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Electrostatic assembly of binary nanoparticle superlattices using protein cages

Nature Nanotechnology volume 8, pages 52–56 (2013)Cite this article

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Abstract

Binary nanoparticle superlattices are periodic nanostructures with lattice constants much shorter than the wavelength of light1,2 and could be used to prepare multifunctional metamaterials3,4. Such superlattices are typically made from synthetic nanoparticles5,6,7,8, and although biohybrid structures have been developed9,10,11,12,13,14,15, incorporating biological building blocks into binary nanoparticle superlattices remains challenging16,17,18. Protein-based nanocages provide a complex yet monodisperse and geometrically well-defined hollow cage that can be used to encapsulate different materials19,20. Such protein cages have been used to program the self-assembly of encapsulated materials to form free-standing crystals21,22 and superlattices at interfaces21,23 or in solution24,25. Here, we show that electrostatically patchy protein cages—cowpea chlorotic mottle virus and ferritin cages—can be used to direct the self-assembly of three-dimensional binary superlattices. The negatively charged cages can encapsulate RNA or superparamagnetic iron oxide nanoparticles, and the superlattices are formed through tunable electrostatic interactions with positively charged gold nanoparticles. Gold nanoparticles and viruses form an AB8fcc crystal structure that is not isostructural with any known atomic or molecular crystal structure and has previously been observed only with large colloidal polymer particles26. Gold nanoparticles and empty or nanoparticle-loaded ferritin cages form an interpenetrating simple cubic AB structure (isostructural with CsCl). We also show that these magnetic assemblies provide contrast enhancement in magnetic resonance imaging.

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Figure 1: Materials used for the assembly of binary protein cage–nanoparticle superlattices.
Figure 2: Self-assembly of three-dimensional binary CCMV–AuNP superlattices.
Figure 3: TEM characterization of the AB8fcc-type (CCMV–AuNP8)fcc superlattice.
Figure 4: Characterization of ABsc-type (aFT–AuNP)sc and (MF–AuNP)sc superlattices.

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Acknowledgements

This work was supported by the Academy of Finland (project 13137582), the Emil Aaltonen Foundation and an Aalto Starting Grant. P.C. thanks the Associazione Italiana per la Ricerca sul Cancro for funding (grant agreement MFAG10545) and the Italian Ministry of Economy and Finance for funding the Project ‘FaReBio di Qualità’. This work made use of the Aalto University Nanomicroscopy Center (Aalto-NMC) premises. The authors thank J. van Lierop, O. Kasyutich, R. Nolte, J. Cornelissen, R. Sepponen, T. Lahtinen and S. van Dijken for discussions and support, and A. Nykänen for TEM support.

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Authors and Affiliations

  1. Department of Applied Physics, Molecular Materials, Aalto University, Espoo, 00076, Finland

    Mauri A. Kostiainen, Panu Hiekkataipale, Jani Seitsonen & Janne Ruokolainen

  2. Advanced Magnetic Imaging Centre, O.V. Lounasmaa Laboratory, School of Science, Aalto University, Espoo, 00076, Finland

    Ari Laiho

  3. St-Jean-Photochimie (SJPC), 725 Trotter Street, Saint-Jean-sur-Richelieu, Quebec, J3B 8J8, Canada

    Vincent Lemieux

  4. National Research Council of Italy (CNR), Institute of Molecular Biology and Pathology, Rome, 00185, Italy

    Pierpaolo Ceci

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  1. Mauri A. Kostiainen
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Contributions

M.A.K. conceived the study and, together with P.H. and A.L., designed the experiments. P.H. contributed to SAXS measurements and cryo-ET data analysis. A.L. performed MRI measurements and data analysis. V.L. synthesized gold nanoparticles. J.S. and J.R. operated the TEM. P.C. prepared cationized magnetoferritin. M.A.K. performed all other experiments and wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Mauri A. Kostiainen.

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Kostiainen, M., Hiekkataipale, P., Laiho, A. et al. Electrostatic assembly of binary nanoparticle superlattices using protein cages. Nature Nanotech 8, 52–56 (2013). https://doi.org/10.1038/nnano.2012.220

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