Skip to main content

Permethylated β-cyclodextrin/pesticide complexes: X-ray structures and thermogravimetric assessment of kinetic parameters for complex dissociation

Abstract

The X-ray crystal structures of the inclusion complexes formed between three pesticides (two organophosphorus insecticides and one chloroacetanilide herbicide) and permethylated β-cyclodextrin (TRIMEB) are reported. The complexes TRIMEB–fenitrothion (1), TRIMEB–fenthion (2) and TRIMEB–acetochlor (3) are members of a commonly occurring isostructural series. The mode of inclusion of the two organophosphate insecticides is very similar, while the acetochlor molecule, which is structurally quite distinct from the two insecticide molecules, adopts a somewhat different position within the TRIMEB cavity. In addition to the structural elucidation of these complexes, their thermal behaviour was investigated using isothermal and non-isothermal thermogravimetry. The isothermal results showed that the dissociation of the guest molecules from the TRIMEB cavities can best be described by two mechanisms, namely a first-order reaction model and a three-dimensional diffusion model. Both the isothermal and non-isothermal methods allowed the determination of the activation energies of the guest loss process for each complex.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

References

  1. Szejtli, J.: Past, present and future of cyclodextrin research. Pure Appl. Chem. 76, 1825–1845 (2004)

    Article  CAS  Google Scholar 

  2. Szejtli, J.: Cyclodextrins in pesticides. Starch 37, 382–386 (1985)

    Article  CAS  Google Scholar 

  3. Morillo, E.: Applications of cyclodextrins in agrochemistry. In: Dodziuk, H. (ed.) Cyclodextrins and Their Complexes, pp. 459–466. Wiley-VCH Verlag GmBH & Co. KgaA, Weinheim (2006)

    Google Scholar 

  4. Kegley, S.E., Hill, B.R., Orne, S.: PAN pesticides database—pesticide registration status. http://www.pesticideinfo.org (2011). Accessed 15 Oct 2011

  5. Kamiya, M., Kameyama, K., Ishiwata, S.: Effects of cyclodextrins on photodegradation of organophosphorus pesticides in humic water. Chemosphere 42, 251–255 (2000)

    Article  Google Scholar 

  6. Vico, R.V., Buján, E.I., de Rossi, R.H.J.: Effect of cyclodextrin on the hydrolysis of the pesticide fenitrothion [O, O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothioate]. Phys. Org. Chem. 15, 858–862 (2002)

    Article  CAS  Google Scholar 

  7. Rougier, N.M., Cruickshank, D.L., Vico, R.V., Bourne, S.A., Caira, M.R., Buján, E.I., de Rossi, R.H.: Effect of cyclodextrins on the reactivity of fenitrothion. Carbohydr. Res. 346, 322–327 (2011)

    Article  CAS  Google Scholar 

  8. Cruickshank, D.L., Rougier, N.M., Vico, R.V., de Rossi, R.H., Buján, E.I., Bourne, S.A., Caira, M.R.: Solid-state structures and thermal properties of inclusion complexes of the organophosphate insecticide fenitrothion with permethylated cyclodextrins. Carbohydr. Res. 345, 141–147 (2010)

    Article  CAS  Google Scholar 

  9. Program SAINT, Version 7.60a, Bruker AXS Inc., Madison, WI, USA (2006)

  10. Program SADABS, Version 2008/1, Bruker AXS Inc., Madison, WI, USA (2008)

  11. Harata, K., Uekama, K., Otagiri, M., Hirayama, F.: Conformation of permethylated cyclodextrins and the host–guest geometry of their inclusion complexes. J. Inclusion Phenom. Mol. Recognit. Chem. 1, 279–293 (1984)

    Article  CAS  Google Scholar 

  12. Mentzafos, D., Mavridis, I.M., Schenk, H.: Crystal structure of the 1:1 complex of heptakis(2,3,6-tri-O-methyl)cyclomaltoheptaose (permethylated β-cyclodextrin) with ethyl laurate. Carbohydr. Res. 253, 39–50 (1994)

