Definition and detection of data-based uniqueness in evaluating bilinear (two-way) chemical measurements

Róbert Rajkó, Hamid Abdollahi, Samira Beyramysoltan, Nematollah Omidikia

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Multivariate curve resolution methods, frequently used in analyzing bilinear data sets, result in ambiguous decomposition in general. Implementing the adequate constraints may lead to reduce the so-called rotational ambiguity drastically, and in the most favorable cases to the unique solution. However, in some special cases, non-negativity constraint as minimal information of the system is a sufficient condition to resolve profiles uniquely. Although, several studies on exploring the uniqueness of the bilinear non-negatively constrained multivariate curve resolution methods have been made in the literature, it has still remained a mysterious question. In 1995, Manne published his profile-based theorems giving the necessary and sufficient conditions of the unique resolution. In this study, a new term, i.e., data-based uniqueness is defined and investigated in details, and a general procedure is suggested for detection of uniquely recovered profile(s) on the basis of data set structure in the abstract space. Close inspection of Borgen plots of these data sets leads to realize the comprehensive information of local rank, and these argumentations furnish a basis for data-based uniqueness theorem. The reported phenomenon and its exploration is a new stage (it can be said fundament) in understanding and describing the bilinear (matrix-type) chemical data in general.Our proposed detection tool is restricted to three-component systems because of the visual limitations of the Borgen plot, but the theorem is universal for systems with more than three components. A recently published experimental four-component system is used for illustrating this theorem in the case of systems with more than three components.

Original languageEnglish
Pages (from-to)21-33
Number of pages13
JournalAnalytica Chimica Acta
Volume855
DOIs
Publication statusPublished - Jan 15 2015

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Keywords

  • Bilinear data set
  • Borgen plot
  • Rotational ambiguity
  • Self-modeling/multivariate curve resolution
  • Uniqueness

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Environmental Chemistry
  • Spectroscopy

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