bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidating Heavy‐Atom‐Tunneling Kinetics in the Cope Rearrangement of Semibullvalene
Authors: Angiolari Federica , Mandelli Giacomo , Huppert Simon , Aieta Chiara , Spezia Riccardo 
Published: June 2024

AbstractIn this work, we characterize the temperature dependence of kinetic properties in heavy atom tunneling reactions by means of molecular dynamics simulations, including nuclear quantum effects (NQEs) via Path Integral theory. To this end, we consider the prototypical Cope rearrangement of semibullvalene. The reaction was studied in the 25–300 K temperature range observing that the inclusion of NQEs modifies the temperature behavior of both free energy barriers and dynamical recrossing factors with respect to classical dynamics. Notably, while in classical simulations the activation free energy shows a very weak temperature dependence, it becomes strongly dependent on temperature when NQEs are included. This temperature behavior shows a transition from a regime where the quantum effects are limited and can mainly be traced back to zero point energy, to a low temperature regime where tunneling plays a dominant role. In this regime, the free energy curve tunnels below the potential energy barrier along the reaction coordinate, allowing much faster reaction rates. Finally, the temperature dependence of the rate constants obtained from molecular dynamics simulations was compared with available experimental data and with semi‐classical transition state theory calculations, showing comparable behaviors and similar transition temperatures from thermal to (deep) tunneling regime.
Improving the Photodynamic Activity of Water‐Soluble Porphyrin–Polysaccharide Complexes by Folic Acid Modification
Authors: Nishimura Kotaro , Kono Nanami , Oshige Ayano , Takahashi Haruko , Yamana Keita , Kawasaki Riku , Ikeda Atsushi 
Published: June 2024

AbstractStudies have shown that folate receptors are highly expressed in various cancer cells. Here, we synthesized folic acid‐conjugated pullulan (FAPL) as a solubilizing agent to improve the photodynamic activity of porphyrin derivative–polysaccharide complexes. The porphyrin derivative–FAPL complex exhibited long‐term stability in an aqueous solution, attributed to the folic acid modification. Furthermore, in vitro and in vivo experiments highlighted the enhanced photodynamic activity of the porphyrin derivative–FAPL complex toward 4T1 breast‐cancer cells, compared with the activities of the porphyrin derivative–pullulan complex and Photofrin. This enhanced activity is attributed to the improvement of intracellular uptake by the folate receptor.
N‐Doped Carbon Coated Bimetallic CoFe2O4 Nanomembranes as An Enhanced Negative Electrode for Asymmetric Supercapacitors
Authors: Li Ruizhi , Li Weiqun , Li Yuhua , Zhu Shengyuan , Ba Xin , Zhou Yingke 
Published: June 2024

AbstractIn‐suit nitrogen‐doped carbon layer coated on CoFe2O4 nanomembrane (NC−CoFe2O4) directly grown on carbon cloth was successfully fabricated. The electrochemical performance was conveniently manipulated by regulating the molar ration of Co2+ : Fe3+ (molar ration=1 : 2, CoFe2O4 nanomembrane, 2.9 F cm−2). Nitrogen‐doped (N‐doped) carbon coating strategy on CoFe2O4 nanomembrane (NC−CoFe2O4) via annealing of polypyrrole (PPy) was presented and NC−CoFe2O4 nanomembranes displayed a prominent capacitance of 12.1 F cm−2 (2563.8 F g−1) at 5 mA cm−2. More important, the composite demonstrated more stable microstructure and showed long‐term cycling stability (16.0 % decrease after 7000 cycles), which was significantly better than the unmodified CoFe2O4 (55.8 % decrease after 1000 cycles). To verify the practicability of the materials, an aqueous asymmetric supercapacitor has been fabricated using NC−CoFe2O4 composite anode and MnO2/CNTs cathode, and the device has a remarkable wide operating voltage range of 1.9 V. In addition, the assembled device has an exceptional specific capacity of 1.3 F cm−2 at 10 mA cm−2, high energy density (43.3 Wh kg−1 at a power density of 642.9 W kg−1), and also with a good capacity retention rate of 84.9 % after 1000 cycles.
Ramie Degumming Waste‐Derived Nitrogen and Molybdenum Dual‐Doped Porous Carbon for High‐Performance Lithium–Sulfur Batteries
Authors: Yang Zhehan , Ruan Qingling , Chen Tiezhu , Ren Xiaolei , Lin Juan , Gu Xingxing 
Published: June 2024

