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Reactions of cyclic thioureas (1,3,4,5-tetramethylimidazol-2-thione and 1,3-dimethylimidazolidin-2-thione) and ureas (1,3,4,5-tetramethylimidazol-2-one and 1,3-dimethylimidazolidin-2-one) with an isolable dialkylsilylene were examined. In these reactions, cyclic thioureas served as sulfur and NHC (N-heterocyclic carbene) sources, and the corresponding silanethione and NHC-derived products formed via silanethione-NHC complexes. Reactions of cyclic ureas with the silylene afforded a new NHC and an isolable azomethine ylide. These reactions involved oxygen atom transfer and 1,3-silyl migrations, which were supported by computational studies., (© 2024 Wiley-VCH GmbH.)

Rise of the mute assassin "carbon monoxide (CO)" levels impact all aerobic life. The elevated rates of CO concentration endure climatic and geographical characteristics that exacerbate air pollution. Herein, a simple approach for hydrothermal leaching (HyTL) of Al 3 TM-Rh 0.5 (Target material (TM)=Zr, V, Ce) and Al 3 TM (TM=Zr, V, Ce) intermetallic compounds produces leached products of ZrO 2 , VO 2 , and CeO 2 with Rhodium (Rh) as an active component. The characterization result reveals the HyTL process and the presence of the active Rh element that elevated the performance of HyTL-Al 3 Zr-Rh 0.5 towards CO conversion compared to other samples. Further, the cubic ZrO 2 phase selectively forms after HyTL at 130 °C even though the formation of the cubic ZrO 2 phase takes place at a high temperature. Moreover, the presence of Rh promotes higher catalytic activity in all the cases with low temperatures. The advancement in the present study towards the catalytic oxidation of CO over the hydrothermally leached ZrO 2 -Rh nanocatalyst guarantees the perspective of the aggregation-activation process., (© 2024 Wiley-VCH GmbH.)

The development of advanced catalysts frequently employs trial-and-error methods and is lack of highly controlled synthesis, resulting in unsatisfactory development efficiency and performance. Here we propose a data-driven prediction coupled with precise synthesis strategy to accelerate the development of single-atom catalysts (SACs) for efficient water purification. The data-driven approach enables the rapid screening and prediction of high-performance SACs from 43 metals-N4 structures comprising transition and main group metal elements, followed by validation and structural modulation for improved performance through a highly controllable hard-template method. Impressively, a well-designed Fe-SAC with a high loading of Fe-pyridine-N4 sites (~3.83 wt%) and highly mesoporous structure, exhibits ultra-high decontamination performance, representing the best Fenton-like activities for sulfonamide antibiotics to date. Furthermore, the optimized Fe-SAC shows excellent robust environmental resistance and cyclic stability with almost 100% degradation efficiency of sulfonamide antibiotics for 100-h continuous operation. Theoretical calculations reveal that Fe-pyridine-N4 sites can reduce the energy barrier of intermediate O* formation, the rate-determining step, resulting in highly selective generation of singlet oxygen. The integration of data-driven method with precise synthesis strategy provides a novel paradigm for the rapid development of high-performance catalysts for environmental field as well as other important fields including sustainable energy and catalysis., (© 2025 Wiley‐VCH GmbH.)

Supramolecular interactions between polymers play a crucial role in the construction of three-dimensional polymer structures with unique physical and chemical properties. In this study, we have fabricated a novel supramolecular miktoarm star copolymer (μ-star) with a cobalt(II) phthalocyanine (CoPc) core using metal-ligand coordination. Axial coordination of the terminal pyridyl group of poly(methyl methacrylate) with the CoPc core of four-armed star-shaped polystyrene provided AB 4 - and A 2 B 4 -type μ-stars through stepwise complexation. The spin-coated polymer films from mixed solutions of CoPcPS 4 and pyPMMA in 1 : 1 or 1 : 2 mass ratios exhibited phase-separated nanodomains with smooth surfaces. Supramolecular interactions in polymer systems provide a unique topology to polymers and affect their bulk morphology., (© 2024 Wiley-VCH GmbH.)

