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Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks


The chemical behaviour of molecules can be significantly modified by confinement to volumes comparable to the dimensions of the molecules. Although such confined spaces can be found in various nanostructured materials, such as zeolites, nanoporous organic frameworks and colloidal nanocrystal assemblies, the slow diffusion of molecules in and out of these materials has greatly hampered studying the effect of confinement on their physicochemical properties. Here, we show that this diffusion limitation can be overcome by reversibly creating and destroying confined environments by means of ultraviolet and visible light irradiation. We use colloidal nanocrystals functionalized with light-responsive ligands that readily self-assemble and trap various molecules from the surrounding bulk solution. Once trapped, these molecules can undergo chemical reactions with increased rates and with stereoselectivities significantly different from those in bulk solution. Illumination with visible light disassembles these nanoflasks, releasing the product in solution and thereby establishes a catalytic cycle. These dynamic nanoflasks can be useful for studying chemical reactivities in confined environments and for synthesizing molecules that are otherwise hard to achieve in bulk solution.

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Figure 1: Reversible self-assembly of azobenzene-functionalized nanoparticles and nanoflasks formation.
Figure 2: Trapping of water within self-assembling nanoflasks.
Figure 3: Quantifying and visualizing the trapping process.
Figure 4: Accelerating chemical reactions in dynamically self-assembling nanoflasks.


  1. 1

    Poole, L. B., Karplus, P. A. & Claiborne, A. Protein sulfenic acids in redox signaling. Annu. Rev. Pharmacol. Toxicol. 44, 325–347 (2004).

    CAS  Article  Google Scholar 

  2. 2

    Tripp, B. C., Smith, K. & Ferry, J. G. Carbonic anhydrase: new insights for an ancient enzyme. J. Biol. Chem. 276, 48615–48618 (2001).

    CAS  Article  Google Scholar 

  3. 3

    Forman, H. J. & Fridovic, I. Superoxide dismutase: a comparison of rate constants. Arch. Biochem. Biophys. 158, 396–400 (1973).

    CAS  Article  Google Scholar 

  4. 4

    Hong, Y. J. & Tantillo, D. J. Consequences of conformational preorganization in sesquiterpene biosynthesis: theoretical studies on the formation of the bisabolene, curcumene, acoradiene, zizaene, cedrene, duprezianene, and sesquithuriferol sesquiterpenes. J. Am. Chem. Soc. 131, 7999–8015 (2009).

    CAS  Article  Google Scholar 

  5. 5

    Yasumoto, T. & Murata, M. Marine toxins. Chem. Rev. 93, 1897–1909 (1993).

    CAS  Article  Google Scholar 

  6. 6

    Nissen, P., Hansen, J., Ban, N., Moore, P. B. & Steitz, T. A. The structural basis of ribosome activity in peptide bond synthesis. Science 289, 920–930 (2000).

    CAS  Article  Google Scholar 

  7. 7

    Faivre, D. & Schuler, D. Magnetotactic bacteria and magnetosomes. Chem. Rev. 108, 4875–4898 (2008).

    CAS  Article  Google Scholar 

  8. 8

    Aizenberg, J., Tkachenko, A., Weiner, S., Addadi, L. & Hendler, G. Calcitic microlenses as part of the photoreceptor system in brittlestars. Nature 412, 819–822 (2001).

    CAS  Article  Google Scholar 

  9. 9

    Li, X. Y. & Liu, D. R. DNA-templated organic synthesis: nature's strategy for controlling chemical reactivity applied to synthetic molecules. Angew. Chem. Int. Ed. 43, 4848–4870 (2004).

    CAS  Article  Google Scholar 

  10. 10

    Kanan, M. W., Rozenman, M. M., Sakurai, K., Snyder, T. M. & Liu, D. R. Reaction discovery enabled by DNA-templated synthesis and in vitro selection. Nature 431, 545–549 (2004).

    CAS  Article  Google Scholar 

  11. 11

    Mal, P., Breiner, B., Rissanen, K. & Nitschke, J. R. White phosphorus is air-stable within a self-assembled tetrahedral capsule. Science 324, 1697–1699 (2009).

    CAS  Article  Google Scholar 

  12. 12

    Yoshizawa, M., Kusukawa, T., Fujita, M. & Yamaguchi, K. Ship-in-a-bottle synthesis of otherwise labile cyclic trimers of siloxanes in a self-assembled coordination cage. J. Am. Chem. Soc. 122, 6311–6312 (2000).

    CAS  Article  Google Scholar 

  13. 13

    Yoshizawa, M., Tamura, M. & Fujita, M. Diels–Alder in aqueous molecular hosts: unusual regioselectivity and efficient catalysis. Science 312, 251–254 (2006).

