期刊
ACS APPLIED MATERIALS & INTERFACES
卷 13, 期 37, 页码 44488-44496出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c13770
关键词
aqueous PET-RAFT polymerization; metal-organic frameworks; low-energy input; protein-polymer bioconjugates; metalloporphyrin
资金
- Research Grant Council of Hong Kong SAR [16304518]
- NSFC-RGC Joint Research Scheme [N_ HKUST607/17]
- Zhongshan City Bureau of Science and Technology [2019AG018]
- IER foundation [HT-JD-CXY-201907]
- Science and Technological Bureau of Guangzhou Huangpu District [2019GH06]
- Guangdong Science and Technology Department [2020A0505090003]
- Research Fund of the Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology [2020B1212030010]
- National Natural Science Foundation of China [51773156, 51703167]
This study demonstrates the design of PET-RAFT photocatalyst from reticular assembled Zr-porphyrinic MOFs and biomacromolecule-based chain transfer agent for efficient bioconjugation in water, showing advantages in manufacturing, catalytic activity, and living characteristics.
Light-driven polymerization, such as photoinduced electron/energy transferreversible addition-fragmentation chain transfer (PET-RAFT) polymerization, enables biological benign conditions and versatile functional polymer structure design, which is readily used in protein-polymer bioconjugates. However, conventional metalloporphyrinic homogeneous catalysts for PET-RAFT polymerization suffer from limited aqueous solubility and tedious purification. Here we demonstrate the design of PET-RAFT photocatalyst from the reticular assembled Zr-porphyrinic metal-organic frameworks (MOFs), along with a biomacromolecule-based chain transfer agent, as efficient bioconjugation tools in water. Our methodology offers manufacturing advantages on bioconjugates under mild conditions such that MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) and cytotoxicity assays have shown the preservation of the protein integrity, bioactivity, and high cell viability after PET-RAFT polymerization. We find that the fast kinetics are benefiting from the ultrahigh loading of metalloporphyrins in MOF-525-Zn. This heterogeneous catalyst also allows us to maintain living characteristics to incorporate myriads of monomers into block copolymers. Other advantages like easy postreaction purification, reusability, and high oxygen tolerance even in an open system are demonstrated. This study provides a tool of highly efficient heterogeneous photocatalysts for polymer-protein bioconjugation in aqueous media and paves the road for biological applications.
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