AbstractThe high energy density and low cost of sulfur make lithium–sulfur batteries one of the most promising candidates for the next generation of energy storage. Nevertheless, the application is still hampered by the shuttle effect of soluble lithium polysulfides (LiPSs) intermediates and slow redox kinetics, resulting in irreversible loss of the active material, severe self‐discharge and poor cycle stability of the electrode. Therefore, in this work, a novel Mo,N co‐doped porous carbon (Mo,N−C) was successfully synthesized by simply calcining a mixture of ramie degumming waste with cost‐effective molybdenum salt, and then employed as the LiPSs anchor. Due to the conductive carbon matrix, abundant porous structures as well as the doping Mo and N heteroatoms, the sluggish redox kinetic of the cathode has been significantly improved and the shuttle phenomenon of LiPSs has been effectively inhibited, consequently, the as‐prepared Mo,N−C/S‐0.4 composite cathode could demonstrate a good initial capacity of 1379.2 mAh g−1 at 0.2 C, and the reversible capacity could remain at 997.5 mAh g−1 after 100 cycles. Even at a high discharge rate of 1.0 C, the capacity could remain at 700.2 mAh g−1 after 400 cycles. This work provides a new avenue for utilizing waste biomass in clean energy storage.
Edge computing collaborative offloading strategy for space‐air‐ground integrated networks
Authors: Xiang Biqun , Zhong Bo , Wang Anhua , Mao Wuping , Liu Liang 
Published: June 2024

SummaryDue to geographical factors, it is impossible to build large‐scale communication network infrastructure in remote areas, which leads to poor network communication quality in these areas and a series of delay‐sensitive tasks cannot be timely processed and responded. Aiming at the problem of limited coverage in remote areas, the space‐air‐ground integrated networks (SAGIN) combined with mobile edge computing (MEC) can provide low latency and high reliability transmission for offloading delay‐sensitive tasks for users in remote areas. Considering the strong limitation of satellite resources in the space‐ground integrated network and insufficient energy of local user equipment, firstly, a satellite‐UAV cluster‐ground three‐layer edge computing network architecture is proposed in this paper. Under the condition that the delay requirements of various ground tasks are met, the task offloading problem is transformed into a Stackelberg game between ground user equipment and edge servers. In addition, it is proved that the existence of Nash equilibrium in non‐cooperative game between ground user equipment by using potential game. Finally, a Nash equilibrium iterative offloading algorithm based on Stackelberg game (NEIO‐SG) is proposed to find the optimal offloading strategy for tasks to minimize the system offloading cost and the optimal forwarding percentage strategy for offloading tasks to maximize the utility function of the edge server. Simulation results show that compared to other baseline algorithms, NEIO‐SG reduces the total system latency during task offloading by about 13 and the energy consumption of the edge server by about 35.
Halogen Bonding to the π‐Systems of Polycyclic Aromatics
Authors: Amonov Akhtam , Scheiner Steve 
Published: June 2024

AbstractThe propensity of the π‐electron system lying above a polycyclic aromatic system to engage in a halogen bond is examined by DFT calculations. Prototype Lewis acid CF3I is placed above the planes of benzene, naphthalene, anthracene, phenanthrene, naphthacene, chrysene, triphenyl, pyrene, and coronene. The I atom positions itself some 3.3–3.4 Å above the polycyclic plane, and the associated interaction energy is about 4 kcal/mol. This quantity is a little smaller for benzene, but is roughly equal for the larger polycyclics. The energy only oscillates a little as the Lewis acid slides across the face of the polycyclic, preferring regions of higher π‐electron density over minima of the electrostatic potential. The binding is dominated by dispersion which contributes half of the total interaction energy.
Insight into Spectral Properties and Solvatochromic Behavior of [b]‐Fused BODIPYs: Experimental and Computational Study
Authors: Ksenofontova Ksenia V. , Shagurin Artyom Yu. , Molchanov Evgeniy E. , Ksenofontov Alexander A. , Sbytov Dmitrii A. , Kalyamanova Yana E. , Danilova Elena A. , Marfin Yuriy S. 
Published: June 2024

