bluuebunny/crossref_metadata_2025_split huggingface dataset:
C−C Bond Formation by Dual Pyrrolidine and Nickel Catalysis: Allylation of Ketones by Allylic Alcohols
Authors: Wright Noah , Townsend Bara , Nicholson Steven , Robinson Joshua , Akien Geoffrey , Ball Anthony K. , Sweeney Joseph B. , Doulcet Julien 
Published: July 2024

AbstractWhilst catalytic ketone allylation using palladium(0) is well–precedented, nickel(0)‐catalysed equivalents of such reactions remain scarce. We report here the first nickel‐catalysed allylation of ketones which uses an easily handled and inexpensive bench‐stable Ni(II) pre‐catalyst. This method avoids generation of stoichiometric by‐products via the use of readily available allyl alcohols, rather than the esters or related derivatives which are often used in such transformations. Under the optimised conditions, 25 monoallylated ketones were obtained in 16% to 98% yield and with high selectivity for the linear (E)‐isomers.
Interfacial Reconstruction Unlocks Inherent Ionic Conductivity of Li‐La‐Zr‐Ta‐O Garnet in Organic Polymer Electrolyte for Durable Room‐Temperature All‐Solid‐State Batteries
Authors: Zhan Xiao , Pang Xikun , Mao Fangqin , Lin Jiande , Li Miao , Zhao Yonghui , Xu Peng , Xu Zhenming , Liao Kaiming , Zhang Qiaobao , Zhang Li 
Published: July 2024

AbstractRigid‐flexible coupled composite polymer electrolytes (CPEs, e.g., polyethylene oxide/Li6.4La3Zr1.4Ta0.6O12, PEO/LLZTO) hold the promise of integrating the respective merits of organic polymer electrolyte and inorganic ceramic fillers to achieve better all‐solid‐state batteries (ASSBs), but commonly suffer from poor synergistic effect owing to the ionically/electronically resistive layer on the ceramic surface. Representatively, the Li2CO3 passivation layer‐isolated LLZTO not only contributes minimally to the Li+ conduction in PEO/LLZTO CPE, but also narrows the available electrochemical window. Herein, an interfacial reconstruction strategy is disclosed based on mild liquid‐phase chemical reaction and subsequent self‐assembly, allowing the detrimental Li2CO3 to fully react with succinic anhydride (SA), and simultaneously constructing a robust ultra‐thin lithium succinate (SALi) ionic conductor shell to eradicate its regeneration. Accordingly, the obtained PEO/LLZTO@SALi (PLS) CPE shows a high room‐temperature ionic conductivity (1.2 × 10−4 S cm−1), a wide electrochemical window (4.8 V), a notable Li+ transference number (0.37), as well as nonflammability and exceptional compatibility with Li metal in Li/Li symmetric cells (2000 h at 0.2 mA cm−2). More encouragingly, the Li/PLS CPE/LiFePO4 full ASSB maintains an ultrahigh capacity retention of 84.3% after 1400 cycles at room temperature. This work propels the design of high‐performance CPEs through the interfacial modulation of inorganic ceramic fillers.
Sex differences in positional behavior of chimpanzees (Pan troglodytes schweinfurthii) living in the dry and open habitat of Issa Valley, Tanzania
Authors: Drummond‐Clarke Rhianna C. , Kivell Tracy L. , Sarringhaus Lauren , Stewart Fiona A. , Piel Alex K. 
Published: July 2024

AbstractObjectivesMany early fossil hominins are associated with savanna‐mosaic paleohabitats, and high sexual dimorphism that may reflect differences in positional behavior between sexes. However, reconstructions of hominin behavior and the selective pressures they faced in an open habitat are limited by a lack of studies of extant apes living in contemporary, analogous habitats. Here, we describe adult chimpanzee positional behavior in the savanna‐mosaic habitat of the Issa Valley, Tanzania, to test whether Issa chimpanzees show larger sex‐differences in positional behavior than their forest‐dwelling counterparts.Materials and MethodsWe quantified and compared adult locomotor and postural behavior across sexes (6 females, 7 males) in the riparian forest (closed) and miombo woodland (open) vegetation types at Issa Valley (13,743 focal observations). We then compared our results to published data of chimpanzee communities living in more forested habitats.ResultsIssa females and males both spent less time arboreally in open vegetation and showed similar locomotor and postural behavior on the same substrates, notably using a high level of suspensory locomotion when arboreal. Females were, however, more arboreal than males during locomotor behavior, as well as compared with females from other communities. Issa males behaved similarly to males from other communities.ConclusionResults suggest that open habitats do not elicit less arboreal behaviors in either sex, and may even select for suspensory locomotion to effectively navigate an open canopy. An open habitat may, however, increase sex differences in positional behavior by driving female arboreality. We suggest this is because of higher energetic demands and predator pressures associated with open vegetation, which are likely exaggerated for reproducing females. These results have implications for the interpretation of how sexual dimorphism may influence reconstructions of hominin positional behavior.
Transsphenoidal retrieval of a needlefish beak remnants from the optic canal
Authors: Sbeih Firas , Zhou Henry W. , Ayoub Noel F. , Ringel Barak , Chiou Carolina A. , Rizzo Joseph F. , Bleier Benjamin S. 
Published: July 2024

