bluuebunny/crossref_metadata_2025_split huggingface dataset:
Boosting Formate Electrooxidation by Heterostructured PtPd Alloy and Oxides Nanowires
Authors: Wang Tian‐Jiao , Sun Li‐Bo , Ai Xuan , Chen Pei , Chen Yu , Wang Xin 
Published: April 2024

AbstractDirect formate fuel cells (DFFCs) receive increasing attention as promising technologies for the future energy mix and environmental sustainability, as formate can be made from carbon dioxide utilization and is carbon neutral. Herein, heterostructured platinum‐palladium alloy and oxides nanowires (PtPd‐ox NWs) with abundant defect sites are synthesized through a facile self‐template method and demonstrated high activity toward formate electrooxidation reaction (FOR). The electronic tuning arising from the heterojunction between alloy and oxides influence the work function of PtPd‐ox NWs. The sample with optimal work function reveals the favorable adsorption behavior for intermediates and strong interaction in the d−p orbital hybridization between Pt site and oxygen in formate, favoring the FOR direct pathway with a low energy barrier. Besides the thermodynamic regulation, the heterostructure can also provide sufficient hydroxyl species to facilitate the formation of carbon dioxide due to the ability of combining absorbed hydrogen and carbon monoxide at adjacent active sites, which contributes to the improvement of FOR kinetics on PtPd‐ox NWs. Thus, heterostructured PtPd‐ox NWs achieve dual regulation of FOR thermodynamics and kinetics, exhibiting remarkable performance and demonstrating potential in practical systems.
Suppressed Lone Pair Electrons Explain Unconventional Rise of Lattice Thermal Conductivity in Defective Crystalline Solids
Authors: Jang Hanhwi , Toriyama Michael Y. , Abbey Stanley , Frimpong Brakowaa , Snyder G. Jeffrey , Jung Yeon Sik , Oh Min‐Wook 
Published: April 2024

AbstractManipulating thermal properties of materials can be interpreted as the control of how vibrations of atoms (known as phonons) scatter in a crystal lattice. Compared to a perfect crystal, crystalline solids with defects are expected to have shorter phonon mean free paths caused by point defect scattering, leading to lower lattice thermal conductivities than those without defects. While this is true in many cases, alloying can increase the phonon mean free path in the Cd‐doped AgSnSbSe3 system to increase the lattice thermal conductivity from 0.65 to 1.05 W m−1 K−1 by replacing 18% of the Sb sites with Cd. It is found that the presence of lone pair electrons leads to the off‐centering of cations from the centrosymmetric position of a cubic lattice. X‐ray pair distribution function analysis reveals that this structural distortion is relieved when the electronic configuration of the dopant element cannot produce lone pair electrons. Furthermore, a decrease in the Grüneisen parameter with doping is experimentally confirmed, establishing a relationship between the stereochemical activity of lone pair electrons and the lattice anharmonicity. The observed “harmonic” behavior with doping suggests that lone pair electrons must be preserved to effectively suppress phonon transport in these systems.
Direct and Inverse Spin Splitting Effects in Altermagnetic RuO2
Authors: Guo Yaqin , Zhang Jing , Zhu Zengtai , Jiang Yuan‐yuan , Jiang Longxing , Wu Chuangwen , Dong Jing , Xu Xing , He Wenqing , He Bin , Huang Zhiheng , Du Luojun , Zhang Guangyu , Wu Kehui , Han Xiufeng , Shao Ding‐fu , Yu Guoqiang , Wu Hao 
Published: April 2024

AbstractRecently, the altermagnetic materials with spin splitting effect (SSE), have drawn significant attention due to their potential to the flexible control of the spin polarization by the Néel vector. Here, the direct and inverse altermagnetic SSE (ASSE) in the (101)‐oriented RuO2 film with the tilted Néel vector are reported. First, the spin torque along the x‐, y‐, and z‐axis is detected from the spin torque‐induced ferromagnetic resonance (ST‐FMR), and the z‐spin torque emerges when the electric current is along the [010] direction, showing the anisotropic spin splitting of RuO2. Further, the current‐induced modulation of damping is used to quantify the damping‐like torque efficiency (ξDL) in RuO2/Py, and an anisotropic ξDL is obtained and maximized for the current along the [010] direction, which increases with the reduction of the temperature, indicating the present of ASSE. Next, by way of spin pumping measurement, the inverse altermagnetic spin splitting effect (IASSE) is studied, which also shows a crystal direction‐dependent anisotropic behavior and temperature‐dependent behavior. This work gives a comprehensive study of the direct and inverse ASSE effects in the altermagnetic RuO2, inspiring future altermagnetic materials and devices with flexible control of spin polarization.
Is boarding compromising our residents' education? A national survey of emergency medicine program directors
Authors: Goldflam Katja , Bradby Cassandra , Coughlin Ryan F. , Cordone Alexis , Bod Jessica , Bright Leah , Merrill Rebecca , Tsyrulnik Alina 
Published: April 2024

