Abstract
Fluorescent ß-cyclodextrin vesicles (ß-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 ß-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 ß-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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J. R. Lakowicz, Principles of fluorescence spectroscopy, Springer, New York, 3rd edn, 2006.
A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Signaling recognition events with fluorescent sensors and switches, Chem. Rev., 1997, 97, 1515–1566.
G. A. Caputo, E. London, Using a novel dual fluorescence quenching assay for measurement of tryptophan depth within lipid Bilayers to determine hydrophobic alpha-helix locations within membranes, Biochemistry, 2003, 42, 3265–3274.
F. Mancin, E. Rampazzo, P. Tecilla, U. Tonellato, Self-assembled fluorescent chemosensors, Chem. - Eur. J., 2006, 12, 1844–1854.
G. Ghale, W. M. Nau, Dynamically Analyte-Responsive Macrocyclic Host-Fluorophore Systems, Acc. Chem. Res., 2014, 47, 2150–2159.
T. Pradhan, H. S. Jung, J. H. Jang, T. W. Kim, C. Kang, J. S. Kim, Chemical sensing of neurotransmitters, Chem. Soc. Rev., 2014, 43, 4684–4713.
R. Martinez-Manez, F. Sancenon, Fluorogenic and chromogenic chemosensors and reagents for anions, Chem. Rev., 2003, 103, 4419–4476.
J. Voskuhl, B. J. Ravoo, Molecular recognition of bilayer vesicles, Chem. Soc. Rev., 2009, 38, 495–505.
H. Valkenier, N. Lopez Mora, A. Kros, A. P. Davis, Visualization and quantification of transmembrane ion transport into giant unilamellar vesicles, Angew. Chem., Int. Ed., 2015, 54, 2137–2141.
B. Gruber, B. König, Self-assembled vesicles with functionalized membranes, Chem. - Eur. J., 2013, 19, 438–448.
M. A. Fox and M. Chanon, Photoinduced electron transfer, Part B, Elsevier, Amsterdam, 1988.
B. Armitage, D. F. O’Brien, Lipid Bilayer Enhanced Photoinduced Electron-Transfer, J. Am. Chem. Soc., 1991, 113, 9678–9679.
B. Armitage, D. F. O’Brien, Vectorial Photoinduced Electron-Transfer between Phospholipid Membrane-Bound Donors and Acceptors, J. Am. Chem. Soc., 1992, 114, 7396–7403.
P. J. Clapp, B. Armitage, P. Roosa, D. F. O’Brien, Efficient Photoinduced Orthogonal Energy and Electron-Transfer Reactions Via Phospholipid Membrane-Bound Donors and Accepters, J. Am. Chem. Soc., 1994, 116, 9166–9173.
G. Steinberg-Yfrach, P. A. Liddell, S. C. Hung, A. L. Moore, D. Gust, T. A. Moore, Conversion of light energy to proton potential in liposomes by artificial photosynthetic reaction centres, Nature, 1997, 385, 239–241.
B. Limburg, G. Laisne, E. Bouwman, S. Bonnet, Enhanced Photoinduced Electron Transfer at the Surface of Charged Lipid Bilayers, Chem. - Eur. J., 2014, 20, 8965–8972.
S. Banerjee, B. König, Molecular Imprinting of Luminescent Vesicles, J. Am. Chem. Soc., 2013, 135, 2967–2970.
S. Banerjee, M. Bhuyan, B. König, Tb(iii) functionalized vesicles for phosphate sensing: membrane fluidity controls the sensitivity, Chem. Commun., 2013, 49, 5681–5683.
A. Müller, B. König, Preparation of luminescent chemosensors by post-functionalization of vesicle surfaces, Org. Biomol. Chem., 2015, 13, 1690–1699.
A. P. Blum, J. K. Kammeyer, A. M. Rush, C. E. Callmann, M. E. Hahn, N. C. Gianneschi, Stimuli-Responsive Nanomaterials for Biomedical Applications, J. Am. Chem. Soc., 2015, 137, 2140–2154.
