Evidence for multiferroicity in single-layer CuCrSe2.

Multiferroic materials, which simultaneously exhibit ferroelectricity and magnetism, have attracted substantial attention due to their fascinating physical properties and potential technological applications. With the trends towards device miniaturization, there is an increasing demand for the persistence of multiferroicity in single-layer materials at elevated temperatures. Here, we report high-temperature multiferroicity in single-layer CuCrSe2, which hosts room-temperature ferroelectricity and 120 K ferromagnetism. Notably, the ferromagnetic coupling in single-layer CuCrSe2 is enhanced by the ferroelectricity-induced orbital shift of Cr atoms, which is distinct from both types I and II multiferroicity. These findings are supported by a combination of second-harmonic generation, piezo-response force microscopy, scanning transmission electron microscopy, magnetic, and Hall measurements. Our research provides not only an exemplary platform for delving into intrinsic magnetoelectric interactions at the single-layer limit but also sheds light on potential development of electronic and spintronic devices utilizing two-dimensional multiferroics.

Strong Interaction between Titanium Carbonitride Embedded in Mesoporous Carbon Nanofibers and Pt Enables Durable Oxygen Reduction.

Platinum (Pt) supported on high surface area carbon has been the most widely used electrocatalyst in proton exchange membrane fuel cell (PEMFC). However, conventional carbon supports are susceptible to corrosion at high potentials, leading to severe degradation of electrochemical performance. In this work, titanium carbonitride embedded in mesoporous carbon nanofibers (m-TiCN NFs) are reported as a promising alternative to address this issue. Benefiting from the interpenetrating conductive pathways inside the one-dimensional (1D) nanostructures and the embedded TiCN nanoparticles (NPs), m-TiCN NFs exhibit excellent stability at high potentials and interact strongly with Pt NPs. Subsequently, m-TiCN NFs-supported Pt NPs deliver remarkably enhanced oxygen reduction reaction (ORR) activity and durability, with negligible activity decay and less than 5% loss of electrochemical surface area（ECSA） after 50 000 cycles. Moreover, the fuel cell assembled by this catalyst delivers a maximum power density of 1.22 W cm-2 and merely 3% loss after 30 000 cycles of accelerated durability tests under U.S. Department of Energy (DOE) protocols. The improved ORR activity and durability are attributed to the superior corrosion resistance of the m-TiCN NF support and the strong interaction between Pt and m-TiCN NFs.

Proteomics analysis of enzyme systems and pathway changes during the moromi fermentation of soy sauce mash.

BACKGROUND: During the brewing of soy sauce, the conversion of multiple substances is driven by various microorganisms and their secreted enzyme systems. Soy sauce mash is an important source of enzyme systems during moromi fermentation, but the changes of enzyme systems in soy sauce mash during moromi fermentation are poorly understood. In order to explore the predominant enzyme systems existing during moromi fermentation and to explain the characteristics of the enzyme system changes, an enzymatic activities assay and 4D-label-free proteomics analysis were conducted on soy sauce mash at different stages of fermentation. RESULTS: The activities of hydrolytic enzymes in soy sauce mash decreased continuously throughout the fermentation process, while most of the characteristic physicochemical substances in soy sauce mash supernatant had already accumulated at the early stage of fermentation. Four hydrolytic enzymes were found to be positively correlated with important physicochemical indexes by principal component analysis and Pearson correlation analysis. The proteomics analysis revealed three highly upregulated enzymes and two enzymes that were present in important metabolic pathways throughout the fermentation process. Furthermore, it was found that Aspergillus oryzae was able to accumulate various nutrients in the soy sauce mash by downregulating most of its metabolic pathways. CONCLUSION: Enzymes present with excellent properties during the moromi fermentation period could be obtained from these results. Meanwhile, the characterization of the metabolic pathways of microorganisms during the moromi fermentation period was revealed. The results provide a basis for more scientific and purposeful improvement of moromi fermentation in the future. © 2024 Society of Chemical Industry.

Highly Crystalline Iridium-Nickel Nanocages with Subnanopores for Acidic Bifunctional Water Splitting Electrolysis.

