bluuebunny/crossref_metadata_2025 huggingface dataset:
Unveiling the Effect of Grain Size on Biodegradation of Magnesium
Authors: Medeiros Mariana P. , Lopes Debora R. , Carvalho Amanda P. , Hohenwarter Anton , Kawasaki Megumi , Cupertino‐Malheiros Livia , Figueiredo Roberto B.
Published: October 2024

It is known that the grain size plays a major role in the mechanical properties of magnesium. The aim of the present study is to evaluate its role in long‐term corrosion rate. Samples of pure magnesium with grain sizes in the range of 0.9–82 μm are produced through severe plastic deformation and annealing treatments. The mechanical properties are evaluated using tensile tests and the corrosion behavior is evaluated using immersion tests in Hank's solution. A maximum yield stress of ≈150 MPa is observed in the sample with 1.8 μm of grain size and an elongation larger than 25% is observed in the ultrafine‐grained sample. Ultrafine‐ and fine‐grained magnesium display uniform corrosion with a decreasing corrosion rate while coarse‐grained magnesium displays localized corrosion with an accelerated corrosion rate. A corrosion rate of ≈0.2 mm year−1 is observed in the ultrafine‐ and fine‐grained magnesium. The corrosion product layer of the fine‐grained magnesium contains elements absorbed from the media. An analysis of the data in the literature suggests that grain refinement changes the corrosion type from localized to uniform corrosion. The exact relationship between grain size and the corrosion rate remains elusive.
Design of VNbTaMox Body‐Centered‐Cubic Refractory High‐Entropy Alloys with Excellent Ultrahigh‐Temperature Mechanical Properties and Ductility
Authors: Wang Meng , Song Jiaxing , Tian Quanwei , Zhong Xiting , Kou Gang , Chen Zhen , Cheng Xingwang
Published: October 2024

To design metal materials that combine high‐temperature strength with room‐temperature ductility, three kinds of body‐centered‐cubic (BCC) refractory high‐entropy alloys (RHEAs) with different Mo element contents are screened and prepared by combining several parameters. The room‐temperature ductility and excellent high‐temperature (1500 °C) mechanical properties are investigated. Combined with the microstructure test, the characteristic of fracture and deformation is also discussed. RHEAs studied herein have great compressive yield strength approximately ranging from 1324.5 to 1424.4 MPa with excellent compressive ductility ranging from 20.7% to 44.2% at room temperature. At 1500 °C, the yield strengths of three RHEAs are over 335.47 MPa at 10−3 s−1 strain rate, which is rarely found in traditional metals materials. The excellent mechanical properties of these three RHEAs at both room and high temperature as a promising material are beneficial to future high‐temperature application.
Fireproof Solid Polymer Electrolyte with Chemically Bonded Phosphorus Toward Stable and Safe Lithium‐Metal Battery
Authors: Li Zhenxi , Zhu Shuangshuang , Gao Shilun , He Yayue , Ding Hang , Yang Dandan , Yang Huabin , Cao Peng‐Fei
Published: October 2024

Lithium‐metal batteries (LMBs) are considered one of the most promising next‐generation high‐energy‐density battery systems. However, the leakage problem and fire hazard of commercial liquid electrolytes hinder their practical applications. Herein, a flame‐retardant solid polymer electrolyte (FRSPE) is fabricated by in situ polymerization of methyl methacrylate (MMA), allyl diglycol carbonate (ADC), and flame‐retardant monomer, i.e., diethyl vinyl phosphonate (DEVP), in which the phosphorus is chemically bonded to the polymer matrix to avoid the parasitic reaction between flame‐retardant molecules with lithium (Li) anode. Compared with the previously reported solid polymer electrolytes (SPEs) possessing free phosphorus, significantly increased efficiency of flame‐retardant and improved electrochemical performance can be achieved. With a wide electrochemical window (≈4.4V), high ionic conductivity (1.8 × 10−4 S cm−1), and superior compatibility with Li anode, the assembled Li/FRSPE/LiFePO4 (LFP) cell exhibits stable cycling over a wide temperature range (capacity retention of 70.9%@1000 cycles and 69.1%@200 cycles at 25 and 80 °C, respectively). Furthermore, the high‐voltage full cells, e.g., Li/LiCoO2 (LCO) and Li/LiNi0.8Co0.1Mn0.1O2 (NCM811), with FRSPE also deliver excellent cycling performance. The current design principle with flame‐retardant chemically bonded in the polymer framework can provide a new pathway for developing practical, safe, and stable LMBs.
Adaptive Optoelectronic Transistor Enabled by Nanoporous Patterning for Low‐Contrast Image Recognition
Authors: Wang Yiru , Hua Jing , He Xiang , Liu Shanshuo , Li Jiahao , Zhang Hongxin , Fu Jingwei , Wang Le , Li Wen , Yi Mingdong , Xie Linghai , Huang Wei , Ling Haifeng
Published: October 2024

