title: Definition and detection of data-based uniqueness in evaluating bilinear (two-way) chemical measurements.
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.
authors.affiliation: Institute of Process Engineering, Faculty of Engineering, University of Szeged, Moszkvai krt. 5-7, H-6725 Szeged, Hungary. Electronic address: rajko@sol.cc.u-szeged.hu.
authors.forename: Róbert
authors.initials: R
authors.lastname: Rajkó
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Zanjan, Iran.
authors.forename: Hamid
authors.initials: H
authors.lastname: Abdollahi
authors.affiliation: Institute of Process Engineering, Faculty of Engineering, University of Szeged, Moszkvai krt. 5-7, H-6725 Szeged, Hungary; Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Zanjan, Iran.
authors.forename: Samira
authors.initials: S
authors.lastname: Beyramysoltan
authors.affiliation: Institute of Process Engineering, Faculty of Engineering, University of Szeged, Moszkvai krt. 5-7, H-6725 Szeged, Hungary; Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Zanjan, Iran.
authors.forename: Nematollah
authors.initials: N
authors.lastname: Omidikia
keywords: Bilinear data set; Borgen plot; Rotational ambiguity; Self-modeling/multivariate curve resolution; Uniqueness