Theoretical Development of Near-Infrared Bioluminescent Systems
Theoretical Development of Near-Infrared Bioluminescent Systems
复制标题
近红外生物发光系统的理论发展
DOI：
10.1002/chem.201800416
复制
发表时间：
2018-07-02
影响因子：
4.3
通讯作者：
Liu, Ya-Jun
中科院分区：
文献类型：
--
作者：
Cheng, Yuan-Yuan;Liu, Ya-Jun
萤火虫的荧光素酶/荧光素酶系统已被用于生物发光成像以监测生物过程。为了提高效率和扩大应用范围，已经做出了一些努力来调谐光发射，特别是努力获得NIR光。然而，这些个案研究并没有共同揭示色彩调谐的本质和机制。本文从理论上研究了各种典型的姜黄素类似物的荧光性质。荧光素和荧光素酶的系统修饰表明，影响发射颜色的基本因素是荧光素上的电荷分布（或电偶极矩），其影响电荷转移以形成光发射体，并且随后影响发射光的强度和波长。分布在荧光素或其类似物的“噻唑酮部分”上的更多负电荷导致红移。在此基础上，我们从理论上设计了最佳的荧光素酶和荧光素酶的近红外光发射组合，这可能会启发新的合成方法和实际应用。
The luciferin/luciferase system of the firefly has been used in bioluminescent imaging to monitor biological processes. In order to enhance the efficiency and expand the application range, some efforts have been made to tune the light emission, especially the effort to obtain NIR light. However, those case-by-case studies have not together revealed the nature and mechanism of the color tuning. In this paper, we theoretically investigated the fluorescence of all kinds of typical oxyluciferin analogues. The present systematical modifications of both oxyluciferin and luciferase indicate that the essential factor affecting the emission color is the charge distribution (or the electric dipole moment) on the oxyluciferin, which impacts on the charge transfer to form the light emitter and, subsequently, influence the strength and wavelength of the emission light. More negative charge distributed on the "thiazolone moiety" of the oxyluciferin or its analogues leads to a redshift. Based on this conclusion, we theoretically designed optimal pairs of luciferin analogue and luciferase for emitting NIR light, which could inspire new synthetic procedures and practical applications.