Photoadaptive neuromorphic device is fundamental for artificial vision system to effectively perceive and accurately process information in complex light scenes. However, adaptive optoelectronic device remains a challenge due to the difficulty in achieving the light‐dependent modulation of charge dynamics. Here, an adaptive optoelectronic transistor enabled by the conformal nanoporous patterning that can perform the biomimetic eye functions and facilitate the precise contrast enhancement under harsh lighting conditions is reported. The enhanced light absorption, photoexciton separation, and charge injection properties are originated from the localized electric field in the nanoporous optoelectronic transistor, which further endow the light intensity‐dependent charge trapping and de‐trapping dynamics, realizing the adaptive decay rate of conduction states. Based on the improved device performances and the adaptive properties, an artificial vision system is constructed to present the biomimetic eye model with visual selective attention functions and a contrast enhancement in the low‐contrast sub‐images. The eye rotation and closing functions, as well as a high recognition accuracy of 95.4% for non‐ideal image with a contrast as low as 0.8% are demonstrated. This study provide an approach for the photoadaptive neuromorphic device and support their visual adaptation applications in biomimetic eye system.
Oligonucleotide‐Linked Lipid Nanoparticles as a Versatile mRNA Nanovaccine Platform
Authors: Im San Hae , Chung Youseung , Duskunovic Nevena , Choi Heewon , Park Su‐Hyung , Chung Hyun Jung
Published: October 2024

An effective delivery platform is crucial for the development of mRNA vaccines and therapeutics. Here, a versatile platform utilizing cholesterol‐modified oligonucleotides (L‐oligo) that bind to the mRNA within lipid nanoparticles (LNP), and enables the effective delivery of the mRNA into target cells is introduced. mRNA incorporated into LNPs via linkage with L‐oligo, termed oligonucleotide‐linked LNP (lnLNP), is superior in cellular uptake and transfection efficiency in target cells in vitro and in vivo, compared to the conventional LNP formulations. It is further applied lnLNP as an mRNA vaccine platform for SARS‐CoV‐2, demonstrating robust induction of neutralizing activity as well as polyfunctional SARS‐CoV‐2‐specific T‐cell response in vivo. The current strategy can be versatilely applied to different LNP platforms, for vaccine and therapeutic applications against various diseases, such as infections and cancers.
Protective and Damaging Mechanisms of Neuromelanin‐Like Nanoparticles and Iron in Parkinson's Disease
Authors: Liu Lizhu , Wang Tianying , Zhou Hao , Zheng Jinyang , Liu Qiang , Wang Wei , Liu Xinxin , Zhang Xiuming , Ge Dongtao , Shi Wei , Sun Yanan
Published: October 2024

