bluuebunny/crossref_metadata_2025_split huggingface dataset:
PGY‐2 emergency medicine residents are more efficient when paired with an early clinical medical student
Authors: Liang Nicole , Jewell Corlin M. , Hekman Dann J. , Shank Christopher , Schnapp Benjamin H. 
Published: October 2024

AbstractObjectivesThere is a concern that provide increased extraneous cognitive load when paired with residents on shift. However, this may be offset by the decrease in extraneous load they may provide to the residents they are paired with by offloading basic patient care tasks. We hypothesized that these forces may not be balanced.MethodsWe conducted a retrospective observational analysis of PGY‐2 emergency medicine residents and junior medical students at a single academic emergency department (ED) in the Midwest. A series of efficiency metrics (relative value unit [RVUs], patients per hour [PPH], time to note completion, and resident assignment to disposition [RATD]) as well as one quality metric (number of return ED visits; “bouncebacks”) were compared for resident shifts in which a student was paired with the resident as well those in which no student was paired utilizing a regression model.ResultsA total of 1844 records met the inclusion criteria (214 shifts with a paired medical student and 1630 without). After covariates were adjusted for, medical student shift status was a statistically significant predictor of increases in PPH (p < 0.0001) and RVUs (p = 0.0161) but was not significantly associated with RATD (p = 0.6941), log‐time to note completion (p = 0.1604), or bounceback status (p = 0.9840). Shifts where residents were paired with medical students were predicted to see an additional 1.131 (95% confidence interval [CI] 0.660–1.602) PPH and produce an additional 1.923 RVUs (95% CI 1.130–3.273) per shift relative to shifts without medical students.ConclusionsWhen junior medical students were paired with a PGY‐2 resident on ED shifts, there was a significant increase in the PPH and RVUs generated when compared with shifts in which no medical student was paired with them.
Salience network segregation mediates the effect of tau pathology on mild behavioral impairment
Authors: Iordan Alexandru D. , Ploutz‐Snyder Robert , Ghosh Bidisha , Rahman‐Filipiak Annalise , Koeppe Robert , Peltier Scott , Giordani Bruno , Albin Roger L. , Hampstead Benjamin M. 
Published: October 2024

AbstractINTRODUCTIONA recently developed mild behavioral impairment (MBI) diagnostic framework standardizes the early characterization of neuropsychiatric symptoms in older adults. However, the joint contributions of Alzheimer's disease (AD) pathology and brain function to MBI remain unclear.METHODSWe test a novel model assessing direct relationships between AD biomarker status and MBI symptoms, as well as mediated effects through segregation of the salience and default‐mode networks, using data from 128 participants with diagnosis of amnestic mild cognitive impairment or mild dementia—AD type.RESULTSWe identified a mediated effect of tau positivity on MBI through functional segregation of the salience network from the other high‐level, association networks. There were no direct effects of AD biomarkers status on MBI.DISCUSSIONOur findings suggest that tau pathology contributes to MBI primarily by disrupting salience network function and emphasize the role of the salience network in mediating relationships between neuropathological changes and behavioral manifestations.Highlights
Network segregation mediates Alzheimer's disease (AD) pathology impact on mild behavioral impairment (MBI).
The salience network is pivotal in linking tau pathology and MBI.
This study used path analysis with AD biomarkers and network integrity.
The study evaluated the roles of salience, default mode, and frontoparietal networks.
This is the first study to integrate MBI with AD biomarkers and network functionality.
Proton‐Coupled Electron Transfer in Photoelectrochemical Alcohol Oxidation Enhanced by Nickel‐Based Cocatalysts
Authors: Gao Bin , Mu Xiaowei , Feng Jianyong , Huang Huiting , Liu Jianming , Liu Wangxi , Zou Zhigang , Li Zhaosheng 
Published: October 2024

