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Complex silica composite nanomaterials templated with DNA origami


Genetically encoded protein scaffolds often serve as templates for the mineralization of biocomposite materials with complex yet highly controlled structural features that span from nanometres to the macroscopic scale1,2,3,4. Methods developed to mimic these fabrication capabilities can produce synthetic materials with well defined micro- and macro-sized features, but extending control to the nanoscale remains challenging5,6. DNA nanotechnology can deliver a wide range of customized nanoscale two- and three-dimensional assemblies with controlled sizes and shapes7,8,9,10,11. But although DNA has been used to modulate the morphology of inorganic materials12,13 and DNA nanostructures have served as moulds14,15 and templates16,17, it remains challenging to exploit the potential of DNA nanostructures fully because they require high-ionic-strength solutions to maintain their structure, and this in turn gives rise to surface charging that suppresses the material deposition. Here we report that the Stöber method, widely used for producing silica (silicon dioxide) nanostructures, can be adjusted to overcome this difficulty: when synthesis conditions are such that mineral precursor molecules do not deposit directly but first form clusters, DNA–silica hybrid materials that faithfully replicate the complex geometric information of a wide range of different DNA origami scaffolds are readily obtained. We illustrate this approach using frame-like, curved and porous DNA nanostructures, with one-, two- and three-dimensional complex hierarchical architectures that range in size from 10 to 1,000 nanometres. We also show that after coating with an amorphous silica layer, the thickness of which can be tuned by adjusting the growth time, hybrid structures can be up to ten times tougher than the DNA template while maintaining flexibility. These findings establish our approach as a general method for creating biomimetic silica nanostructures.

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This Letter is dedicated to the memory of Q. Huang, who initiated the project along with C.F. and X.L. We thank Z. Liu (Shanghai Technical Platform for Testing and Characterization on Inorganic Materials, CASSIC, China) for providing technical support, Y. Li (South China Normal University, China) for providing diatom specimens, and the BL16B1/BL19U2 beamline at Shanghai Synchrotron Radiation Facility (SSRF) for ongoing support in data collection and molecular dynamics simulation. This project was supported by National Science Foundation of China (grant numbers 21390414, 21329501, 21603262 and 21675167), National Key R&D Program of China (grant numbers 2016YFA0201200 and 2016YFA0400900) and the Key Research Program of Frontier Sciences, CAS (grant number QYZDJ-SSW-SLH031). L.W., C.F. and H.Y. thank the National Key R&D Program of China (grant number 2016YFA0400900). H.Y., F.Z. and Y.L. thank the US National Science Foundation, Office of Naval Research, Army Research Office, National Institutes of Health, and Department of Energy for financial support. W.L. and D.Z. thank the National Science Foundation of China (grant numbers U1463206 and 21733003), National Key R&D Program of China (grant number 2018YFA0209401) and Key Basic Research Program of the Science and Technology Commission of Shanghai Municipality (grant number 17JC1400100).

Author information

C.F. and H.Y. supervised the research. X.L., C.F. and H.Y. conceived the research, designed the experiments. F.Z. designed the DNA nanostructures. X.J. and X.L. carried out silicification experiments and characterization. M.P. analysed EM and AFM data. P.L. carried out molecular dynamics simulations. W.L. and D.Z. provided silicification characterization and discussion. B.Z. carried out FTIR and Raman experiments. All authors analysed data. X.L., F.Z., X.J., M.P., D.Z., C.F. and H.Y. interpreted data and wrote the paper.

Competing interests

The authors declare no competing interests.

Correspondence to Hao Yan or Chunhai Fan.

Supplementary information

  1. Supplementary Information

    This file contains Supplementary Methods, additional discussions, Supplementary Tables S1-S7, Supplementary Figures 1-80, DNA sequences and additional references.

  2. Video 1 Rotation of a DNA origami silicification tetrahedron framework visualized by TEM.

    This video is related to Figure 3b. The sample holder rotation angle is from -30° to +30°, 2.5° each frame.

  3. Video 2 Rotation of a DNA origami silicification cube framework (~0°) visualized by TEM.

    This video is related to Figure 3b. The sample holder rotation angle is from -30° to +30°, 2.5° each frame.

  4. Video 3 Rotation of a DNA origami silicification cube framework (~45°) visualized by TEM.

    This video is related to Figure 3b. The sample holder rotation angle is from -30° to +30°, 2.5° each frame.

  5. Video 4 Rotation of a DOS tetrahedron framework loaded with two gold nanorods visualized by TEM.

    This video is related to Figure 4f. The sample holder rotation angle is from -30° to +30°, 2.5° each frame.

  6. Source data for Figure 2

  7. Source data for Figure 4

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Further reading

Fig. 1: Schematic illustration and molecular dynamics simulation of DOS strategy.
Fig. 2: Geometrically precise control of DOS structures.
Fig. 3: Representative complex DOS nanostructures.
Fig. 4: Nanomechanical studies on DOS nanostructures.


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