Application of Chemometrics in Separation Science

Abstract Chemometrics aims at extracting maximum information through the application of statistics and mathematics to problems of a chemical nature. Over the years, chemometrics has become an important chemical discipline with a significant impact in analytical chemistry, including the incorporation of significant improvements in design and selection of optimal experimental procedures, calibration of analytical instrumentation, and advanced methods for analysis of chemical data. The application of chemometrics methods to separation science, mainly chromatography and capillary electrophoresis, has followed the same increasing trend as in any other field of analytical chemistry. However, reviews on the application of chemometrics in separation science have been very scarce. Therefore, in this paper, the development of chemometrics in chromatography and capillary electrophoresis will be presented with a view of the current state of the‐art and with the prospects for the future.

[1]  Robert E. Synovec,et al.  Parallel column liquid chromatography with a single multi-wavelength absorbance detector for enhanced selectivity using chemometric analysis , 2003 .

[2]  C. Baggiani,et al.  Multivariate analysis of the selectivity for a pentachlorophenol-imprinted polymer. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[3]  C. Horváth,et al.  Intraparticle Mass Transfer in High‐Speed Chromatography of Proteins , 1997, Biotechnology progress.

[4]  Y. Heyden,et al.  Robustness tests on the United States Pharmacopoeia XXVI HPLC assay for ginsenosides in Asian and American ginseng using an experimental design , 2005 .

[5]  Romà Tauler,et al.  Fast chromatography of complex biocide mixtures using diode array detection and multivariate curve resolution , 2004 .

[6]  Yizeng Liang,et al.  Analysis of volatile components from Cortex cinnamomi with hyphenated chromatography and chemometric resolution. , 2004, Journal of pharmaceutical and biomedical analysis.

[7]  M. Gennaro,et al.  Chemometrically assisted simultaneous separation of 21 aromatic sulfonates in ion-interaction RP-HPLC , 2000 .

[8]  W. Yawei,et al.  Chemometrics methods for the investigation of methylmercury and total mercury contamination in mollusks samples collected from coastal sites along the Chinese Bohai Sea. , 2005, Environmental pollution.

[9]  Stephen P. Gurden,et al.  Use of eigenvalues for determining the number of components in window factor analysis of spectroscopic and chromatographic data , 1995 .

[10]  Vladimír Wsól,et al.  Central composite design as a powerful optimisation technique for enantioresolution of the rac-11-dihydrooracin--the principal metabolite of the potential cytostatic drug oracin. , 2002, Journal of biochemical and biophysical methods.

[11]  Carlos Herrero,et al.  Classification of apple fruits according to their maturity state by the pattern recognition analysis of their polyphenolic compositions , 2005 .

[12]  Károly Héberger,et al.  Quantitative structure–retention relationships XIV: Prediction of gas chromatographic retention indices for saturated O-, N-, and S-heterocyclic compounds , 2004 .

[13]  H. Wan,et al.  Chemometric modeling of neurotransmitter amino acid separation in normal and reversed migration micellar electrokinetic chromatography. , 2001, Journal of chromatography. A.

[14]  W. Maher,et al.  Measurement of arsenic species in marine macroalgae by microwave-assisted extraction and high performance liquid chromatography-inductively coupled plasma mass spectrometry , 2002 .

[15]  Desire L. Massart,et al.  Using singular value ratio for resolving peaks in HPLC-DAD data sets , 2005 .

[16]  M. Jalali-Heravi,et al.  Use of second-order calibration for residue screening of some triazines in the presence of coeluting interferences by gas chromatography–selected ion mass spectrometry , 2005 .

[17]  C. Poole,et al.  Chemometric classification of the solvent properties (selectivity) of commonly used gas chromatographic stationary phases , 1995 .

[18]  K. Héberger,et al.  Principal component analysis of polarity and interaction parameters in inverse gas chromatography. , 2001, Journal of chromatographic science.

[19]  D. Massart,et al.  Exploratory chemometric analysis of the classification of pharmaceutical substances based on chromatographic data. , 2000, Journal of chromatography. A.