AbstractUsing biomass oxidation reactions instead of water oxidation reactions is optimal for accomplishing biomass conversion and effective hydrogen generation. Here, we report that α‐Fe2O3 photoanodes with a NiOOH cocatalyst exhibit excellent performance for photoelectrochemical oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA). The conversion efficiency for HMF reaches 98.5 %, while the selectivity for FDCA is 94.2 %. We revealed that HMF is oxidized through a spontaneous proton‐coupled electron transfer (PCET) process with the high‐valent phase of the Ni‐based catalyst. The dangling oxygen and bridging oxygen of the high‐valent phase species serve as proton‐accepting sites. Furthermore, we pointed out that the deprotonated bond dissociation free energy difference between the catalysts and alcohols is the thermodynamic trigger for the PCET process. This study provides a reasonable explanation for the alcohol oxidation reaction, which is beneficial for designing biomass conversion systems.
Synthesis and Structural Characterization of Carbazole‐Tailored Luminescent Triarylmethyl Radical and its Stable Cation
Authors: Tang Chunlin , Zhu Yuxin , Jin Jian , Zhang Shuai , Zhou Kang , He Zikai 
Published: October 2024

AbstractThe development of novel luminescent radicals, characterized by their unique doublet emission, endows a significant challenge. In this study, we reported the synthesis of a luminescent neutral radical, BCzAnM‐R, tailored by two carbazolyl groups and an anthryl group to achieve a nonalternant structure. It exhibited near‐infrared emission with a peak at 1020 nm in toluene. Interestingly, its corresponding cation, BCzAnM‐C, was synthesized through an unconventional SnCl2‐mediated reduction‐aromatization‐oxidation reaction in one‐pot and gram‐scale. The cation demonstrated remarkable stability for up to weeks in ambient conditions and facilitated the silica‐gel chromatography isolation as an organic salt with SnCl3− as the counter ion. The carbazolyl groups effectively modulate molecular structures, photophysical properties, and stabilities. Notably, BCzAnM‐R represents the first luminescent triarylmethyl radical with two carbazolyl groups directly attached to the central carbon.
Dual‐Anionic Coordination Manipulation Induces Phosphorus and Boron‐Rich Gradient Interphase Towards Stable and Safe Sodium Metal Batteries
Authors: Feng Yi‐Hu , Liu Mengting , Qi Wenli , Liu Haoliang , Liu Qiang , Yang Chao , Tang Yongwei , Zhu Xu , Sun Shuai , Li Yuan‐Meng , Chen Tian‐Ling , Xiao Bing , Ji Xiao , You Ya , Wang Peng‐Fei 
Published: October 2024

AbstractHigh‐voltage sodium metal batteries (SMBs) present a viable pathway towards high‐energy‐density sodium‐based batteries due to the competitive cost advantage and abundant supply of sodium resources. However, they still suffer from severe capacity decay induced by the notorious decomposition of the electrolyte under high voltage and unstable cathode/electrolyte interphase (CEI). In addition, the high reactivity of Na metal and flammable electrolytes push SMBs to their safety limits. Herein, a special dual‐anion aggregated Na+ solvation structure is designed in a nonflammable trimethyl phosphate‐based localized high‐concentration electrolyte, and a gradient CEI enriched with phosphorus and boron compounds is formed on the cathode. This thin and stable interphase effectively suppresses the parasitic reaction, improves the interfacial stability of the cathode, and facilitates Na+ transport through the interface by the synergistic effect of multi‐components, thus optimizing the cycling stability and safety of SMBs. The Na0.95Ni0.4Fe0.15Mn0.3Ti0.15O2//Na batteries employing such electrolyte provide a discharge capacity of 167.5 mAh g−1 and high retention in the capacity of 85.2 % after 800 cycles at 1 C. This approach offers a general strategy for the design of flame‐retardant high‐voltage electrolytes and the practical application of SMBs.
Catalytically Active Site Mapping Realized through Energy Transfer Modeling
Authors: Thompson William J. , Maldeni Kankanamalage Buddhima K. P. , Thaggard Grace C. , Park Kyoung Chul , Martin Corey R. , Niu Jia , Byers Jeffery A. , Shustova Natalia B. 
Published: October 2024

AbstractThe demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.
Amorphous Nanobelts for Efficient Electrocatalytic Ammonia Production
Authors: Su Ziming , Chen Xiangyu , Sun Mingke , Yang Xiuyi , Kang Jianxin , Cai Zhi , Guo Lin 
Published: October 2024