Developing efficient bifunctional materials is highly desirable for overall proton membrane water splitting. However, the design of iridium materials with high overall acidic water splitting activity and durability, as well as an in-depth understanding of the catalytic mechanism, is challenging. Herein, we successfully developed subnanoporous Ir3Ni ultrathin nanocages with high crystallinity as bifunctional materials for acidic water splitting. The subnanoporous shell enables Ir3Ni NCs optimized exposure of active sites. Importantly, the nickel incorporation contributes to the favorable thermodynamics of the electrocatalysis of the OER after surface reconstruction and optimized hydrogen adsorption free energy in HER electrocatalysis, which induce enhanced intrinsic activity of the acidic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Together, the Ir3Ni nanocages achieve 3.72 A/mgIr(η=350 mV) and 4.47 A/mgIr(η=40 mV) OER and HER mass activity, which are 18.8 times and 3.3 times higher than that of commercial IrO2 and Pt, respectively. In addition, their highly crystalline identity ensures a robust nanostructure, enabling good catalytic durability during the oxygen evolution reaction after surface oxidation. This work provides a new revenue toward the structural design and insightful understanding of metal alloy catalytic mechanisms for the bifunctional acidic water splitting electrocatalysis.

A Redox Flow Battery-Integrated Rechargeable H2/O2 Fuel Cell.

The practical application of the H2/O2 proton-exchange membrane fuel cell (PEMFC) is being greatly limited by the use of high-cost Pt as electrode catalysts. Furthermore, the H2/O2 PEMFC is nonrechargeable and thus precludes kinetics energy recovery when equipped on electric vehicles and peak power regulation when combined to power grids. Here, we demonstrate a rechargeable H2/O2 PEMFC through embedding a redox flow battery into a conventional H2/O2 PEMFC. This flow battery employs H2/O2 reactive redox pairs such as NO3-/NO-Br2/Br- and H4SiW12O40/H5SiW12O40 whose redox potentials are as close as possible to those of O2/H2O and H2/H2O, respectively, so that the chemical potential losses during their reactions with O2 at the cathode and H2 at the anode were minimized. More importantly, the electrochemical reversibility allows the H2/O2 reacted redox pairs to be easily regenerated through fuel cell discharging on catalyst-free carbon electrodes at a low overpotential and brings in the fuel cell both chemical and electrical rechargeability, thereby realizing integrated functions of electricity generation- storage as well as efficient operation (achieving an open-circuit potential of 0.96 V and a peak power density of 0.57 W/cm2, which are comparable to a conventional H2/air PEMFC) with catalyst-free carbon electrodes.

Low-Electronegativity Cationic High-Entropy Doping to Trigger Stable Anion Redox Activity for High-Ni Co-Free Layered Cathodes in Li-Ion Batteries.

LiNi0.8 Co0.1 Mn0.1 O2 (NCM-811) exhibits the highest capacity in commercial lithium-ion batteries (LIBs), and the high Ni content (80 %) provides the only route for high energy density. However, the cationic structure instability arisen from the increase of Ni content (>80 %) limits the further increase of the capacity, and inevitable O2 release related to anionic structure instability hinders the utilization of anion redox activity. Here, by comparing various combinations of high-entropy dopants substituted Co element, we propose a low-electronegativity cationic high-entropy doping strategy to fabricate the high-Ni Co-free layered cathode (LiNi0.8 Mn0.12 Al0.02 Ti0.02 Cr0.02 Fe0.02 O2 ) that exhibits much higher capacity and cycling stability. Configurational disorder originated from cationic high-entropy doping in transition metal (TM) layer, anchors the oxidized lattice oxygen ((O2 )n- ) to preserve high (O2 )n- content, triggering the anion redox activity. Electron transfer induced by applying TM dopants with lower electronegativity than that of Co element, increases the electron density of O in TM-O octahedron (TM-O6 ) configuration to reach higher (O2 )n- content, resulting in the higher anion redox activity. With exploring the stabilization effect on both cations and anions of high-entropy doping and low-electronegativity cationic modified anion redox activity, we propose an innovative and variable pathway for rationally tuning the properties of commercial cathodes.

Symmetry-Induced Regulation of Pt Strain Derived from Pt3 Ga Intermetallic for Boosting Oxygen Reduction Reaction.