AbstractBackgroundBoarding patients in the emergency department (ED) potentially affects resident education. Program director (PD) perceptions of the impact of boarding on their trainees have not been previously described.MethodsWe surveyed a cross‐sectional convenience sample of emergency medicine PDs using a mixed‐methods approach to explore their perceptions of how boarding has affected their residents' training. Descriptive data were reported as percentages and differences were calculated using Pearson's chi‐square test, withp < 0.05 considered significant. A framework model was used to qualitatively analyze free‐text responses.ResultsA total of 170 responses were collected, for a response rate of 63%. Most respondents felt that boarding had at least some effect on resident education with 29%, 35%, 18%, and 12% noting “a little,” “a moderate amount,” “a lot,” and “a great deal,” respectively, and 5% noting “no effect at all.” Respondents perceived a negative impact of boarding on resident education and training, with 80% reporting a “somewhat” or “extremely negative” effect, 18% feeling neutral, and 2% noting a “somewhat positive” effect. Most noted a “somewhat” or “extremely negative” effect on resident education in managing ED throughput (70%) and high patient volumes (66%). Fifty‐four percent noted a “somewhat” or “extremely negative” impact on being involved in the initial workup of undifferentiated patients. Thirty‐two percent saw a “somewhat” or “extremely positive” effect on learning the management of critically ill patients. Qualitative analysis of challenges, mitigation strategies, and resident feedback emphasized the lack of exposure to managing departmental patient flow, impact on bedside teaching, and need for flexibility in resident staffing.ConclusionsMost PDs agree that boarding negatively affects resident education and identify several strategies to mitigate the impact. These findings can help inform future interventions to optimize resident learning in the complex educational landscape of high ED boarding.
Heat‐related fatalities in North Carolina 1999–2017
Authors: McClure Elizabeth S. , Ranapurwala Shabbar I. , Nocera Maryalice , Richardson David B. 
Published: April 2024

AbstractObjectivesResearch shows the highest rates of occupational heat‐related fatalities among farm laborers and among Black and Hispanic workers in North Carolina (NC). The Hispanic population and workforce in NC have grown substantially in the past 20 years. We describe the epidemiology of heat‐related fatal injuries in the general population and among workers in NC.MethodsWe reviewed North Carolina death records and records of the North Carolina Office of the Chief Medical Examiner to identify heat‐related deaths (primary International Classification of Diseases, Tenth Revision diagnosis code: X30 or T67.0‐T67.9) that occurred between January 1, 1999, and December 31, 2017. Decedent age, sex, race, and ethnicity were extracted from both the death certificate and the medical examiner's report as well as determinations of whether the death occurred at work.ResultsIn NC between 1999 and 2017, there were 225 deaths from heat‐related injuries, and 25 occurred at work. The rates of occupational heat‐related deaths were highest among males, workers of Hispanic ethnicity, workers of Black, multiple, or unknown race, and in workers aged 55–64. The highest rate of occupational heat‐related deaths occurred in the agricultural industry.ConclusionsSince the last report (2001), the number of heat‐related fatalities has increased, but fewer were identified as workplace fatalities. Rates of occupational heat‐related deaths are highest among Hispanic workers. NC residents identifying as Black are disproportionately burdened by heat‐related fatalities in general, with a wider apparent disparity in occupational deaths.
Divergent Associations of Slow‐Wave Sleep versus Rapid Eye Movement Sleep with Plasma Amyloid‐Beta
Authors: Rosenblum Yevgenia , Pereira Mariana , Stange Oliver , Weber Frederik D. , Bovy Leonore , Tzioridou Sofia , Lancini Elisa , Neville David A. , Klein Nadja , de Wolff Timo , Stritzke Mandy , Kersten Iris , Uhr Manfred , Claassen Jurgen A. H. R. , Steiger Axel , Verbeek Marcel M. , Dresler Martin 
Published: April 2024

