INIFTA   05425
INSTITUTO DE INVESTIGACIONES FISICO-QUIMICAS TEORICAS Y APLICADAS
Unidad Ejecutora - UE
artículos
Título:
Comparative analysis of complexation of pesticides (fenitrothion, methylparathion, parathion) and their ester-analogues by beta-cylodextrin
Autor/es:
E. N. COSCARELLO; D. J. BARBIRIC; E. A. CASTRO; R. V. VICO; E. I. BUJÁN; R. H. DE ROSSI
Revista:
JOURNAL OF STRUCTURAL CHEMISTRY
Editorial:
SPRINGER
Referencias:
Lugar: Heidelberg; Año: 2009 vol. 50 p. 671 - 679
ISSN:
0022-4766
Resumen:
The complexation by -cyclodextrin (-CD) of three organophosphorus pesticides, fenitrothion,
parathion and methylparathion, and of their carboxylic ester analogues was analyzed
using PM3 and molecular mechanics methods. The objective was to elucidate structural features
and energy changes that accompany the complexation and could possibly affect the hydrolysis
process, which is catalyzed by -CD in the case of carboxylic esters but inhibited for
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
parathion and methylparathion, and of their carboxylic ester analogues was analyzed
using PM3 and molecular mechanics methods. The objective was to elucidate structural features
and energy changes that accompany the complexation and could possibly affect the hydrolysis
process, which is catalyzed by -CD in the case of carboxylic esters but inhibited for
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
-cyclodextrin (-CD) of three organophosphorus pesticides, fenitrothion,
parathion and methylparathion, and of their carboxylic ester analogues was analyzed
using PM3 and molecular mechanics methods. The objective was to elucidate structural features
and energy changes that accompany the complexation and could possibly affect the hydrolysis
process, which is catalyzed by -CD in the case of carboxylic esters but inhibited for
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
-CD in the case of carboxylic esters but inhibited for
the pesticides, in alkaline medium. The complexation of fenitrothion was further explored,
since experiments proved its hydrolysis is relatively less inhibited and progresses mainly
through a different pathway than that usually accepted. The results of this study show that
complex structures involving esters enable effective interactions between the guest carbonyl
and the rim of the host; methylparathion and parathion, however, appear to be deeply included
in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH
-CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable
for the carboxylic esters but not for the two pesticides. Different complex geometries
resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being
prone to an attack by the -CD, but favoring instead the approach of an external OH-CD, but favoring instead the approach of an external OH
group, in agreement with the experiment.
K e y w o r d s: supramolecular complexes, -cyclodextrin, inclusion compounds, semiempirical
calculations, pesticides.
calculations, pesticides.
supramolecular complexes, -cyclodextrin, inclusion compounds, semiempirical
calculations, pesticides.