Pt-based fuel cell catalysts with excellent activity and stability for proton-exchange membrane fuel cells (PEMFCs) have been developed through strain regulation in recent years. Herein, this work demonstrates that symmetry-induced strain regulation of Pt surface of PtGa intermetallic compounds can greatly enhance the catalytic performance of the oxygen reduction reaction (ORR). With the strain environment varies derived from the lattice mismatch of analogous PtGa core but different symmetry, the Pt surface of the PtGa alloy and the Pt3 Ga (Pm 3 ¯ $\bar{3}$ m) precisely realize 0.58% and 2.7% compressive strain compared to the Pt3 Ga (P4/mmm). Experimental and theoretical results reveal that when the compressive stress of the Pt lattice increases, the desorption process of O* intermediates becomes accelerated, which is conducive to oxygen reduction. The Pt3 Ga (Pm 3 ¯ $\bar{3}$ m) with high symmetry and compressive Pt surface exhibit the highest mass and specific activities of 2.18 A mgPt -1 and 5.36 mA cm-2 , respectively, which are more than one order of magnitude higher than those of commercial Pt/C catalysts. This work demonstrates that material symmetry can be used to precisely modulate Pt surface stress to enhance the ORR, as well as provide a distinct platform to investigate the relationship between Pt compressibility and catalytic activity.

Recent Strategies for the Synthesis of Phase-Pure Ultrathin 1T/1T' Transition Metal Dichalcogenide Nanosheets.

The past few decades have witnessed a notable increase in transition metal dichalcogenide (TMD) related research not only because of the large family of TMD candidates but also because of the various polytypes that arise from the monolayer configuration and layer stacking order. The peculiar physicochemical properties of TMD nanosheets enable an enormous range of applications from fundamental science to industrial technologies based on the preparation of high-quality TMDs. For polymorphic TMDs, the 1T/1T' phase is particularly intriguing because of the enriched density of states, and thus facilitates fruitful chemistry. Herein, we comprehensively discuss the most recent strategies for direct synthesis of phase-pure 1T/1T' TMD nanosheets such as mechanical exfoliation, chemical vapor deposition, wet chemical synthesis, atomic layer deposition, and more. We also review frequently adopted methods for phase engineering in TMD nanosheets ranging from chemical doping and alloying, to charge injection, and irradiation with optical or charged particle beams. Prior to the synthesis methods, we discuss the configuration of TMDs as well as the characterization tools mostly used in experiments. Finally, we discuss the current challenges and opportunities as well as emphasize the promising fields for the future development.

Pyrazine-linked Iron-coordinated Tetrapyrrole Conjugated Organic Polymer Catalyst with Spatially Proximate Donor-Acceptor Pairs for Oxygen Reduction in Fuel Cells.

Nitrogen-coordinated iron (Fe-N4 ) materials represent the most promising non-noble electrocatalysts for the cathodic oxygen reduction reaction (ORR) of fuel cells. However, molecular-level structure design of Fe-N4 electrocatalyst remains a great challenge. In this study, we develop a novel Fe-N4 conjugated organic polymer (COP) electrocatalyst, which allows for precise design of the Fe-N4 structure, leading to unprecedented ORR performance. At the molecular level, we have successfully organized spatially proximate iron-pyrrole/pyrazine (FePr/Pz) pairs into fully conjugated polymer networks, which in turn endows FePr sites with firmly covalent-bonded matrix, strong d-π electron coupling and highly dense distribution. The resulting pyrazine-linked iron-coordinated tetrapyrrole (Pz-FeTPr) COP electrocatalyst exhibits superior performance compared to most ORR electrocatalysts, with a half-wave potential of 0.933 V and negligible activity decay after 40,000 cycles. When used as the cathode electrocatalyst in a hydroxide exchange membrane fuel cell, the Pz-FeTPr COP achieves a peak power density of ≈210 mW cm-2 . We anticipate the COP based Fe-N4 catalyst design could be an effective strategy to develop high-performance catalyst for facilitating the progress of fuel cells.

Layered Inorganic Silicate Aerogel Pillared by Nanoclusters for High Temperature Thermal Insulation.

