Kinetics of ABTS derived radical cation scavenging by bucillamine, cysteine, and glutathione. Catalytic effect of Cu2 + ions

- Decay of ABTS
- + is governed by pseudo-first order kinetics
- H+ ions display second order inhibition with all the studied thiols
- BUC exhibits zero order kinetics to ABTS
- + with H+-catalysis at pH > 2.7
- Cu2 + ions show strong catalysis for all the species in the order BUC > Cys > GSH
- Significant effects of EDTA and bathocuproine disulfonate were observed

Kinetics of reduction of the stable radical cation derived from 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) in reaction with the anti-rheumatic drug bucillamine (BUC) and two reference thiols - cysteine (Cys) and glutathione (GSH) was followed spectrophotometrically in acidic medium with 10-fold molar excess of the reductant. Decay of the radical is governed by pseudo-first order kinetics with small deviation in the case of GSH. H+ ions displayed second order inhibition of the reaction with all the studied compounds. The reaction of BUC exhibits zero order kinetics to the radical at lower acidities with a moderate acceleration of the reaction rate by H+ ions. A significant catalytic effect of Cu2 + ions on the reactions with all the reductants was observed. The most sensitive to Cu2 +-catalysis was the reaction of BUC with the radical cation, while Cu2 + ions showed much lower effect on the reaction with GSH. The presence of EDTA strongly inhibited the reactions and equalized the reaction rates for all the reductants. A Cu(I) selective chelator bathocuproine disulfonate reduced the reaction rate with Cys, but accelerated the reaction with BUC at the lower acidities. The experimental results were rationalized in the framework of the mechanism of reductive chelation. The conclusions may have important consequences for interpretation of antioxidant capacity assays, such as TEAC, utilizing the ABTS derived radical cation.