Bond selection in the photoisomerization reaction of anionic green fluorescent protein and kindling fluorescent protein chromophore models.
The chromophores of the most widely known fluorescent proteins (FPs) are derivatives of a core p-hydroxybenzylidene-imidazolinon-5-one (HBI) motif, which usually occurs as a phenolate anion. Double bond photoisomerization of the exocyclic bridge of HBI is widely held to be an important internal conversion mechanism for FP chromophores. Herein we describe the ground and excited-state electronic structures and potential energy surfaces of two model chromophores: 4- p-hydroxybenzylidiene-1,2-dimethyl-imidazolin-5-one anion (HBDI), representing green FPs (GFPs), and 2-acetyl-4-hydroxybenylidene-1-methyl-imidazolin-5-one anion (AHBMI), representing kindling FPs (KFPs). These chromophores differ by a single substitution, but we observe qualitative differences in the potential energy surfaces which indicate inversion of bond selection in the photoisomerization reaction. Bond selection is also modulated by whether the reaction proceeds from a Z or an E conformation. These configurations correspond to fluorescent and nonfluorescent states of structurally characterized FPs, including some which can be reversibly switched by specific illumination regimes. We explain the difference in bond selectivity via substituent stabilization effects on a common set of charge-localized chemical structures. Different combinations of these structures give rise to both optically active (planar) and twisted intramolecular charge-transfer (TICT) states of the molecules. We offer a prediction of the gas-phase absorption of AHBMI, which has not yet been measured. We offer a hypothesis to explain the unusual fluorescence of AHBMI in DMF solution, as well as an experimental proposal to test our hypothesis.
Olsen
Seth
S
Centre for Computational Molecular Science, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, St. Lucia, QLD 4072 Australia. s.olsen1@uq.edu.au
Smith
Sean C
SC
D004126:Dimethylformamide / Q000737:chemistry; D005453:Fluorescence; D049452:Green Fluorescent Proteins / Q000737:chemistry*; D048288:Imidazolines / Q000737:chemistry*; D008956:Models, Chemical; D010777:Photochemistry; D012996:Solutions
C502519:4-hydroxybenzylidene-1,2-dimethylimidazolinone; D048288:Imidazolines; D012996:Solutions; D049452:Green Fluorescent Proteins; D004126:Dimethylformamide