Angewandte Chemie International Edition最新文献

Numerous reactions within metabolic pathways have been reported to occur nonenzymatically, supporting the hypothesis that life arose upon a primitive nonenzymatic precursor to metabolism. However, most of those studies reproduce individual transformations or segments of pathways without providing a common set of conditions for classes of reactions that span multiple pathways. In this study, we search across pathways for common nonenzymatic conditions for a recurring chemical transformation in metabolism: alkene hydration. The mild conditions that we identify (Fe oxides such as green rust) apply to all hydration reactions of the rTCA cycle and gluconeogenesis, including the hydration of phosphoenolpyruvate (PEP) to 2-phosphoglycerate (2PGA), which had not previously been reported under nonenzymatic conditions. Mechanistic insights were obtained by studying analogous substrates and through anoxic and radical trapping experiments. Searching for nonenzymatic conditions across pathways provides a complementary strategy to triangulate conditions conducive to the nonenzymatic emergence of a protometabolism.

With the increasing sales of electric vehicles, lots of spent lithium-ion batteries (LIBs) assembled with LiFePO4 (LFP) cathodes will retire in the next few years, posing a significant challenge for their effective and environmentally-friendly recycling. The main reason why spent LFP cathodes fail to re-utilize lies in the lattice defects caused by lithium loss and structural defects resulting from stress accumulation. In this work, we propose an in-situ granule reconstruction strategy to directly regenerate spent LFP black mass (S-BM) using glycerol in industry settings. The hydroxyl groups abundant in glycerol serves as electron donor that help reduce Fe (III) and repair Fe-Li antisite defects (FeLi). Additionally, the chelating properties of glycerol intervene with structurally disintegrated particles, inhibiting Oswald ripening effect and promoting bonding of grain boundaries to generate lamellar microcrystals with homogeneous grain size, recover their morphology and crystal structure after a facile annealing procedure. Furthermore, the regenerated LFP restores Fe-O bonds which further inhibits structural distortion and improve Li+ migration kinetics. As a result, the regenerated industrial LFP black mass (R-BM) exhibits superior lithium storage performance with a discharge capacity of 123.2 mA h g-1 after 500 cycles at 5.0 C (a capacity retention rate of 93.1%).

Herein, a copper(I)-catalyzed asymmetric 1,4-hydroarsination of β-substituted α,β-unsaturated esters is achieved in moderate to excellent yields with high to excellent enantioselectivity, based on the proposed nucleophilic [Cu]-AsPh2 species. As for α-substituted α,β-unsaturated esters, a 1,4-hydroarsination/enantioselective protonation event occurs smoothly in satisfying results. Furthermore, β-substituted α,β-unsaturated ketone, α,β-unsaturated amide, and α,β-unsaturated phosphine sulfide are well applied in the present catalytic system. Finally, some control experiments show that HAsPh2 is activated through coordination with the copper(I) catalyst and HAsPh2 exhibits inferior soft Lewis basicity to HPPh2 in the presence of a copper(I)-bisphosphine complex.

Sn-based perovskites have emerged as one of the most promising environmentally-friendly photovoltaic materials. Nonetheless, the low-cost production and stable operation of Sn-based perovskite solar cells (PSCs) are still limited by the costly hole transport layer (HTL) and the under-optimized interfacial carrier dynamics. Here, we innovatively developed a halogen radical chemical bridging strategy that enabled to remove the HTL and optimize the perovskite-substrate heterointerface for constructing high-performance, simplified Sn-based PSCs. The modification of ITO electrode by highly active chlorine radicals could effectively mitigate the surface oxygen vacancies, alter the chemical constitutions, and favorably down-shifted the work function of ITO surface to be close to the valence band of perovskites. As a result, the interfacial energy barrier was reduced by 0.20 eV and the carrier dynamics were optimized at the ITO/perovskite heterointerface. Encouragingly, the efficiency of HTL-free Sn-based PSCs was enhanced from 6.79% to 14.20%, representing the record performance for the Sn perovskite photovoltaics in the absence of HTL. Notably, the target device exhibited enhanced stability for 2000 h. The Cl-RCB strategy is also versatile to construct Pb-based and mixed Sn-Pb HTL-free PSCs, achieving efficiencies of 22.27% and 21.13%, respectively, all representing the advanced device performances for the carrier transport layer-free PSCs.