AbstractOne‐dimensional (1D) amorphous nanomaterials combine the advantages of high active site concentration of amorphous structure, high specific surface area and efficient charge transfer of 1D materials, so they present promising opportunities for catalysis. However, how to achievie the balance between the high orientation of 1D morphology and the isotropy of amorphous structure is a significant challenge, which severely obstructs the controllable preparation of 1D amorphous materials. Guided by the hard‐soft acids‐bases theory, here we develop a general strategy for preparing 1D amorphous nanomaterials through the precise modulation of bond strength between metal ions and organic ligands for a moderated fastness. The soft base dodecanethiol (DT) is multifunctionally served as both structure‐regulating agent and morphology‐directing agent. Compared with the borderline acids (e.g. Fe2+, Co2+, Ni2+) to construct amorphous structure, soft acid of Cu+ which produced crystalline nanobelts can still be amorphized by reducing the hardness of Cu ions through redox reaction to weak Cu−SR bond. Due to the combined advantages of amorphous structure and one‐dimensional morphology, amorphous CuDT nanobelts exhibited excellent electrocatalytic activity in electrochemical nitrate reduction, outperformed most of the reported Cu‐based catalysts. This work will effectively bridge the gap between traditional 1D crystalline nanomaterials synthesis and their amorphization preparation.
Nickel Dynamics Switches the Selectivity of CO2 Hydrogenation
Authors: González José Manuel , Sabadell‐Rendón Albert , Kaźmierczak Kamila , Euzenat Florian , Montroussier Nicolas , Curulla‐Ferré Daniel , López Núria 
Published: October 2024

AbstractThe Reverse Water Gas‐Shift reaction (CO2+H2
CO+H2O) allows to balance syn‐gas under industrial conditions. Nickel has been suggested as a potential catalyst but the temperature required is too high, more than 800 °C, limiting practical implementation but when lowering the temperature methanation occurs. Simulations via Density Functional Theory on well‐defined surfaces have systematically failed to reproduce these experimental results. But under reaction conditions, Ni surfaces are not static and DFT models coupled to microkinetics show that low temperatures (high CO coverages) drive the generation of Ni adatoms that are the active sites for methanation. At higher temperatures, the adatom population decreases, and the selectivity towards CO increases. Thus the mechanism behind the selectivity switch is driven by the dynamics induced by reaction intermediates. Our work contributes to the inclusion of dynamic aspects of materials under reaction conditions in the understanding of complex catalytic behaviour.
Anion Exchange Membrane Water Electrolysis at 10 A ⋅ cm−2 Over 800 Hours
Authors: Zheng Yiwei , Ma Wenchao , Serban Ariana , Allushi Andrit , Hu Xile 
Published: October 2024

AbstractAnion exchange membrane water electrolyzer (AEMWE) is a potentially cost‐effective technology for green hydrogen production. Although the normal current densities of AEMWEs are below 3 A ⋅ cm−2, operating them at higher current densities represents an efficient, but little‐explored approach to decrease the total cost of hydrogen production. We show here that a benchmark AEMWE has an operational lifetime of only seconds at an ultrahigh current density of 10 A ⋅ cm−2. By using a more conductive and robust AEM, and judicious choices of ionomers, catalyst, and porous transport layer, we have developed AEMWEs that stably operate at 10 A ⋅ cm−2 with extended lifetimes. The optimized AEMWE has an operational lifetime of more than 800 hours, a 5‐order magnetite improvement over the current benchmark. The cell voltage is only 2.3 V at 10 A ⋅ cm−2, comparable to those of the state‐of‐the‐art devices operating at current densities lower than 3 A ⋅ cm−2. This work demonstrates the potential of ultrahigh current density AEMWEs.
Hydrogen‐Bonded Complexes of HPN⋅ and HNP⋅ Radicals with Carbon Monoxide
Authors: Jiang Junjie , Huang Longtian , Zhu Bifeng , Fan Wenbin , Wang Lina , Zhang Igor Ying , Fang Wei , Trabelsi Tarek , Francisco Joseph S. , Zeng Xiaoqing 
Published: October 2024

