Nano-baskets of Calix[4]-1,3-crown in Emulsion Membranes for Selective Extraction of Alkali Metal Cations

doi:10.1016/S1004-9541(13)60628-X

摘要/Abstract

摘要： Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (4.4%, by mass) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 mol·L^-1) and ammonium carbonate (0.4 mol·L^-1) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 r·min^-1), and initial solute concentration (100 mg·L^-1). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.

关键词: nano-basket, inclusion, calixcrown, emulsion liquid membrane, alkali metals

Abstract: Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (4.4%, by mass) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 mol·L^-1) and ammonium carbonate (0.4 mol·L^-1) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 r·min^-1), and initial solute concentration (100 mg·L^-1). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.

Key words: nano-basket, inclusion, calixcrown, emulsion liquid membrane, alkali metals

Bahram Mokhtari, Kobra Pourabdollah. Nano-baskets of Calix[4]-1,3-crown in Emulsion Membranes for Selective Extraction of Alkali Metal Cations[J]. Chinese Journal of Chemical Engineering, 2013, 21(11): 1313-1318.

Bahram Mokhtari, Kobra Pourabdollah. Nano-baskets of Calix[4]-1,3-crown in Emulsion Membranes for Selective Extraction of Alkali Metal Cations[J]. Chin.J.Chem.Eng., 2013, 21(11): 1313-1318.

参考文献

1 Li, N.N., “Separating hydrocarbons with liquid membranes”, U.S. Pat., 3410794 (1968).

2 Kumbasar, R.A., Sahin, I., “Separation and concentration of cobalt from ammoniacal solutions containing cobalt and nickel by emulsion liquid membranes using 5,7-dibromo-8-hydroxyquinoline (DBHQ)”, J. Membr. Sci., 164, 712-718 (2008).

3 Correia, P.F., de Carvalho, J.M.R., “Recovery of phenol from phenolic resin plant effluents by emulsion liquid membranes”, J. Membr. Sci., 225, 41-49 (2003).

4 Frankenfeld, J.W., Chan, R.P., Li, N.N., “Extraction of copper by liquid membranes”, Sep. Sci. Technol., 16, 385-402 (1981).

5 Hou, W., Papadopoulos, K.D., “Stability of water-in-oil-in-water type globules”, Chem. Eng. Sci., 51 (22), 5043-5051 (1996).

6 Mokhtari, B., Pourabdollah, K., “Effect of crown size and upper moieties in nano-baskets of diacid calix[4]arene-1,2-crowns-3,4,5,6 on the extraction of s-block metals”, J. Coord. Chem., 64 (17), 3081-3091 (2011).

7 Mokhtari, B., Pourabdollah, K., Dalali, N., “Applications of nano-baskets of calixarenes in chromatography”, Chromatographia, 73, 829-847 (2011).

8 Mokhtari, B., Pourabdollah, K., “Medical applications of nano-baskets”, J. Coord. Chem., 64 (18), 3189-3204 (2011).

9 Mokhtari, B., Pourabdollah, K., Dalali, N., “Analytical applications of calixarenes from 2005 up-to-date”, J. Incl. Phenom. Macrocycl. Chem., 69, 1-55 (2011).

10 Baeyer, A., “Ueber die verbindungen der aldehyde mit den phenolen”, Chem. Ber., 5 (1), 280-282 (1872).

11 Zinke, A., Ziegler, E., “Zur kenntnis des härtungsprozesses von phenol- formaldehyd-harzen, X. mitteilung”, Chem. Ber., 77, 264-272 (1944).

12 Gutsche, C.D., Muthukrishnan, R., “Calixarenes. 1. Analysis of the product mixtures by the bas-catalyzed condensation of formaldehyde with para-substituted phenols”, J. Org. Chem., 43 (25), 4905-4936 (1978).

13 Chen, X., Ji, M., Fisher, D.R., Wai, C.M., “Ionizable calixarene-crown ethers with high selectivity for radium over light alkaline earth metal ions”, Inorg. Chem., 38 (23), 5449-5452 (1999).

14 Wang, S., Elshani, S., Wai, C.M., “Selective extraction of mercury with ionizable crown ethers in supercritical carbon dioxide”, Anal. Chem., 67 (5), 919-923 (1995).

15 Kim, J.S., Shon, O.J., Ko, J.W., Cho, M.H., Yu, I.Y., Vicens, J., “Synthesis and metal ion complexation studies of proton-ionizable calix[4]azacrown ethers in the 1,3-alternate conformation”, J. Org. Chem., 65 (8), 2386-2392 (2000).

16 Talanov, V.S., Roper, E.D., Buie, N.M., Talanova, G.G., “A new fluorogenic mono-ionizable calix[4]arene dansylcarboxamide as a selective chemosensor of soft metal ions, Tl⁺ and Hg²⁺”, Tetrahedron Lett., 48 (45), 8022-8025 (2007).

