bluuebunny/crossref_metadata_2025 huggingface dataset:
In situ Construction of Single‐Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production
Authors: Li Jie , Zhou Jie , Wang Xiao‐Han , Guo Can , Li Run‐Han , Zhuang Huifen , Feng Wenhai , Hua Yingjie , Lan Ya‐Qian
Published: August 2024

Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal‐covalent organic frameworks (MCOFs) with both small‐sized metal clusters and nitrogen‐rich ligands, named COF‐Cu3TG. Based on our design, small‐sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen‐rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single‐atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2‐Ru‐N2 electron bridge (Ru‐SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g−1 h−1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru‐SAEB were reasonably inferred, further confirming the rationality of the Ru‐SAEB configuration. A sufficiently proximity between the small‐sized Cu3 cluster and the Ru‐SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru‐SAEB for efficient photocatalytic hydrogen production.
Construction of Highly Porous and Robust Hydrogen‐Bonded Organic Framework for High‐Capacity Clean Energy Gas Storage
Authors: Wang Jia‐Xin , Zhang Xu , Jiang Chenghao , Zhang Teng‐Fei , Pei Jiyan , Zhou Wei , Yildirim Taner , Chen Banglin , Qian Guodong , Li Bin
Published: August 2024

Development of highly porous and robust hydrogen‐bonded organic frameworks (HOFs) for high‐pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double‐walled framework to target highly porous and robust HOF (ZJU‐HOF‐5a) for extraordinary CH4 and H2 storage. ZJU‐HOF‐5a features a minimized twofold interpenetration with double‐walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m2 g−1 and 1976 m2 cm−3 among the reported HOFs so far. ZJU‐HOF‐5a thus exhibits an extremely high volumetric H2 uptake of 43.6 g L−1 at 77 K/100 bar and working capacity of 41.3 g L−1 under combined swing conditions (77 K/100 bar→160 K/5 bar), and also impressive methane storage performance with a 5–100 bar working capacity of 187 (or 159) cm3 (STP) cm−3 at 270 K (or 296 K), outperforming most of the reported porous organic materials. Single‐crystal X‐ray diffraction studies on CH4‐loaded ZJU‐HOF‐5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH4 storage capacities. Combined with high stability, super‐hydrophobicity, and easy recovery, ZJU‐HOF‐5a is placed among the most promising materials for H2 and CH4 storage applications.
Electrochemiluminescence Enhanced by a Non‐Emissive Dual Redox Mediator
Authors: Adamson Natasha S. , Blom Steven J. , Doeven Egan H. , Connell Timothy U. , Hadden Callum , Knežević Sara , Sojic Neso , Fracassa Alessandro , Valenti Giovanni , Paolucci Francesco , Ding Jialian , Wang Yafeng , Su Bin , Hua Carol , Francis Paul S.
Published: August 2024

A sulfonated tris(1‐phenylpyrazolato)iridium(III) complex ([Ir(sppz)3]3−) serves as a proof‐of‐concept non‐emissive enhancer of the widely used ECL detection system of tris(2,2′‐bipyridine)ruthenium(II) ([Ru(bpy)3]2+) with tri‐n‐propylamine (TPrA) co‐reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi‐excitation of the luminophore. Using self‐interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)3]2+ ECL intensity using [Ir(sppz)3]3− was obtained without its concomitant emission. The most prominent enhancement (11‐fold) occurred at low potentials associated with the ‘indirect’ co‐reactant ECL pathway, which translated to between 2‐ and 6‐fold enhancement when the luminophore was immobilised on microbeads as a general model for enhanced ECL assays.
Interface Synergy of Exposed Oxygen Vacancy and Pd Lewis Acid Sites Enabling Superior Cooperative Photoredox Synthesis
Authors: Huang Zhi‐Sang , Wang Yin‐Feng , Qi Ming‐Yu , Conte Marco , Tang Zi‐Rong , Xu Yi‐Jun
Published: August 2024

Photo‐driven cross‐coupling of o‐arylenediamines and alcohols has emerged as an alternative for the synthesis of bio‐active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (VO) and Pd Lewis acid sites for benzimidazole and hydrogen (H2) coproduction over Pd‐loaded TiO2 nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of VO optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine molecules via Lewis acid‐base pair interactions and driving the condensation process. Furthermore, VO and Pd synergistically promote interfacial charge transfer and separation. This work offers new insightful guidance for the rational design of semiconductor‐based photocatalysts with interface synergy at the molecular level towards the high‐performance coproduction of renewable fuels and value‐added feedstocks.
Vertically Fluorinated Graphene Encapsulated SiOx Anode for Enhanced Li+ Transport and Interfacial Stability in High‐Energy‐Density Lithium Batteries
Authors: Huang Lin‐Bo , Zhao Lu , Ma Zhi‐Feng , Zhang Xing , Zhang Xu‐Sheng , Lu Zhuo‐Ya , Li Ge , Luo Xiao‐Xi , Wen Rui , Xin Sen , Meng Qinghai , Guo Yu‐Guo
Published: August 2024