AbstractPhosphorus mononitride (PN) is a carrier of phosphorus in the interstellar medium. As the simplest derivatives of PN, the radical species HPN⋅ and HNP⋅ have remained elusive. Herein, we report the generation, characterization, and photochemistry of HPN⋅ and HNP⋅ in N2‐matrix at 3 K. Specifically, HPN⋅ was formed as a weakly bonded complex with CO in the matrix by 254 nm photolysis of the novel phosphinyl radical HPNCO⋅. The ⋅NPH−CO complex is extremely unstable, as it undergoes spontaneous isomerization to the lower‐energy isomer ⋅PNH−CO through fast quantum mechanical tunneling (QMT) with a half‐life of 6.1 min at 3 K. Upon further irradiation at 254 nm, the reverse conversion of ⋅PNH−CO to ⋅NPH−CO along with dehydrogenation to yield PN was observed. The characterization ⋅NPH−CO and ⋅PNH−CO with matrix‐isolation IR spectroscopy is supported by D, 15N, and 13C isotope labeling and quantum chemical calculations at the XYGJ‐OS/AVTZ level of theory, and the mechanism by hydrogen atom tunneling is consistent with multidimensional instanton theory calculations.
Hydrogenation Reactions with Heterobimetallic Complexes
Authors: Abhyankar Preshit C. , Thomas Christine M. 
Published: October 2024

AbstractHydrogenations are fundamentally and industrially important reactions that are atom economical paths to synthesize value‐added products from feedstock chemicals. The cooperative effects of two or more metal centers in multimetallic active sites is a successful strategy to activate small molecules and facilitate catalytic reactions, and this strategy has been recently applied to catalytic hydrogenation reactions. Furthermore, heterobimetallic complexes have been well‐documented to provide novel reaction pathways and improved selectivity, compared to their homo‐bimetallic and monometallic analogues. This minireview provides a historical perspective on the development of heterobimetallic catalysts for the hydrogenation of unsaturated substrates and describes recent developments in this burgeoning research area.
Phenanthridine‐based Covalent Organic Frameworks for Boosting Overall Solar H2O2 Production
Authors: Yue Jie‐Yu , Luo Jing‐Xian , Pan Zi‐Xian , Xu Qing , Yang Peng , Tang Bo 
Published: October 2024

AbstractSolar‐driven H2O2 production via the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) dual channels is green and sustainable but severely restricted by the sluggish reaction kinetics. Constructing intriguing photocatalysts with effective active centers is a shortcut to breaking the kinetic bottleneck with great significance. Herein, we synthesize two novel neutral phenanthridine‐based covalent organic frameworks (PD‐COF1 and PD‐COF2) for photosynthesizing H2O2. Compared to the no phenanthridine counterpart (AN‐COF), the H2O2 photosynthetic activities of PD‐COF1 and PD‐COF2 are markedly boosted. In air and pure water without sacrificial agents, under Xe lamp and natural sunlight, the H2O2 photogeneration rate of PD‐COF2 is 6103 and 3646 μmol g−1 h−1, respectively. Further experimental and theoretical inspections demonstrate that introducing phenanthridine units into COFs smoothly modulates the charge carrier dynamics and thermodynamically favors the generation of crucial OOH* and OH* intermediates in the ORR and WOR paths, respectively. Additionally, this is the first time the neutral phenanthridine moiety serves as the photooxidation unit for 2e− WOR towards H2O2 photoproduction. The current work sheds light on exploring novel catalytic centers for high‐performance H2O2 evolution.
Near‐Infrared‐Emitting Helically Twisted Conjugated Frameworks Consisting of Alternant Donor‐π‐Acceptor Units and Multiple Boron Atoms
Authors: Dong Jiaqi , Chen Lingjuan , Feng Qingliang , Yang Deng‐Tao 
Published: October 2024