AbstractTwo π‐extended derivatives of boron‐dipyrromethene (BODIPY) – unsymmetrical benzo[b]‐fused BODIPY 1 and symmetrical naptho[b]‐fused BODIPY 2 – were synthesized. Spectroscopic and photophysical properties of the synthesized fluorescent dyes were investigated in various organic media. Both BODIPY 1 and BODIPY 2 distinguished by bathochromically shifted absorption and emission bands compared to their non‐fused derivatives, while possessing green (526–543 nm) and red (664–708 nm) absorbance and fluorescence, respectively. Spectral characteristics of the investigated fluorescent dyes were found to be weakly depended on solvent polarizability in case of BODIPY 1 and greatly influenced by both solvent polarizability and dipolarity in case of BODIPY 2. Quantum chemical calculations were used to clarify the relationships between geometry/electronic structure and spectral properties/solvatochromic behavior of BODIPY 1 and BODIPY 2.
Applications of Surface Plasmon Resonance (SPR) to the Study of Diverse Protein‐Ligand Interactions
Authors: Burris Dana M. , Gillespie Samuel W. , Campbell Emma Joy , Ice S. Nick , Yadav Vikas , Picking William D. , Lorson Christian L. , Singh Kamal 
Published: June 2024

AbstractFunctional characterization of enzymes/proteins requires determination of the binding affinity of small molecules or other biomolecules with the target proteins. Several available techniques, such as proteomics and drug discovery strategies, require a precise and high‐throughput assay for rapid and reliable screening of potential candidates for further testing. Surface plasmon resonance (SPR), a well‐established label‐free technique, directly measures biomolecular affinities. SPR assays require immobilization of one interacting component (ligand) on a conductive metal (mostly gold or silver) and a continuous flow of solution containing potential binding partner (analyte) across the surface. The SPR phenomenon occurs when polarized light excites the electrons at the interface of the metal and the dielectric medium to generate electromagnetic waves that propagate parallel to the surface. Changes in the refractive index due to interaction between the ligand and analyte are measured by detecting the reflected light, providing real‐time data on kinetics and specificity. A prominent use of SPR is identifying compounds in crude plant extracts that bind to specific molecules. Procedures that utilize SPR are becoming increasingly applicable outside the laboratory setting, and SPR imaging and localized SPR (LSPR) are cheaper and more portable alternative for in situ detection of plant or mammalian pathogens and drug discovery studies. LSPR, in particular, has the advantage of direct attachment to test tissues in live‐plant studies. Here, we describe three protocols utilizing SPR‐based assays for precise analysis of protein‐ligand interactions. © 2024 Wiley Periodicals LLC.This article was corrected on 06 July 2024. See the end of the full text for details.Basic Protocol 1: SPR comparison of binding affinities of viral reverse transcriptase polymorphismsBasic Protocol 2: SPR screening of crude plant extract for protein‐binding agentsBasic Protocol 3: Localized SPR–based antigen detection using antibody‐conjugated gold nanoparticles
A Plastic‐Crystal Electrolyte Layer Promotes Interfacial Stability of Ni‐Rich Oxide Cathode in Li6PS5Cl‐Based All‐Solid‐State Rechargeable Li Batteries
Authors: Ma Ruojian , Liu Yaning , Fang Ruyi , Zhang Jun , Wang Ya‐Hui , Huang Hui , Gan Yongping , He Xinping , Xia Xinhui , Zhang Wenkui , Xia Yang , Xin Sen 
Published: June 2024

AbstractUnfavorable parasitic reactions between the Ni‐rich layered oxide cathode and the sulfide solid electrolyte have plagued the realization of all‐solid‐state rechargeable Li batteries. The accumulation of inactive by‐products (P2Sx, S, POxn− and SOxn−) at the cathode‐sulfide interface impedes fast Li‐ion transfer, which accounts for sluggish reaction kinetics and significant loss of cathode capacity. Herein, we proposed an easily scalable approach to stabilize the cathode electrochemistry via coating the cathode particles by a uniform, Li+‐conductive plastic‐crystal electrolyte nanolayer on their surface. The electrolyte, which simply consists of succinonitrile and Li bis(trifluoromethanesulphonyl)imide, serves as an interfacial buffer to effectively suppress the adverse phase transition in highly delithiated cathode materials, and the loss of lattice oxygen and generation of inactive oxygenated by‐products at the cathode‐sulfide interface. Consequently, an all‐solid‐state rechargeable Li battery with the modified cathode delivers high specific capacities of 168 mAh g−1 at 0.1 C and a high capacity retention >80 % after 100 cycles. Our work sheds new light on rational design of electrode‐electrolyte interface for the next‐generation high‐energy batteries.
Reactive power management in variable frequency transformer (VFT)‐integrated multi‐machine power systems: A STATCOM‐based approach
Authors: Sheikh Aabid Hussain , Bakhsh Farhad Ilahi 
Published: June 2024

