bluuebunny/crossref_metadata_2025_split huggingface dataset:
Topological Magnetic Textures Mediated Magnetocaloric Effect in Janus Monolayer
Authors: He Weiwei , Tang Ziming , Yin Yan , Yi Min , Gong Qihua 
Published: January 2025

AbstractTopological magnetic textures (TMTs) such as skyrmions, merons, and vortices are promising for next‐generation spintronic technology. Here, the prospect of TMTs in cooling technology is explored, and the influence of TMTs on magnetocaloric effect (MCE) in typical Janus monolayers (symmetry‐broken VSi2N4 derivatives) that exhibit prominent Dzyaloshinskii–Moriya interaction (DMI) is specifically elaborated. It is found that the Janus monolayers VSi2N2P2, VSi2N2As2 and VSi2NAs3 allow for versatile TMTs including bimerons, meron pairs and skyrmions. Skyrmions and bimerons are demonstrated to remain stable up to 100 K. Under external magnetic fields, TMTs either experience shrinkage or exhibit a significant magnetization reversal. This results in TMTs‐mediated MCE driven by topological magnetic‐to‐ferromagnetic phase transition, which intrinsically differs from the conventional MCE driven by paramagnetic‐to‐ferromagnetic phase transition. The TMTs‐mediated MCE is revealed to benefit from a combination of pseudo‐first‐order and second‐order phase transition and thus exhibit a broader operating temperature range. These findings offer an in‐depth understanding on the role of TMTs in MCE of Janus monolayers and can inspire nanoscale 2D cooling science and technology.
An Artificial L‐ReLU Neuron with Asymmetric Diffusive Memristor for High‐Accuracy Neuromorphic Systems
Authors: Zou Jianxun , Feng Zhe , Qian Zhibin , Wu Zuheng , Zheng Jingqi , Gao Lubo , Yang Ruotong , Guo Wenbin , Lin Zhihao , Hao Yang , Wang Haochen , Ruan Hao , Xu Zuyu , Zhu Yunlai , Zhang Xumeng , Dai Yuehua 
Published: January 2025

AbstractArtificial neurons with leaky rectified linear unit (L‐ReLU) function can effectively process negative information, enhancing the neuromorphic systems capbility to handle negative values. Memristive devices show great potential in building compact and bio‐plausible artificial neurons, however, a neuron device that supports L‐ReLU functions is still lacking. In this work, a compact L‐ReLU neuron is proposed based on a bipolar asymmetrical diffusive memristor. Utilizing intercalation and leveraging the migration diffusion ratio of Ag ions, devices meeting the characteristics of the L‐ReLU function are fabricated (Ag/TaOx/SiOx/Pt). Thus, the constructed neuron can encode the positive and negative input information into positive and negative spikes, respectively, with L‐ReLU‐like response function. In addition, to address the problem that the frequency only has positive values, a vector frequency (VF) is defined to describe the frequency of the positive and negative spikes. Moreover, a convolutional neural network and You‐Only‐Look‐Once version 3 (YOLOv3) network are constructed with the L‐ReLU neurons for gesture language recognition and target detection tasks, respectively. The network based on L‐ReLU neurons can avoid negative information squandering, showing a higher inference accuracy than the network with ReLU neurons. The results show that the neurons can offer a promising platform for building high‐accuracy neuromorphic systems.
Biological and Mechanical Limitations for Chronic Fast‐Scan Cyclic Voltammetry Sensor Design
Authors: Perillo Mason L. , Gupta Bhavna , Saxena Akash , Veltri Alexandra P. , Li Wen , Siegenthaler James R. , Purcell Erin K. 
Published: January 2025

AbstractFast‐scan cyclic voltammetry (FSCV) is a popular approach for real‐time neurochemical sensing. Using a carbon‐fiber microelectrode (CFME), sensitive neurochemical sensing can be achieved in the acute setting with sub‐second resolution for monoamine neurotransmitters. However, to study neuropsychiatric conditions and neurological functions, it is often of interest to perform longitudinal monitoring of neurotransmitters over chronic timepoints. Despite notable successes, there remains substantial room for improvement in chronic neurochemical sensing performance. Electrode fouling and cellular encapsulation that can occur following surgical implantation can lead to diminished sensor performance over time. Additionally, working and reference electrodes can suffer from etching and polarization that can hinder their longevity and stability. Here, this work reviews current challenges facing chronic neurochemical sensors and discusses state‐of‐the‐art advancements in electrode material and device design choices. This work covers how the biological environment can negatively affect sensing performance and how device design can mitigate these effects. This work also provides examples of state‐of‐the‐art electrode technologies that have been developed to improve chronic neurochemical sensing. Improvements in FSCV as a tool for chronic neurotransmitter sensing will open new opportunities to study neurodegenerative and neuropsychiatric diseases, develop feedback systems for neuromodulation, and explore the neurochemical underpinnings of normal brain function and behavior.
Photonic Crystal Enhanced Microscopy on a 2D Photonic Crystal Surface
Authors: Liu Weinan , Li Siyan , Chow Edmond , Bhaskar Seemesh , Fang Ying , Cunningham Brian T. 
Published: January 2025