Achieving high energy density has always been the goal of lithium‐ion batteries (LIBs). SiOx has emerged as a compelling candidate for use as a negative electrode material due to its remarkable capacity. However, the huge volume expansion and the unstable electrode interface during (de)lithiation, hinder its further development. Herein, we report a facile strategy for the synthesis of surface fluorinated SiOx (SiOx@vG−F), and investigate their influences on battery performance. Systematic experiments investigations indicate that the reaction between Li+ and fluorine groups promotes the in situ formation of stable LiF‐rich solid electrolyte interface (SEI) on the surface of SiOx@vG−F anode, which effectively suppresses the pulverization of microsized SiOx particles during the charge and discharge cycle. As a result, the SiOx@vG−F enabled a higher capacity retention of 86.4 % over 200 cycles at 1.0 C in the SiOx@vG−F||LiNi0.8Co0.1Mn0.1O2 full cell. This approach will provide insights for the advancement of alternative electrode materials in diverse energy conversion and storage systems.
Spiro‐Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles
Authors: Shang Jihai , Wang Zhihua , Sun Chunlin , Wang Renjie , Hua Xinqiang , Feng Lijun , Yuan Chengshan , Liu Zitong , Zhang Hao‐Li , Xu Jialiang , Shao Xiangfeng
Published: August 2024

Integration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro‐conjugation plays an important role in the geometric and electronic structures of spiro‐HSEs. The bowl depth of DCSs moiety becomes larger in the spiro‐HSEs. Owing to the Jahn‐Teller (J‐T) effect, two DCSs segments of spiro‐HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro‐HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value‐added functionalities. The emissive property is enhanced by converting the thiophene rings of S‐doped spiro‐HSE into thiophene S,S‐dioxides. A chiroptical polycycle could be produced by ring‐opening of the edge benzene of Se‐doped spiro‐HSE. The covalent adduct of Te‐doped spiro‐HSE with Br2 forms non‐centrosymmetric halogen‐bonded networks, resulting in the high performance second‐order nonlinear optics (NLO).
Simultaneous Structural and Electronic Engineering on Bi‐ and Rh‐co‐doped SrTiO3 for Promoting Photocatalytic Water Splitting
Authors: Pan Zhenhua , Vequizo Junie Jhon M. , Yoshida Hiroaki , Li Jianuo , Zheng Xiaoshan , Chu Chiheng , Wang Qian , Cai Mengdie , Sun Song , Katayama Kenji , Yamakata Akira , Domen Kazunari
Published: August 2024

Activating metal ion‐doped oxides as visible‐light‐responsive photocatalysts requires intricate structural and electronic engineering, a task with inherent challenges. In this study, we employed a solid (template)‐molten (dopants) reaction to synthesize Bi‐ and Rh‐codoped SrTiO3 (SrTiO3 : Bi,Rh) particles. Our investigation reveals that SrTiO3 : Bi,Rh manifests as single‐crystalline particles in a core (undoped)/shell (doped) structure. Furthermore, it exhibits a well‐stabilized Rh3+ energy state for visible‐light response without introducing undesirable trapping states. This precisely engineered structure and electronic configuration promoted the generation of high‐concentration and long‐lived free electrons, as well as facilitated their transfer to cocatalysts for H2 evolution. Impressively, SrTiO3 : Bi,Rh achieved an exceptional apparent quantum yield (AQY) of 18.9 % at 420 nm, setting a new benchmark among Rh‐doped‐based SrTiO3 materials. Furthermore, when integrated into an all‐solid‐state Z‐Scheme system with Mo‐doped BiVO4 and reduced graphene oxide, SrTiO3 : Bi,Rh enabled water splitting with an AQY of 7.1 % at 420 nm. This work underscores the significance of simultaneous structural and electronic engineering and introduces the solid‐molten reaction as a viable approach for this purpose.
Electrical conductivity enhancement in polyaniline films via mixed ion‐electron conductive fillers
Authors: Abdalla Sahar , Telfah Ahmad , Ferjani Hela , Tavares Carlos J. , Etzkorn Johannes
Published: August 2024

The influence of mixed ion‐electronic conductive fillers on the physical characteristics of protonated polyaniline (P‐PANI) nanocomposite films is investigated by incorporating titanium nanoparticles (TiNPs) and lithium trifluoromethanesulfonate () at various concentrations. The introduction of into the P‐PANI matrix results in the appearance of additional X‐ray diffraction peaks ascribed to a titanium phase, confirming the presence of TiNPs. The incorporation of leads to changes in intensities, linewidths, and diffraction angles, indicating interactions between ions and nitrogen atoms in the matrix. The bandgap energy for the pristine P‐PANI film is 3.40 eV, being reduced to 3.29 eV upon incorporating in the P‐PANI matrix. An increase in the concentration of in the P‐PANI/TiNPs composite films with decreasing TiNPs concentration leads to a continuous increase in bandgap energy to 3.59 eV. The electrical conductivity of pristine P‐PANI is 0.49 mS/cm. The addition of TiNPs increases the conductivity to 2.16 mS/cm, while the addition of LiOTf increases it to 1.72 mS/cm. Notably, (P‐PANI)/TiNPs nanocomposite films with 7:3 and 5:5 wt.% ratios exhibit superior electrical conductivity compared with individual (P‐PANI)/TiNPs and (P‐PANI)/LiOTf films, attributed to effective ionic‐electronic coupling at phase‐separated region interfaces. This study reveals impact of and on the structural, optical, and electrical properties of P‐PANI nanocomposite films, thereby enhancing their potential for integration into advanced electronic and optoelectronic devices.
Impact of hydrolysis on the quantification of sulfonated acrylamide copolymers by size exclusion chromatography with UV detection
Authors: Gonçalves Cecília C. R. , Duncke Angela C. P. , Maqueira Luis , Creatto Eduardo J. , Limberger Jones , Pérez‐Gramatges Aurora
Published: August 2024

