers from the liquid chromatography coupled with mass spectrometry (LC-MS) data is reported. The main challenge consists not in the chemometrics analysis of LC-MS data, bu...

The main goal of exploratory data analysis is to reveal clusters of objects, local changes of data density, outlying objects and/or influential sources of data variance. These different aspects of data exploration can sometimes be accomplished simultaneously with the use of one algorithm, the projection algorithm (PA). In this paper, the PA is desc...

In this article a robust version of SIMCA, based on spherical principal component analysis [N. Locantore, J.S. Marron, D.G. Simpson, N. Tripoli, J.T. Zhang, K.L. Cohen, Robust principal component analysis for functional data (with comments), Test 8 (1999) 1–74], is introduced for chemometrics community. The efficiency of the new approach is compare...

An efficient methodology for dealing with missing values and outlying observations simultaneously in principal component analysis (PCA) is proposed. The concept described in the paper consists of using a robust technique to obtain robust principal components combined with the expectation maximization approach to process data with missing elements....

We have developed a new user-friendly graphical interface for robust calibration with a collection of m-files, called TOMCAT (TOolbox for Multivariate CAlibration Techniques). The graphical interface and its routines are freely available and programmed in MATLAB 6.5, probably one of the most popular programming environments in the chemometrics comm...

Presence of outliers in chemical data affects all least squares models, which are extensively used in chemometrics for data exploration and modeling. Therefore, more and more attention is paid to the so-called robust models and robust statistics that aim to construct models and estimates describing well data majority. Moreover, construction of robu...

The graphical interface is equipped with a collection of m-files and its routines are freely available. These were developed under MATLAB 6.5, one of the most popular programming environments among chemometricians. The graphical interface allows a user to apply the implemented methods in an easy way and it gives reach possibilities to visualize the...

This article presents a selection of the relevant issues that emerge at the interface between chromatography and chemometrics. In the first part, we present advantages and drawbacks of applying signal-enhancement, warping and mixture-analysis methods. In the second part, we discuss typical examples of misuse and abuse of chemometrics that can occur...

A quantitative structure-retention relationship analysis was performed on the chromatographic retention data of 90 peptides, measured by gradient elution reversed-phase liquid chromatography, and a large set of molecular descriptors computed for each peptide. Such approach may be useful in proteomics research in order to improve the correct identif...

In this paper the performance of three alignment algorithms, correlation optimized warping, parametric time warping and semi-parametric time warping, is compared on real chromatograms. Among these, parametric time warping is the simplest and fastest; generally less than 1s is required to align two chromatograms. It does not require the optimization...

Several chemometric techniques were compared for their performance to determine the orthogonality and similarity between chromatographic systems. Pearson's correlation coefficient (r) based color maps earlier were used to indicate selectivity differences between systems. These maps, in which the systems were ranked according to decreasing or increa...

Proton nuclear magnetic resonance (1H NMR) spectroscopic analysis of mixtures has been used extensively for a variety of applications ranging from the analysis of plant extracts, wine, and food to the evaluation of toxicity in animals. For example, NMR analysis of urine samples has been used extensively for biomarker discovery and, more simply, for...

Uniform subset selection - Kennard and Stone algorithm [1] R.W. Kennard, L.A. Stone, Computer aided design of experiments, Technometrics 11 (1969) 137-148. [2] M. Daszykowski, B. Walczak, D.L. Massart, Representative subset selection, Analytica Chimica Acta, 468 (2002) 91-103.

The goal of this study is to derive a methodology for modeling the biological activity of non-nucleoside HIV Reverse Transcriptase (RT) inhibitors. The difficulties that were encountered during the modeling attempts are discussed, together with their origin and solutions. With the selected multivariate techniques: robust principal component analysi...

In this paper, a fast strategy for determining the total antioxidant capacity of Chinese green tea extracts is developed. This strategy includes the use of experimental techniques, such as fast high-performance liquid chromatography (HPLC) on monolithic columns and a spectrophotometric approach to determine the total antioxidant capacity of the ext...

A data set consisting of fourteen isotopic ratios or quantities derived from such ratios for samples of acetylsalicylic acid (aspirin), commercialized by various pharmaceutical companies from different countries, was analyzed. The goal of the data analysis was to explore whether results can be linked to geographical origin or other features such as...