The free-standing multiscale porous NiFeCoZn high-entropy-alloy is in-situ constructed on the surface of NiZn intermetallic and Ni heterojunction over nickel foam (NiFeCoZn/NiZn-Ni/NF) by one scalable electroplating-annealing-etching protocal. The as-made NiFeCoZn/NiZn-Ni/NF fulfills the outstanding electrocatalytic performances with the small overpotentials (η ₅₀₀ = 184/348 mV), low Tafel slopes, as well as exceptional long-term catalytic durability for 400 h in alkaline solution toward both hydrogen evolution reaction and oxygen evolution reaction.

Comprehensive Summary

In the endeavor of searching for highly active and stable electrocatalysts toward overall water splitting, high-entropy-alloys have been the intense subjects owing to their advanced physicochemical property. The non-noble metal free-standing multiscale porous NiFeCoZn high-entropy-alloy is in situ constructed on the surface layer of NiZn intermetallic and Ni heterojunction over nickel foam (NiFeCoZn/NiZn-Ni/NF) by one scalable dealloying protocal to fulfill the outstanding bifunctional electrocatalytic performances toward overall water splitting. Because of the high-entropy effects and specific hierarchical porous architecture, the as-made NiFeCoZn/NiZn-Ni/ NF displays high intrinsic catalytic activities and durability toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. In particular, the in-situ construction of bimodal porous NiFeCoZn high-entropy-alloy results in the small overpotentials (η ₁₀₀₀ = 254/409 mV for HER and OER), low Tafel slopes, and exceptional long-term catalytic durability for 400 h. Expressively, the electrolyzer constructed with NiFeCoZn/NiZn-Ni/NF as both cathode and anode exhibits a low cell voltage of 1.72 V to deliver the current density of 500 mA·cm^–2 for overall water splitting. This work not only provides a facile and scalable protocol for the preparation of self-supporting high-entropy-alloy nanocatalysts but also enlightens the engineering of high performance bifunctional electrocatalysts toward water splitting.

Carbon dots (CDs)-based long persistent luminescence (LPL) composites with a tunable duration in an ultrawide range from second- to hour-level are designed and prepared for the first time. The relationship of energy levels between excited states of CDs and charged-transfer (CT) states of the corresponding composites plays a pivotal role in activating LPL and regulating the LPL durations. These LPL composites have been preliminarily employed in dynamic displaying systems.

Comprehensive Summary

Duration-tunable afterglow materials have garnered considerable attention in various applications. Herein, carbon dots (CDs)-based long persistent luminescence (LPL) composites with a tunable duration in an ultrawide range of seconds-to-hours levels were designed and prepared for the first time. In contrast to the established CD-based afterglow materials, we reported that CD-based composites exhibit LPL in the form of exciplexes and long-lived charge-separated states, enabling the LPL to be prolonged from several seconds to over one hour, exceeding the typical regulation range (limited to 1 min). Further studies revealed that the relationship between the excited and charge-transfer states of CDs plays a pivotal role in activating the LPL and regulating its duration. Furthermore, these composites exhibited high photoluminescence (PL) quantum yields of up to 60.63%, and their LPL was robust under ambient conditions, even in aqueous media. Their robust and superior LPL performance endows these composites with a strong competitive advantage in dynamic display systems, such as tags for time-resolved data encryption and displays of the remaining time of takeaways. This study offers an approach to preparing CDs-based LPL composites with tunable durations and may provide new insights for the development of rare-earth-free LPL materials.

Comprehensive Summary

In the last few years, organic solar cells (OSCs) have made significant progress in photovoltaic performance, mainly due to the innovative development of active layer materials, especially Y-series and related derivatives as acceptors which have become the key factor that boosts the power conversion efficiency. Recently, to achieve high-performance OSCs, an emerging molecular design strategy of applying flexible alkyl units as linkers to construct non-fully conjugated acceptors has been developed and addressed great attention. This review highlights the non-fully conjugated photovoltaic materials with Y-series backbone that enable high-performance OSCs. Impressive OSCs have been achieved by some representative non-fully conjugated material systems. The related molecular design strategies are discussed in detail. Finally, a brief summary and future prospect are provided in advancing the non-fully conjugated photovoltaic materials with Y-series backbone towards the brighter future.

