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Regioselective surface encoding of nanoparticles for programmable self-assembly

Nature Materials volume 18, pages 169–174 (2019)Cite this article

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A Publisher Correction to this article was published on 12 December 2018

This article has been updated

Abstract

Surface encoding of colloidal nanoparticles with DNA is fundamental for fields where recognition interaction is required, particularly controllable material self-assembly. However, regioselective surface encoding of nanoparticles is still challenging because of the difficulty associated with breaking the identical chemical environment on nanoparticle surfaces. Here we demonstrate the selective blocking of nanoparticle surfaces with a diblock copolymer (polystyrene-b-polyacrylic acid). By tuning the interfacial free energies of a ternary system involving the nanoparticles, solvent and copolymer, controllable accessibilities to the nanoparticles’ surfaces are obtained. Through the modification of the polymer-free surface region with single-stranded DNA, regioselective and programmable surface encoding is realized. The resultant interparticle binding potential is selective and directional, allowing for an increased degree of complexity of potential self-assemblies. The versatility of this regioselective surface encoding strategy is demonstrated on various nanoparticles of isotropic or anisotropic shape and a total of 24 distinct complex nanoassemblies are fabricated.

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Fig. 1: Directional and programmable encapsulated NPs.
Fig. 2: Fabrication of rseNPs.
Fig. 3: Control of the uncovered area.
Fig. 4: Programmable self-assemblies built from rseNPs.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Change history

  • 12 December 2018

    In the version of this Article originally published, the diblock copolymer structure in Fig. 2a showed a single bond between the carbon and the oxygen atoms; it should have been a double bond. This has been corrected in all versions of the Article.

References

  1. Xia, Y., Xiong, Y., Lim, B. & Skrabalak, S. E. Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? Angew. Chem. Int. Ed. 48, 60–103 (2009).

    Article  CAS  Google Scholar 

  2. Huang, X., Neretina, S. & El-Sayed, M. A. Gold nanorods: from synthesis and properties to biological and biomedical applications. Adv. Mater. 21, 4880–4910 (2009).

    Article  CAS  Google Scholar 

  3. Prodan, E., Radloff, C., Halas, N. J. & Nordlander, P. A hybridization model for the plasmon response of complex nanostructures. Science 302, 419–422 (2003).

    Article  CAS  Google Scholar 

  4. Sun, Y. G. & Xia, Y. N. Shape-controlled synthesis of gold and silver nanoparticles. Science 298, 2176–2179 (2002).

    Article  CAS  Google Scholar 

  5. Xia, Y. N. et al. One-dimensional nanostructures: Synthesis, characterization, and applications. Adv. Mater. 15, 353–389 (2003).

    Article  CAS  Google Scholar 

  6. Langille, M. R., Zhang, J., Personick, M. L., Li, S. & Mirkin, C. A. Stepwise evolution of spherical seeds into 20-fold twinned icosahedra. Science 337, 954–957 (2012).

    Article  CAS  Google Scholar 

  7. Jin, R. C. et al. Controlling anisotropic nanoparticle growth through plasmon excitation. Nature 425, 487–490 (2003).

    Article  CAS  Google Scholar 

  8. Zhu, M., Aikens, C. M., Hollander, F. J., Schatz, G. C. & Jin, R. Correlating the crystal structure of a thiol-protected Au-25 cluster and optical properties. J. Am. Chem. Soc. 130, 5883–5884 (2008).

    Article  CAS  Google Scholar 

  9. Alivisatos, A. P. Semiconductor clusters, nanocrystals, and quantum dots. Science 271, 933–937 (1996).

    Article  CAS  Google Scholar 

  10. Sun, S. H. & Zeng, H. Size-controlled synthesis of magnetite nanoparticles. J. Am. Chem. Soc. 124, 8204–8205 (2002).

    Article  CAS  Google Scholar 

  11. Lee, J.-H., Gibson, K. J., Chen, G. & Weizmann, Y. Bipyramid-templated synthesis of monodisperse anisotropic gold nanocrystals. Nat. Commun. 6, 7571 (2015).