    Article  CAS  Google Scholar 

  13. Sheldrick, G.M.: A short history of SHELX. Acta Crystallogr. Sect. A. A64, 112–122 (2008)

    Article  CAS  Google Scholar 

  14. Song, Z.-W.: 2-Chloro-N-chloromethyl-N-(2-ethyl-6-methylphenyl)acetamide. Acta Crystallogr. Sect. E. E64, o991 (2008)

    Article  CAS  Google Scholar 

  15. Cambridge Structural Database and Cambridge Structural Database System. Conquest, Version 1.13, Cambridge Crystallographic Data Centre, University Chemical Laboratory: Cambridge, England (2011)

  16. Galwey, A.K., Brown, M.E.: Kinetic Background to thermal analysis and calorimetry, Chap. 3. In: Brown, M.E. (ed.) Handbook of Thermal Analysis and Calorimetry, pp. 147–224. Elsevier Science, Amsterdam (1998)

    Google Scholar 

  17. Vyazovkin, S., Wight, C.A.: Isothermal and nonisothermal reaction kinetics in solids: in search of ways toward consensus. J. Phys. Chem. A 101, 8279–8284 (1997)

    Article  CAS  Google Scholar 

  18. Vyazovkin, S., Wight, C.A.: Isothermal and non-isothermal kinetics of thermally stimulated reactions of solids. Int. Rev. Phys. Chem. 17, 407–433 (1998)

    Article  CAS  Google Scholar 

  19. Ozawa, T.: A new method of analysing thermogravimetric data. Bull. Chem. Soc. Jpn. 38, 1881–1886 (1965)

    Article  CAS  Google Scholar 

  20. Flynn, J.H., Wall, L.A.: A quick, direct method for the determination of activation energy from thermogravimetric data. J. Polym. Sci. Part B Polym. Lett. 4, 323–328 (1966)

    Article  CAS  Google Scholar 

  21. Zhang, N., Li, J.-H., Cheng, Q.-T., Zhu, M.-W.: Kinetic studies on the thermal dissociation of β-cyclodextrin-benzyl alcohol inclusion complex. Thermochim. Acta 235, 105–116 (1994)

    Article  CAS  Google Scholar 

  22. Neoh, T.L., Yamauchi, K., Yoshii, H., Furuta, T.: Kinetic study of thermally stimulated dissociation of inclusion complex of 1-methylcyclopropene with α-cyclodextrin by thermal analayis. J. Phys. Chem. B 112, 15914–15920 (2008)

    Article  CAS  Google Scholar 

  23. Li, J.-H., Zhang, N., Li, X.-T., Wang, J.-Y., Tian, S.-J.: Kinetic studies on the thermal dissociation of the inclusion complex of β-cyclodextrin with cinnamic aldehyde. J. Therm. Anal. 49, 1527–1533 (1997)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This material is based on research supported by the National Research Foundation (NRF) under Grant number 67381. MRC and DLC express their thanks to the NRF and the University of Cape Town for financial assistance. Financial assistance from Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Fondo para la Investigaciόn Científica y Tecnolόgica (FONCYT), Ministerio de Ciencia y Tecnología (MINCyT), Córdoba (Argentina) and support from the National University of Córdoba are greatly acknowledged. This work was carried out as part of a bilateral cooperation project supported by the NRF (South Africa) and MINCyT (Argentina). NMR is a grateful recipient of a fellowship from CONICET (Argentina).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mino R. Caira.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 289 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Cruickshank, D.L., Rougier, N.M., Maurel, V.J. et al. Permethylated β-cyclodextrin/pesticide complexes: X-ray structures and thermogravimetric assessment of kinetic parameters for complex dissociation. J Incl Phenom Macrocycl Chem 75, 47–56 (2013). https://doi.org/10.1007/s10847-012-0145-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-012-0145-5

Keywords

  • Pesticides
  • Inclusion complexes
  • Permethylated β-cyclodextrin
  • Single crystal X-ray diffraction
  • Thermal decomposition kinetics