Key Scientists

In this paper, two novel organic photothermal cocrystals (MTC and MFC) were rapidly prepared by coprecipitation method. Compared with MTC, the introduction of highly electronegative fluorine in MFC results in a stronger charge transfer interaction and a tighter crystal packing structure between MeCz and F₄TCNQ. Consequently, the absorption range of MFC is extended to the NIR-II region and has a high photothermal conversion efficiency of 54.6%. At the same time, we chose MFC and flexible substrate HPDMS to combine and prepare a flexible wearable heater, which exhibited potential application value in the field of light-driven local thermotherapy.

Comprehensive Summary

The organic cocrystal strategy has provided a convenient and efficient platform for preparing organic photothermal materials. However, the rapidly directional preparation of cocrystals with desirable photothermal properties remains challenging due to a lack of suitable design ideas. Here, two new photothermal cocrystals, MTC and MFC, based on acceptor molecules (TCNQ and F₄TCNQ) with different electron-withdrawing capacities were quickly prepared by the coprecipitation method, aiming to explore the effect of charge transfer (CT) interaction on photothermal properties. Compared with MTC, the stronger intermolecular CT interaction in MFC facilitates extending the absorption range (from the NIR-I to the NIR-II region) and enhancing the non-radiative transition process. Under the 808 nm laser irradiation, the photothermal conversion efficiency (PCE) of MFC is 54.6%, whereas MTC displays a mere 36.8%. The MFC cocrystal was further combined with a flexible polymer substrate (HPDMS) to prepare a flexible wearable heater (HPDMS@MFC), which exhibits excellent NIR-II photothermal performance. This work points out a research direction for the rapid assembly of efficient photothermal cocrystals and additionally provides an extensive application prospect for organic photothermal cocrystals in the field of wearable devices.

N-Heterocyclic carbenes (NHCs) serve as organocatalysts for the [3 + 3] annulation of readily available N-Ts indolin-3-ones with ynals in the presence of oxidant condition via an intermediate alkynyl acylazolium. The method provides pyrano[3,2-b]indol-2-ones with moderate to high yields. Further transformations lead to diverse densely-functionalized carbazoles with potential electroluminescent materials and other bioactivities.

Comprehensive Summary

We report herein an unprecedented N-heterocyclic carbene-catalyzed formal [3 + 3] annulation of ynals with N-Ts indolin-3-ones under the oxidation condition affording the functionalized pyrano[3,2-b]indol-2-ones. The alkynyl acylazoliums via the combination of a carbene with ynals in the presence of oxidate proved to be the important intermediates for the success of this transformation. This method features a broad substrate scope and mild conditions, including axially chiral skeletons with suitable substitutions.

A comprehensive overview was conducted on the design strategies for nanozymes with intrinsic catalytic specificity. Additionally, supplemental strategies were summarized to achieve the selectivity of nanozymes for analytical applications.

Comprehensive Summary

We have compiled eight promising strategies for enhancing the specificity and selectivity of nanozymes, as depicted in the comprehensive summary above. Enzymes exhibit intricate and sophisticated structures, including substrate channels and active sites, which can inform the design of nanozymes. Replication of these structural features and the application of facet engineering/doping techniques can significantly enhance the catalytic specificity of nanozymes. Alternatively, the use of Molecularly Imprinted Polymers (MIPs) to coat nanozymes represents an effective approach to impart substrate specificity. Furthermore, several straightforward stopgap strategies have been devised to improve nanozyme specificity for analytical applications, such as the integration of biorecognition elements and nanozyme sensor arrays through surface modification.

Key Scientists

The first scalable total synthesis and stereochemical assignment of talaroconvolutin A and talarofuranone are presented.

Comprehensive Summary

The first total synthesis of talaroconvolutin A (1.1 g obtained) and talarofuranone has been achieved using accessible materials (12 steps, 7.5% and 8.2% yields, respectively). Convergent routes involved intramolecular Diels−Alder reactions in two approaches for creating the decalin moiety. Additionally, an unprecedented DMP-mediated domino reaction resulted in the deoxy-tetramic acid system. These syntheses not only establish the absolute configuration of talaroconvolutin A but also enable further collaborative studies of this type of ferroptosis inducers.