    Article  CAS  Google Scholar 

  12. Nie, Z., Petukhova, A. & Kumacheva, E. Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. Nat. Nanotech. 5, 15–25 (2010).

    Article  CAS  Google Scholar 

  13. Li, F., Josephson, D. P. & Stein, A. Colloidal assembly: the road from particles to colloidal molecules and crystals. Angew. Chem. Int. Ed. 50, 360–388 (2011).

    Article  CAS  Google Scholar 

  14. Kuzyk, A. et al. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 483, 311–314 (2012).

    Article  CAS  Google Scholar 

  15. Park, S. Y. et al. DNA-programmable nanoparticle crystallization. Nature 451, 553–556 (2008).

    Article  CAS  Google Scholar 

  16. Shevchenko, E. V., Talapin, D. V., Kotov, N. A., O’Brien, S. & Murray, C. B. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006).

    Article  CAS  Google Scholar 

  17. Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, 2418–2421 (2002).

    Article  CAS  Google Scholar 

  18. Nykypanchuk, D., Maye, M. M., van der Lelie, D. & Gang, O. DNA-guided crystallization of colloidal nanoparticles. Nature 451, 549–552 (2008).

    Article  CAS  Google Scholar 

  19. Singh, G. et al. Self-assembly of magnetite nanocubes into helical superstructures. Science 345, 1149–1153 (2014).

    Article  CAS  Google Scholar 

  20. Alivisatos, A. P. et al. Organization of ‘nanocrystal molecules’ using DNA. Nature 382, 609–611 (1996).

    Article  CAS  Google Scholar 

  21. Edwardson, T. G. W., Lau, K. L., Bousmail, D., Serpell, C. J. & Sleiman, H. F. Transfer of molecular recognition information from DNA nanostructures to gold nanoparticles. Nat. Chem. 8, 162–170 (2016).

    Article  CAS  Google Scholar 

  22. Xu, X., Rosi, N. L., Wang, Y., Huo, F. & Mirkin, C. A. Asymmetric functionalization of gold nanoparticles with oligonucleotides. J. Am. Chem. Soc. 128, 9286–9287 (2006).

    Article  CAS  Google Scholar 

  23. Liu, W., Halverson, J., Tian, Y., Tkachenko, A. V. & Gang, O. Self-organized architectures from assorted DNA-framed nanoparticles. Nat. Chem. 8, 867–873 (2016).

    Article  CAS  Google Scholar 

  24. Liu, W. et al. Diamond family of nanoparticle superlattices. Science 351, 582–586 (2016).

    Article  CAS  Google Scholar 

  25. Shen, C. et al. Site-specific surface functionalization of gold nanorods using DNA origami clamps. J. Am. Chem. Soc. 138, 1764–1767 (2016).

    Article  CAS  Google Scholar 

  26. Maye, M. M., Nykypanchuk, D., Cuisinier, M., van der Lelie, D. & Gang, O. Stepwise surface encoding for high-throughput assembly of nanoclusters. Nat. Mater. 8, 388–391 (2009).

    Article  CAS  Google Scholar 

  27. Pan, Y., Gao, J. H., Zhang, B., Zhang, X. X. & Xu, B. Colloidosome-based synthesis of a multifunctional nanostructure of silver and hollow iron oxide nanoparticles. Langmuir 26, 4184–4187 (2010).

    Article  CAS  Google Scholar 

  28. Walther, A. & Mueller, A. H. E. Janus particles: synthesis, self-assembly, physical properties, and applications. Chem. Rev. 113, 5194–5261 (2013).

    Article  CAS  Google Scholar 

  29. Chen, Q. et al. Supracolloidal reaction kinetics of Janus spheres. Science 331, 199–202 (2011).

    Article  CAS  Google Scholar 

  30. Xing, H. et al. DNA-directed assembly of asymmetric nanoclusters using Janus nanoparticles. ACS Nano 6, 802–809 (2012).

