Synthesis of a Rhodamine-Appended Cyclophane as a Fluorescence Host in Water


A cationic water-soluble cyclophane (1a) having a rhodamine moiety as a red-fluorescence fluorophore was prepared by reaction of a monoamine derivative of tetraaza[]paracyclophane having three N-t-butoxycarbonyl-β-alanine residues with rhodamine B isothiocyanate, followed by removal of the protecting groups. The guest-binding behavior of 1a toward anionic guests such as dabsyl derivative and 4-(1-pyrene)butanoate was investigated by fluorescence spectroscopy. The results suggested the formation of host-guest complexes with a stoichiometric ratio of 1:1 and the binding constants (K) of the host-guest complexes were evaluated.

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Hayashida, O. and Kaku, Y. (2014) Synthesis of a Rhodamine-Appended Cyclophane as a Fluorescence Host in Water. Advances in Chemical Engineering and Science, 4, 401-408. doi: 10.4236/aces.2014.44044.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Langton, M.J. and Beer, P.D. (2012) Sulfate-Selective Binding and Sensing of a Fluorescent [3]Rotaxane Host System. Chemistry - A European Journal, 18, 14406-14412.
[2] Pagliari, S., Corradini, R., Galaverna, G., Sforza, S., Dossena, A., Montalti, M., Prodi, L., Zaccheroni, N. and Marchelli, R. (2004) Enantioselective Fluorescence Sensing of Amino Acids by Modified Cyclodextrins: Role of the Cavity and Sensing Mechanism. Chemistry - A European Journal, 10, 2749-2758.
[3] Ocak, U., Ocak, M., Surowiec, K., Liu, X. and Bartsch, R.A. (2009) Metal Ion Complexation in Acetonitrile by Upper-Rim Allyl-Substituted, Di-Ionized Calix[4]Arenes Bearing Two Dansyl Fluorophores. Tetrahedron, 65, 7038-7047.
[4] Hayashida, O. and Hamachi, I. (2004) Fluorophore Appended Saccharide Cyclophane: Self-Association, Fluorescent Properties, Heterodimers with Cyclodextrins, and Cross-Linking Behavior with Peanut Agglutinin of Dansyl-Modified Saccharide Cyclophane. The Journal of Organic Chemistry, 69, 3509-3516.
[5] Saha, S., Ravikumar, I. and Ghosh, P. (2011) A Fluorophoric-Axle-Based, Nonfluororescent, Metallo anti-[3]Pseudorotaxane: Recovery of Fluorescence by Means of an Axle Substitution Reaction. Chemistry - A European Journal, 17, 13712-13719.
[6] Odashima, K., Itai, A., Iitaka, Y. and Koga, K. (1985) Biomimetic Studies Using Artificial Systems. 3. Design, Synthesis, And Inclusion Complex Forming Ability of A Novel Water-Soluble Paracyclophane Possessing Diphenylmethane Skeletons. The Journal of Organic Chemistry, 50, 4478-4484.
[7] Hayashida, O., Ogawa, N. and Uchiyama, M. (2007) Surface Recognition and Fluorescence Sensing of Histone by Dansyl-Appended Cyclophane-Based Resorcinarene Trimer. Journal of the American Chemical Society, 129, 13698-13705.
[8] Hayashida, O., Eguchi, C., Kimura, K., Oyama, Y. and Shioji, K. (2010) Guest Binding, Cellular Uptake, and Molecular Delivery of Water-Soluble Cyclophanes Having a Pyrene Moiety. Chemistry Letters, 39, 1321-1322.
[9] Slavik, J. (1982) Anilinonaphthalene Sulfonate as a Probe of Membrane Composition and Function. Biochimica et Biophysica Acta - Reviews on Biomembranes, 694, 1-25.
[10] Patra, D., Ozdemir, F., Miranda, O.R., Samanta, B., Sanyal, A. and Rotello, V.M. (2009) Formation and Size Tuning of Colloidal Microcapsules via Host-Guest Molecular Recognition at the Liquid-Liquid Interface. Langmuir, 25, 13852-13854.
[11] Bindman, N.A. and van der Donk, W.A. (2013) A General Method for Fluorescent Labeling of the N-Termini of Lanthipeptides and Its Application to Visualize Their Cellular Localization. Journal of the American Chemical Society, 135, 10362-10371.
[12] Wu, J., Zou, Y., Li, C., Sicking, W., Piantanida, I., Yi, T. and Schmuck, C. (2012) A Molecular Peptide Beacon for the Ratiometric Sensing of Nucleic Acids. Journal of the American Chemical Society, 134, 1958-1961.
[13] Liu, D., Wang, S., Swierczewska, M., Huang, X., Bhirde, A.A., Sun, J., Wang, Z., Yang, M., Jiang, X. and Chen, X. (2012) Highly Robust, Recyclable Displacement Assay for Mercuric Ions in Aqueous Solutions and Living Cells. ACS Nano, 6, 10999-11008.
[14] Hayashida, O. and Kaku, Y. (2013) Synthesis of Dabsyl-Appended Cyclophanes and Their Heterodimer Formation with Pyrene-Appended Cyclophanes. The Journal of Organic Chemistry, 78, 10437-10442.
[15] Odashima, K., Itai, A., Iitaka, Y., Arata, Y. and Koga, K. (1980) Inclusion Complex Formation in A Particular Geometry by A Water-Soluble Paracyclophane in Aqueous Solution—NMR Studies. Tetrahedron Letters, 21, 4347-4350.
[16] Goncalves, M.S.T. (2009) Fluorescent Labeling of Biomolecules with Organic Probes. Chemical Reviews, 109, 190-212.

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