Visible Light Triggerable CO Releasing Micelles.

Carbon monoxide (CO), along with nitric oxide and hydrogen sulfide, is one of a trinity of known gasotransmitters, or endogenously produced gaseous molecules that signal and regulate a panoply of physiological functions. CO releasing molecules (CORMs) are chemical tools that enable the study and application of this ephemeral gas, that, ideally, release CO on-demand when externally stimulated. Surveying the available triggers, photolysis is potentially advantageous: It is contactless and grants practitioners unparalleled spatial and temporal control. However, current phototriggered CORMs are capricious and do not meet current needs. Presented here is a highly efficient platform for the visible light triggered release of CO gas. This platform is built on a unique CO containing functionality, the cyclopropenone, which undergoes facile decarbonylation through visible light (470 nm) mediated photoredox catalysis. Due to the exothermic strain-release that occurs upon formation of CO, this photoreaction is rapid, quantitative, and has tunable release rates. To render this photo-CORM water-soluble, deliverable, and to keep reactants in proximity, necessary components were polymerized into block copolymers that self-assemble into CO releasing micelles (CORMIs). This platform was compared directly to other state-of-the-art CORMs, showing significantly improved CO production efficiency, lower toxicity, tunable release rates, and consistent efficacy in and settings.