A Two-Dimensional (Magnetic Field and Concentration) Electron Paramagnetic Resonance Method for Analysis of Multispecies Complex Equilibrium Systems. Information Content of EPR Spectra

• Published in: Journal of the American Chemical Society 2001-08, Vol.123 (31), p.7646-7654
• Main Authors: Rockenbauer, Antal, Szabó-Plánka, Terézia, Árkosi, Zsuzsanna, Korecz, László
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0102888

A two-dimensional simulation method has been developed for the interpretation of electron paramagnetic resonance (EPR) spectra consisting of a multitude of strongly overlapping signal components. The set of EPR spectra for complex equilibrium systems is analyzed simultaneously as a function of metal and ligand concentrations and pH. The formation constants of the various species are adjusted together with the magnetic parameters of the component EPR spectra. At most 10 EPR-active and 5 EPR-silent species can be involved to simulate a maximum of 36 experimental spectra, while the number of adjusted parameters is at most 100. Statistical parameters are suggested to give the confidence intervals for parameter estimation and to distinguish alternative speciation models. The efficiency of the program is demonstrated for the copper(II)−l-asparagine system, in which 10 species, including 3 pairs of isomers, are characterized with magnetic parameters and formation constants. On the basis of the magnetic parameters, a structural assignment is made for the detected species. The two-dimensional approach can also supply the formation constant of the EPR-silent species, as demonstrated for the copper(II)−glycyl-l-serine system.