Abstract
Water-soluble, self-assembled nanocapsules composed of a functional bilayer membrane and enclosed guest molecules can provide smart (that is, condition responsive) sensors for a variety of purposes. Owing to their outstanding optical and redox properties, perylene bisimide chromophores are interesting building blocks for a functional bilayer membrane in a water environment. Here, we report water-soluble perylene bisimide vesicles loaded with bispyrene-based energy donors in their aqueous interior. These loaded vesicles are stabilized by in situ photopolymerization to give nanocapsules that are stable over the entire aqueous pH range. On the basis of pH-tunable spectral overlap of donors and acceptors, the donor-loaded polymerized vesicles display pH-dependent fluorescence resonance energy transfer from the encapsulated donors to the bilayer dye membrane, providing ultrasensitive pH information on their aqueous environment with fluorescence colour changes covering the whole visible light range. At pH 9.0, quite exceptional white fluorescence could be observed for such water-soluble donor-loaded perylene vesicles.
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References
Guo, X. & Szoka, F. C. Chemical approaches to triggerable lipid vesicles for drug and gene delivery. Acc. Chem. Res. 36, 335–341 (2003).
Litvinchuk, S. et al. Synthetic pores with reactive signal amplifiers as artificial tongues. Nature Mater. 6, 576–580 (2007).
Bhosale, S. et al. Photoproduction of proton gradients with II-stacked fluorophore scaffolds in lipid bilayers. Science 313, 84–86 (2006).
Steinberg-Yfrach, G. et al. Conversion of light energy to proton potential in liposomes by artificial photosynthetic reaction centres. Nature 385, 239–241 (1997).
Ringsdorf, H., Schlarb, B. & Venzmer, J. Molecular architecture and function of polymeric oriented systems - models for the study of organization, surface recognition, and dynamics of biomembranes. Angew. Chem. Int. Ed. 27, 113–158 (1988).
Discher, D. E. & Eisenberg, A. Polymer vesicles. Science 297, 967–973 (2002).
Stupp, S. I. et al. Supramolecular materials: self-organized nanostructures. Science 276, 384–389 (1997).
Kunitake, T. Synthetic bilayer-membranes—molecular design, self-organization, and application. Angew. Chem. Int. Ed. 31, 709–726(1992).
Fuhrhop, J. H., Liman, U. & Koesling, V. A macrocyclic tetraether bolaamphiphile and an oligoamino α, ω-dicarboxylate combine to form monolayered, porous vesicle membranes, which are reversibly sealed by EDTA and other bulky anions. J. Am. Chem. Soc. 110, 6840–6845 (1988).
Seo, S. H., Chang, J. Y. & Tew, G. N. Self-assembled vesicles from an amphiphilic ortho- phenylene ethynylene macrocycle. Angew. Chem. Int. Ed. 45, 7526–7530 (2006).
Moon, K. S., Kim, H.-J., Lee, E. & Lee, M. Self-assembly of T-shaped aromatic amphiphiles into stimulus-responsive nanofibers. Angew. Chem. Int. Ed. 46, 6807–6810 (2007).
Schade, B., Ludwig, K., Böttcher, C., Hartnagel, U. & Hirsch, A. Supramolecular structure of 5-nm spherical micelles with D3 symmetry assembled from amphiphilic [3:3]-hexakis adducts of C60. Angew. Chem. Int. Ed. 46, 4393–4396 (2007).
Tanaka, Y., Miyachi, M. & Kobuke, Y. Selective vesicle formation from calixarenes by self-assembly. Angew. Chem. Int. Ed. 38, 504–506 (1999).
Shklyarevskiy, I. O. et al. Magnetic deformation of self-assembled sexithiophene spherical nanocapsules. J. Am. Chem. Soc. 127, 1112–1113 (2005).
Ryu, J.-H., Hong, D.-J. & Lee, M. Aqueous self-assembly of aromatic rod building blocks. Chem. Commun. 1043–1054 (2008).
Vriezema, D. M. et al. Self-assembled nanoreactors. Chem. Rev. 105, 1445–1489 (2005).