AbstractDigital‐resolution biosensing based on resonant reflection from photonic crystals (PC) has demonstrated significant potential for detection of proteomic and genomic biomarkers in serology, infectious disease diagnostics, and cancer diagnostics. An important intrinsic characteristic of resonant metamaterial surfaces is that enhanced electromagnetic fields are not uniformly distributed, resulting in spatially variable light‐matter interactions with nanoparticle tags that signal the presence of biomarker molecules. In this work, the spatial uniformity of resonantly enhanced, surface‐confined electromagnetic fields of a 1D PC is compared with a 2D PC with fourfold symmetry. When illuminated with unpolarized light, the simultaneously excited electromagnetic fields of transverse electric and transverse magnetic modes of the 2D PC present equally strong but complementary spatial distribution, leading to a >100% increased average near‐field intensity accompanied with a >50% compressed standard deviation compared to the 1D PC. Utilizing Photonic Resonator Absorption Microscopy (PRAM) to experimentally measure the absorption uniformity of ≈80 nm gold nanoparticles distributed upon the PC surface, a >100% improvement of the signal uniformity is observed when using the 2D PC. Overall, improvement in AuNP detection contrast, uniformity, and point spread function is demonstrated by PRAM performed upon a 2D PC surface.
Photoredox Hydroacylative Dearomatization of Indoles with Aromatic Carboxylic Acids
Authors: Qu Chuan‐Hua , Zhu Lin , Chen Shan‐Shan , Peng Hong‐Bo , Zhang Si‐Si , Song Gui‐Ting 
Published: January 2025

AbstractHerein we reported for the first time a photocatalytic dearomative hydroacylation reaction of electron‐deficient indoles with readily available aromatic acids through a phosphoranyl radical‐assisted deoxygenative process. A range of racemic and optically active 2‐acylindoline derivatives were obtained in good yields (up to 94%) with good diastereoselectivity. The synthetic robustness is highlighted by the enantioselective dearomatization of indoles and the late‐stage modification of natural products and pharmaceutical molecules. This protocol features broad substrate scope and mild reaction conditions, providing a reliable entry to developing deoxygenative strategies in dearomatization reactions. Preliminary mechanistic studies and DFT calculations suggest that a Giese‐type radical addition pathway should be involved.
Mechanochemical Pd‐Catalyzed Cross‐Coupling of In‐Situ Generated Reformatsky Zn‐Enolates
Authors: Čarný Tomáš , Mravcová Dominika , Steinhüblová Barbora , Šebesta Radovan 
Published: January 2025

AbstractTransition‐metal‐catalyzed α‐arylations of carbonyl compounds have shown to be a useful strategy for the late‐stage synthesis of α‐arylesters. However, the use of strong basic conditions and difficult handling necessary for the in‐situ preparation of enolates is a major disadvantage. On the other hand, using Reformatsky zinc‐enolates can overcome these challenges. Moreover, mechanochemical in‐situ activation of zinc is even more beneficial. Herein, we report mechanochemical Pd‐catalyzed cross‐coupling between in‐situ generated Reformatsky Zn‐enolates and aryl halides. This operationally simple procedure affords α‐arylated esters or amides using an affordable catalytic system. Reactions were carried under air and ambient conditions using granulated zinc without the need for its pre‐activation. Less reactive and commercially more affordable aryl bromides afforded the desired products in good to excellent yields in comparison to aryl iodides. The optimized conditions were applied in scale‐up reaction and in the synthesis of α‐arylated esters, amides, and derivatives of natural products.
Phosphorus Fluoride Exchange (PFEx) Click Chemistry: 2‐Substituted‐Alkynyl‐1‐Cyclotriphosphazene (SACP) Hubs for Diversity Oriented Clicking
Authors: Wang Zifei , Vishwakarma Dharmendra S. , Sun Shoujun , Huang Qiyao , Pati Soumyaranjan , Johnson Robert M. , Rufrano Michael R. , Gembicky Milan , Homer Joshua A. , Moses John E. 
Published: January 2025

