Angewandte Chemie International Edition

doi: 10.1002/anie.202313868pmid: 37899658

Solar‐to‐chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar‐driven photothermal system coupling a dual‐metal single‐atom catalyst (DSAC) with adjacent Ni−N4 and Fe−N4 pair sites is designed for boosting gas‐solid CO2 reduction with H2O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 μmol g−1 h−1), CH4 (135.35 μmol g−1 h−1) and CH3OH (59.81 μmol g−1 h−1), which are equivalent to 1.70‐fold, 1.27‐fold and 1.23‐fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d‐band center of Fe atom is efficiently regulated in non‐interacting Ni and Fe dual‐atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar‐driven photothermal CO2 reduction to initial CO production.

Chemo‐dynamic therapy (CDT) based on the Fenton or Fenton‐like reaction has emerged as a promising approach for cancer treatment. However, autophagy‐mediated self‐protection mechanisms of cancer cells pose a significant challenge to the efficacy of CDT. Herein, we developed metal‐DNA nanocomplexes (DACs‐Mn) to enhance CDT via DNAzyme inhibition of autophagy. Specifically, Mn‐based catalyst in DACs‐Mn was used to generate highly hydroxyl radicals (⋅OH) that kill cancer cells, while the ATG5 DNAzyme incorporated into DACs‐Mn inhibited the expression of autophagy‐associated proteins, thereby improving the efficacy of CDT. By disrupting the self‐protective pathway of cells under severe oxidative stress, this novel approach of DACs‐Mn was found to synergistically enhance CDT in both in vitro and in vivo models, effectively amplifying tumor‐specific oxidative damage. Notably, the Metal‐DNA nanocomplexes can also induce immunogenic cell death (ICD), thereby inhibiting tumor metastasis. Specifically, in a bilateral tumor model in mice, the combined approach of CDT and autophagy inhibition followed by immune checkpoint blockade therapy shown significant potential as a novel and effective treatment modality for primary and metastatic tumors.

The development of flexible, room‐temperature phosphorescence (RTP) materials remains challenging owing to the quenching of their unstable triplet excitons via molecular motion. Therefore, a polymer matrix with Tg higher than room temperature is required to prevent polymer segment movement. In this study, a RTP material was developed by incorporating a 4‐biphenylboronic acid (BPBA) phosphor into a poly(vinylidene fluoride) (PVDF) matrix (Tg=−27.1 °C), which exhibits a remarkable UV‐light‐dependent oxygen consumption phosphorescence with a lifetime of 1275.7 ms. The adjustable RTP performance is influenced by the crystallinity and polymorph (α, β, and γ phases) fraction of PVDF, therefore, the low Tg of the PVDF matrix enables the polymeric segmental motion upon microwave irradiation. Consequently, a reduction in the crystallinity and an increase in the α phase fraction in PVDF film induces RTP after 2.45 GHz microwave irradiation. These findings open up new avenues for constructing crystalline and phase‐dependent RTP materials while demonstrating a promising approach toward microwave detection.

doi: 10.1002/anie.202312494pmid: 37703211

We report two novel three‐dimensional copper‐benzoquinoid metal–organic frameworks (MOFs), [Cu4L3]n and [Cu4L3 ⋅ Cu(iq)3]n (LH4=1,4‐dicyano‐2,3,5,6‐tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal–organic extended solids. The coordination between the mixed‐valence metal and redox‐non‐innocent ligand L, which promotes through‐bond charge transfer between Cu metal sites, allows better metal‐ligand orbital overlap of the d‐π conjugation, leading to strong long‐range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly‐covalent Cu(III), non‐innocent ligand, and pore environments of these bench stable Cu(III)‐containing frameworks on multielectron transfer and electrochemical properties.