BODIPY-Derived Photoremovable Protecting Groups Unmasked with Green Light

Abstract

Photoremovable protecting groups derived from meso-substituted BODIPY dyes release acetic acid with green wavelengths >500 nm. Photorelease is demonstrated in cultured S2 cells. The photocaging structures were identified by our previously proposed strategy of computationally searching for carbocations with low-energy diradical states as a possible indicator of a nearby productive conical intersection. The superior optical properties of these photocages make them promising alternatives to the popular o-nitrobenzyl photocage systems.

Smart Nanostructures for Cargo Delivery: Uncaging and Activating by Light

“…Thus, the protected and inactive molecules/compounds, which have high activity when free, become unprotected and uncaged leading to their activation, followed by their delivery and release at the desired biological site such as via binding to cell receptors or specific intracellular release (Figure 3a). 32,35,53,55,56 A wide-variety of photo-uncaging compounds have been reported based on o -nitrobenzyl, o -nitro-phenethyl, indoline, quinoline, amino-coumarin, perylene, nitrophenyl, nitrophenyl-propyloxy compounds, ruthenium photocages, nitrodibenzofuran (NDBF), boron-dipyrromethene derivatives, and so forth. 35,53,55–58 Nanocarriers including gold (Au) NPs, 59 micelles, 60 liposomes, 61 and peptide-based nanocarriers 35 have been reported to demonstrate photocaging/uncaging behavior.…”

“…32,35,53,55,56 A wide-variety of photo-uncaging compounds have been reported based on o -nitrobenzyl, o -nitro-phenethyl, indoline, quinoline, amino-coumarin, perylene, nitrophenyl, nitrophenyl-propyloxy compounds, ruthenium photocages, nitrodibenzofuran (NDBF), boron-dipyrromethene derivatives, and so forth. 35,53,55–58 Nanocarriers including gold (Au) NPs, 59 micelles, 60 liposomes, 61 and peptide-based nanocarriers 35 have been reported to demonstrate photocaging/uncaging behavior. Various cargos such as thiols, 35 platinum(II) complexes, 57 diphospho-myo-inositol pentakisphosphates (InsP 7 ), 62 cyclooxygenase-2 enzyme inhibitors, 63 copper complexes, 58 and anticancer drugs/prodrugs (e.g., camptothecin, coumarin, 5-fluorouracil, doxorubicin (DOX)) 43,59,60,64 have been shown to be protected and carried by the photocaging nanocarriers.…”

Calcium Uncaging with Visible Light

“…Subsequently several chromophores have been used for uncaging of biological signaling molecules with blue light 16–21 . Photochemical protecting groups sensitive to green light have also been reported 22–24 , but to our knowledge no biological studies have appeared with these probes. Some of these probes are very important additions to the arsenal of caged compounds available for use by biologists, however none of them offer the same generality of carbon-heteroatom bond scission that is part of ortho -nitrobenzyl photochemistry.…”

Near‐IR Light‐Mediated Cleavage of Antibody–Drug Conjugates Using Cyanine Photocages

“…[21] There have been several recent advances in the area of light-mediated drug delivery, including steps toward using tissue-compatible longer wavelengths. [22–34] The strategy reported here has promising characteristics: initiation with 690 nm light, the traceable emissive properties of the cyanine scaffold, and the use of broadly-employed monoclonal antibodies. Below is described the synthesis of the bioconjugatable cyanine photocage, characterization of the uncaging reaction, and cellular evaluation.…”