Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nám. 2, 166 10, Prague, Czech Republic.
Angew Chem Int Ed Engl. 2017 Jan 24;56(5):1334-1337. doi: 10.1002/anie.201610491. Epub 2016 Dec 27.
The development of fluorogenic reactions which lead to the formation of fluorescent products from two nonfluorescent starting materials is highly desirable, but challenging. Reported herein is a new concept of fluorescent product formation upon the inverse electron-demand Diels-Alder reaction of 1,2,4,5-tetrazines with particular trans-cyclooctene (TCO) isomers. In sharp contrast to known fluorogenic reagents the presented chemistry leads to the rapid formation of unprecedented fluorescent 1,4-dihydropyridazines so that the fluorophore is built directly upon the chemical reaction. Attachment of an extra fluorophore moiety is therefore not needed. The photochemical properties of the resulting dyes can be easily tuned by changing the substitution pattern of the starting 1,2,4,5-tetrazine. We support the claim with NMR measurements and rationalize the data by computational study. Cell-labeling experiments were performed to demonstrate the potential of the fluorogenic reaction for bioimaging.
强烈希望开发将两种非荧光起始材料转化为荧光产物的荧光反应，但这极具挑战性。本文报道了一种新的荧光产物形成概念，即通过特定的反电子需求 Diels-Alder 反应将 1,2,4,5-四嗪与反式环辛烯（TCO）异构体反应生成。与已知的荧光试剂形成鲜明对比的是，所提出的化学方法导致了前所未有的荧光 1,4-二氢哒嗪的快速形成，从而使荧光团直接构建在化学反应上。因此，不需要额外的荧光团部分。通过改变起始 1,2,4,5-四嗪的取代模式，可以轻松调节所得染料的光化学性质。我们通过 NMR 测量支持这一说法，并通过计算研究对数据进行了合理化。进行了细胞标记实验以证明该荧光反应在生物成像中的潜力。