Although a widely used and important industrial chemical, carbon disulfide (CS 2 ) poses a number of hazards due to its volatility and toxicity. As such, the development of multifunctional materials for the selective capture and easy recognition of CS 2 is one of the crucial issues. Herein, we demonstrate completely selective CS 2 adsorption among trials involving H 2 O, alcohols, volatile organic compounds (including thiol derivatives), N 2 , H 2 , O 2 , CH 4 , CO, NO, and CO 2 . We also showcase its fine detection using remarkable luminescent response in a gold(I)-based metal-organic framework (MOF) of {Zn II (pz)[Au I (CN) 2 ] 2 } (pz=pyrazine; 1) with a two-fold interpenetration network. Ex situ single crystal X-ray diffraction for 1 and CS 2 -accommodated 1 suggested that the Au ⋅⋅⋅ Au atoms are not only luminescent centers but also act as interaction sites for CS 2 modulating the Au ⋅⋅⋅ Au contacts. These experiments revealed the specificity of CS 2 and how changes in the CS 2 -induced structure. Based on the obtained structural transformation, 1 exhibited a sensitive detecting ability for CS 2 with an ultrafast response time of less than 10 s. Moreover, ex situ time-resolved photoluminescence analyses developed in this work implied that CS 2 varied the energetic relaxation at the excited states related to the luminescent efficiency of the resultant MOF system., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The development of smart materials capable of separating dihydrogen isotopologues has risen recently. Among potential candidates, the flexible MIL-53 (Al) has been gaining attention due to its structural flexibility providing the so-called ''breathing mechanism'' that can be useful to separate hydrogen isotopologues selectively. In the present work, an in situ continuous wave electron paramagnetic resonance investigation has been proven as a sensitive technique to follow the isotopologue-selective adsorption-desorption of dihydrogen species on the paramagnetic metal-doped MIL-53 (Al 0.99 Cr 0.01 ) and MIL-53 (Al 0.99 V 0.01 ), respectively. The presence of paramagnetic spin probes such as Cr 3+ and V 4+ inside the MIL-53 framework allows for monitoring the framework transition including the 2 nd transition step that selectively occurs at p>100 mbar when D 2 gas is adsorbed on the pores at 23 K. Furthermore, investigation of D 2 desorption from MIL-53 (Al 0.99 V 0.01 ) by temperature-dependent hyperfine spectroscopy provides a more detailed analysis of the D 2 desorption process on a microscopic scale with respect to the embedded spin probe., (© 2025 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The development of efficient and durable oxygen evolution reaction (OER) catalysts is crucial for advancing proton exchange membrane water electrolysis (PEMWE) technology, especially in the pursuit of non-iridium alternatives. Herein, we report a Zn, W co-doped Ru 3 Zn 0.85 W 0.15 O x (RZW) ternary oxide catalyst that exhibits a low overpotential of 200 mV and remarkable stability for over 4000 hours at 10 mA cm -2 in 0.1 M HClO 4 . The incorporation of highly electronegative W facilitates the efficient capture of electrons released from the sacrificial Zn species during OER, and subsequently mediated to Ru sites. The observed enhancement in electron density within the stable Ru-O-W motifs substantially improves the anti-overoxidation properties of the Ru active sites. Our findings highlight the importance of strategic metal doping in modulating the electronic structure of OER catalysts during operation, thereby facilitating the development of practical and long-lasting water electrolysis technologies., (© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Both enantiomers of functionalized Hajos-Parrish ketone (HPK) analogs were prepared with excellent diastereoselectivities and enantioselectivities using the same chiral catalyst under two slightly different conditions. In condition A, dioxane was used as the solvent with 3 equivalents of water. In condition B, acetonitrile was used as the solvent with 30 equivalents of water, followed by epimerization with a base in a one-pot. The reaction consisted of a domino reaction including a diphenylprolinol silyl ether-mediated asymmetric Michael reaction and an intramolecular Henry reaction. In the Michael reaction, depending on the solvent and water amounts, syn- and anti-isomers were selectively synthesized with excellent enantioselectivity, in which the absolute configuration at C5 (indanone numbering) was opposite. The subsequent Henry reaction was diastereoselective, in which the C5 substituent controlled the three chiral centers in a highly diastereoselective manner. The final base treatment in condition B caused epimerization, changing the configuration at C6. Switching more than two chiral centers with high enantioselectivity is extremely difficult using the same chiral catalyst; the present reaction is a very rare enantiodivergent reaction that switches five continuous chiral centers with high enantioselectivity., (© 2024 Wiley-VCH GmbH.)

Hollandite-type α-MnO 2 exhibits exceptional promise in current industrial applications and in advancing next-generation green energy technologies, such as multivalent (Mg 2+ , Ca 2+ , and Zn 2+ ) ion battery cathodes and aerobic oxidation catalysts. Considering the slow diffusion of multivalent cations within α-MnO 2 tunnels and the catalytic activity at edge surfaces, ultrasmall α-MnO 2 particles with a lower aspect ratio are expected to unlock the full potential. In this study, ultrasmall α-MnO 2 (<10 nm) with a low aspect ratio (c/a ≈ 2) is synthesized using a newly developed alcohol solution process. This material demonstrates exceptional performance across various multivalent battery systems, primarily due to the significantly reduced cation diffusion distance. Notably, an ultrasmall α-MnO 2 -graphene composite achieves high capacity with low overpotential when paired with an F-free electrolyte in Ca battery. Regarding aerobic oxidation catalysis, the nanosizing of α-MnO 2 has a profound impact on aerobic oxidation catalysis. The increased efficiency of oxidative conversion reactions, such as the oxidation of 1-phenylethanol, is attributed to the greatly expanded active surface area of the catalyst. The versatile functionality of ultrasmall α-MnO 2 underscores its potential to revolutionize energy storage and catalysis, offering broad applicability in next-generation green energy technologies., (© 2025 Wiley‐VCH GmbH.)

The antiausterity strategy in anticancer drug discovery has attracted much attention as a way to exterminate cancer cells under nutrient deprived conditions which are commonly found in solid tumors. These tumors under low nutrient stress are known to be malignant and often resist conventional drug therapy. As a potential drug candidate, we focused on the meroterpenoid natural product callistrilone O which has demonstrated extremely potent antiausterity properties toward PANC-1 pancreatic carcinoma in vitro. Here, we report for the first time the total synthesis of callistrilone O in seven steps from phloroglucinol. A Friedel-Crafts-type Michael addition and an oxidative [3 + 2] cycloaddition with Fetizon's reagent were used to construct the molecular skeleton. The preferential cytotoxicity of callistrilone O was also evaluated with multiple starvation-resistant cancer cell lines under low nutrient conditions. Furthermore, callistrilone O was found to strongly suppress B16 melanoma tumor growth without critical toxicity in vivo. Overall, this study presents a novel anticancer agent candidate from natural products with a concise synthetic route which can be readily applied to the synthesis of derivatives., (© 2025 Wiley‐VCH GmbH.)

Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). Owing to covalency competition, the OER process on spinel oxides often follows an arduous adsorbate evolution mechanism (AEM) pathway. Herein, we propose a novel rare-earth sites substitution strategy to tune the lattice oxygen redox of spinel oxides and bypass the AEM scaling relationship limitation. Taking NiCo 2 O 4 as a model, the incorporation of Ce into the octahedral site induces the formation of Ce-O-M (M=Ni, Co) bridge, which triggers charge redistribution within NiCo 2 O 4 . The developed Ce-NiCo 2 O 4 exhibits remarkable OER activity with a low overpotential, satisfactory electrochemical stability, and good practicability in anion-exchange membrane water electrolyzer. Theoretical analyses reveal that OER on Ce-NiCo 2 O 4 surface follows a more favorable lattice oxygen mechanism (LOM) pathway and non-concerted proton-electron transfers compared to pure NiCo 2 O 4 , as also verified by pH-dependent behavior and in situ Raman analysis. The 18 O-labeled electrochemical mass spectrometry provides direct evidence that the oxygen released during the OER originates from the lattice oxygen of Ce-NiCo 2 O 4 . We discover that electron delocalization of Ce 4f states triggers charge redistribution in NiCo 2 O 4 through the Ce-O-M bridge, favoring antibonding state occupation of Ni-O bonding in [Ce-O-Ni] unit site, thereby activating lattice oxygen redox of NiCo 2 O 4 in OER. This work provides a new perspective for designing highly active spinel oxides for OER and offers significant insights into the rare-earth-enhanced LOM mechanism., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Managing safety and supply-chain risks associated with lithium-ion batteries (LIBs) is an urgent task for sustainable development. Aqueous proton batteries are attractive alternatives to LIBs because using water and protons addresses these two risks. However, most host materials undergo large volume changes upon H + intercalation, which induces intraparticle cracking to accelerates parasitic reactions. Herein, we report that Mo 3 Nb 2 O 14 bronze exhibits reversible H + intercalation (200 mAh g -1 ) with a Coulombic efficiency of 99.7 % owing to near-zero volume change and solid-solution-type phase transition. Combination of experimental and theoretical analyses clarifies that rotation and shrinkage of open tunnels, which consist of flexible corner-sharing Mo/NbO n polyhedra, relieve local structural distortions upon H + intercalation to suppress intraparticle cracking. The prototype full cell of an aqueous proton battery with a Mo 3 Nb 2 O 14 anode operates stably over 1000 charge/discharge cycles. This study reveals the importance of implementing distortion-relieving voids in host materials to reduce volume change upon charge/discharge., (© 2024 Wiley-VCH GmbH.)