AbstractPhosphorus Fluoride Exchange (PFEx) is a new click chemistry technology that hinges on the creation of innovative hubs to unlock its potential and broaden its applications. In this study, we outline some guiding principles for PFEx hub development and validate these principles by developing a new hub, 2‐substituted‐alkynyl‐1‐cyclotriphosphazenes (SACPs). These SACPs serve as versatile PFEx hubs with stable functionality and orthogonal reactivity, exemplifying their utility within the Diversity Oriented Clicking (DOC) framework. We demonstrate that SACPs interact with various 1,3‐dipoles, enabling the synthesis of phosphorus‐rich compounds through sequential cycloaddition and PFEx reactions, thus pioneering new synthetic routes for wide application of click chemistry.
Elucidating the Oxidation Process and Enhanced Stability of Black Phosphorus through NTCDA Passivation: A Molecular Dynamics Study
Authors: Kaddar Youness , Mansouri Zouhir , Benyoussef Abdelilah , El Fatimy Abdelouahed , Mounkachi Omar 
Published: January 2025

AbstractUnderstanding the oxidation mechanisms of black phosphorus (BP) at the atomic scale is essential for developing effective passivation strategies to enhance its stability in ambient conditions. To explore this, the effects of O2 and H2O molecules on BP layers are elucidated using reactive force field (ReaxFF) molecular dynamics simulations at constant concentrations of molecules and room temperature. As a potential solution, the passivation efficacy of 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA) is evaluated. The initial oxidation processes are analyzed through atomic structural changes, charge dynamics, and radial distribution functions. Moreover, the thickness of the oxidized BP layers is quantitatively determined. Results show that elevated O2 concentrations significantly accelerate oxidation and increase the thickness of the oxidized layers, while H2O has a weaker influence. The interaction between O⁻ and H⁺ ions in H2O reduces its interaction with BP, but O2 molecules cause H2O to become negatively charged, allowing it to interact with P⁺ ions. Importantly, passivating BP with NTCDA effectively mitigates oxidation, creating a protective layer that repels O2 molecules. Ultimately, this study reveals the initial oxidation and passivation processes of BP layers, offering crucial theoretical insights to guide experimental methods and practical applications in semiconductor devices.
Surface Strengthening of Polymer Composite Dielectrics for Superior High‐Temperature Capacitive Energy Storage
Authors: Wang Zepeng , Zhao Yanlong , Yang Minhao , Yan Huarui , Xu Chao , Tian Bobo , Zhang Chong , Xie Qing , Dang Zhi‐Min 
Published: January 2025

AbstractPolymer dielectrics for high‐temperature capacitive energy storage suffer from low energy density and poor efficiency, which is mainly attributed to the exponential growth of conduction loss at high electric fields. Here, a surface strengthening strategy to inhibit the electrode‐limited conduction loss of polymer composite dielectrics is reported. The surface phase of polymer composite dielectrics is strengthened by the in situ generated ultrafine silicon oxide (SiO2) nanoparticles while the bulk phase is strengthened by incorporating commercially available SiO2 nanoparticles. These wide bandgap SiO2 nanoparticles can not only restrict the movement of macromolecular chains, but also act as deep traps to capture the charge carriers. As a result, the charge transport at the electrode/dielectric interface and in the bulk phase of dielectric is significantly restrained, thereby leading to a decrease in conduction loss. The resultant film can deliver a discharged energy density of 4.26 J cm⁻3 at 200 °C, which increased by 1274.19% compared with that of pristine film. The strategy of employing surface strengthening to suppress the conduction loss of polymer composite dielectrics can be easily extended to other polymers to improve the high‐temperature insulation and capacitive energy storage performances.
Highly selective deep eutectic solvents for the recovery of lithium from high sodium concentration aqueous solutions
Authors: Xue Ke , Liu Hai , Kou Peng , Zhou Yan , Zhang Yan , Zhu Zhaoyou , Qi Jianguang , Wang Yinglong 
Published: January 2025

AbstractEfficient and selective extraction of lithium from sodium‐rich systems is crucial for meeting the growing demand for lithium and achieving green development goals. In this study, we synthesized three hydrophobic deep eutectic solvents (HDES) using trioctylphosphine oxide and β‐diketones for the separation of alkali metal ions. Experimental results indicated that the chosen extractants exhibit excellent Li+ extraction capability under alkaline conditions, and the extraction capacity of HDES for Li+ is superior to that of their components. Thermodynamic function calculations revealed that the Li+ extraction reaction is exothermic. A study of the factors affecting Li+ extraction efficiency and separation coefficients, and the recyclability of HDES, was conducted, achieving efficient recovery of lithium from solutions. Additionally, Fourier‐transform infrared spectroscopy analysis and quantum chemical calculations elucidated the extraction mechanism. This study aims to provide a theoretical basis and a green approach for the selective recovery of Li+ from high Na/Li aqueous solutions.
Tissue Eosinophils Threshold and its Association with Adult‐Onset Asthma in Chronic Rhinosinusitis
Authors: Kowatanamongkon Patlada , Snidvongs Kornkiat , Korrungruang Potjanee , Chotikawichean Nutpacha , Kanjanawasee Dichapong , Mongkolkul Kittichai , Chitsuthipakorn Wirach 
Published: January 2025