[20]  Feng Luan,et al.  Prediction of retention time of a variety of volatile organic compounds based on the heuristic method and support vector machine , 2005 .

[21]  E. Forgács,et al.  Relationship between the hydrophobicity and specific hydrophobic surface area of pesticides determined by high-performance liquid chromatography compared with reversed-phase thin-layer chromatography , 1997 .

[22]  J. Smeyers-Verbeke,et al.  Measurement uncertainty from validation and duplicate analysis results in HPLC analysis of multivitamin preparations and nutrients with different galenic forms. , 2003, Journal of pharmaceutical and biomedical analysis.

[23]  Yi-Zeng Liang,et al.  Quality control of herbal medicines. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[24]  D. Westerlund,et al.  Derivatization of dipeptides with 4-fluoro-7-nitro-2,1,3-benzoxadiazole for laser-induced fluorescence and separation by micellar electrokinetic chromatography , 1995 .

[25]  K. Héberger Empirical correlations between gas-chromatographic retention data and physical or topological properties of solute molecules , 1989 .

[26]  A. Bogomolov,et al.  Mutual peak matching in a series of HPLC–DAD mixture analyses , 2003 .

[27]  A. Felinger,et al.  Curve fitting to asymmetrical chromatograms by the extended Kalman filter in frequency domain. , 1994, Talanta.

[28]  Y. Heyden,et al.  Uncertainty assessment from robustness testing applied on an LC assay for R-timolol and other related substances in S-timolol maleate , 2005 .

[29]  P. Minkiewicz,et al.  Identification and determination of milk and soybean protein preparations using enzymatic hydrolysis followed by chromatography and chemometrical data analysis , 2004 .

[30]  W. Windig,et al.  A Noise and Background Reduction Method for Component Detection in Liquid Chromatography/Mass Spectrometry , 1996 .

[31]  K. Héberger,et al.  Discrimination between linear and non-linear models describing retention data of alkylbenzenes in gas-chromatography , 1990 .

[32]  R. Matsuda,et al.  Prediction of measurement precision of apparatus using a chemometric tool in electrochemical detection of high-performance liquid chromatography. , 2003, Journal of chromatography. A.

[33]  Federico Marini,et al.  Supervised pattern recognition to discriminate the geographical origin of rice bran oils: A first study , 2003 .

[34]  Sarah C. Rutan,et al.  Steady state kinetic model constraint for Multivariate Curve Resolution-Alternating Least Squares analysis , 2005 .

[35]  L. Gunnarsson,et al.  Experimental design as a tool when evaluating stationary phases for the capillary electrochromatographic separation of basic peptides. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[36]  N. S. Wu,et al.  Statistical moment analysis and deconvolution of overlapping chromatographic peaks , 1991 .

[37]  D. L. Massart,et al.  Purity assessment and resolution of tetracycline hydrochloride samples analysed using high-performance liquid chromatography with diode array detection , 1999 .

[38]  Z. Pápai,et al.  Application of a new mathematical function for describing chromatographic peaks. , 2001, Journal of chromatography. A.

[39]  K. Héberger,et al.  Quantitative structure–retention relationships: VI. Thermodynamics of Kováts retention index–boiling point correlations for alkylbenzenes in gas chromatography , 1999 .

[40]  Vassilis Gaganis,et al.  Accurate determination of aromatic groups in heavy petroleum fractions using HPLC-UV-DAD , 2001 .

[41]  Attila Felinger,et al.  Deconvolution of Overlapping Skewed Peaks , 1994 .

[42]  K. Bächmann,et al.  Capillary preconditioning for analysis of anions using indirect UV detection in capillary zone electrophoresis: Systematic investigation of alkaline and acid prerinsing techniques by designed experiments , 1998 .

[43]  Maria Chiara Pietrogrande,et al.  Statistical study of peak overlapping in multicomponent chromatograms: importance of the retention pattern , 1995 .

[44]  A. Siouffi,et al.  Optimization methods in chromatography and capillary electrophoresis. , 2000, Journal of chromatography. A.

