Single- and multi-component chiral supraparticles as modular enantioselective catalysts
Single- and multi-component chiral supraparticles as modular enantioselective catalysts
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作为模块化对映选择性催化剂的单组分和多组分手性超粒子
DOI：
10.1038/s41467-019-12134-4
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发表时间：
2019-10-23
影响因子：
16.6
通讯作者：
Kotov, Nicholas A.
中科院分区：
文献类型：
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作者：
Li, Si;Liu, Juan;Kotov, Nicholas A.
以外泌体、内体和衣壳为代表的纳米级生物组装体在所有生命系统中起着至关重要的作用。来自无机纳米颗粒（NPs）的超颗粒（SP）复制了这些生物组装体的结构特征，但尚不清楚它们是否可以模仿其生化功能。在这里，我们表明，手性ZnS纳米粒子自组装成70-100纳米的SP，显示亚纳米级的孔隙度与组成纳米粒子之间的间隙空间。类似于光合细菌细胞器，这些SP可以作为光催化剂，对映选择性地将L-或D-酪氨酸（Tyr）转化为二酪氨酸（diTyr）。实验数据和分子动力学模拟表明，光催化反应的手性偏向与间隙空间的手性环境和对映体优先分配到SP中有关，ZnS与Au NPs的共组装可以进一步增强这种手性偏向。除了复制生物纳米组装体的特定功能外，这些发现还为生物医学和其他需求建立了酚类对映选择性氧化偶联的途径。
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.