bluuebunny/crossref_metadata_2025_split huggingface dataset:
Accelerating Li‐Ion Diffusion in LiFePO4 by Polyanion Lattice Engineering
Authors: Wang Xinxin , Yu Anyang , Jiang Tian , Yuan Shijun , Fan Qi , Xu Qingyu 
Published: October 2024

AbstractDespite the widespread commercialization of LiFePO4 as cathodes in lithium‐ion batteries, the rigid 1D Li‐ion diffusion channel along the [010] direction strongly limits its fast charge and discharge performance. Herein, lattice engineering is developed by the planar triangle BO33− substitution on tetrahedron PO43− to induce flexibility in the Li‐ion diffusion channels, which are broadened simultaneously. The planar structure of BO33− may further provide additional paths between the channels. With these synergetic contributions, LiFe(PO4)0.98(BO3)0.02 shows the best performance, which delivers the high‐rate capacity (66.8 mAh g−1 at 50 C) and long cycle stability (ultra‐low capacity loss of 0.003% every cycle at 10 C) at 25 °C. Furthermore, excellent rate performance (34.0 mAh g−1 at 40 C) and capacity retention (no capacity loss after 2500 cycles at 10 C) at −20 °C are realized.
Dual Fe/I Single‐Atom Electrocatalyst for High‐Performance Oxygen Reduction and Wide‐Temperature Quasi‐Solid‐State Zn‐Air Batteries
Authors: Du Meng , Chu Bingxian , Wang Qichen , Li Cheng , Lu Yu , Zhang Zhan , Xiao Xin , Xu Cong‐Qiao , Gu Meng , Li Jun , Pang Huan , Xu Qiang 
Published: October 2024

AbstractOxygen reduction reaction (ORR) electrocatalysts are essential for widespread application of quasi‐solid‐state Zn‐air batteries (ZABs), but the well‐known Fe‐N‐C single‐atom catalysts (SACs) suffer from low activity and stability because of unfavorable strong adsorption of oxygenated intermediates. Herein, the study synthesizes dual Fe/I single atoms anchored on N‐doped carbon nanorods (Fe/I‐N‐CR) via a metal–organic framework (MOF)‐mediated two‐step tandem‐pyrolysis method. Atomic‐level I doping modulates the electronic structure of Fe‐Nx centers via the long‐range electron delocalization effect. Benefitting from the synergistic effect of dual Fe/I single‐atom sites and the structural merits of 1D nanorods, the Fe/I‐N‐CR catalyst shows excellent ORR activity and stability, superior to Pt/C and Fe or I SACs. When the Fe/I‐N‐CR is employed as cathode for quasi‐solid‐state ZABs, a high power density of 197.9 mW cm−2 and an ultralong cycling lifespan of 280 h at 20 mA cm−2 are both achieved, greatly exceeding those of commercial Pt/C+IrO2 (119.1 mW cm−2 and 47 h). In addition, wide‐temperature adaptability and superior stability from −40 to 60 °C are realized for the Fe/I‐N‐CR‐based quasi‐solid‐state ZABs. This work provides a MOF‐mediated two‐step tandem‐pyrolysis strategy to engineer high‐performance dual SACs with metal/nonmetal centers for ORR and sustainable ZABs.
Physical Degradation of Anode Catalyst Layer in Proton Exchange Membrane Water Electrolysis
Authors: Xu Shuwen , Liu Han , Zheng Nanfeng , Tao Hua Bing 
Published: October 2024