Key points
Penetrating orbital trauma from marine creatures, especially needlefish, should be considered after injuries sustained in open water.
Advances in endoscopic sinus surgery have enabled surgeons to remove certain orbital foreign bodies through endoscopic endonasal approaches.
3D segmentation is a valuable pre‐operative tool in complex endoscopic orbital cases.
Enantioselective S‐Alkylation of Sulfenamides by Phase‐Transfer Catalysis
Authors: Champlin Andrew T. , Kwon Na Yeon , Ellman Jonathan A. 
Published: July 2024

AbstractA general phase‐transfer catalyst (PTC) mediated enantioselective alkylation of N‐acylsulfenamides is reported. Essential to achieving high selectivity was the use of the triethylacetyl sulfenamide protecting group along with aqueous KOH as the base under biphasic aqueous conditions to enable the reaction to be performed at −40 °C. With these key parameters, enantiomeric ratios up to 97.5 : 2.5 at the newly generated chiral sulfur center were achieved with an inexpensive cinchona alkaloid derived PTC. Broad scope and excellent functional group compatibility was observed for a variety of S‐(hetero)aryl and branched and unbranched S‐alkyl sulfenamides. Moreover, to achieve high selectivity for the opposite enantiomer, a pseudoenantiomeric catalyst was designed and synthesized from inexpensive cinchonidine. Given that sulfoximines are a bioactive pharmacophore of ever‐increasing interest, selected product sulfilimines were oxidized to the corresponding sulfoximines with subsequent reductive cleavage affording the free‐NH sulfoximines in high yields. The utility of the disclosed method was further demonstrated by the efficient asymmetric synthesis of atuveciclib, a phase I clinical candidate for which only chiral HPLC separation had previously been reported for isolation of the desired (R)‐sulfoximine stereoisomer.
Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High‐Voltage Ultrahigh‐Ni Cathode
Authors: Wu Kang , Ran Peilin , Yin Wen , He Lunhua , Wang Baotian , Wang Fangwei , Zhao Enyue , Zhao Jinkui 
Published: July 2024

AbstractHigh‐voltage ultrahigh‐Ni cathodes (LiNixCoyMn1−x−yO2, x≥0.9) can significantly enhance the energy density and cost‐effectiveness of Li‐ion batteries beyond current levels. However, severe Li−Ni antisite defects and their undetermined dynamic evolutions during high‐voltage cycling limit the further development of these ultrahigh‐Ni cathodes. In this study, we quantify the dynamic evolutions of the Li−Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh‐Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li−Ni antisite defects and controlled Ni migrations are essential for achieving stable high‐voltage cycling structures in ultrahigh‐Ni cathodes. This is further demonstrated by the optimized ultrahigh‐Ni cathode, where reduced dynamic evolutions of the Li−Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.
Radiocatalytic Synthesis of Acetic Acid from CH4 and CO2
Authors: Mu Bo‐Shuai , Zhang Yugang , Peng Mi , Tu Zhiyu , Guo Zhenbo , Shen Siyong , Xu Yang , Liang Weiqiu , Wang Xianglin , Wang Meng , Ma Ding , Liu Zhibo 
Published: July 2024

AbstractThe C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion.
Lanthanide‐Based Molecular Magnetic Semiconductors
Authors: Li Lei , Ding You‐Song , Zheng Zhiping 
Published: July 2024

