Advertisement

Thermosensitive gels incorporating cyclic monoazatetrathioether units for the selective extraction of class b metal ions

  • K. ChayamaEmail author
  • T. Hirooka
  • S. Iwatsuki
Original Article
  • 11 Downloads

Abstract

A cyclic monoaza–tetrathia-crown ether, 1-aza-4,7,11,14-tetrathiacyclohexadecane (ATCH) unit have been introduced into the temperature responsive polymer, poly-N-iso-propyl-acryl-amide. The synthesized copolymers were examined for the selective extraction of soft metal ions such as silver(I) and copper(I) ions. The ratio between N-isopropylacrylamide group and cyclic monoazatetrathioether group in the copolymer was clarified by the determination of sulfur atoms in aqueous solution of the copolymer by means of ICP-AES measurements of the sulfur atoms. It varied in the range of 55:1 to 269:1. Each lower critical solution temperature of the copolymer solution was determined spectrophotometrically by the relative absorbance change at 750 nm via temperature of the copolymer solution. Metal ion extraction using the copolymer with an appropriate counter anion such as picrate, nitrate or perchlorate ion was examined. Soft metal ions such as silver(I) and copper(I) ion were extracted selectively into the solid polymer phase. Extraction behaviors of silver(I) and copper(I) ions with the copolymer incorporating cyclic mono-aza-tetra-thio-ethers have been compared with the copolymer incorporating the acyclic analogues 9-aza-3,6,12,15-tetrathiaheptadecane (ATH). The extraction behavior of silver(I) ion with the copolymer of cyclic ATCH was different from that with the copolymer of acyclic ATH, because of the steric effect of cyclic monoazatetrathioether part.

Keywords

Thermosensitive gel Thiacrown ether Monoazatetrathioether Silver(I) ion Copper(I) ion 

Notes

Acknowledgements

This work was supported by JSPS20550089, Grant-in-Aid for Scientific Research(C).

