Spectrophotometric thermodynamic analysis of methylene blue aggregation in water by chemometrics; what comes in the presence of different cyclodextrins?

Abstract

Spectrophotometry has been utilized to characterize the thermodynamic/dynamic properties of self-aggregation of methylene blue (MB) in water, particularly while interacting with a modulator like different cyclodextrins (α-, β-, hydroxypropyl-β- (HP-β-), and γ-CDs). These systems comprise many interactions that make such chemical systems sophisticated. We developed a mathematical modeling-fitting analysis for the simultaneous quantitative analysis of thermodynamic parameters of chemical reactions, relying on the fitting algorithm. Through analyzing simulated photometric titration data, we demonstrate the simultaneous determination of thermodynamic parameters of the different guest/host interactions. This first has brought the need for the calculation of the visible-light absorption spectrum and the thermodynamic parameters for the pure dimerization system. Therefore, the multiwavelength spectral-mole ratio data of aqueous solutions of MB over a concentration range of 2.5 × 10^-5 to 4.5 × 10^-5 M while temperature is changing; or being titrated with CDs solutions at various temperatures were collected, augmented, and then have been fed to solid mathematical routines to determine the potential existence of dimeric aggregates. The results of thermodynamics indicated that the positions of the monomer/dimer equilibria do not alter by the presence of α-CD. The apparent dimerization was suppressed upon addition of β- or HP-β-CDs, while the addition of γ-CD enhanced the dimerization.

Keywords: Cyclodextrins; Dimerization; Guest/host interaction; Mathematical modeling; Methylene blue; Thermodynamic parameters.