AbstractThe proton exchange membrane water electrolysis (PEMWE) is a promising technology for green hydrogen production. However, the wide‐spread application of PEMWE is hindered by the insufficient lifetime due to the degradation of anode material and structure, thus it is crucial first to understand the degradation mechanisms of PEMWE in actual applications. Generally, the degradation in anode side can be classified as chemical degradation and physical degradation. The considerable research focus from academia to enhance performance and durability is mainly by chemical methods. However, based on the experience from industry, many of the performance and lifetime limitations originated from physical factors. Herein, the impact of the physical characteristic of anode catalyst layer (ACL) on performance and durability of PEMWE is investigated, including cracking and deformation of ACL, swelling and creeping of ionomers, and detachment of catalyst particles. Finally, an outlook of future research focus is provided, based on the demand of developing efficient and durable industrial PEMWE devices.
Ni‐Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings
Authors: Trinidad Martín M. , Maya Celia , Galindo Agustín , Carmen Nicasio M. 
Published: October 2024

AbstractWe report the Ni‐catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.
Copper‐Powder‐Mediated Tandem Hydroamination Cyclization‐Hydrocyanation of Alkyne‐Tethered Ketoximes Toward Cyano‐Substituted Cyclic Nitrones
Authors: Han Wen‐Jun , Yang Fang‐Long , Hu Zhiyuan , Chen Wenxia , Liu Shun , Guo Ke , Yang Xin‐Yuan , Cheng Bin 
Published: October 2024

AbstractA copper‐powder‐mediated tandem hydroamination cyclization–hydrocyanation of alkyne‐tethered ketoximes is described by using TMSCN as a commercially available cyanating reagent. This methodology provides an alternative strategy for the synthesis of a series of structurally important cyano‐substituted cyclic nitrones. The hydrocyanation process exhibits distinct regioselectivity depending on the substituent pattern of the alkyne moiety. Moreover, the synthesized products were shown to be capable of undergoing various derivatization reactions.
Temperature‐Induced Changes in Multifin‐Schottky Barrier FinFETs: An Analog/RF Linearity Investigation
Authors: Shalini V , Kumar Prashanth 
Published: October 2024

AbstractIn this script, a Gallium Nitride (GaN)‐based FinFET structure is proposed with a multi‐channel device that is designed and simulated. Here, the 3D‐Sentaures TCAD simulator is used to investigate the analog/radio frequency performance and linearity of the MultiFin‐Schottky Barrier FinFET with different temperatures of 100–400 K. The proposed device underwent a temperature analysis, where critical parameters include drain current, ION/IOFF ratio, Transconductance (gm), higher‐order terms (gm2 and gm3), Gain Bandwidth Product (GBP), Cut‐off Frequency (fT), Transit Time (τ), Transconductance Generation Factor (TGF), Transconductance Frequency Product (TFP), Voltage Input Intercept Point (VIP2, VIP3), Input Intercept Point (IIP3), and Third Order Intermodulation Distortion (IMD3) is thoroughly examined. Thus, the proposed GaN‐based FinFET validates as a strong potential contender for GaN‐based analog/RF applications.
Loss of Carbamoyl Phosphate Synthetase 1 Potentiates Hepatocellular Carcinoma Metastasis by Reducing Aspartate Level
Authors: Chen Siyuan , Tang Qin , Hu Manqiu , Song Sijie , Wu Xiaohong , Zhou You , Yang Zihan , Liao Siqi , Zhou Li , Wang Qingliang , Liu Hongtao , Yang Mengsu , Chen Zhe‐Sheng , Zhao Wei , He Song , Zhou Zhihang 
Published: October 2024

