Interfacial Hydrogen Atom Transfer by nanohybrids based on Humic Acid Like Polycondensates

Novel nanohybrid materials were prepared by covalent grafting of a polyphenolic polymer [Humic Acid Like Polycondensate (HALP)] on SiO2 nanoparticles. Four nanohybrids were so-produced, using four different types of SiO2 i.e. three Aerosil flame-made nanoparticles with nominal specific surface area of 50, 90 and 300 m(2)/g, herein codenamed OX50, A90, A300 respectively, plus a colloidal SiO2[S300] with SSA=300 m(2)/g. The antioxidant activity of the SiO2-HALP nanohybrids was evaluated by assessing their kinetics for Hydrogen Atom Transfer [HAT] to DPPH radicals. When normalized per same HALP concentration, bigger NPs SiO2[OX50]-HALP NPs can scavenge 280 μmoles of DPPH radicals per gram of HALP, while [A90]-HALP and [A300]-HALP NPs can scavenge 514 and 832 μmoles of DPPH radicals per gram of HALP, respectively. The colloidal SiO2[S300]-HALP can scavenge fewer DPPH radicals (252 μmoles) per gram of HALP. Based on detailed kinetic data it is shown that (i) surface grafted HALPs perform 300% better HAT than non-grafted HALP in solution. (ii) By controlling the particle type and grafting-loading, we can control/optimize the HAT performance: when grafted on the appropriate SiO2 surface the HALP macromolecules are able to quench up to 0.8 mmoles of DPPH-radical per gram of HALP.