Parkinson's disease (PD) pathology speculates that neuromelanin (NM) and iron ions play a significant role in physiological and pathological conditions of PD. Because the difficult accessibility of NM has limited targeted research, synthetic melanin‐like nanoparticles have been used to instead. In this report, the eumelanin and pheomelanin‐like polydopamine (PDA) nanoparticles are prepared that can be used to simulate natural NM with or without chelating iron ion and studied the redox effects in vitro and in vivo on neuronal cells and PD. The synthetic pheomelanin‐like PDA nanoparticles have much stronger redox activity than eumelanin‐like PDA nanoparticles without or with iron ion. They can protect neurons by scavenging reactive oxygen species (ROS), while cause neuronal cell death and PD due to excessive binding of iron ions. This work provides new evidence for the relationship among two structural components of NM and iron in PD as well as displays the different effects on the roles of eumelanin and pheomelanin in redox activity under physiological or pathological conditions, which provide a new effective choice for cellular and animal models of PD and offer theoretical guidance for targeted treatment and mechanism research on PD.
Sterically Hindered Organogels with Self‐Healing, Impact Response, and High Damping Properties
Authors: Cheng Jianfeng , Fu Songbao , Ma Shitao , Zhang Zhipeng , Ma Chunfeng , Zhang Guangzhao
Published: October 2024

Organogel materials are vital for impact or shock resistance because of their highly tailored dynamic properties. However, concurrently achieving excellent anti‐impact and damping performances, high stability, and self‐healing properties is challenging. Herein, a novel intelligent protective organogel (IPO) comprising a dynamic boronic ester containing poly(urethane–urea) as the network skeleton with a matching mesh size is synthesized, the network precisely entraps the hyperbranched fluid used as the bulky solvent via steric hindrance. The IPO exhibits self‐healing ability, excellent impact responsiveness (a 1950‐fold increase in flow stress under various impact speeds), and energy dissipation (the loss factor >0.8 from 10−4  to 104 Hz). The IPO maintains its dynamic mechanical properties during hot pressing and hydrolysis, exhibiting  high stability. Furthermore, the IPO exhibits omnibearing protection. When used as a protective coating, the IPO dissipates the impact force by 87% and 89% of control upon passive and active impact, respectively. When used as a shock pad, it attenuates 91% of the amplitude in the high‐frequency vibrations. This study offers a novel perspective on the synthesis of tailored sterically hindered organogel and provides valuable insights into the development of next‐generation intelligent protective materials that exhibit impact and vibration resistance.
Hybrid Screen Printable Electrolyte for Large‐Scale Flexible Electrochromic Display Production
Authors: Leite Fábio A. S. , Wierzchowiec Piotr , Pinheiro Carlos , Maggini Laura , Bonifazi Davide
Published: October 2024

This study presents the development of a novel screen printable quasi‐solid polymer electrolyte (p‐QSPE) for Electrochromic Displays (ECDs) applications. p‐QSPE is composed of three key components: polyvinylidene fluoride (PVDF), a high‐dielectric constant polymer that ensures high ionic conductivity in solid‐state; glyceril propoxy triacrylate (GPTA), a UV‐cross‐linkable monomer that provides structure and durability for overprinting; titanium dioxide (TiO₂) nanoparticles, which modulate the electrolyte's rheological properties for screen printing; reducing the solvent (PC:EC) content to only 35.90 wt.%. Electrochemical Impedance Spectroscopy (EIS) revealed that this well‐designed formulation achieved an ionic conductivity of 1.17 × 10−3 S cm−1 at room temperature, surpassing the threshold required for commercial applications. Moreover, p‐QSPE facilitated the production of fully screen printed ECDs in an industrial printing line, streamlining their production process and achieving an optimal balance between printability, overprint resilience, and device performance. Operational tests for the ECDs showed fast switching times (<6 s for t90 and <2 s for t75) across a wide temperature range (−20 °C to 80 °C). Additionally, the electrolyte demonstrated low charge consumption (2.10 ± 0.11 mC cm−2) and a lifespan exceeding 10 000 cycles. These results highlight the potential of p‐QSPE as a screen printable, high‐performance electrolyte, capable of advancing ECD manufacturing by enabling the production of fully screen‐printed, performing ECDs.
UV­B Persistent Luminescence of CaF2:Gd3+ for Radiation Labeling and Tracing
Authors: Zhao Wenting , Li Leipeng , Li Tao , Qiu Jianrong , Yang Yanmin
Published: October 2024

