bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cancer‐Associated Fibroblast‐Induced Remodeling of Tumor Microenvironment in Recurrent Bladder Cancer
Authors: Liang Ting , Tao Tao , Wu Kai , Liu Lisha , Xu Wuwu , Zhou Dewang , Fang Hu , Ding Qiuxia , Huang Guixiao , Wu Song 
Published: September 2023

AbstractBladder carcinoma (BC) recurrence is a major clinical challenge, and targeting the tumor microenvironment (TME) is a promising therapy. However, the relationship between individual TME components, particularly cancer‐associated fibroblasts (CAFs), and tumor recurrence is unclear. Here, TME heterogeneity in primary and recurrent BC is investigated using single‐cell RNA sequence profiling of 62 460 cells. Two cancer stem cell (CSC) subtypes are identified in recurrent BC. An inflammatory CAF subtype, ICAM1+ iCAFs, specifically associated with BC recurrence is also identified. iCAFs are found to secrete FGF2, which acts on the CD44 receptor of rCSC‐M, thereby maintaining tumor stemness and epithelial‐mesenchymal transition. Additionally, THBS1+ monocytes, a group of myeloid‐derived suppressor cells (MDSCs), are enriched in recurrent BC and interacted with CAFs. ICAM1+ iCAFs are found to secrete CCL2, which binds to CCR2 in MDSCs. Moreover, elevated STAT3, NFKB2, VEGFA, and CTGF levels in iCAFs reshape the TME in recurrent tumors. CCL2 inhibition in an in situ BC mouse model suppressed tumor growth, decreased MDSCs and Tregs, and fostered tumor immune suppression. The study results highlight the role of iCAFs in TME cell–cell crosstalk during recurrent BC. The identification of pivotal signaling factors driving BC relapse is promising for the development of novel therapies.
Flexibility Tuning of Dual‐Metal S─Fe─Co─N5 Catalysts with O‐Axial Ligand Structure for Electrocatalytic Water Splitting
Authors: Su Hui , Song Shaojia , Li Ning , Gao Yangqin , Li Peng , Ge Lei , Ma Tianyi 
Published: September 2023

AbstractThe electrocatalytic performance of metal–nitrogen–carbon (M─N─C) single‐atom catalysts remains a significant challenge due to their rigid active center. Controllable tuning of the local microenvironment and electronic structure is critical for M─N─C single‐metal site catalysts in improving the electrochemical performance and exploring the reaction mechanism. Herein, Co─N4 is selected as a benchmark among various M─N─C catalysts based on theoretical prediction and experimental studies. A dual‐metal S─Fe─Co─N5 catalyst is constructed by embedding Fe and S into the structure of Co─N4 motifs. Theoretical analysis and in situ characterizations illustrate that the active sites will in situ combine an O‐axial ligand to form S─Fe─Co─N5─O structure during the oxygen evolution reaction (OER), which can reduce the reaction energy of O*→OOH*. The Ab Initio Molecular Dynamics simulations and deformation energy for H*/O* adsorption reveal that the Fe─Co and S─Fe bonds exhibit flexible characteristics compared to the Co/Fe─N bonds. This flexibility of S─Fe─Co─N5─O structure facilitates the OER performance by reducing the OOH*→O2, which is the OER rate‐determining step, resulting in superior performance. The optimized S─Fe─Co─N5─O catalyst exhibits excellent OER (260 mV@50 mA cm−2) and hydrogen evolution reaction (138 mV@10 mA cm−2) performance in alkaline electrolytes. The reported regulation strategy ameliorates the micro‐environment of Co─N4 with tunable flexibility, which helps allow a basic comprehension of the electrochemical reaction mechanism.
Bifunctional Oxygen Electrocatalyst of Co4N and Nitrogen‐Doped Carbon Nanowalls/Diamond for High‐Performance Flexible Zinc–Air Batteries
Authors: Zhang Chuyan , Huang Nan , Zhai Zhaofeng , Liu Lusheng , Chen Bin , Yang Bing , Jiang Xin , Yang Nianjun 
Published: September 2023