    Article  CAS  Google Scholar 

  31. Wang, F., Cheng, S., Bao, Z. & Wang, J. Anisotropic overgrowth of metal heterostructures induced by a site-selective silica coating. Angew. Chem. Int. Ed. 52, 10344–10348 (2013).

    Article  CAS  Google Scholar 

  32. Chen, T. et al. Hotspot-induced transformation of surface-enhanced Raman scattering fingerprints. ACS Nano 4, 3087–3094 (2010).

    Article  CAS  Google Scholar 

  33. Li, Y. L., Liu, Z. Y., Yu, G. M., Jiang, W. & Mao, C. D. Self-assembly of molecule-like nanoparticle clusters directed by DNA nanocages. J. Am. Chem. Soc. 137, 4320–4323 (2015).

    Article  CAS  Google Scholar 

  34. Liu, K. et al. Step-growth polymerization of inorganic nanoparticles. Science 329, 197–200 (2010).

    Article  CAS  Google Scholar 

  35. Walker, D. A., Leitsch, E. K., Nap, R. J., Szleifer, I. & Grzybowski, B. A. Geometric curvature controls the chemical patchiness and self-assembly of nanoparticles. Nat. Nanotech. 8, 676–681 (2013).

    Article  CAS  Google Scholar 

  36. Choueiri, R. M. et al. Surface patterning of nanoparticles with polymer patches. Nature 538, 79–83 (2016).

    Article  CAS  Google Scholar 

  37. Chen, T., Yang, M., Wang, X., Tan, L. H. & Chen, H. Controlled assembly of eccentrically encapsulated gold nanoparticles. J. Am. Chem. Soc. 130, 11858–11859 (2008).

    Article  CAS  Google Scholar 

  38. Torza, S. & Mason, S. G. Three-phase interactions in shear and electrical fields. J. Colloid. Interface. Sci. 33, 67–83 (1970).

    Article  CAS  Google Scholar 

  39. Boettcher, M. & McManus, M. T. Choosing the right tool for the job: RNAi, TALEN, or CRISPR. Mol. Cell 58, 575–585 (2015).

    Article  CAS  Google Scholar 

  40. Love, J. C., Estroff, L. A., Kriebel, J. K., Nuzzo, R. G. & Whitesides, G. M. Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem. Rev. 105, 1103–1170 (2005).

    Article  CAS  Google Scholar 

  41. Zhang, L. & Eisenberg, A. Morphogenic effect of added ions on crew-cut aggregates of polystyrene-b-poly(acrylic acid) block copolymers in solutions. Macromolecules 29, 8805–8815 (1996).

    Article  CAS  Google Scholar 

  42. Hurst, S. J., Lytton-Jean, A. K. R. & Mirkin, C. A. Maximizing DNA loading on a range of gold nanoparticle sizes. Anal. Chem. 78, 8313–8318 (2006).

    Article  CAS  Google Scholar 

  43. Yang, M. et al. Mechanistic investigation into the spontaneous linear assembly of gold nanospheres. Phys. Chem. Chem. Phys. 12, 11850–11860 (2010).

    Article  CAS  Google Scholar 

  44. Nikoobakht, B. & El-Sayed, M. A. Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method. Chem. Mater. 15, 1957–1962 (2003).

    Article  CAS  Google Scholar 

  45. Orendorff, C. J. & Murphy, C. J. Quantitation of metal content in the silver-assisted growth of gold nanorods. J. Phys. Chem. B 110, 3990–3994 (2006).

    Article  CAS  Google Scholar 

  46. Scarabelli, L., Coronado-Puchau, M., Giner-Casares, J. J., Langer, J. & Liz-Marzan, L. M. Monodisperse gold nanotriangles: size control, large-scale self-assembly, and performance in surface-enhanced Raman scattering. ACS Nano 8, 5833–5842 (2014).

    Article  CAS  Google Scholar 

  47. Kou, X., Sun, Z., Yang, Z., Chen, H. & Wang, J. Curvature-directed assembly of gold nanocubes, nanobranches, and nanospheres. Langmuir 25, 1692–1698 (2009).