ObjectiveRecent evidence shows that during slow‐wave sleep (SWS), the brain is cleared from potentially toxic metabolites, such as the amyloid‐beta protein. Poor sleep or elevated cortisol levels can worsen amyloid‐beta clearance, potentially leading to the formation of amyloid plaques, a neuropathological hallmark of Alzheimer disease. Here, we explored how nocturnal neural and endocrine activity affects amyloid‐beta fluctuations in the peripheral blood.MethodsWe acquired simultaneous polysomnography and all‐night blood sampling in 60 healthy volunteers aged 20–68 years. Nocturnal plasma concentrations of amyloid‐beta‐40, amyloid‐beta‐42, cortisol, and growth hormone were assessed every 20 minutes. Amyloid‐beta fluctuations were modeled with sleep stages, (non)oscillatory power, and hormones as predictors while controlling for age and participant‐specific random effects.ResultsAmyloid‐beta‐40 and amyloid‐beta‐42 levels correlated positively with growth hormone concentrations, SWS proportion, and slow‐wave (0.3–4Hz) oscillatory and high‐band (30–48Hz) nonoscillatory power, but negatively with cortisol concentrations and rapid eye movement sleep (REM) proportion measured 40–100 minutes previously (all t values > |3|, p values < 0.003). Older participants showed higher amyloid‐beta‐40 levels.InterpretationSlow‐wave oscillations are associated with higher plasma amyloid‐beta levels, whereas REM sleep is related to decreased amyloid‐beta plasma levels, possibly representing changes in central amyloid‐beta production or clearance. Strong associations between cortisol, growth hormone, and amyloid‐beta presumably reflect the sleep‐regulating role of the corresponding releasing hormones. A positive association between age and amyloid‐beta‐40 may indicate that peripheral clearance becomes less efficient with age. ANN NEUROL 2024;96:46–60
Small Ionic‐Liquid‐Based Molecule Drives Strong Adhesives
Authors: Liu Kai , Wu Peiyi 
Published: April 2024

AbstractNature has inspired scientists to fabricate adhesive materials for applications in many burgeoning areas. However, it is still a significant challenge to develop small‐molecule adhesives with high‐strength, low‐temperature and recyclable properties, although these merits are of great interest in various aspects. Herein, we report a series of strong adhesives based on low‐molecular‐weight molecular solids driven by the terminal modification of ionic liquids (ILs) and subsequent supramolecular self‐assembly. The emergence of high strength and liquid‐to‐solid transitions for these supramolecular aggregates relies on modifying IL with a high melting point motif and enriching the types of noncovalent interactions in the original ILs. Using this strategy, we demonstrate that our IL‐based molecular solids can efficiently obtain a high adhesion strength (up to 8.95 MPa). Importantly, we elucidate the mechanism underlying the reversible and strong adhesion enabled by monomer‐to‐polymer transitions. These fundamental findings provide guidance for the design of high‐performance supramolecular adhesive materials.
Selective Arylation of RNA 2′‐OH Groups via SNAr Reaction with Trialkylammonium Heterocycles
Authors: Chatterjee Sayantan , Xiao Lu , Zhong Wenrui , Feng Sheng , Kool Eric T. 
Published: April 2024

AbstractSmall‐molecule reactions at the 2′‐OH groups of RNA enable useful applications for transcriptome technology and biology. To date, all reactions have involved carbonyl acylation and mechanistically related sulfonylation, limiting the types of modifications and properties that can be achieved. Here we report that electron‐deficient heteroaryl species selectively react with 2′‐OH groups of RNA in water via SNAr chemistry. In particular, trialkyl‐ammonium (TAA)‐activated aromatic heterocycles, prepared in one step from aryl chloride precursors, give high conversions to aryl ether adducts with RNAs in aqueous buffer in ~2–3 h. Remarkably, a TAA triazine previously used only for reaction with carboxylic acids, shows unprecedented selectivity for RNA over water, reacting rapidly with 2′‐OH groups while exhibiting a half‐life in water of >10 days. We further show that a triazine aryl species can be used as a probe at trace‐level yields to map RNA structure in vitro. Finally, we prepare a number of functionalized trialkylammonium triazine reagents and show that they can be used to covalently label RNA efficiently for use in vitro and in living cells. This direct arylation chemistry offers a simple and distinct structural scaffold for post‐synthetic RNA modification, with potential utility in multiple applications in transcriptome research.
N‐(sulfonio)sulfilimin‐Reagenzien: Nicht‐oxidierende Quellen von elektrophilen Stickstoffatomen für Skeletal Editing
Authors: Heilmann Tobias , Lopez‐Soria Juan M. , Ulbrich Johannes , Kircher Johannes , Li Zhen , Worbs Brigitte , Golz Christopher , Mata Ricardo A. , Alcarazo Manuel 
Published: April 2024