X. Ma, Y. L. Zhao, Biomedical Applications of Supramolecular Systems Based on Host-Guest Interactions, Chem. Rev., 2015, 115, 7794–7839.
Y. Kang, K. Guo, B. J. Li, S. Zhang, Nanoassemblies driven by cyclodextrin-based inclusion complexation, Chem. Commun., 2014, 50, 11083–11092.
E. M. M. Del Valle, Cyclodextrins and their uses: a review, Process Biochem., 2004, 39, 1033–1046.
F. Sallas, R. Darcy, Amphiphilic cyclodextrins - Advances in synthesis and supramolecular chemistry, Eur. J. Org. Chem., 2008, 957–969.
P. Falvey, C. W. Lim, R. Darcy, T. Revermann, U. Karst, M. Giesbers, A. T. M. Marcelis, A. Lazar, A. W. Coleman, D. N. Reinhoudt, B. J. Ravoo, Bilayer vesicles of amphiphilic cyclodextrins: Host membranes that recognize guest molecules, Chem. - Eur. J., 2005, 11, 1171–1180.
J. H. Schenkel, A. Samanta, B. J. Ravoo, Self-Assembly of Soft Hybrid Materials Directed by Light and a Magnetic Field, Adv. Mater., 2014, 26, 1076–1080.
S. K. M. Nalluri, J. B. Bultema, E. J. Boekema, B. J. Ravoo, Photoresponsive Molecular Recognition and Adhesion of Vesicles in a Competitive Ternary Supramolecular System, Chem. - Eur. J., 2011, 17, 10297–10303.
N. Nayak, K. R. Gopidas, Unusual self-assembly of a hydrophilic ß-cyclodextrin inclusion complex into vesicles capable of drug encapsulation and release, J. Mater. Chem. B, 2015, 3, 3425–3428.
C. W. Lim, B. J. Ravoo, D. N. Reinhoudt, Dynamic multivalent recognition of cyclodextrin vesicles, Chem. Commun., 2005, 5627–5629.
M. Trapani, A. Romeo, T. Parisi, M. T. Sciortino, S. Patane, V. Villari, A. Mazzaglia, Supramolecular hybrid assemblies based on gold nanoparticles, amphiphilic cyclodextrin and porphyrins with combined phototherapeutic action, RSC Adv., 2013, 3, 5607–5614.
C. Conte, A. Scala, G. Siracusano, N. Leone, S. Patane, F. Ungaro, A. Miro, M. T. Sciortino, F. Quaglia, A. Mazzaglia, Nanoassembly of an amphiphilic cyclodextrin and Zn(ii)-phthalocyanine with the potential for photodynamic therapy of cancer, RSC Adv., 2014, 4, 43903–43911.
J. Voskuhl, U. Kauscher, M. Gruener, H. Frisch, B. Wibbeling, C. A. Strassert, B. J. Ravoo, A soft supramolecular carrier with enhanced singlet oxygen photosensitizing properties, Soft Matter, 2013, 9, 2453–2457.
N. Kandoth, E. Vittorino, M. T. Sciortino, T. Parisi, I. Colao, A. Mazzaglia, S. Sortino, A Cyclodextrin-Based Nanoassembly with Bimodal Photodynamic Action, Chem. - Eur. J., 2012, 18, 1684–1690.
F. Polo, F. Rizzo, M. Veiga-Gutierrez, L. De Cola, S. Quici, Efficient Greenish Blue Electrochemiluminescence from Fluorene and Spirobifluorene Derivatives, J. Am. Chem. Soc., 2012, 134, 15402–15409.
F. Kamel, Epidemiology. Paths from pesticides to Parkinson’s, Science, 2013, 341, 722–723.
C. M. Tanner, F. Kamel, G. W. Ross, J. A. Hoppin, S. M. Goldman, M. Korell, C. Marras, G. S. Bhudhikanok, M. Kasten, A. R. Chade, K. Comyns, M. B. Richards, C. Meng, B. Priestley, H. H. Fernandez, F. Cambi, D. M. Umbach, A. Blair, D. P. Sandler, J. W. Langston, Rotenone, Paraquat, and Parkinson’s Disease, Environ. Health Perspect., 2011, 119, 866–872.