The rational design of efficient electrocatalysts with controllable structure and composition is crucial for enhancing the lifetime and cost-effectiveness of oxygen reduction reaction (ORR). PtCo nanocrystals have gained attention due to their exceptional activity, yet suffer from stability issues in acidic media. Herein, an active and highly stable electrocatalyst is developed, namely 3D Pt 7 Co 3 @Pt core-shell nanodendrites (NDs), which are formed through the self-assembly of small Pt nanoparticles (≈6 nm). This unique structure significantly improves the ORR with an enhanced mass activity (MA) of 0.54 A mg Pt -1 , surpassing that of the commercial Pt/C (com-Pt/C) catalyst by three fold (0.17 A mg Pt -1 ). The well-organized dendritic morphology, along with the Pt-rich shell, contributes significantly to the observed high catalytic activity and superior stability for acidic ORR, which exhibit a loss of 2.1% in MA and, impressively, an increase of 12.0% in specific activity (SA) after an accelerated durability test (ADT) of 40,000 potential-scanning cycles. This work offers insights for improving the design of highly stable Pt-based electrocatalysts for acidic ORR., (© 2025 Wiley‐VCH GmbH.)

Twistronics, a novel engineering approach involving the alignment of van der Waals (vdW) integrated two-dimensional materials at specific angles, has recently attracted significant attention. Novel nontrivial phenomena have been demonstrated in twisted vdW junctions (the so-called magic angle), such as unconventional superconductivity, topological phases, and magnetism. However, there have been only few reports on integrated vdW layers with large twist angles θ t , such as twisted interfacial Josephson junctions using high-temperature superconductors. Herein, vdW homojunctions of the thin-magnetic flakes, Fe 3 GeTe 2 (FGT), with large θ t ranging from 0° to 90°, without inserting any tunnel barriers are assembled. Nevertheless, these vdW homojunctions exhibit tunnel-magnetoresistance (TMR) like behavior (pseudo-TMR (PTMR) effect) with the ratios highly sensitive to the θ t values, revealing that the vdW gap at the junction interface between the twisted FGT layers behaves like a tunnel barrier and the θ t serves a control parameter for PTMR by drastically varying magnitudes of the lattice-mismatch and the subsequent appearance of antiferromagnetic (AFM) spin alignment. First-principles calculations considering vacuum gaps indicate strong dependence of TMR on the θ t driven by the sixfold screw rotational symmetry of bulk FGT. The present homojunctions hold promise as a platform for novel AFM spin-dependent phenomena and spintronic applications., (© 2025 Wiley‐VCH GmbH.)

Organic hydrides can store hydrogen via chemical bonding under ambient conditions, enabling the safe storage and transportation of hydrogen gas using the same infrastructure for gasoline. However, in previous research, most organic hydrides have been produced from petroleum, and therefore replacing them with earth-abundant or renewable compounds is essential to ensure sustainability. This study demonstrates dihydrolevoglucosenone (CyreneTM), which is a biodegradable liquid ketone that is produced directly from biomass without pretreatments on an industrial scale, as a new renewable organic hydride. CyreneTM (hydrogen acceptor) is hydrogenated under ambient hydrogen pressure with a highly durable metal complex catalyst to produce 1,6-anhydro-3,4-dideoxy-β-D-threo-hexopyranose (Cyrene-OH, hydrogen adduct). Cyrene-OH stores hydrogen via chemical bonding under ambient conditions, and is dehydrogenated by heating in the presence of the same catalyst to release hydrogen gas and reproduce CyreneTM. This study reports the first attempt to apply compounds, which can be produced directly from biomass on an industrial scale, to organic hydrides, and promotes the development of earth-abundant biomass for sustainable hydrogen storage., (© 2025 Wiley‐VCH GmbH.)

Open fluidics, allowing liquid in a flow channel to interact with the external environment, is a revolutionary concept. However, fabricating a highly stable open fluidic device of arbitrary complexity, while maintaining reconfigurability, is still a challenge. This is achieved by the use of a patterned substrate and liquids that are covered with functional, readily available hydrophobic particles, providing great flexibility in the construction and use of open fluidic structures. Decorated with a coating of modified carbon nanotubes (CNTs) to encapsulate the fluids, the study capitalizes on the photothermal characteristics of CNTs to fabricate a device to probe the effects of temperature on tumor chemotherapy. The strategy substantially increases the availability and potential use of open fluidic devices., (© 2024 Wiley‐VCH GmbH.)

The rational design of artificial supramolecular structures with specific properties and functions hinges the comprehensive understanding of the coordination and noncovalent interactions driving self-assembly. Herein, the self-assembly of supramolecular systems through octahedral coordination between Ni(II) ions and a flexible tripeptide was theoretically investigated using quantum chemical calculations. These calculations utilized the B3LYP functional with the polarizable continuum model. Our results indicate that tridentate sites have a greater propensity for coordination, and that the presence of chloride anions and conformational shifts enhance bidentate and monodentate coordination. Insights into the effect of counter anions on the stability of octahedral coordination and the prerequisites for self-assembly were gained by determining the stable conformation and potential reaction pathways of the tripeptide before and after adding chloride anions through an efficient automated conformational search. The formation of intramolecular hydrogen bonding interactions during the conformational changes was also studied using model calculations. Possible processes for initial self-assembly of tripeptide were proposed. This study enhances the fundamental understanding of the conformational behavior of building blocks during supramolecular formation and advance the potential for constructing future bioinspired complexes., (© 2024 The Author(s). ChemPlusChem published by Wiley-VCH GmbH.)

