Green-light photocleavable meso-methyl BODIPY building blocks for macromolecular chemistry

Abstract

We report the design of easily accessible, meso-methyl BODIPY monomers and their incorporation into photoclippable macromolecules.

meso-Methyl BODIPY Photocages: Mechanisms, Photochemical Properties, and Applications

“…In a different approach, a meso -methyl BODIPY diol AA-type bifunctional monomer and a clickable, azide-functionalized AB-type heterobifunctional monomer were prepared ( 61a and 61b , respectively, Scheme C). The BODIPY-based monomers were incorporated into water-soluble macromolecular systems, namely polyurethane hydrogels and a brush-like poly­(organo)­phosphazene, which were demonstrated to undergo selective cleavage in response to green light (λ irr = 550 nm) . Photo-cross-linking/curing of hydrogels was achieved by BODIPY-caged amines that can cross-link with dialdehydes upon photorelease, which allows spatiotemporal control over gel stiffness .…”

“…The BODIPY-based monomers were incorporated into watersoluble macromolecular systems, namely polyurethane hydrogels and a brush-like poly(organo)phosphazene, which were demonstrated to undergo selective cleavage in response to green light (λ irr = 550 nm). 95 Photo-cross-linking/curing of hydrogels was achieved by BODIPY-caged amines that can cross-link with dialdehydes upon photorelease, which allows spatiotemporal control over gel stiffness. 96 An alkyne-functionalized meso-methyl BODIPY phosphoramidite derivative (62, Scheme 6D) was developed as a 5′-cap and incorporated in oligonucleotides via solid-phase synthesis.…”

Recent progress in studies of photocages

“…Teasdale et al described the respective AA-type and ABtype bifunctional BODIPY monomers 19A and 20A, which were incorporated into the corresponding small molecule model compounds 19 and 20 (Figure 11a). [30] They can be photolyzed upon the irradiation of green light. In addition, the authors employed monomer 19A as a photocleavable linker in a pale purple color hydrogel (Figure 11b) that undergoes 365 nm light promoted photolysis to release green fluorescence.…”

“…In contrast to photocages without the sulphonic acid group(16) and with only one sulphonic acid group (17) readily passing through the cell membrane, the analog photocage 18 with two sulphonic acid groups has difficulty passing through cell membranes. Thus, the disulfonated BODIPY photocage is potential for use in the modulation of extracellular proteins and cell-surface receptors while monosulfonated BODIPY photocages can modulate intracellular targets.Teasdale et al described the respective AA-type and ABtype bifunctional BODIPY monomers 19A and 20A, which were incorporated into the corresponding small molecule model compounds 19 and 20 (Figure11a) [30]. They can be photolyzed upon the irradiation of green light.…”

Transient Photodegradability of Photostable Gel Induced by Simultaneous Treatment with Acid and UV–Light for Phototuning of Optically Functional Materials

“…[12][13][14][15] In general, they are integrated with photocleavable moieties in polymeric networks as a cross-linker. [13,[16][17][18][19] The photoinduced cleavage of the cross-linker causes swelling [4,20] and stiffness reduction [21][22][23] of materials, in addition to decomposition, [24,25] which facilitates photoprocessing for material tuning. However, photodegradable materials must be handled in the dark or under illuminations with specific wavelength light to prevent undesired material damages and deformations; otherwise, they and applied reactivity to a polymethyl methacrylate (PMMA) network as a novel cross-linker to realize the two incompatible functions of photodegradability and photostability.…”