    Article  CAS  Google Scholar 

  48. Park, K., Koerner, H. & Vaia, R. A. Depletion-induced shape and size selection of gold nanoparticles. Nano. Lett. 10, 1433–1439 (2010).

    Article  CAS  Google Scholar 

  49. Chen, H. et al. Plasmon coupling in clusters composed of two-dimensionally ordered gold nanocubes. Small 5, 2111–2119 (2009).

    Article  CAS  Google Scholar 

  50. Asakura, S. & Oosawa, F. On interaction between two bodies immersed in a solution of macromolecules. J. Chem. Phys. 22, 1255–1256 (1954).

    Article  CAS  Google Scholar 

  51. Berr, S. S. Solvent isotope effects on alkyltrimethylammonium bromide micelles as a function of alkyl chain-length. J. Phys. Chem. 91, 4760–4765 (1987).

    Article  CAS  Google Scholar 

  52. Bakshi, M. S. & Kaur, I. Head-group-induced structural micellar transitions in mixed cationic surfactants with identical hydrophobic tails. Colloid Polym. Sci. 281, 10–18 (2003).

    Article  CAS  Google Scholar 

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Acknowledgements

This work is supported by the University of Chicago and the NSF CAREER Award (DMR-1555361) to Y.W. D.L. acknowledges the Martha Ann and Joseph A. Chenicek Graduate Research Fund and HHMI International Student Research Fellowship. This research used resources of the Center for Functional Nanomaterials at Brookhaven National Laboratory, which is supported by US DOE Office of Science Facilities under Contract DE-SC0012704. O.G. gratefully acknowledges the support by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under grant no. DE-SC0008772.

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Author notes

  1. Gang Chen

    Present address: Department of Chemistry, University of Central Florida, Orlando, FL, USA

  2. These authors contributed equally: Gang Chen, Kyle J. Gibson

Authors and Affiliations

  1. Department of Chemistry, The University of Chicago, Chicago, IL, USA

    Gang Chen, Kyle J. Gibson, Di Liu, Huw C. Rees, Jung-Hoon Lee & Yossi Weizmann

  2. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Weiwei Xia, Ruoqian Lin, Huolin L. Xin & Oleg Gang

  3. Department of Chemical Engineering, Columbia University, New York, NY, USA

    Oleg Gang

  4. Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY, USA

    Oleg Gang

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Contributions

G.C. and Y.W. conceived the idea. G.C. and D.L. designed the experiments and developed the methodology. During the revision, H.C.R. and K.J.G. helped with the NP synthesis, K.J.G. performed the polymer encapsulation and self-assemblies, J.-H.L. helped with the microscopy. W.X., R.L. and H.L.X. performed the microscopy for the 3D tomograms. H.L.X. and O.G. analysed the data for the 3D reconstructions. Y.W. supervised the project. G.C., D.L., K.J.G., H.C.R. and Y.W. analysed the data and wrote the paper.

Corresponding author

Correspondence to Yossi Weizmann.

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Supplementary information

Supplementary Information

Supplementary Video Legends 1–6, Supplementary Figures 1–37, Supplementary Tables 1 and 2 and Supplementary References

Supplementary Video 1

3D tomographic reconstruction of v-AuNC partially encapsulated nanostructure

Supplementary Video 2

Full rotation of 3D tomographic reconstruction of c-AuNC self-assembly with AuNS

Supplementary Video 3

Full rotation of 3D tomographic reconstruction of c-AuNC partially encapsulated nanostructure

Supplementary Video 4

Half rotation at slower speed of 3D tomographic reconstruction of c-AuNC partially encapsulated nanostructure

Supplementary Video 5

3D tomographic reconstruction showing detailed surface structure of the c-AuNC through a sliding partition plane

Supplementary Video 6

Full rotation of 3D tomographic reconstruction of c-AuNC self-assembly with AuNS

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Chen, G., Gibson, K.J., Liu, D. et al. Regioselective surface encoding of nanoparticles for programmable self-assembly. Nature Mater 18, 169–174 (2019). https://doi.org/10.1038/s41563-018-0231-1

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