A kinetic study of the photodynamic effect on tryptophan methyl ester and tryptophan octyl ester in DOPC vesicles

POSADAZ A.; CORREA N.M.; BIASUTTI M. A.; GARCIA N. A.

PHOTOCHEMISTRY AND PHOTOBIOLOGY

WILEY-BLACKWELL PUBLISHING, INC

Año: 2010 vol. 86 p. 96 - 103

0031-8655

The photodynamic effect on tryptophan methyl ester (trpME) and tryptophan octyl ester (trpOE), using the O2(1Dg)-photosensitizers Rose Bengal (RB) and Perinaphthenone (PN) has been studied in large unilamellar vesicles (LUVs) of the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) by stationary photolysis and time-resolved methods. This work reports on the influence of both the site (O2(1Dg)) generation and the location of the tryptophan derivatives (trpD), on the photo-oxidation process in a compartmentalized system. The apparent rate constant values for chemical quenching of O2(1Dg) by trpOE (kr,app), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg)-photosensitizers Rose Bengal (RB) and Perinaphthenone (PN) has been studied in large unilamellar vesicles (LUVs) of the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) by stationary photolysis and time-resolved methods. This work reports on the influence of both the site (O2(1Dg)) generation and the location of the tryptophan derivatives (trpD), on the photo-oxidation process in a compartmentalized system. The apparent rate constant values for chemical quenching of O2(1Dg) by trpOE (kr,app), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg)) generation and the location of the tryptophan derivatives (trpD), on the photo-oxidation process in a compartmentalized system. The apparent rate constant values for chemical quenching of O2(1Dg) by trpOE (kr,app), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg) by trpOE (kr,app), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.kr,app), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg) (kr,app ⁄ kt,app), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg) is generated in the aqueous pseudophase. For trpME, the kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.kr,app ⁄ kt,app values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O2(1Dg) attack in a microheterogeneous medium as compared with water.2(1Dg) attack in a microheterogeneous medium as compared with water.