Skip to main content
Log in

Annulated Mesoporous Silica as Potent Lanthanide Ion Adsorbents and Magnetic Resonance Contrast Enhancing Agents

  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Abstract

We report a series of SBA-15 type mesoporous silica (MS) possessing functional annulated rings of different sizes obtained by post-synthesis grafting with diamines containing backbones and different numbers of carbon atoms as efficient magnetic resonance imaging (MRI) contrasting agents. Interestingly, lanthanide ion adsorption assays in aqueous solutions of pH 7 at room temperature showed that adsorption efficiency was higher for materials with rings than those without rings. Furthermore, annulated MS synthesized with 1,5-diaminopetane exhibited selective chelation with smaller Yb(III) ions owing to the “macrocyclic effect” of the cation cavity that offers a “best fit.” Additionally, Gd(III) ions chelated with the material modified by 1, 5-diaminopetane denoted as Gd@annulated-MS exhibited high r2/r1 relaxivities of 12, 12, and 28 while measured with 7.0 T (300 MHz), 9.4 T (400 MHz), and 11.4 T (500 MHz), respectively. Finally, the nanoscale parent materials for annulated modification were successfully synthesized for further in vivo applications. The MS materials thus obtained open auxiliary avenues for selective lanthanide ion absorption via manipulation of the annular ring size to be potentially applied in new generation MRI contrast agents.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. K. Ariga, A. Vinu, Y. Yamauchi, Q. Ji, J.P. Hill, Bull. Chem. Soc. Jpn. 85, 1 (2012)

    Article  CAS  Google Scholar 

  2. A.M. Liu, K. Hidajat, S. Kawi, D.Y. Zhao, Chem. Commun. 13, 1145 (2000)

    Article  Google Scholar 

  3. J. Brown, R. Richer, L. Mercier, Microporous Mesoporous Mater. 37, 41 (2000)

    Article  CAS  Google Scholar 

  4. M. Kubo, H. Ushiyama, A. Shimojima, T. Okubo, Adsorption 17, 211 (2011)

    Article  CAS  Google Scholar 

  5. F. Fajula, D. Brunel, Microporous Mesoporous Mater. 48, 119 (2001)

    Article  CAS  Google Scholar 

  6. H.S. Huang, K.H. Chang, N. Suzuki, Y. Yamauchi, C.C. Hu, K.C.W. Wu, Small 9, 2520 (2013)

    Article  CAS  Google Scholar 

  7. Y.-T. Liao, C.-W. Huang, C.-H. Liao, J.C.S. Wu, K.C.W. Wu, Appl. Energ. 100, 75–80 (2012)

    Article  CAS  Google Scholar 

  8. K. Ariga, Y. Yamauchi, G. Rydzek, Q. Ji, Y. Yonamine, K.C.W. Wu, J.P. Hill, Chem. Lett. 43, 36 (2014)

    Article  CAS  Google Scholar 

  9. V. Malgras, Q. Ji, Y. Kamachi, T. Mori, F.-K. Shieh, K.C.-W. Wu, K. Ariga, Y. Yamauchi, Bull. Chem. Soc. Jpn 88, 1171 (2015)

    Article  CAS  Google Scholar 

  10. K. Ariga, A. Vinu, J.P. Hill, T. Mori, Coord. Chem. Rev. 251, 2562 (2007)

    Article  CAS  Google Scholar 

  11. I.I. Slowing, J.L. Vivero-Escoto, C.-W. Wu, V.S.Y. Lin, Adv. Drug Del. Rev. 60, 1278 (2008)

    Article  CAS  Google Scholar 

  12. C.-C. Huang, C.-Y. Tsai, H.-S. Sheu, K.-Y. Chuang, C.-H. Su, U.S. Jeng, F.-Y. Cheng, C.-H. Su, H.-Y. Lei, C.-S. Yeh, ACS Nano 5, 3905 (2011)

    Article  CAS  Google Scholar 

  13. Y.-S. Lin, C.-P. Tsai, H.-Y. Huang, C.-T. Kuo, Y. Hung, D.-M. Huang, Y.-C. Chen, C.-Y. Mou, Chem. Mater. 17, 4570 (2005)

    Article  CAS  Google Scholar 

  14. Y.-S. Lin, C.L. Haynes, Chem. Mater. 21, 3979 (2009)

    Article  CAS  Google Scholar 

  15. J. Kim, H.S. Kim, N. Lee, T. Kim, H. Kim, T. Yu, I.C. Song, W.K. Moon, T. Hyeon, Angew. Chem. Int. Ed. 47, 8438 (2008)

    Article  CAS  Google Scholar 

  16. C.-P. Tsai, Y. Hung, Y.-H. Chou, D.-M. Huang, J.-K. Hsiao, C. Chang, Y.-C. Chen, C.-Y. Mou, Small 4, 186 (2008)

    Article  CAS  Google Scholar 

  17. T. Schaeffter, H. Dahnke, in Molecular Imaging I, vol. 185/1, ed. by W. Semmler, M. Schwaiger (Springer, Berlin, 2008), p. 75