AbstractRational design of heterogeneous catalysts with unique structural and electronic properties is one of the major challenges to improve the activity toward the reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), the bottleneck in the construction of air cathodes for the next‐generation flexible zinc–air batteries (ZABs). Herein, density functional theory calculations are combined with experimental attempts to exploit the roles of the electronic effects at the interface between Co4N nanoparticles and nitrogen‐doped carbon nanowalls/diamond (d‐NCNWs/D) toward the ORR and OER activities. The vacancy defect‐induced Co‐pyridinic N─C bond optimizes the electronic structure of Co 3d orbitals and balances the adsorption energies of intermediates along the reaction pathways. Consequently, as‐synthesized Co4N@d‐NCNWs/D composites exhibit superior bifunctional oxygen catalytic activity. The overpotential of the OER is as low as 340 mV at 10 mA cm−2 and the high half‐wave potential reaches 0.83 V for the ORR. As a binder‐free and flexible ZABs cathode, this composite exhibits an open circuit voltage of 1.41 V and excellent bendable stability, proving its promising potential for the assembly of wearable devices. This work offers theoretical evidence and a controllable strategy to design high‐performance ZAB cathodes for their application in smart electronic devices.
From Plastic Waste to Treasure: Selective Upcycling through Catalytic Technologies
Authors: Yue Shuai , Wang Pengfei , Yu Bingnan , Zhang Tao , Zhao Zhiyong , Li Yi , Zhan Sihui 
Published: September 2023

AbstractThe huge amount of plastic wastes has become a pressing global environmental problem, leading to severe environmental pollution and resource depletion through conventional downcycling technologies like incineration and landfilling. In contrast, selective upcycling of various plastics offers a promising solution for converting waste plastics into valuable products. This review provides a comprehensive overview of the recent advancements in innovative catalytic technologies, including thermocatalysis, electrocatalysis, and photocatalysis. Special emphasis is placed on elucidating the reaction mechanisms, activating designated chemical bonds for high selectivity, and elaborating the above techniques in terms of reaction conditions and products. Finally, the application prospects and future development trends in plastic catalysis are discussed, providing valuable insights for realizing a sustainable circular plastic economy.
Modulating Anion Redox Reactions and Structural Evolution Through Fe‐Substitution in Li6CoO4 Hyper‐Lithiated Sacrificial Cathodes
Authors: Lee Wontae , Lee Hyobin , Byeon Yunseong , Kim Jong Hwa , Choi Woosung , Choi Munhyeok , Park Min‐Sik , Yoon Won‐Sub 
Published: September 2023

AbstractUtilizing hyper‐lithiated materials can offer a variety of options for designing high‐energy lithium‐ion batteries. As sacrificial cathodes, they compensate for the initial loss of Li+ at the anode. During the first delithiation process, a Fe‐substituted Li6CoO4 (Li5.7Co0.7Fe0.3O4) supplies a large amount of Li+. Especially, the peroxide species formation and oxygen evolution are suppressed even though the charge compensation of oxygen is facilitated in Li5.7Co0.7Fe0.3O4. From a structural viewpoint, the anti‐fluorite structure changes to defective disordered phases during the Li+ extraction, and the proportion of the electrochemical‐inactive phase is more dominant in the case of Li5.7Co0.7Fe0.3O4 at the end of the charge. Consequently, the delithiated LixCo0.7Fe0.3O4 is deactivated in subsequent cycles, reducing unexpected electrochemical reactions after the Li+ provision as sacrificial cathodes. These findings provide a comprehensive understanding of the reaction mechanism of hyper‐lithiated materials and represent a significant step forward in developing high‐performance sacrificial cathodes.
Integratable Paper‐Based Iontronic Power Source for All‐In‐One Disposable Electronics
Authors: Peng Puguang , Yang Feiyao , Wang Zhonglin , Wei Di 
Published: September 2023

AbstractWith the emergence of disposable electronics, compatible safe, flexible, and recyclable power sources have become a critical challenge. Here, an ultra‐thin paper‐based iontronic power source is enabled by highly efficient translational Li+ transport within 2D nanofluidic channels of graphene oxide under a salinity gradient and the fine‐tuned interfacial redox reactions. The paper‐based source can generate volumetric power and energy densities of 438.02 mW cm−3 and 30.02 mWh cm−3, respectively. Its areal power density is 1095.05 mW cm−2, surpassing most flexible batteries. It maintains a working state when bent or even cut and can be simply recycled by incineration. By filling 2D nanofluidic inks in different pens, the power source can be drawn on paper when needed, which not only overcomes the inherent defect of self‐discharge for most batteries but also enables writing directly on any insulating substrates. Furthermore, all‐in‐one disposable electronics comprised of an energy management system (paper‐based triboelectric nanogenerator and iontronic power source) and wireless sensing system (temperature sensor with NFC circuits) are integrated onto one piece of paper by duplex printing, demonstrating the huge potential of such integratable iontronic power sources for soft, wireless, and conformable disposable electronics.
Addressing the Sluggish Kinetics of Sulfur Redox for High‐Energy Mg–S Batteries
Authors: Li Zhenyou , Welle Alexander , Vincent Smobin , Wang Liping , Fuchs Stefan , Riedel Sibylle , Roy Ananyo , Bosubabu Dasari , García‐Lastra Juan Maria , Fichtner Maximilian , Zhao‐Karger Zhirong 
Published: September 2023

