390
J Incl Phenom Macrocycl Chem (2010) 67:385–391
References
at room temperature for half an hours. Then poly[(phenyl
glycidyl ether)-co-formaldehyde] was added into reaction
mixture and heated under refluxed for 16 h. The reaction
was checked by TLC. The cooled mixture was filtered and
evaporated. Resulting solid was washed three times with
water. Yield of dark pink colour product comes out
1. Gutsche, C.D.: Calixarenes. The Royal Chemical Society, Cam-
bridge (1989)
2. Vicens, J., Bohmer, V. (eds.): Calixarenes: a versatile class of
macrocyclic compounds. Kluwer, Dordrecht (1986)
´
3. Gomez-Kaifer, M., Reddy, P.A., Gutsche, C.D., Echegoyen, L.:
Elelctroactive calixarenes. 1. Redox and cation binding properties
¨
1
63%; m.p. [350 °C. H-NMR (400 MHz DMSO): d 2.49
of calixquinones. J. Am. Chem. Soc. 116, 3580–3587 (1994)
(s, 6H, –CH3), 3.16–3.63 (br., 59H, –CH2–, –CH–, –OH,
ArCH2Ar, –N–CH2–), 4.23 (d, 4H, J = 19.6 Hz,
ArCH2Ar), 6.33–6.86 (br., 25H, ArH). Anal. Calcd. for
C80H94N2O20; 68.46, C; 6.75, H; 2.00, N. Found: 68.53, C;
6.68, H; 2.06, N.
´
´
4. Stastny, V., Lhotak, P., Michlova, V., Stibor, I., Sykora, J.: Novel
biscalix[4]arene-based anion receptors. Tetrahedron 58, 7207–
7211 (2002)
5. Ikeda, A., Shinkai, S.: Novel cavity design using calix[n]arene
skeletons: toward molecular recognition and metal binding.
Chem. Rev. 97, 1713–1734 (1997)
6. Wong, M.S., Xia, P.F., Lo, P.K., Sun, X.H., Wong, W.Y.,
Shuang, S.M.: Synthesis of oligophenylene-substituted calix[4]
crown-4 s and their silver(I) ion-induced nanocones formation.
J. Org. Chem. 71, 940–946 (2006)
7. Sun, X.H., Li, W., Xia, P.F., Luo, H.-B., Wei, Y., Wong, M.S.,
Cheng, Y.-K., Shuang, S.J.: Phenyl-calix[4]arenebased fluores-
cent sensors: cooperative binding for carboxylates. J. Org.Chem.
72, 2419–2426 (2007)
Sorption procedure
The sorption capacities of the synthesized calix[4]arene
derivative (4) was determined by the following technique
[14]: an aqueous solution (10 mL) containing Na2Cr2O7 or
Na2HAsO4 solution at a concentration of 1.0 9 10-4
M
8. Wong, M.S., Zhang, X.L., Chen, D.Z., Cheng, W.H.: Synthesis
and fluorescence enhancement of oligophenylene-substituted
calix[4]arene assemblies. Chem. Commun. 138–139 (2003)
9. Arnaud-Neu, F., Barrett, G., Harris, S.J., Owens, M., McKervey,
M.A., Schwing-Weill, M.J., Schwinte, P.: Cation complexation
by chemically modified calixarenes. 5. Protonation constants for
calixarene carboxylates and stability constants of their alkali and
alkaline-earth complexes. Inorg. Chem. 32, 2644–2650 (1993)
10. Ghidini, E., Ugozzoli, F., Ungaro, R., Harkema, S., Abu El-Fadl,
A., Reinhoudt, D.N.: Complexation of alkali metal cations by
conformationally rigid, stereoisomeric calix[4]arene crown
ethers: a quantitative evaluation of preorganization. J. Am. Chem.
Soc. 112, 6979–6985 (1990)
11. Shinkai, S., Otsuka, T., Fujimoto, K., Matsuda, T.: Metal selec-
tivity of conformational isomers derived from p-tert-butylca-
lix[4]arene. Chem. Lett. 19, 835–838 (1990)
12. Tuntulani, T., Thavornyutikarn, P., Poompradub, S., Jaiboon, N.,
Ruangpornvisuti, V., Chaichit, N., Asfari, Z., Vicens, J.:
Synthesis of tripodal aza crown ether calix[4]arenes and their
supramolecular chemistry with transition-, alkali metal ions and
anions. Tetrahedron 58, 10277–10285 (2002)
(for dichromate) and 1 9 10-5 (for Na2HAsO4ꢀ7H2O) and
25 mg of the sorbent were mixed in a stoppered flask that
was shaken at 175 rpm, 25 °C for 1 h. The sorbent was
separated before measurements. The residual dichromate
concentration of aqueous solute was determined spectro-
photometrically by UV–vis analyses at 346 nm. The con-
centration of arsenate ion remaining in aqueous phase was
determined by ContrAA 300 spectrometer. The effect of
pH was studied by adjusting the pH of aqueous solutions
using dilute HCl and KOH solutions at 25 °C. The exper-
iments were performed in triplicate.
Blank experiments showed that no dichromate and
arsenate sorption occurred in the absence of calix[4]arene.
The percent sorption (S %) was calculated according to
Eq. 1;
S % ¼ ðC0 ꢁ CÞ=C0 ꢂ 100
ð1Þ
13. Roundhill, D.M., Koch, H.F.: Methods and techniques for the
selective extraction and recovery of oxoanions. Chem. Soc. Rev.
31, 60–67 (2002)
14. Akceylan, E., Yilmaz, M., Bartsch, R.A.: Immobilization of
cyclic alkylamine calix[4]arene derivatives on merrifield resin:
evaluation of extraction ability toward dichromate. J. Macromol.
Sci. Pure Appl. Chem. 43, 477–486 (2006)
where C0 and C are the initial and final concentrations of
the dichromate ion before and after the sorption,
respectively.
Selectivity Studies
15. Memon, S., Tabakci, M., Roundhill, D.M., Yilmaz, M.: Synthesis
and evaluation of the Cr(VI) extraction ability of amino/nitrile
calix[4]arenes immobilized onto a polymeric backbone. React.
Funct. Polym. 66, 1342–1349 (2006)
16. Yilmaz, A., Memon, S., Yilmaz, M.: Synthesis and study of
allosteric effects on extraction behavior of novel calixarene-
based dichromate anion receptors. Tetrahedron 58, 7735–7740
(2002)
17. Tabakci, M., Memon, S., Yilmaz, M., Roundhill, D.M.: Synthesis
and extraction studies of a versatile calix[4]arene-based ‘‘proton-
switchable extractant’’ for toxic metals and dichromate anions.
J.Incl. Phenom. Macrocycl. Chem. 45, 267–270 (2003)
18. Bayrakci, M., Ertul, S., Sahin, O., Yilmaz, M.: Synthesis of two
new p-tert-butylcalix[4]arene b-ketoimin derivatives for
Selectivity studies of 4 were performed in presence of
nitrate (NO3-), sulphate (SO42-) and chloride (Cl-) anions
since they could be present more than dichromate anions in
aqueous solutions. For this propose, anions were used as
corresponded with one hundred-fold of dichromate anion
concentration and determined according to literature [45].
Acknowledgements We would like to thank The Scientific and
Technological Research Council of Turkey (TUBITAK Grant
No. 107T873) and The Research Foundation of Selcuk University
(BAP) for financial support of this work.
123