[45]  F. Rius,et al.  Using second-order calibration to identify and quantify aromatic sulfonates in water by high-performance liquid chromatography in the presence of coeluting interferences. , 2003, Journal of chromatography. A.

[46]  Margriet M. W. B. Hendriks,et al.  Preprocessing and exploratory analysis of chromatographic profiles of plant extracts , 2005 .

[47]  R. Alén,et al.  Chemometric investigation on structural changes in pine kraft lignin during pulping , 2000 .

[48]  I. Wilson,et al.  Cyclosporin A-induced changes in endogenous metabolites in rat urine: a metabonomic investigation using high field 1H NMR spectroscopy, HPLC-TOF/MS and chemometrics. , 2004, Journal of pharmaceutical and biomedical analysis.

[49]  Rafael Cela,et al.  Multi-objective optimisation using evolutionary algorithms: its application to HPLC separations , 2003 .

[50]  V. Stocchi,et al.  Solid-phase microextraction gas chromatography/mass spectrometry: a new method for species identification of truffles. , 2005, Rapid communications in mass spectrometry : RCM.

[51]  R. Kaliszan,et al.  New stationary phases for the high-performance liquid chromatographic separation of nucleosides and cyclic nucleotides synthesis and chemometric analysis of retention data , 1996 .

[52]  J. Saurina,et al.  Determination of amino acids in overlapped capillary electrophoresis peaks by means of partial least-squares regression. , 2000, Journal of chromatography. A.

[53]  Y. Wang,et al.  Simultaneous determination of six main nucleosides and bases in natural and cultured Cordyceps by capillary electrophoresis. , 2004, Journal of chromatography. A.

[54]  P. Araujo A new high performance liquid chromatography multifactor methodology for systematic and simultaneous optimisation of the gradient solvent system and the instrumental/experimental variables , 2000 .

[55]  D. Kaniansky,et al.  Capillary zone electrophoresis in wide bore capillary tubes with fiber-coupled diode array detection. , 2003, Journal of chromatography. A.

[56]  N. Şanlı,et al.  Modelling retention in liquid chromatography of polyphenolic acids prediction of solvent composition and pH of the mobile phase , 2005 .

[57]  S. Klemenc,et al.  In common batch searching of illicit heroin samples--evaluation of data by chemometrics methods. , 2001, Forensic science international.

[58]  D. Kaniansky,et al.  Determination of orotic acid in urine by capillary zone electrophoresis in tandem-coupled columns with diode array detection. , 2003, Journal of chromatography. A.

[59]  Z. Pápai,et al.  Determination of chromatographic peak parameters by non-linear curve fitting using statistical moments. , 2002, The Analyst.

[60]  K. Jinno,et al.  Characterisation of important interactions controlling retention behaviour of analytes in reversed-phase high-performance liquid chromatography , 1998 .

[61]  R. Kaliszan,et al.  Separation of nitroaromatics and their transformation products in soil around ammunition plants: New high performance liquid chromatographic charge transfer stationary phases , 1998 .

[62]  Y. Guillaume,et al.  Chemometric method to optimize chiral separation of imidazole derivatives by capillary electrophoresis. , 1999, Talanta.

[63]  A. Mannschreck,et al.  Determining enantiomeric excess from overlapping HPLC peaks: discussion of errors in the methods , 2004 .

[64]  K. Héberger,et al.  Influence of extraction parameters and medium on efficiency of solid-phase microextraction sampling in analysis of aliphatic aldehydes , 1999 .

[65]  Károly Héberger,et al.  Correlation between retention indices and quantum-chemical descriptors of ketones and aldehydes on stationary phases of different polarity , 2001 .

[66]  Jian-hui Jiang,et al.  Estimation of chemical rank of a three-way array using a two-mode subspace comparison approach , 2003 .

[67]  K Danzer,et al.  Method development for the determination of anthocyanins in red wines by high-performance liquid chromatography and classification of German red wines by means of multivariate statistical methods. , 2000, Journal of chromatography. A.

