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Hierarchically engineered nanostructures from compositionally anisotropic molecular building blocks

Nature Materials volume 21, pages 1434–1440 (2022)Cite this article

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Abstract

The inability to synthesize hierarchical structures with independently tailored nanoscale and mesoscale features limits the discovery of next-generation multifunctional materials. Here we present a predictable molecular self-assembly strategy to craft nanostructured materials with a variety of phase-in-phase hierarchical morphologies. The compositionally anisotropic building blocks employed in the assembly process are formed by multicomponent graft block copolymers containing sequence-defined side chains. The judicious design of various structural parameters in the graft block copolymers enables broadly tunable compositions, morphologies and lattice parameters across the nanoscale and mesoscale in the assembled structures. Our strategy introduces advanced design principles for the efficient creation of complex hierarchical structures and provides a facile synthetic platform to access nanomaterials with multiple precisely integrated functionalities.

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Fig. 1: Hierarchical nanostructures constructed from GBCP-based CAMBBs.
Fig. 2: Hierarchical nanostructures constructed from (A-alt-B)-b-C-type GBCPs.
Fig. 3: Diversity of side-chain compositions of (A-alt-B)-b-C-type GBCPs and independent tunability between superstructure and substructure.
Fig. 4: CAMBBs beyond (A-alt-B)-b-C-type GBCPs.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

Code availability

The code generated during the current study is available from the corresponding authors upon reasonable request.

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Acknowledgements

M.Z. acknowledges support from the National Science Foundation (NSF; DMR-2003875). J.A.J. acknowledges support from Eni S.p.A. through the MIT Energy Initiative and an NSF award (CHE-1629358). C.O.O. acknowledges support from an NSF award (DMR-1945966). W.L. acknowledges support from the National Natural Science Foundation of China (21925301). X.F. thanks the China Scholarship Council (CSC no. 201706240130) for the financial support for his visit at Yale University. A.N.L. thanks the NSF Graduate Research Fellowship for supporting her research. The research used resources of the CMS beamline (11-BM) of the National Synchrotron Light Source II, a US Department of Energy Office of Science User Facility operated for the US Department of Energy Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. We also thank R. Li (Brookhaven National Laboratory) and B. Q. Mercado (Yale) for their technical assistance with SAXS measurements during the COVID-19 pandemic.

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Author notes

  1. These authors contributed equally: Ruiqi Liang, Yazhen Xue, Xiaowei Fu.

Authors and Affiliations

  1. Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA

    Ruiqi Liang, Yazhen Xue, Xiaowei Fu, An N. Le & Mingjiang Zhong

  2. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu, China

    Xiaowei Fu

  3. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China

    Qingliang Song, Yicheng Qiang, Qiong Xie & Weihua Li

  4. Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Ruiqi Dong & Chinedum O. Osuji

  5. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Zehao Sun & Jeremiah A. Johnson

  6. Department of Chemistry, Yale University, New Haven, CT, USA

    Mingjiang Zhong

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Contributions

R.L., Y.X., X.F., J.A.J. and M.Z. designed the research. R.L., Y.X. and X.F. performed all synthetic work; R.L., Y.X., X.F., A.N.L, Z.S. and R.D. conducted the structure and property characterization; Q.S., Y.Q., Q.X. and W.L. conducted the DPD simulations; and R.L., Y.X., X.F. and M.Z. analysed the data. R.L., Y.X., X.F., A.N.L., C.O.O., J.A.J., W.L. and M.Z. wrote the paper.

Corresponding authors

Correspondence to Jeremiah A. Johnson or Mingjiang Zhong.

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Supplementary Information

Supplementary Figs. 1–157 and Tables 1–4.

Source data

Source Data Fig. 2

Raw SAXS data used in Fig. 2a.

Source Data Fig. 3

Raw SAXS data used in Fig. 3b,d.

Source Data Fig. 4

Raw SAXS data used in Fig. 4a–c.

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Liang, R., Xue, Y., Fu, X. et al. Hierarchically engineered nanostructures from compositionally anisotropic molecular building blocks. Nat. Mater. 21, 1434–1440 (2022). https://doi.org/10.1038/s41563-022-01393-0

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