C. Nistor, A. Oubina, M. P. Marco, D. Barcelo, J. Emneus, Competitive flow immunoassay with fluorescence detection for determination of 4-nitrophenol, Anal. Chim. Acta, 2001, 426, 185–195.
R. Gao, N. Choi, S. I. Chang, S. H. Kang, J. M. Song, S. I. Cho, D. W. Lim, J. Choo, Highly sensitive trace analysis of paraquat using a surface-enhanced Raman scattering microdroplet sensor, Anal. Chim. Acta, 2010, 681, 87–91.
H. Fang, X. Zhang, S. J. Zhang, L. Liu, Y. M. Zhao, H. J. Xu, Ultrasensitive and quantitative detection of paraquat on fruits skins via surface-enhanced Raman spectroscopy, Sens. Actuators, B, 2015, 213, 452–456.
Z. N. Liu, J. G. Du, C. C. Qiu, L. H. Huang, H. Y. Ma, D. Z. Shen, Y. Ding, Electrochemical sensor for detection of p-nitrophenol based on nanoporous gold, Electrochem. Commun., 2009, 11, 1365–1368.
J. H. Ko, J. H. Moon, N. Kang, J. H. Park, H.-W. Shin, N. Park, S. Kang, S. M. Lee, H. J. Kim, T. K. Ahn, J. Y. Lee, S. U. Son, Engineering of Sn-porphyrin networks on the silica surface: sensing of nitrophenols in water, Chem. Commun., 2015, 51, 8781–8784.
F. Guillo, B. Hamelin, L. Jullien, J. Canceill, J. M. Lehn, L. Derobertis, H. Driguez, Synthesis of Symmetrical Cyclodextrin Derivatives Bearing Multiple Charges, Bull. Soc. Chim. Fr., 1995, 132, 857–866.
U. Kauscher, M. C. A. Stuart, P. Drucker, H. J. Galla, B. J. Ravoo, Incorporation of Amphiphilic Cyclodextrins into Liposomes as Artificial Receptor Units, Langmuir, 2013, 29, 7377–7383.
I. Gomezorellana, D. Hallen, The Thermodynamics of the Binding of Benzene to Beta-Cyclodextrin in Aqueous-Solution, Thermochim. Acta, 1993, 221, 183–193.
E. Siimer, M. Kobu, M. Kurvits, Thermochemical Study of Cyclodextrin Inclusion Complexes, Thermochim. Acta, 1990, 170, 89–95.
G. L. Bertrand, J. R. Faulkner, S. M. Han, D. W. Armstrong, Substituent Effects on the Binding of Phenols to Cyclodextrins in Aqueous-Solution, J. Phys. Chem., 1989, 93, 6863–6867.
M. V. Rekharsky, Y. Inoue, Complexation thermodynamics of cyclodextrins, Chem. Rev., 1998, 98, 1875–1917.
B. Valeur, Molecular Fluorescence: Principles and Applications, Wiley-VCH Verlag GmbH, Weinheim, 2001.
E. P. Serjeant and B. Dempsey, Ionisation constants of organic acids in aqueous solution, Pergamon Press, New York, 1979.
A. Credi, L. Prodi, Inner filter effects and other traps in quantitative spectrofluorimetric measurements: Origins and methods of correction, J. Mol. Struct., 2014, 1077, 30–39.
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Schibilla, F., Stegemann, L., Strassert, C.A. et al. Fluorescence quenching in β-cyclodextrin vesicles: membrane confinement and host-guest interactions. Photochem Photobiol Sci 15, 235–243 (2016). https://doi.org/10.1039/c5pp00226e
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DOI: https://doi.org/10.1039/c5pp00226e