Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol S(N)Ar chemistry.
Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol S(N)Ar chemistry.
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DOI：
10.1038/nchem.2686
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发表时间：
2017-04
期刊：
影响因子：
21.8
通讯作者：
Spokoyny AM
中科院分区：
文献类型：
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作者：
Qian EA;Wixtrom AI;Axtell JC;Saebi A;Jung D;Rehak P;Han Y;Moully EH;Mosallaei D;Chow S;Messina MS;Wang JY;Royappa AT;Rheingold AL;Maynard HD;Král P;Spokoyny AM
大多数生物分子本质上是原子精确的，这是一个重要的特征，可以合理地设计它们的识别和结合特性。然而，由于现有化学方法的固有局限性和适当设计的功能构建块的可用性，赋予混合纳米颗粒类似的精度一直具有挑战性。在这里，我们报告了一种新的方法来形成原子级精确和高度可调的混合纳米分子与定义良好的三维。用五氟芳基封端的连接体对原子精确簇进行功能化，产生尺寸可调的刚性簇纳米分子。这些物质易于用各种含巯基的分子和大分子进行修饰。组装在室温下在温和条件下在数小时内进行，并且所得纳米分子由于其完全共价性而表现出高稳定性。我们进一步证明了这些纳米分子接枝与nanomolecules可以表现出显着提高对蛋白质的结合亲和力。最终，开发的策略允许快速生成用于调查多价相互作用的精确分子组装体。
The majority of biomolecules are intrinsically atomically precise, an important characteristic that enables rational engineering of their recognition and binding properties. However, imparting similar precision to hybrid nanoparticles has been challenging due to inherent limitations of the existing chemical methods and availability of properly designed functional building blocks. Here we report a new approach to form atomically precise and highly tunable hybrid nanomolecules with well-defined three-dimensionality. Perfunctionalization of atomically precise clusters with pentafluoroaryl-terminated linkers produces size-tunable rigid cluster nanomolecules. These species are amenable to facile modification with a variety of thiol-containing molecules and macromolecules. Assembly proceeds at room temperature within hours under mild conditions, and the resulting nanomolecules exhibit high stabilities due to their full covalency. We further demonstrate how these nanomolecules grafted with saccharides can exhibit dramatically improved binding affinity toward a protein. Ultimately, the developed strategy allows the rapid generation of precise molecular assemblies for investigating multivalent interactions.