ABSTRACTIntroductionTissue eosinophil counts (TEC) might serve as a biomarker linking chronic rhinosinusitis (CRS) and the presence of adult‐onset asthma. This study aimed to determine if TEC in sinus mucosa/polyps in CRS patients is an independent indicator of asthma and to identify its optimal cut‐off point.MethodsThis cross‐sectional study was conducted on primary CRS patients scheduled for surgery. All patients were assessed by a pulmonologist for asthma diagnosis. Tissues were collected during surgery and evaluated for TEC. Logistic regression and receiver operating characteristic analysis were used to determine significant factors and the optimal cut‐off points of TEC associated with asthma.ResultsA total of 103 CRS patients were included. Ten patients (9.7%) had underlying asthma, while 13 (12.6%) were first diagnosed by the pulmonologist. TEC ≥40 cells per high‐powered field (HPF) exhibited a significant correlation with asthma (area under the curve = 0.71, p < 0.001). The sensitivity of this cut‐off point was 0.70 (95% confidence interval [CI] = 0.47–0.87), and specificity was 0.66 (95% CI = 0.55–0.76). Positive predictive value and negative predictive value were 0.37 and 0.88, respectively. The cut‐off point significantly associated with the presence of asthma, with an adjusted odds ratio of 3.13 (95% CI = 1.05–9.35, p = 0.04), controlling for polyps, allergic rhinitis, and computerized tomography (CT) score.ConclusionTEC in CRS patients can help determine the presence of adult‐onset asthma, with an optimal threshold of ≥40 cells/HPF. This threshold is significantly associated with asthma independent of polyps, allergy, and CT score.
The MR1/MAIT cell axis enhances dystrophic neurite development in Alzheimer's disease
Authors: Wyatt‐Johnson Season K. , Ackley Samantha , Warren Jalyn , Priya Raj , Wan Jun , Liu Sheng , Brutkiewicz Randy R. 
Published: January 2025

AbstractINTRODUCTIONPlaques are a hallmark feature of Alzheimer's disease (AD). We found that the loss of mucosal‐associated invariant T (MAIT) cells and their antigen‐presenting molecule MR1 caused a delay in plaque pathology development in AD mouse models. However, it remains unknown how this axis is impacting dystrophic neurites.METHODSBrain tissue from 5XFAD mice and those that are MR1 deficient (MR1 KO), were analyzed for dystrophic neurites, amyloid plaques, and synapses via immunofluorescence, RNA sequencing, enzyme‐linked immunosorbent assay, and western blot.RESULTSIn 8‐month‐old 5XFAD/MR1 KO mice, there was reduced expression of lysosomal‐associated membrane protein 1, ubiquitin, and n‐terminal amyloid precursor protein in the hippocampus compared to 5XFAD mice (P < 0.05). 5XFAD/MR1 KO mice also had less insoluble amyloid beta 40 (P < 0.001) and higher levels of postsynaptic density protein 95 (P < 0.01) in the hippocampus.DISCUSSIONOur data contribute additional mechanistic insight into the detrimental role of the MR1/MAIT cell axis in AD pathology development.Highlights
5XFAD mice lacking the innate immune MR1/MAIT (mucosal‐associated invariant T) cell axis (5XFAD/MR1 KO) have reduced numbers of dystrophic neurite markers in the hippocampus at 8 months of age.
Hippocampal tissue transcriptional analyses showed reduced expression of genes encoding classical dystrophic neurite markers in 5XFAD/MR1 KO mice.
5XFAD/MR1 KO mice had less insoluble amyloid beta 40 and increased levels of the post‐synaptic marker, postsynaptic density protein 95, in the hippocampus than did MR1+ 5XFAD mice.
An Amorphous Donor‐Acceptor Conjugated Polymer with Both High Charge Carrier Mobility and Luminescence Quantum Efficiency
Authors: Wang Mingcong , Xia Guangjie , Yang Chen , Zhang Lu , Nikolka Mark , Zhang Weimin , Cendra Camila , Liu Wanli , Zhao Shunan , Zeng Jinfeng , Zou Cao , Gorenflot Julien , Salleo Alberto , Laquai Frédéric , Sirringhaus Henning , McCulloch Iain , Chen Hu 
Published: January 2025

