Laser-Accelerated Mass Transport in Oxygen Reduction Via a Graphene-Supported Silver-Iron Oxide Heterojunction.

Mass-transport acceleration is essential toward enhanced electrocatalytic performance yet rarely recognized under irradiation, because light is usually reported to improve charge transfer. We studied laser-enhanced mass transport through the heterojunction between Ag and semiconductor Fe2O3 situated on graphene for oxygen reduction reaction. Because of the decreased mass-transport resistance by 59% under 405 nm laser irradiation, the current density can be enhanced by 180%, which is also supported by a theoretical calculation. This laser-enhanced mass transport was attributed to local photothermal heating and the near-field local enhancement. Easier desorption of OH- species occurring between the Fe and Ag centers under the laser accelerates the mass-transport centers.

Extension of C. elegans lifespan using the ·NO-delivery dinitrosyl iron complexes.

The ubiquitous and emerging physiology function of endogenous nitric oxide in vascular, myocardial, immune, and neuronal systems prompts chemists to develop a prodrug for the controlled delivery of ·NO in vivo and for the translational biomedical application. Inspired by the discovery of natural [Fe(NO)2] motif, herein, we develop the synthetic dinitrosyl iron complexes (DNICs) [Fe2(µ-SR)2(NO)4] (1) as a universal platform for the O2-triggered release of ·NO, for the regulation of ·NO-release kinetics (half-life = 0.6-27.4 h), and for the activation of physiological function of ·NO. Using C. elegans as a model organism, the ·NO-delivery DNIC 1 regulates IIS signaling pathway, AMPK signaling pathway, and mitochondrial function pathway to extend the lifespan and to delay the aging process based on the lifespan analysis, SA-ßgal activity assay, and next-generation RNA sequencing analysis. This study unveils the anti-aging effect of ·NO and develops DNICs as a chemical biology probe for the continued discovery of unprecedented NO physiology.

Heterojunctions of silver-iron oxide on graphene for laser-coupled oxygen reduction reactions.

We report a two-step hybridization of N-doped graphene and Ag-decorated Fe2O3 hematite to realize a balanced oxygen adsorption/desorption equilibrium and a laser-coupled ORR (LORR). The stable plateau currents with n values of 3.9 in a wide potential range (0.2-0.7 V) and 7.5% peroxide inhibition of the LORR are found to be directly associated with the Ag/Fe2O3 heterojunction, where interactions of semiconductor band gap excitation and plasmonic resonance-induced hot electrons are proposed to occur.