Bioinspired Silicification Reveals Structural Detail in Self-Assembled Peptide Cages.

Bioinspired Silicification Reveals Structural Detail in Self-Assembled Peptide Cages.
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DOI:
10.1021/acsnano.7b07785
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发表时间:
2018-02-27
期刊:
影响因子:
17.1
通讯作者:
Woolfson DN
Woolfson DN
中科院分区:
材料科学1区
文献类型:
--
作者:
Galloway JM;Senior L;Fletcher JM;Beesley JL;Hodgson LR;Harniman RL;Mantell JM;Coombs J;Rhys GG;Xue WF;Mosayebi M;Linden N;Liverpool TB;Curnow P;Verkade P;Woolfson DN

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了解自组装软物质纳米结构中的分子是如何组织的,对于改进下一代纳米材料的设计至关重要。成像这些组件可能具有挑战性,通常需要处理,例如染色或嵌入,这可能会损坏或模糊特征。另一种选择是利用生物激发矿化,模仿某些生物体如何使用生物分子来模板矿物形成。在此之前,我们已经报道了自组装肽笼(SAGEs)的设计和表征。在SAGE中,两个互补的,3倍对称的肽中心结合形成一个六边形晶格,它弯曲并闭合形成SAGE纳米颗粒。由于六边形不能单独平铺到球体上,因此网络还必须包含非六边形。虽然sage的六边形超微结构已被成像,但这些缺陷尚未被观察到。在这里,我们展示了带正电荷的SAGEs生物模板有一层薄薄的保护性二氧化硅涂层。电子显微镜显示,这些SiO2-SAGEs在干燥时不会坍塌,而是保持其三维形状。原子力显微镜显示了SiO2-SAGE表面的六边形和不规则特征网络。这些尺寸(7.2 nm±1.4 nm宽,内角119.8°±26.1°)符合设计的SAGE网络和SAGE组件的粗粒度建模。SiO2-SAGEs可渗透到小分子(< 2nm),但不能渗透到较大的生物分子(> 6nm)。因此,受生物启发的硅化提供了一种温和的技术,可以保留软物质纳米颗粒用于成像,揭示尺寸小于10纳米的结构细节,同时保持理想的特性,例如对小分子的渗透性。
Understanding how molecules in self-assembled soft-matter nanostructures are organized is essential for improving the design of next-generation nanomaterials. Imaging these assemblies can be challenging and usually requires processing, e.g., staining or embedding, which can damage or obscure features. An alternative is to use bioinspired mineralization, mimicking how certain organisms use biomolecules to template mineral formation. Previously, we have reported the design and characterization of Self-Assembled peptide caGEs (SAGEs) formed from de novo peptide building blocks. In SAGEs, two complementary, 3-fold symmetric, peptide hubs combine to form a hexagonal lattice, which curves and closes to form SAGE nanoparticles. As hexagons alone cannot tile onto spheres, the network must also incorporate nonhexagonal shapes. While the hexagonal ultrastructure of the SAGEs has been imaged, these defects have not been observed. Here, we show that positively charged SAGEs biotemplate a thin, protective silica coating. Electron microscopy shows that these SiO2-SAGEs do not collapse, but maintain their 3D shape when dried. Atomic force microscopy reveals a network of hexagonal and irregular features on the SiO2-SAGE surface. The dimensions of these (7.2 nm ± 1.4 nm across, internal angles 119.8° ± 26.1°) are in accord with the designed SAGE network and with coarse-grained modeling of the SAGE assembly. The SiO2-SAGEs are permeable to small molecules (<2 nm), but not to larger biomolecules (>6 nm). Thus, bioinspired silicification offers a mild technique that preserves soft-matter nanoparticles for imaging, revealing structural details <10 nm in size, while also maintaining desirable properties, such as permeability to small molecules.
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