Würthner, F. Generating a photocurrent on the nanometer scale. Science, 314, 1693–1694 (2006).
Schryver, F. C. et al. Energy dissipation in multichromophoric single dendrimers. Acc. Chem. Res. 38, 514–522 (2005).
Wasielewski, M. R. Energy, charge, and spin transport in molecules and self-assembled nanostructures inspired by photosynthesis. J. Org. Chem. 71, 5051–5066 (2006).
Schmidt-Mende, L. et al. Self-organized discotic liquid crystals for high-efficiency organic photovoltaics. Science 293, 1119–1122 (2001).
Zhang, X., Chen, Z. & Würthner, F. Morphology control of fluorescent nanoaggregates by co-self-assembly of wedge- and dumbbell-shaped amphiphilic perylene bisimides. J. Am. Chem. Soc. 129, 4886–4887 (2007).
Bigay, J., Gounon, P., Robineau, S. & Antonny, B. Lipid packing sensed by ArfGAP1 couples COPI coat disassembly to membrane bilayer curvature. Nature 426, 563–566 (2003).
Tajima, K. & Aida, T. Controlled polymerizations with constrained geometries. Chem. Commun. 2399–2412 (2000).
Mueller, A. & O'Brien, D. F. Supramolecular materials via polymerization of mesophases of hydrated amphiphiles. Chem. Rev. 102, 727–757 (2002).
Giacomelli, C., Schmidt, V. & Borsali, R. Nanocontainers formed by self-assembly of poly(ethyleneoxide)-b-poly(glycerolmonomethacrylate) drug conjugates. Macromolecules 40, 2148–2157 (2007).
Sauer, M., Streich, D. & Meier, W. pH-Sensitive nanocontainers. Adv. Mater. 13, 1649–1651 (2001).
Lakowicz, J. R. Principles of Fluorescence Spectroscopy (Plenum, 1999).
Riddle, J. A., Jiang, X., Huffman, J. & Lee, D. Signal-amplifying resonance energy transfer: A dynamic multichromophore array for allosteric switching. Angew. Chem. Int. Ed. 46, 7019–7022 (2007).
Sagawa, T., Fukugawa, S., Yamada, T. & Ihara, H. Self-assembled fibrillar networks through highly oriented aggregates of porphyrin and pyrene substituted by dialkyl l-glutamine in organic media. Langmuir 18, 7223–7228 (2002).
Marti, A. A., Jockusch, S., Stevens, N., Ju, J. & Turro, N. J. Fluorescent hybridization probes for sensitive and selective DNA and RNA detection. Acc. Chem. Res. 40, 402–409 (2007).
Shiraishi, Y., Tokitoh, Y. & Hirai, T. pH- and H2O-Driven triple-mode pyrene fluorescence. Org. Lett. 8, 3841–3844 (2006).
Medintz, I. L., Uyeda, H. T., Goldman, E. R. & Mattoussi, H. Quantum dot bioconjugates for imaging, labelling and sensing. Nature Mater. 4, 435–446 (2005).
Ajayaghosh, A., Praveen, V. K., Vijayakumar, C. & George, S. J. Molecular wire encapsulated into pi organogels: efficient supramolecular light-harvesting antennae with colour-tunable emission. Angew. Chem. Int. Ed. 46, 6260–6265 (2007).
Abbel, R. et al. White-light emitting hydrogen-bonded supramolecular copolymers based on pi-conjugated oligomers. J. Am. Chem. Soc. 131, 833–843 (2009).
Acknowledgements
We thank the DFG (grant project: Wu 317/10) and the Alexander von Humboldt Foundation (fellowship for X.Z.) for financial support and Georg Krohne for his help with TEM measurements.
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F.W. conceived and designed the experiments. X.Z., S.R. and M.M.S-S. performed the experiments. X.Z. and F.W. co-wrote the paper.
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Zhang, X., Rehm, S., Safont-Sempere, M. et al. Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems. Nature Chem 1, 623–629 (2009). https://doi.org/10.1038/nchem.368
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DOI: https://doi.org/10.1038/nchem.368
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