bluuebunny/crossref_metadata_2025_split huggingface dataset:
Running the Risk: Road‐Crossing Behavior in Wild Chimpanzees (Pan troglodytes) in an Anthropogenic Habitat in Uganda
Authors: Tellier Marie , Druelle François , Cibot Marie , Baruzaliire Johnmary , Sabiiti Tom , McLennan Matthew R. 
Published: February 2025

ABSTRACTRecent research highlights the behavioral flexibility of wild chimpanzees in response to human‐induced changes in their environment, including agricultural and infrastructural development. The expansion of road networks threatens chimpanzee populations across Africa. Studying their road‐crossing behavior, especially outside protected areas where road impacts are greatest, helps identify factors influencing their choices and flexibility. This study seeks to gain a deeper understanding of how chimpanzees navigate busy roads and assess the danger posed by roads. Such insights are needed to develop effective conservation strategies in regions facing escalating human impact, including recommendations for the design and management of traffic on existing and future roads. Using a dataset of 129 video‐recorded road crossings spanning 38 months, we analyzed the behavioral adjustments of chimpanzees in Bulindi, Uganda, when crossing a recently paved, busy main road within their home range. Using generalized linear mixed models, we investigated chimpanzee risk perception, protective and cooperative behaviors, vigilance, and progression order during road crossings. We identified variations in their behavior according to age‐sex of individuals, group composition, and level of risk. We found that Bulindi chimpanzees exhibit behavioral strategies to reduce risks of collision or close encounters with humans on the road, as previously described. However, they were less vigilant than expected. We suggest that the chimpanzees have developed tolerance of the risks presented by the road, owing to their long history of crossing it before it was tarmacked and widened, and their familiarity with local people and motor traffic. Our results provide further evidence of the flexibility of wild chimpanzees. However, road crossings remain highly risky for large mammals like great apes, necessitating measures to mitigate the impact of road development on this and other endangered species (e.g. speed bumps, police enforcement, public awareness raising).
Universal Reagent for Mild and Stereospecific Nucleophilic Substitution of Alcohols with Amines
Authors: Bechara William S. , Sagamanova Irina K. , Thai‐Savard Léa , Dauphinais Maxime , Régnier Sophie , Noël Charlotte , Jarvis Scott B. D. , Charette André B. 
Published: February 2025

AbstractA user‐friendly reagent for mild and general activation of alcohols towards bimolecular nucleophilic substitution (SN2) leveraging diverse nucleophiles, including primary and secondary amines is reported herein. The new ion‐paired reagent discovery was based upon the putative zwitterionic betaine intermediate of the Mitsunobu reaction and enabled the one‐step conversion of enantioenriched alcohols to valuable chiral C−X bonds (where X=N, C, S, O or halide). The described activating reagent has also been applied to a one‐step methylation reaction using methanol and to an intermolecular amination/intramolecular cyclization sequence that generates heterocycles, such as tetrahydroisoquinolines. This work provides the first evidence by X‐ray crystallography of a protonated betaine as intermediate in the Mitsunobu reaction.
Lactate‐Modulating Nanozyme‐Mediated Mitochondrial Respiration Block for Tumor Immunosuppression Remodeling
Authors: Zhao Senfeng , Hou Jianing , Deng Liu , Qi Ziyu , Tao Na , Ruan Wenjie , Zheng Jia , Wang Wei , Xu Qianqian , Saiding Qimanguli , Kong Na , Liu You‐Nian , Tao Wei 
Published: February 2025

AbstractAbnormal lactate metabolism in tumor cells leads to immune escape in the tumor microenvironment. Intervening in specific lactate metabolic pathways while blocking downstream pyruvate influx holds great promise for overcoming conventional lactate‐targeted therapy limitations such as short half‐life, insufficient lactate consumption, and pathological microenvironment elasticity. Herein, a nanocatalytic medicine based on carbondoping engineered copper nitride enzyme (Cu3N−C NE) with enhanced lactate oxidase (LOX) activity was carefully designed. Computational results revealed that the introduction of C favors activation of the hydroxyalkyl C−H bond in lactate by the polarization of adjacent hydroxyl groups, correspondingly facilitating the abstraction of hydrogen atoms from the desired α‐C−H and α‐C−O−H groups in lactate via the hydrogen atom‐transfer (HAT) process. The Cu3N−C NEs could downregulate lactate levels in tumor cells for robust remodeling of the immunosuppressive microenvironment and further block as‐generated pyruvate to influx into the mitochondrial respiration, achieving lactate homeostasis reprogramming. Our study provides a proof‐of‐concept design of next‐generation lactate‐modulation nanomedicine via heteroatom‐doping and evolution with the additional potential to expedite the industrial production of lactate to pyruvate.
Porphyrin‐Based Covalent Organic Frameworks for CO2 Photo/Electro‐Reduction
Authors: Sun Tingting , Wang Zhi , Wang Yuhui , Xu Qingmei , Wang Kang , Jiang Jianzhuang 
Published: February 2025