Size exclusion chromatography with UV detection (SEC‐UV) is a precise method for quantifying polyacrylamides in water. However, its accuracy can be compromised in complex matrices due to chemical degradation of the polymer. This study focuses on the impact of hydrolysis on quantifying sulfonated polyacrylamide copolymers (PAM‐AMPS) via SEC‐UV, analyzing key influencing factors. Using controlled hydrolysis, hydrolyzed copolymer (HPAM‐AMPS) standards with varying hydrolysis degree (HD) (HD = 7%–33%) were prepared without significant changes in polymer chain size. SEC‐UV analysis revealed that quantification accuracy is highly dependent on hydrolysis extent. Errors are minimal for HD up to 10%, but significantly higher for HDs of 22%–33%. Furthermore, this effect is modulated by polymer concentration. Our findings indicate that there are two compensating factors for the decrease in molar absorptivity due to amide‐to‐carboxylate substitution: the sulfonate group acting as an additional chromophore, and a redshift in absorption spectra due to hydrogen bonding at higher concentrations. This interplay between HD and concentration in this type of sulfonated polyacrylamide can help reduce quantification errors in complex aqueous samples prone to chemical degradation, like those found in environmental and subsurface applications.
Effects of temporal hydrologic shifts on the population biology of an endangered freshwater fish in a dryland river ecosystem
Authors: Richmond Jonathan Q. , Gould Philip R. , Pareti Jennifer , Aitken Andrew , Morrissette Eric , Backlin Adam R. , Dellith Chris , Fisher Robert N.
Published: August 2024

Species occupying dryland river ecosystems often experience “boom‐and‐bust” demographic cycles that coincide with shifts in habitat availability. Knowing whether declines are within natural thresholds versus those caused by acute human disturbance is critical for managing protected species. We investigated temporal shifts in abundance and habitat use of an endangered population of the threespine stickleback Gasterosteus aculeatus in southern California, where a Mediterranean climate leads to ephemeral habitat in one of the regions' least hydrologically modified rivers, the Santa Clara River. We conducted population surveys over a period of below‐average rainfall in the upper watershed in Soledad Canyon, with predefined reaches surveyed multiple times per year to capture different hydrologic conditions. Abundances were stable across years but varied significantly depending on location, with some reaches remaining dry and others drying seasonally to varying degrees. Occupancy models showed that the presence of stable perennial reaches, drying regime, and other site‐specific factors were important predictors of habitat use, and that certain reaches may be key to ensuring source‐sink dynamics as flow dissipates over the dry season. Low occupancy in two sections was driven by different predominant mechanisms, one by diel cycles of evapotranspiration and the other by cattails (Typha spp.), with both having greater effects during the hotter, drier parts of the year. As dryland river ecosystems are vulnerable to the effects of anthropogenic‐induced climate change, this study demonstrates how temporal monitoring can delimit dry‐state benchmarks for improving management interventions (i.e., translocation and habitat restoration) for protected species under conditions that are predicted to worsen in the coming years.
Response of wild aquatic insect communities to thermal variation through comparative landscape transcriptomics
Authors: Gamboa Maribet , Gotoh Yusuke , Doloiras‐Laraño Arnelyn , Watanabe Kozo
Published: August 2024

Fluctuations in temperature are recognized as a potent driver of selection pressure, fostering genomic variations that are crucial for the adaptation and survival of organisms under selection. Notably, water temperature is a pivotal factor influencing aquatic organism persistence. By comprehending how aquatic organisms respond to shifts in water temperature, we can understand their potential physiological adaptations to environmental change in one or multiple species. This, in turn, contributes to the formulation of biologically relevant guidelines for the landscape scale transcriptome profile of organisms in lotic systems. Here, we investigated the distinct responses of seven stream stonefly species, collected from four geographical regions across Japan, to variations in temperature, including atmospheric and water temperatures. We achieved this by assessing the differences in gene expression through RNA‐sequencing within individual species and exploring the patterns of community‐genes among different species. We identified 735 genes that exhibited differential expressions across the temperature gradient. Remarkably, the community displayed expression levels differences of respiration and metabolic genes. Additionally, the diversity in molecular functions appeared to be linked to spatial variation, with water temperature differences potentially contributing to the overall functional diversity of genes. We found 22 community‐genes with consistent expression patterns among species in response to water temperature variations. These genes related to respiration, metabolism and development exhibited a clear gradient providing robust evidence of divergent adaptive responses to water temperature. Our findings underscore the differential adaptation of stonefly species to local environmental conditions, suggesting that shared responses in gene expression may occur across multiple species under similar environmental conditions. This study emphasizes the significance of considering various species when assessing the impacts of environmental changes on aquatic insect communities and understanding potential mechanisms to cope with such changes.
Construction of a Defective Chiral Covalent Organic Framework for Fluorescence Recognition of Amino Acids
Authors: Yuan Luhai , Tang Xihao , Zhang Kai , Chen Hong , Yang Xi , Fan Jun , Xie Mubiao , Zheng Shengrun , Cai Songliang
Published: August 2024