AbstractHepatocellular carcinoma (HCC) is one of the most lethal cancers worldwide. Numerous studies have shown that metabolic reprogramming is crucial for the development of HCC. Carbamoyl phosphate synthase 1 (CPS1), a rate‐limiting enzyme in urea cycle, is an abundant protein in normal hepatocytes, however, lacking systemic research in HCC. It is found that CPS1 is low‐expressed in HCC tissues and circulating tumor cells, negatively correlated with HCC stage and prognosis. Further study reveals that CPS1 is a double‐edged sword. On the one hand, it inhibits the activity of phosphatidylcholine‐specific phospholipase C to block the biosynthesis of diacylglycerol (DAG), leading to the downregulation of the DAG/protein kinase C pathway to inhibit invasion and metastasis of cancer cells. On the other hand, CPS1 promotes cell proliferation by increasing intracellular S‐adenosylmethionin to enhance the m6A modification of solute carrier family 1 member 3 mRNA, a key transporter for aspartate intake. Finally, CPS1 overexpressing adeno‐associated virus can dampen HCC progression. Collectively, this results uncovered that CPS1 is a switch between HCC proliferation and metastasis by increasing intracellular aspartate level.
Persistent Photoluminescence and Mechanoluminescence of a Highly Sensitive Pressure and Temperature Gauge in Combination with a 3D‐Printable Optical Coding Platform
Authors: Zheng Teng , Luo Jiangcheng , Peng Dengfeng , Peng Liang , Woźny Przemysław , Barzowska Justyna , Kamiński Mikołaj , Mahlik Sebastian , Moszczyński Jan , Soler‐Carracedo Kevin , Rivera‐López Fernando , Hemmerich Hanoch , Runowski Marcin 
Published: October 2024

AbstractDistinct types of luminescence that are activated by various stimuli in a single material offer exciting developmental opportunities for functional materials. A versatile sensing platform that exhibits photoluminescence (PL), persistent luminescence (PersL), and mechanoluminescence (ML) is introduced, which enables the sensitive detection of temperature, pressure, and force/stress. The developed Sr2MgSi2O7:Eu2+/Dy3+ material exhibits a linear relationship between ML intensity and force and can be used as an ML stress sensor. Additionally, the bandwidth of the PL emission band and the PL lifetime of this material are remarkably sensitive to temperature, with values of ≈0.05 nm K−1 and 1.29%/K, respectively. This study demonstrates PersL pressure sensing for the first time, using long‐lasting (seconds) lifetime as a manometric parameter. The developed material functions as an exceptionally sensitive triple‐mode visual pressure sensor; specifically, it exhibits: i) a sensitivity of ≈−297.4 cm GPa−1 (8.11 nm GPa−1) in bandshift mode, ii) a sensitivity of ≈272.7 cm−1/GPa (14.8 nm GPa−1) in bandwidth mode, and iii) a sensitivity of 42%GPa−1 in PL‐lifetime mode, which is the highest value reported to date. Notably, anti‐counterfeiting, night‐vision safety‐sign, 8‐bit optical‐coding, and QR‐code applications that exhibit intense PersL are demonstrated by 3D‐printing the studied material in combination with a polymer.
Cognition in (pre)symptomatic Dutch‐type hereditary and sporadic cerebral amyloid angiopathy
Authors: van Dort Rosemarie , Kaushik Kanishk , Rasing Ingeborg , van der Zwet Reinier G. J. , Schipper Manon R. , van der Grond Jeroen , van Rooden Sanneke , van Zwet Erik W. , Terwindt Gisela M. , Middelkoop Huub A. M. , Hart Ellen P. , van Osch Matthias J. P. , van Walderveen Marianne A. A. , Wermer Marieke J. H. 
Published: October 2024

AbstractINTRODUCTIONCerebral amyloid angiopathy (CAA) is a main cause of cognitive dysfunction in the elderly. We investigated specific cognitive profiles, cognitive function in the stage before intracerebral hemorrhage (ICH), and the association between magnetic resonance imaging (MRI) based cerebral small vessel disease (cSVD) burden in CAA because data on these topics are limited.METHODSWe included Dutch‐type hereditary CAA (D‐CAA) mutation carriers with and without ICH, patients with sporadic CAA (sCAA), and age‐matched controls. Cognition was measured with a standardized test battery. Linear regression was performed to assess the association between MRI‐cSVD burden and cognition.RESULTSD‐CAA ICH− mutation carriers exhibited poorer global cognition and executive function compared to age‐matched controls. Patients with sCAA performed worse across all cognitive domains compared to D‐CAA ICH+ mutation carriers and age‐matched controls. MRI‐cSVD burden is associated with decreased processing speed.DISCUSSIONCAA is associated with dysfunction in multiple cognitive domains, even before ICH, with increased MRI‐cSVD burden being associated with slower processing speed.Highlights
Cognitive dysfunction is present in early disease stages of cerebral amyloid angiopathy (CAA) before the occurrence of symptomatic intracerebral hemorrhage (sICH).
Presymptomatic Dutch‐type CAA (D‐CAA) mutation carriers show worse cognition than age‐matched controls.
More early awareness of cognitive dysfunction in CAA before first sICH is needed.
Increased cerebral small vessel disease CAA‐burden on magnetic resonance imaging is linked to a decrease in processing speed.
Comparison of brief olfactory and cognitive assessments to neuroimaging biomarkers in the prediction of cognitive decline and dementia in the MCSA cohort
Authors: Devanand Davangere P. , Lee Seonjoo , Luchsinger José A. , Knopman David , Vassilaki Maria , Motter Jeffrey N. 
Published: October 2024

