Angewandte Chemie最新文献

In the Communication (e18517), André K. Eckhardt and co-workers demonstrate the advantageous properties of solid para-hydrogen (p-H₂) matrices for electron paramagnetic resonance spectroscopy by investigating the 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) radical and an in situ generated P-centered mono-radical. The spectral resolution of the P-centered radical in p-H₂ is roughly enhanced by a factor of three compared to argon.

Aqueous zinc metal batteries (AZMBs) are attractive for stationary energy storage due to their low cost and high safety. However, parasitic side reactions and severe Zn dendrites hinder practical implementation. Here, we propose the anion/cation dehydration shielding force as an effective guideline for electrolyte engineering that prioritizes anion-cation coordination structure. The methodology identifies 2-ethoxyethanol solvent as optimal components, enhancing Zn²⁺ diffusion kinetics and suppressing water activity through anion-dominated coordination chemistry. The preferential reduction of OTF⁻ enables fluorine-rich solid electrolyte interphase formation with high Zn²⁺ conductivity and excellent mechanical robustness, protecting Zn anode from side reaction and dendrite growth. As a result, the designed electrolyte enables symmetric Zn||Zn pouch cells to achieve 1500 h cycling with a remarkable cumulative capacity of 30 Ah cm⁻² under demanding conditions (20 and 10 mAh cm⁻²). More importantly, Ah-level pouch cells set extremely excellent durability milestones, maintaining 1400 cycles (4.2 months/3000 h operation) while outperforming most reported Zn metal counterparts in comparable capacity ranges.

Diese Arbeit demonstriert eine Kaskadenstrategie für die selektive Synthese von Propylenoxid (PO) durch Kopplung der anodischen H₂O₂-Erzeugung mit der TS-1-katalysierten Propylenepoxidierung. Durch die Immobilisierung von TS-1 auf einer Gasdiffusionsschicht erreicht das System eine hohe PO-Produktivität bei effizienter H₂O₂-Nutzung und bietet damit eine sicherere und umweltfreundlichere Alternative zur herkömmlichen PO-Produktion.

Beim Bestrahlen eines Gemischs aus einem Photoinitiator, einem Metallsalz und einem Monomer in einem alkoholischen Lösungsmittel oder in wässriger Lösung entsteht in einem einfachen Zugang ein plasmonisches Polymer-Metall-Nanokomposit.

Despite growing research efforts on inorganic lead halide perovskite nanocrystals, the mechanistic understanding of nucleation and growth kinetics remains insufficient for achieving precise morphology and crystal structure control. Herein, by simply modulating the concentrations of primitive ligands (e.g., I⁻ and oleylamine) into conventional synthetic strategies, CsPbI₃ perovskites, ranging from zero-dimensional quantum dots to unique one-dimensional nanowires/nanorods and ginkgo leaf-like architectures, can be realized. Mechanistic studies suggests that capping agents compete for adsorption on specific crystal facets, a finding further confirmed by density functional theory (DFT) calculations. Simultaneously, the crystal structures of the products undergo a phase transition from cubic to orthorhombic symmetry driven by lattice distortion that disrupts the crystal symmetry. In addition, temperature-dependent photoluminescence studies revealed that the electron-phonon coupling strengths of longitudinal optical (LO) phonons (γ_LO = 73.14 meV and $$ = 28.74 meV) of CsPbI₃ nanorods were much lower (γ_LO = 103.25 meV and E_LO = 33.62 meV) than those of ginkgo leaf-like CsPbI₃ superstructures, limiting multi-phonon-assisted non-radiative pathways. As a result, CsPbI₃ nanorods display a strong polarization dependence with a polarization degree of up to ∼0.49. These results not only demonstrates novel perovskite nanocrystals but also provide a versatile platform for tailoring perovskite NCs with combined morphological diversity and tunable optical properties.

Selective functionalization of [n]cycloparaphenylenes ([n]CPPs) has remained a significant synthetic challenge due to their inherent ring strain. In this study, we present the synthesis of a [9]CPP derivative in which bromo groups are orderly introduced at the 2,5-positions of three benzene rings in the [9]CPP framework, each separated by two phenylene units. The use of our developed Au-mediated CPP synthetic method enabled efficient and scalable access to the target compound in five steps with an overall yield of 37%. The resulting molecule exhibited phosphorescence at low temperature, arising from the heavy-atom effect of the bromo substituents. Furthermore, post-functionalization through Pd-catalyzed coupling reactions demonstrated multisite π-extension and afforded a chiral nanohoop exhibiting exceptional chiroptical performance (|g_lum| = 0.100).

