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Topological defects in liquid crystals as templates for molecular self-assembly

Nature Materials volume 15, pages 106–112 (2016)Cite this article

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Abstract

Topological defects in liquid crystals (LCs) have been widely used to organize colloidal dispersions and template polymerization, leading to a range of assemblies, elastomers and gels. However, little is understood about molecular-level assembly processes within defects. Here, we report that nanoscopic environments defined by LC topological defects can selectively trigger processes of molecular self-assembly. By using fluorescence microscopy, cryogenic transmission electron microscopy and super-resolution optical microscopy, we observed signatures of molecular self-assembly of amphiphilic molecules in topological defects, including cooperativity, reversibility and controlled growth. We also show that nanoscopic o-rings synthesized from Saturn-ring disclinations and other molecular assemblies templated by defects can be preserved by using photocrosslinkable amphiphiles. Our results reveal that, in analogy to other classes of macromolecular templates such as polymer–surfactant complexes, topological defects in LCs are a versatile class of three-dimensional, dynamic and reconfigurable templates that can direct processes of molecular self-assembly.

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Figure 1: Disclination lines and amphiphiles.
Figure 2: Self-assembly of amphiphiles in LC defects.
Figure 3: Controlled growth of assemblies in defects.
Figure 4: Dependence of standard free energy of self-assembly on amphiphile tail-length and head-group type.
Figure 5: Reversible formation and in situ crosslinking of molecular assemblies of amphiphiles templated by a −1/2 ‘Saturn-ring’ disclination line formed about microparticles.
Figure 6: Self-assembly of amphiphiles in LC defects.

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Acknowledgements

This work was supported by the National Science Foundation (under awards DMR-1121288 (MRSEC) and CBET-1263970), the Army Research Office (W911-NF-11-1-0251 and W911-NF-14-1-0140), and the National Institutes of Health (CA108467 and AI092004). STORM imaging and analysis was performed at the Biochemistry Optical Core, University of Wisconsin-Madison.

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  1. Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706-1691, USA

    Xiaoguang Wang, Daniel S. Miller, Emre Bukusoglu & Nicholas L. Abbott

  2. Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA

    Juan J. de Pablo

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Contributions

X.W., J.J.d.P. and N.L.A. designed the experiments. X.W., D.S.M. and E.B. performed the experimental work. X.W. and N.L.A. analysed the data. X.W., D.S.M., J.J.d.P. and N.L.A. wrote the paper. N.L.A. supervised the research. All authors discussed the progress of research and reviewed the manuscript.

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Correspondence to Nicholas L. Abbott.

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Wang, X., Miller, D., Bukusoglu, E. et al. Topological defects in liquid crystals as templates for molecular self-assembly. Nature Mater 15, 106–112 (2016). https://doi.org/10.1038/nmat4421

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