AbstractA key challenge for practical magnesium–sulfur (Mg–S) batteries is to overcome the sluggish conversion kinetics of sulfur cathodes, achieving a high energy density and long‐lasting battery life. To address this issue, a doping strategy is demonstrated in a model Ketjenblack sulfur (KBS) cathode by introducing selenium with a high electronic conductivity. This leads to a significantly enhanced charge transfer in the resultant KBS1−xSex cathodes, giving rise to a higher S utilization and less polysulfide dissolution. Compared to the bare S cathode, the S‐Se composite cathodes exhibit a higher capacity, smaller overpotentials, and improved efficiency, serving as better benchmark compounds for high‐performance Mg–S batteries. First principles calculations reveal a charge transport mechanism via electron polaron diffusion in the redox end‐products, that enhances the reaction kinetics. By suppressing polysulfide dissolution in the electrolyte, the use of the KBS1−xSex cathodes also enables a more uniform anode reaction, and thereby significantly extends the cyclability of the cells. To improve the performance, further efforts are made by implementing a Mo6S8 modified separator into the cell. With an optimized cathode composition of KBS0.86Se0.14, the cell applying modified separator shows an improvement of capacity retention by >50% after 200 cycles.
Pseudo‐eye‐of‐the‐tiger sign in cerebellar ataxia with neuropathy and vestibular areflexia syndrome (CANVAS)
Authors: Abreu Vasco Sousa , Silva José Sá , Igreja Liliana , Malaquias Maria João , Pinto Catarina Mendes 
Published: September 2023

AbstractThe well‐known eye‐of‐the‐tiger sign features bilateral and symmetrical changes in the globus pallidus, with a central area of high signal and peripheral low signal on T2‐weighted MRI. Although formally considered pathognomonic of pantothenate kinase‐associated neurodegeneration (PKAN), there are other neurodegenerative or genetic diseases showing similar findings. Cerebellar ataxia with neuropathy and vestibular areflexia syndrome (CANVAS) is a late‐onset ataxia, that was recently associated with biallelic AAGGG repeat expansion in the RFC1 gene. Although its predominant MRI finding is cerebellar atrophy, there may be other less common associated findings. Our aim is to present two cases of CANVAS with associated (pseudo‐)eye‐of‐the‐tiger sign, highlighting the possibility of yet another differential diagnosis for this imaging sign.
Is “Water in Salt” Electrolytes the Ultimate Solution? Achieving High Stability of Organic Anodes in Diluted Electrolyte Solutions Via a Wise Anions Selection
Authors: Nimkar Amey , Alam Khorsed , Bergman Gil , Levi Mikhael D. , Major Dan Thomas , Shpigel Netanel , Aurbach Doron 
Published: September 2023

AbstractThe introduction of the water‐in‐salt (WIS) electrolytes concept to prevent water splitting and widen the electrochemical stability window, has spurred extensive research efforts toward development of improved aqueous batteries. The successful implementation of these electrolyte solutions in many electrochemical systems shifts the focus from diluted to WIS electrolyte solutions. Considering the high costs and the tendency of these nearly saturated solutions to crystallize, this trend can be carefully re‐evaluated. Herein we show that the stability of organic electrodes comprising the active material perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA), is strongly influenced by the solvation character of the anions rather than the concentration of the electrolyte solution. Even though the charging process of PTCDA involves solely insertion of cations (i.e., principal counter‐ions), surprisingly, the dominant factor influencing its electrochemical performance, including long‐term electrode stability, is the type of the co‐ions (i.e., electrolytic anions). Using systematic electrochemical analysis combined with theoretical simulations, we show that the selection of kosmotropic anions results in fast fading of the PTCDA anodes, while a selection of chaotropic anions leads to excellent stability, even at electrolytes concentrations as low as 0.2 M. These findings provide a new conceptual approach for designing advanced electrolyte solutions for aqueous batteries.
Chiral Deep Eutectic Solvents Enable Full‐Color and White Circularly Polarized Luminescence from Achiral Luminophores
Authors: Wen Xin , Du Sifan , Zhang Li , Liu Minghua 
Published: September 2023