[68]  K. Héberger Evaluation of polarity indicators and stationary phases by principal component analysis in gas–liquid chromatography , 1999 .

[69]  Ru-Qin Yu,et al.  Mitigating model deficiency in three-way data analysis by the combination of background constraining and iterative correcting techniques , 2003 .

[70]  R. Kaliszan Chromatography and capillary electrophoresis in modelling the basic processes of drug action , 1999 .

[71]  Károly Héberger,et al.  Chemometrics in Hungary (the last 10 years) , 2004 .

[72]  Y. Guillaume,et al.  Chemometric approach to the treatment of benzodiazepine separation and peak broadening in capillary electrophoresis. , 1999, Journal of chromatography. A.

[73]  F. X. Rius,et al.  Development and validation of a method for determining pesticides in groundwater from complex overlapped HPLC signals and multivariate curve resolution , 2005 .

[74]  Károly Héberger,et al.  Comparative analysis of different plant oils by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. , 2002, Journal of chromatography. A.

[75]  A Felinger,et al.  Decoding complex multicomponent chromatograms. , 2001, Analytical chemistry.

[76]  B. Walczak,et al.  Fuzzy warping of chromatograms , 2005 .

[77]  G. Wynia,et al.  Development and validation of a capillary electrophoresis method within a pharmaceutical quality control environment and comparison with high-performance liquid chromatography , 1997 .

[78]  Károly Héberger,et al.  Classification and replacement test of HPLC systems using principal component analysis , 2005 .

[79]  Desire L. Massart,et al.  Uniform shell designs for optimization in reversed-phase liquid chromatography , 1989 .

[80]  M. Jalali-Heravi,et al.  Prediction of electrophoretic mobilities of sulfonamides in capillary zone electrophoresis using artificial neural networks. , 2001, Journal of chromatography. A.

[81]  Cristina M Quintella,et al.  Doehlert matrix: a chemometric tool for analytical chemistry-review. , 2004, Talanta.

[82]  J. Carstensen,et al.  Aligning of single and multiple wavelength chromatographic profiles for chemometric data analysis using correlation optimised warping , 1998 .

[83]  K. Héberger,et al.  Principal component analysis of biogenic amines and polyphenols in Hungarian wines. , 2002, Journal of agricultural and food chemistry.

[84]  R. Kaliszan Retention data from affinity high-performance liquid chromatography in view of chemometrics. , 1998, Journal of chromatography. B, Biomedical sciences and applications.

[85]  M. Görgényi,et al.  Structure-retention relationships in the gas chromatography of N,N-dialkylhydrazones , 1996 .

[86]  A. Cavazzini,et al.  Stochastic−Dispersive Theory of Chromatography , 1999 .

[87]  H. Abdollahi,et al.  Differentiation of bovine and porcine gelatins using principal component analysis. , 2004, Journal of pharmaceutical and biomedical analysis.

[88]  A. Cichelli,et al.  High-performance liquid chromatographic analysis of chlorophylls, pheophytins and carotenoids in virgin olive oils: chemometric approach to variety classification. , 2004, Journal of chromatography. A.

[89]  R. Kaliszan,et al.  Mechanism of separation on cholesterol-silica stationary phase for high-performance liquid chromatography as revealed by analysis of quantitative structure-retention relationships. , 1998, Journal of pharmaceutical and biomedical analysis.

[90]  A. G. Frenich,et al.  Partial least-squares and principal component regression of multi-analyte high-performance liquid chromatography with diode-array detection , 1996 .

[91]  Vicki Morris,et al.  Optimization of the capillary electrophoresis separation of ranitidine and related compounds , 1997 .

[92]  Multivariate calibration methods for quantification in strongly overlapping capillary electrophoretic peaks. , 2001, Journal of chromatography. A.

[93]  Joe M. Davis,et al.  Verification of statistical-overlap theory in micellar electrokinetic chromatography , 2005, Analytical and bioanalytical chemistry.

[94]  Yi-Zeng Liang,et al.  Correction of retention time shifts for chromatographic fingerprints of herbal medicines. , 2004, Journal of chromatography. A.