AbstractDie Eintopfsynthese von λ4‐Dibenzothiophen‐5‐imino‐N‐dibenzothiophenium triflat (1) im Multigramm‐Maßstab wird vorgestellt. Diese Verbindung reagiert mit Rh2(esp)2 (esp=α,α,α′,α′‐tetramethyl‐1,3‐benzol‐dipropionsäure) zu einem Rhodium koordinierten Sulfonitren, das die elektrophile Nitreneinheit auf Olefine transferieren kann. Unter Verwendung von Indenen als Substrate werden Isoquinoline in guten Ausbeuten erhalten. Wir vermuten, dass nach der Bildung des entsprechenden N‐sulfonioaziridins eine Ringerweiterung über den selektiven C−C‐Bindungsbruch und der damit einhergehenden Eliminierung von Dibenzothiophen stattfindet. Überraschenderweise liefert die Reaktion mit 1‐Arylcyclobutenen 1‐Cyano‐1‐arylcyclopropane als Produkte. Unsere dazu durchgeführten Rechnungen lassen vermuten, dass die Aziridinbildung in diesem Fall nicht bevorzugt ist. Stattdessen werden die zunächst gebildeten Sulfilimin substituierten Cyclobutylcarbokationen unter Ringkontraktion in die isolierten Cyclopropane umgewandelt. Beide Reaktionsvorschriften sind einfach in der Durchführung, tolerieren eine Reihe von funktionellen Gruppen – eingeschlossen oxidationsempfindlicher Alkohole und Aldehyde – und ermöglichen die Herstellung von 15N‐markierten Produkten. Diese Resultate demonstrieren das Potential von Verbindung 1 als alternativer Weg zur selektiven Übertragung von Stickstoffatomen auf organische Moleküle.
Non‐Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High‐Voltage NCM811‐Li Batteries
Authors: Wang Zhijie , Che Xiangli , Wang Danni , Wang Yanyan , He Xiaomei , Zhu Ye , Zhang Biao 
Published: April 2024

AbstractLithium (Li) metal batteries (LMBs) with nickel (Ni)‐rich layered oxide cathodes exhibit twice the energy density of conventional Li‐ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent‐based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering of fluorine (F)‐free ethers to mitigate electrode surface reactivity in high‐voltage Ni‐rich LMBs. By merely extending the alkyl chains of traditional ethers, we effectively reduce the catalytic reactivity of the cathode towards the electrolyte at high voltages, which suppresses the oxidation decomposition of the electrolyte, microstructural defects and rock‐salt phase formation in the cathode, and gas release issues. The high‐voltage Ni‐rich NCM811‐Li battery delivers capacity retention of 80 % after 250 cycles with a high Coulombic efficiency of 99.85 %, even superior to that in carbonate electrolytes. Additionally, this strategy facilitates passivation of the Li anode by forming a robust solid‐electrolyte interphase, boosting the Li reversibility to 99.11 % with a cycling life of 350 cycles, which outperforms conventional F‐free ether electrolytes. Consequently, the lifespan of practical LMBs has been prolonged by over 100 % and 500 % compared to those in conventional carbonate‐ and ether‐based electrolytes, respectively.
An Indocyanine Green‐Based Nanoprobe for In Vivo Detection of Cellular Senescence
Authors: Baker Andrew G. , Hartono Muhamad , Ou Hui‐Ling , Popov Andrea Bistrović , Brown Emma L. , Joseph James , Golinska Monika , González‐Gualda Estela , Macias David , Ge Jianfeng , Denholm Mary , Morsli Samir , Sanghera Chandan , Else Thomas R. , Greer Heather F. , Vernet Aude , Bohndiek Sarah E. , Muñoz‐Espín Daniel , Fruk Ljiljana 
Published: April 2024

