Modeling pH-Dependent Biomolecular Photochemistry

J Chem Theory Comput. 2024 Jan 23;20(2):842-855. doi: 10.1021/acs.jctc.3c00980. Epub 2024 Jan 10.

Abstract

The tuning mechanism of pH can be extremely challenging to model computationally in complex biological systems, especially with respect to the photochemical properties. This article reports a protocol aimed at modeling pH-dependent photodynamics using a combination of constant-pH molecular dynamics and semiclassical nonadiabatic molecular dynamics simulations. With retinal photoisomerization in Anabaena sensory rhodopsin (ASR) as a testbed, we show that our protocol produces pH-dependent photochemical properties, such as the isomerization quantum yield or decay rates. We decompose our results into single-titrated residue contributions, identifying some key tuning amino acids. Additionally, we assess the validity of the single protonation state picture to represent the system at a given pH and propose the most populated protein charge state as a compromise between cost and accuracy.

MeSH terms

  • Anabaena* / chemistry
  • Hydrogen-Ion Concentration
  • Photochemistry
  • Rhodopsin* / chemistry

Substances

  • Rhodopsin