A rapid synthetic protocol for N,O-bidentate difluoroboron chromophores was achieved via cascade C—H functionalization and difluoroboronation reaction from readily accessible feedstock chemicals in one shot.

Comprehensive Summary

Organic difluoroboron complexes are a kind of potential platforms for a wide range of applications owing to their excellent photophysical properties. Herein, we have explored a simple and direct synthesis methodology for a library of N,O-bidentate difluoroboron complexes from quinoxalin-2(1H)-ones and ketones in one shot. The photophysical properties of the generated complexes were evaluated and the application potential of these compounds on subcellular imaging was also explored.

Nineteen new cadinane-involving sesquiterpenoid dimer, artemordins A—S (1—19) were isolated from Artemisia ordosica. Notably, artemordins A—F (1—6) were the first examples of two cadinane units connected by unprecedented C—C single bond with an oxido-rearranged 6/5/6/6 fused ring system; artemordins G—J (7—10) were biogenetically formed by [4 + 2] cycloaddition and possessed a novel 5/6/6/6/6/6/5—heptacyclic fused ring system. Artemordins B and H (2 and 8) exhibited inhibitory activities on three hepatoma cell lines with IC₅₀ values of 26.9 and 25.1 μmol/L (HepG2), 29.5 and 18.3 μmol/L (Huh7), 19.7 and 15.7 μmol/L (SK-Hep-1).

Comprehensive Summary

Nineteen new cadinane-involving sesquiterpenoid dimers, artemordins A—S (1—19), together with 13 known SDs (20—32) were isolated from Artemisia ordosica. Their structures and absolute configurations were established by comprehensive spectral analyses, X-ray single crystal diffraction, theoretical ECD, and NMR calculations. Chemically, artemordins A—F (1—6) were the first examples of two cadinane units constructed by unprecedented C-3−C-15′ or C-3−C-13′ single bond with an oxido-rearranged 6/5/6/6 fused ring system; artemordins G—K (7—11) were biogenetically connected by [4 + 2] cycloaddition reaction and artemordins G—J (7—10) possessed a novel 5/6/6/6/6/6/5-heptacyclic fused ring system. Artemordins L—S (12—19) were formed by esterification, which involved three different types of sesquiterpenoids. Antihepatoma assay suggested that the most active compounds, artemordins B and H (2 and 8), exhibited inhibitory activities on three hepatoma cell lines with IC₅₀ values of 26.9 and 25.1 μmol/L (HepG2), 29.5 and 18.3 μmol/L (Huh7), 19.7 and 15.7 μmol/L (SK-Hep-1).

A new class of rigid-featured chiral tridentate Phenol-2NO ligands, that incorporate the advantages of both the phenol skeleton and pyrroloimidazolone-based N-oxide moiety, was rationally designed and developed. This represented the first activation of phenol-type ligand/metal complex by an achiral organic base as the additive in asymmetric catalysis.

Comprehensive Summary

The privileged C ₂-symmetric rigid phenol-type ligand is more attractive but challenging in asymmetric catalysis. Herein, we designed and synthesized a class of rigid-featured chiral tridentate Phenol-2NO ligands, that incorporate the advantages of both the phenol skeleton and pyrroloimidazolone-based N-oxide moiety, from readily available L-prolinamides in operationally simple two steps and up to 44% overall yield. More importantly, using an achiral quinoline derivative as an additive, the newly developed Phenol-2NO ligand could serve as the anioic ligand upon deprotonative activation to coordinate to Zn(II) to form a highly enantioselective catalyst for the asymmetric Michael-type Friedel-Crafts alkylation reaction of indoles with 2,3-dioxopyrrolidines. Excellent yields (up to 90%) and high enantioselectivities (up to 99% ee) are obtained for a wide range of substrates under mild conditions. Experiments and DFT calculations revealed the reaction mechanism and the origins of the enantioselectivity. This also represented the first activation of phenol-type ligand/metal complex by an achiral organic base as the additive in asymmetric catalysis.