Investigating the effect of flexible constraints on the accuracy of self‐modeling curve resolution methods in the presence of perturbations. (20th April 2016)

• Record Type: Journal Article
• Authors: Rahimdoust Mojdehi, Nahal; Sawall, Mathias; Neymeyr, Klaus; Abdollahi, Hamid
• Is Part Of: Journal of chemometrics. Volume 30:Number 5(2016)
• Page Start: 252
• Page End: 267
• Publication Date: 2016-04-20
• Subjects: chemometrics -- hard constraints -- soft constraints -- polygon inflation algorithm -- area of feasible solution; Chemistry -- Mathematics -- Periodicals; Chemistry -- Statistical methods -- Periodicals; 542.85
• DOI: 10.1002/cem.2787
• Languages: English
• ISSNs: 0886-9383

Abstract

Abstract : Self‐modeling curve resolution methods have continuously been improved during recent years. Many efforts have been made on curve resolution methods to reduce the rotational ambiguity by means of different types of constraints. Choosing proper constraints and cost functions is critically important for the reduction of the rotational ambiguity because the constraints have a direct influence on the accuracy of the area of feasible solution (AFS). In this work, we introduce a new improved cost function, which serves to apply nonnegativity, unimodality, equality, and closure constraints. We also investigate the reduction of the AFS under hard and soft constraints. Another point of this work is to evaluate the accuracy and precision of the reduced AFS in the presence of noise and perturbations, under hard and soft implementation of nonnegativity, unimodality, equality, and closure constraints. A comparison is given between the reduced AFS with soft constraints (small deviations from constraints are accepted) and the reduced AFS under hard constraints (restrictedly forced constraints). A graphical visualization of this comparison is presented for various model problems. The results show that an AFS computation with soft constraints provides more reliable results, especially in the presence of noise. The test problems substantiate significant advantages of soft constraints over hard constraints because the obtained profiles are closer to the potentially true noisy profiles, which contain small deviations from ideal responses. Using tunable parameters ϵ, γ, ω, δ is one of the advantages of soft constrained cost function that allows the small deviations from ideal responses. Ultimately, soft constraints can help to reduce the lack‐of‐fit, and they are a proper instrument to handle the effect of noise on the AFS. Copyright © 2016 John Wiley & Sons, Ltd. Abstract : Self‐modeling curve resolution methods have continuously been improved during recent years. Many efforts have been made on curve resolution methods to reduce the rotational ambiguity by means of different types of constraints. In this work, we introduce a new improved cost function, which serves to apply non‐negativity, unimodality, equality, and closure constraints under polygon inflation algorithm. We also investigate the reduction of the AFS under soft constraints (small deviations from constraints are accepted) and hard constraints (restrictedly forced constraints).