AbstractPhoto/electro‐catalytic CO2 reduction into high‐value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post‐modification capability, and excellent stability, porphyrin‐based covalent organic frameworks (COFs) have emerged as attractive photo/electro‐catalysts towards CO2 reduction. In this review, the research progress of the porphyrin‐based COFs for photo/electro‐catalytic CO2 reduction is summarized including the design principles, catalytic performance, and reaction mechanism. In addition, this review also presents some challenges and prospects for the application of porphyrin‐based COFs in photo/electro‐catalytic CO2 reduction, laying the base for both fundamental research and application efforts.
Urea Complete Conversion to Compound Fertilizer in Industrial‐Scale Tandem Reactors
Authors: Hu Jun , Li Shan‐Qing , Gao Xintong , Zhang Fei , Yuan Zhi‐Xiang , Wu Tong , Jin Qing‐Feng , Chen Ping , Zheng Yao , Qiao Shi‐Zhang 
Published: February 2025

AbstractA compound fertilizer with NH4H2PO4 and KH2PO4 offer significant advantages in enhancing both crop yield and quality. Ammonia (NH3) is essential for the synthesis of the compound fertilizer, which was produced by an energy intensive chemical process. Developing efficient and environmental friendly methods to produce ammonia‐containing compound fertilizers is crucial and extremely challenging. Here, we present a tandem catalysis system capable of achieving complete conversion of abundant urea into compound fertilizer in industrial‐scale reactors by combining electrochemical and subsequent chemical processes. In a typical cycle, with the use of 200 g urea, 1580 g of solid compound fertilizer (KH2PO4 and NH4H2PO4) and 232 L of pure H2 are produced without any further separation process. The key to the realization of this system is to precisely control the rate of urea consumption and NO2− formation in electrochemical process. By maintaining a precise molar concentration ratio of urea to NO2− at 1/2 in electrolyte, urea can completely react with NO2− to form N2, while CNO− can be converted into NH4+ to form compound fertilizer in the second step of H3PO4 treatment, achieving complete conversion of urea without by‐products formation. This method remarkably reduces H2 production potential while allowing for extraction of ammonia from urea‐containing wastewater or urine to create pure compound fertilizer at an anticipated lower price than that of current market.
Three‐Dimensional Metal–Organic Frameworks with Selectively Activated Aromatic Rings for High‐Capacity and High‐Rate Lithium‐Ion Storage
Authors: Li Sha , Lin Jiande , Wang Huiqun , Zhou Shiyuan , Guo Xiangyang , Zhan Xiao , Tao Hongwei , Hu Haitao , He Zhengyou , Liao Honggang , Zhan Dongping , Zhang Li 
Published: February 2025

AbstractMetal–organic frameworks (MOFs) are considered promising candidates for anode materials in Li‐ion batteries (LIBs) owing to their designable structure, abundant active sites, and well‐organized porosity. However, the structural factors governing active site utilization and Li‐ion storage kinetics remain inadequately understood. In particular, the Li‐ion storage behaviors of aromatic rings with high LUMO energy levels and situated in varying chemical environments remain a highly debated issue. Herein, a new cobalt‐based MOF (Co‐NTTA, NTTA ligand: 5,5′,5′′‐((4,4′,4′′‐nitrilotris (benzoyl)) tris‐(azanediyl)) triisophthalic acid), featuring aromatic rings situated in diverse local environments, is deliberately designed and synthesized. Experimental characterizations and first‐principles calculations have verified the occurrence of a reversible electrochemical reaction involving a total of 51 electrons among the NTTA ligands, cobalt cations, and Li+ ions. Unlike the traditional concept of superlithiation, the three inner aromatic rings are selectively activated by π‐aromatic conjugation networks and π
π stacking, contributing to a reversible 6‐electron pseudocapacitive Li+ intercalation reaction. Conversely, the three outer aromatic rings remain inert toward Li+ ions. Impressively, the Co‐NTTA MOF anode, with selectively activated aromatic rings, delivers a reversible capacity of up to 956 mAh g−1 at 200 mA g−1 and demonstrates exceptional high‐rate durability, further supporting a 4.3 V lithium‐ion hybrid electrochemical capacitor with high energy/power density.
A Wide Band Gap Germanate with the Largest Second Harmonic Generation Response Created by Hypoxic Strategy
Authors: Song Qi‐Chang , Hu Chun‐Li , Kong Fang , Mao Jiang‐Gao 
Published: February 2025

