bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Physical Consistency of an Open Quantum Region with a Classical Reservoir in Molecular Simulation
Authors: Panahian Jand Sara , Kühne Thomas D. , Delle Site Luigi 
Published: August 2024

AbstractThe possibility of treating a molecular liquid in an open region at ab initio electronic resolution embedded in a classical reservoir of energy and particles, is investigated. Because of its challenging properties and its relevance in many field of current research, the system chosen as prototype of molecular liquid is water at room conditions. A numerical protocol based on the mathematical model of open particle system is applied and the results are compared with results of a full ab initio simulation of reference. The key conclusion is that one can claim the existence of a mandatory minimal size of the quantum region in which structural and electronic properties reproduce those of reference and, at the same time, the exchange of molecules with the environment takes place as expected. This work provides a proof of concept about the possibility to systematically define a physically well founded open quantum system embedded in a classical environment. In turn, the proof of concept is a key information for the design of numerically efficient algorithms for ab initio molecular dynamics simulations of open systems.
Genetic Regulatory Perturbation of Gene Expression Impacted by Genomic Introgression in Fiber Development of Allotetraploid Cotton
Authors: Chen Xinyuan , Hu Xiubao , Li Guo , Grover Corrinne E. , You Jiaqi , Wang Ruipeng , Liu Zhenping , Qi Zhengyang , Luo Xuanxuan , Peng Yabin , Zhu Mengmeng , Zhang Yuqi , Lu Sifan , Zhang Yuan‐ming , Lin Zhongxu , Wendel Jonathan F. , Zhang Xianlong , Wang Maojun 
Published: August 2024

AbstractInterspecific genomic introgression is an important evolutionary process with respect to the generation of novel phenotypic diversity and adaptation. A key question is how gene flow perturbs gene expression networks and regulatory interactions. Here, an introgression population of two species of allopolyploid cotton (Gossypium) to delineate the regulatory perturbations of gene expression regarding fiber development accompanying fiber quality change is utilized. De novo assembly of the recipient parent (G. hirsutum Emian22) genome allowed the identification of genomic variation and introgression segments (ISs) in 323 introgression lines (ILs) from the donor parent (G. barbadense 3–79). It documented gene expression dynamics by sequencing 1,284 transcriptomes of developing fibers and characterized genetic regulatory perturbations mediated by genomic introgression using a multi‐locus model. Introgression of individual homoeologous genes exhibiting extreme low or high expression bias can lead to a parallel expression bias in their non‐introgressed duplicates, implying a shared yet divergent regulatory fate of duplicated genes following allopolyploidy. Additionally, the IL N182 with improved fiber quality is characterized, and the candidate gene GhFLAP1 related to fiber length is validated. This study outlines a framework for understanding introgression‐mediated regulatory perturbations in polyploids, and provides insights for targeted breeding of superior upland cotton fiber.
Giant Piezoelectric Effect Induced by Porosity in Inclined ZnO Thin Films
Authors: Pelayo Garcia Manuel , Saddik Karim Ben , Baghini Mahdieh Shojaei , Hughes Dave Allan , Gibson Des , García Basilio Javier , García Nuñez Carlos 
Published: August 2024

AbstractPiezoceramics have been the common choice for sensing applications, however their integration with other electronics is limited due to their large size. Also, environmental concerns have been limiting the use of ceramics due to their lead content, toxic for humans. Piezoelectric crystalline thin films have arisen as alternative materials offering compatibility with miniaturization and integrated processes, though their piezoelectric properties are low (d33 < 15 pC N−1) compared to ceramics (d33 > 300 pC N−1), hindering their applicability. Several methods have been studied aiming to improve the piezoelectric output of thin films, including doping or the less investigated inclusion of porosity. However, they all require complex techniques that increase the cost. In this work, a giant electromechanical d33 coefficient of 115.6 pC N−1 has been obtained inducing porosity in inclined ZnO thin films via oblique angle deposition, which is beyond record values reported for doped ZnO thin films and an order of magnitude higher than standard ZnO thin films (11.6 pC N−1). Morphology, composition, crystal structure, porosity, and piezoelectricity are reported for standard and inclined films. Finite element simulations have been carried out to investigate the performance of the piezoelectric‐enhanced thin films in an ultrasonic pulse‐echo setup.
s‐Tetrazine‐Bridged 2,2′‐Bipyrimidine as Superior Atom‐Economic Multi‐Charge Cathode Material for Lithium‐Ion Batteries
Authors: Xiao Shengqiang , Zhang Jie , Ren Tianlu , Xiang Zhipeng , Piao Jinhua , Wan Kai , Fu Zhiyong , Liang Zhenxing 
Published: August 2024