References

  1. 1.
    Saitoh, T., Ohyama, T., Takamura, K., Sakurai, T., Kaise, T., Matsubara, C.: Extraction of Iron(II)-Tris(1, 10-phenanthrolinato) chelate into the polymer phase formed from an aqueous solution of poly(N-isopropylacrylamide). Anal. Sci. 13, 1 (1997)CrossRefGoogle Scholar
  2. 2.
    Zhang, J., Peppas, N.A.: Synthesis and characterization of pH- and temperature-sensitive poly (methacrylic acid)/poly (N-isopropylacrylamide) interpenetrating polymeric networks. Macromolecules 33, 102 (2000)CrossRefGoogle Scholar
  3. 3.
    Lustig, S.R., Everlof, G.J., Jaycox, G.D.: Stimuli-responsive polymers. 5. Azobenzene modified polyaramides containing atropisomeric binaphthyl linkages:  tuning chiroptical behavior with light and heat. Macromolecules 34, 2364 (2001)CrossRefGoogle Scholar
  4. 4.
    Saitoh, T., Yoshida, Y., Matsubara, C.: Concentration of nonylphenol and its polyethoxylated derivatives by polymer-mediated extraction. J. Chromatogr. A 891, 69 (2000)CrossRefGoogle Scholar
  5. 5.
    Chayama, K., Sano, Y., Iwatsuki, S.: Pyridinium-based task-specific Ionic Liquid with a monothioether group for selective extraction of class b metal ions. Anal. Sci. 31, 1115 (2015)CrossRefGoogle Scholar
  6. 6.
    Shimojo, K.: Solvent extraction in analytical separation techniques. Anal. Sci. 34, 1345 (2018)CrossRefGoogle Scholar
  7. 7.
    Toita, M., Morita, K., Hirayama, N.: Formation of minimal third phase in ionic liquid extraction system with trioctylphosphine oxide and its possible application to extraction concentration. Anal. Sci. 34, 1063 (2018)CrossRefGoogle Scholar
  8. 8.
    Sekimoto, T., Nishihama, S., Yoshizuka, K.: Extraction of lithium from salt lake brine with tributyl phosphate and an ionic liquid. Solv. Extr. Res. Dev. Jpn 25, 117 (2018)CrossRefGoogle Scholar
  9. 9.
    Kanazawa, H., Sunamoto, T., Ayano, E., Matsushima, Y., Kikuchi, A., Okano, T.: Temperature-responsive liquid chromatography. 2. Effects of hydrophobic groups in N-isopropylacrylamide copolymer-modified silica. Anal. Chem. 69, 823 (1997)CrossRefGoogle Scholar
  10. 10.
    Kanazawa, H., Sunamoto, T., Ayano, E., Matsushima, Y., Kikuchi, A., Okano, T.: Temperature-responsive chromatography using poly-(N-isopropylacrylamide) hydrogel-modified silica. Anal. Sci. 18, 45–48 (2002)CrossRefGoogle Scholar
  11. 11.
    Zhang, R., Yang, G., Xin, P., Qi, L., Chen, Y.: Preparation of poly(N-isopropylacrylamide)-grafted polymer monolith for hydrophobic interaction chromatography of proteins. J. Chromatogr. A 1216, 2404 (2009)CrossRefGoogle Scholar
  12. 12.
    Takeshita, K., Ishida, K., Matsumura, T., Nakano, Y.: Thermal-swing extraction of cadmium(II) by thermosensitive polymer gel crosslinked with encapsulating hexadentate ligand. Chem. Lett. 36, 1032 (2007)CrossRefGoogle Scholar
  13. 13.
    Takeshita, K., Matsumura, T., Nakano, Y.: Thermal-Swing Extraction Separation of Am(III) and Eu(III) with Poly-NIPA Gel Crosslinked with TPEN Derivative. J. Nucl. Sci. Technol. 44, 1481 (2007)CrossRefGoogle Scholar
  14. 14.
    Takeshita, K., Matsumura, T., Nakano, Y.: Separation of Americium(III) and Europium(III) by thermal-swing extraction using thermosensitive polymer gel. Prog. Nucl. Eng. 50, 466 (2008)CrossRefGoogle Scholar
  15. 15.
    Segawa, M., Kobayashi, S., Tsuji, H., Chayama, K.: Selective collection of metal ions with trithioether derivative and poly-N-isopropylacrylamide. Bunseki Kagaku 53, 1223 (2004)CrossRefGoogle Scholar
  16. 16.
    Chayama, K., Morita, Y., Iwatsuki, S.: Thermosensitive gels incorporating polythioether units for the selective extraction of class b metal ions. J. Chromatogr. A 1217, 6785 (2010)CrossRefGoogle Scholar
  17. 17.
    Chayama, K., Kurihara, C., Tsuji, H., Sekido, E.: Solvent extraction of metal ions with acyclic monoazatetrathioethers. Bunseki Kagaku 47, 1077 (1998)CrossRefGoogle Scholar
  18. 18.
    Rosen, W., Bush, D.H.: Octahedral nickel(II) complexes of some cyclic polyfunctional thioethers. Inorg. Chem. 9, 262 (1970)CrossRefGoogle Scholar
  19. 19.
    Ochrymowycz, L.A., Mak, C.P., Michna, J.D.: Synthesis of macrocyclic polythiaethers. J. Org. Chem. 39, 2079 (1974)CrossRefGoogle Scholar
  20. 20.
    Chayama, K., Awano, N., Tamari, Y., Tsuji, H., Sekido, E.: Solvent extraction of metal ions with cyclic monoazatetrathioethers. Bunseki Kagaku 42, 687 (1993)CrossRefGoogle Scholar
  21. 21.
    Iwatsuki, S., Ichiyama, A., Tanooka, S., Toyama, M., Katagiri, K., Kawahata, M., Yamaguchi, K., Danjo, H., Chayama, K.: Thermosensitive gels incorporating polythioether units for the selective extraction of class b metal ions. Dalton Trans. 45, 12548 (2016)CrossRefGoogle Scholar
  22. 22.
    Sekido, E., Chayama, K., Muroi, M.: Liquid-liquid extraction of univalent class b metal ions by the thiacrown compound 4′-picrylaminobenzo-1,4,8,11-tetra-thiacyclopentadec-13-ene. Talanta 32, 797 (1985)CrossRefGoogle Scholar
  23. 23.
    Chayama, K., Sekido, E.: Liquid-liquid extraction of metal ions by cyclic and acyclic tetrathio ethers. Anal. Sci. 3, 535 (1987)CrossRefGoogle Scholar
  24. 24.
    Chayama, K., Sekido, E.: Effect of counter anion on extractive spectrophotometric determination of copper(ii) with thiacrown compounds. Anal. Sci. 4, 511 (1988)CrossRefGoogle Scholar
  25. 25.
    Chayama, K., Sekido, E.: Extraction behavior of silver ion with cyclic and acyclic tetrathio ethers and the molecular structures of the silver complexes. Anal. Sci. 6, 883 (1990)CrossRefGoogle Scholar
  26. 26.
    Chayama, K., Sekido, E.: Liquid–liquid extraction of copper(II) with cyclic and acyclic tetrathioethers. Anal. Chim. Acta 248, 511 (1991)CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Science and EngineeringKonan UniversityKobeJapan

Personalised recommendations