Skip to main content
SpringerLink
Log in

Molecular Modeling to Predict the Optimal Mineralogy of Smectites as Binders of Aflatoxin

  • Original Paper
  • Published:
Clays and Clay Minerals

Abstract

Numerous experiments have verified that smectites can adsorb aflatoxin B1 (AfB1) effectively and the efficiency of this process depends heavily on the chemical, physical, and mineralogical characteristics of the smectite. Several relationships between these characteristics and AfB1 sorption have been determined experimentally, but the molecular mechanisms underlying these were not investigated. In the current study the effects of charge density, type of exchange cation, and charge origin (octahedral vs. tetrahedral) on AfB1 sorption on smectites were analyzed by a series of molecular simulations. The calculations confirmed the formation of water bridges between carbonyl groups of AfB1 molecules and interlayer cations. Flat orientation of AfB1 molecules on smectite surfaces was also confirmed. For larger amounts of AfB1 molecules in the intercalates, self-association of two AfB1 molecules bound by π–π interaction was shown. The thermodynamics of AfB1 sorption depends heavily on the water content in the structure, being optimal for basal distances corresponding to two layers of water. A clear preference for sorption of AfB1 on smectites with bivalent cations (Ba2+, Ca2+) and an octahedral origin of its layer charge was confirmed and this was explained as steric hindrance between hydrated ions and AfB1 molecules, which tend to lie flat on smectite surfaces devoid of ions. Ba-montmorillonite with a charge of 0.4 per half unit cell was shown to have the smallest and thus the best potential energy of adsorption compared to the other layer charges.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

Data Availability

On request from Marek Szczerba.

References

  • Awuor, A. O., Yard, E., Daniel, J. H., Martin, C., Bii, C., Romoser, A., Oyugi, E., Elmore, S., Amwayi, S., Vulule, J., Zitomer, N. C., Rybak, M. E., Phillips, T. D., Montgomery, J. M., & Lewis, L. S. (2017). Evaluation of the efficacy, acceptability and palatability of calcium montmorillonite clay used to reduce aflatoxin B1 dietary exposure in a crossover study in Kenya. Food Additives & Contaminants, Part A, 34, 93–102.

    Article  Google Scholar 

  • Barrientos-Velazquez, A. L., & Deng, Y. (2020). Reducing competition of pepsin in aflatoxin adsorption by modifying a smectite with organic nutrients. Toxins, 12, 28.

    Article  Google Scholar 

  • Barrientos-Velazquez, A. L., Arteaga, S., Dixon, J. B., & Deng, Y. (2016a). The effects of pH, pepsin, exchange cation, and vitamins on aflatoxin adsorption on smectite in simulated gastric fluids. Applied Clay Science, 120, 17–23.

    Article  Google Scholar 

  • Barrientos-Velazquez, A. L., Marroquin Cardona, A., Liu, L., Phillips, T., & Deng, Y. (2016b). Influence of layer charge origin and layer charge density of smectites on their aflatoxin adsorption. Applied Clay Science, 132-133, 281–289.

    Article  Google Scholar 

  • Berendsen, H. J. C., Postma, J. P. M., van Gunsteren, W. F., & Hermans, J. (1981). Interaction models for water in relations to protein hydration. In B. Pullman (Ed.), Intermolecular Forces (The Jerusalem Symposia on Quantum Chemistry and Biochemistry) (Vol. 14, pp. 331–342). Springer.

    Chapter  Google Scholar 

  • Colvin, B. M., Sangster, L. T., Haydon, K. D., Beaver, R. W., & Wilson, D. M. (1989). Effect of a high affinity aluminosilicate sorbent on prevention of aflatoxicosis in growing pigs. Veterinary and Human Toxicology, 31, 46–48.

    Google Scholar 

  • Cygan, R. T., Liang, J. J., & Kalinichev, A. G. (2004). Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field. Journal of Physical Chemistry B, 108, 1255–1266.

    Article  Google Scholar 

  • Deng, Y., & Szczerba, M. (2011). Computational evaluation of bonding between aflatoxin B1 and smectite. Applied Clay Science, 54, 26–33.

    Article  Google Scholar 

  • Deng, Y., Barrientos-Velazquez, A. L., Billes, F., & Dixon, J. B. (2010). Bonding mechanisms between aflatoxin B1 and smectite. Applied Clay Science, 50(1), 92–98.

    Article  Google Scholar 

  • Deng, Y., Liu, L., Barrientos-Velazquez, A. L., & Dixon, J. B. (2012). The determinative role of the exchange cation and layer-charge density of smectite on Aflatoxin adsorption. Clays and Clay Minerals, 60, 374–386.

    Article  Google Scholar 

  • Jaynes, W., Zartman, R., & Hudnall, W. (2007). Aflatoxin B1 adsorption by clays from water and corn meal. Applied Clay Science, 36(1-3), 197–205.

    Article  Google Scholar 

  • Kannewischer, I., Tenorio, A. M. G., White, G. N., & Dixon, J. B. (2006). Smectite clays as adsorbents of aflatoxin B1: Initial steps. Clay Science, 12(Supplement 2), 199–204.

    Google Scholar 

  • Khan, A., Akhtar, M. S., Akbar, S., Khan, K. S., Iqbal, M., Barrientos-Velazquez, A. L., & Deng, Y. (2022). Effects of Metal-Polycation Pillaring and Exchangeable Cations on Aflatoxin Adsorption by Smectite. Clays and Clay Minerals, 70, 155–164.