Layered inorganic material, with large-area interlayer surface and interface, provides an essential material platform for constructing new configuration of functional materials. Herein, a layered material pillared with nanoclusters realizing high temperature thermal insulation performance is demonstrated for the first time. Specifically, systematic synchrotron radiation spectroscopy and finite element calculation analysis show that ZrOx nanoclusters served as "pillars" to effectively produce porous structures with enough boundary defect while maintaining the layered structure, thereby significantly reducing solid state thermal conductivity (≈0.32 W m-1  K-1 , 298-573 K). Moreover, the layered inorganic silicate material assembled aerogel also exhibits superior thermal insulation performance from room temperature (0.034 W m-1  K-1 , 298 K, air conditions) to high temperature (0.187 W m-1  K-1 , 1073 K, air conditions) and largely enhanced compressive strength (42 kPa at 80% compression), which is the best layered material-based aerogel that has achieved synergistic improvement in thermal and mechanical performance so far. Layered inorganic silicate aerogel pillared by nanoclusters will pave a new avenue for the design of advanced thermal insulation materials under extreme conditions.

Effect of Sequential Inoculation of Tetragenococcus halophilus and Wickerhamomyces anomalus on the Flavour Formation of Early-Stage Moromi Fermented at a Lower Temperature.

Microbial inoculation in moromi fermentation has a great influence on the physicochemical and flavour properties of soy sauces. This work investigated the effect of inoculating Tetragenococcus halophilus and Wickerhamomyces anomalus on the flavour formation of early-stage moromi (30 days) fermented at a lower temperature (22 °C) by determining their physicochemical and aroma changes. The results showed that single yeast or LAB inoculation increased the production of amino nitrogen, lactic acid and acetic acid, as well as free amino acids and key flavour components. Particularly, the sequential inoculation of T. halophilus and W. anomalus produced more free amino acids and aromatic compounds, and there might be synergistic effects between these two strains. More characteristic soy sauce flavour compounds, such as benzaldehyde, HEMF, guaiacol and methyl maltol were detected in the sequentially inoculated moromi, and this sample showed higher scores in savoury, roasted and caramel intensities. These results confirmed that sequential inoculation of T. halophilus and W. anomalus could be a choice for the future production of moromi with good flavour and quality under a lower temperature.

Astellolides R-W, Drimane-Type Sesquiterpenoids from an Aspergillus parasiticus Strain Associated with an Isopod.

Sesquiterpenoids with a cage-like multiring frame are rarely found in nature. Mining of the isopod-derived fungus Aspergillus parasiticus SDU001 by the one strain-many compounds (OSMAC) strategy unexpectedly led to the discovery of fungal drimane-type sesquiterpenoids astellolide R (1), featuring an unusual cage-like 6/6/5/6/5 pentacyclic ring system, astellolide S (2), possessing a rare nicotinic acid building block, and astellolides T-W (3-6). Their structures were comprehensively assigned by spectroscopic data analysis, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Furthermore, compounds 3 and 5 exhibited anti-inflammatory activity by inhibiting the lipopolyssacharide-induced NO production in RAW264.7 macrophages with IC50 values of 6.1 ± 0.8 and 6.8 ± 0.8 µM, respectively. A putative biosynthetic pathway for 1 is proposed. Our results enlarge the chemical space of the drimane-type sesquiterpenoids generated from endophytic fungi.

Ultrafast Superfilling Construction of a Metal Artificial Interface for Long-Term Stable Zinc Anodes.

Zinc (Zn)-metal anodes are promising candidates for large-scale, highly safe energy-storage systems. However, their cycling life is associated with instability issues such as dendritic growth, corrosion, and hydrogen evolution. Introducing an artificial metal interface is expected to help overcome this challenge owing to the optimization of the absorption, nucleation, and growth of Zn2+ . In this study, an ultrafast, universal, and cost-effective superfilling approach is developed to construct a metal artificial interface decorated Zn anode in situ. Most zincophilic metals, including Sn, Cu, and Ag, can be used to construct a homogenous interface without any restrictions on the size, morphology, or curvature of the substrates. With Sn as a proof-of-concept demonstration, the as-obtained Sn@Zn anode is conducive for the homogenous Zn nuclei and 2D diffusion of Zn2+ ions. Symmetric cells with Sn@Zn electrodes can be operated for over 900 h at different current densities. This superior performance contributes to the attractive electrochemical characteristics of both coin and scaled-up Sn@Zn//ß-MnO2 cells. Given the facile and cost-effective fabrication and recyclability of the cells, this work enables the efficient design and exploration of Zn anodes for research, industrialization, and commercialization purposes.