AbstractA novel design strategy to construct bright and narrow near‐infrared (NIR) emission materials with suppressed shoulder peaks can significantly enhance their performance in various applications. Herein, we have successfully synthesized a series of helically twisted D‐π‐A conjugated systems bridged by boron atoms, achieving bright red to near‐infrared (NIR) emissions with notably narrow full‐width at half‐maximum (FWHM) values of 35 nm (0.08 eV) and photoluminescence quantum yields (PLQY) up to 80 %. These compounds display red‐shifted emissions up to 753 nm in higher concentrations. Cis/trans configurational isomers of multi‐boron‐bridged molecule BN3 exhibit similar photophysical properties. The unique combination of boron‐induced coordination‐enhanced charge transfer (CE‐CT) and the helically twisted conjugated framework is pivotal in achieving the red‐shifted, narrowband emission. X‐ray crystallographic analysis of BN2 and BN3‐a reveals that the extension of boron‐bridged D‐π‐A skeletons significantly increases the distortion of the skeleton. Systematic theoretical calculations show how the boron CE‐CT mechanism, in conjunction with the helical twist, leads to the narrowing of emission bands while simultaneously red‐shifting them into the NIR region. This work could open new avenues for the development of advanced materials with tailored optical properties, particularly in the challenging and highly sought‐after NIR spectrum.
The use of surgical sealant to repair intubation‐related tracheal injury
Authors: Cox C. , Crerar‐Gilbert A. , Madden B. 
Published: October 2024

SummaryThis case study describes the management of a tracheal injury following emergency intubation in a 56‐year‐old man. After collapsing from heavy alcohol ingestion, intubation was performed using a bougie, leading to a punctate tracheal wound. Initial conservative treatment with antibiotics was followed by bronchoscopy, revealing a tracheal laceration. Rigid bronchoscopy was then performed, and the wound was closed using BioGlue® surgical sealant. The patient made a full recovery, with follow‐up bronchoscopy confirming complete healing. This case highlights the effectiveness of BioGlue® as a minimally invasive alternative for tracheal wound closure, reducing the need for more complex interventions.
Photoinduced Selective Hydrogenation of Nitroarenes Mediated by Ag@ZnO Nanocomposite via a Facile Green In Situ Approach
Authors: Hazarika Biswajyoti , Hazarika Biplop Jyoti , Ahmed Md. Juned K. 
Published: October 2024

ABSTRACTA facile and environmentally benign methodology has been adopted for the synthesis of novel core–shell Ag@ZnO nanocomposite using Imperata cylindrica (L.) leaf extract. Characterization was performed by UV–Vis, FT‐IR, PL, SEM‐EDX, TEM‐SAED, and XRD. The nanocomposite demonstrated excellent efficiency in the reduction of various nitroarenes to their corresponding arylamines under visible light irradiation at room temperature. The advantages of this catalyst encompass its ease of accessibility, operational simplicity, and minimal loading to achieve high yields with excellent selectivity. It is effective across a broad range of substrates in short reaction times with green solvent. The heterogenous nature of the catalyst ensures exceptional reusability, highlighting its efficacy and versatility in organic transformations.
Well Defined Phosphine Free Ni‐Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines
Authors: Maji Ankur , Singh Ovender , Sharma Keshav , Kumari Sheela , Ghosh Kaushik 
Published: October 2024

AbstractIn this work, we unveil a novel synthesis of bench stable Ni (II) complexes supported by tetradentate Schiff‐base ligands and the complexes were devoid of any phosphine or phosphine‐based ligand. These Ni‐complexes were successfully applied for the dehydrogenation of secondary alcohols for ketone and ketazine syntheses. Secondary alcohols with different functional groups were well tolerated during catalytic cycle. Moreover, we successfully extended this protocol for the synthesis of biologically significant ketones and ketazines. On the basis of various control experiments, probable reaction pathway was proposed, and an acceptorless alcohol dehydrogenation mechanism was suggested.
Application of Hawkes Volatility in the Observation of Filtered High‐Frequency Price Process in Tick Structures
Authors: Lee Kyungsub 
Published: October 2024

ABSTRACTThe Hawkes model is suitable for describing self and mutually exciting random events. In addition, the exponential decay in the Hawkes process allows us to calculate the moment properties of the model. However, owing to the complexity of the model and formula, few studies have examined the Hawkes volatility. In this study, we derive a variance formula that is directly applicable under the general settings of both unmarked and marked Hawkes models for tick‐level price dynamics. In the marked model, the linear impact function and possible dependency between the marks and underlying processes are considered. The Hawkes volatility is applied to the mid‐price process filtered at 0.1‐s intervals to show reliable results. Furthermore, intraday estimation is expected to widely utilized in real‐time risk management. We also note the increasing predictive power of the intraday Hawkes volatility over time and examine the relationship between futures and stock volatilities.