INS14-1364
NIR Photocontrolled RAFT Polymerization
Topic
S14. The 2nd PSK / CCS-PD Joint Symposium on Frontiers in Polymer Science and Engineering
When and Where
Oct 1, 2026
11:10 - 11:35
Room 203
Session Chairs
Hui Joon PARK
Presenter(s)
Zesheng An (Jilin University)
Co-Author(s)
Abstract
Near-infrared (NIR) photocontrolled reversible addition–fragmentation chain-transfer (RAFT) polymerization in aqueous media offers superior spatiotemporal control, deep tissue penetration, and high biocompatibility. However, its efficiency is hindered by photocatalyst aggregation, oxygen inhibition, and restricted access to ultrahigh-molecular-weight (UHMW) polymers. Here, we present three complementary strategies to overcome these bottlenecks via tailored colloidal, supramolecular, and cascade enzymatic platforms.
First, we developed a supramolecular NIR photoenzyme (SNIRPE) by co-assembling GOx and tetrasulfonated zinc phthalocyanine. This spatially confined biocatalyst-photocatalyst complex exploits substrate channeling to photosenstize enzymatically produced H2O2 in situ under 730 nm light. SNIRPE operates at low catalyst loadings (50 ppb) and produces UHMW polymers in volumes scaled up to 100 mL.
Second, we established a colloidal system using a surfactant (Brij 98) to stabilize hydrophobic NIR dyes. In tandem with GOx for in situ deoxygenation, this formulation enabled high-throughput aqueous RAFT in 96-well plates at low catalyst loadings (4 ppm) to yield UHMW polymers.
Third, to suppress aggregation of water-soluble dyes without surfactants, we developed a host–guest supramolecular approach. Complexation of an anionic phthalocyanine with a cationic biphen[3]arene macrocycle (WQP3) effectively disaggregated the photocatalyst, accelerating polymerization kinetics. This system maintained outstanding oxygen tolerance and controlled polymerization through thick porcine tissue barriers.
Together, these systems establish a highly efficient, oxygen-tolerant aqueous RAFT platform, paving the way for advanced biomaterials fabrication and in vivo polymerizations.
First, we developed a supramolecular NIR photoenzyme (SNIRPE) by co-assembling GOx and tetrasulfonated zinc phthalocyanine. This spatially confined biocatalyst-photocatalyst complex exploits substrate channeling to photosenstize enzymatically produced H2O2 in situ under 730 nm light. SNIRPE operates at low catalyst loadings (50 ppb) and produces UHMW polymers in volumes scaled up to 100 mL.
Second, we established a colloidal system using a surfactant (Brij 98) to stabilize hydrophobic NIR dyes. In tandem with GOx for in situ deoxygenation, this formulation enabled high-throughput aqueous RAFT in 96-well plates at low catalyst loadings (4 ppm) to yield UHMW polymers.
Third, to suppress aggregation of water-soluble dyes without surfactants, we developed a host–guest supramolecular approach. Complexation of an anionic phthalocyanine with a cationic biphen[3]arene macrocycle (WQP3) effectively disaggregated the photocatalyst, accelerating polymerization kinetics. This system maintained outstanding oxygen tolerance and controlled polymerization through thick porcine tissue barriers.
Together, these systems establish a highly efficient, oxygen-tolerant aqueous RAFT platform, paving the way for advanced biomaterials fabrication and in vivo polymerizations.
