Importance of Polarizable Embedding for Absorption Spectrum Calculations of Arabidopsis thaliana Cryptochrome 1

J Phys Chem B. 2024 Jul 4;128(26):6283-6290. doi: 10.1021/acs.jpcb.4c02168. Epub 2024 Jun 24.

Abstract

Cryptochromes are essential flavoproteins for circadian rhythms and avian magnetoreception. Flavin adenine dinucleotide (FAD), a chromophore within cryptochromes, absorbs blue light, initiating electron transfer processes that lead to a biological signaling cascade. A key step in this cascade is the formation of the FAD semiquinone radical (FADH), characterized through a specific red-light absorption. The absorption spectra of FADH in cryptochromes are, however, significantly different from those recorded for the cofactor in solution, primarily due to protein-induced shifts in the absorption peaks. This study employs a multiscale approach, combining molecular dynamics (MD) simulations with quantum mechanical/molecular mechanical (QM/MM) methodologies, to investigate the influence of protein dynamics on embedded FADH absorption. We emphasize the role of the protein's polarizable environment in the shaping of the absorption spectrum, crucial for accurate spectral predictions in cryptochromes. Our findings provide valuable insights into the absorption process, advancing our understanding of cryptochrome functioning.

MeSH terms

  • Arabidopsis Proteins / chemistry
  • Arabidopsis Proteins / metabolism
  • Arabidopsis* / chemistry
  • Arabidopsis* / metabolism
  • Cryptochromes* / chemistry
  • Cryptochromes* / metabolism
  • Flavin-Adenine Dinucleotide* / chemistry
  • Flavin-Adenine Dinucleotide* / metabolism
  • Molecular Dynamics Simulation*
  • Quantum Theory*

Substances

  • Cryptochromes
  • Flavin-Adenine Dinucleotide
  • Arabidopsis Proteins
  • CRY1 protein, Arabidopsis