Novel polyketide from Fusarium verticillioide G102 as NPC1L1 inhibitors.

One novel polyketide, fusaritide A (1), was isolated from a marine fish-derived halotolerant fungal strain Fusarium verticillioide G102. The structure was determined through extensive spectroscopic analysis and high-resolution electrospray ionization mass spectrometry. Fusaritide A (1) with unprecedented structure reduced cholesterol uptake by inhibiting Niemann-Pick C1-Like 1 (NPC1L1).

Interconvertible Pyridone Alkaloids from the Marine-Derived Fungus Penicillium oxalicum QDU1.

Eleven new pyridone alkaloids, penicipyridones A-K (1-11), and three new tetramic acids, tolypocladenols D-F (12-14), were isolated from rice media cultures of the marine-derived fungus Penicillium oxalicum QDU1. Their structures, including absolute configurations, were determined by comprehensive analyses of spectroscopic data, electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction data. Interestingly, several of the penicipyridones undergo interconversions between hydroxy and methoxy groups at C-4 in acidic MeOH solution. Furthermore, in an acidic aqueous solution, OH-4 could be replaced by diverse substituent groups. Compounds 1, 4, 5, 8, 10, 11, and 14 exhibited moderate inhibitory effects on NO production in the LPS-induced RAW264.7 macrophages, with IC50 values ranging from 9.2 to 19 µM.

Hierarchical palladium catalyst for highly active and stable water oxidation in acidic media.

Acidic water electrolysis is of great importance for boosting the development of renewable energy. However, it severely suffers from the trade-off between high activity and long lifespan for oxygen evolution catalysts on the anode side. This is because the sluggish kinetics of oxygen evolution reaction necessitates the application of a high overpotential to achieve considerable current, which inevitably drives the catalysts far away from their thermodynamic equilibrium states. Here we demonstrate a new oxygen evolution model catalyst-hierarchical palladium (Pd) whose performance even surpasses the benchmark Ir- and Ru-based materials. The Pd catalyst displays an ultralow overpotential (196 mV), excellent durability and mitigated degradation (66 µV h-1) at 10 mA cm-2 in 1 M HClO4. Tensile strain on Pd (111) facets weakens the binding of oxygen species on electrochemical etching-derived hierarchical Pd and thereby leads to two orders of magnitudes of enhancement of mass activity in comparison to the parent Pd bulk materials. Furthermore, the Pd catalyst displays the bifunctional catalytic properties for both oxygen and hydrogen evolutions and can deliver a current density of 2 A cm-2 at a low cell voltage of 1.771 V when fabricated into polymer electrolyte membrane electrolyser.

Molecular identification and physiological functional analysis of NtNRT1.1B that mediated nitrate long-distance transport and improved plant growth when overexpressed in tobacco.

