γ-Cyclodextrin modulates the chemical reactivity by multiple complexation

J. Fernández-Rosas, M. Pessêgo, M. Cepeda-Plaza, N. Basilio, M. Parajó, P. Rodríguez-Dafonte, L. García-Río

Resultado de la investigación: Article

4 Citas (Scopus)

Resumen

Multiple complexation by γ-CD has been studied by self-diffusion coefficients (DOSY) and chemical kinetics experiments in which 4-methoxybenzenesulfonyl chloride (MBSC) solvolysis was used as a chemical probe. The addition of a surfactant as a third component to the reaction mixture induced a very complex reactivity pattern that was explained on the basis of multiple complexation phenomena and surfactant self-assembly to form micelles. A cooperative effect that yielded a ternary complex formed by cyclodextrin-surfactant-MBSC was observed. The larger cavity of γ-CD in comparison with β-CD is responsible for the change from the competitive complexation mechanism predominant with β-CD to a cooperative/competitive mixed mechanism operating for the larger derivative. The cavity size in γ-CD is large enough to bind two surfactant alkyl chains with a cooperative effect. Water molecules released by the formation of 1 : 1 host-guest complexes made the cavity more hydrophobic and promoted further inclusion. A reduction in the available volume of the cavity should be considered on binding a second guest.

Idioma originalEnglish
Páginas (desde-hasta)1213-1224
Número de páginas12
PublicaciónOrganic and Biomolecular Chemistry
Volumen13
N.º4
DOI
EstadoPublished - 28 ene 2015

Huella dactilar

Chemical reactivity
Cyclodextrins
Complexation
Surface-Active Agents
reactivity
surfactants
cavities
chlorides
solvolysis
Micelles
Reaction kinetics
Self assembly
self assembly
micelles
reaction kinetics
diffusion coefficient
inclusions
Derivatives
Molecules
Water

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Citar esto

Fernández-Rosas, J., Pessêgo, M., Cepeda-Plaza, M., Basilio, N., Parajó, M., Rodríguez-Dafonte, P., & García-Río, L. (2015). γ-Cyclodextrin modulates the chemical reactivity by multiple complexation. Organic and Biomolecular Chemistry, 13(4), 1213-1224. https://doi.org/10.1039/c4ob02113d
Fernández-Rosas, J. ; Pessêgo, M. ; Cepeda-Plaza, M. ; Basilio, N. ; Parajó, M. ; Rodríguez-Dafonte, P. ; García-Río, L. / γ-Cyclodextrin modulates the chemical reactivity by multiple complexation. En: Organic and Biomolecular Chemistry. 2015 ; Vol. 13, N.º 4. pp. 1213-1224.
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Fernández-Rosas, J, Pessêgo, M, Cepeda-Plaza, M, Basilio, N, Parajó, M, Rodríguez-Dafonte, P & García-Río, L 2015, 'γ-Cyclodextrin modulates the chemical reactivity by multiple complexation', Organic and Biomolecular Chemistry, vol. 13, n.º 4, pp. 1213-1224. https://doi.org/10.1039/c4ob02113d

γ-Cyclodextrin modulates the chemical reactivity by multiple complexation. / Fernández-Rosas, J.; Pessêgo, M.; Cepeda-Plaza, M.; Basilio, N.; Parajó, M.; Rodríguez-Dafonte, P.; García-Río, L.

En: Organic and Biomolecular Chemistry, Vol. 13, N.º 4, 28.01.2015, p. 1213-1224.

Resultado de la investigación: Article

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AU - Pessêgo, M.

AU - Cepeda-Plaza, M.

AU - Basilio, N.

AU - Parajó, M.

AU - Rodríguez-Dafonte, P.

AU - García-Río, L.

PY - 2015/1/28

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N2 - Multiple complexation by γ-CD has been studied by self-diffusion coefficients (DOSY) and chemical kinetics experiments in which 4-methoxybenzenesulfonyl chloride (MBSC) solvolysis was used as a chemical probe. The addition of a surfactant as a third component to the reaction mixture induced a very complex reactivity pattern that was explained on the basis of multiple complexation phenomena and surfactant self-assembly to form micelles. A cooperative effect that yielded a ternary complex formed by cyclodextrin-surfactant-MBSC was observed. The larger cavity of γ-CD in comparison with β-CD is responsible for the change from the competitive complexation mechanism predominant with β-CD to a cooperative/competitive mixed mechanism operating for the larger derivative. The cavity size in γ-CD is large enough to bind two surfactant alkyl chains with a cooperative effect. Water molecules released by the formation of 1 : 1 host-guest complexes made the cavity more hydrophobic and promoted further inclusion. A reduction in the available volume of the cavity should be considered on binding a second guest.

AB - Multiple complexation by γ-CD has been studied by self-diffusion coefficients (DOSY) and chemical kinetics experiments in which 4-methoxybenzenesulfonyl chloride (MBSC) solvolysis was used as a chemical probe. The addition of a surfactant as a third component to the reaction mixture induced a very complex reactivity pattern that was explained on the basis of multiple complexation phenomena and surfactant self-assembly to form micelles. A cooperative effect that yielded a ternary complex formed by cyclodextrin-surfactant-MBSC was observed. The larger cavity of γ-CD in comparison with β-CD is responsible for the change from the competitive complexation mechanism predominant with β-CD to a cooperative/competitive mixed mechanism operating for the larger derivative. The cavity size in γ-CD is large enough to bind two surfactant alkyl chains with a cooperative effect. Water molecules released by the formation of 1 : 1 host-guest complexes made the cavity more hydrophobic and promoted further inclusion. A reduction in the available volume of the cavity should be considered on binding a second guest.

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Fernández-Rosas J, Pessêgo M, Cepeda-Plaza M, Basilio N, Parajó M, Rodríguez-Dafonte P y otros. γ-Cyclodextrin modulates the chemical reactivity by multiple complexation. Organic and Biomolecular Chemistry. 2015 ene 28;13(4):1213-1224. https://doi.org/10.1039/c4ob02113d