Hom-Gel'fand–Dorfman Super-bialgebras and Hom-Lie Conformal Superalgebras

The aim of this paper is to introduce and study Hom-Gel'fand–Dorfman super-bialgebras and Hom-Lie conformal superalgebras. In this paper, we provide different ways for constructing HomGel'fand–Dorfman super-bialgebras. Also, we obtain some infinite-dimensional Hom-Lie superalgebras from affinization of Hom-Gel'fand–Dorfman super-bialgebras. Finally, we give a general construction of Hom-Lie conformal superalgebras from Hom-Lie superalgebras and establish the equivalence between quadratic Hom-Lie conformal superalgebras and Hom-Gel'fand–Dorfman super-bialgebras.     

捕捉环加成反应中的有机亚铜中间体构筑氮杂环化合物研究进展

铜(I)盐催化的环加成反应,如叠氮-炔[3+2]环加成(Cu AAC)、不饱和化合物与异氰基化合物的[3+2]环加成、硝酮-炔的环加成(Kinugasa反应)是构建多类氮杂环的高效合成方法,被广泛应用于有机合成的各个领域.近年来,针对几类环加成反应中产生的有机亚铜中间体的多样性转化吸引了国内外很多课题组的注意,基于对这些环加成反应中有机亚铜中间体的捕捉,多类串联及多组分反应得以发展,从而成功实现了一系列多取代杂环或稠环结构的高效构建.本综述总结了这一领域的研究进展,按照所经历的有机亚铜中间体的类型进行分类,包括:(1)Cu AAC反应中产生的三氮唑亚铜中间体;(2)炔烃与异氰化合物[3+2]环加成反应中产生的2H-吡咯基亚铜中间体;(3) Kinugasa反应中产生的烯醇亚铜中间体.期望此综述能够有助于研究者了解有机亚铜中间体捕捉策略的发展、应用现状及不足之处,进一步推动铜催化转化的发展.     

Amperometric sandwich-type aptasensor based on peroxidase mimetic Au@Pt for the carcinoembryonic antigen

For sensitive analysis of cancer biomarker carcinoembryonic antigen (CEA), an amperometric sandwich-type aptasensor is proposed based on a signal amplification strategy of Au@Pt bimetallic nanoprobes. As the excellent catalytic activity to hydrogen peroxide (H₂O₂), core-shell Au@Pt nanoparticles are employed as nanoprobes by conjugating directly with the secondary aptamer of CEA (Apt-II). Due to the synergic recognition effect of dual aptamers and the excellent catalytic activity of nanoprobes, this amperometric sandwich-type aptasensor for CEA exhibits high specificity and good sensitivity with a limit of detection of 0.31 ng/mL, along with a wide linear range from 0.1 ng/mL to 100 ng/mL.     

Didepside Formation by the Nonreducing Polyketide Synthase Preu6 of Preussia isomera Requires Interaction of Starter Acyl Transferase and Thioesterase Domains

Orsellinic acid (OA) derivatives are produced by filamentous fungi using nonreducing polyketide synthases (nrPKSs). The chain-releasing thioesterase (TE) domains of such nrPKSs were proposed to also catalyze dimerization to yield didepsides, such as lecanoric acid. Here, we use combinatorial domain exchanges, domain dissections and reconstitutions to reveal that the TE domain of the lecanoric acid synthase Preu6 of Preussia isomera must collaborate with the starter acyl transferase (SAT) domain from the same nrPKS. We show that artificial SAT-TE fusion proteins are highly effective catalysts and reprogram the ketide homologation chassis to form didepsides. We also demonstrate that dissected SAT and TE domains of Preu6 physically interact, and SAT and TE domains of OA-synthesizing nrPKSs may co-evolve. Our work highlights an unexpected domain–domain interaction in nrPKSs that must be considered for the combinatorial biosynthesis of unnatural didepsides, depsidones, and diphenyl ethers.     