AbstractIn order to improve power system stability and suppress low power oscillations, active power regulation using variable frequency transformer (VFT) plays an important role. The literature has already documented in‐depth research on active power transfer control principles of VFT. The VFT, which is basically a wound rotor induction machine consumes reactive power because of magnetizing winding. In terms of the power flow interchange in a two‐area power system incorporating VFT, this work gives an extensive analysis to comprehend the reactive power needs under various operating circumstances. In the context of reactive power compensation, the present study explores two distinct methodologies: the implementation of a fixed shunt capacitor and the utilization of an artificial neural network (ANN)‐based static synchronous compensator (STATCOM). The STATCOM‐based control technique outperforms the conventional fixed shunt capacitor by demonstrating improved capabilities in reducing reactive power imbalances and stabilizing the power system. Further, a control scheme based on voltage regulation is implemented for integrating the STATCOM to enhance the fault ride through capability of a three‐phase bus fault. Additionally, two‐area test system is exposed to a reactive load shift to evaluate the operation of STATCOM, which restores the bus voltage to its pre‐specified value.
Impacts of molecular drivers in aortic dissection
Authors: Tian Cuihong , Chen Yequn , Tan Xuerui 
Published: June 2024

AbstractBackgroundAortic dissection (AD) is a lethal cardiovascular emergency involving high mortality and disability. However, its specific pathogenesis remains to be elucidated.MethodsA bibliometric analysis based on the Web of Science database, VOSviewer software and Citex platforms was conducted to have a knowledge of the development trends, frontiers and hot spots of AD. Subsequently, the top five AD‐related genes from the titles and abstracts of published literature were searched. Lastly, the roles of the top five genes and their encoded proteins in the onset of AD were reviewed.ResultsThe bibliometrics showed that most studies are exploring the molecular drivers related to AD, especially gene mutations. The top five AD‐related genes were transforming growth factor‐β (TGFB)‐related genes, elastin (ELN), fibrillin‐1 (FBN1), angiotensinogen (AGT) and matrix metalloproteinase 9 (MMP9). In particular, regulation of the structure of elastic fiber by TGFB‐related genes, ELN and FBN1, appears to be the principal mechanism contributing to AD onset. Activation of the renin‐angiotensin system is the principal mechanism by which AGT triggers AD. MMP9 promotes the formation and development of AD by degrading extracellular matrix components.ConclusionTGFB, ELN, FBN1, AGT and MMP9 are the five top molecular drivers of AD, providing a comprehensive mechanistic insight into AD.
From One's Heart to the Mind of Others: A Study in School‐Aged Children
Authors: Zammuto Marta , Ottaviani Cristina , Bianchi Dora , Laghi Fiorenzo , Lonigro Antonia 
Published: June 2024

ABSTRACTStudies have shown a significant association between effective parasympathetic modulation of the heart and processes linked to social cognition. Particularly, Quintana and colleagues documented a relation between vagally‐mediated heart rate variability (vmHRV) and performance on a theory of mind (ToM) task, namely, the Reading the Mind in the Eyes Test (RMET), in a sample of university students. The purpose of the present study was to test whether such result would extend to a sample of school‐aged children (7–9 years old) using the child version of the RMET. In addition, the Eyes Test Revised was administered as it is more suitable to evaluate ToM during childhood. Results supported the positive association between vmHRV and ToM abilities, replicating and extending previous results obtained in young adults. The current study adds to the existing literature pointing to HRV as a putative biomarker of social cognition abilities.
Associations of Household and Neighborhood Contexts and Hair Cortisol Among Mexican‐Origin Adolescents From Low‐Income Immigrant Families
Authors: Ip Ka I , Wen Wen , Sim Lester , Chen Shanting , Kim Su Yeong 
Published: June 2024

