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通过主体-客体超分子相互作用实现动态纳米表面重构。

Dynamic nanosurface reconfiguration by host-guest supramolecular interactions.

机构信息

Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.

出版信息

Nanoscale. 2022 Mar 7;14(9):3599-3608. doi: 10.1039/d1nr05315a.

Abstract

The dynamic functionalization of the nanoparticle surface with biocompatible coatings is a critical step towards the development of functional nano-sized systems. While covalent approaches have been broadly exploited in the stabilization of nanoparticle colloidal systems, these strategies hinder the dynamic nanosurface chemical reconfiguration. Supramolecular strategies based on specific host-guest interactions hold promise due to their intrinsic reversibility, self-healing capabilities and modularity. Host/guest couples have recently been implemented in nanoparticle platforms for the exchange and release of effector molecules. However, the direct exchange of biocompatible hydrophilic oligomers ( peptides) for the modulation of the surface charge and chemical properties of nanoparticles still remains a challenge. Here, we show the intracellular reconfiguration of nanoparticles by a host/guest mechanism with biocompatible oligomeric competitors. The surface of gold nanoparticles was functionalized with cyclodextrin hosts and the guest exchange was studied with biocompatible mono and divalent adamantyl competitors. The systematic characterization of the size and surface potential of the host/guest nanoparticles allowed the optimization of the binding and the stabilization properties of these supramolecular systems. The host/guest-mediated direct reconfiguration of the peptide layer at the surface of nanoparticles is achieved by controlling the valence of adamantane-equipped peptides. This work demonstrates that host/guest supramolecular systems can be exploited for the direct exchange of pendants at the surface of nanoparticles and the intracellular dynamic chemical reconfiguration of biocompatible colloidal systems.

摘要

纳米粒子表面的动态功能化是开发功能性纳米系统的关键步骤。虽然共价方法已广泛应用于稳定纳米粒子胶体系统,但这些策略阻碍了纳米表面的动态化学重构。基于特定主客体相互作用的超分子策略由于其内在的可逆性、自修复能力和模块性而具有广阔的应用前景。主客体偶联物最近已被应用于纳米颗粒平台,用于效应分子的交换和释放。然而,直接交换生物相容性的亲水低聚物(如多肽)以调节纳米颗粒的表面电荷和化学性质仍然是一个挑战。在这里,我们通过生物相容性的低聚物竞争物的主客体机制展示了纳米颗粒的细胞内重构。金纳米粒子的表面用环糊精主体功能化,并研究了生物相容性的单核和二价金刚烷配体的客体交换。对主客体纳米粒子的尺寸和表面电势的系统表征允许优化这些超分子系统的结合和稳定性能。通过控制金刚烷化肽的价态,可以实现纳米粒子表面肽层的主客体介导的直接重构。这项工作证明,主客体超分子系统可用于纳米粒子表面侧链的直接交换以及生物相容性胶体系统的细胞内动态化学重构。

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