    Article  Google Scholar 

  • Kubena, L. F., Harvey, R. B., Huff, W. E., & Corrier, D. E. (1990). Efficacy of a hydrated sodium calcium aluminosilicate to reduce the toxicity of aflatoxin and T-2 toxin. Poultry Science, 69, 1078–1086.

    Article  Google Scholar 

  • Laird, D. A. (2006). Influence of layer charge on swelling of smectites. Applied Clay Science, 34, 74–87.

    Article  Google Scholar 

  • Magnoli, A. P., Cabaglieri, L. R., Magnoli, C. E., Monge, J. C., Miazzo, R. D., Peralta, M. F., Salvano, M. A., Rosa, C. A. R., Dalcero, A. M., & Chiacchiera, S. M. (2008). Bentonite performance on broiler chickens fed with diets containing natural levels of aflatoxin B1. Revista Brasileira De Medicina Veterinaria, 30, 55–60.

    Google Scholar 

  • Maki, C. R., Thomas, A. D., Elmore, S. E., Romoser, A. A., Harvey, R. B., Ramirez-Ramirez, H. A., & Phillips, T. D. (2016). Effects of calcium montmorillonite clay and aflatoxin exposure on dry matter intake, milk production, and milk composition. Journal of Dairy Science, 99, 1039–1046.

    Article  Google Scholar 

  • Masimango, N., Remacle, J., & Ramaut, J. (1979). Elimination of aflatoxin B1 from contaminated media by swollen clays. Annales de la Nutrition et de l'Alimentation, 33, 137–147.

    Google Scholar 

  • Mitchell, N. J., Xue, K. S., Lin, S., Marroquin-Cardona, A., Brown, K. A., Elmore, S. E., Tang, L., Romoser, A., Gelderblom, W. C., Wang, J. S., & Phillips, T. D. (2014). Calcium montmorillonite clay reduces AFB1 and FB1 biomarkers in rats exposed to single and co-exposures of aflatoxin and fumonisin. Journal of Applied Toxicology, 34, 795–804.

    Article  Google Scholar 

  • Phillips, T. D., Kubena, L. F., Harvey, R. B., Taylor, D. R., & Heidelbaugh, N. D. (1988). Hydrated sodium calcium aluminosilicate: A high affinity sorbent for aflatoxin. Poultry Science, 67, 243–247.

    Article  Google Scholar 

  • Plimpton, S. (1995). Fast parallel algorithms for short-range molecular dynamics. Journal of Computational Physics, 117, 1–19.

    Article  Google Scholar 

  • Pollock, B. H., Elmore, S., Romoser, A., Tang, L., Kang, M. S., Xue, K., Rodriguez, M., Dierschke, N. A., Hayes, H. G., Hansen, H. A., Guerra, F., Wang, J. S., & Phillips, T. (2016). Intervention trial with calcium montmorillonite clay in a south Texas population exposed to aflatoxin. Food Additives & Contaminants, Part A, 33, 1346–1354.

    Google Scholar 

  • Rudbeck, M. (2006). Potassium(I) in water from Theoretical Calculations. Diploma thesis, Department of Mathematics, Uppsala University, Uppsala, Sweden, pp. 51.

  • Smith, D. W. (1977). Ionic hydration enthalpies. Journal of Chemical Education, 54, 540–541.

    Article  Google Scholar 

  • Szczerba, M., Kalinichev, A. G., & Kowalik, M. (2020). Intrinsic hydrophobicity of smectite basal surfaces quantitatively probed by molecular dynamics simulations. Applied Clay Science, 188, 105497.

    Article  Google Scholar 

  • Wang, J., Wolf, R. M., Caldwell, J. W., Kollman, P. A., & Case, D. A. (2004). Development and testing of a general amber force field. Journal of Computational Chemistry, 25, 1157–1174.

    Article  Google Scholar 

  • Wang, W., Tian, G., Zong, L., Zhou, Y., Kang, Y., Wang, Q., & Wang, A. (2017). From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water. Journal of Environmental Sciences (China), 51, 31–43.

    Article  Google Scholar 

Download references

Acknowledgements

We are very thankful for the helpful comments by the Editor-in-Chief, the Associate Editor, and by two anonymous reviewers. The authors acknowledge financial support from the United States Department of Agriculture. This work was also supported by the Polish Grid Infrastructure PL-Grid infrastructure.

Code Availability

Not applicable

Funding

United States Department of Agriculture, PLGRID.

Author information

Authors and Affiliations

  1. Institute of Geological Sciences, Polish Academy of Sciences, Kraków, 31002, Poland

    Marek Szczerba & Mariola Kowalik-Hyla

  2. Department of Soil and Crop Sciences, Texas A&M University, College Station, TX, 77843-2474, USA

    Youjun Deng

Authors
  1. Marek Szczerba
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Youjun Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mariola Kowalik-Hyla
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Marek Szczerba: molecular simulations, analysis of results, writing manuscript, Youjun Deng: revision of data, writing manuscript, Mariola Kowalik: molecular simulations.

Corresponding author

Correspondence to Marek Szczerba.

Ethics declarations

Conflicts of Interest

Not applicable.

Additional information

Associate Editor: Eric Ferrage

Supplementary Information

ESM 1

(DOCX 2026 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Szczerba, M., Deng, Y. & Kowalik-Hyla, M. Molecular Modeling to Predict the Optimal Mineralogy of Smectites as Binders of Aflatoxin. Clays Clay Miner. 70, 824–836 (2022). https://doi.org/10.1007/s42860-023-00219-7

Download citation

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s42860-023-00219-7

Keywords

Search

Navigation