AbstractNitrogen‐containing heterocyclic molecules feature metal resource‐independence, flexible conjugation structure and fast charge storage kinetics, making them promising to be used as the electrode material in lithium‐ion batteries. However, an insufficiently high capacity (<400 mAh g−1) seriously threatens their practical application. Herein, a novel molecule, viz. 3,6‐bis(2‐pyrimidinyl)‐1,2,4,5‐tetrazine (DPmT), is developed by inserting an electron‐withdrawing π‐bridge unit of s‐tetrazine between two pyrimidine rings, in which a dense assembly of multiple active sites is realized. The DTmP exhibits a remarkable atom economy of 40 g (mol e)−1, which refers to the molecule mass per unit of charge transferred. The cathode material of DPmT yields a high capacity of 653 mAh g−1 and an energy density of 1188 Wh kg−1 at 50 mA g−1 at 70 °C. And 80% capacity retention is achieved after 500 cycles at 500 mA g−1, confirming its superior cyclability. Spectroscopy studies and theoretical calculations are performed to investigate the charge storage process. First, the C═N and N═N are claimed as plausible binding sites for the lithium ions. Second, the introduction of s‐tetrazine significantly enhances molecular planarity, thereby promoting charge delocalization and molecular stability. This work provides a novel strategy for designing atom‐economic multi‐charge electrode materials with high capacity.
Mechanistically Understanding the Correlation Between Dynamic Interface Variation and Stability of Surface Coating on the NMC811 Materials
Authors: Lyu Siqi , Yu Jian , Guo Xiao‐Hua , Bu Xudong , Sun Lei , Li Na , Chen Hao‐Sen , Song Wei‐Li , Yu Xiqian , Jiao Shuqiang 
Published: August 2024

AbstractLiNi0.8Co0.1‐Mn0.1O2 (NMC811) is widely used in high energy density lithium‐ion batteries, while dynamic variation of liquid‐solid interface induced by oxygen release/evolution results in unexpected performance decay. Surface coating is an effective strategy in promoting the stability of NMC811 materials, and both coating composition and nanostructure arrangement would substantially impact the dynamic variation of liquid‐solid interfaces. To understand such dynamic variation, here evolution and stability of two selected NMC811 materials coated with oxides (the same oxide composition but different nanostructure arrangements) are compared, i.e., concentration uniform core‐shell NMC811 (CUCS811) and concentration gradient core‐shell NMC811 (CGCS811). The gas evolution from the home‐setup operando gas monitors (at 45 and 65 °C) implies that CUCS811 presents more operation and thermal stability because of less amount of CO2 and CH4 along with prolonged interval time in gas production. Composition variation of interfaces indicates that CUCS811 presents more stable interfacial evolution behaviors since more F‐ and P‐rich species for stabilizing the solid‐electrolyte interfaces are detected. The stability analysis suggests that uniform arrangement of Al2O3 and boride in the coating is prone to prevent the interface from degradation upon dynamic interface variation, which is useful in promoting the performance stability of NMC811 positive electrode materials.
Are interns prepared? A summary of current transition to residency preparation courses content
Authors: Davis Mallory , Okoli Donna , House Joseph , Santen Sally 
Published: August 2024