A Conformational Restriction Strategy for the Control of CRISPR/Cas Gene Editing with Photoactivatable Guide RNAs**

The CRISPR/Cas system is one of the most powerful tools for gene editing. However, approaches for precise control of genome editing and regulatory events are still desirable. Here, we report the spatiotemporal and efficient control of CRISPR/Cas9- and Cas12a-mediated editing with conformationally restricted guide RNAs (gRNAs). This approach relied on only two or three pre-installed photo-labile substituents followed by an intramolecular cyclization, representing a robust synthetic method in comparison to the heavily modified linear gRNAs that often require extensive screening and time-consuming optimization. This tactic could direct the precise cleavage of the genes encoding green fluorescent protein (GFP) and the vascular endothelial growth factor A (VEGFA) protein within a predefined cutting region without notable editing leakage in live cells. We also achieved light-mediated myostatin (MSTN) gene editing in embryos, wherein a new bow-knot-type gRNA was constructed with excellent OFF/ON switch efficiency. Overall, our work provides a significant new strategy in CRISPR/Cas editing with modified circular gRNAs to precisely manipulate where and when genes are edited.     

Mechanism of Cations Suppressing Proton Diffusion Kinetics for Electrocatalysis

Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton transfer rate and then tune electrocatalytic performance. However, the mechanism for regulating proton transfer remains ambiguous. Here, we quantify the cation effect on proton diffusion in solution by hydrogen evolution on microelectrodes, revealing the rate can be suppressed by more than 10 times. Different from the prevalent opinions that proton transport is slowed down by modified electric field, we found water structure imposes a more evident effect on kinetics. FTIR test and path integral molecular dynamics simulation indicate that proton prefers to wander within the hydration shell of cations rather than to hop rapidly along water wires. Low connectivity of water networks disrupted by cations corrupts the fast-moving path in bulk water. This study highlights the promising way for regulating proton kinetics via a modified water structure.     

Multi-Resonance Building-Block-Based Electroluminescent Material: Lengthening Emission Maximum and Shortening Delayed Fluorescence Lifetime

Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials are considered a class of organic materials with exceptional electronic and optical properties, which make them promising for the applications in organic light-emitting diodes (OLEDs). In this study, we improved, synthesized, and characterized a multiple-resonance type emitter based on the assembly of MR-building blocks (MR-BBs). By optimizing the geometric arrangement of MR-BBs, we were able to generate narrowband emission in the longer wavelength region and shorten the delayed excited-state lifetime, resulting in improved emission efficiency compared to the parent molecule. Our proof-of-concept molecule, m-DBCz, exhibited narrowband yellowish-green TADF emission with a full width at half-maximum of 32 nm and a small singlet-triplet energy gap of 0.04 eV. The OLED developed using m-DBCz as the emitter demonstrated electroluminescence at 548 nm and achieved a high external quantum efficiency (EQE) of 34.9 %. Further optimization of the device resulted in a high external quantum efficiency of 36.3 % and extremely low efficiency roll-off, with EQE values of 30.1 % and 27.7 % obtained even at high luminance levels of 50 000 and 100 000 cd m⁻². These results demonstrate the full potential of MR-TADF materials for applications on ultrahigh-luminance OLEDs.     

Palladium and Ruthenium Dual-Single-Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd₁−Ru₁ single-atom-sites supported on porous ionic polymers (Pd₁−Ru₁/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd- or Ru-site catalyst, the dual single-atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single-Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd₁−Ru₁/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd₁/PIPs for the rate-determining step. The synergetic effect between neighboring single sites Pd₁ and Ru₁ not only enhanced the overall activity, but also stabilized Pd^II active sites. The discovery of synergetic effects between single sites can deepen our understanding of single-site catalysts at the molecular level.     

Unlocking Charge Transfer Limitations for Extreme Fast Charging of Li-Ion Batteries

Extreme fast charging (XFC) of high-energy Li-ion batteries is a key enabler of electrified transportation. While previous studies mainly focused on improving Li ion mass transport in electrodes and electrolytes, the limitations of charge transfer across electrode–electrolyte interfaces remain underexplored. Herein we unravel how charge transfer kinetics dictates the fast rechargeability of Li-ion cells. Li ion transfer across the cathode–electrolyte interface is found to be rate-limiting during XFC, but the charge transfer energy barrier at both the cathode and anode have to be reduced simultaneously to prevent Li plating, which is achieved through electrolyte engineering. By unlocking charge transfer limitations, 184 Wh kg⁻¹ pouch cells demonstrate stable XFC (10-min charge to 80 %) which is otherwise unachievable, and the lifetime of 245 Wh kg⁻¹ 21700 cells is quintupled during fast charging (25-min charge to 80 %).     

Cooperative Ni(Co)-Ru-P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self-powered H2 Production

Water electrolysis for H₂ production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru₁−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm⁻², respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm⁻² at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru₁−NiCoP optimize H* adsorption, and enhance adsorption of *N₂H₂ to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H₂ production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h⁻¹ m⁻².