We report the inclusion of carboxy- and amine-substituted molecular nanodiamonds (NDs) adamantane, diamantane, and triamantane by β-cyclodextrin and γ-cyclodextrin (β-CD and γ-CD), which have particularly well-suited hydrophobicity and symmetry for an optimal fit of the host and guest molecules. We studied the host-guest interactions in detail and generally observed 1:1 association of the NDs with the larger γ-CD cavity, but observed 1:2 association for the largest ND in the series (triamantane) with β-CD. We found higher binding affinities for carboxy-substituted NDs than for amine-substituted NDs. Additionally, cyclodextrin vesicles (CDVs) were decorated with d-mannose by using adamantane, diamantane, and triamantane as non-covalent anchors, and the resulting vesicles were compared with the lectin concanavalin A in agglutination experiments. Agglutination was directly correlated to the host-guest association: adamantane showed lower agglutination than di- or triamantane with β-CDV and almost no agglutination with γ-CDV, whereas high agglutination was observed for di- and triamantane with γ-CDV.
Fluorescent β-cyclodextrin vesicles (β-CDV) that display host cavities available for host-guest interactions at the vesicle surface were prepared by incorporation of the hydrophobic spirobifluorene-based dye 1 into the membrane of unilamellar vesicles. Fluorescence quenching of dye 1 was observed in the presence of different quenchers. Methyl viologen 2 does not quench dye 1 because it does not bind to β-CDV. 4-Nitrophenol 3 and 4-nitrophenol covalently connected to adamantane 4 quench the fluorescence of dye 1 in neutral solution, but by different mechanisms according to lifetime measurements. The quenching efficiency of 3 is pH dependent due to the presence of the phenolate form. Competition experiments with excess host and guest showed that 3 is likely to diffuse in and out of the membrane, while 4 forms an inclusion complex with β-CDV leading to close contact and efficient quenching. Our findings confirm that this dynamic supramolecular system is a versatile model to investigate quenching and recognition processes in bilayer membranes.
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