AbstractBackgroundThe transition from medical student to emergency medicine resident is a critical point in training. Medical students start residency with different levels of understanding and some are not meeting the emergency medicine (EM) Level 1 milestones. Residency preparation courses (RPCs) were created to fill this gap and prepare medical students for residency.ObjectivesThe objective was to review content from current RPC curricula to determine the content that should be included in an EM‐specific transition to residency preparation course.MethodsWe collected curricula from RPC course directors at different institutions and reviewed and coded the topics into categories: (1) didactics, (2) procedures, and (3) unique topics (defined as nontraditional topics that did not fit squarely into didactics or procedures).ResultsWe obtained content from 13 different RPC curricula. Length of the courses ranged from one to 8 weeks with the mean being three weeks. Most courses were taught within a larger medical school course and were not specific to EM (62%). The most frequently taught didactic topics were airway interventions (85%), critical care (69%), and chest pain/shortness of breath (62%). Most programs included a simulation component (92%) and the most common procedures included airway interventions (69%); lines—central, arterial, and Cordis (69%); lumbar puncture (62%); and ultrasound (62%). Many of the courses had unique or special features taught within the curriculum. The most frequently taught unique content were sessions on self‐awareness and self‐regulation (85%) and advanced communication (69%).ConclusionsAfter multiple RPC curricula content was reviewed, a set of basic curriculum has been determined and supported by the content analysis. By including a standardized curriculum within RPC's, this will help better prepare medical students and create a standard for medical students entering EM residency and may allow intern orientations to focus on higher level skills.
The non‐flowering plants of a near‐polar forest in East Gondwana, Tasmania, Australia, during the Early Eocene Climatic Optimum
Authors: Slodownik Miriam A. 
Published: August 2024

AbstractPremiseThe Cenozoic Macquarie Harbour Formation (MHF) hosts one of the oldest and southernmost post‐Cretaceous fossil plant assemblages in Australia. Coinciding with the Early Eocene Climatic Optimum (EECO) and predating the breakup of Australia from Antarctica, it offers critical data to study the diversity and extent of the Austral Polar Forest Biome, and the floristic divergence between Australasia and South America resulting from the Gondwana breakup.MethodsThe micromorphology and macromorphology of new fossil plant compressions from the MHF were described and systematically analyzed. Previously published non‐flowering plant records were reviewed and revised. Macrofossil abundance data were provided. The flora was compared with other early Paleogene assemblages from across the Southern Hemisphere.ResultsTwelve species of non‐flowering plants were identified from the macrofossil record. Conifers include Araucariaceae (Araucaria macrophylla, A. readiae, A. timkarikensis sp. nov., and Araucarioides linearis), Podocarpaceae (Acmopyle glabra, Dacrycarpus mucronatus, Podocarpus paralungatikensis sp. nov., and Retrophyllum sp.), and Cupressaceae (Libocedrus microformis). Dacrycarpus linifolius was designated a junior synonym of D. mucronatus. Further components include a cycad (Bowenia johnsonii, Zamiaceae), a pteridosperm (Komlopteris cenozoicus, Umkomasiaceae), and a fern (Lygodium dinmorphyllum, Schizaeaceae).ConclusionsThe fossil assemblage represents a mixed near‐polar forest with a high diversity of conifers. The morphology and preservation of several species indicate adaptations to life at high latitudes. The coexistence of large‐ and small‐leaved conifers implies complex, possibly open forest structures. Comparisons with contemporaneous assemblages from Argentina support a circumpolar biome during the EECO, reaching from southern Australia across Antarctica to southern South America.
P‐doped RuSe2 on Porous N‐Doped Carbon Matrix as Catalysts for Accelerated Sulfur Redox Reactions
Authors: Li Bin , Wang Peng , Yuan Jia , Song Ning , Feng Jinkui , Xiong Shenglin , Xi Baojuan 
Published: August 2024

AbstractMonocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe2, manifesting the further enhanced conductivity compared with original RuSe2, facilitating charge transfer and further modulating the d‐band center of RuSe2, thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm−2, even under high sulfur loading of 8.0 mg cm−2 and a lean electrolyte condition (5.0 μL mg−1). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium‐sulfur batteries and potentially other domains as well.
S−S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution
Authors: Yue Haoyu , Guo Zhongnan , Zhou Ziwen , Zhang Xuemeng , Guo Wenjing , Zhen Shuang , Wang Pu , Wang Kang , Yuan Wenxia 
Published: August 2024