AbstractMagnetic semiconductors, with integrated properties of ferromagnets and semiconductors, are significant for developing next‐generation spintronic devices. Herein two atomically precise clusters of dysprosium(III) tellurides, formulated respectively as [Na2(15‐crown‐5)3(py)2][(η5‐Cp*Dy)5(Te)6](py)4 (Dy5Te6, Cp*=pentamethylcyclopentadienyl; py=pyridine) and [K(2,2,2‐cryptand)]2[(η5‐Cp*Dy)6(Te3)(Te2)2(Te)3] (Dy6Te10), are reported. Crystallographic studies revealed the presence of multifarious tellurido ligands within the polyhedral cluster cores. Spectroscopic and magnetic studies showed that both clusters are single‐molecule magnets exhibiting slow magnetic relaxation behaviors at low temperatures and semiconductors with low optical band gaps comparable to benchmark semiconductors. These clusters represent probably the first lanthanide‐based molecular magnetic semiconductors.
Study on the influence of unloading disturbance of initial load stress on the microstructure and thermodynamic behavior of granular coal
Authors: Niu Hui‐yong , Sun Si‐wei , Sun Qing‐qing , Wang Hai‐yan , Pan Hong‐Yu , Yang Xi , Yu Xiao‐dong 
Published: July 2024

AbstractWith the advancement of coal mining, the pre‐mining stress on the coal seam increases. After mining, the coal seam fractures and unloads, leaving granular coal in the goaf with a high risk of spontaneous combustion. To investigate the oxidation behavior and underlying mechanisms of granular coal in goafs at various depths, fresh coal was subjected to static stresses ranging from 4 to 16 MPa and then underwent unloading treatment to generate granular coal with varying initial stresses. Subsequently, simulations of granular coal in goafs at various depths were conducted. Structural characteristics (pores and functional groups) and oxidation heat production performance of the granular coal after unloading were analyzed using a low‐temperature nitrogen adsorption instrument, a Fourier infrared spectrometer, and a simultaneous thermal analysis system. The findings suggest that as the initial loading stress increases, the number of micropores and mesopores within the unloaded bulk coal decreases, while the number of macropores increases. Furthermore, important oxidation‐active structures, including ‐OH, ‐CH3, ‐CH2‐, C=O, and ‐COOH, gradually increase, with a slight decrease observed after exceeding 8 MPa. The pressure‐unloading process leads to a gradual decrease in the characteristic temperature of the bulk coal, with the characteristic temperature increasing after exceeding 8 MPa, although it still remains lower than that of the raw coal. As the burial depth of the goaf increases, the oxidation behavior of the unloaded granular coal becomes more pronounced, leading to an increased tendency and risk of spontaneous combustion. If the initial loading stress on deep coal seams is excessive, the oxidation heat production capacity of the resulting unloaded granular coal may be slightly diminished, yet it still poses a significant disaster risk. The research results can provide valuable insights for mitigating and managing spontaneous combustion risks in coal seam mining operations conducted at different depths.
Crystallinity and rheological behavior of polyetheretherketone during nonisothermal conditions
Authors: MacLennan Ruaraidh , Douglas Paula , Millar Bronagh , Aravand Ali 
Published: July 2024

AbstractSolidification models are key during simulation of several industrial processes involving thermoplastics. For simplicity, crystallinity is often not considered within these models, despite it being responsible for the phase transition. Several advanced methods, which consider crystallinity as the onset of solidification have been proposed in literature however, these have primarily been applied to classical homopolymers such as polypropylene (PP). The focus of this study is to develop a model that can capture the rheological response observed during the transition from liquid‐like to solid‐like behavior in injection molding grade polyetheretherketone (PEEK) due to crystallinity. Isothermal rheological experiments are performed alongside dynamic scanning calorimetry (DSC) characterization to correlate relative crystallinity to the apparent increase in viscosity. The model is extended to nonisothermal processes through the incorporation of the Nakamura model. Nonisothermal crystallization rheology experiments are performed and compared with a simulation of the oscillating rheometer process for validation. The modeled viscosity response and crystallization half‐time reproduced the experimental data with sufficient accuracy at low cooling rates, with an error of less than 5% up to cooling rates of 20°C min−1. This shows that the method is an accurate means of obtaining the rheological response during crystallization in a numerical simulation.
Preparation and study of polydimethylsiloxane/polytetrahydrofuran blended soft‐segment‐based passive cooling polyurethane materials
Authors: Ma Haosen , Zhang Zhenyu , He Yu , Zhou Yan , Zhang Xiwen , Liu Xiangdong , Yang Yuming 
Published: July 2024

