Abstract
The ability to guide the assembly of nanosized objects reversibly with external stimuli, in particular light, is of fundamental importance, and it contributes to the development of applications as diverse as nanofabrication and controlled drug delivery. However, all the systems described to date are based on nanoparticles (NPs) that are inherently photoresponsive, which makes their preparation cumbersome and can markedly hamper their performance. Here we describe a conceptually new methodology to assemble NPs reversibly using light that does not require the particles to be functionalized with light-responsive ligands. Our strategy is based on the use of a photoswitchable medium that responds to light in such a way that it modulates the interparticle interactions. NP assembly proceeds quantitatively and without apparent fatigue, both in solution and in gels. Exposing the gels to light in a spatially controlled manner allowed us to draw images that spontaneously disappeared after a specific period of time.
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References
Nie, Z. H., Petukhova, A. & Kumacheva, E. Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. Nature Nanotech. 5, 15–25 (2010).
Park, E. J. et al. Using light to covalently immobilize and pattern nanoparticles onto surfaces. Langmuir 28, 10934–10941 (2012).
Pascall, A. J. et al. Light-directed electrophoretic deposition: a new additive manufacturing technique for arbitrarily patterned 3D composites. Adv. Mater. 26, 2252–2256 (2014).
Sun, C., Lee, J. S. H. & Zhang, M. Q. Magnetic nanoparticles in MR imaging and drug delivery. Adv. Drug Deliv. Rev. 60, 1252–1265 (2008).
Chertok, B. et al. Iron oxide nanoparticles as a drug delivery vehicle for MRI monitored magnetic targeting of brain tumors. Biomaterials 29, 487–496 (2008).
Lalatonne, Y., Richardi, J. & Pileni, M. P. Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals. Nature Mater. 3, 121–125 (2004).
Das, S. et al. Dual-responsive nanoparticles and their self-assembly. Adv. Mater. 25, 422–426 (2013).
Singh, G. et al. Self-assembly of magnetite nanocubes into helical superstructures. Science 345, 1149–1153 (2014).
Petit, C., Russier, V. & Pileni, M. P. Effect of the structure of cobalt nanocrystal organization on the collective magnetic properties. J. Phys. Chem. B 107, 10333–10336 (2003).
Li, Y., Zhang, X. L., Qiu, Z. R., Qiao, R. & Kang, Y. S. Investigation of Co nanoparticle assemblies induced by magnetic field. J. Ind. Eng. Chem. 14, 22–27 (2008).
Jang, J. T. et al. Critical enhancements of MRI contrast and hyperthermic effects by dopant-controlled magnetic nanoparticles. Angew. Chem. Int. Ed. 48, 1234–1238 (2009).
Ranganath, K. V. S. & Glorius, F. Superparamagnetic nanoparticles for asymmetric catalysis—a perfect match. Catal. Sci. Tech. 1, 13–22 (2011).
Gawande, M. B., Branco, P. S. & Varma, R. S. Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of sustainable methodologies. Chem. Soc. Rev. 42, 3371–3393 (2013).
Yavuz, C. T. et al. Low-field magnetic separation of monodisperse Fe3O4 nanocrystals. Science 314, 964–967 (2006).
Cho, M. H. et al. A magnetic switch for the control of cell death signalling in in vitro and in vivo systems. Nature Mater. 11, 1038–1043 (2012).
Lee, J. H. et al. Artificial control of cell signaling and growth by magnetic nanoparticles. Angew. Chem. Int. Ed. 49, 5698–5702 (2010).
Yang, Y., Erb, R. M., Wiley, B. J., Zauscher, S. & Yellen, B. B. Imaginary magnetic tweezers for massively parallel surface adhesion spectroscopy. Nano Lett. 11, 1681–1684 (2011).
Demirörs, A. F., Pillai, P. P., Kowalczyk, B. & Grzybowski, B. A. Colloidal assembly directed by virtual magnetic moulds. Nature 503, 99–103 (2013).
Erb, R. M., Son, H. S., Samanta, B., Rotello, V. M. & Yellen, B. B. Magnetic assembly of colloidal superstructures with multipole symmetry. Nature 457, 999–1002 (2009).
He, L. et al. Magnetic assembly of nonmagnetic particles into photonic crystal structures. Nano Lett. 10, 4708–4714 (2010).
He, L., Wang, M. S., Ge, J. P. & Yin, Y. D. Magnetic assembly route to colloidal responsive photonic nanostructures. Acc. Chem. Res. 45, 1431–1440 (2012).
Wei, Y. H., Han, S. B., Kim, J., Soh, S. L. & Grzybowski, B. A. Photoswitchable catalysis mediated by dynamic aggregation of nanoparticles. J. Am. Chem. Soc. 132, 11018–11020 (2010).
Piech, M., George, M. C., Bell, N. S. & Braun, P. V. Patterned colloid assembly by grafted photochromic polymer layers. Langmuir 22, 1379–1382 (2006).
Manna, A. et al. Optimized photoisomerization on gold nanoparticles capped by unsymmetrical azobenzene disulfides. Chem. Mater. 15, 20–28 (2003).
Klajn, R., Wesson, P. J., Bishop, K. J. M. & Grzybowski, B. A. Writing self-erasing images using metastable nanoparticle ‘inks’. Angew. Chem. Int. Ed. 48, 7035–7039 (2009).
Chovnik, O., Balgley, R., Goldman, J. R. & Klajn, R. Dynamically self-assembling carriers enable guiding of diamagnetic particles by weak magnets. J. Am. Chem. Soc. 134, 19564–19567 (2012).