AbstractDeveloping efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R‐type NbS2 loaded by amorphous RuSx nanoparticles with S−S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm−2 in acid, and also low Tafel slope of 51.05 mV dec−1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S−S bonds, resulting in electron‐rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S−S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.
Solution Versus On‐Surface Synthesis of Peripherally Oxygen‐Annulated Porphyrins through C−O Bond Formation
Authors: Deyerling Joel , Berionni Berna Beatrice , Biloborodov Dmytro , Haag Felix , Tömekce Sena , Cuxart Marc G. , Li Conghui , Auwärter Willi , Bonifazi Davide 
Published: August 2024

AbstractThis study investigates the synthesis of tetra‐ and octa‐O‐fused porphyrinoids employing an oxidative O‐annulation approach through C−H activation. Despite encountering challenges such as overoxidation and instability in conventional solution protocols, successful synthesis was achieved on Au(111) surfaces under ultra‐high vacuum (UHV) conditions. X‐ray photoelectron spectroscopy, scanning tunneling microscopy, and non‐contact atomic force microscopy elucidated the preferential formation of pyran moieties via C−O bond formation and subsequent self‐assembly driven by C−H⋅⋅⋅O interactions. Furthermore, the O‐annulation process was found to reduce the HOMO–LUMO gap by lifting the HOMO energy level, with the effect rising upon increasing the number of embedded O‐atoms.
Ni‐Catalyzed Enantioselective Reductive Cyclization/Amidation and Amination of 1,6‐Enynes and 1,7‐Enynes
Authors: Hu Shengwei , Wang Xiaoqin , Wu Tianbao , Ding Zhengtian , Wang Minyan , Kong Wangqing 
Published: August 2024

AbstractTransition‐metal‐catalyzed hydroamination of unsaturated hydrocarbons is an appealing synthetic tool for the construction of high value‐added chiral amines. Despite significant progress in the asymmetric hydroamination of alkenes, allenes, and 1,3‐dienes, asymmetric hydroamination of 1,6‐enynes or 1,7‐enynes remains rather limited due to the enormous challenges in controlling the chemoselectivity and stereoselectivity of the reaction. Herein, we report a Ni‐catalyzed chemo‐ and enantioselective reductive cyclization/amidation and amination of 1,6‐enynes and 1,7‐enynes using dioxazolones or anthranils as nitrene‐transfer reagents. This mild, modular, and practical protocol provides rapid access to a variety of enantioenriched 2‐pyrrolidone and 2‐piperidone derivatives bearing an aminomethylene group at the 4‐position in good yields (up to 83 %) with excellent enantioselectivities (46 examples, up to 99 % ee). Mechanistic experiments and density functional theory calculations indicate that the reaction is initiated by hydronickelation of alkynes followed by migratory insertion into alkenes, rather than by a [2+2+1] oxidative addition process of nickel to alkenes and alkynes.
Coronene‐Based 2D Networks by On‐Surface Skeletal Rearrangement of Sumanene Precursors
Authors: Pérez‐Elvira Elena , Barragán Ana , Gallardo Aurelio , Santos José , Martín‐Fuentes Cristina , Lauwaet Koen , Gallego José M. , Miranda Rodolfo , Sakurai Hidehiro , Urgel José I. , Björk Jonas , Martín Nazario , Écija David 
Published: August 2024

AbstractThe design of novel low‐dimensional carbon materials is at the forefront of modern chemistry. Recently, on‐surface covalent synthesis has emerged as a powerful strategy to synthesize previously precluded compounds and polymers. Here, we report a scanning probe microscopy study, complemented by theoretical calculations, on the sequential skeletal rearrangement of sumanene‐based precursors into a coronene‐based organometallic network by stepwise intra‐ and inter‐molecular reactions on Au(111). Interestingly, upon higher annealing, the formed organometallic networks evolve into two‐dimensional coronene‐based covalently linked patches through intermolecular homocoupling reactions. A new reaction mechanism is proposed based on the role of C−Au−C motifs to promote two stepwise carbon‐carbon couplings to form cyclobutadiene bridges. Our results pave avenues for the conversion of molecular precursors on surfaces, affording the design of unexplored two‐dimensional organometallic and covalent materials.
Experimental studies on mechanism whereby premixed chamber length and equivalence ratio collaboratively influence self‐excited thermoacoustic instability
Authors: Zhang Yuanhang , Du Yongbo , Zhang Jingkun , Che Defu 
Published: August 2024

