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Creators/Authors contains: "Li, Jialuo"

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  1. null (Ed.)
  2. In this work, we designed and fabricated a nanoscopic sugar-based magnetic hybrid material that is capable of tackling environmental pollution posed by marine oil spills, while minimizing potential secondary problems that may occur from microplastic contamination. These readily-defined magnetic nanocomposites were constructed through co-assembly of magnetic iron oxide nanoparticles (MIONs) and a degradable amphiphilic polymer, poly(ethylene glycol)- b -dopamine-functionalized poly(ethyl propargyl glucose carbonate)- b -poly(ethyl glucose carbonate), PEG- b -PGC[(EPC-MPA)- co -(EPC-DOPA)]- b -PGC(EC), driven by supramolecular co-assembly in water with enhanced interactions provided via complexation between dopamine and MIONs. The composite nanoscopic assemblies possessed a pseudo -micellar structure, with MIONs trapped within the polymer framework. The triblock terpolymer was synthesized by sequential ring-opening polymerizations (ROPs) of two glucose-derived carbonate monomers, initiated by a PEG macroinitiator. Dopamine anchoring groups were subsequently installed by first introducing carboxylic acid groups using a thiol–yne click reaction, followed by amidation with dopamine. The resulting amphiphilic triblock terpolymers and MIONs were co-assembled to afford hybrid nanocomposites using solvent exchange processes from organic solvent to water. In combination with hydrophobic interactions, the linkage between dopamine and iron oxide stabilized the overall nanoscopic structure to allow for the establishment of a uniform globular morphology, whereas attempts at co-assembly with the triblock terpolymer precursor, lacking dopamine side chains, failed to afford well-defined nanostructures. The magnetic hybrid nanoparticles demonstrated high oil sorption capacities, ca. 8 times their initial dry weight, attributed, in part, to large surface areas leading to effective contact between the nanomaterials and hydrocarbon pollutants. Moreover, the naturally-derived polymer framework undergoes hydrolytic degradation to break down into byproducts that include glucose, ethanol and dopamine if not recovered after deployment, alleviating concerns of potential microplastic generation and persistence. 
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  3. Abstract

    2D metal–organic frameworks (2D‐MOFs) have recently emerged as promising materials for gas separations, sensing, conduction, and catalysis. However, the stability of these 2D‐MOF catalysts and the tunability over catalytic environments are limited. Herein, it is demonstrated that 2D‐MOFs can act as stable and highly accessible catalyst supports by introducing more firmly anchored photosensitizers as bridging ligands. An ultrathin MOF nanosheet‐based material, Zr‐BTB (BTB = 1,3,5‐tris(4‐carboxyphenyl)benzene), is initially constructed by connecting Zr6‐clusters with the tritopic carboxylate linker. Surface modification of the Zr‐BTB structure was realized through the attachment of porphyrin‐based carboxylate ligands on the coordinatively unsaturated Zr metal sites in the MOF through strong Zr‐carboxylate bond formation. The functionalized MOF nanosheet, namely PCN‐134‐2D, acts as an efficient photocatalyst for1O2generation and artemisinin production. Compared to the 3D analogue (PCN‐134‐3D), PCN‐134‐2D allows for fast reaction kinetics due to the enhanced accessibility of the catalytic sites within the structure and facile substrate diffusion. Additionally, PCN‐134(Ni)‐2D exhibits an exceptional yield of artemisinin, surpassing all reported homo‐ or heterogeneous photocatalysts for the artemisinin production.

     
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