AbstractNonlinear optical material is one of the core components for modern laser equipment. The second harmonic generation (SHG) intensity and optical band gap are two key indicators of such materials. Herein, a wide band gap germanate, Li3(OH)PbGeO4, with the largest SHG intensity has been created successfully by hypoxic strategy via traditional hydrothermal reactions. The cations in this structure all coordinate with oxygen anions at their lowest coordination number, forming polar PbO3 triangular pyramid and noncentrosymmetric GeO4, LiO4 tetrahedrons. Li3(OH)PbGeO4 exhibits a remarkable SHG response of about 27×KH2PO4 (KDP), 54 % higher than the previous record. The band gap of Li3(OH)PbGeO4 can reach to 3.74 eV, exceeding most inorganic germanates with SHG intensity larger than 3×KDP. Structural analysis and PAWED calculations indicate that its strong SHG response is due to the synergistic effects from PbO3, GeO4 and LiO4 groups. Furthermore, Li3(OH)PbGeO4 can also present compelling broadband white‐light emission with a high color‐rendering index of up to 93. Our work not only breaks the record of SHG intensity in germanates but also provides an effective strategy in exploring new inorganic optical functional crystals.
Boosting Li−CO2 Battery Performance via High‐Entropy Alloy Catalysts: Insights into Configurational Entropy Effect
Authors: Wen Zhang , Mu Xiaowei , Sun Xinyi , Xu Zhenming , Zheng Mingbo , Zhou Haoshen , He Ping 
Published: February 2025

AbstractLi−CO2 batteries have attracted considerable attention for their ability to combine CO2 fixation and conversion with high‐density energy storage. However, sluggish kinetics of CO2 reduction and evolution reactions at cathodes lead to large overpotentials and poor cyclic stability. To address this issue, it is critical to develop advanced cathode catalysts. High‐entropy alloys (HEAs), a new class of catalysts, have exhibited exceptional catalytic activities in various electrochemical reactions. Nevertheless, the intrinsic relationship between mix configurational entropy (▵Smix) and catalytic properties of HEAs remains unclear. Herein, we prepared a series of quinary FeCoNiCuRu alloys with different ▵Smix values supported on carbon nanofibers as cathode catalysts in Li−CO2 batteries. Experimental and computational results reveal a positive correlation between ▵Smix and catalytic activity, attributed to charge redistribution among elements with different electronegativities. The Li−CO2 battery using the alloy catalyst with the maximum ▵Smix value delivers the largest capacity of 6160 mAh g−1, the lowest charge potential plateau below 4.0 V, and remarkable cycling stability (550 cycles/5500 h), surpassing most reported Ru‐based catalysts. Furthermore, fabrication of pouch cells with low noble metal loading demonstrates the practical potential of HEAs for Li−CO2 batteries. This work provides insights into high‐entropy engineering for advanced electrocatalysts in Li−CO2 batteries.
Spin State Regulation for Peroxide Activation: Fundamental Insights and Regulation Mechanisms
Authors: Jiang Zicong , Tong Kangbo , Li Zhi , Tao Hengcong , Zhu Mingshan 
Published: February 2025

AbstractPeroxides are widely used in environmental applications due to their strong oxidizing properties, however, traditional activation methods often face challenges such as uncontrolled reactive oxygen species (ROS) generation and high energy barriers. Recent advancements in spin state regulation provide a promising alternative to enhance the efficiency of peroxide activation. This review provides an overview of spin fundamentals and discusses the key factors affecting spin state in catalytic materials, including crystal field configuration, ligand environment, and valence changes. Subsequently, the role of electron spin state in peroxide activation is comprehensively analyzed, with a focus on how spin state regulation can tune adsorption energy, lower energy barriers, facilitate electron transfer between transition metals and peroxides, and promote selective ROS generation. Finally, this review briefly outlines the practical applications of peroxide activation in water treatment and concludes with a summary and perspectives on future research directions. This review aims to provide a comprehensive perspective on the role of spin state regulation in advancing peroxide activation strategies.
Boosting Lithium Storage Performance of Small‐Molecule Organic Cathodes through Synergistic Molecular Engineering and Nanostructure Design
Authors: Peng Huiling , Han Yu , Zhang Lei , Geng Yaheng , Yu Zehao , Xu Chen , Yuan Yizhi , Zhou Zhiqun , Liang Xiao , Zhu Jian , Zhu Zhiqiang 
Published: February 2025