The design and synthesis of chiral covalent organic frameworks (COFs) with controlled defect sites are highly desirable but still remain largely unexplored. Herein, we report the synthesis of a defective chiral HD‐TAPB‐DMTP COF by modifying the chiral monomer helicid (HD) into the framework of an achiral imine‐linked TAPB‐DMTP COF using a chiral monomer exchange strategy. Upon the introduction of the chiral HD unit, the obtained defective chiral HD‐TAPB‐DMTP COF not only displays excellent crystallinity, large specific surface area (up to 2338 m2/g) and rich accessible chiral functional sites but also exhibits fluorescence emission, rendering it a good candidate for discrimination of amino acids. Notably, the resultant defective chiral HD‐TAPB‐DMTP COF can be used as a fluorescent sensor for enantioselective recognition of both tyrosine and phenylalanine enantiomers in water, showing enhanced fluorescent responses for the L conformations over those of the D conformations with the enantioselectivity factors being 1.84 and 2.02, respectively. Moreover, molecular docking simulations uncover that stronger binding affinities between chiral HD‐TAPB‐DMTP COF and L‐tyrosine/L‐phenylalanine in comparison to those with D‐tyrosine/D‐phenylalanine play important roles in enantioselective determination. This work provides new insights into the design and construction of highly porous defective chiral COFs for enantioselective fluorescence recognition of amino acids.
Bewertung und Ertüchtigung von Bestandsbrücken
Authors: Pelke Eberhard
Published: August 2024

Zwei historiografische Kurzskizzen führen in die Begrifflichkeiten von Instandsetzung, Zustands‐ und Tragfähigkeitsbewertung zwischen 1700 und 2010 ein und werfen einen Blick auf die Entwicklung des Nachrechnens von Brückenbeständen. Anhand von Projektskizzen werden die versteckten Sicherheiten von bestehenden Straßenbrücken herausgearbeitet und Vorgehensweisen zur Erzielung leistungsfähiger Bauwerksertüchtigungen abgeleitet. Reale objektspezifische Verkehrslastmodelle, messwertkalibrierte Tragwerksanalysen und additive und zerstörungsarme Verstärkungsmethoden stehen dabei im Mittelpunkt. Einige kritische Anmerkungen zu Planungsbeschleunigungen und dem derzeitigen Zulassungswesen zusammen mit dem Wunsch, dass sich der Brückenbau im gemeinsamen Leitziel „Verkehr“ wiederfinden möge, weiten die Defintion der Ertüchtigung ganzheitlich auf und bieten so die Chance, eine Diskussion über den sinnvollen Umgang mit Bestandsbrücken im Zuge unserer Straßeninfrastruktur anzuregen.
Development and Upscaling of a Waterborne Formulation for High‐Energy Density NMC811 Cathodes
Authors: Sananes‐Israel Susan , Urdampilleta Idoia , Kvasha Galyna , Landa‐Medrano Imanol , de Meatza Iratxe
Published: August 2024

The pursuit of high‐energy lithium‐ion cells has led to an increase in the fraction of nickel in the LiNixMnyCozO2 (NMC, with x+y+z=1) layered oxide, a state‐of‐the‐art cathode material in electric vehicles. NMC is usually processed using organic solvents that are non‐sustainable. Nevertheless, increasing the Ni fraction entails a decrease in the electrode stability and the processability of this material in water. In this work, high‐nickel NMC materials have been subjected to water processing. In an initial stage, water sensitivity of the materials has been studied. Then, the formulation has been adapted to enhance the NMC fraction without penalizations in the electrochemical performance and compared to an organic solvent‐based formulation. The recipe developed, consisting of 93 % of NMC, has been successfully upscaled to a semi‐industrial coating line. The pH buffering has been observed as a critical step to mitigate lithium leaching and implement this process in an industrial environment. The obtained electrodes have been tested in single‐layer pouch cells using silicon‐based negative electrodes, also processable in water‐based slurries. The resulting cells provide limited cycling life due to the low cyclability of the negative electrode but evidence that it is industrially viable to manufacture high‐energy cells consisting only of water‐processed electrodes.
Corporate business strategy, CEO's managerial ability, and environmental disclosure: The perspective of stakeholder theory
Authors: Cahyono Suham , Harymawan Iman , Djajadikerta Hadrian Geri , Noman Abu Hanifa Md.
Published: August 2024

The adoption of business strategies at the corporate level is often associated with the resource‐based view theory. However, many scholars have not definitively determined whether aligning business strategies with the principles of the resource‐based view theory is consistent with the perspective presented by stakeholder theory. This study examines the relationship between corporate business strategies and environmental disclosure. Specifically, we investigate whether CEO's managerial ability may strengthen the association by emphasizing stakeholder theory to address this inquiry. Using a sample of 1243 publicly traded companies registered with the Carbon Disclosure Project (CDP) from 2015 to 2021, our findings indicate that a firm's chosen business strategy significantly influences its environmental disclosure practices. In particular, we observe that firms pursuing an innovation‐oriented business strategy (prospectors) are less inclined to disclose, initiate, or increase their environmental disclosures compared with those following a cost‐efficient business strategy (defenders). To address endogeneity and ensure robustness, we conduct a battery of tests, including the entropy balancing approach, two‐step generalized method of the moment using Arellano‐Bond estimation, Heckman two‐stage regression, and coarsened exact matching. This study offers valuable insights into the determinants of firms' environmental disclosure practices, with significant implications for policymakers, investors, and other stakeholders interested in promoting sustainability and corporate responsibility.
Three Undescribed Furanoditerpenoids from the Tinospora crispa that Inhibit NO Production
Authors: Van Quoc Nguyen , Huu Tai Bui , Hai Yen Pham , Huy Hoang Nguyen , Thuy Hang Dan Thi , Thanh Huong Phan Thi , Anh Bang Ngo , Thi Dung Duong , Thi Trang Do , Giang Le Duc , Van Kiem Phan
Published: August 2024

