Tunable assembly of hybrid colloids induced by regioselective depletion


Assembling colloidal particles using site-selective directional interactions into predetermined colloidal superlattices with desired properties is broadly sought after, but challenging to achieve. Herein, we exploit regioselective depletion interactions to engineer the directional bonding and assembly of non-spherical colloidal hybrid microparticles. We report that the crystallization of a binary colloidal mixture can be regulated by tuning the depletion conditions. Subsequently, we fabricate triblock biphasic colloids with controlled aspect ratios to achieve regioselective bonding. Without any surface treatment, these biphasic colloids assemble into various colloidal superstructures and superlattices featuring optimized pole-to-pole or centre-to-centre interactions. Additionally, we observe polymorphic crystallization, quantify the abundancy of each form using algorithms we developed and investigate the crystallization process in real time. We demonstrate selective control of attractive interactions between specific regions on an anisotropic colloid with no need of site-specific surface functionalization, leading to a general method for achieving colloidal structures with yet unforeseen arrangements and properties.

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Fig. 1: Selective crystallization of PS and TPM spheres.
Fig. 2: Schematic illustration of particle fabrication and representative SEM images.
Fig. 3: 1D assemblies induced by Pluronic F127.
Fig. 4: Polymorphism in 2D assemblies induced by pluronic F127.
Fig. 5: Tracking of the formation of polymorphs.
Fig. 6: Assemblies via centre-to-centre interactions.

Data availability

The experimental data that support the findings of this study are available within the article, its Supplementary Information files and from the authors upon reasonable request. Raw data that support the findings of this study are publicly available at https://nyu.box.com/v/NM-Regioselective-Depletion.

Code availability

The MATLAB scripts used for the polymorphism analysis are available at https://github.com/VRGParticles/Tunable-Assembly-of-Hybrid-Colloids-NatureMat-2020/ under the GNU GPL-3.0 licence.


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This work was supported through funding from Department of Energy under grant award no. DE-SC0007991. Partial support for the salary of X.Z. from the Donors of the American Chemical Society Petroleum Research Fund under grant number 56280-ND7 is acknowledged. We acknowledge M.D. Ward, D.G. Grier, J. Oh, Z. Gong, M. He, C. Shillingford and R. Rahman for helpful discussions. The Zeiss Merlin field emission SEM was acquired through the support of the NSF under award no. DMR-0923251.

Author information




M.L., X.Z., D.J.P. and M.W. conceived the project. M.L. and X.Z. developed the particle fabrication methods. M.L. performed experiments. V.G. developed the algorithms for image analysis. M.L., X.Z., D.J.P. and M.W analysed the experimental results. M.L., X.Z., V.G., D.J.P. and M.W. discussed the results and wrote the manuscript.

Corresponding author

Correspondence to Marcus Weck.

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Supplementary information

Supplementary Information

Supplementary Video Legends 1–5, Notes 1–3, Figs. 1–15, Tables 1–3 and references.

Supplementary Video 1

Large area observation of polymorphic formation of the brick-wall and herringbone patterns

Supplementary Video 2

Seed 1 formation and growth

Supplementary Video 3

Seed 2 and seed 3 formation and growth

Supplementary Video 4

Super seed formation and growth

Supplementary Video 5

Assembly process of Colloidal membranes

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Liu, M., Zheng, X., Grebe, V. et al. Tunable assembly of hybrid colloids induced by regioselective depletion. Nat. Mater. (2020). https://doi.org/10.1038/s41563-020-0744-2

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