[95]  C. Poole,et al.  Mixture-design approach to retention prediction using the solvation parameter model and ternary solvent systems in reversed-phase liquid chromatography , 1998 .

[96]  A. Felinger Critical peak resolution in multicomponent chromatograms. , 1997, Analytical chemistry.

[97]  J. Fekete,et al.  Determination of two metabolites of albendazole, albendazole-sulfoxide and albendazole-sulfone in cow's milk using an HPLC method —A systematic approach to optimise extraction conditions , 1998 .

[98]  Y. Daali,et al.  Capillary electrophoresis and high-performance anion exchange chromatography for monitoring caseinoglycomacropeptide sialylation. , 2001, Journal of pharmaceutical and biomedical analysis.

[99]  D. Massart,et al.  Minimal number of chromatographic test parameters for the characterisation of reversed-phase liquid chromatographic stationary phases. , 2002, Journal of chromatography. A.

[100]  Zhide Hu,et al.  Study of quantitative structure-mobility relationship of the peptides based on the structural descriptors and support vector machines , 2005 .

[101]  Y. Guillaume,et al.  Optimising mobile phase composition, its flow-rate and column temperature in HPLC using taboo search. , 2000, Talanta.

[102]  Y. Heyden,et al.  Selection of orthogonal chromatographic systems based on parametric and non-parametric statistical tests , 2005 .

[103]  F. Safa,et al.  Chemometric approach in optimization of micellar liquid chromatographic separation of some halogenated phenols , 2005 .

[104]  P. Eilers,et al.  New background correction method for liquid chromatography with diode array detection, infrared spectroscopic detection and Raman spectroscopic detection. , 2004, Journal of chromatography. A.

[105]  M. Gennaro,et al.  A chemometric investigation of the effect of the cheese-making process on contents of biogenic amines in a semi-hard Italian cheese (Toma) , 2003 .

[106]  Yi-Zeng Liang,et al.  Development of high-performance liquid chromatographic fingerprints for distinguishing Chinese Angelica from related umbelliferae herbs. , 2005, Journal of chromatography. A.

[107]  Josef Havel,et al.  Neural networks for optimization of high-performance capillary zone electrophoresis methods: A new method using a combination of experimental design and artificial neural networks , 1998 .

[108]  M. Görgényi,et al.  Correlation of retention indices with van der Waals’ volumes and surface areas: Alkanes and azo compounds , 1995 .

[109]  Josef Havel,et al.  Artificial neural networks based on genetic input selection for quantification in overlapped capillary electrophoresis peaks. , 2004, Talanta.

[110]  M. Abraham,et al.  Relationships between the chromatographic hydrophobicity indices and solute descriptors obtained by using several reversed-phase, diol, nitrile, cyclodextrin and immobilised artificial membrane-bonded high-performance liquid chromatography columns , 1998 .

[111]  J. Fekete,et al.  A new approach for development of rugged sample preparation of metabolites of albendazole in cow milk , 1999 .

[112]  Y. Heyden,et al.  Chemometric comparison of recent chromatographic and electrophoretic methods in a quantitative structure-retention and retention-activity relationship context. , 2003, Journal of chromatography. A.

[113]  Maria Chiara Pietrogrande,et al.  HRGC separation performance evaluation by a simplified fourier analysis approach , 1996 .

[114]  M. C. Ortiz,et al.  Optimization of the chromatographic conditions for the determination of hormones by gas chromatography with mass spectrometry detection , 2005 .

[115]  Willem Windig,et al.  The use of the Durbin-Watson criterion for noise and background reduction of complex liquid chromatography/mass spectrometry data and a new algorithm to determine sample differences , 2005 .

[116]  S. Reinikainen,et al.  Improved kinetic data from analysis of complex hydrocarbon mixtures by using SIMCA , 2005 .

[117]  Tonghua Li,et al.  Overlapping spectra resolution using non-negative matrix factorization. , 2005, Talanta.

