Extending the Palette of Green Coumarin Photocages – Oligonucleotide Fragmentation and Superior 5’-Caps

Abstract

The possibilities of dicyanocoumarin (DCCM)-modified oligonucleotides are expanded to not just allow their release and therefore activation with green light (OFF→ON) but to also now offer a solution for their fragmentation after exposure to green light (ON→OFF). Furthermore, an answer to the decreasing uncaging quantum yields often faced when working with red-shifted photocages is given and showed that rigidified DCCM 5’-caps outperform their predecessors. Those two new 5’-caps with ATTO 390 motif or julolidine core are compatible with copper(I)-catalyzed alkyne-azide cycloadditions (CuAACs) and therefore suitable for efficient caging through cyclization or more bioconjugation reactions. Due to their planarization, they even experience an additional red-shift which is important for their use in biological applications.