The combination between visualization nanozyme and tumor vascular normalization contributes to the therapy of breast cancer.

Nanozymes that mimic natural enzyme–like activities have gradually emerged in cancer therapy. To overcome the bottlenecks of single-mode nanozymes, including “off-target” toxicity and ineffectiveness toward metastatic cancers, we designed magnetic nanoparticle–based multifunctional visualized immunomodulatory nanozymes. Besides the partial initiation of the prime immune response by intrinsic immunogenicity, as a smart drug delivery system with a temperature- and pH-sensitive dual response to the tumor microenvironment, these nanozymes released immune agonists to boost enhanced systemic immune response, eventually ameliorating the cancer immune microenvironment through many aspects: activating dendritic cells, improving the function of CD8 ⁺ T cells, and decreasing the population of myeloid-derived suppressor cells, which inhibited both primary and metastatic cancers. Mechanistically, these nanozymes regulated the reactive oxygen species–related Akt signaling pathway and consequently activated cell apoptosis–related signaling pathways, which provided a deeper understanding of the synergistic mechanism of multifunctional nanozymes. Our findings offer a promising imaging-guided cocktail therapy strategy through immunomodulatory nanozymes.

Facile evaluation of formation kinetics of key intermediate is crucial for a comprehensive understanding of electrochemical ammonia oxidation reaction (AOR) mechanisms and the design of efficient electrocatalysts. Currently, elucidating the formation kinetics of key intermediate associated with rate‐determining step is still challenging. Herein, 4‐phtalamide‐N‐(4′‐methylcoumarin) naphthalimide (CF) is developed as a molecular probe to detect N₂H₄ intermediate during AOR via electrochemiluminescence (ECL) and further investigated the formation kinetics of N₂H₄ on Pt catalysts with different crystal planes. CF probe can selectively react with N₂H₄ to release ECL substance luminol. Thus, N₂H₄ intermediate as a key intermediate can be sensitively and selectively detected by ECL during AOR. For the first time, Pt(100) facet is discovered to exhibit faster N₂H₄ formation kinetics than Pt(111) facet, which is further confirmed by Density functional theory calculation and the finite element simulation. The AOR mechanism under the framework of Gerischer and Mauerer is further validated by examining N₂H₄ formation kinetics during the dimerization process (NH₂ coupling). The developed ECL active probe and the discovered facet‐dependent formation kinetics of key intermediates provide a promising new tool and strategy for the understanding of electrochemical AOR mechanisms and the design of efficient electrocatalysts.