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Systematic Theoretical Investigation on the Light Emitter of Firefly

Abstract : This is a systematic theoretical investigation on all the possible light emitters of firefly using a multireference method. Six chemical forms of oxyluciferin (OxyLH(2)) molecules/anions were studied by a multistate complete active space second-order perturbation (MS-CASPT2) method in vacuum and dimethyl sulfoxide. The calculated results and subsequent analysis excluded enol-OxyLH(2), keto-OxyLH(2), and enolate-OxyLH(-) as possible light emitters. The remaining three candidates, phenolate-enol-OxyLH(-), phenolate-keto-OxyLH(-), and OxyL(2-), were further investigated in protein by a MS-CASPT2/molecular mechanics (MM) study to explain the natural bioluminescence of firefly. By comparison of the MS-CASPT2/MM calculated results of phenolate-enol-OxyLH(-), phenolate-keto-OxyLH(-), and OxyL(2-) with the experimental observation and detailed analysis, we concluded that the direct decomposition excited-state product of firefly dioxetanone in vivo and the only light emitter of firefly in natural bioluminescence is the first singlet excited state (S(1)) of phenolate-keto-OxyLH(-).
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https://hal-upec-upem.archives-ouvertes.fr/hal-00692848
Contributor : Isabelle Navizet <>
Submitted on : Tuesday, May 1, 2012 - 3:25:40 PM
Last modification on : Thursday, March 19, 2020 - 11:52:03 AM

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S.-F. Chen, Y.-J. Liu, Isabelle Navizet, N. Ferre, W.-H. Fang, et al.. Systematic Theoretical Investigation on the Light Emitter of Firefly. Journal of Chemical Theory and Computation, American Chemical Society, 2011, 7 (3), pp.798--803. ⟨10.1021/ct200045q⟩. ⟨hal-00692848⟩

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