Persistent luminescence (PersL) has attracted considerable attention in the last two decades for its potential applications in the fields of emergency indicators, energy‐saving lighting, biomedical imaging, and dynamic anti‐counterfeiting. However, the wavelengths of PersL reported so far usually fall into the visible and near‐infrared range. The preparation of advanced optical materials bearing UV PersL remains elusive. Here the PersL characteristic of CaF2:Gd3+ is systematically studied. After exposure to X‐ray radiation, CaF2:Gd3+ continues to emit UV­‐B (UVB) PersL peaking at 313 nm, corresponding to the 6P7/2 → 8S7/2 transition of Gd3+. By virtue of X‐ray photoelectron spectroscopy measurements, the valence variation model is excluded to explain the UVB PersL of CaF2:Gd3+. Finally, it is demonstrated that such UVB PersL of CaF2:Gd3+ can be used for static labeling and dynamic tracing.
Synthesis of Vinyl Sulfones and Benzoxathiins via Base‐Catalyzed Reactions of o‐Hydroxyaryl Thiosulfonates and Ynones
Authors: Tang Delin , Zhang Fang , Luo Jinyun , Cai Zhihua , He Lin , Du Guangfen
Published: October 2024

The cyclization reaction and hydrosulfonylation reaction of ynones have been simultaneously realized through a single operation. Under the mediation of cesium carbonate, different S‐(α‐hydroxyaryl) aryl thiosulfonates reacted with various ynones to produce functionalized vinyl sulfones in 37%–83% yields with E‐selectivity. At the same time, a variety of benzoxathiins were formed in 42%–97% yields.
Catalyst‐Controlled Regiodivergent C−H Alkynylation of 2‐Pyridylthiophenes
Authors: Gui Yuting , Zhao Yaokun , Li Xingchi , Liang Taoyuan , Zhao Shuangliang , Zhang Zhuan
Published: October 2024

Different catalysts are presented to overcome or augment a substrate's innate regioselectivity. Rhodium was found to overcome the innate C3‐selectivity via chelation‐assisted rhodation. Conversely, palladium was found to enhance the innate C5‐selectivity via electrophilic palladation. These reactions allow for the formation of a diverse range of synthetically versatile C3‐ and C5‐alkynylated products from 2‐pyridylthiophenes. Notably, this strategy was successfully employed in the straightforward synthesis of π‐extended functionalized 2‐pyridylthiophenes, which could be converted into more valuable compounds.
Visible‐Light Photoredox‐Catalyzed Trifunctionalization of Unactivated Alkenes via Diamidation and Cyano Migration
Authors: Mohamathu Ghouse Abuthayir , Maheswari Bathula , Murthy Akondi Srirama
Published: October 2024

A visible‐light‐promoted, nitrogen‐centered radical‐initiated trifunctionalization of 5‐hexenonitriles via diamidation and 1,4‐cyano migration, using 1 mol% fac‐Ir(ppy)3 as the photoredox catalyst, is reported. In this protocol, the O‐acylhydroxylamine derivative acts as a bifunctional reagent, and the carbonitrile solvent also participates in the reaction. This transformation proceeds at room temperature, yielding a wide range of functionalized β‐amino nitriles, including the derivatives of natural products and pharmaceuticals.
Social, Economic, and Environmental Impacts of Bio‐Based Versus Fossil‐Derived Polyethylene Production
Authors: Trucillo Paolo , Rizzo Marianna , Errico Daniela , Di Maio Ernesto
Published: October 2024

The urgency to achieve carbon neutrality underlines the importance of shifting from carbon‐based fossils to renewable resources. Bio‐based polyethylene (bio‐PE) is a key component of this transition, which is obtained from natural and renewable sources such as sugarcane. The environmental impact of bio‐PE and fossil‐based PE production is compared building ad‐hoc sustainability indicators while exploring environmental, social, economic, and energetic aspects to provide a comprehensive evaluation. This methodology involves analyzing the entire lifecycle of both processes for polyethylene production, from extraction/harvesting to post‐disposal actions, such as mechanical recycling or incineration. The main goal is to represent numerous sustainability indicators on a radar diagram, thus comparing process scores of sustainability. Bio‐PE production has significantly higher scores than fossil carbon PE in terms of global warming potential (from cradle‐to‐gate), safety, and contribution to ozone depletion. Additionally, bio‐PE offers a quite better scenario in terms of mass input and energy operating costs. On one side, bio‐PE exhibits similar potential of eutrophication and acidification; on the other side, it also guarantees almost same potential revenues. This can address the choice to the most sustainable post‐disposal method, that regards the mechanical separation and re‐introduction of end‐of‐life PE into the manufacturing process.
Untreated Natural Wood‐Based Triboelectric Nanogenerator for Floor Charge Energy Harvesting
Authors: Antony Liya , Giuri Antonella , Mastria Rosanna , Kovalska Evgeniya , Kirkwood James , Danaa Alshammari , Russo Saverio , Craciun Monica F. , Rizzo Aurora
Published: October 2024

