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Two-dimensional nanomaterials have potential as a new class of antioxidants that combine physical barrier function with ultrahigh surface area for free radical scavenging. This work presents the first measurements of the chemical reactivities of graphene-based materials toward a set of model free radicals and reactive oxygen species using electron paramagnetic resonance spectroscopy (EPR) and sacrificial dye protection assays. Graphene-based materials are shown to protect a variety of molecular targets from oxidation by these species, and to be highly effective as hydroxyl-radical scavengers. When the hydroxyl radical is produced photolytically, the overall antioxidant effect is a combination of preventative antioxidant activity (UV absorption) and ˙OH radical scavenging. Few-layer graphene is more active than monolayer graphene oxide, despite its lower surface area, which indicates that the primary scavenging sites are associated with the sp(2)-carbon network rather than oxygen-containing functional groups. To explain this trend, we propose that GO is a weak hydrogen donor, due to the non-phenolic nature of most OH groups on GO, which reside at basal sp(3)-carbon sites that do not allow for radical resonance stabilization following hydrogen donation. As an example application of graphene antioxidant behavior, we show that encapsulation of TiO2 nanoparticles in graphene nanosacks reduces undesired photo-oxidative damage to nearby organic target molecules, which suggests graphene encapsulation as a new approach to managing adverse environmental or health impacts of redox-active nanomaterials.

Iridium pincer complexes (POCOP)Ir(CO) (POCOP = κ3-C6H3-1,3-[OP(tBu)2]2) and substituted POCOP derivatives catalyze deoxygenation of glycerol to n-propanol and 1,3-propanediol in good yield under moderate conditions (acidic aqueous dioxane, 200 °C, 80 bar H2). Catalyst solubility in the polar reaction mixture is improved by incorporation of a polar moiety in the para position of the POCOP phenyl ring, with the best results obtained with a dimethylamino substituent.