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CALIXARENES
Calixarenes are cyclic oligomers which are formed by the condensation reaction of formaldehyde and para substituted phenol derivatives. It is promising to apply these molecules as active ligands in electrochemical and/or optical sensors (optrodes), since they are capable of binding alkali / alkali earth metal ions or biogene amines, neutral molecules, anions etc. selectively depending on their tailored substituents. The name is derived from the Greek word „calix” meaning vase (or chalice), and arene refers to the aromatic building blocks.
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UV/vis spectroscopy is an excellent tool to determine equililbrium constants when the participating molecules exhibit absorption maxima at different locations. Threfore this method was used to determine equilibrium constants of complex formation of calixarenes having chromogenic or auxochrome substituents [1-6].
FT-IR spectroscopy is a powerful technique to observe chemical structural changes in macrocycles caused by complex formation [7-10]. However, many difficulties occur during the analysis of IR spectra of these molecules since their great size results in very complex vibrational spectra. Because of that the full assignment of the spectra is impossible, however, a tentative assignment can be given by using model compounds. The full assignment of tetrahydroxy-calix[4]arene based on ab initio calculations has recently been presented by Billes and Mohammed-Ziegler [11].
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The complexation of lithium ion by three chromoionophoric calix[4]arenes were studied by H-1 and Li-7 NMR spectroscopy [12].
Most of our results obtained by UV/vis and NMR spectroscopy are summarized in Ref. [13].
Tetraundecyl-calix[4]resorcinarene was found to be able to mimic a natural potassium selective ion channel. In our recent paper [14] the structural properties of this molecule and its interactions with alkali ions were studied by quantum chemical methods.
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We are happy for writing a review on calixarenes entitled "Optical spectroscopy and theoretical studies in calixarene chemistry" [15].
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Selected publications:
1. KUBINYI M., MOHAMMED-ZIEGLER, I., GROFCSIK A., BITTER I., JONES, W. J.: Spectroscopic Study of Complex Formation between Alkali Metal Ions and Chromogenic Calixarene Derivatives, J. Mol. Structure, 408, 543-546 (1997).
2. BITTER I., GRÜN A., TOKE L., BALÁZS B., MOHAMMED-ZIEGLER, I., GROFCSIK A., KUBINYI M.: Novel chromogenic pyridinium derivatives of calix[4]arenes, II., Tetrahedron, 53(49), 16867-16876 (1997).
3. MOHAMMED-ZIEGLER I., KUBINYI M., GROFCSIK A., GRÜN A., BITTER I.: Spectroscopic study of complex formation between aliphatic amines and chromogenic calix[4]arene derivatives, J. Mol. Structure, 480-481, 289-292 (1999).
4. MOHAMMED-ZIEGLER I., POÓR B., KUBINYI M., GROFCSIK A., GRÜN A., BITTER I.: Spectroscopic study of molecular recognition of ions by calix[4]arene derivatives, J. Inclu. Phenomena and Macrocyclic Chem. 35(1), 349-353, (1999).
5. MOHAMMED-ZIEGLER I.: Investigation of the selective complex forming properties of some calix[4]arene derivatives, Magy. Kém. Foly., 107(6), 265-267, JUN (2001) (a Ph. D. értekezés összefoglalása).
6. MOHAMMED-ZIEGLER I., POÓR B., KUBINYI M., GROFCSIK A., GRÜN A., BITTER I.: Spectroscopic study on complex formation of chromogenic bridged calixarenes with aliphatic amines, J. Mol. Structure, 650(1-3), 39-44 (2003).
7. MOHAMMED-ZIEGLER I.: Selective complex formation of some chromogenic calix[4]arene derivatives detected by Fourier transform infrared spectroscopy 1. Solution experiments, Spectrochimica Acta A, 59(1), 19-23 (2003).
8. MOHAMMED-ZIEGLER I.: Selective complex formation of some chromogenic calix[4]arene derivatives detected by Fourier transform infrared spectroscopy 2. Solid experiments, Spectrochimica Acta A, 59(14), 3239-3251 (2003).
9. MOHAMMED-ZIEGLER I., GRÜN A., Complex formation between aliphatic amines and chromogenic calix[4]arene derivatives studied by FT-IR spectroscopy, Spectrochimica Acta A, 62(1-3), 506-517, (2005).
10. MOHAMMED-ZIEGLER I., HAMDI, A., ABIDI, R., VICENS, J.: Selective complex formation of some tetraamido-type calix[4]arene derivatives detected by Fourier transform infrared spectroscopy, Supramolecular Chem. 18(3), 219-234 (2006).
11. BILLES F. and MOHAMMED-ZIEGLER I.: Ab initio equilibrium geometry and vibrational spectroscopic study of 25,26,27,28 -tetrahydroxycalix[4]arene, Supramolecular Chem., 14(5), 451-459 (2002).
12. MOHAMMED-ZIEGLER I., SZÖLLÖSY Á., KUBINYI M., GROFCSIK A., GRÜN A., BITTER I.: 1H and 7Li NMR study of complex formation between lithium cation and some pyridinium derivatives of calix[4]arenes, Supramolecular Chem., 16(6), 415-422 (2004).
13. MOHAMMEDNÉ ZIEGLER I.: Kalix[4]arén-származékok szelektív komplex-képzésének spektroszkópiai vizsgálata, Ph. D. értekezés, Budapesti Muszaki és Gazdaságtudományi Egyetem, Budapest, 2000 / Investigation of the selective complex forming properties of some calix[4]arene derivatives, Ph. D. dissertation, Budapest University of Technology and Economics, Budapest, 2000. (in Hungarian)
14. BILLES F., MOHAMMED-ZIEGLER, I., MIKOSCH, H.: Transportation Behavior of Alkali Ions through a Cell Membrane Ion Channel. A Quantum Chemical Description of a Simplified Isolated Model, J. Mol. Modeling, 18(8), 3627-3637 (2012).
15. MOHAMMED-ZIEGLER I., BILLES F.: Optical spectroscopy and theoretical studies in calixarene chemistry (review), J. Inclu. Phenom. Macrocycl. Chem., 58(1-2), 19-42 (2007).
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For the full list of publications go to :
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