Phytochemical study on the methanol extract of the stems of Tinospora crispa (L.) Hook.f. & Thomson led to the isolation of thirteen compounds including three undescribed cis‐clerodane‐type furanoditerpenoids (1–3) and ten known ones (4–13). Their chemical structures were determined by IR, HR‐ESI‐MS, 1D‐, and 2D‐NMR spectra. Compounds 2–4, 6 and 8 inhibited moderately NO production in LPS activated RAW 264.7 cells with the IC50 values of 83.5, 57.6, 75.3, 78.1, and 74.7 μM, respectively.
N,S‐Doped Zeolite‐Templated Carbon Like Supported NixFeySz as an Efficient Bifunctional Catalyst for Rechargeable Zinc Air Batteries
Authors: Loupias Lola , Boulé Roald , Benbakoura Nora , Compère Steven , Rousseau Julie , Maziere Laetitia , Pailloux Frédéric , Mauchamp Vincent , Pacaud Jérôme , Célérier Stéphane , Servat Karine , Napporn Teko W. , Morais Claudia , Sachse Alexander , Habrioux Aurélien
Published: August 2024

A still unexplored class of heterostructured bifunctional catalysts for oxygen evolution (OER) and reduction (ORR) reactions is investigated: Ni−Fe sulfides deposited onto a N,S‐co‐doped zeolite‐templated carbon (ZTC) substrate achieved upon the impregnation of a ZTC with thiourea and Ni and Fe precursors (Ni/Fe atomic ratio of 1). By heat‐treating the impregnated ZTC substrate at 700 °C under N2 atmosphere the efficient bifunctional catalyst is generated. A difference of only 0.76 V is measured between the potential required to drive an OER current density of 10 mA cm−2 and the ORR half‐wave potential. Using electrochemical measurements and physico‐chemical characterizations, it is evidenced that OER activity results from the presence of a sulfide containing both Fe and Ni whereas the ORR activity originates from the N,S‐doped ZTC substrate. The selectivity of the ORR process is improved through the presence of sulfide phases. Compared to more conventional carbon substrate such as N,S‐co‐doped reduced graphene oxide, high specific surface area ZTC favors high ORR performances. The functional ZTC material was further successfully implemented as bifunctional air electrode in a coin‐type Zn‐air battery.
(La0.8Sr0.2)0.95Mn0.5Fe0.5O3Perovskite as anEfficient Bi‐Functional Electrocatalyst for Oxygen‐Involved Reaction and Zn‐Air Batteries
Authors: Bao Xinjun , Xia Sunan , Hou Jiwei , He Guangjun , He Bin , Zhang Zejie , Zhou Debi , Wang Hong‐En
Published: August 2024

The perovskite‐type oxide (La0.8Sr0.2)0.95Mn0.5Fe0.5O3, synthesized using lanthanum resources recovered from polishing powder waste and manganese resources obtained from zinc anode mud, was obtained via a facile polymer‐assisted combustion method, and further applied in zinc‐air batteries.The crystal phase and microstructure features of the thus‐obtained nanoparticles were characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), and nitrogen adsorption‐desorption measurements. The results showed that the (La0.8Sr0.2)0.95Mn0.5Fe0.5O3 particles, with nanoscale size, possess a high specific surface area and a suitable Mn3+/Mn4+ molar ratio, which will benefit both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). As expected, the thus‐fabricated (La0.8Sr0.2)0.95Mn0.5Fe0.5O3 electrode exhibits a high current density of 71.2 and 85.2 mA cm−2 at −0.2 V and 0.6 V vs. Hg/HgO, respectively, which is superior to that of the commercial Pt/C catalyst (58 and 31 mA cm−2, respectively).Subsequently, this compound oxide can be an air electrode in a rechargeable zinc‐air battery. The assembled battery, using (La0.8Sr0.2)0.95Mn0.5Fe0.5O3 as the cathode, exhibits a discharge voltage of 1.05~1.16 V and a charge voltage of 2.03~2.13 V under 15 mA cm−2 for 150 h.The excellent electrochemical results presented in this study highlight the potential of (La0.8Sr0.2)0.95Mn0.5Fe0.5O3 as a highly efficient and commercially viable bifunctional electrocatalyst for applications in rechargeable zinc‐air batteries.
Low‐temperature performance of Na‐ion batteries
Authors: Li Meng , Zhuo Haoxiang , Jing Qihang , Gu Yang , Liao Zhou , Wang Kuan , Hu Jiangtao , Geng Dongsheng , Sun Xueliang , Xiao Biwei
Published: August 2024