AbstractINTRODUCTIONWe evaluated impaired odor identification and global cognition as simple, cost‐effective alternatives to neuroimaging biomarkers to predict cognitive decline and dementia in the Mayo Clinic Study of Aging.METHODSSix hundred forty‐seven participants (mean 8.1, standard deviation 3.4 years’ follow‐up) had the following baseline procedures: modified Blessed Information Memory Concentration Test (BIMCT), 12‐item Brief Smell Identification Test (BSIT), structural brain magnetic resonance imaging (MRI), and positron emission tomography (PET) imaging with 11C‐Pittsburgh compound B (11C‐PiB) and fluorodeoxyglucose (FDG; subset).RESULTSCognitive decline developed in 102 participants and dementia in 34 participants. In survival analyses, PiB PET showed robust prediction for cognitive decline. Impaired BSIT, impaired BIMCT, MRI, and FDG measures were also significant predictors. The combination of demographics + BSIT + BIMCT showed strong predictive utility (C‐index 0.81), similar to demographics + PiB PET (C‐index 0.80). Similar but stronger results were obtained for prediction of dementia.DISCUSSIONImpairment in both odor identification test and global cognition was comparable to PiB PET for predicting cognitive decline and dementia.Highlights
In 647 participants in the population‐based Mayo Clinic Study of Aging, several clinical markers and biomarkers each predicted cognitive decline or dementia during an average 8 years of follow‐up.
The combination of the demographic variables of age, sex, and education with a brief odor identification test (BSIT) and a global cognitive test (Blessed Information Memory Concentration Test) showed strong predictive utility (C‐index 0.81) for cognitive decline that was similar to the demographic variables combined with Pittsburgh Compound B amyloid imaging (C‐index 0.80).
Combining a brief odor identification test with a brief cognitive test needs consideration as a simple, cost‐effective option in the clinical assessment of individuals at risk of cognitive decline and dementia, as well as a potential tool to identify individuals who may benefit from disease‐modifying treatments and to screen participants for prevention trials.
n‐ZrS3/p‐ZrOS Photoanodes with NiOOH/FeOOH Oxygen Evolution Catalysts for Photoelectrochemical Water Oxidation
Authors: Tian Zhangliu , Wang Meng , Chen Ganwen , Chen Jie , Da Yumin , Zhang Hanqian , Jiang Rui , Xiao Yukun , Cui Baihua , Jiang Chonglai , Ding Yishui , Yang Jinlin , Sun Zejun , Han Cheng , Chen Wei 
Published: October 2024

