Towards the solution of the eluent elimination problem in high-performance liquid chromatography-infrared spectroscopy measurements by chemometric methods

Krisztina István, R. Rajkó, G. Keresztury

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29 Citations (Scopus)

Abstract

The high-performance liquid chromatography-infrared spectroscopy (HPLC-IR) technique utilizing on-line flow through cell (FTC) detection has an inherent practical problem: strong absorption bands of the eluent may mask valuable analytical regions of the IR spectrum. The experimentalists' answer to this challenge is physical elimination of the chromatographic eluent before spectroscopic detection, which however results in off-line measurement of spectra. In the present work, the capabilities of some chemometric algorithms using iteratively applied multi-way methods such as parallel factor analysis (PARAFAC) and PARAFAC2, developed with the aim of overcoming the problems of eluent elimination are examined and evaluated. Test calculations done on simulated liquid chromatographic infrared (LC-IR) data cubes have shown that although PARAFAC2 performs much better than the simple PARAFAC method, it does not give correct decompositions, just like multivariate curve resolution with alternative least squares (MCR-ALS) and related bilinear data based methods. In search for a better solution, a method named objective subtraction of solvent spectrum with iterative use of PARAFAC and PARAFAC2 (OSSS-IU-PARAFAC and OSSS-IU-PARAFAC2) has been developed. Calculations performed with the corresponding Matlab program developed by the authors and run with the appropriate functions in PLS_Toolbox yielded very promising results in evaluations of both simulated and real HPLC-IR data sets, after necessary data pretreatments.

Original languageEnglish
Pages (from-to)154-163
Number of pages10
JournalJournal of Chromatography A
Volume1104
Issue number1-2
DOIs
Publication statusPublished - Feb 3 2006

Fingerprint

High performance liquid chromatography
Factor analysis
Statistical Factor Analysis
Infrared spectroscopy
Spectrum Analysis
High Pressure Liquid Chromatography
Masks
Least-Squares Analysis
Absorption spectra
Infrared radiation
Decomposition
Liquids

Keywords

  • Chemometrics
  • Flow through cell method
  • HPLC-IR
  • OSSS-IU-PARAFAC
  • PARAFAC and PARAFAC2
  • Solvent elimination

ASJC Scopus subject areas

  • Analytical Chemistry

Cite this

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title = "Towards the solution of the eluent elimination problem in high-performance liquid chromatography-infrared spectroscopy measurements by chemometric methods",
abstract = "The high-performance liquid chromatography-infrared spectroscopy (HPLC-IR) technique utilizing on-line flow through cell (FTC) detection has an inherent practical problem: strong absorption bands of the eluent may mask valuable analytical regions of the IR spectrum. The experimentalists' answer to this challenge is physical elimination of the chromatographic eluent before spectroscopic detection, which however results in off-line measurement of spectra. In the present work, the capabilities of some chemometric algorithms using iteratively applied multi-way methods such as parallel factor analysis (PARAFAC) and PARAFAC2, developed with the aim of overcoming the problems of eluent elimination are examined and evaluated. Test calculations done on simulated liquid chromatographic infrared (LC-IR) data cubes have shown that although PARAFAC2 performs much better than the simple PARAFAC method, it does not give correct decompositions, just like multivariate curve resolution with alternative least squares (MCR-ALS) and related bilinear data based methods. In search for a better solution, a method named objective subtraction of solvent spectrum with iterative use of PARAFAC and PARAFAC2 (OSSS-IU-PARAFAC and OSSS-IU-PARAFAC2) has been developed. Calculations performed with the corresponding Matlab program developed by the authors and run with the appropriate functions in PLS_Toolbox yielded very promising results in evaluations of both simulated and real HPLC-IR data sets, after necessary data pretreatments.",
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AB - The high-performance liquid chromatography-infrared spectroscopy (HPLC-IR) technique utilizing on-line flow through cell (FTC) detection has an inherent practical problem: strong absorption bands of the eluent may mask valuable analytical regions of the IR spectrum. The experimentalists' answer to this challenge is physical elimination of the chromatographic eluent before spectroscopic detection, which however results in off-line measurement of spectra. In the present work, the capabilities of some chemometric algorithms using iteratively applied multi-way methods such as parallel factor analysis (PARAFAC) and PARAFAC2, developed with the aim of overcoming the problems of eluent elimination are examined and evaluated. Test calculations done on simulated liquid chromatographic infrared (LC-IR) data cubes have shown that although PARAFAC2 performs much better than the simple PARAFAC method, it does not give correct decompositions, just like multivariate curve resolution with alternative least squares (MCR-ALS) and related bilinear data based methods. In search for a better solution, a method named objective subtraction of solvent spectrum with iterative use of PARAFAC and PARAFAC2 (OSSS-IU-PARAFAC and OSSS-IU-PARAFAC2) has been developed. Calculations performed with the corresponding Matlab program developed by the authors and run with the appropriate functions in PLS_Toolbox yielded very promising results in evaluations of both simulated and real HPLC-IR data sets, after necessary data pretreatments.

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