A breakthrough in the treatment of solid tumors requires primary tumor ablation and remission of metastasis. Photodynamic therapy (PDT) may meet these requirements, but current photosensitizers poorly infiltrate dense tumors and insufficiently stimulate the immune system. We introduce LUZ51, a small bacteriochlorin that features strong near-infrared absorption, high photostability, moderate lipophilicity, amphiphilicity, and appropriate singlet oxygen quantum yield. LUZ51 has a fast cellular uptake via passive diffusion and EC50s of 5–15 nM range for a light dose of 1 J/cm². It seamlessly crosses biological barriers and accumulates in tumors. Mice with CT26 tumors cured in one treatment (0.15 mg/kg and 20 J/cm²) resisted tumor rechallenge. Treatment of mice with 5 mm orthotopic 4T1 tumors enabled cures, with the associated inhibition of metastasis. The blood half-life is 82 min and no skin photosensitivity was detected. Small-size LUZ51 enables tissue-agnostic PDT, with strong local and systemic effects.

The uniformity of self-assembled monolayers (SAMs) and the interfacial defects in perovskite films significantly affect the performance of inverted perovskite solar cells (IPSCs). Herein, we develop an innovative interface molecular locking (IML) strategy synergized with SAMs to enhance the properties of buried interface. Specifically, two SAMs—(4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)phosphonic acid (MeO-PhPACz) and 5-indoleboronic acid (5-IBA)—are employed to combine their advantages and form an enhanced SAM (E-SAM). Due to the strong π–π interactions between MeO-PhPACz and 5-IBA, the E-SAM exhibits a denser and more uniform morphological coverage. Introducing thiabendazole (TBZ) additive into the perovskite precursor further ameliorates the buried interface properties through its self-assembly behavior, owing to its large molecular dipole moment and strong interactions with the E-SAM. This strategy not only achieves favorable energy level alignment but also improves the crystallinity and reduces the trap density of perovskite films, thereby significantly enhancing hole extraction and suppressing non-radiative recombination. Consequently, both (FA_0.95MA_0.05)_0.95Cs_0.05Pb(I_0.95Br_0.05)₃ and FA_0.95Cs_0.05PbI₃-based IPSCs achieve high efficiencies exceeding 26.0%, along with significantly enhanced stability. Notably, (FA_0.95MA_0.05)_0.95Cs_0.05Pb(I_0.95Br_0.05)₃ solar cells deliver a high voltage of 1.21 V, one of the highest reported among IPSCs with a 1.56 eV bandgap. Our findings provide unique insights into achieving high-performance IPSCs by synergistically engineering buried interface.

Membrane proteins in biology achieve highly efficient selective molecular recognition and transmembrane transport by constructing sub-nanometer channels. However, achieving comparable selectivity in artificial protein-based membranes remains a formidable challenge, primarily due to the difficulty of precisely tailoring sub-nanometer pore sizes. Here, we present a breakthrough in the fabrication of proteinaceous nanofiltration membranes with precisely defined sub-nanometer pores. A robust protein membrane with pore sizes of 0.62–0.81 nm is formed at the air/water interface via a thiol-disulfide exchange reaction. Subsequent crosslinking with polyphenol further reduces the pore size to ∼0.4 nm, while simultaneously inverting surface charge from positive to negative and markedly enhancing ion sieving performance. As a proof-of-concept, the crosslinked amyloid-like protein membrane achieves 98.24% rejection of MgCl₂ and an excellent Mg²⁺/Li⁺ selectivity of 88.65 in a simulated salt-lake brine, surpassing the performance of most polymer membranes reported to date. Additionally, this membrane demonstrates versatility in separating anions with different valences, removing heavy metal ions, and eliminating persistent organic pollutants, while exhibiting excellent chemical stability and anti-fouling capability in acidic, alkaline, and organic solvent environments. By harnessing the precision of biological channels, this work offers a paradigm shift for next-generation biomimetic ion separation, environmental remediation, and water purification applications.

Benzo-fused mono- and di-azines constitute privileged scaffolds in pharmaceuticals and functional materials; however, achieving site-selective remote benzocyclic C─H functionalization on these motifs remains a formidable challenge due to the lack of an ideal tethering site for directing group (DG) and the tendency of heteroatom to deactivate metal catalysts. Herein, we report a robust isoquinoline-based directing template that enables catalytic, site-selective C5─H functionalization of benzo-fused azines. The template recruits the substrate through reversible N-coordination, allowing the strong σ-donating isoquinolinyl arm to position the metal catalyst for precise activation of the remote C5─H bond. This design facilitates efficient alkenylation with a broad range of alkenes, which are otherwise inaccessible with conventional stoichiometric nitrile-based templates reported in the literature. Notably, this new class of directing template unlocks the unprecedented C5─H alkynylation, further demonstrating the pivotal role of structural tuning of the directing entity in facilitating diverse C5─H functionalization transformations. Various key intermediates have been intercepted by single-crystal X-ray diffraction, and complementary spectroscopic analyses to shed light on the mechanism of the catalytic cycle. The mechanistic study also discloses that the cooperativity exists between the directing template (DT) and the template chaperone (TC) in the catalytic cycle.