Sodium‐ion batteries (NIBs) have become an ideal alternative to lithium‐ion batteries in the field of electrochemical energy storage due to their abundant raw materials and cost‐effectiveness. With the progress of human society, the requirements for energy storage systems in extreme environments, such as deep‐sea exploration, aerospace missions, and tunnel operations, have become more stringent. The comprehensive performance of NIBs at low temperatures (LTs) has also become an important consideration. Under LT conditions, challenges such as increased viscosity of electrolyte, abnormal growth of solid electrolyte interface, and poor contact between collector and electrode materials emerge. The aforementioned issues hinder the diffusion kinetics of sodium ions (Na+) at the electrode/electrolyte interface and cause rapid degradation of battery performance. Consequently, the optimization of electrolyte composition and cathode/anode materials becomes an effective approach to improve LT performance. This review discusses the conduction behavior and limiting factors of Na+ in both solid electrodes and liquid electrolytes at LT. Furthermore, it systematically reviews the recent research progress of LT NIBs from three aspects: cathode materials, anode materials, and electrolyte components. This review aims to provide a valuable reference for developing high‐performance LT NIBs.
Synthesis of a Multi‐Stimulus Responsive RGB Fluorescent Organic Molecule Based on Dark Through‐Bond Energy Transfer Mechanism
Authors: Li Kuiliang , Xie Wenqiang , Zhang Minggui , Fu Dexin , Hu Duo‐Duo , Yang Ping
Published: August 2024

In this study, a novel multi‐stimulus responsive RGB fluorescent organic molecule, RTPE‐NH2, was designed and synthesized based on the combination of aggregation‐induced emission tetraphenylethylene (TPE) luminophore and acid‐responsive fluorescent molecular switch Rhodamine B. RTPE‐NH2 exhibits aggregation‐induced emission behavior, as well as UV irradiation‐stimulus and acid‐stimulus responsive fluorescence properties. It could emit orange‐red (R), green(G), and blue(B) light in both solution and PMMA film under 365 nm excitation. The dark through‐bond energy transfer (DTBET) mechanism was proposed and supported by control experiments and TD‐DFT calculations. The synthesis and application of RTPE‐NH2 could accelerate the development of organic smart materials with high sensitivity and excellent optical properties.
Visible‐Light Mediated Nickel‐Catalyzed Asymmetric Difunctionalizations of Alkenes
Authors: Zhao Han‐Tong , Lin Jia‐Ni , Shu Wei
Published: August 2024

Difunctionalizations of alkenes represent one of the most straightforward protocols to build molecular complexity due to the simultaneous construction of two vicinal bonds cross π‐bond of alkenes. It is extremely attractive yet challenging to control the stereochemistry outcome of this event. Over the past years, visible‐light and Ni‐catalyzed asymmetric difunctionalizations of alkenes provide an environmental benign and promising solution for the construction of saturated carbon centers with the control of regio‐ and enantioselectivity. In this Concept, the initiative and progress of regio‐ and enantioselective difunctionalizations of alkenes enabled by visible‐light and nickel catalysis has been summarized. Moreover, further efforts and directions for the development of visible‐light mediated Ni‐catalyzed asymmetric difunctionalizations of alkenes has been discussed.
Synthesis and Anticancer Evaluation of Disubstituted Benzimidazoles via One‐Pot Telescopic Grinding Approach
Authors: Das Soumyadip , Thansila Parvin N. , Maiti Barnali , Padmaja R. D. , Prathima T. S. , Balamurali M. M. , Chanda Kaushik
Published: August 2024

Benzimidazole compounds are known for their broad spectrum therapeutic potentials. A small library of benzimidazole derivatives were designed and synthesized via a one‐pot telescopic grinding approach. The ability of these molecules as proposed anticancer agents were evaluated by their potential to bind to two important cancer pathway protein targets, human estrogen receptors and cyclin dependant kinases, 3ERT and 5FGK respectively. Further nucleic acid binding and reactive oxygen species (ROS) scavenging capacity being in the scope for anticancer potential evaluations, the ability of these molecules have been evaluated for the same. Further, to support the experimental and computational results, AI‐assisted tools were employed to predict the anticancer activity (PASS) as well as to identify false positives (PAINS). Also, the druggability of the proposed compounds was evaluated by following their pharmacokinetic parameters – ADME.
Influence of 3D Structural Design on the Electrochemical Performance of Aluminum Metal as Negative Electrode for Li‐Ion Batteries
Authors: Ricci Marco , Marras Sergio , Krammer Martin , Palanivel Molaiyan , Proietti Zaccaria Remo , Paolella Andrea
Published: August 2024

Aluminum (Al) is one of the most promising active materials for producing next‐generation negative electrodes for lithium (Li)‐ion batteries. It features low density, high specific capacity, and low working potential, making it ideal for producing energy‐dense cells. However, this material loses its electrochemical activity within 100 cycles, making it practically unusable. Several claims in the literature support the idea that a dual degradation mechanism is at play. First, the slow diffusion of Li in the Al matrix causes the electrochemical reactions to be partly irreversible, making the initial capacity of the cell drop. Second, the stress caused by cycling make the active material pulverize and lose activity. Recent work shows that shortening the diffusion path of Li by 3D structuring is an effective way to mitigate the first capacity loss mechanism, while alloying Al with other elements effectively mitigates the second one. In this work, we demonstrate that the benefits of 3D structuring and alloying are cumulative and that a mesh made of an Al‐magnesium alloy performs better than both a pure Al foil and a foil of an Al−Mg alloy.
Cooperative Anion‐π and C−H−Cl Interactions in Multifunctional Naphthalene‐Based Receptors for Chloride Recognition: Cage‐Size Modulation Through Substitution Patterns
Authors: Zayene Olfa , Hu Jun , Damond Aurélie , Roc Chantal , Marrot Jérôme , Gaucher Anne , Salpin Jean‐Yves , Prim Damien
Published: August 2024

