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On the influence of water on the electronic structure of firefly oxyluciferin anions from absorption spectroscopy of bare and monohydrated ions in vacuo
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2013 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 135, no 17, 6485-6493 p.Article in journal (Refereed) Published
Abstract [en]

A complete understanding of the physics underlying the varied colors of firefly bioluminescence remains elusive because it is difficult to disentangle different enzyme-lumophore interactions. Experiments on isolated ions are useful to establish a proper reference when there are no microenvironmental perturbations. Here, we use action spectroscopy to compare the absorption by the firefly oxyluciferin lumophore isolated in vacuo and complexed with a single water molecule. While the process relevant to bioluminescence within the luciferase cavity is light emission, the absorption data presented here provide a unique insight into how the electronic states of oxyluciferin are altered by microenvironmental perturbations. For the bare ion we observe broad absorption with a maximum at 548 ± 10 nm, and addition of a water molecule is found to blue-shift the absorption by approximately 50 nm (0.23 eV). Test calculations at various levels of theory uniformly predict a blue-shift in absorption caused by a single water molecule, but are only qualitatively in agreement with experiment highlighting limitations in what can be expected from methods commonly used in studies on oxyluciferin. Combined molecular dynamics simulations and time-dependent density functional theory calculations closely reproduce the broad experimental peaks and also indicate that the preferred binding site for the water molecule is the phenolate oxygen of the anion. Predicting the effects of microenvironmental interactions on the electronic structure of the oxyluciferin anion with high accuracy is a nontrivial task for theory, and our experimental results therefore serve as important benchmarks for future calculations.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2013. Vol. 135, no 17, 6485-6493 p.
Keyword [en]
Action spectroscopy, Broad absorptions, Influence of water, Molecular dynamics simulations, Non-trivial tasks, Phenolate oxygen, Time dependent density functional theory, Water molecule, Density functional theory, Electronic structure, Experiments, Molecular dynamics, Molecules, Negative ions, Phosphorescence, Bioluminescence, luciferase, luciferin, oxyluciferin, unclassified drug, water, absorption, absorption spectroscopy, article, binding site, calculation, complex formation, crystal structure, dissociation, microenvironment, qualitative analysis, static electricity, Animals, Anions, Color, Electrochemistry, Enzyme-Linked Immunosorbent Assay, Fireflies, Indoles, Luminescence, Mass Spectrometry, Models, Chemical, Models, Molecular, Molecular Dynamics Simulation, Pyrazines, Spectrometry, Mass, Electrospray Ionization, Stereoisomerism
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-198736DOI: 10.1021/ja311400tISI: 000318469100023PubMedID: 23557511Scopus ID: 2-s2.0-84877042198OAI: oai:DiVA.org:kth-198736DiVA: diva2:1059096
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QC 20161222

Available from: 2016-12-22 Created: 2016-12-21 Last updated: 2016-12-22Bibliographically approved

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