Simultaneous Kinetic and Thermodynamic-Based Assay to Determine the Hydrogen Peroxide (H2O2) Scavenging Activity of Berry Extracts by Using Reaction Calorimetry

Abstract

This work determines the radical scavenging activity of antioxidants and berry extracts based on the heat generated during their reaction with hydrogen peroxide, under isothermal condition (25 °C). After addition of H2O2 to a water solution containing antioxidants, an exothermic heat flow appeared. After an initial damping time, the signal decayed exponentially, following a first-order kinetic. Through an iterative fitting routine, both thermodynamic (ΔH) and kinetic (k) information were achieved. Such approach was applied toward relevant food antioxidants, revealing that the fastest reactivity (k) was for tannic acid > gallic acid > caffeic acid > ascorbic acid. Interestingly, k was inversely correlated with ΔH (r = −0.96) and with the DPPH test (r = −0.98). Apparently, strong radical scavengers show faster kinetics and lower ΔH-values, as expected, respectively, from a high reactivity toward peroxyl radical and efficient delocalization capacity. Such approach was finally applied to berry extracts (mixed grape seed and skin; chokeberries; grape seed; goji berries). The resulting ΔH-values were correlated with three indices, namely, total phenol, amperometry, and DPPH test. However, k-values largely deviated from these indices. Such discrepancy was explained considering that none of these indices is a “true” measure of the kinetic of the reaction, but only express an apparent concentration. Conversely, reaction calorimetry provides directly and simultaneously both thermodynamic and kinetic properties of the radical scavenging reactivity of antioxidants or natural extracts.