Models of pesticides inside cavities of molecular dimensions. A role of the guest inclusion in the dechlorination process.
The reduction mechanism of the pesticide vinclozoline (3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione) was studied in nonaqueous solvents in the confined environment of a cyclodextrin (CD) cavity. The effect of the cavity dimensions on the mechanism of the redox process was evaluated using glucose as a reference and using three cyclodextrin molecules of different cavity sizes, namely, alphaCD, betaCD, and gammaCD. In the absence of CD the main reduction product of vinclozoline in the first reduction step is dichloroaniline. An addition of glucose leads to a quantitative change of mechanism with 10 products in total. Addition of CD, however, leads exclusively to dechlorination of the phenyl ring. The degree of dechlorination depends strongly on the choice of cyclodextrin molecule. The importance of the complex formation equilibria in the change of the mechanism is supported by a series of semiempirical AM1 quantum-mechanical calculations. Very good correlation (correlation coefficient 0.995) was obtained between the complex stabilization energy of the inclusion complex and the degree of pesticide dechlorination. Additionally, we were able to show that the complexes are stabilized by the formation of intermolecular hydrogen bonds between the host and guest species. CD molecules do not simply act as proton donors in a nonaqueous environment, but also protect parts of the molecule included within the cavity and steer the degradation process toward fewer products.
Hromadová
Magdaléna
M
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, 18223 Prague, Czech Republic.
Pospísil
Lubomír
L
Fanelli
Nicolangelo
N
Giannarelli
Stefania
S
D002713:Chlorine / Q000737:chemistry*; D003505:Cyclodextrins / Q000737:chemistry; D004572:Electrolysis; D006358:Hot Temperature; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D010575:Pesticides / Q000737:chemistry*
D003505:Cyclodextrins; D010575:Pesticides; D002713:Chlorine