NDLI: Decomposition Reaction of Dioxetanone in Firefly Bioluminescence by Computer Experiment

Content Provider	Springer Nature Link
Author	Wada, Naohisa Sakai, Hirori
Copyright Year	2005
Abstract	Firefly luciferin (Ln) reacts with molecular oxygen in the presence of the enzyme luciferase (E), the Mg$^{+2}$ ion and ATP to form a four-membered cyclic peroxide, so-called dioxetanone, which has not yet been observed by spectrophotometric techniques. Subsequently, dioxetanone decomposes into carbon dioxide (CO$_{2}$) and electronically excited oxyluciferin (Oxyln$^{−∗}$), emitting yellow-green light. In order to clarify the characteristics of the elementary reaction path from dioxetanone to Oxyln$^{−∗}$, the potential energy curve of the singlet ground-state (S$_{0}$-PEC) along the reaction coordinate was obtained by the intrinsic reaction coordinate (IRC) calculations using the AM1 Hamiltonian. Furthermore, the potential energy curve of the singlet excited-state (S$_{1}$-PEC) was calculated, because dioxetanone decomposes to Oxyln$^{−∗}$ along the reaction coordinate. The S$_{1}$-PEC relative to S$_{0}$-PEC was estimated at each point of the reaction coordinate using the INDO/S, where only the singly-excited configuration interactions (CI) constructed from 20 occupied and 20 unoccupied molecular orbitals (MOs) were considered. As a result of these calculations, it was concluded that (1) firefly dioxetanone might not be an intermediate but rather be in an unstable transition state; (2) the S$_{0}$-PEC has an activation barrier of 37.5 kcal/mol for dioxetanone formation and the reaction is exothermic along the S$_{0}$-PEC; (3) the S$_{1}$-PEC approaches the S$_{0}$-PEC in a concave manner where dioxetanone decomposes to efficiently produce Oxyln$^{−∗}$; and (4) rupturing of an O–O bond in dioxetanone can trigger the coming and going of electrons in a “cradle" motion mediated by S$_{0}$- and S$_{1}$-PECs in the chemiexcitation step toward Oxyln$^{−∗}$.
Starting Page	403
Ending Page	412
Page Count	10
File Format	PDF
ISSN	00920606
Journal	Journal of Biological Physics
Volume Number	31
Issue Number	3-4
e-ISSN	15730689
Language	English
Publisher	Kluwer Academic Publishers
Publisher Date	2005-01-01
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	dioxetanone firefly bioluminescence oxyluciferin semiempirical molecular orbital method transition state Neurosciences Bioinformatics Polymer Sciences Statistical Physics Condensed Matter Biophysics/Biomedical Physics
Content Type	Text
Resource Type	Article
Subject	Cell Biology Atomic and Molecular Physics, and Optics Molecular Biology Biophysics

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Decomposition reaction of dioxetanone in firefly bioluminescence by computer experiment.

Decomposition Reaction of Dioxetanone in Firefly Bioluminescence by Computer Experiment

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The Physics of Cell Membranes

Photosynthesis: From Natural Towards Artificial

Author Index Volume 29 (2003)

Homochirality in Bio-Organic Systems and Glyceraldehyde in the Formose Reaction

Protein Structure from X-Ray Diffraction

Decomposition Reaction of Dioxetanone in Firefly Bioluminescence by Computer Experiment

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Decomposition reaction of dioxetanone in firefly bioluminescence by computer experiment.

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Contents Volume 29 (2003)

Physics of Ion Channels

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Photosynthesis: From Natural Towards Artificial

Author Index Volume 29 (2003)

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Decomposition Reaction of Dioxetanone in Firefly Bioluminescence by Computer Experiment