Colloidal clathrate crystals self-assembled from hard polyhedral shapes in computer simulations are stabilized by entropy compartmentalization, whereby hosts and guests contribute unequally to the entropy. This creative solution to satisfying the laws of thermodynamics suggests new ways to make colloidal crystals with open cages and hierarchical host–guest structures.
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References
Laramy, C. R., O’Brien, M. N. & Mirkin, C. A. Crystal Engineering with DNA. Nat. Rev. Mater. 4, 201–224 (2019). A review article that summarizes the plethora of crystal structures possible for DNA-grafted nanoparticles.
Damasceno, P. F., Engel, M. & Glotzer, S. C. Predictive self-assembly of polyhedra into complex structures. Science 337, 453–457 (2012). This paper reports a multitude of crystal structures self-assembled from 101 different shapes solely through entropy maximization.
Anderson, J. A., Glaser, J. & Glotzer, S. C. HOOMD-blue: a Python package for high-performance molecular dynamics and hard particle Monte Carlo simulations. Comput. Mater. Sci. 173, 109363 (2020). A GPU-accelerated, open-source Python package for molecular simulations of shaped nanoparticles.
Lin, H. et al. Clathrate colloidal crystals. Science. 355, 931–935 (2017). This paper reports the first colloidal clathrate self-assembled in the lab.
Lee, S., Teich, E. G., Engel, M. & Glotzer, S. C. Entropic colloidal crystallization pathways via fluid–fluid transitions and multi-dimensional prenucleation motifs. Proc. Natl Acad. Sci. USA 116, 14843–14851 (2019). This paper reports simulations of self-assembled, entropic colloidal crystals with 92-, 244- and 432-particle unit cells.
Patchkovskii, S. & Tse, J. S. Thermodynamic stability of hydrogen clathrates. Proc. Natl Acad. Sci. USA 100, 14645–14650 (2003). First principles theoretical study showing that individual H2 molecule guests and clusters of H2 freely rotate inside the cages of a type-II hydrogen clathrate made in the lab.
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This is a summary of: Lee, S. et al. Entropy compartmentalization stabilizes open host–guest colloidal clathrates. Nat. Chem. https://doi.org/10.1038/s41557-023-01200-6 (2023).
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Route to complex colloidal crystals through entropy compartmentalization. Nat. Chem. 15, 901–902 (2023). https://doi.org/10.1038/s41557-023-01227-9
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DOI: https://doi.org/10.1038/s41557-023-01227-9