    Chapter  Google Scholar 

  18. P. Hermann, J. Kotek, V. Kubicek, I. Lukes, Dalton Trans. 23, 3027 (2008)

    Article  Google Scholar 

  19. L. De Cola, D.L. Smailes, L.M. Vallarino, Inorg. Chem. 25, 1729 (1986)

    Article  Google Scholar 

  20. V. Alexander, Chem. Rev. 95, 273 (1995)

    Article  CAS  Google Scholar 

  21. S. Aime, C. Carrera, D.D. Castelli, S.G. Crich, E. Terreno, Angew. Chem. Int. Ed. 2005, 44 (1813)

    Google Scholar 

  22. É. Tóth, R.D. Bolskar, A. Borel, G. González, L. Helm, A.E. Merbach, B. Sitharaman, L.J. Wilson, J. Am. Chem. Soc. 127, 799 (2005)

    Article  Google Scholar 

  23. V.C. Pierre, M. Botta, K.N. Raymond, J. Am. Chem. Soc. 127, 504 (2005)

    Article  CAS  Google Scholar 

  24. K.M.L. Taylor, J.S. Kim, W.J. Rieter, H. An, W. Lin, W. Lin, J. Am. Chem. Soc. 130, 2154 (2008)

    Article  CAS  Google Scholar 

  25. F.-K. Shieh, C.-T. Hsiao, H.-M. Kao, Y.-C. Sue, K.-W. Lin, C.-C. Wu, X.-H. Chen, L. Wan, M.-H. Hsu, J.R. Hwu, C.-K. Tsung, K.C.W. Wu, RSC Adv. 3, 25686 (2013)

    Article  CAS  Google Scholar 

  26. I. Persson, P. D’Angelo, S. De Panfilis, M. Sandström, L. Eriksson, Chem. Eur. J. 14, 3056 (2008)

    Article  CAS  Google Scholar 

  27. P. D’Angelo, A. Zitolo, V. Migliorati, I. Persson, Chem. Eur. J. 16, 684 (2010)

    Article  Google Scholar 

  28. R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, J.J. Christensen, D. Sen, Chem. Rev. 85, 271 (1985)

    Article  CAS  Google Scholar 

  29. M. Bottrill, L. Kwok, N.J. Long, Chem. Soc. Rev. 35, 557 (2006)

    Article  CAS  Google Scholar 

  30. W. Wong, K. W. Chan, in Rare Earth Coordination Chemistry, ed. by Chun-Hui Huang (Wiley, Hoboken, 2010), p. 407

    Chapter  Google Scholar 

  31. C.-T. Tsai, Y.-C. Pan, C.-C. Ting, S. Vetrivel, A.S.T. Chiang, G.T.K. Fey, H.-M. Kao, Chem. Commun. 33, 5018 (2009)

    Article  Google Scholar 

  32. Q. He, J. Shi, X. Cui, J. Zhao, Y. Chen, J. Zhou, J. Mater. Chem. 19, 3395 (2009)

    Article  CAS  Google Scholar 

  33. R.M. Cassidy, S. Elchuk, N.L. Elliot, L.W. Green, C.H. Knight, B.M. Recoskie, Anal. Chem. 58, 1181 (1986)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We would like to thank the Ministry of Science and Technology (MOST) for the funding support (103-2113-M-008-001; 104-2119-M-008-010). For T1/T2 measurements, we thank Ms. Jenny Wu at Instrument Development Center in National Cheng Kung University, Taiwan, and S. M. A. and Y. Y. extend their sincere appreciation to the Deanship of Scientific Research at King Saud University for funding this Prolific Research Group (PRG-1436-19).

Author Contributions

S C. Wang and Y. S. Hsu contributed to the sample synthesis. C. T. Hsiao, C. C. Wu, and Y. C. Sue contributed to the SEM and TEM images. S. M. Alshehri and Y. Yamauchi contributed to figures revision. S. C. Wang, S. M. Alshehri, Y. Yamauchi, and F. K. Shieh primarily wrote the manuscript, which was revised by J. E. Chen, K. C. W. Wu and F. K. Shieh. All authors contributed to discussions and manuscript review.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Kevin C.-W. Wu or Fa-Kuen Shieh.

Ethics declarations

Conflict of Interest

The authors declare no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, SC., Hsu, YS., Hsiao, CT. et al. Annulated Mesoporous Silica as Potent Lanthanide Ion Adsorbents and Magnetic Resonance Contrast Enhancing Agents. J Inorg Organomet Polym 26, 165–171 (2016). https://doi.org/10.1007/s10904-015-0280-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10904-015-0280-8

Keywords

Navigation