Efficient Firefly Chemi/Bioluminescence: Evidence for Chemiexcitation Resulting from the Decomposition of a Neutral Firefly Dioxetanone Molecule

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• 作者：Lu铆s Pinto da Silva ; A. Joel M. Santos ; Joaquim C. G. Esteves da Silva
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：January 10, 2013
• 年：2013
• 卷：117
• 期：1
• 页码：94-100
• 全文大小：375K
• 年卷期：v.117,no.1(January 10, 2013)
• ISSN：1520-5215

文摘

Both experimental and theoretical methodologies were employed in order to study the possibility of excited state oxyluciferin being formed as the result of the decomposition of a neutral dioxetanone. Excitation measurements in water (at different pH values) and in methanol, along with computational calculations, demonstrated that the hydroxyl-benzothiazole group of firefly dioxetanone and six oxyluciferin analogues is only deprotonated in conditions not in line with the firefly bioluminescence reaction. Thus, a new mechanism involving a neutral firefly dioxetanone must be presented in order to explain the chemiexcitation of oxyluciferin. It was also studied for the first time the interaction between a molecule involved in the bioluminescence reaction (neutral firefly dioxetanone) and the real second conformation of firefly luciferase.