[118]  Attila Felinger,et al.  Improvement of the signal-to-noise ratio of chromatographic peaks by Fourier transform , 1991 .

[119]  Desire L. Massart,et al.  Application of Derringer's desirability function for the selection of optimum separation conditions in capillary zone electrophoresis , 1996 .

[120]  M. León-Camacho,et al.  HPLC analysis of tocopherols and triglycerides in coffee and their use as authentication parameters , 2001 .

[121]  B. W. Wright,et al.  An improved optimization algorithm and a Bayes factor termination criterion for sequential projection pursuit , 2005 .

[122]  F. Bianchi,et al.  High-performance anion-exchange chromatography coupled with pulsed amperometric detection and capillary zone electrophoresis with indirect ultra violet detection as powerful tools to evaluate prebiotic properties of fructooligosaccharides and inulin. , 2004, Journal of chromatography. A.

[123]  T. Wheat,et al.  Drug identification in biological matrices using capillary electrophoresis and chemometric software. , 1996, Journal of chromatography. B, Biomedical applications.

[124]  A. Ulrici,et al.  A study of the relationships among acidity, sugar and furanic compound concentrations in set of casks for Aceto Balsamico Tradizionale of Reggio Emilia by multivariate techniques , 2005 .

[125]  Attila Felinger Superposition of chromatographic retention patterns , 1995 .

[126]  Z. Pápai,et al.  Analysis of peak asymmetry in chromatography. , 2002, Journal of chromatography. A.

[127]  W. Bockelmann,et al.  Effect of defined-strain surface starters on the ripening of Tilsit cheese , 2004 .

[128]  I. Wilson,et al.  A combined (1)H NMR and HPLC-MS-based metabonomic study of urine from obese (fa/fa) Zucker and normal Wistar-derived rats. , 2005, Journal of pharmaceutical and biomedical analysis.

[129]  D. Massart,et al.  Robustness testing of chiral separations by capillary electrophoresis using highly-sulfated cyclodextrins. , 2003, Journal of chromatography. A.

[130]  J. Wieling,et al.  Rational experimental design for bioanalytical methods validation. Illustration using an assay method for total captopril in plasma. , 1996, Journal of chromatography. A.

[131]  Philippe Hubert,et al.  Development of response models for optimising HPLC methods , 2004 .

[132]  Y. Heyden,et al.  Selection of reversed-phase liquid chromatographic columns with diverse selectivity towards the potential separation of impurities in drugs. , 2004, Journal of chromatography. A.

[133]  Use of artificial neural networks in capillary zone electrophoresis , 1999 .

[134]  K. Rasmussen,et al.  Automated on-line dialysis for sample preparation and HPLC analysis of antidepressant drugs in human plasma. Inhibition of interaction with the dialysis membrane. , 1998, Journal of pharmaceutical and biomedical analysis.

[135]  Richard G. Brereton,et al.  A comparison of deconvolution methods as applied to high performance liquid chromatography-diode array detector-electrospray mass spectrometry of 2- and 3-hydroxypyridine at varying pH in the presence of severely tailing peak shapes , 1999 .

[136]  F. Rius,et al.  Second-order bilinear calibration for determining polycyclic aromatic compounds in marine sediments by solvent extraction and liquid chromatography with diode-array detection , 2003 .

[137]  Francesco Dondi,et al.  Fourier analysis of multicomponent chromatograms. Recognition of retention patterns , 1992 .

[138]  O. Åström,et al.  Separation of ibuprofen, codeine phosphate, their degradation products and impurities by capillary electrophoresis. I. Method development and optimization with fractional factorial design. , 1998, Journal of chromatography. A.

[139]  Károly Héberger,et al.  Partial least squares modeling of retention data of oxo compounds in gas chromatography , 2000 .

[140]  Willem Windig,et al.  Fast interpretation of complex LC/MS data using chemometrics , 2001 .

[141]  R. Zhao,et al.  Artificial neural network classification based on capillary electrophoresis of urinary nucleosides for the clinical diagnosis of tumors. , 1998, Journal of chromatography. A.