Single- and multi-component chiral supraparticles as modular enantioselective catalysts

Si Li, Juan Liu, Naomi S. Ramesar, Hendrik Heinz, Liguang Xu (), Chuanlai Xu and Nicholas A. Kotov ()
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Si Li: Jiangnan University
Juan Liu: University of Colorado Boulder, Boulder
Naomi S. Ramesar: University of Michigan
Hendrik Heinz: University of Colorado Boulder, Boulder
Liguang Xu: Jiangnan University
Chuanlai Xu: Jiangnan University
Nicholas A. Kotov: University of Michigan

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract Nanoscale biological assemblies exemplified by exosomes, endosomes and capsids, play crucial roles in all living systems. Supraparticles (SP) from inorganic nanoparticles (NPs) replicate structural characteristics of these bioassemblies, but it is unknown whether they can mimic their biochemical functions. Here, we show that chiral ZnS NPs self-assemble into 70–100 nm SPs that display sub-nanoscale porosity associated with interstitial spaces between constituent NPs. Similarly to photosynthetic bacterial organelles, these SPs can serve as photocatalysts, enantioselectively converting L- or D-tyrosine (Tyr) into dityrosine (diTyr). Experimental data and molecular dynamic simulations indicate that the chiral bias of the photocatalytic reaction is associated with the chiral environment of interstitial spaces and preferential partitioning of enantiomers into SPs, which can be further enhanced by co-assembling ZnS with Au NPs. Besides replicating a specific function of biological nanoassemblies, these findings establish a path to enantioselective oxidative coupling of phenols for biomedical and other needs.

Date: 2019
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DOI: 10.1038/s41467-019-12134-4

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