AbstractSmall‐molecule organic carbonyl compounds (SMOCCs) featuring high theoretical capacities are promising cathodes for lithium‐ion batteries (LIBs), but facing challenges in cycling stability and rate performance owing to their high solubility in organic electrolytes and low conductivity. Herein, we propose a novel architecture wherein nanosized SMOCCs with N‐heterocycle‐extended π‐conjugation are uniformly immobilized on reduced graphene oxide (rGO). This approach leverages the N‐heterocycles to create additional active sites and strengthen π‐π interactions with rGO, while the homogeneous distribution of nanosized SMOCCs on rGO facilitates efficient charge transport and electrolyte infiltration. As a demonstration, we synthesize a composite material using dipyrido[3’,2’:5,6;2′′,3′′:7,8]quinoxalino[2,3‐i]dipyrido[3,2‐a:2’,3’‐c] phenazine‐10,21‐dione (DQDPD) as the active component, which exhibits remarkable electrochemical properties in LIBs, including an ultrahigh capacity of 505 mAh g−1 at 0.2 A g−1, exceptional cycle stability with 82 % capacity retention after 3000 cycles at 5 A g−1, and outstanding rate capability of 290 mAh g−1 at 10 A g−1. Our approach, which integrates molecular engineering and nanostructure design, provides a novel paradigm for simultaneously realizing high capacity, long lifespan, and rapid rate capability in SMOCCs.
Metal Nanoclusters as Highly Efficient, Versatile Type‐II Photoinitiators via Generating Radicals from Non‐Conventional Hydrogen Donors
Authors: Chen Zijie , Tang Jin , Zheng Letian , Ren An , Ma Liang , Li Qi 
Published: February 2025

AbstractDevelopment of highly efficient photocatalysis or photoinitiation systems that are applicable to various types of illumination source is critical to virtually all the light‐driven applications. Here, we report a generalizable strategy to achieve highly sensitive, versatile photoinitiation systems based on the combination of metal nanoclusters with non‐conventional hydrogen donors (co‐initiators). Discovery of this type‐II photoinitiation pathway in metal nanoclusters not only improves their two‐photon initiation sensitivity by up to three‐orders‐of‐magnitude, it further opens the door for metal nanoclusters to trigger the photopolymerization using the low‐power UV light‐emitting diodes. Different from molecular type‐II photoinitiators, we found that the selection rules of hydrogen donors for metal nanoclusters are largely dependent on their ligand structures. More importantly, using electron paramagnetic resonance and mass spectroscopy, we for the first time demonstrate that the photoexcited metal nanoclusters can function as versatile hydrogen atom abstractors which generate various types of previously unreported thiyl and nitrogen‐centered radicals. This finding indicates the broad opportunity of the future application of metal nanoclusters in light‐driven organic synthesis and radical chemistry.
Selective Hydrodisulfuration of Alkenes with Dithiosulfonate
Authors: Li Wenhao , Wei Haonan , Wang Baoxu , He Xihang , Jiang Yao , Nie Mengna , Yan Hang , Hu Zijing , Gao Qianwen , Qu Shuanglin , Wang Xi 
Published: February 2025

AbstractIn this study, we have discovered the versatility of the dithiosulfonate reagent (ArSO2‐SSR) in transition metal catalyzed selective hydrodisulfuration of unactivated alkenes. The hydrodisulfuration displays a unique Markovnikov selectivity with a Salen‐cobalt complex, while an anti‐Markovnikov selectivity is observed when employing a nickel/bidentate N‐donor ligand. Furthermore, precise control over nickel/ligand enables the successful achievement of remote site‐selective hydrodisulfuration for both internal and terminal alkenes via a chain‐walking process. In these processes, silanes are employed as a hydride source. Mechanistic insights into these innovative catalytic systems are also elucidated. Experimental findings suggest that Markovnikov hydrodisulfuration is likely to proceed through radical substitution on dithiosulfonate reagents, while nickel catalyzed anti‐Markovnikov selectivity and remote site‐selectivity likely occur via the radical addition of the reductively formed dithiosulfonate radical anion ([ArSO2‐SSR]⋅−) to alkyl Ni(II) species (alkyl‐Ni(II)LnX) and subsequent reductive elimination on Ni(III) intermediate (alkyl–Ni(III)Ln(X)‐SSR) as the key steps based on DFT calculation analysis.
Surface‐like NOx Reduction at an Atomically‐Precise Tricopper Cluster
Authors: Beamer Andrew W. , Buss Joshua Alan 
Published: February 2025