After the publication of "Direct formation of hard-magnetic tetrataenite in bulk alloy castings" Ivanov et al., Advanced Science 10 (2022) 2204315, the authors identified a potential misinterpretation of the experimental data. Further work confirms that the original conclusions cannot be supported, and accordingly the paper is retracted. X-ray diffraction shows the presence of (Fe,Ni) 3 P, giving additional Bragg peaks that were previously attributed to tetrataenite. Extra Bragg reflections observed in transmission electron diffraction, and earlier considered to be superlattice reflections from tetrataenite, instead result from oxidation of the sample surface during preparation. Measurements of magnetic hysteresis show no regions of high coercivity of the kind expected when tetrataenite is present. It is concluded that as-cast bulk samples of Fe-Ni-P-(C) show no evidence of tetrataenite on any length scale. Nevertheless, the addition of phosphorus should remain of interest in ongoing efforts to manufacture tetrataenite., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

An all-solid-state fluoride-ion battery (FIB) is one of the promising candidates for the next-generation battery owing to its high energy density and high safety. For the practical application of FIBs, it is an urgent task to operate FIBs at lower temperatures. However, there are still two major difficulties in conventional conversion-type pure metal cathodes: low F - ion conductivities and poor cycle stabilities. Here, the conversion-type Sn-based intermetallic alloy is proposed as a new cathode that can overcome the above issues. The present CoSn 2 cathode retains the discharge capacity of 229 mAh g -1 after 250 cycles, even at 60 °C. CoSn 2 is decomposed into CoF 2 and SnF 2 nanocrystals in the charging process, and the nanoscale network structure of SnF 2 provides the fast F - ion conduction path throughout the cathode, facilitating the battery operation at lower temperatures. Moreover, the formed CoF 2 and SnF 2 phases are merged into the original CoSn 2 phase in the discharging process, leading to a highly reversible redox reaction and the high cycle stability of CoSn 2 . These findings should pave the way to enhance the performance of all-solid-state FIBs at lower temperatures., (© 2024 Wiley‐VCH GmbH.)

Oxygen in solids usually exists in an O 2- ionic state. As a result, it loses its magnetic nature of a single atom, wherein two unpaired electrons exist in its outer 2p orbitals. Here, it is shown that an unconventional stable ionic state of O - is realized in a new semiconductor material Sr 2 AlO 4 , leading to an intrinsic p-orbital ferromagnetism stable until ≈900 K. Experimental and theoretical investigations have clarified that one-fourth of the oxygen atoms in Sr 2 AlO 4 are insufficiently bonded in the crystal structure, resulting in a unique O - -state and p-orbital ferromagnetism. To date, the O - state is reported to exist only in non-equilibrium conditions, and p-orbital magnetism is only suggested in impurity bands with small ferromagnetic moments. The present work provides a new route for creating ferromagnetism in semiconductors and exploring new p-orbital physics and chemistry. In addition, the material shows elastic-mechanoluminescence that may enable unprecedented mechano-photonic-spintronics., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The future of environmental monitoring, medical diagnostics, and industrial safety depends on developing room-temperature, long-term operable, stable, miniaturized, ultrahigh-performance sensors integrated into the Internet of Things (IoT). While noble metals and high-entropy alloys (HEAs) lead in addressing the limitations of conventional transition-metal dichalcogenides (TMDs) like MoS₂, they face challenges such as high-cost, limited availability, and fabrication complexity. To address this, multifunctional, cost-effective, humidity-insensitive novel phase Ti₀.₅Zn₀.₅ (TiZn) alloy nanoparticle-decorated MoS₂ nanosheets (MoS₂&#95;NP) is developed for ultra-selective and highly sensitive triethylamine (TEA) vapor detection at room temperature (RT). This exhibited a 24-fold increase in response compared to MoS₂, with a high signal-to-noise ratio, negligible humidity interference, sensitivity of 9.92 × 10⁻⁵ ppm⁻¹ at RT, and a detection limit of 48 ppm. The enhanced catalytic activity and defect concentration, the reduction of the edge oxidation resulting in strong Fermi-level pinning, and the relatively high adsorption energy lead to a target gas-specific carrier-type response, demonstrating the potential of binary alloy nanoparticles (NPs) as decorative materials for enhanced sensing applications. The superior performance of the sensor led to the development of a TEA detection prototype interfaced with a mobile device via IoT for continuous monitoring, enhancing practicality and usability by offering immediate access to critical information., (© 2024 Wiley‐VCH GmbH.)

Phonon dynamics in organic-inorganic hybrid perovskites (OIHPs) exhibit inherent complexity driven by the intricate interactions between rotatable organic cations and dynamically disordered inorganic octahedra, mediated by hydrogen bonding. This study aims to address this complexity by investigating the thermal transport behavior of MAPbCl 3 as a gateway to the OIHPs family. The results reveal that the ultralow thermal conductivity of MAPbCl 3 arises from a synergistic interplay of exceptionally low phonon velocities, short phonon lifetimes, and phonon mean free paths approaching the Regel-Ioffe limit. Additionally, the thermal conductivity of MAPbCl 3 approaches its theoretical amorphous limit across a broad temperature range, with its thermal transport behavior transitioning from crystal-like to more liquid-like during the orthorhombic-to-cubic phase transitions. Furthermore, a phonon drag effect is observed at 17 K, with Umklapp scattering serving as the predominant phonon resistive mechanism in the orthorhombic phase. In contrast, dynamic lattice distortions caused by the jumping rotation of MA + cations become the primary factors influencing thermal transport in the cubic phase., (© 2024 Wiley‐VCH GmbH.)