17 Li, J., Zhong, Z., Chen, Y., Lu, X., “A novel type of double-calixcrown: Spirobiscalix[4]crowns”, Tetrahedron Lett., 39 (36), 6507-6510 (1998).

18 Mohapatra, P.K., Ansari, S.A., Sarkar, A., Bhattacharyya, A., Manchanda, V.K., “Evaluation of calix-crown ionophores for selective separation of radio-cesium from acidic nuclear waste solution”, Anal. Chim. Acta, 571 (2), 308-314 (2006).

19 Mokhtari, B., Pourabdollah, K., Dallali, N., “A review of calixarene applications in nuclear industries”, J. Radioanal. Nucl. Chem., 287 (3), 92-934 (2011).

20 Mokhtari, B., Pourabdollah, K., Dalali, N., “Molecule and ion recognition of nano-baskets of calixarenes since 2005”, J. Coord. Chem., 64 (5), 743-794 (2011).

21 Mokhtari, B., Pourabdollah, K., “Solvent extraction of alkali metals by di-ionizable nano-baskets”, J. Coord. Chem., 64 (23), 4029-4053 (2011).

22 Mokhtari, B., Pourabdollah, K., “Binding mechanisms of nano-baskets towards alkali metals. Isothermal titration calorimetric study”, J. Therm. Anal. Calorim., 110 (3), 1043-1051 (2012).

23 Mokhtari, B., Pourabdollah, K., “Extraction of s-block metals by nano- baskets of calix[4]crown-3”, Can. J. Chem., 90 (6), 560-566 (2012).

24 Mokhtari, B., Pourabdollah, K., “Structure optimization of di-ionizable calixarene nano-baskets for competitive solvent extraction of alkali and alkaline earth metals”, B. Korean Chem. Soc., 32 (11), 3855-3860 (2011).

25 Mokhtari, B., Pourabdollah, K., “Effect of crown ring size and upper moiety on the extraction of s-block metals by ionizable calixcrown nano-baskets”, Bull. Korean Chem. Soc., 32 (11), 3979-3990 (2011).

26 Mokhtari, B., Pourabdollah, K., “Binding and extraction of alkali and alkaline earth metals by nano-baskets of calix[4]arene-1,2-crown-3 conformers”, J. Inclu. Phenom. Macrocycl. Chem., 73, 269-277 (2012).

27 Mokhtari, B., Pourabdollah, K., “Competitive solvent extraction of alkaline earth metals by ionizable nano-baskets of calixarene”, Supramol. Chem., 23 (10), 696-702 (2011).

28 Mokhtari, B., Pourabdollah, K., “Extraction of vanadyl porphyrins in crude oil by inclusion dispersive liquid-liquid microextraction and nano-baskets of calixarene”, J. Inclu. Phenom. Macrocycl. Chem., 74, 183-189 (2012).

29 Mokhtari, B., Pourabdollah, K., “Dispersive enhancement in liquid-liquid microextraction by dual supramolecular role of nano-baskets”, Supramol. Chem., 24 (4), 255-263 (2012).

30 Mokhtari, B., Pourabdollah, K., “Metabolic fingerprints by nano-baskets of 1,2-alternate calixarene and emulsion liquid membranes”, B. Korean Chem. Soc., 33 (7), 2320-2324 (2012).

31 Mokhtari, B., Pourabdollah, K., “Application of nano-baskets in metabolomics”, J. Inclu. Phenom. Macrocycl. Chem., DOI: 10.1007/s10847-012-0233-6 (2012). (in press)

32 Mokhtari, B., Pourabdollah, K., “Applications of calixarene nano-baskets in pharmacology”, J. Inclu. Phenom. Macrocycl. Chem., 73, 1-15 (2012).

33 Mokhtari, B., Pourabdollah, K., “Applications of nano-baskets in drug development: high solubility and low toxicity”, Drug Chem. Toxicol., 36 (1), 119-132 (2013).

34 Mokhtari, B., Pourabdollah, K., “Preparation and characterization of bonded-phases of calixarene-sulfonyl-carboxamides in partial-cone conformation for determination of salbutamol in livestock by nano- mediated bonded-phases: Nano-baskets of calixarene in partial-cone conformation”, J. Chilean Chem. Soc., 57 (2), 1150-1154 (2012).

35 Mokhtari, B., Pourabdollah, K., “Chromatographic separation of clenbuterol by bonded-phases bearing nano-baskets of p-tert-calix[4]-1,2-crown-3; -crown-4; -crown-5; and -crown-6”, J. Sci. Food Agricult., 92 (13), 2679-2688 (2012).