AbstractThere is an urgent need to improve conventional cancer‐treatments by preventing detrimental side effects, cancer recurrence and metastases. Recent studies have shown that presence of senescent cells in tissues treated with chemo‐ or radiotherapy can be used to predict the effectiveness of cancer treatment. However, although the accumulation of senescent cells is one of the hallmarks of cancer, surprisingly little progress has been made in development of strategies for their detection in vivo. To address a lack of detection tools, we developed a biocompatible, injectable organic nanoprobe (NanoJagg), which is selectively taken up by senescent cells and accumulates in the lysosomes. The NanoJagg probe is obtained by self‐assembly of indocyanine green (ICG) dimers using a scalable manufacturing process and characterized by a unique spectral signature suitable for both photoacoustic tomography (PAT) and fluorescence imaging. In vitro, ex vivo and in vivo studies all indicate that NanoJaggs are a clinically translatable probe for detection of senescence and their PAT signal makes them suitable for longitudinal monitoring of the senescence burden in solid tumors after chemotherapy or radiotherapy.
Umbrella‐Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features
Authors: Endo Masaya , Aoyama Shinji , Tsuchido Yoshitaka , Catti Lorenzo , Yoshizawa Michito 
Published: April 2024

AbstractTo develop new hybrid micelles with alkyl/polyaromatic core–shell structures, we synthesized umbrella‐shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2–3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation significantly enhances the stability of the micellar structures against dilution (up to 9 μM) and heat (up to >120 °C). The highly condensed hexadecyl core of the hybrid micelle, as indicated by solvatochromic guest probes, displays increased uptake ability toward large alkylated metallodyes. Interestingly, efficient uptake of aromatic macrocycles (i.e., [n]cycloparaphenylenes) by the present micelle provides pseudorotaxane‐shaped host–guest composites with high emissivity (ΦF=up to 35 %). Internal multi‐alkylation of an aromatic micelle can thus successfully enhance its assembly stability/guest uptake functions.
Two‐Dimensional Conjugated Metal–Organic Frameworks with a Ring‐in‐Ring Topology and High Electrical Conductance
Authors: Yang Mingyu , Zhang Yi , Zhu Renlong , Tan Junjun , Liu Jinxin , Zhang Wei , Zhou Meng , Meng Zheng 
Published: April 2024

AbstractElectrically conducting two‐dimensional (2D) metal–organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high‐performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M–DHHBTN (M=Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M–DHHBTN are elucidated through comprehensive analyses involving powder X‐ray diffraction, theoretical simulations, and high‐resolution transmission electron microscope. Optical‐pump terahertz‐probe spectroscopic measurements unveiled carrier mobility in DHHBTN‐based 2D MOFs spanning from 0.69 to 3.10 cm2 V−1 s−1. Among M–DHHBTN famility, Cu‐DHHBTN displayed high electrical conductivity reaching 0.21 S cm−1 at 298 K with thermal activation behavior. This work leverages the “branched conjugation” of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double‐pore structures for future applications.
Angiogenic and anti‐angiogenic factors during the post‐hatching growth of the quail (Coturnix coturnix japonica) spleen
Authors: Bayram Bayram , Liman Narin , Alan Emel , Sağsöz Hakan 
Published: April 2024

AbstractVascular endothelial growth factor (VEGF) family members are responsible for endothelial cells' growth, proliferation, migration, angiogenesis, vascular permeability, and differentiation and proliferation of non‐endothelial cell types. VEGF and its receptors are found in mammalian lymphoid organs. The present study was conceived to determine (a) the presence and localization of angiogenic VEGF and its receptors (Fms‐like tyrosine kinase 1 [Flt1/fms], fetal liver kinase 1 [Flk1]/kinase insert domain receptor [KDR], Fms‐like tyrosine kinase 4 [Flt4]) and vascular endothelial growth inhibitor (VEGI) in the quail spleen; and (b) whether their expressions in the spleen components change during the post‐hatching growth of the organ, using immunohistochemistry. Immunohistochemical stainings showed that VEGI, VEGF, and VEGF receptors were expressed in many components, including the vascular endothelial and smooth muscle cells, ellipsoid‐associated cells (EACs), and immune cells, of quail spleen and that VEGF and its receptors' immunostaining intensity scores (ISs) varied depending on the post‐hatching growth period, while VEGI‐IS did not change. In addition, ISs of VEGI, VEGF, Flt1/fms, and Flt4 in EACs were weak to moderate, while flk1/KDR‐IS in EACs adjacent to the capsule of Schweigger‐Seidel sheaths (ellipsoids) was higher than other proteins, supports a more important and specific role of Flk1/KDR in the EAC function. These specific expressions of VEGI, VEGF, flt1/fms, flk1/KDR, and flt4 proteins in splenic cell types suggest their particular roles, in the functional development of splenic components and thus, are critical to post‐hatching maturation of quail spleen. These findings indicate that the expression levels of VEGF, Flt1/fms, and Flt4, except Flk1/KDR, are low in the quail spleen, and only a few components of the spleen express VEGF, Flt1/fms, and Flt4 under normal conditions.