    CAS  Article  Google Scholar 

  14. 14

    Sastre, G. & Corma, A. The confinement effect in zeolites. J. Mol. Catal. A 305, 3–7 (2009).

    CAS  Article  Google Scholar 

  15. 15

    Chu, Y. Y., Han, B., Zheng, A. M. & Deng, F. Influence of acid strength and confinement effect on the ethylene dimerization reaction over solid acid catalysts: a theoretical calculation study. J. Phys. Chem. C 116, 12687–12695 (2012).

    CAS  Article  Google Scholar 

  16. 16

    Kundu, P. K., Olsen, G. L., Kiss, V. & Klajn, R. Nanoporous frameworks exhibiting multiple stimuli responsiveness. Nature Commun. 5, 3588 (2014).

    Article  Google Scholar 

  17. 17

    Wei, Y.-S. et al. Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework. Nature Commun. 6, 8348 (2015).

    CAS  Article  Google Scholar 

  18. 18

    Fallah-Araghi, A. et al. Enhanced chemical synthesis at soft interfaces: a universal reaction–adsorption mechanism in microcompartments. Phys. Rev. Lett. 112, 028301 (2014).

    Article  Google Scholar 

  19. 19

    Yang, D. Y. et al. Enhanced transcription and translation in clay hydrogel and implications for early life evolution. Sci. Rep. 3, 3165 (2013).

    Article  Google Scholar 

  20. 20

    Komisarski, M., Osornio, Y. M., Siegel, J. S. & Landau, E. M. Tailored host–guest lipidic cubic phases: a protocell model exhibiting nucleic acid recognition. Chem. Eur. J. 19, 1262–1267 (2013).

    CAS  Article  Google Scholar 

  21. 21

    Crosby, J. et al. Stabilization and enhanced reactivity of actinorhodin polyketide synthase minimal complex in polymer–nucleotide coacervate droplets. Chem. Commun. 48, 11832–11834 (2012).

    CAS  Article  Google Scholar 

  22. 22

    Shevchenko, E. V., Talapin, D. V., Murray, C. B. & O'Brien, S. Structural characterization of self-assembled multifunctional binary nanoparticle superlattices. J. Am. Chem. Soc. 128, 3620–3637 (2006).

    CAS  Article  Google Scholar 

  23. 23

    Macfarlane, R. J. et al. Nanoparticle superlattice engineering with DNA. Science 334, 204–208 (2011).

    CAS  Article  Google Scholar 

  24. 24

    Sanchez-Iglesias, A. et al. Hydrophobic interactions modulate self-assembly of nanoparticles. ACS Nano 6, 11059–11065 (2012).

    CAS  Article  Google Scholar 

  25. 25

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

    CAS  Article  Google Scholar 

  26. 26

    Kalsin, A. M. et al. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 312, 420–424 (2006).

    CAS  Article  Google Scholar 

  27. 27

    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).

    CAS  Article  Google Scholar 

  28. 28

    Lee, J.-W. & Klajn, R. Dual-responsive nanoparticles that aggregate under the simultaneous action of light and CO2 . Chem. Commun. 51, 2036–2039 (2015).

    CAS  Article  Google Scholar 

  29. 29

    Das, S. et al. Dual-responsive nanoparticles and their self-assembly. Adv. Mater. 25, 422–426 (2013).

    CAS  Article  Google Scholar 

  30. 30

    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).

    CAS  Article  Google Scholar 

  31. 31

    Manna, A. et al. Optimized photoisomerization on gold nanoparticles capped by unsymmetrical azobenzene disulfides. Chem. Mater. 15, 20–28 (2003).

    CAS  Article  Google Scholar 

  32. 32

    Klajn, R., Bishop, K. J. M. & Grzybowski, B. A. Light-controlled self-assembly of reversible and irreversible nanoparticle suprastructures. Proc. Natl Acad. Sci. USA 104, 10305–10309 (2007).

    CAS  Article  Google Scholar 

  33. 33

    Biedermann, F., Uzunova, V. D., Scherman, O. A., Nau, W. M. & De Simone, A. Release of high-energy water as an essential driving force for the high-affinity binding of cucurbit[n]urils. J. Am. Chem. Soc. 134, 15318–15323 (2012).

    CAS  Article  Google Scholar 

  34. 34

    Biedermann, F., Vendruscolo, M., Scherman, O. A., De Simone, A. & Nau, W. M. Cucurbit[8]uril and blue-box: high-energy water release overwhelms electrostatic interactions. J. Am. Chem. Soc. 135, 14879–14888 (2013).

    CAS  Article  Google Scholar 

  35. 35

    Biedermann, F., Nau, W. M. & Schneider, H.-J. The hydrophobic effect revisited—studies with supramolecular complexes imply high-energy water as a noncovalent driving force. Angew. Chem. Int. Ed. 53, 11158–11171 (2014).

