How Does the Local Electrostatic Field Influence Emitted Wavelengths and Bioluminescent Intensities of Modified Heteroaromatic Luciferins?

• Published in: The journal of physical chemistry. B Vol. 119; no. 33; pp. 10399 - 10405
• Main Authors: Zhou, Jian-Ge, Williams, Quinton L, Walters, Wilbur, Deng, Zhen-Yan
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 20.08.2015
• Subjects: Bioluminescence; Electrostatic fields; Emittance; Fireflies; Indoles - chemistry; Luminescent Measurements; Models, Molecular; Molecular Conformation; Molecular orbitals; Oscillator strengths; Pyrazines - chemistry; Residues; Static Electricity; Thermodynamics; Wavelengths
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.5b03827

The firefly chromophore, oxyluciferin, is in the pocket of the firefly luciferase and is surrounded by the side-chains of some amino acid residues. The charged residues produce the local electrostatic field (LEF) around the oxyluciferin. The emitted wavelengths and intensities of the oxyluciferin and its heterocyclic analogs under the LEF are examined. The common overlapping volumes of the HOMO and LUMO explain why the oscillator strengths vary under the LEF. Three average E x change rates of the first excited energy are introduced to measure what luciferins are more sensitive to the LEF. The first excited energies and intensities in two enzymatic-like microenvironments are simulated via the LEF. The oscillator strengths and the net electric charges of the O6′ and the O4 are applied to explain the experimental bioluminescent intensities.