AbstractHerein, chiral deep eutectic solvents (DES) are prepared by lauric acid as hydrogen bond donors (HBD) and chiral menthol as hydrogen bond acceptors (HBA). When achiral fluorescent molecules are dopedin the menthol‐based chiral DES, they emit circularly polarized luminescence (CPL) with handedness controlled by the molecular chirality (l or d) of menthol. Remarkably, the strategy is universal and a series of achiral fluorescent molecules can be endowed with CPL activity, showing a full‐color and white CPL upon appropriate mixing, which paves the way to prepare white CPL materials. Interestingly, CPL appears only in a certain temperature range in the DES. Variable‐temperature spectra and other characterization methods reveal that the H‐bond network in the chiral DES plays an important role in inducing CPL. This work unveils how the interior structure as well as the hydrogen‐bond network of a chiral DES can transfer its chirality to achiral luminophores for the first time and realizes a full‐color and white CPL in a DES.
Atroposelective Synthesis of C−N Vinylindole Atropisomers by Palladium‐Catalyzed Asymmetric Hydroarylation of 1‐Alkynylindoles
Authors: Zhan Li‐Wen , Lu Chuan‐Jun , Feng Jia , Liu Ren‐Rong 
Published: September 2023

AbstractTransition‐metal‐catalyzed hydroarylation of unsymmetrical internal alkynes remains challenging because of the difficulty in controlling regioselectivity and stereoselectivity. Moreover, the enantioselective hydroarylation of alkynes using organoboron reagents has not been reported. Herein, we report for the first time that palladium compounds can catalyze the hydroarylation of 1‐alkynylindoles with organoborons for the synthesis of chiral C−N atropisomers. A series of rarely reported vinylindole atropisomers was synthesized with excellent regio‐, stereo‐ (Z‐selectivity), and enantioselectivity under mild reaction conditions. The ready availability of organoborons and alkynes and the simplicity, high stereoselectivity, and good functional group tolerance of this catalytic system make it highly attractive.
A Porphyrin Iron(III) π‐Dication Species and its Relevance in Catalyst Design for the Umpolung of Nucleophiles
Authors: Engbers Silène , Guo Yisong , Klein Johannes E. M. N. 
Published: September 2023

AbstractIsoporphyrins have recently been identified as remarkable species capable of turning the nucleophile attached to the porphyrin ring into an electrophile, thereby providing umpolung of reactivity (Inorg. Chem. 2022, 61, 8105–8111). They are generated by nucleophilic attack on an iron(III) π‐dication, a class of species that has received scant attention. Here, we explore the effect of the porphyrin meso‐substituent and report a iron(III) π‐dication bearing the meso‐tetraphenylporphyrin (TPP) ligand. We provide an extensive study of the species by UV/Vis absorption, 2H NMR, EPR, applied field Mössbauer, and resonance Raman spectroscopy. We further explore the system's highly dynamic and tunable properties and address the nature of the axial ligands as well as the conformation of the porphyrin ring. The insights presented are essential for the rational design of catalysts for the umpolung of nucleophiles. Such catalytic avenues could for example provide a novel method for electrophilic chlorinations. We further examine the importance of electronic tuning of the porphyrin by nature of the meso‐substituent as a factor in catalyst design.
Luminescence modulation of Tb/Eu@Polysulfone films for advanced anti‐counterfeiting
Authors: Monteiro Bernardo , Avó João , Moro Artur J. , Pereira Cláudia C. L. 
Published: September 2023

AbstractHerein, we present the successful preparation of emissive polysulfone thin films doped with tetracoordinated Tb3+ and Eu3+ complexes, with emission co‐regulated by simultaneous excitation light and heat with controllable emissive pattern. We suggest a ligand driven light induced interaction with polymeric organic host that promotes increased emission in the blue region. Our system lays on dynamic irreversible generation of emissive color from green to cyan. Under commercial 366 nm UV lamp, the unambiguously selected pre‐chosen pattern will emit brighter than non‐irradiated film in the blue region of visible spectrum.
Flexible strain sensors with high sensitivity and large monitoring range prepared by biaxially stretching conductive polymer composites with a bilayer structure
Authors: Li Jiayi , Xiang Dong , Zhao Chunxia , Li Hui , Zhou Lihua , Wang Li , Yan Guilong , Li Zhenyu , Wang Ping , Wang Bin , Wu Yuanpeng 
Published: September 2023

