(274d) Calixarene Based Receptors for Molecules and Ions of Environmental or Bio-Medical Importance

Calixarenes due to their cup-shaped architecture can recognize, selectively bind and separate anions, cations and neutral organic molecules or bio-molecules. This property opens wide perspectives for a practical application of calixarenes in chemistry, physics, biology, material science, nanotechnology. The next results achieved by the IOC NASU organophosphorus chemists will be presented.

Calix[4]arenes functionalized with phosphine oxide groups effectively transport trivalent europium and americium ions from an aqueous HNO3 solution to an organic phase. The increase in Eu3+ and Am3+ distribution coefficients by a factor of up to 200 for the calixarenes comparing to the industrial extractants is observed [1,2]. (Joint project STCU (RUS-09) / ISTC (2068) with the Khlopin Radium Institute and the Nikolaev Institute of Inorganic Chemistry RAN (Russia)).

Calixarene based Electronic Nose is developed for the next purposes: monitoring of hazardous pollutants in environment, quality control in food industry and agriculture, quality control of perfumes and beverages, detection of drugs and explosives in customer service [3-5]. (Joint project with the Institute of Semiconductors Physics NASU).

Calixarenes for nanomedicine application (drug delivery systems, diagnostics, drug design scaffolds) are synthesized. The calixarene-methylene-bis-phosphonic acids synthesized are very efficient phosphatase inhibitors [6]. The calix[4]arenesulfonylamidines influence on Mg2+, ATP-dependent calcium pumps [7]. The effect of the calixarenes on the Ca2+ exchange might be useful for identification of the role of the Mg2+,ATP-dependent Ca2+ pumps of the sarcoplasmic reticulum and plasma membrane in regulation of free Ca2+ concentration in cells. (Joint project with the Institute of Bioorganic and Petrochemistry NASU and the Palladin Institute of Biochemistry NASU).

References

[1] Atamas L., Klimchuk O., Rudzevich V., Pirozhenko V., Kalchenko V., Smirnov I., Babain V., Efremova T., Varnek A., Wipff G., Arnaud-Neu F., Roch M., Saadioui M., Bohmer V. New organophosphorus calix[4]arene ionophores for trivalent lanthanide and actinide cations. J. Supramolecular Chemistry. 2002. 2. 421-427. [2] Klimchik O., Atamas L., Miroshnichenko V., Kalchenko V., Smirnov I., Babain V., Varnek A., Wipff G. New wide rim phosphomethylated calix[4]arenes in extraction of americium and europium. J.Inclusion Phenomena and Macrocyclic Chemistry. 2004. 49. 47?56. [3] Shirshov Y., Snopok B., Rengevich O., Kalchenko V., Coleman A. Relaxation of nanostructured molecular materials under the influence of solvent vapor. In book: Frontiers of multifunctional nanosystems. Eds.: E.Buzaneva, P.Scarf. Kluwer Academic Publishers. The Netherlands. 2002. p.347-368. [4] Kalchenko V.I., KoshetsI.A. Matsas E.P., Kopylov O.N., Solovyov A.V., Kazantseva Z.I., Shirshov Yu.M. Calixarene based QCM sensors array and it's response to volatile organic vapours. Materials Science. 2002. 20. 73-88. [5] Filenko D., Kazantseva Z., Ivanova K., Rabinovych O., Kukla A., Shirshov Yu., Kalchenko V., Rangelow I. Calixarene-coated nanoparticle gold films for chemical recognition system. Proceedings of the IEEE Sensors 2004 Conference, Vienna, Austria, October 24-27, 2004, pp. 669-672. [6] Vovk A.I., Kalchenko V.I., Cherenok S.O. Kukhar V.P., Muzychka O.V., Lozynsky M.O. Calix[4]arene methylenebisphopshonic acids as calf intestine phosphatase inhibitors. Org. Biomol. Chem. 2004. 2. 3162-3166. [7] Rodik R., Boiko V., Danylyuk O., Suwinska K., Tsymbal I., Slinchenko N., Babich L., Shlykov S., Kosterin S., Lipkowski J., Kalchenko V. Calix[4]arenesulfonylamidines. Synthesis, structure and influence on Mg2+,ATP-dependent calcium pumps. Tetrahedron Letters. Submitted.