AbstractSelf‐excited thermoacoustic instability (SETAI) is a dangerous phenomenon in combustion equipment. While it is widely acknowledged that SETAI behavior is determined by the couple between pressure and heat release oscillation, their phase difference is difficult to predict, which impedes the development of SETAI control technology. With the aim of passive control technology development, this paper conducted experiment on a premixed hedge combustor to explore the mechanism whereby premixed chamber length (LP) and equivalence ratio (φ) collaboratively influence SETAI behavior. Results showed LP mainly affects the pressure mode shape within premixed chamber and consequently alters the phase difference between pressure and flowrate oscillation at combustion chamber inlet. Changing φ gives rise to different reaction time‐lag (τ), thus altering the phase difference between flowrate and reaction heat release oscillation. By introducing this flowrate oscillation, how LP and φ collaboratively determine phase difference between pressure oscillation and heat release oscillation was clarified. The mechanisms identified in this study are consistent with the emerging rationalization of the factors contributing to SETAI, and also provides better understanding on Rayleigh criterion and guidance for SETAI control. With further work on heat release and flow rate measurement, as well as the development on τ description, SETAI can be better predicted and controlled.
Neural canal ridges: A novel osteological correlate of postcranial neuroanatomy in dinosaurs
Authors: Atterholt Jessie , Wedel Mathew J. , Tykoski Ron , Fiorillo Anthony R. , Holwerda Femke , Nalley Thierra K. , Lepore Taormina , Yasmer John 
Published: August 2024

AbstractIn this article, we document the widespread presence of bony ridges in the neural canals of non‐avian dinosaurs, including a wide diversity of sauropods, two theropods, a thyreophoran, and a hadrosaur. These structures are present only in the caudal vertebrae. They are anteroposteriorly elongate, found on the lateral walls of the canal, and vary in size and position both taxonomically and serially. Similar bony projections into the neural canal have been identified in extant teleosts, dipnoans, and urodelans, in which they are recognized as bony spinal cord supports. In most non‐mammals, the dura mater that surrounds the spinal cord is fused to the periosteum of the neural canal, and the denticulate ligaments that support the spinal cord can pass through the dura and periosteum to anchor directly to bone. The function of these structures in dinosaurs remains uncertain, but in sauropods they might have stabilized the spinal cord during bilateral movement of the tail and use of the tail as a weapon. Of broader significance, this study emphasizes that important new discoveries at the gross anatomical level can continue to be made in part by closely examining previously overlooked features of known specimens.
Partially substituting alfalfa hay with hemp forage promotes the health and well‐being of goats via altering ruminal and plasma metabolites and metabolic pathways
Authors: Ran Tao , Luo Guowang , Yue Yipeng , Xu Zhipeng , Shi Zunji , Lei Zhaomin , Yang Wenzhu , Wu Duanqin 
Published: August 2024

AbstractHemp forage (HF) seems a suitable forage for ruminants for its high nutritional value and rich phytochemicals that exert health and growth‐promoting activities. We investigated the effects of hemp‐related phytochemicals on rumen and plasma metabolism using metabolome when partially substituting alfalfa hay with HF in goat diets. Numbers of differential metabolites linearly increased with increasing HF substituting rate, approximately 50% of which were phytochemicals. Metabolic pathway enrichment analysis showed that the inclusion of HF greatly promoted steroid hormone biosynthesis, one carbon pool by folate, and retinol metabolism pathways in both rumen and plasma, which are beneficial for promoting animal health and well‐being and enhancing the quality of animal products. Some phytochemicals showed inhibitory activities on the growth of certain ruminal bacteria; meanwhile, the detected intermediate metabolites indicated degradation of the phytochemicals by ruminal microbes. These phytochemicals work individually and synergistically to alter ruminal and plasma metabolic pathways, thus exerting benefits in promoting the health and well‐being of animals.