AbstractIn order to prepare a flexible strain sensor with a large monitoring range, high sensitivity and excellent stability, a polyolefin elastomer (POE)/carbon nanotubes (CNTs) conductive polymer composite with a bilayer structure was prepared by biaxially stretching in this work. The results showed that the bilayer structured nanocomposites had better processability and better stability than monolayer CNT/POE nanocomposites during biaxial stretching. The biaxial stretching process could promote the dispersion and planar orientation of CNTs within the polymer, improving the crystallinity of nanocomposites and the sensing performance of strain sensors. The optimal stretching ratios (SRs) of bilayer structured nanocomposites were studied. The 8 wt% CNT/POE‐POE strain sensor with an SR of 2.5 exhibited a high sensitivity (gauge factor/GF = 72604.7 at 900% strain), wide strain range (0%–900%), and stable cycling performance (1000 cycles at 30% strain), showing a broad application prospect in wearable electronic devices. This study provides a valuable method for efficiently manufacturing high performance and low‐cost flexible strain sensors.
Physical property characterizations of natural rubber nanocomposites through experimental techniques, models and CRR concept
Authors: Velayudhan Prajitha , Paduvilan Jibin Keloth , Patanair Bindu , Sidharthan Sisanth Krishnageham , Kaliyathan Abitha Vayyaprontavida , Delpouve Nicolas , Saiter‐Fourcin Allisson , Thomas Sabu 
Published: September 2023

AbstractIn this research, the combinations of silica (SiO2), with either graphite (GR) or graphene oxide (GO), are studied as hybrid reinforcements of natural rubber (NR). Whereas individual improvements of rigidity, strength or ductility can be obtained depending on the composition, a synergistic reinforcement is specifically evidenced after addition of GO/SiO2 with a 3:1 ratio. For this formulation, both strength and modulus drastically increase while keeping the strain at break at a decent level. From the confrontation of all tensile tests results with theoretical reinforcement models, a good correlation between the experimental data and the Guth Gold model is observed, which reveals that the mechanical properties should essentially be governed by the filler/matrix interactions. This assumption has been discussed through the cooperative rearranging region (CRR) concept, by analyzing the calorimetric response of the nanocomposites at the glass transition. Not only the 3:1 GO/SiO2 composition is the only one for which the glass transition clearly shifts to higher temperatures, its CRR average size is also the lowest in comparison with reference NR. This result, interpreted as the signature of the most efficient intercalation of the fillers, matches well with the steep strain hardening recorded for this nanocomposite.
Photocatalyst‐ and Transition Metal‐Free Light‐Induced Borylation Reactions
Authors: Bhanja Rosalin , Bera Shyamal Kanti , Mal Prasenjit 
Published: September 2023

AbstractThe increasing global warming concerns have propelled a surge in the demand for sustainable energy sources within the domain of synthetic organic chemistry. A particularly prominent area of research has been the development of mild synthetic strategies for generating heterocyclic compounds. Heterocyclic compounds containing boron have notably risen to prominence as pivotal reagents in a myriad of organic transformations, showcasing their wide‐ranging applicability. This comprehensive review is aimed at collecting the literature pertaining to borylation reactions induced by light, specifically focusing on photocatalyst‐free and transition metal‐free methodologies. The central emphasis is on delving into selective mechanistic investigations. The amalgamation and analysis of these research insights elucidate the substantial potential inherent in eco‐friendly approaches for synthesizing heterocyclic compounds, thus propelling the landscape of sustainable organic chemistry.
Escherichia coli cytosine deaminase: Structural and biotechnological aspects
Authors: Vosough Parisa , Vafadar Asma , Naderi Samaneh , Alashti Shayan Khalili , Karimi Sara , Irajie Cambyz , Savardashtaki Amir , Taghizadeh Saeed 
Published: September 2023

AbstractSuicide gene therapy involves introducing viral or bacterial genes into tumor cells, which enables the conversion of a nontoxic prodrug into a toxic‐lethal drug. The application of the bacterial cytosine deaminase (bCD)/5‐fluorocytosine (5‐FC) approach has been beneficial and progressive within the current field of cancer therapy because of the enhanced bystander effect. The basis of this method is the preferential deamination of 5‐FC to 5‐fluorouracil by cancer cells expressing cytosine deaminase (CD), which strongly inhibits DNA synthesis and RNA function, effectively targeting tumor cells. However, the poor binding affinity of toward 5‐FC compared to the natural substrate cytosine and/or inappropriate thermostability limits the clinical applications of this gene therapy approach. Nowadays, many genetic engineering studies have been carried out to solve and improve the activity of this enzyme. In the current review, we intend to discuss the biotechnological aspects of Escherichia coli CD, including its structure, functions, molecular cloning, and protein engineering. We will also explore its relevance in cancer clinical trials. By examining these aspects, we hope to provide a thorough understanding of E. coli CD and its potential applications in cancer therapy.