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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

Støchkel, K. (author)
Aarhus University, Denmark
Hansen, C. N. (author)
Aarhus University, Denmark
Houmøller, J. (author)
Aarhus University, Denmark
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Linares, Mathieu (author)
Linköpings universitet,Beräkningsfysik,Tekniska högskolan
Anggara, K. (author)
Aarhus University, Denmark
Linares, M. (author)
Norman, Patrick (author)
Linköpings universitet,Beräkningsfysik,Tekniska högskolan
Nogueira, F. (author)
University of Coimbra, Portugal
Maltsev, O. V. (author)
Technical University of Munich, Germany
Hintermann, L. (author)
Technical University of Munich, Germany
Nielsen, S. B. (author)
Aarhus University, Denmark
Naumov, P. (author)
New York University of Abu Dhabi, U Arab Emirates
Milne, B. F. (author)
University of Coimbra, Portugal
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 (creator_code:org_t)
2013-04-17
2013
English.
In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 135:17, s. 6485-6493
  • Journal article (peer-reviewed)
Abstract Subject headings
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  • 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.

Subject headings

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)
NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

Keyword

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
TECHNOLOGY

Publication and Content Type

ref (subject category)
art (subject category)

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