Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems

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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Figure 1: Formation of donor-loaded perylene bisimide vesicles in aqueous solution by changes in spontaneous curvatures.
Figure 2: Preparation procedures and morphologies of unloaded and loaded perylene bisimide vesicles, and donor-loaded polymerized perylene bisimide vesicles.
Figure 3: Spectral overlap of bispyrene-based donors and bilayer perylene bisimide membrane as acceptor at different pH.
Figure 4: pH-dependent energy transfer from encapsulated donors to bilayer perylene membrane acceptor for donor-loaded polymerized vesicles.
Figure 5: Time-resolved fluorescence spectra of donor-loaded polymerized vesicles in aqueous solution.

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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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Correspondence to Frank Würthner.

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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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