AbstractThis study introduces a series of novel passive‐cooling polyurethane materials (SiTPUs) by incorporating hydroxybutane‐terminated polydimethylsiloxane (OH‐PDMS)/polytetrahydrofuran (PTMG)‐mixed soft segments. Wide‐angle x‐ray scattering (WAXS) and small‐angle x‐ray scattering (SAXS) analyses revealed that with an increase in the OH‐PDMS content, the material exhibited enlarged grain sizes, reduced crystallinity, and the formation of larger‐sized microphase “structures with different compatibilities. The sample with a PDMS proportion of 40% (SiTPU‐40) demonstrates outstanding passive cooling performance, achieving a reflectance of 70.2% in the solar spectrum and a high atmospheric window emissivity of 91.6% without needing metal additives, resulting in a cooling effect of 10.8°C compared with that of pure thermoplastic polyurethane (TPU). Static contact angle tests indicated that introducing OH‐PDMS considerably enhanced the self‐cleaning performance of the material, with a PDMS proportion of 50% (SiTPU‐50) achieving the highest contact angle of 112°. Overall, this multi‐soft segment design optimizes passive cooling performance and enhances self‐cleaning capabilities, thus offering new possibilities for extensive material applications, especially in wearable technology and architectural surface coatings.
Natural flavonoids as promising lactate dehydrogenase A inhibitors: Comprehensive in vitro and in silico analysis
Authors: Yırtıcı Ümit 
Published: July 2024

AbstractThe inhibitory potential of 17 flavonoids on lactate dehydrogenase A (LDHA), a key enzyme in the downstream process of aerobic glycolysis in cancer cells, is investigated. Fisetin exhibited excellent inhibitory activity (IC50 = 0.066 µM). Quercetin 3‐β‐D‐glucoside, quercetin 3‐galactoside, luteolin, neoeriocitrin, and luteolin 7‐O‐β‐D‐glucoside showed good inhibitory activity (IC50 = 1.397–15.730 µM). Biochanin A, baicalein, quercetin, scutellarein‐7‐glucuronide, diosmetin, baicalein 7‐O‐β‐D‐glucuronide, and apigenin 7‐apioglucoside demonstrated moderate inhibitory activity (IC50 = 33.007–86.643 µM). Eriodictyol, quercetin 7‐O‐β‐D‐glucoside, apigenin 7‐O‐β‐D‐glucoside, and epicatechin were inactive. The Lineweaver–Burk plot showed that fisetin competitively inhibits NADH binding (Ki = 0.024 µM). Ki values for other compounds were calculated using the Cheng–Prusoff equation (Ki = 0.2799–2.1661 µM). The study revealed that the inhibitory effect of flavonoids varies with the number and position of OH groups and bound sugars. Molecular docking analyses indicated that flavonoids exhibited strong interactions with the NADH binding site of LDHA through hydrophobic interactions and hydrogen bonds. Molecular dynamic simulations tested the stability of the fisetin‐LDHA complex over 100 ns and showed fisetin's high binding affinity to LDHA, maintaining strong hydrogen bonds. The binding energy of fisetin with LDHA was −33.928 kcal/mol, indicating its effectiveness as an LDHA inhibitor. Consequently, flavonoids identified as strong inhibitors could be potential cancer treatment sources through LDHA inhibition.
Multilayer Porous Fe/Co‐N‐MWCNT Electrocatalyst For Rechargeable Zinc‐Air Batteries
Authors: Ma Lijuan , Wang Han , Zang Jing , Wang Xinna , Li Hao , Li Yanwei , Li Yanhui 
Published: July 2024

AbstractThe design of efficient, stable, low‐cost non‐precious metal‐based electrocatalysts with enhanced oxygen reduction reaction (ORR) activity has garnered significant attention in the scientific community. This study introduces a novel electrocatalyst, Fe/Co‐N‐MWCNT, synthesized through the in‐situ growth of ZIF‐8 and Fe/Co‐Phen on multi‐walled carbon nanotubes (MWCNTs), followed by pyrolysis at varying temperatures to optimize its properties. The inclusion of Fe and Co during the pyrolysis process facilitated the creation of metal active sites and Fe−Co, enhancing electron transfer and ORR activity. Compared to Pt/C (E1/2=0.854 V, JL=4.90 mA cm−2), Fe/Co‐N‐MWCNT exhibited a similar half‐wave potential (E1/2=0.812 V) and an improved limiting current density (JL=5.37 mA cm−2). Moreover, Fe/Co‐N‐MWCNT displayed remarkable stability, showing only a 7 mV negative shift in E1/2 after 2000 cycles. Ampere response testing indicated a current decay of only 7.8 % for Fe/Co‐N‐MWCNT after 10000 s, while Pt/C experienced a decay of about 18.4 %. The exceptional catalytic stability of Fe/Co‐N‐MWCNT positions it as a promising candidate for rechargeable zinc‐air batteries, attributed to its high pyridinic nitrogen content, unique structure, and abundant metal active sites.
An Azaryl‐Ketone‐Based Thermally Activated Delayed Fluorophore with Aggregation‐Induced Emission for Efficient Organic Light‐Emitting Diodes with Slow Efficiency Roll‐Offs
Authors: Chen Wen‐Cheng , Su Yaozu , Wu Xiaohui , Wang Ruicheng , Jin Jia‐Ming , Zheng Fan , Liu Xiao‐Long , Zhang Yuzhen , He Nian , Sun Yuxi , Zeng Qingming , Huo Yanping 
Published: July 2024

