Gas Evolution as a Tool to Study Reaction Kinetics Under Biomimetic Conditions.

The field of bioorthogonal chemistry is rapidly growing, presenting successful applications of organic and transition metal-catalysed reactions in cells and living systems (in vivo). The development of such reactions typically proceeds through many iterative steps focused on biocompatibility and fast reaction kinetics to ensure product formation. However, obtaining kinetic data, even under simulated biological (biomimetic) conditions, remains a challenge due to substantial concentrations of salts and biomolecules hampering the use of typically employed solution-phase analytical techniques. In this study, we explored the suitability of gas evolution as a probe to study kinetics under biomimetic conditions. As proof of concept, we show that the progress of two transition metal-catalysed bioorthogonal chemical reactions can be accurately monitored, regardless of the complexity of the medium. As such, we introduce a protocol to gain more insight into the performance of a catalytic system under biomimetic conditions to further progress iterative catalyst development for in vivo applications.

Boosting Electrochemical Oxygen Reduction Performance of Iron Phthalocyanine through Axial Coordination Sphere Interaction.

Precise regulation of the electronic states of catalytic sites through molecular engineering is highly desired to boost catalytic performance. Herein, a facile strategy was developed to synthesize efficient oxygen reduction reaction (ORR) catalysts, based on mononuclear iron phthalocyanine supported on commercially available multi-walled carbon nanotubes that contain electron-donating functional groups (FePc/CNT-R, with "R" being -NH2 , -OH, or -COOH). These functional groups acted as axial ligands that coordinated to the Fe site, confirmed by X-ray photoelectron spectroscopy and synchrotron-radiation-based X-ray absorption fine structure. Experimental results showed that FePc/CNT-NH2 , with the most electron-donating -NH2 axial ligand, exhibited the highest ORR activity with a positive onset potential (Eonset =1.0 V vs. reversible hydrogen electrode) and half-wave potential (E1/2 =0.92 V). This was better than the state-of-the-art Pt/C catalyst (Eonset =1.00 V and E1/2 =0.85 V) under the same conditions. Overall, the functionalized FePc/CNT-R assemblies showed enhanced ORR performance in comparison to the non-functionalized FePc/CNT assembly. The origin of this behavior was investigated using density functional theory calculations, which demonstrated that the coordination of electron-donating groups to FePc facilitated the adsorption and activation of oxygen. This study not only demonstrates a series of advanced ORR electrocatalysts, but also introduces a feasible strategy for the rational design of highly active electrocatalysts for other proton-coupled electron transfer reactions.