Shiraishi, Y. et al. Spiropyran-modified gold nanoparticles: reversible size control of aggregates by UV and visible light irradiations. ACS Appl. Mater. Interfaces 6, 7554–7562 (2014).
Liu, D. B. et al. Resettable, multi-readout logic gates based on controllably reversible aggregation of gold nanoparticles. Angew. Chem. Int. Ed. 50, 4103–4107 (2011).
Ueda, M., Kim, H. B. & Ichimura, K. Photocontrolled aggregation of colloidal silica. J. Mater. Chem. 4, 883–889 (1994).
Bell, N. S. & Piech, M. Photophysical effects between spirobenzopyran–methyl methacrylate-functionalized colloidal particles. Langmuir 22, 1420–1427 (2006).
Zhang, J., Whitesell, J. K. & Fox, M. A. Photoreactivity of self-assembled monolayers of azobenzene or stilbene derivatives capped on colloidal gold clusters. Chem. Mater. 13, 2323–2331 (2001).
Klajn, R. Immobilized azobenzenes for the construction of photoresponsive materials. Pure Appl. Chem. 82, 2247–2279 (2010).
Satoh, T., Sumaru, K., Takagi, T. & Kanamori, T. Fast-reversible light-driven hydrogels consisting of spirobenzopyran-functionalized poly(N-isopropylacrylamide). Soft Matter 7, 8030–8034 (2011).
Stumpel, J. E., Liu, D. Q., Broer, D. J. & Schenning, A. Photoswitchable hydrogel surface topographies by polymerisation-induced diffusion. Chem. Eur. J. 19, 10922–10927 (2013).
Xie, X. J., Crespo, G. A., Mistlberger, G. & Bakker, E. Photocurrent generation based on a light-driven proton pump in an artificial liquid membrane. Nature Chem. 6, 202–207 (2014).
Florea, L. et al. Photo-chemopropulsion—light-stimulated movement of microdroplets. Adv. Mater. 43, 7339–7345 (2014).
Maity, C., Hendriksen, W. E., van Esch, J. H. & Eelkema, R. Spatial structuring of a supramolecular hydrogel by using a visible-light triggered catalyst. Angew. Chem. Int. Ed. 54, 998–1001 (2015).
Shi, Z., Peng, P., Strohecker, D. & Liao, Y. Long-lived photoacid based upon a photochromic reaction. J. Am. Chem. Soc. 133, 14699–14703 (2011).
Klajn, R. Spiropyran-based dynamic materials. Chem. Soc. Rev. 43, 148–184 (2014).
Fasting, C. et al. Multivalency as a chemical organization and action principle. Angew. Chem. Int. Ed. 51, 10472–10498 (2012).
Lee, J.-W. & Klajn, R. Dual-responsive nanoparticles that aggregate under the simultaneous action of light and CO2 . Chem. Commun. 51, 2036–2039 (2015).
Zheng, Y. B. et al. Surface-enhanced Raman spectroscopy to probe photoreaction pathways and kinetics of isolated reactants on surfaces: flat versus curved substrates. Nano Lett. 12, 5362–5368 (2012).
Zdobinsky, T., Maiti, P. S. & Klajn, R. Support curvature and conformational freedom control chemical reactivity of immobilized species. J. Am. Chem. Soc. 136, 2711–2714 (2014).
Klajn, R. et al. Metal nanoparticles functionalized with molecular and supramolecular switches. J. Am. Chem. Soc. 131, 4233–4235 (2009).
Moldt, T. et al. Tailoring the properties of surface-immobilized azobenzenes by monolayer dilution and surface curvature. Langmuir 31, 1048–1057 (2015).
Wang, D. W. et al. How and why nanoparticle's curvature regulates the apparent pKa of the coating ligands. J. Am. Chem. Soc. 133, 2192–2197 (2011).
Liu, Y. Z., Lin, X. M., Sun, Y. G. & Rajh, T. In situ visualization of self-assembly of charged gold nanoparticles. J. Am. Chem. Soc. 135, 3764–3767 (2013).
Xia, H. B., Su, G. & Wang, D. Y. Size-dependent electrostatic chain growth of pH-sensitive hairy nanoparticles. Angew. Chem. Int. Ed. 52, 3726–3730 (2013).
Onoda, M., Uchiyama, S., Santa, T. & Imai, K. A photoinduced electron-transfer reagent for peroxyacetic acid, 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole, based on the method for predicting the fluorescence quantum yields. Anal. Chem. 74, 4089–4096 (2002).
Narayanan, R. & El-Sayed, M. A. Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability. J. Phys. Chem. B 109, 12663–12676 (2005).
Acknowledgements
This work was supported by the European Research Council (grant number 336080), the Israel Science Foundation (grant number 1463/11) and the Gerhardt Schmidt-Minerva Center on Supramolecular Architectures.
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R.K. conceived and designed the experiments. P.K.K., D.S., R.L., B.M. and M.B. performed the experiments. H.Z., T.U. and D.M. contributed materials and/or analysis tools. R.K. wrote the manuscript. All the authors discussed the results and commented on the manuscript.
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Kundu, P., Samanta, D., Leizrowice, R. et al. Light-controlled self-assembly of non-photoresponsive nanoparticles. Nature Chem 7, 646–652 (2015). https://doi.org/10.1038/nchem.2303
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DOI: https://doi.org/10.1038/nchem.2303
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