AbstractOrganic semiconducting polymers play a pivotal role in the development of field‐effect transistors (OFETs) and organic light‐emitting diodes (OLEDs), owing to their cost‐effectiveness, structural versatility, and solution processability. However, achieving polymers with both high charge carrier mobility (μ) and photoluminescence (PL) quantum yield (Φ) remains a challenge. In this work, we present the design and synthesis of a novel donor‐acceptor π‐conjugated polymer, TTIF‐BT, featuring a di‐Thioeno[3,2‐b] ThioenoIndeno[1,2‐b] Fluorene (TTIF) backbone as the donor component. TTIF‐BT exhibits comparable hole mobility and enhanced interchain‐mediated emissions compared to state‐of‐the‐art semiconducting IDT‐BT, leading to a remarkable Φ ⋅ μ value of ~0.084 cm2 V−1 s−1. Through time‐resolved absorption and PL techniques, we propose a model to extract the spectral weight of interchain‐mediated emissions, yielding 62 % in TTIF‐BT. Our results introduce a high‐performance semiconducting polymer, which has potential use in next‐generation organic optoelectronic devices, including electrically‐driven polymer lasers and active‐matrix display technologies.
Remote Carbon Monoxide Spillover Improves Tandem Urea Electrosynthesis
Authors: Li Jia‐Yuan , Li Yue‐Fei , Li Lin‐Sen , Jiang Zhao , Chen Yu , Xia Bao Yu 
Published: January 2025

AbstractElectrocatalytic urea synthesis from carbon dioxide (CO2) and nitrate (NO3−) offers a promising alternative to traditional industrial methods. However, current catalysts face limitations in the supplies of CO* and Nrelated* intermediates, and their coupling, resulting in unsatisfactory urea production efficiency and energy consumption. To overcome these challenges, we carried out tandem electrosynthesis approach using ruthenium dioxide‐supported palladium‐gold alloys (Pd2Au1/RuO2). This catalyst system effectively catalyzes CO2‐to‐CO* conversion on Pd2Au1 and NO3−‐to‐NH2* conversion on RuO2. Crucially, the minimized work function difference between two components promotes remote CO* spillover from Pd2Au1 to RuO2, improving effective coupling of CO* and NH2* for urea production. Our catalyst demonstrated exceptional performance, achieving a record‐high Faradaic efficiency for urea (FEurea) of 75.6±0.5 % and a urea production rate (rurea) of 73.5±0.8 mmol gcat−1 h−1. Notably, this was accomplished with an ultralow energy consumption of 18.9 kWh kgurea−1. We also successfully demonstrate the long‐term stability of our catalyst in a flow cell, achieving over 160 h of uninterrupted urea and formate production with consistent profitability. This achievement represents a significant step towards the large‐scale practical application of sustainable urea electrosynthesis.
Regioisomeric π‐Extended Nanographene with Long‐Lived Phosphorescence Afterglow
Authors: Kumar Viksit , Venugopal Geethu , Jadhav Ashok Badrinarayan , Dongre Sangram D. , Gonnade Rajesh , Kumar Jatish , Ruer Paul C. , Hupp Benjamin , Steffen Andreas , Babu Sukumaran Santhosh 
Published: January 2025

AbstractThe cutouts of graphene sheets, particularly those with a nonplanar topology, present vast opportunities for advancement. Even a slight deviation from the planar structure can lead to intriguing (chiro)optical features for helically twisted nanographenes. In this context, we introduce two regioisomeric π‐extended nanographenes that exhibit distinct excited‐state characteristics. The helicene structure and the photophysical features can be easily tuned by changing the connecting position of the nanographene to the carbazole core (2,7− and 3,6−). Single‐crystal X‐ray diffraction analysis confirmed the formation of nanographenes with bent and helical conformations. Both derivatives exhibited thermally activated delayed fluorescence at room temperature and phosphorescence at low temperatures. Notably, the nanographene with the bent structure displayed an impressive red afterglow lasting over 30 seconds, in contrast to the very weak afterglow observed in the helical structure. DFT calculations revealed the existence of an isoenergetic higher triplet state (T8) and comparatively weak spin‐orbit coupling (T1‐S0), thereby enabling the bent nanographene to exhibit a long‐lived component and strong afterglow. Our findings highlight the significance of regioisomeric nanographenes with exceptional optical properties and offer a deeper understanding of the structure–property relationship in nonplanar nanographenes.