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Colloids with valence and specific directional bonding

Abstract

The ability to design and assemble three-dimensional structures from colloidal particles is limited by the absence of specific directional bonds. As a result, complex or low-coordination structures, common in atomic and molecular systems, are rare in the colloidal domain. Here we demonstrate a general method for creating the colloidal analogues of atoms with valence: colloidal particles with chemically distinct surface patches that imitate hybridized atomic orbitals, including sp, sp2, sp3, sp3d, sp3d2 and sp3d3. Functionalized with DNA with single-stranded sticky ends, patches on different particles can form highly directional bonds through programmable, specific and reversible DNA hybridization. These features allow the particles to self-assemble into ‘colloidal molecules’ with triangular, tetrahedral and other bonding symmetries, and should also give access to a rich variety of new microstructured colloidal materials.

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Figure 1: DNA patchy particle fabrication.
Figure 2: Control of patch size.
Figure 3: Specific directional bonding between colloidal atoms observed with optical microscopes.
Figure 4: Step-wise sequential kinetics of supracolloidal reactions.

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Acknowledgements

We thank M. T. Elsesser, D. Kraft, and G.-R. Yi for discussions. This work was supported partially by the MRSEC Program of the National Science Foundation under award number DMR-0820341. Additional financial support was provided by the National Science Foundation (ChE-0911460). We acknowledge support from the MRI programme of the National Science Foundation under award number DMR-0923251 for the purchase of a Zeiss field emission scanning electron microscope.

Author information

Authors and Affiliations

Authors

Contributions

V.N.M. and D.J.P. thought of patchy particles and how to make them. D.R.B. developed the functionalization of patches. Yufeng Wang and Yu Wang optimized the control of patch size and DNA functionalization, performed the experiments, and collected and analysed the data. A.D.H. helped with particle synthesis. L.F. designed the DNA sequences and modelled the kinetics. M.W. and D.J.P. supervised the project. D.J.P., Yufeng Wang and Yu Wang wrote the paper with revisions from all of the authors.

Corresponding authors

Correspondence to Marcus Weck or David J. Pine.

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Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Figures 1-5, Supplementary Equation 1 and Supplementary Table 1. (PDF 8222 kb)

ABn colloidal molecules

A collection of ABn (n=1-4) colloidal molecules assembled from monovalent, divalent, trivalent or tetravalent particles at the central position. Particles were suspended in an aqueous PBS buffer solution (pH=7.4) containing surfactant (1% w/w Pluronic F127). The system had been stabilized for a few hours at 25˚C and the video was taken at 25˚C. The video is acquired and displayed at real time. Scale bar, 2 μm. (MOV 2646 kb)

Kinetics of AB4 colloidal molecule formation

Starting from a bare tetravalent particle, the kinetics is followed as four monovalent particles are assembled onto the tetravalent particle successively. The time intervals between each set of clips are indicated below the videos. Particles were suspended in an aqueous PBS buffer solution (pH=7.4) containing surfactant (1% w/w Pluronic F127). The video was taken at 25˚C, immediately after a rapid quench from 55˚C. The video is acquired at 24 fr/s and played at a rate shown in the upper left corner. Scale bar, 3 μm. (MOV 8191 kb)

Polymerization kinetics of the assembly of complementary divalent particles

A linear polymer chain starts from a divalent particle, which picks up other single divalent particles sequentially. Particles were suspended in an aqueous PBS buffer solution (pH=7.4) containing surfactant (1% w/w Pluronic F127). The video was taken at 25˚C, immediately after a rapid quench from 55˚C. The video is acquired at 10 fr/s and played at a rate indicated in the lower left corner. Scale bar, 2 μm. (MOV 7971 kb)

Kinetics of AB3 colloidal molecule formation

Trivalent particles act as central atoms, picking up monovalent particles one at a time. Most trivalent particles assemble a monovalent particle before the first trivalent particles pick up a second monovalent one. The same is true for the next assembly step. Only after most trivalent particles have acquired two monovalent particles do third particles begin to attach. Particles were suspended in an aqueous PBS buffer solution (pH=7.4) containing surfactant (1% w/w Pluronic F127). The video was taken at 25˚C, immediately after a rapid quench from 55˚C. The video is acquired at 24 fr/s and played at a rate indicated in the lower left corner. Scale bar, 3 μm. (MOV 14804 kb)

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Wang, Y., Wang, Y., Breed, D. et al. Colloids with valence and specific directional bonding. Nature 491, 51–55 (2012). https://doi.org/10.1038/nature11564

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