    CAS  Article  Google Scholar 

  36. 36

    Grego, A., Muller, A. & Weinstock, I. A. Stepwise-resolved thermodynamics of hydrophobic self-assembly. Angew. Chem. Int. Ed. 52, 8358–8362 (2013).

    CAS  Article  Google Scholar 

  37. 37

    Heaven, M. W., Dass, A., White, P. S., Holt, K. M. & Murray, R. W. Crystal structure of the gold nanoparticle N(C8H17)4Au25(SCH2CH2Ph)18 . J. Am. Chem. Soc. 130, 3754–3755 (2008).

    CAS  Article  Google Scholar 

  38. 38

    Zhu, M., Lanni, E., Garg, N., Bier, M. E. & Jin, R. Kinetically controlled, high-yield synthesis of Au25 clusters. J. Am. Chem. Soc. 130, 1138–1139 (2008).

    CAS  Article  Google Scholar 

  39. 39

    Kondo, M., Takemoto, M., Matsuda, T., Fukae, R. & Kawatsuki, N. Photoinduced change in mechanical properties of anthracene polymers containing flexible side chains. Bull. Chem. Soc. Jpn 83, 1333–1337 (2010).

    CAS  Article  Google Scholar 

  40. 40

    Xu, J. F., Chen, Y. Z., Wu, L. Z., Tung, C. H. & Yang, Q. Z. Dynamic covalent bond based on reversible photo 4+4 cycloaddition of anthracene for construction of double-dynamic polymers. Org. Lett. 15, 6148–6151 (2013).

    CAS  Article  Google Scholar 

  41. 41

    Bouas-Laurent, H., Castellan, A., Desvergne, J. P. & Lapouyade, R. Photodimerization of anthracenes in fluid solution: structural aspects. Chem. Soc. Rev. 29, 43–55 (2000).

    CAS  Article  Google Scholar 

  42. 42

    Jain, P. K., Huang, X. H., El-Sayed, I. H. & El-Sayed, M. A. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine. Acc. Chem. Res. 41, 1578–1586 (2008).

    CAS  Article  Google Scholar 

  43. 43

    Harris, N., Ford, M. J. & Cortie, M. B. Optimization of plasmonic heating by gold nanospheres and nanoshells. J. Phys. Chem. B 110, 10701–10707 (2006).

    CAS  Article  Google Scholar 

  44. 44

    Neumann, O. et al. Solar vapor generation enabled by nanoparticles. ACS Nano 7, 42–49 (2013).

    CAS  Article  Google Scholar 

  45. 45

    Fox, M. A. & Olive, S. Photo-oxidation of anthracene on atmospheric particulate matter. Science 205, 582–583 (1979).

    CAS  Article  Google Scholar 

  46. 46

    Alonso, R., Jimenez, M. C. & Miranda, M. A. Stereodifferentiation in the compartmentalized photooxidation of a protein-bound anthracene. Org. Lett. 13, 3860–3863 (2011).

    CAS  Article  Google Scholar 

  47. 47

    Alonso, R., Yamaji, M., Jimenez, M. C. & Miranda, M. A. Enhanced photostability of the anthracene chromophore in aqueous medium upon protein encapsulation. J. Phys. Chem. B 114, 11363–11369 (2010).

    CAS  Article  Google Scholar 

  48. 48

    Tung, C. H. & Guan, J. Q. Regioselectivity in the photocycloaddition of 9-substituted anthracenes incorporated within nafion membranes. J. Org. Chem. 63, 5857–5862 (1998).

    CAS  Article  Google Scholar 

  49. 49

    Arumugam, S., Vutukuri, D. R., Thayumanavan, S. & Ramamurthy, V. A styrene based water soluble polymer as a reaction medium for photodimerization of aromatic hydrocarbons in water. J. Photochem. Photobiol. A 185, 168–171 (2007).

    CAS  Article  Google Scholar 

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This work was supported by the European Research Council (grant no. 336080; R.K.), the NSF Division of Materials Research (grant no. 1309765; P.K.) and the American Chemical Society Petroleum Research Fund (grant no. 53062-ND6; P.K.). The authors thank R. Neumann and his group for the use of their gas chromatograph and T. Zdobinsky for technical assistance.

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R.K. conceived the project. H.Z., T.U., M.S., K.K., D.M., P.K.K. and J.-W.L. performed the experiments and analysed the data. P.K. and S.S. performed the computer simulations. R.K. wrote the paper.

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Correspondence to Rafal Klajn.

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The authors declare no competing financial interests.

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Zhao, H., Sen, S., Udayabhaskararao, T. et al. Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks. Nature Nanotech 11, 82–88 (2016).

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