This study introduces a novel approach for chloride recognition utilizing multifunctional naphthalene‐based receptors. By strategically modifying the substitution patterns on tetrafluoropyridines, a series of new receptors with customized cavities and enhanced binding capabilities were developed. Density functional theory (DFT) calculations and experimental studies combining NMR spectroscopy and mass spectrometry confirmed the efficacy of these receptors in capturing chloride ions. The relative chloride affinity order determined experimentally is in agreement with DFT predictions. The synergistic effect of anion‐π and C‐H…Cl interactions, mediated by the TFP groups, played a crucial role in achieving high binding affinity. This work provides valuable insights for designing future anion receptors with improved performance.
Internal Electric Fields and Structural Instabilities in Insulating Transition Metal Compounds: Influence on Optical Properties
Authors: Sánchez‐Movellán I. , García‐Fernández P. , García‐Lastra J. M. , Aramburu J. A. , Moreno M.
Published: August 2024

This work reviews new ideas developed in the last two decades which play a key role for understanding the optical properties of insulating materials containing transition metal (TM) cations. Initially, this review deals with compounds involving d4 and d9 ions where the local structure of the involved MX6 complexes (M=dn cation, X=ligand) is never cubic but distorted, a fact widely ascribed to the Jahn‐Teller (JT) effect. Nevertheless, that assumption is often wrong as the JT coupling requires an orbitally degenerate ground state in the initial geometry a condition not fulfilled even if the lattice is tetragonal. For this reason, the equilibrium geometry of d4 and d9 complexes in low symmetry lattices, is influenced by two factors: (i) The effects, usually ignored, of the internal electric field, ER, due to the rest of lattice ions on the active electrons localized in the MX6 unit. (ii) The existence of structural instabilities driven by vibronic interactions that lead to negative force constants. As first examples of these ideas, we show that the equilibrium structure, electronic ground state of KZnF3:Cu2+, K2ZnF4:Cu2+ and K2CuF4 obey to different causes and only in KZnF3:Cu2+ the JT effect takes place. These ideas also explain the local structure and optical properties of CuF2, CrF2 or KAlCuF6 compounds where the JT effect is symmetry forbidden and those of layered copper chloroperovskites where the orthorhombic instability explains the red shift of one d−d transition under pressure. In a second step, this review explores stable systems involving d3, d5 or d9 cations, where the internal electric field, ER, is responsible for some puzzling phenomena. This is the case of ruby and emerald that surprisingly exhibit a different color despite the Cr3+‐O2− distance is the same. A similar situation holds when comparing the normal (KMgF3) and the inverted (LiBaF3) perovskites doped with Mn2+ having the same Mn2+‐F distance but clearly different optical spectra. The role of ER is particularly remarkable looking for the origin of the color in the historical Egyptian Blue pigment based on CaCuSi4O10.
Non‐overlapping placement of macro cells based on reinforcement learning in chip design
Authors: Yu Tao , Gao Peng , Wang Fei , Yuan Ru‐Yue
Published: August 2024

Due to the increasing complexity of chip design, existing placement methods still have many shortcomings in dealing with macro cells coverage and optimization efficiency. Aiming at the problems of layout overlap, inferior performance, and low optimization efficiency in existing chip design methods, this paper proposes an end‐to‐end placement method, SRLPlacer, based on reinforcement learning. First, the placement problem is transformed into a Markov decision process by establishing the coupling relationship graph model between macro cells to learn the strategy for optimizing layouts. Secondly, the whole placement process is optimized after integrating the standard cell layout. By assessing the public benchmark ISPD2005, the proposed SRLPlacer can effectively solve the overlap problem between macro cells while considering routing congestion and shortening the total wire length to ensure routability.
Anti‐signal recognition particle antibodies induce cardiac diastolic dysfunction via oxidative stress injury
Authors: Zhang Hao , Shi Yunjing , Fan Yingze , Zhu Dehao , Qiu Zeping , Chi Huihui , Hu Qiongyi , Xie Liangzhe , Sun Yue , Liu Honglei , Cheng Xiaobing , Ye Junna , Shi Hui , Zhou Zhuochao , Meng Jianfen , Teng Jialin , Yang Chengde , Jin Wei , Su Yutong
Published: August 2024

Objectives

Anti‐signal recognition particle (SRP) antibodies, markers of immune‐mediated necrotising myopathy, are reportedly related to cardiac involvement; however, whether they are pathogenic to the myocardium remains unclear. We aimed, therefore, to explore the pathogenicity of anti‐SRP antibodies against the myocardium through in vivo and in vitro studies.