Graphene nanoribbons (GNRs) with low band gap and strong near-infrared (NIR) absorption are potential candidates for optoelectronic and biomedical applications. In this context, imide-based GNRs are promising, but there are no rational design principles that yield these robust GNRs with strong NIR absorption. Here, we demonstrate a rational synthesis route to achieve NIR-absorbing imide-based robust GNRs by exploring the bay region of polyperylene (PP). Using the oxidative Diels-Alder reaction, we have successfully introduced mono and diimide functional groups on PP. After cyclodehydrogenation, the resultant GNRs, benzoperylene imide GNR (BPI-GNR) and coronene diimide GNR (CDI-GNR), show oscillatory edge geometry with strong NIR absorption (up to 1000 nm) and optical band gap of ~1.3 eV. Computational studies also indicate that imide substituents play an important role in fine-tuning the optoelectronic properties of GNRs. Moreover, these GNRs are solution-processable and can be made into thin films via spray coating. Owing to the strong NIR absorption and imide substitutions, BPI and CDI-GNRs show good photothermal conversion with excellent cyclic stability.

Natural protein-protein communications, such as those between transcription factors (TFs) and RNA polymerases/ribosomes, underpin cell-free biosensing systems operating on the transcription/translation (TXTL) paradigm. However, their deployment in field analysis is hampered by the delayed response (hour-level) and the complex composition of in vitro TXTL systems. For this purpose, we present a de novo-designed ligand-responsive artificial protein-protein communication (LIRAC) by redefining the connection between TFs and non-interacting CRISPR/Cas enzymes. By rationally designing a chimeric DNA adaptor and precisely regulating its binding affinities to both proteins, LIRAC immediately transduces target-induced TF allostery into rapid CRISPR/Cas enzyme activation within a homogenous system. Consequently, LIRAC obviates the need for RNA/protein biosynthesis inherent to conventional TXTL-based cell-free systems, substantially reducing reaction complexity and time (from hours to 10 minutes) with improved sensitivity and tunable dynamic range. Moreover, LIRAC exhibits excellent versatility and programmability for rapidly and sensitively detecting diverse contaminants, including antibiotics, heavy metal ions, and preservatives. It also enables the creation of a multi-protein communication-based tristate logic for the intelligent detection of multiple contaminants. Integrated with portable devices, LIRAC has been proven effective in the field analysis of environmental samples and personal care products, showcasing its potential for environmental and health monitoring.

The global crisis of bacterial infections is exacerbated by the escalating threat of microbial antibiotic resistance. Nanozymes promise to provide ingenious solutions. Here, we reported a homogeneous catalytic structure of Pt nanoclusters with finely tuned metal-organic framework (ZIF-8) channel structures for the treatment of infected wounds. Catalytic site normalization showed that the active site of the Pt aggregates structure with fine-tuned pore modifications structure had a catalytic capacity of 14.903 ×105 min-1, which was 18.7 times higher than that of the Pt particles in monodisperse state in ZIF-8 (0.793 ×105 min-1). In situ tests revealed that the change from homocleavage to heterocleavage of hydrogen peroxide at the interface of the nanozyme was one of the key reasons for the improvement of nanozyme activity. Density-functional theory and kinetic simulations of the reaction interface jointly determine the role of the catalytic center and the substrate channel together. Metabolomics analysis showed that the developed nanozyme, working in conjunction with reactive oxygen species, could effectively block energy metabolic pathways within bacteria, leading to spontaneous apoptosis and bacterial rupture. This pioneering study elucidates new ideas for the regulation of artificial enzyme activity and provides new perspectives for the development of efficient antibiotic substitutes.

Organic Materials. An all-natural structural material is simultaneously strengthened and toughened through its interfacial interlocking structure and intermolecular interactions, as reported by Shu-Hong Yu et al. in their Research Article (e202408458).