Although recent physiological studies demonstrate that flue-cured tobacco preferentially utilizes nitrate ( NO 3 - ) or ammonium nitrate (NH4NO3), and possesses both high- and low-affinity uptake systems for NO 3 - , little is known about the molecular component(s) responsible for acquisition and translocation in this crop. Here we provide experimental data showing that NtNRT1.1B with a 1,785-bp coding sequence exhibited a function in mediating NO 3 - transport associated with tobacco growth on NO 3 - nutrition. Heterologous expression of NtNRT1.1B in the NO 3 - uptake-defective yeast Hp△ynt1 enabled a growth recovery of the mutant on 0.5 mM NO 3 - , suggesting a possible molecular function of NtNRT1.1B in the import of NO 3 - into cells. Transient expression of NtNRT1.1B::green fluorescent protein (GFP) in tobacco leaf cells revealed that NtNRT1.1B targeted mainly the plasma membrane, indicating the possibility of NO 3 - permeation across cell membranes via NtNRT1.1B. Furthermore, promoter activity assays using a GFP marker clearly indicated that NtNRT1.1B transcription in roots may be down-regulated by N starvation and induced by N resupply, including NO 3 - , after 3 days' N depletion. Significantly, constitutive overexpression of NtNRT1.1B could remarkably enhance tobacco growth by showing a higher accumulation of biomass and total N, NO 3 - , and even NH 4 + in plants supplied with NO 3 - ; this NtNRT1.1B-facilitated N acquisition/accumulation could be strengthened by short-term 15N- NO 3 - root influx assays, which showed 15%-20% higher NO 3 - deposition in NtNRT1.1B-overexpressors as well as a high affinity of NtNRT1.1B for NO 3 - at a K m of around 30-45 µM. Together with the detection of NtNRT1.1B promoter activity in the root stele and shoot-stem vascular tissues, and higher NO 3 - in both xylem exudate and the apoplastic washing fluid of NtNRT1.1B-transgenic lines, NtNRT1.1B could be considered as a valuable molecular breeding target aiming at improving crop N-use efficiency by manipulating the absorption and long-distance distribution/transport of nitrate, thus adding a new functional homolog as a nitrate permease to the plant NRT1 family.

Even-Odd-Layer-Dependent Ferromagnetism in 2D Non-van-der-Waals CrCuSe2.

Van der Waals (vdW) layered materials with strong magnetocrystalline anisotropy have attracted significant interest as the long-range magnetic order in these systems can survive even when their thicknesses is reduced to the 2D limit. Even though the interlayer coupling between the neighboring magnetic layers is very weak, it has a determining effect on the magnetism of these atomic-thickness materials. Herein, a new 2D ferromagnetic material, namely, non-vdW CuCrSe2 nanosheets with even-odd-layer-dependent ferromagnetism when laminated from an antiferromagnetic bulk is reported. Monolayer and even-layer CuCrSe2 exhibit the anomalous Hall effect and a significantly enhanced magnetic ordering temperature of more than 125 K. In contrast, the linear Hall effect exists in the odd-layer samples. Theoretical calculations indicate that the layer-dependent magnetic coupling is attributable to the orbital shift of the Cr atoms in the CrSe2 layers owing to the Cu-induced breaking of the centrosymmetry. Thus, this work sheds light on the exotic magnetic properties of layered materials that exhibit phenomena beyond weak interlayer interactions.

Retarding the Shuttling Ions in the Electrochromic TiO2 with Extensive Crystallographic Imperfections.

To understand the role of structure imperfections on the performance of electrochromic transition metal oxide (ETMO) is challenging for the design of efficient smart windows. Herein, we investigate the performance evolution with tunable crystallographic imperfections for rutile TiO2 nanowire film (TNF). Structure imperfections, originating mainly from the copious oxygen deficiency, are apt to cumulatively retard the shuttling ions, resulting in the response rate for raw TNF being less than the half that of TNF annealed at 500 °C. We describe ion accommodation sites as a convolution of normal site and abnormal site, in which the normal site performs reversible coloration but the abnormal site contributes only to charge storage, which gives a rationale for the non-linear coloration and rate capability loss. These findings give a clear picture of the ion shuttling process, which is insightful for enhancing the electrochromic performance via structure reprogramming.

Mesoporous multi-shelled hollow resin nanospheres with ultralow thermal conductivity.

Hollow nanostructures exhibit enclosed or semi-enclosed spaces inside and the consequent features of restricting molecular motion, which is crucial for intrinsic physicochemical properties. Herein, we developed a new configuration of hollow nanostructures with more than three layers of shells and simultaneously integrated mesopores on every shell. The novel interior configuration expresses the characteristics of periodic interfaces and abundant mesopores. Benefiting from the suppression of gas molecule convection by boundary scattering, the thermal conductivity of mesoporous multi-shelled hollow resin nanospheres reaches 0.013 W m-1 K-1 at 298 K. The designed interior mesostructural configuration of hollow nanostructures provides an ideal platform to clarify the influence of nanostructure design on intrinsic physicochemical properties and propels the development of hollow nanostructures.