Nanoplatforms with donor-acceptor Stenhouse adduct molecular switch for enzymatic reactions remotely controlled with near-infrared light

Visible light-responsive materials: the (photo)chemistry and applications of donor–acceptor Stenhouse adducts in polymer science

“…130 The design of the DASA-functionalized BCP is similar to the enzyme nanoreactors previously reported for DASA-based nanoreactors 129 consisting of a PEG-block and a hydrophobic block made from a random copolymer of methacrylate-derived DASA monomers (10 mol%, secondgeneration) and phenyl methacrylate. 130 Two different types of particles were shown: For the first one, the UCNPs were coated with a layer of enzymes (glucose, lactate or urate oxidases, approximately 10 nm thick) and then with a polymer layer (approximately 20-60 nm thick layer for particles with a hydrodynamic diameter of B200-280 nm). For the second one, the UCNPs were coated with a mesoporous layer of silica, loaded with cargo (D-luciferin or SYTOÀ nucleic acid stain), and subsequently coated with the polymer layer.…”

“…This approach enabled the introduction of second-and third-generation DASAs, 114,129 and has the advantage that pentafluorophenyl(meth)acrylates are hydrophobic, compatible with free radical and RAFT polymerization, and also substantially more stable towards hydrolysis in comparison to other groups used to install amines on polymers. More recently, other groups have relied on this functionalization strategy 130,131 or expanded it by using N-methyl-1,3-propanediamine as linker to couple first-generation DASAs. 132 Moreover, polymer gels functionalized with pendant DASAs were synthesized from networks made of pentafluorophenylacrylate and hexamethylene diacrylate as a crosslinker.…”

“…The system was mainly presented as enzyme nanoreactor platform (first type of particles), but for the second type of particles, visible and NIR light-induced cargo release in a luciferase-transfected CT26 tumor-bearing mouse model or in cell assays was also demonstrated. 130 However, no information on the morphology or ordering of the DASA-functionalized BCP gating membrane was provided, neither before nor after photoswitching.…”

“…To date, the largest group of DASA-polymers studied are side-chain functionalized linear copolymers 83,92,96,100,114,117,124,126 and diblock copolymers. 100,129,130,132,133 DASAs have also been incorporated as polymer end-groups, 115,116,118,134 in telechelic linear polymers, 118 as well as pending groups in polymer networks 91,118,119,128 and branched polymers (Fig. 11).…”

Exploring Emergent Properties in Enzymatic Reaction Networks: Design and Control of Dynamic Functional Systems

“…In addition to directly photoswitching molecules that interact with the enzyme (via the active site or allosteric interactions), one could alter the kinetics by controlling the accessibility of the substrate toward the enzyme, as demonstrated by encapsulating enzymes in vesicles or polymersomes and controlling the transport of substrate using light. − The latter example, presented in Figure c, was based on polymersomes containing a DASA dye in the polymer shell, allowing switching between semipermeable states . These DASA polymersomes were filled with Est and then mixed with Ur containing polymersomes that were permeable and light insensitive.…”