Methods

Total immunoglobulin G (IgG), purified from patients with positive anti‐SRP antibodies, was passively transferred into C57BL/6 mice. Cardiac function was evaluated via echocardiography and the ventricular pressure–volume loop; cardiac histological changes were analysed using haematoxylin–eosin staining, picrosirius red staining, immunofluorescence and immunohistochemistry. Additionally, reactive oxygen species (ROS) formation was evaluated by dihydroethidium (DHE) staining; mitochondrial morphology and function were evaluated using transmission electron microscopy and seahorse mitochondrial respiration assay, respectively. The myositis cohort at our centre was subsequently reviewed in terms of cardiac assessments.

Results

After the passive transfer of total IgG from patients with positive anti‐SRP antibodies, C57BL/6 mice developed significant left ventricular diastolic dysfunction (LVDD). Transcriptomic analysis and corresponding experiments revealed increased oxidative stress and mitochondrial damage in the hearts of the experimental mice. Cardiomyocytes exposed to anti‐SRP‐specific IgG, however, recovered normal mitochondrial metabolism after treatment with N‐acetylcysteine, an ROS scavenger. Moreover, patients positive for anti‐SRP antibodies manifested worse diastolic but equivalent systolic function compared to their counterparts after propensity score matching.

Conclusion

Anti‐SRP antibodies may play a pathogenic role in the development of LVDD by promoting ROS production and subsequent myocardial mitochondrial impairment. The inhibition of oxidative stress was effective in reversing anti‐SRP antibody‐induced LVDD.
Integrating open education practices with data analysis of open science in an undergraduate course
Authors: Bakermans Marja H.
Published: August 2024

The open science movement produces vast quantities of openly published data connected to journal articles, creating an enormous resource for educators to engage students in current topics and analyses. However, educators face challenges using these materials to meet course objectives. I present a case study using open science (published articles and corresponding datasets) and open educational practices in a capstone course. While engaging in current topics of conservation, students trace connections in the research process, learn statistical analyses, and recreate analyses using the programming language R. I assessed the presence of best practices in open articles and datasets, examined student selection in the open grading policy, surveyed students on their perceived learning gains, and conducted a thematic analysis on student reflections. First, articles and datasets met just over half of the assessed fairness practices, which increased with the publication date. There was a marginal difference in how assessment categories were weighted by students, with reflections highlighting appreciation for student agency. In course content, students reported the greatest learning gains in describing variables, while collaborative activities (e.g., interacting with peers and instructor) were the most effective support. The most effective tasks to facilitate these learning gains included coding exercises and team‐led assignments. Autocoding of student reflections identified 16 themes, and positive sentiments were written nearly 4x more often than negative sentiments. Students positively reflected on their growth in statistical analyses, and negative sentiments focused on how limited prior experience with statistics and coding made them feel nervous. As a group, we encountered several challenges and opportunities in using open science materials. I present key recommendations, based on student experiences, for scientists to consider when publishing open data to provide additional educational benefits to the open science community.
Comparative adult preference–larval performance relationship between a specialist and a generalist tephritid: Implication for predicting field host‐range
Authors: Lauciello Noémie , Mille Christian Gilbert , Hafsi Abir , Jacob Vincent , Duyck Pierre‐François
Published: August 2024

Phytophagous insects differ in their degree of specialization to their host plants. It ranges from monophagous or oligophagous species that can only develop on a single host plant, or family of host plants, to extremely polyphagous species that can develop on plants from many distinct botanical families. The aim of this study was to compare the larval performance and adult preference of a highly generalist species, the Queensland fruit fly (Bactrocera tryoni) and a highly specialist species, the breadfruit fruit fly (B. umbrosa) among several fruits covering both species' host range. (i) larval performance was tested on 16 fruit species, and (ii) a female preference was tested on a subset of five fruit species. In addition, (iii) a field survey was carried out on 11 fruit species. B. umbrosa infested only Artocarpus fruits in the field. Accordingly, B. umbrosa larvae survived and developed only on fruits belonging to the Artocarpus genus. Female B. umbrosa did not lay their eggs on non‐Artocarpus fruits, except Terminalia catappa. Female B. tryoni, on the other hand, made little selection between the fruits tested, and its larvae developed on 13 of the 16 fruit species tested. The larval performance of both species, adjusted when tested by female preference, predicted in large part the fruit infestation in the field. These data are essential to better estimate invasion risk where the species are not established.
Effects of 1‐methylcyclopropene combined with modified atmosphere on postharvest quality and cell wall metabolism of Zizania latifolia
Authors: Wu Kunlin , Niu Ben , Han Yanchao , Fang Xiangjun , Liu Ruiling , Chen Huizhi , Chen Hangjun , Wu Weijie , Gao Haiyan
Published: August 2024

During postharvest storage, the metabolism of cell wall components greatly affects the quality of fruits and vegetables. Utilizing 1‐methylcyclopropene (1‐MCP) as an ethylene receptor inhibitor and modified atmosphere (MA) separately or in combination (1‐MCP+MA) were investigated for their impact on Zizania latifolia quality during postharvest storage. The treatments effectively controlled firmness increase, color degradation, and reductions in soluble protein, reducing sugar, total phenol, and ascorbic acid content, with the combined 1‐MCP+MA showing the most significant effect. These treatments also moderately changed soluble pectin, protopectin, cellulose, and hemicellulose content, preserving the activities of essential enzymes and the expression of enzyme genes. The combined treatment particularly demonstrated superior preservation capabilities, holding promise for reducing postharvest losses and maintain the storage quality of edible produce, offering insights for efficient postharvest storage and freshness maintenance of fruits and vegetables.