A series of CoFe 2 O 4 materials derived from metal-organic framework were successfully constructed by the solvent-thermal method. The morphology of a typical sample CoFe 2 O 4 -1 was mostly in the form of a cubic rod-like structure with a size distribution of 3.2±0.2 μm, while a small amount of the structure presented hexagonal shape with uniform size dispersion. The XPS characterization results confirmed that the CoFe 2 O 4 -1 material contained Co 3+ (Co 2+ /Co 3+ =0.98), and the redox reaction between Co 2+ and Fe 3+ produced more Fe 2+ (Fe 2+ /Fe 3+ =1.63), leading to the production of more O V on the surface of the CoFe 2 O 4 -1 material (O V %=0.34), thereby facilitating the efficient adsorption of the efficient adsorption of heavy metal ions (HMIs). CoFe 2 O 4 -1/GCE as a typical electrode presented excellent performance for the detection of multiple HMIs. The results should be attributed to the good electrical conductivity and large electrochemically active surface area of CoFe 2 O 4 -1/GCE, accelerating the transport of ions and charges in the system. Interestingly, there are interaction mechanisms between the HMIs when performing simultaneous detection, suggesting the detection of target ions can be facilitated by adding additional ions. This study provides new research insights for the development of highly sensitive electrochemical sensors for real-time environmental monitoring., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Traditional selectivity of gas sensors determined by the magnitude of the response value has significant limitations. The distinctive inversion sensing behavior not only defies the traditional sensing theory but also provides insight into defining selectivity. Herein, the novel definition of selectivity is established in a study with VO 2 (M1). The sensing behavior of VO 2 (M1) is investigated after its synthesis conditions optimization by machine learning. In gases of the same nature, VO 2 (M1) shows remarkably selective for NH 3 marked with unique resistance increase behavior. Such anomalous behavior is attributed to the formation of the Schottky junction between VO 2 (M1) and the electrode. The "work function-electron affinity" relation is summarized as the selectivity coefficient, a parameter for predicting the selectivity of the sensing material effectively., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The synthesis and biosynthesis of the complex saxitoxin (STX) structure have garnered significant interest. Previously, we hypothesized that the tricyclic skeleton of STX originates from the monocyclic precursor 11-hydroxy-IntC'2 during biosynthesis, although direct evidence has been lacking. In this study, we identified conditions to synthesize a proposed tricyclic biosynthetic intermediate, 12,12-dideoxy-decarbamoyloxySTX (dd-doSTX), along with its 6-epimer (6-epi-dd-doSTX) and a bicyclic compound, in a single step from di-Boc protected 11-hydroxy-IntC'2. The reaction mechanism involves successive aza-Michael addition of a guanidino amine to the conjugated olefin. Notably, both dd-doSTX and 6-epi-dd-doSTX were detected in a toxin-producing cyanobacterium, suggesting that the biosynthetic enzymes may generate these compounds via similar mechanisms., (© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

A synthetic method of tertiary alcohols was developed based on the formal umpolung addition of aryl ketones with electrophiles utilizing the [1,2]-phospha-Brook rearrangement under Brønsted base catalysis. The addition reaction of α-hydroxyphosphonates, derived from alkyl aryl- and diaryl ketones, with electrophiles such as phenyl vinyl sulfone, afforded phosphates having a tertiary alkyl group, which were readily convertible to the corresponding tertiary benzylic alcohols. This operationally simple protocol provides efficient complementary access to tertiary alcohols that are difficult to synthesize by conventional methods., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The paddlewheel-type dimetal core ([M 2 ]) is a ubiquitous motif in the nodes in coordination polymers (CPs) and metal-organic frameworks (MOFs). However, their preparation has relied on ligand-substitution-labile metal ions owing to challenges associated with crystallization. Consequently, examples featuring ligand-substitution-inert metal ions, such as Ru or Rh, are scarce. This study presents the synthesis of novel reticular imine-linked CPs incorporating the paddlewheel-type diruthenium(II, II) ([Ru 2 II,II ]; 1-Ru) or dirhodium(II, II) ([Rh 2 II,II ]; 1-Rh) subunits. The synthetic approach involved a Schiff base dehydration condensation reaction between p-formylbenzoate-bridged [Ru 2 II,II ] or [Rh 2 II,II ] precursors (i. e., CHO-Ru and CHO-Rh, respectively) and 2,5-dimethyl-1,4-phenylenediamine in a 1 : 2 ratio. The catalytic activities of 1-Ru and 1-Rh for the photochemical reduction of CO 2 in a heterogeneous system depended on the metal site. The 1-Ru system exhibited exceptional selectivity, generating 3.0×10 4  μmol g -1 of CO after 24 h of irradiation, whereas the 1-Rh system generated a lower amount of CO (3.2×10 3  μmol g -1 ). The catalytic activity of 1-Ru ranked with that of all relevant catalytic systems. This study paves the way for the exploration of [Ru 2 II,II ]- or [Rh 2 II,II ]-based polymers with open metal site-dependent functional properties., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The electrochemical CO 2 reduction reaction (CO 2 RR) has been extensively studied because it can be leveraged to directly convert CO 2 into valuable hydrocarbons. Among the various catalysts, copper nanoclusters (Cu NCs) exhibit high selectivity and efficiency for producing CO 2 RR products owing to their unique geometric/electronic structures. However, the influence of protective ligands on the CO 2 RR performance of Cu NCs remains unclear. In this study, it is shown that different thiolate ligands, despite having nearly identical geometries, can substantially affect the electrochemical stability of Cu 14 NCs in the CO 2 RR. Notably, Cu 14 NCs protected by 2-phenylethanethiolate exhibit greater stability and achieve a relatively higher selectivity (≈40%) for formic acid production compared with the cyclohexanethiolate-protected counterpart. These insights are crucial for designing Cu NCs that are both stable and highly selective, enhancing their efficacy for electrochemical CO 2 reduction., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Hydrogen boride (HB) sheet is a new class of 2D materials comprising hydrogen and boron, synthesized through ion-exchange and exfoliation techniques. HB sheets can release hydrogen (H 2 ) under light irradiation and is predicted to be a promising H 2 storage material. However, its application is limited to the UV region. One approach to enable a visible-light-driven system is the utilization of plasmonic metallic nanoparticles. The present study reports H 2 release from copper (Cu) nanoparticle-modified HB sheet (HB/Cu) under visible-light irradiation. Copper nanoparticles possess unique and strong plasmonic responses in the visible-light range, making them ideal light absorbers in this system. HB/Cu nanocomposites are synthesized using a simple mixture of copper acetate and HB sheets in acetonitrile, where HB sheets reduced copper ions to metal copper nanoparticles. The photoirradiation results shows that HB/Cu nanocomposites released more H 2 than the bare HB sheets under visible-light irradiation. This is probably due to the plasmonic photothermal effect of copper metal, which enhances H 2 generation from the HB sheets. This material offers a viable and cost-effective approach for developing visible-light-sensitive systems., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Tin (Sn)-based catalysts have been widely studied for electrochemical CO 2 reduction reaction (CO 2 RR) to produce formic acid, but the intricate influence of the structural sensitivity in single-atom Sn (e.g., Sn-N-C) and polyatomic Sn (e.g., SnO x and SnS x ; x=1,2) on their pH-dependent performance remains enigmatic. Herein, we integrate large-scale data mining (with >2,300 CO 2 RR catalysts from available experimental literature during the past decade), ab initio computations, machine learning force field accelerated molecular dynamic simulations, and pH-field coupled modelling to unravel their pH dependence. We reveal a fascinating contrast: the electric field response of the binding strength of *OCHO on Sn-N 4 -C and polyatomic Sn exhibits opposite behaviors due to their differing dipole moment changes upon *OCHO formation. Such response leads to an intriguing opposite pH-dependent volcano evolution for Sn-N 4 -C and polyatomic Sn. Subsequent experimental validations of turnover frequency and current density under both neutral and alkaline conditions well aligned with our theoretical predictions. Most importantly, our analysis suggests the necessity of distinct optimization strategies for *OCHO binding energy on different types of Sn-based catalysts., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Triple-stranded helical lanthanide MOFs with CO 2 adsorption properties were investigated. Lanthanide MOFs ([Eu 0.1 Tb 0.9 (hfa) 3 (dpa)] n ) are composed of lanthanide luminophores (Eu(III) and/or Tb(III) ions), fluorinated antenna ligands (hfa: hexafluoroacetylacetonate), and polyamide-type linker ligands (dpa: 4-(diphenylphosphoryl)-N-(4-(diphenylphosphoryl)phenyl)benzamide). The cylindrical structure was characterized by single-crystal X-ray analysis, thermogravimetric analysis, and gas adsorption measurements. The inner surfaces of the cylindrical channels were covered with the fluorine atoms of the hfa ligands. The emission intensity ratio (I Eu /I Tb ) in [Eu 0.1 Tb 0.9 (hfa) 3 (dpa)] n is affected by the CO 2 gas adsorption behavior. The change in I Eu /I Tb value was caused by the intermolecular interactions between the CO 2 gas molecules and the fluorinated ligands, resulting in an electronic structural change of the lowest triplet excited state in the photosensitized hfa ligands., (© 2024 Wiley-VCH GmbH.)

