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Pathway-controlled formation of mesostructured all-DNA colloids and superstructures

Nature Nanotechnology volume 13, pages 730–738 (2018)Cite this article

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Abstract

DNA has traditionally been used for the programmable design of nanostructures by exploiting its sequence-defined supramolecular recognition. However, control on larger length scales or even hierarchical materials that translate to the macroscale remain difficult to construct. Here, we show that the polymer character of single-stranded DNA (ssDNA) can be activated via a nucleobase-specific lower critical solution temperature, which provides a unique access to mesoscale structuring mechanisms on larger length scales. We integrate both effects into ssDNA multiblock copolymers that code sequences for phase separation, hybridization and functionalization. Kinetic pathway guidance using temperature ramps balances the counteracting mesoscale phase separation during heating with nanoscale duplex recognition during cooling to yield a diversity of complex all-DNA colloids with control over the internal dynamics and of their superstructures. Our approach provides a facile and versatile platform to add mesostructural layers into hierarchical all-DNA materials. The high density of addressable ssDNA blocks opens routes for applications such as gene delivery, artificial evolution or spatially encoded (bio)materials.

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Fig. 1: Kinetic pathway guidance towards multilevel control of hierarchical all-DNA structures exploiting competing interactions.
Fig. 2: LCST behaviour of ssDNA.
Fig. 3: Pathway-controlled formation of tunable and addressable metastable all-DNA microgel architectures.
Fig. 4: Control over microgel size and physical state in protocell-like particles.
Fig. 5: Single-step capsule formation via matching the dynamics of core–shell hybridization and core dissolution during cooling.
Fig. 6: Supraparticulate assemblies, cellular hydrogels and light-triggered hybrid DNA/Au-NP colloids.

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Acknowledgements

This work was funded via the ERC Starting Grant TimeProSAMat (677960). S.L. is funded through a scholarship of the FCI. We thank A. Kuehne for critically reading the manuscript.

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Authors and Affiliations

  1. Institute for Macromolecular Chemistry, University of Freiburg, Freiburg, Germany

    Rémi Merindol

  2. Freiburg Materials Research Center, University of Freiburg, Freiburg, Germany

    Sebastian Loescher

  3. Freiburg Center for Interactive Materials and Bioinspired Technologies, University of Freiburg, Freiburg, Germany

    Avik Samanta

  4. Freiburg Institute for Advanced Studies (FRIAS), University of Freiburg, Freiburg, Germany

    Andreas Walther

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Contributions

R.M. and A.W. conceived the project, designed the experiments and analysed the data. R.M., S.L. and A.S. carried out the experiments. A.W. supervised the project. R.M. and A.W. wrote the manuscript.

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Correspondence to Andreas Walther.

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Supplementary information

Supplementary Information

Supplementary Text, Supplementary Figures 1–8, Supplementary Table 1 and Supplementary References

Supplementary Video 1

Photobleaching of crosslinked core–shell all-DNA microgels

Supplementary Video 2

Photobleaching of core–shell all-DNA protocells with liquid DNA core

Supplementary Video 3

Photothermal ejection of ssDNA from core–shell all-DNA protocells with liquid DNA core and Au-NPs embedded inside the shells

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Merindol, R., Loescher, S., Samanta, A. et al. Pathway-controlled formation of mesostructured all-DNA colloids and superstructures. Nature Nanotech 13, 730–738 (2018). https://doi.org/10.1038/s41565-018-0168-1

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