ABSTRACTAlthough neighborhood contexts serve as upstream determinants of health, it remains unclear how these contexts “get under the skin” of Mexican‐origin youth, who are disproportionately concentrated in highly disadvantaged yet co‐ethnic neighborhoods. The current study examines the associations between household and neighborhood socioeconomic status (SES), neighborhood racial–ethnic and immigrant composition, and hair cortisol concentration (HCC)—a physiological index of chronic stress response—among Mexican‐origin adolescents from low‐income immigrant families in the United States. A total of 297 (54.20% female; mage = 17.61, SD = 0.93) Mexican‐origin adolescents had their hair cortisol collected, and their residential addresses were geocoded and merged with the American Community Survey. Neighborhoods with higher Hispanic‐origin and foreign‐born residents were associated with higher neighborhood disadvantage, whereas neighborhoods with higher non‐Hispanic White and domestic‐born residents were associated with higher neighborhood affluence. Mexican‐origin adolescents living in neighborhoods with a higher proportion of Hispanic‐origin residents showed lower levels of HCC, consistent with the role of the ethnic enclave. In contrast, adolescents living in more affluent neighborhoods showed higher levels of HCC, possibly reflecting a physiological toll. No association was found between household SES and HCC. Our findings underscore the importance of taking sociocultural contexts and person–environment fit into consideration when understanding how neighborhoods influence adolescents’ stress physiology.
Rare bird forecast: A combined approach using a long‐term dataset of an Arctic seabird and a numerical weather prediction model
Authors: Senzaki Masayuki , Tamura Kenta , Watanabe Yoshiaki , Watanabe Megumi , Sato Tomonori 
Published: June 2024

AbstractWildlife observation is a popular activity, and sightings of rare or difficult‐to‐find animals are often highly desired. However, predicting the sighting probabilities of these animals is a challenge for many observers, and it may only be possible by limited experts with intimate knowledge and skills. To tackle this difficulty, we developed user‐friendly forecast systems of the daily observation probabilities of a rare Arctic seabird (Ross's Gull Rhodostethia rosea) in a coastal area in northern Japan. Using a dataset gathered during 16 successive winters, we applied a machine learning technique of self‐organizing maps and explored how days with gull sightings were related to the meteorological pressure patterns over the Sea of Okhotsk (Method A). We also built a regression model that explains the relationship between gull sightings and local‐scale environmental factors (Method B). We then applied these methods with the operational global numerical weather prediction model (a computer simulation application about the fluid dynamics of Earth's atmosphere) to forecast the daily observation probabilities of our target. Method A demonstrated a strong dependence of gull sightings on the 16 representative weather patterns and forecasted stepwise observation probabilities ranging from 0% to 85.7%. Method B also showed that the strength of the northerly wind and the advancement of the season explained gull sightings and forecasted continuous observation probabilities ranging from 0% to 95.5%. Applying these two methods with the operational global numerical weather prediction model successfully forecasted the varied observation probabilities of Ross's Gull from 1 to 5 days ahead from November to February. A 2‐year follow‐up observation also validated both forecast systems to be effective for successful observation, especially when both systems forecasted higher observation probabilities. The developed forecast systems would therefore allow cost‐effective animal observation and may facilitate a better experience for a variety of wildlife observers.
Long‐term data reveal fitness costs of anthropogenic prey depletion for a subordinate competitor, the African wild dog (Lycaon pictus)
Authors: Reyes de Merkle Johnathan , Creel Scott , Becker Matthew S. , Goodheart Ben , Mweetwa Thandiwe , Mwape Henry , Dröge Egil , Simpamba Twakundine 
Published: June 2024

AbstractWithin carnivore guilds, dominant competitors (e.g., lions, Panthera leo) are limited primarily by the density of prey, while subordinate competitors (e.g., African wild dogs, Lycaon pictus) have been limited by the density of dominant competitors. Historically, the fitness and population density of subordinate competitors have not been tightly linked to prey density. However, populations of large herbivores have declined substantially across sub‐Saharan Africa due to human impacts, and where prey depletion is severe, fitness costs for competitive subordinates may begin to outweigh the benefits of competitive release. Using long‐term intensive monitoring of African wild dogs in Zambia's Luangwa Valley Ecosystem (LVE), we tested the effects of prey depletion on survival and reproduction. We hypothesized that African wild dog fitness would be lower in prey‐depleted areas, despite lower lion densities. Our study area included four contiguous regions that varied in protection level, prey density, and lion density. We fit Bayesian Cormack–Jolly–Seber and closed‐capture models to estimate effects on survival and population density, and generalized linear models to estimate effects on reproductive success. We found that the LVE is a stronghold for African wild dogs, with an estimated median density of 4.0 individuals/100 km2. Despite this high density, survival and reproduction differed among regions, and both components of fitness were substantially reduced in the region with the lowest prey density. Anthropogenic prey depletion is becoming an important limiting factor for African wild dogs. If prey depletion (or any other form of habitat degradation) becomes severe enough that its fitness costs outweigh the benefits of competitive release, such changes can fundamentally alter the balance between limiting factors for competitively subordinate species.