دورية أكاديمية
Constructing the Mechanism of Dinoflagellate Luciferin Bioluminescence Using Computation.
| العنوان: | Constructing the Mechanism of Dinoflagellate Luciferin Bioluminescence Using Computation. |
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| المؤلفون: | Phun GS; Department of Chemistry, University of California Irvine, Irvine, California 92617, United States., Rappoport D; Department of Chemistry, University of California Irvine, Irvine, California 92617, United States., Furche F; Department of Chemistry, University of California Irvine, Irvine, California 92617, United States., Gibson TR; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Tretiak S; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.; Center for Integrated Nanotechnologies (CINT), Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States. |
| المصدر: | The journal of physical chemistry letters [J Phys Chem Lett] 2023 Jul 06; Vol. 14 (26), pp. 6001-6008. Date of Electronic Publication: 2023 Jun 22. |
| نوع المنشور: | Journal Article |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 101526034 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1948-7185 (Electronic) Linking ISSN: 19487185 NLM ISO Abbreviation: J Phys Chem Lett Subsets: MEDLINE |
| أسماء مطبوعة: | Original Publication: Washington, D.C. : American Chemical Society |
| مواضيع طبية MeSH: | Firefly Luciferin*/chemistry , Dinoflagellida*, Luciferins ; Stereoisomerism ; Luminescent Measurements |
| مستخلص: | Dinoflagellate luciferin bioluminescence is unique since it does not rely on decarboxylation but is poorly understood compared to that of firefly, bacteria, and coelenterata luciferins. Here we computationally investigate possible protonation states, stereoisomers, a chemical mechanism, and the dynamics of the bioluminescence intermediate that is responsible for chemiexcitation. Using semiempirical dynamics, time-dependent density functional theory static calculations, and a correlation diagram, we find that the intermediate's functional group that is likely responsible for chemiexcitation is a 4-member ring, a dioxetanol, that undergoes [2π + 2π] cycloreversion and the biolumiphore is the cleaved structure. The simulated emission spectra and luciferase-dependent absorbance spectra agree with the experimental data, giving support to our proposed mechanism and biolumiphore. We also compute circular dichroism spectra of the intermediate's four stereoisomers to guide future experiments in differentiating them. |
| المشرفين على المادة: | 5TBB02N29K (Firefly Luciferin) 0 (Luciferins) |
| تواريخ الأحداث: | Date Created: 20230622 Date Completed: 20230707 Latest Revision: 20230718 |
| رمز التحديث: | 20240829 |
| DOI: | 10.1021/acs.jpclett.3c01053 |
| PMID: | 37347959 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1948-7185 |
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| DOI: | 10.1021/acs.jpclett.3c01053 |