As an exceptional carrier for localized drug delivery to tumors, hydrogels can achieve prolonged drug release through careful design and adjustments, effectively targeting cancer cells and minimizing side effects. This study investigates a novel dual-responsive hydrogel system designed for the delivery of nanomedicines, focusing on drug release and the local antitumor efficacy of SN-38-cholesterol nanoparticles (SN-38-chol NPs) and polydopamine NPs (PDA NPs)/poly(n-isopropylacrylamide) (pNIPAM) hydrogels. By combining the thermosensitive properties of pNIPAM with the near-infrared (NIR) responsiveness of PDA NPs, the hydrogel aims to enhance on-demand drug release. SN-38-chol NPs, known for their stability and small size, are incorporated into the hydrogel to improve drug release dynamics. The investigation reveals a drug release cycle of over three weeks, maintaining sensitivity to both temperature and NIR light for controlled drug release. In vivo studies demonstrate the high tumor growth inhibition performance of the system after photothermal treatment induced by 808 nm NIR light. These results suggest that the drug-carrying hydrogel system holds promise for diverse applications in chemical and physical therapies, including the treatment of malignant wounds, post-surgery wound healing, and direct tumor treatment. This study establishes the potential of SN-38-chol NPs and PDA NPs/pNIPAM hydrogels as effective platforms for chemo-phototherapy., (© 2024 The Author(s). Macromolecular Bioscience published by Wiley‐VCH GmbH.)

Compared to the outstanding development in the synthesis of Si-B single bonded species, borylsilanes and their application to organic synthesis, the chemistry of Si=B double bonded species, borasilenes and boratasilenes have only made little progress, first of all, due to the difficulties in accessing such double bonds. Herein we report the synthesis of the first Si=B analogue of a vinyl halide, a bromoboratasilene, via formal borylene insertion to the coordination sphere of a monoatomic Si(0) complex, using a dihaloborane as the borylene source. The treatment of bromoboratasilene toward neutral or anionic Lewis bases gives access to new boratasilenes, all of which were proved to possess significant Si=B double bond character by XRD analysis and DFT calculations. These results demonstrate exciting strategies to synthesize new types of Si=B double bonded species which should further progress the chemistry of boron, silicon-containing molecules., (© 2024 Wiley-VCH GmbH.)