AbstractPhotoelectrochemical water splitting offers a promising approach for carbon neutrality, but its commercial prospects are still hampered by a lack of efficient and stable photoelectrodes with earth‐abundant materials. Here, we report a strategy to construct an efficient photoanode with a coaxial nanobelt structure, comprising a buried‐ZrS3/ZrOS n−p junction, for photoelectrochemical water splitting. The p‐type ZrOS layer, formed on the surface of the n‐type ZrS3 nanobelt through a pulsed‐ozone‐treatment method, acts as a hole collection layer for hole extraction and a protective layer to shield the photoanode from photocorrosion. The resulting ZrS3/ZrOS photoanode exhibits light harvesting with good photo‐to‐current efficiencies across the whole visible region to over 650 nm. By further employing NiOOH/FeOOH as the oxygen evolution reaction cocatalyst, the ZrS3/ZrOS/NiOOH/FeOOH photoanode yields a photocurrent density of ~9.3 mA cm−2 at 1.23 V versus the reversible hydrogen electrode with an applied bias photon‐to‐current efficiency of ~3.2 % under simulated sunlight irradiation in an alkaline solution (pH=13.6). The conformal ZrOS layer enables ZrS3/ZrOS/NiOOH/FeOOH photoanode operation over 1000 hours in an alkaline solution without obvious performance degradation. This study, offering a promising approach to fabricate efficient and durable photoelectrodes with earth‐abundant materials, advances the frontiers of photoelectrochemical water splitting.
Modulating Pore Wall Chemistry Empowers Sonodynamic Activity of Two‐Dimensional Covalent Organic Framework Heterojunctions for Pro‐Oxidative Nanotherapy
Authors: Wu Ruohui , Hua Mengying , Lu Yanjia , Chen Liang , Chen Yu , Hu Zhongqian 
Published: October 2024

AbstractCovalent organic frameworks (COFs) have garnered growing interest in the field of biomedicine; however, their application in sonodynamic therapy remains underexplored due to limited understanding of their intrinsic activity and structure–property relationships. Here, we present a pore wall chemistry modulation strategy for empowering sonodynamic activity to two‐dimensional (2D) COF heterojunctions through in situ growth of COFs on bismuth oxycarbonate nanosheets (B NSs). Compared to the negligible sonodynamic effects observed in the pristine B NSs, the 2D heterojunction with vinyl‐decorated COF pore walls demonstrates a 3.6‐fold enhancement in sonocatalytic singlet oxygen generation. This performance also significantly outperforms that of isoreticular COFs functionalized with methoxy or non‐substituted groups. Mechanistic studies reveal that the vinyl groups in the B@COF (BC) heterojunction facilitate the separation and transfer of charge carriers while also enhancing the adsorption of oxygen molecules. Furthermore, peroxymonosulfate (PMS) loading into the porous COFs boosts the therapeutic efficacy of antitumor nanotherapy via sonocatalytic dual oxidative species generation. These findings underscore the critical role of pore wall chemistry in modulating the sonocatalytic properties of COFs, and advance the development of COF‐based sonosensitizers for pro‐oxidative applications.
Ferroelectric Dipoles Tailoring Solid‐Electrolyte‐Interphase Chemistry to Enable Reversible Lithium Metal Batteries
Authors: Xu Baolei , Zhang Chunxiao , Wang Wenran , Zhu Hai , Ma Li , Wang Meiyu , Liang Chaoping , Zhou Liangjun , Wang Li , Chen Libao , Ivey Douglas G. , Wei Weifeng 
Published: October 2024

