title: Role of Protonation State and Solvation on the pH Dependent Optical Properties of Bromocresol Green.
abstract: pH sensors play a key role in many industrial and diagnostic applications. Mostly their usage is based on experience, and in many cases the working mechanisms of these sensors are not known in detail, thereby hindering a systematic improvement of such sensors for specific applications. In this report, we present results from combined quantum chemical and molecular mechanics calculations of molecular structures and optical absorption properties of bromocresol green (BRG) in aqueous solution with varying pH value. In the acidic pH range, this chromophore has an intense band with absorption maximum at 444 nm and in the basic pH regime the absorption spectra show a redshift toward 613 nm. In order to identify the molecular structures responsible for this pH dependent optical behavior the closed and open forms of BRG are studied using static approaches considering in each case the three possible protonated states namely, neutral, anionic, and dianionic. For the most significant forms, i.e. the open forms of BRG, extensive modeling based on the integrated approach has been carried out, where the structure and dynamics were studied using hybrid QM/MM molecular dynamics, while the excitation energy calculations were carried out using time dependent density functional theory wherein the surrounding solvent was described as polarizable continuum, semicontinuum, or via a molecular mechanics force-field. The anionic and dianionic forms of BRG have been recognized as molecular forms responsible for its acidic and basic pH behavior, respectively. In contrast to the case of solvatochromic probes, the different protonation states determine the optical behavior in different pH values for pH probes. Hence, the level of solvent description appears to be of minor importance. Independent of the level of theory used to describe the solvent, all models reproduce the spectral features of BRG in different pH and also the pH induced redshift in good agreement with experiment.
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology , SE-10691 Stockholm, Sweden.
authors.forename: N Arul
authors.initials: NA
authors.lastname: Murugan
authors.affiliation: Technische Hochschule Wildau , Hochschulring 1, 15745 Wildau, Brandenburg, Germany.
authors.forename: Sigurd
authors.initials: S
authors.lastname: Schrader
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology , SE-10691 Stockholm, Sweden.
authors.forename: Hans
authors.initials: H
authors.lastname: Ågren