Competitive formation of molecular inclusion complexes of chlordecone and beta-hexachlorocyclohexane with natural cyclodextrins: DFT and molecular dynamics study

ContextChlordecone (CLD) and beta-hexachlorocyclohexane (beta-HCH) are chlorinated pesticides that coexist as persistent organic pollutants in the groundwater of several countries in the Caribbean, being an environmental issue. This work evaluates theoretically the competitive formation of host-guest complexes pesticides@cyclodextrines (CDs) as an alternative for water purification and selective separation of pesticides.MethodsQuantum mechanical calculations based on density functional theory (DFT) and classical molecular dynamics (MD) simulations were used to achieve information on geometries, energies, structure, and dynamics of guest-host complexes in the gas phase, implicit solvent medium, and in aqueous solutions.ResultsDFT studies showed that interactions of both pesticides with CDs are mediated by steric factors and guided by maximization of the hydrophobic interactions either with the other pesticide or with the CD cavity's inner atoms. MD results corroborate the formation of stable complexes of both pesticides with the studied CDs. alpha-CD exhibited a preference for the smaller beta-HCH molecule over the CLD that could not perturb the formed complex.ConclusionsThe simulation of competitive formation with gamma-CD illustrated that this molecule could accommodate both pesticides inside its cavity. These results suggest that CDs with smaller cavity sizes such as alpha-CD could be used for selective separation of beta-HCH from CLD in water bodies, while gamma-CD could be used for methods that aim to remove both pesticides at the same time.