AbstractSolid‐electrolyte interphase (SEI) plays a decisive role in building reliable Li metal batteries. However, the scarcity of anions in Helmholtz layer (HL) caused by electrostatic repulsion usually leads to the inferior SEI derived from solvents, resulting in dendrites and ‘dead’ Li. Therefore, regulating the distribution of anions in electric double layer (EDL) and continuously introducing more anions into HL to tailor anions‐derived SEI is crucial for achieving stable Li plating/stripping. Herein, by jointly utilizing the controlled defects of reduced graphene oxide (rGO) and the oriented dipoles of ferroelectric BaTiO3 (BTO), the rGO‐BTO composite layer sustainedly brings more TFSI− and NO3− into anion‐defecient HL, promoting favorable decomposition of anions and guiding the generation of robust and fast‐Li+‐transport SEI containing more inorganics LiF and Li3N species. Thus, the resulting Li deposit shows smooth and dense morphologies without dendrites, leading to high average Coulombic efficiency. The Li//Cu@rGO‐BTO (10 mAh cm−2 plated Li) cell exhibits an enhanced Li plating/stripping stability (2700 h) and a higher rate capability. The LiFePO4 full cell (N/P≈6.3) using rGO‐BTO displays an enhanced capacity retention (82.0 % @ 430 cycles). This work provides a new insight on the construction of robust SEI by regulating the distribution of anions within EDL.
Photo‐Triggered Fluorescence Polyelectrolyte Nanoassemblies: Manipulate and Boost Singlet Oxygen in Photodynamic Therapy
Authors: Yao Yongkang , Chen Shangjun , Yan Chenxu , Wang Junyou , Liu Jianjun , Zhu Wei‐Hong , Fan Chunhai , Guo Zhiqian 
Published: October 2024

AbstractPhotodynamic therapy (PDT) is a clinically approved therapeutic modality that has shown great potential for cancer treatment. However, there exist two major problems hindering PDT applications: the nonspecific phototoxicity requiring patients to stay in dark post‐PDT, and the limited photodynamic efficiency. Herein, we report a photo‐triggered porphyrin polyelectrolyte nanoassembling (photo‐triggered PPN) strategy, in which porphyrin photosensitizer and photoswitchable energy accepter are assembled into polyelectrolyte micelles by a combined force of charge interaction and metal‐ligand coordination. The polyelectrolyte‐based PPN exhibits good biocompatibility, and bestows a unique “confining isolated” inner microenvironment for fully overcoming the π–π stacking of porphyrins with significant photodynamic efficiency (123‐fold enhancement). Due to the high Förster resonance energy transfer (FRET) (91.5 %) between porphyrin and photoswitch in closed‐form, we could use light as a specific trigger to modulate photoswitch between closed‐ and open‐form, and manipulate the 1O2 generation in three stages: pre‐PDT (quenching 1O2 generation), during PDT (activating 1O2 generation), and post‐PDT (silencing 1O2 generation). This de novo strategy has for the first time realized remotely manipulating and boosting 1O2 generation in PDT, well resolving the critical and general challenges of limited photodynamic efficiency and side effects from nonspecific phototoxicity.
Resolving Structures of Paramagnetic Systems in Chemistry and Materials Science by Solid‐State NMR: The Revolving Power of Ultra‐Fast MAS
Authors: Koppe Jonas , Sanders Kevin J. , Robinson Thomas C. , Lejeune Arthur L. , Proriol David , Wegner Sebastian , Purea Armin , Engelke Frank , Clément Raphaële J. , Grey Clare P. , Pell Andrew J. , Pintacuda Guido 
Published: October 2024

AbstractUltra‐fast magic‐angle spinning (100+kHz) has revolutionized solid‐state NMR of biomolecular systems but has so far failed to gain ground for the analysis of paramagnetic organic and inorganic powders, despite the potential rewards from substantially improved spectral resolution. The principal blockages are that the smaller fast‐spinning rotors present significant barriers for sample preparation, particularly for air/moisture‐sensitive systems, and are associated with low sensitivity from the reduced sample volumes. Here, we demonstrate that the sensitivity penalty is less severe than expected for highly paramagnetic solids and is more than offset by the associated improved resolution. While previous approaches employing slower MAS are often unsuccessful in providing sufficient resolution, we show that ultra‐fast 100+kHz MAS allows site‐specific assignments of all resonances from complex paramagnetic solids. Combined with more reliable rotor materials and handling methods, this opens the way to the routine characterization of geometry and electronic structures of functional paramagnetic systems in chemistry, including catalysts and battery materials. We benchmark this approach on a hygroscopic luminescent Tb3+ complex, an air‐sensitive homogeneous high‐spin Fe2+ catalyst, and a series of mixed Fe2+/Mn2+/Mg2+ olivine‐type cathode materials.