N-Sulfinylimines derived from ortho-alkynylbenzaldehydes were efficiently converted into the corresponding 4-sulfinylisoquinolines in good to excellent yields. The reaction proceeds via cyclization followed by intermolecular migration of the sulfinyl group from the nitrogen atom to the silver-bound carbon of the resulting cyclized vinylsilver intermediate with the aid of either a counteranion or a nucleophilic species. Moreover, the Ag-catalyzed reaction in the presence of quinidine acetate as a chiral nucleophilic cocatalyst yielded chiral isoquinolines with high enantioselectivities through a dynamic kinetic asymmetric transformation (DYKAT)., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Ozonation water treatment technology has attracted increasing attention due to its environmental benign and high efficiency. Rutile PbO 2 is a promising anode material for electrochemical ozone production (EOP). However, the reaction mechanism underlying ozone production catalyzed by PbO 2 was rarely studied and not well-understood, which was in part due to the overlook of the electrochemistry-driven formation of oxygen vacancy (O V ) of PbO 2 . Herein, we unrevealed the origin of the EOP activity of PbO 2 starting from the electrochemical surface state analysis using density functional theory (DFT) calculations, activity analysis, and catalytic volcano modeling. Interestingly, we found that under experimental EOP potential (i. e., a potential around 2.2 V vs. reversible hydrogen electrode), O V can still be generated easily on PbO 2 surfaces. Our subsequent kinetic and thermodynamic analyses show that these O V sites on PbO 2 surfaces are highly active for the EOP reaction through an interesting atomic oxygen (O*)-O 2 coupled mechanism. In particular, rutile PbO 2 (101) with the "in-situ" generated O V exhibited superior EOP activities, outperforming the (111) and (110) surfaces. Finally, by catalytic volcano modeling, we found that PbO 2 is close to the theoretical optimum of the reaction, suggesting a superior EOP performance of rutile PbO 2 . All these analyses are in good agreement with previous experimental observations in terms of EOP overpotentials. This study provides the first volcano model to explain why rutile PbO 2 is among the best metal oxide materials for EOP and provides new design guidelines for this rarely studied but industrially promising reaction., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes with excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. A racemic variant of the reaction is synergistically promoted by catalytic N-heterocyclic carbene (NHC) and organic base, whereas chiral amino alcohol-derived bifunctional NHC enables a catalytic enantioselective variant. The reaction likely involves the generation of enolized zinc homoenolate via ring-opening of zinc cyclopropoxide and enolization of the resulting homoenolate, followed by its addition to the cyclopropene as a prochiral allylzinc nucleophile. Our mechanistic investigations highlighted the transient nature of enolized homoenolate, which, once generated from thermodynamically predominant cyclopropoxide, immediately proceeds to allylzincation with cyclopropene. The NHC not only promotes the rate-determining generation of enolized homoenolate but also engages in the allylzincation process. The resulting cyclopropylzinc species undergoes partial in situ protonation while partially remaining intact, thereby leaving an opportunity for trapping with an external electrophile., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The production of ammonia (NH 3 ) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH 3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N 2 . We draw inspiration from this structural enzymology, and design a two-component metal-sulfur-carbon (M-S-C) catalyst composed of sulfur-doped carbon-supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO 3 - ) to NH 3 . The catalyst demonstrates a remarkable NH 3 yield rate of ~37 mg L -1  h -1 and a Faradaic efficiency of ~97 % for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP-surface nearby. Such process results in a more energetically accessible pathway for NO 3 - reduction on Ru NPs co-existing with SAs. This study proves a better understanding of how M-S-Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism-based catalyst design., (© 2024 Wiley-VCH GmbH.)

Optical properties in solids, such as refractive index and absorption, hold vast applications ranging from solar panels to sensors, photodetectors, and transparent displays. However, first-principles computation of optical properties from crystal structures is a complex task due to the high convergence criteria and computational cost. Recent progress in machine learning shows promise in predicting material properties, yet predicting optical properties from crystal structures remains challenging due to the lack of efficient atomic embeddings. Here, Graph Neural Network for Optical spectra prediction (GNNOpt) is introduced, an equivariant graph-neural-network architecture featuring universal embedding with automatic optimization. This enables high-quality optical predictions with a dataset of only 944 materials. GNNOpt predicts all optical properties based on the Kramers-Krönig relations, including absorption coefficient, complex dielectric function, complex refractive index, and reflectance. The trained model is applied to screen photovoltaic materials based on spectroscopic limited maximum efficiency and search for quantum materials based on quantum weight. First-principles calculations validate the efficacy of the GNNOpt model, demonstrating excellent agreement in predicting the optical spectra of unseen materials. The discovery of new quantum materials with high predicted quantum weight, such as SiOs, which host exotic quasiparticles with multifold nontrivial topology, demonstrates the potential of GNNOpt in predicting optical properties across a broad range of materials and applications., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The development of highly efficient electrocatalysts for the sluggish anodic oxygen evolution reaction (OER) is crucial to meet the practical demand for water splitting. In this study, an effective approach is proposed that simultaneously enhances interfacial interaction and catalytic activity by modifying Fe 2 O 3 /CoS heterojunction using Ru doping strategy to construct an efficient electrocatalytic oxygen evolution catalyst. The unique morphology of Ru doped Fe 2 O 3 (Ru-Fe 2 O 3 ) nanoring decorated by CoS nanoparticles ensures a large active surface area and a high number of active sites. The designed Ru-Fe 2 O 3 /CoS catalyst achieves a low OER overpotential (264 mV) at 10 mA cm -2 and demonstrates exceptional stability even at high current density of 100 mA cm -2 , maintaining its performance for an impressive duration of 90 h. The catalytic performance of this Ru-Fe 2 O 3 /CoS catalyst surpasses that of other iron-based oxide catalysts and even outperforms the state-of-the-art RuO 2 . Density functional theory (DFT) calculation as well as experimental in situ characterization confirm that the introduction of Ru atoms can enhance the interfacial electron interaction, accelerating the electron transfer, and serve as highly active sites reducing the energy barrier for rate determination step. This work provides an efficient strategy to reveal the enhancement of electrocatalytic oxygen evolution activity of heterojunction catalysts by doping engineering., (© 2024 Wiley‐VCH GmbH.)

Owing to sluggish reaction kinetics and high potential, oxygen evolution reaction (OER) electrocatalysts face a trade-off between activity and stability. Herein, an innovative topological strategy is presented for preparing 2D multimetallic (oxy)hydroxide, including ternary CoFeZn, quaternary CoFeMnZn, and high-entropy CoFeMnCuZn. The key to the synthesis lies in using Ca-rich brownmillerite oxide as a precursor, which possesses inherent structural flexibility enabling tailored elemental adjustments and topologically transforms from a point-shared structure of metal-oxygen octahedrons into an edge-shared structure under alkaline conditions. The presence of Zn in the catalysts causes a shift in the center of the O2p band toward the Fermi level, resulting in more Co 4+ species, which drive holes into oxygen ligands to promote intramolecular oxygen coupling. The triggered lattice oxidation mechanism is identified by detecting peroxo-like (O 2 2- ) negative species using tetramethylammonium chemical probe, along with 18 O isotope labeling experiments. As a result, the catalyst demonstrates an overpotential of 267 mV at 10 mA cm -2 , ranking it among the top-performing non-Ni-based catalysts. Importantly, the catalysts also show high Fe-leaching resistance during OER compared to conventional NiFe and CoFe hydroxides/(oxy)hydroxides. The assembled zinc-air battery enables stable operation for over 225 h at a low charging voltage of 1.93 V., (© 2024 Wiley‐VCH GmbH.)

