Study on Complex Formation of Fluorescein-p-Sulfonatocalix[4]arene by Spectroscopic Methods


The aqueous solution of p-Sulfonatocalix[4]arene-fluorescein complex has been studied based on fluorescence and 1H NMR spectroscopic results. It has been found that the fluorescence intensity quenches regularly upon addition of p-SCX4. The proposed interaction mechanism between p-SCX4 and FL indicates that FL partially goes into the cavity of p-SCX4 with the help of strong electrostatic and π-π* interaction. The quenching constants and stability constants are determined by p-SCX4-FL systems. The proposed inclusion complex is discussed on 1H NMR results. Results are consistent with experimental data obtained from NMR spectroscopy.

Share and Cite:

Gawhale, S. , Thakare, Y. , Malkhede, D. and Chaudhari, G. (2014) Study on Complex Formation of Fluorescein-p-Sulfonatocalix[4]arene by Spectroscopic Methods. Optics and Photonics Journal, 4, 237-245. doi: 10.4236/opj.2014.49024.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Shinkai, S., Araki, K., Mastsuda, T., Nishijama, N., Ikeda, H., Takasuand, I. and Iwamoto, M. (1990) NMR and Crystallographic Studies of a p-Sulfonatocalix[4]arene-Guest Complex. Journal of the American Chemical Society, 112, 9053-9058.
[2] Lakowicz, J.R. (2006) Principles of Fluorescence Spectroscopy. 3rd Edition, Springer, Berlin.
[3] Shinkai, S. (1993) Calixarenes—The Third Generation of Supramolecules. Tetrahydron, 49, 8933-8968.
[4] Alexis, M., Alberto, S., Gerhard, A. and Enrique, M. (2011) Host-Guest Interactions between Calixarenes and Cp2NbCl2. Journal of Organometallic Chemistry, 696, 2419-2527.
[5] Kunsagi-Matea, S., Szabo, K., Lemlia, B., Bitter, I., Nagy, G. and Kollar, L. (2005) Host-Guest Interaction between Water-Soluble Calix[6]arene Hexasulfonate and p-Nitrophenol. Thermochimica Acta, 425, 121-126.
[6] Zhou, Y.Y., Ding, X.P., Fang, X.L., Li, T., Tang, D.B. and Lu, Q. (2011) Studies on the Inclusion Behavior of Amphiphilic p-Sulfonatocalix[4]arene with Ascorbic Acid by Spectrofluorometric Titrations. Optics and Photonic Journal, 1, 59-64.
[7] Zhou, Y.Y., Lu, Q., Liu, C., She, S. and Wang, L. (2006) Study on the Inclusion Behavior of p-Sulphonatocalix[4]arene with 9-Amino-Acridine by Spectrofluorometric Titrations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 63, 423-426.
[8] da Sliva, D.L., do Couto Tavares, E., de Souza Conegero, L., de Fatima, A., Pilli, R.A. and Fernandes, S.A. (2011) NMR Studies of Inclusion Complexation of the Pyrrolizidine Alkaloid Retronecine and p-Sulfonic Acid Calix[6]arene. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 69, 149-155.
[9] Wang, K., Guo, D.S., Zhang, H.Q., Li, D., Zheng, X.L. and Liu, Y. (2009) Highly Effective Binding of Viologens by p-Sulfonatocalixarenes for the Treatment of Viologen Poisoning. Journal of Medicinal Chemistry, 52, 6402-6412.
[10] Mareeswaran, P.M., Babu, E., Sathish, V., Kim, B., Woo, S.I. and Rajagopa, S. (2014) P-Sulfonatocalix[4]arene as a Carrier for Curcumin. New Journal of Chemistry, 38, 1336-1345.
[11] Miskolczy, Z. and Biczok L. (2009) Inclusion Complex Formation of Ionic Liquids with 4-Sulfonatocalixarenes Studied by Competitive Binding of Berberine Alkaloid Fluorescent Probe. Chemical Physics Letters, 477, 80-84.
[12] Liu, Y., Han, B.-H. and Chen, Y.-T. (2002) Molecular Recognition and Complexation Thermodynamics of Dye Guest Molecules by Modified Cyclodextrins and Calixarenesulfonates. The Journal of Physical Chemistry B, 106, 4678-4687.
[13] Liu, Y., Han, B.-H. and Chen, Y.-T. (2000) Inclusion Complexation of Acridine Red Dye by Calixarenesulfonates and Cyclodextrins: Opposite Fluorescent Behavior. The Journal of Organic Chemistry, 65, 6227-6230.
[14] Fei, X.N., Zhang, Y., Zhu, S., Liu, L.J. and Yu, L. (2013) Spectral Study and Protein Labeling of Inclusion Complex between Dye and Calixarene Sulfonate. Applied Spectroscopy, 67, 520-525.
[15] Arena, G., Contino, A., Gulino, F.G., Magri, A., Sciotto, D. and Ungaro, R. (2000) Complexation of Small Neutral Organic Molecules by Water Soluble Calix[4]arenes. Tetrahedron Letters, 41, 9327-9330.
[16] Steed, J.W. and Atwood, J.L. (2009) Supramolecular Chemistry. Wiley Publication, Hoboken.
[17] Sliwa, W. and Kozlowski, C. (2009) Calixarenes and Resorcinarenes. Wiley Publication, Hoboken.
[18] Gutsche, D.C. (2008) Calixarene: An Introduction. Royal Society of Chemistry, London.
[19] Brayant, W.S., Guzei, I.A., Rheigold, A.L., Merola, J.S. and Gibson, H.W. (1998) A Study of the Complexation of Bis(m-Phenylene) Crown Ethers and Secondary Ammonium Ions. The Journal of Organic Chemistry, 63, 7634-7639.
[20] Sahin, O. and Yilmaz, M. (2011) Synthesis and Fluorescence Sensing Properties of Novel Pyrene-Armed Calix[4]- arene Derivatives. Tetrahedron, 67, 3501-3508.
[21] Zhang, Y.L., Pham, T.H., Pena, M.S., Agbaria, R.A. and Warner, I.M. (1998) Spectroscopic Studies of Brilliant Cresyl Blue/Water-Soluble Sulfonated Calix[4]arene Complex. Applied Spectroscopy, 52, 952-957.
[22] Bourson, J. and Valeur, B. (1989) Ion-Responsive Fluorescent Compounds. 2. Cation-Steered Intramolecular Charge Transfer in a Crowned Merocyanine. The Journal of Physical Chemistry, 93, 3871-3876.
[23] Valeur, B. (2001) Molecular Fluorescence Principles and Applications. Wiley-VCH, Weinheim.
[24] Asfari, M.-Z., Bohmer, V., Harrowfield, J. and Jacques, V. (2001) Calixarene 2001. Springer, Berlin.

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.