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An adaptive supramolecular hydrogel comprising self-sorting double nanofibre networks

A Publisher Correction to this article was published on 29 January 2018

This article has been updated


Novel soft materials should comprise multiple supramolecular nanostructures whose responses (for example, assembly and disassembly) to external stimuli can be controlled independently. Such multicomponent systems are present in living cells and control the formation and break-up of a variety of supramolecular assemblies made of proteins, lipids, DNA and RNA in response to external stimuli; however, artificial counterparts are challenging to make. Here, we present a hybrid hydrogel consisting of a self-sorting double network of nanofibres in which each network responds to an applied external stimulus independent of the other. The hydrogel can be made to change its mechanical properties and rates of release of encapsulated proteins by adding Na2S2O4 or bacterial alkaline phosphatase. Notably, the properties of the gel depend on the order in which the external stimuli are applied. Multicomponent hydrogels comprising orthogonal stimulus-responsive supramolecular assemblies would be suitable for designing novel adaptive materials.

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Fig. 1: Schematic representation of formation of a SDN hydrogel, and molecular structures of hydrogelators and fluorescence probes.
Fig. 2: Evaluation for self-sorting of NPmoc-F(4-F)F and Phos-cycC6.
Fig. 3: Stimuli response behaviours of NPmoc-F(4-F)F and Phos-cycC6.
Fig. 4: Brownian motions of beads in Phos-cycC6 solution and Phos/HO-cycC6 gel.
Fig. 5: Stimuli-responsiveness of the self-sorting double network (SDN) hydrogel.
Fig. 6: Stimulus order recognition of the SDN hydrogel.

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Change history

  • 29 January 2018

    In the version of this Article originally published online, in Fig. 4b, in the lower-right image, the value of r was incorrect; it should have read ‘r = 0.72’. This has now been corrected in all versions of the Article.


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The authors thank M. Suginome and Y. Nagata (Kyoto University) for CD spectra measurements, N. Yamada (Kyoto Insititute of Technology) for their kind support with rheological measurements, and Y. Sato (Carl Zeiss Microimaging Co.) for CLSM imaging with the Airyscan unit. H.S. acknowledges JSPS Research Fellowships for Young Scientists (16J10716). The authors acknowledge financial support from The Mitsubishi Foundation. This work was also supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Chemistry for Multimolecular Crowding Biosystems” (JSPS KAKENHI Grant No. 17H06348).

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Authors and Affiliations



H.S. and I.H. conceived the project and designed the experiments. H.S., T.F. and W.T. performed all the experiments. H.S., S.M. and K.U. analysed rheological properties. The paper was written by H.S., R.K. and I.H. and edited by all the co-authors.

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Correspondence to Itaru Hamachi.

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The authors declare no competing financial interests.

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Supplementary information

Supplementary Information

Supplementary materials and methods, Supplementary Figures 1–36, and captions of Supplementary Videos


Supplementary Video 1

Brownian motion of 300 nm nanobeads (30 sec) in Phos-cycC6 nanofibres before and after the addition of BAP

Supplementary Video 2

Brownian motion of 300 nm nanobeads (5 min) in SDN hydrogels before and after the addition of Na2S2O4

Supplementary Video 3

Brownian motion of 300 nm nanobeads (3 h) in Na2S2O4-added SDN hydrogels before and after the addition of BAP

Supplementary Video 4

Brownian motion of 300 nm nanobeads (3 h) in SDN hydrogels before and after the addition of BAP

Supplementary Video 5

Brownian motion of 300 nm nanobeads (5 min) in BAP-treated SDN hydrogels before and after the addition of Na2S2O4

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Shigemitsu, H., Fujisaku, T., Tanaka, W. et al. An adaptive supramolecular hydrogel comprising self-sorting double nanofibre networks. Nature Nanotech 13, 165–172 (2018).

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