36 Mokhtari, B., Pourabdollah, K., “Preparation and characterization of bonded-phases of nano-baskets bearing sulfonyl-carboxamide”, J. Liq. Chromatogr. Related Technol., DOI: 10.1080/10826076.2011.643524 (2012). (in press)

37 Mokhtari, B., Pourabdollah, K., “Separation and preconcentration of 2,3,7,8-tetrachlorodibenzo-p-dioxin in blood samples by inclusion emulsion membranes and its determination by gas chromatography”, Talanta, 100, 349-355 (2012).

38 Mokhtari, B., Pourabdollah, K., “Investigation of ionizable nano-baskets of calix[4]-1,2-crown-3 by differential pulse voltammetry”, J. Coord. Chem., 64 (23), 4079-4087 (2011).

39 Mokhtari, B., Pourabdollah, K., “Binding survey of ionizable calix[4]-1,2-crown-3 nano-baskets by differential pulse voltammetry”, Electroanalysis, 24 (2), 219-223 (2012).

40 Mokhtari, B., Pourabdollah, K., “Voltammetric study of nano-baskets of calix[4]-1,3-crowns-5, -crowns-6 complexes”, Electrochim. Acta, 76, 363-367 (2012).

41 Mokhtari, B., Pourabdollah, K., “Electrochemical study of structural effects in complexation of nano-baskets: Calix[4]-1,2-crown-3, -crown-4, -crown-5, -crown-6”, Synth. React. Inorg. Org., 42 (8), 1091-1097 (2012).

42 Mokhtari, B., Pourabdollah, K., “Electrochemical investigation of nano-baskets of calix[4]-1,3-crowns-5,6 complexes”, J. Inclu. Phenom. Macrocycl. Chem., 76, 385-390 (2013).

43 Li, H., Zhang, Y., Wang, X., Xiong, D., Bai, Y., “Calixarene capped quantum dots as luminescent probes for Hg²⁺ ions”, Mater. Lett., 61 (7), 1474-1477 (2007).

44 Mokhtari, B., Pourabdollah, K., “Advances in binding ability and extractive applications of nano-baskets of calixarene”, Asian J. Chem., 23 (11), 4717-4734 (2011).

45 Ersoz, M., “Transport of mercury through liquid membranes containing calixarene carriers”, Adv. Colloid Interface Sci., 134-135, 96-104 (2007).

46 Ding, C., Qu, K., Li, Y., Hu, K., Liu, H., Ye, B., Wu, Y., Zhang, S., “Preparation and characterization of six calixarene bonded stationary phases for high performance liquid chromatography”, J. Chromatogr. A, 1170, 73-81 (2007).

47 Cornforth, J.W., Hart, P.D., Nicholls, G.A., Rees, R.J., Stock, J.A., “Antituberculous effects of certain surface-active polyoxyethylene ethers”, Br. J. Pharmacol. Chemother., 10 (1), 73-88 (1955).

48 Rodik, R.V., Boyko, V.I., Kalchenko, V.I., “Calixarenes in bio-medical researches”, Curr. Med. Chem., 16 (13), 1630-1655 (2009).

49 Fatima, A., Fernandes, S.A., Sabino, A.A., “Calixarenes as new platforms for drug design”, Curr. Drug Discov. Technol., 6 (2), 151-170 (2009).

50 Mokhtari, B., Pourabdollah, K., “Binding study of ionizable calix[4]-1,3-crowns-5,6 nano-baskets by differential pulse voltammetry”, J. Electrochem. Soc., 159 (3), K61-K65 (2012).

51 Walkowiak, W., Charewicz, W.A., Kang, S.I., Yang, I.W., Pugia, M.J., Bartsch, R.A., “Effect of structural variations within lipophilic dibenzocrown ether carboxylic acids on the selectivity and efficiency of competitive alkali-metal cation solvent extraction into chloroform”, Anal. Chem., 62 (18), 2018-2021 (1990).

52 Bartsch, R.A., Czech, B.P., Kang, S.I., Stewart, L.E., Walkowiak, W., Charewicz, W.A., Heo, G.S., Son, B. “High lithium selectivity in competitive alkali metal solvent extraction by lipophilic crown carboxylic acids”, J. Am. Chem. Soc., 107 (17), 4997-4998 (1985).

53 Bartsch, R.A., “Effects of structural variation within proton-ionizable crown ethers upon the selectivity and efficiency of solvent extraction of alkali metal and alkaline earth cations”, Extract. Ion Exch., 7 (5), 829-854 (1989).

54 Kikukawa, K., He, G.X., Abe, A., Goto, T., Arata, R., Ikeda, T., Wada, F., Matsuda, T., “New applications of crown ethers. Part 6. Structural effects of bis(benzocrown ether)s and substituted benzocrown ethers on solvent extraction and complexation of alkali-metal cations”, J. Chem. Soc., Perkin Trans., 2, 135-141 (1987).

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