Understanding the spin-dependent activity of nitrogen-coordinated single metal atom (M-N-C) electrocatalysts for oxygen reduction and evolution reactions (ORR and OER) remains challenging due to the lack of structure-defined catalysts and effective spin manipulation tools. Herein, both challenges using a magnetic field integrated heterogeneous molecular electrocatalyst prepared by anchoring cobalt phthalocyanine (CoPc) deposited carbon black on polymer-protected magnet nanoparticles, are addressed. The built-in magnetic field can shift the Co center from low- to high-spin (HS) state without atomic structure modification, affording one-order higher turnover frequency, a 50% increased H 2 O 2 selectivity for ORR, and a ≈4000% magnetocurrent enhancement for OER. This catalyst can significantly minimize magnet usage, enabling safe and continuous production of a pure H 2 O 2 solution for 100 h from a 100 cm 2 electrolyzer. The new strategy demonstrated here also applies to other metal phthalocyanine-based catalysts, offering a universal platform for studying spin-related electrochemical processes., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Hydrogen boride (HB) nanosheets are recognized as a safe and lightweight hydrogen carrier, yet their hydrogen (H 2 ) generation technique has been limited. In the present study, nitrogen-containing organic heterocycles are mixed with HB nanosheets in acetonitrile solution for visible-light-driven H 2 generation. After exploring various nitrogen-containing heterocycles, the mixture of 1,10-phenanthroline molecules (Phens) and HB nanosheets exhibited significant H 2 generation even under visible light irradiation. The quantum efficiency for H 2 generation of the mixture of HB nanosheets and Phens is 0.6%. Based on spectroscopic and electrochemical analyses and density functional theory (DFT) calculations, it is determined that radical species generated from Phens with electrons and protons donated by HB nanosheets are responsive to visible light for H 2 generation. The HB nanosheets/Phens mixture presented in this study can generate H 2 using renewable energy sources such as sunlight without the need for complex electrochemical systems or heating mechanisms and is expected to serve as a lightweight hydrogen storage/release system., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Multi-layer plastic films are widely used in various fields especially for packaging, but due to complex composition, it is very difficult to recover single-material polymers or high-purity monomers from them after usage. In this study, we proposed a hydrothermal process for recycling PET/PE (PET: Polyethylene terephthalate; PE: Polyethylene) films. PET can be hydrolyzed to monomers of terephthalic acid (TPA) and ethylene glycol (EG). Using a hydrothermal system equipped with two filters, PE, TPA, and EG were collected separately, indicating the simultaneous material and chemical recycling of PET/PE films was firstly achieved. At 300 °C and 10 MPa for 60 min, PET conversion reached around 100 %, and TPA yield of 83.0 % was obtained with a high TPA purity of 96.1 %. In addition, the effect of the holding time on PET conversion, TPA yield, EG yield, and TPA purity was studied. This research opened up a new and sustainable pathway to recycle multi-layer plastic films in both lab and industry., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist in developing crystalline solids that have similar degrees of flexibility as in solution. Herein, we report the preparation of the new flexible crystalline metal complex [Cd(CF 3 SO 3 ) 2 (4-spy) 4 ] (4-spy=4-styrylpyridine), which contains photoreactive 4-spy ligand. Unlike traditional solids, this metal complex displays solution state-like [2+2] photocycloaddition reactivity. Specifically, UV irradiation of the crystalline material leads to formation of the same diverse array of dimers and cis isomer that are generated by photoreaction in the solution state. In addition, the photoresponsive flexibility of the solid leads to a photosalient effect and photo-induced formation of pores. The origin of the solution state-like photoreactivity of the solid is related to properties of the Cd(II) cation and fluorinated CF 3 SO 3 anion, and the multi-orientational arrangement of the 4-spy ligands., (© 2024 Wiley-VCH GmbH.)

Nanofluidic ionic diodes have attracted much attention due to their unique functions as unidirectional ion transportation ability and promising applications from molecular sensing, and energy harvesting to emerging neuromorphic devices. However, it remains a challenge to fabricate diode-like nanofluidic systems with ultrathin film thickness <100 nm. Herein the formation of ultrathin ionic diodes from hybrid nanoassemblies of nanoporous (NP) SiO 2 nanofilms and polyelectrolyte layer-by-layer (LbL) multilayers is described. Ultrathin ionic diodes are prepared by integrating polyelectrolyte multilayers onto photo-oxidized NP SiO 2 nanofilms obtained from silsesquioxane-containing block copolymer thin films as a template. The obtained ultrathin ionic diodes exhibit ion current rectification (ICR) properties with high ICR factor = ≈20 under low ionic strength and asymmetric pH conditions. It is concluded that this ICR behavior arises from effective ion accumulation and depletion at the interface of NP SiO 2 nanofilms and LbL multilayers attributed to high ion selectivity by combining the experimental data and theoretical calculations using finite element methods. These results demonstrate that the hybrid nano assemblies of NP SiO 2 nanofilms and polyelectrolyte LbL multilayers have potential applications for (bio)sensing materials and integrated ionic circuits for seamless connection of human-machine interfaces., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Here an electrical stimulation system is described for maturing microfiber-shaped cardiac tissue (cardiac microfibers, CMFs). The system enables stable culturing of CMFs with electrical stimulation by placing the tissue between electrodes. The electrical stimulation device provides an electric field covering whole CMFs within the stimulation area and can control the beating of the cardiac microfibers. In addition, CMFs under electrical stimulation with different frequencies are examined to evaluate the maturation levels by their sarcomere lengths, electrophysiological characteristics, and gene expression. Sarcomere elongation (14% increase compared to control) is observed at day 10, and a significant upregulation of electrodynamic properties such as gap junction protein alpha 1 (GJA1) and potassium inwardly rectifying channel subfamily J member 2 (KCNJ2) (maximum fourfold increase compared to control) is observed at day 30. These results suggest that electrically stimulated cultures can accelerate the maturation of microfiber-shaped cardiac tissues compared to those without electrical stimulation. This model will contribute to the pathological research of unexplained cardiac diseases and pharmacologic testing by stably constructing matured CMFs., (© 2024 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)