The combustion of nitrogen‐containing fuels and increasing use of nitrogen‐rich fertilizers is accumulating NOx pollutants in the environment. Copper is an attractive catalyst material for reductive NOx remediation, yet ambiguity persists regarding the elementary bond‐making and bond‐breaking steps occurring at the catalyst interface. Starting from a molecular tricuprous µ3‐oxo complex (1), an unusually reduced and highly reactive surface‐like cluster (2) has been prepared. Characterization data and electronic structure calculations are consistent with 2 featuring σ‐aromaticity that primes the tricopper core for two‐electron chemistry. Cluster 2 mediates catalytic reductive coupling of NO to N2, proceeding through N2O, via sequential oxygen atom transfer steps. Stoichiometric reduction of NO3– and NO2– is also disclosed, mapping the complete denitrification cycle at an atomically‐precise molecular cluster.
Inverse Electron Demand Diels–Alder Reaction on M3N@C80 (M=Lu, Sc): Reactivity and Reversibility Enable Chemical Separation of Metallofullerenes
Authors: Sun Yue , Abella Laura , Emge Thomas J. , Zhu Sheng , Li Yanbang , Ferraro Ian , Li Anyin , Stevenson Steven , Poblet Josep M. , Rodríguez‐Fortea Antonio , Zhang Jianyuan 
Published: February 2025

AbstractEndohedral metallofullerenes are chemically more inert compared to empty fullerenes, primarily due to their intramolecular electron transfer. In this work, we report an inverse electron demand Diels–Alder (IEDDA) reaction on M3N@C80 (M=Lu, Sc), where they show significantly higher reactivity than empty fullerenes. The molecular structures of the [4+2] cycloadducts were unambiguously characterized. Moreover, the cycloadducts can fully revert to pristine M3N@C80 via retro‐cycloaddition upon thermal treatment. With the unusual reactivity and reversibility, the IEDDA reaction enables an effective separation approach for metallofullerenes from their soot extracts, opening path to efficient and economical scale‐up synthesis of metallofullerenes in laboratory and industrial settings.
On‐Paper Enzyme‐Linked and Metal‐Linked Immunosorbent Assays for Low‐Cost Decentralized Testing of Carcinoembryonic Antigen
Authors: Mermiga Electra , Pagkali Varvara , Soulis Dionysios , Kokkinos Christos , Economou Anastasios 
Published: February 2025

AbstractThis work reports two simplified paper‐based approaches for immunosensing of carcinoembryonic antigen (CEA) in serum. On‐paper enzyme‐linked immunosorbent assay (p‐ELISA) (using enzymatic generation of a colored product) and metal‐linked immunosorbent assay (p‐MeLISA) (using gold nanoparticles (AuNPs) as labels) were implemented using low‐cost diagnostic bio‐conjugated paper mini disks as platforms for the fast colorimetric immunosensing of CEA in human serum. The colour intensity was captured with a commercial scanner and analyzed using an open‐source software. Different parameters of the preparation of the bioconjugated disks and of the immunoassays were studied and, under the selected conditions, LODs of 0.4 ng mL−1 with p‐ELISA and 0.1 ng mL−1 with p‐MeLISA were achieved while recoveries of CEA in serum samples were in the range from 88 to 112 % with coefficient of variation of <12 %. The assay time was 90 s for p‐ELISA and 85 s for p‐MeLISA. The immunoassays exhibited satisfactory selectivity in the presence of other cancer biomarkers and good stability under storage. Thanks to simple and rapid fabrication and modification, simple analysis protocol, affordability (<0.05 € per device), equipment‐free quantification, low sample and reagents requirments, stability and satisfactory analytical characteristics, these approaches are fit‐for‐purpose for assay of CEA in serum at the point‐of care in resource‐limited settings.