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Angew Chem Int Ed Engl. 2019 Jun 13. doi: 10.1002/anie.201906329. [Epub ahead of print]

Resolving Optical and Catalytic Activities in Thermoresponsive Nanoparticles by Permanent Ligation with Temperature-Sensitive Polymers.

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School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, 30332, USA.
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China.
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640, China.


Thermoresponsive nanoparticles (NPs) represent an important hybrid material comprising functional NPs with temperature-sensitive polymer ligands. Strikingly, significant discrepancies in optical and catalytic properties of thermoresponsive noble-metal NPs have been reported, and have yet to be unraveled. Reported herein is the crafting of Au NPs, intimately and permanently ligated by thermoresponsive poly(N-isopropylacrylamide) (PNIPAM), in situ using a starlike block copolymer nanoreactor as model system to resolve the paradox noted above. As temperature rises, plasmonic absorption of PNIPAM-capped Au NPs red-shifts with increased intensity in the absence of free linear PNIPAM, whereas a greater red-shift with decreased intensity occurs in the presence of deliberately introduced linear PNIPAM. Remarkably, the absence or addition of free linear PNIPAM also accounts for non-monotonic or switchable on/off catalytic performance, respectively, of PNIPAM-capped Au NPs.


block copolymers; catalytic activity; nanoparticles; nanoreactors; optical properties


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