Abstract
<jats:p> Small-molecule catalysts are pursued as they are widely used in fundamental and applied chemistry. Herein, we report that tetracarboxyphenyl iron porphyrin (FeTCPP) is a superior water-soluble catalyst for the reduction of N‑oxides and endoperoxides. Through screening tetraphenyl iron porphyrin (FeTPP) derivatives, we found FeTCPP performed best and only 0.4% FeTCPP could efficiently reduce the N‑oxide to tertiary amine. Impressively, FeTCPP catalytically reduced the endoperoxide of artemisinin to generate a main product while the known activator, heme, led to multiple products. The inactivity of the main product against tumor cells and malaria parasites will help in understanding the antimalarial and anticancer activities of artemisinin. Finally, we successfully applied FeTCPP in the reduction of transitionally-formed endoperoxide during direct chemiluminescence by isoluminol. Whether isoluminol is free or labelled with proteins, FeTCPP generated stronger chemiluminescence than hemin and increased the detection sensitivity by 20-fold. An undeniable advantage of FeTCPP is that it prefers to the low concentration of H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> used in direct chemiluminescence detection. FeTCPP thereby could save 95% hydrogen peroxide (H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> ) compared to the traditional hemin catalyst. As isoluminol-based direct chemiluminescence detection is a routine test in clinics and hospitals, the wide application of FeTCPP will produce tremendous economic and environmental value. </jats:p>