Triboelectric nanogenerators (TENGs) represent an emerging technology that converts mechanical energy into electrical energy. Nonetheless, the most efficient TENGs are based on synthetic plastics or chemically treated materials. This study demonstrates a chemical‐free, natural wood‐based TENG with performance comparable to chemically treated wood‐TENGs. The natural wood is paired with different polymers as an opposite layers in contact‐separation mode, using various electrodes. The pristine wood‐polytetrafluoroethylene (PW: PTFE) TENG device with a large area of 3 × 3 cm2 exhibits a high open circuit voltage of 110 V, a short‐circuit current of 0.72 µA, and generates charge of 23.6 ± 0.3 nC. Finally, to illustrate the viability of PW: PTFE triboelectric devices for practical applications, a prototype with a 20 × 18 cm2 active area is discreetly inserted beneath a carpet to harness the energy generated by individuals walking or running across its surface. The cyclic nature of human motion ensures a sustained regimen of contact and separation, thereby yielding a consistent output of voltage and current, with a maximum open circuit voltage of 110 V, a short‐circuit current of 193 µA, and a charge of 3.5 µC. These findings suggest that pristine wood is a promising material for low‐cost and environmentally friendly TENGs.
Electrocatalytic Reduction of Nitrate/Nitrite to Ammonia on CuCo Nanoparticles Decorated N‐doped Carbon
Authors: Cang Chuanfei , Hua Rong , Shen Guoqing , Ma Mengxue , Chen Yu , Zheng Haoquan
Published: October 2024

Electrocatalytic nitrate (NO3−)/nitrite (NO2−) reduction of ammonia (NH3) provides energy‐saving and sustainable methods for NH3 synthesis. However, both reactions involve multiple electrons and multiple protons, making the reaction process complex with many by‐products. Thus, efficient catalysts are needed to improve the selectivity and yield of ammonia. Herein, the CuCo nanoparticles decorated N‐doped carbon (CuCo‐NC) derived from zeolitic imidazolate framework (ZIF) with a cross‐shaped leaf structure has been synthesized as electrocatalysts for NO3−/ NO2− reduction. The obtained CuCo‐NC possesses Cu‐doped Co metallic nanoparticles, and hierarchical structure, and demonstrated to exhibit good activity and selectivity in electrocatalytic NO3−/NO2− reduction to NH3 synthesis. In the electrocatalytic NO3− reduction of NH3, the Faraday efficiency of NH3 reached 97% and the yield reached 7.17 mg h−1 cm−2 at −0.3 V. In the electrocatalytic NO2− reduction of NH3, the Faraday efficiency of NH3 reached 92% and the yield reached 8.34 mg h−1 cm−2 at −0.3 V, demonstrating good stability in the cyclic electrolysis of both reactions. The CuCo‐NC with a cross‐shaped leaf structure exhibits excellent electrocatalytic NO3−/NO2− reduction activity of CuCo‐NC and therefore highlights the promising potential of bimetallic electrocatalysts for NH3 synthesis.
Water‐Based Activated Carbon Ink for Printed Flexible Biodegradable Supercapacitors
Authors: Sharma Neha , Kandregula Ganapathi Rao , Koshy Aarju Mathew , Ramanujam Kothandaraman , Ray Debdutta , Swaminathan Parasuraman
Published: October 2024