AbstractAchieving the concurrent manifestation of thermally activated delayed fluorescence (TADF) and aggregation‐induced emission (AIE) within a single molecular system is highly sought after for organic light‐emitting diodes (OLEDs), yet remains rare. In this study, we present a novel TADF‐AIE dye, named PQMO‐PXZ, which has been designed, synthesized, and systematically characterized. Our comprehensive investigation, which includes structural analysis, theoretical calculations, and optical studies, evaluates the potential of PQMO‐PXZ for integration into OLEDs. Unlike existing azaryl‐ketone‐based emitters, PQMO‐PXZ exhibits red‐shifted emission and enhanced luminescence efficiency, due to its rigid structure and strong intramolecular charge transfer characteristics. Significantly, PQMO‐PXZ demonstrates pronounced AIE properties and TADF with a short delayed lifetime. When utilized as the emissive core, OLED devices based on PQMO‐PXZ achieve a respectable external quantum efficiency of up to 11.8 % with minimal efficiency roll‐off, underscoring PQMO‐PXZ's promise as a highly efficient candidate for OLED applications.
Statistical Analysis of Solid Electrolyte Interface Formation: Correlation of Gas Composition, Electrochemical Data and Performance
Authors: Klick Sebastian , Graff Karl Martin , Stahl Gereon , Figgemeier Egbert , Sauer Dirk Uwe 
Published: July 2024

AbstractThe SEI is a crucial yet little understood component of lithium‐ion batteries. The specific formation processes creating the SEI are still a matter of current research. In our paper, we analyse the electrochemical processes by incremental capacity analysis (ICA) and correlate these results with the evolved gas species and subsequent performance of the cells. 101 cells in total divided in three groups with different electrolytes performed a formation cycle. Afterwards gas‐samples of half of the cells were extracted for analysis. We found a good correlation between variations of gas composition and noticeable ICA‐data. Furthermore we explore correlations between formation and initial cell performance after a total of 10 cycles. Our results open new possibilities for a better understanding of formation processes.
On the Selection of the Current Collector for Water Processed Activated Carbon Electrodes for Their Application in Electrochemical Capacitors
Authors: Luís Paulo , Martin‐Fuentes Silvia , Arnaiz María , Ajuria Jon 
Published: July 2024

AbstractElectrode manufacturing for electrochemical energy storage technologies often relies on hazardous fluorine‐containing compounds and toxic organic solvents. To align with sustainability goals and reduce costs, there is a pressing need for water‐processable alternatives. These alternatives can halve electrode processing costs and ease regulatory burdens. While progress has been made with water‐processed graphite electrodes using eco‐friendly binders, challenges persist for high‐mass loading activated carbon (AC) electrodes. This study investigates the impact of modified aluminium current collectors on water‐processed AC electrodes, focusing on compatibility, processability, and electrochemical performance. Various aluminium foils, including etched and carbon‐coated types, were evaluated. The results show that modifications at the interface significantly improve the wetting properties and mechanical stability. Electrochemical tests revealed that carbon‐coated aluminium provided the lowest internal resistance and highest rate capability due to intimate contact between the electrode components. In contrast, etched aluminium foil exhibited higher contact resistance and poorer performance. Ageing studies demonstrated that carbon‐coated foils maintained better electrochemical performance over time, as the carbon layer reduced degradation reactions and contact resistance. These findings suggest that uniformly carbon‐coated aluminium current collectors are the optimal choice for high‐power electrochemical capacitors, balancing performance, sustainability, and cost‐efficiency.