Flexible and printed supercapacitors (SCs) have emerged as reliable power sources for wearable and portable electronics. However, developing these SCs as sustainable and eco‐benign, with high electrochemical performance, remains a challenge. Herein, scalable fabrication of SCs is demonstrated by formulating an activated carbon (AC) printable ink for the direct ink writing (DIW) of SCs. A water‐based ink is prepared using a bio‐degradable cellulose‐based, sodium carboxymethylcellulose (Na CMC), binder replacing the typically used fluorinated binders, which are not environmentally friendly. Na CMC provides a stable ink dispersion with added mechanical and chemical stability to the printed SCs. The AC‐Na CMC electrode produced 127.8 mF cm−2 of specific capacitance. This AC‐Na CMC ink is used to develop fully printed film‐SCs and micro‐SCs (m‐SCs). The m‐SC is fabricated with a printing resolution of 150 µm on photo paper. Using DIW enables scalable production, which is demonstrated by printing an array of m‐SCs to power a micro‐LED. The printed m‐SC also demonstrates high mechanical flexibility, retaining 89.6% of its original capacitance at a bending angle of 90⁰. Na CMC as binder and photopaper as the substrate results in the production of biodegradable SCs extending their applicability to the field of transient electronics.
Monolayer Sodium Titanate Nanobelts as a Highly Efficient Anode Material for Sodium‐Ion Batteries
Authors: Xia Qingbing , Liang Yaru , Cooper Emily R. , Ko Cheng‐Lin , Hu Zhe , Li Weijie , Chou Shulei , Knibbe Ruth
Published: October 2024

Monolayer atomic crystals show significant advantages in improving charge storage kinetics for electrode materials. While notable progress is made, challenges remain in producing nanocrystals with desirable configurations, dimensions, and crystallographic properties. Here, 1D single‐crystal nanobelts assembled from monolayer sodium titanate nanobelts are reported with highly exposed active sites as anode materials for sodium‐ion batteries (SIBs). The unique structural properties of the 1D single‐crystal nanobelts offer excellent electrochemical activity, electrochemo‐mechanical stability, and well‐maintained structural integrity, leading to highly efficient sodium ion storage performance. Insights into the electrochemical reaction processes, as revealed by in situ transmission electron microscopy, in situ synchrotron X‐ray diffraction, and theoretical calculations, indicate that the 1D single‐crystal nanobelts enable favorable sodium ion storage kinetics and a low‐strain characteristic. This facilitates fast charge/discharge capability and long‐term cycling stability for up to 5000 cycles at 20 C. Moreover, the 1D single‐crystal nanobelts demonstrate practical applicability. A pouch cell assembled with the 1D single‐crystal nanobelts anode and iron‐based Prussian blue cathode exhibits highly stable cycling, achieving a low capacity fading ratio of ≈0.05% per cycle over 150 cycles. This study provides an innovative design principle to enhance the charge storage capability of electrode materials through intelligent structural nanoengineering.
Correlating the Photoshunt with Charge‐Collection Losses in Organic Solar Cells
Authors: Kim Eunchi , Christen Leonard , Kirchartz Thomas
Published: October 2024

The low charge carrier mobility of molecular materials is one of the key obstacles to achieving higher efficiencies in organic photovoltaics. Therefore, understanding and quantifying charge collection losses owing to low mobility is an important challenge in organic photovoltaics and other emerging photovoltaic technologies. Here, an approach is proposed to use the photoshunt and its dependence on light intensity as an easily accessible indicator of charge‐collection losses. The physical meaning of the photoshunt is explored using drift‐diffusion simulations and an analytical model. The results show that the recombination current visible as the photoshunt is decreasing with increasing charge carrier mobility. Furthermore, a framework is presented for evaluating the short‐circuit current losses in experimental data using a photoshunt. The study reveals that the charge‐collection efficiency at shortcircuit is strongly influenced by the charge carrier mobility and light intensity.
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

Objectives

There 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.

Methods

We 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.

Results

A 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.

Conclusions

When 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

INTRODUCTION

A 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.

METHODS

We 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.

RESULTS

We 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.

DISCUSSION

Our 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

Using 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

The 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

High‐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

The 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

One‐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

The 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

Anion 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

Phosphorus 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

Hydrogenations 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

Solar‐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

A 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

This 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

A 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

In 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

The 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.