bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tissue Mechanics and Hedgehog Signaling Crosstalk as a Key Epithelial–Stromal Interplay in Cancer Development
Authors: Karunasagara Shanika , Taghizadeh Ali , Kim Sang‐Hyun , Kim So Jung , Kim Yong‐Jae , Taghizadeh Mohsen , Kim Moon‐Young , Oh Kyu‐Young , Lee Jung‐Hwan , Kim Hye Sung , Hyun Jeongeun , Kim Hae‐Won 
Published: July 2024

AbstractEpithelial‐stromal interplay through chemomechanical cues from cells and matrix propels cancer progression. Elevated tissue stiffness in potentially malignant tissues suggests a link between matrix stiffness and enhanced tumor growth. In this study, employing chronic oral/esophageal injury and cancer models, it is demonstrated that epithelial–stromal interplay through matrix stiffness and Hedgehog (Hh) signaling is key in compounding cancer development. Epithelial cells actively interact with fibroblasts, exchanging mechanoresponsive signals during the precancerous stage. Specifically, epithelial cells release Sonic Hh, activating fibroblasts to produce matrix proteins and remodeling enzymes, resulting in tissue stiffening. Subsequently, basal epithelial cells adjacent to the stiffened tissue become proliferative and undergo epithelial‐to‐mesenchymal transition, acquiring migratory and invasive properties, thereby promoting invasive tumor growth. Notably, transcriptomic programs of oncogenic GLI2, mechano‐activated by actin cytoskeletal tension, govern this process, elucidating the crucial role of non‐canonical GLI2 activation in orchestrating the proliferation and mesenchymal transition of epithelial cells. Furthermore, pharmacological intervention targeting tissue stiffening proves highly effective in slowing cancer progression. These findings underscore the impact of epithelial‐stromal interplay through chemo‐mechanical (Hh‐stiffness) signaling in cancer development, and suggest that targeting tissue stiffness holds promise as a strategy to disrupt chemo‐mechanical feedback, enabling effective cancer treatment.
Origin of O2 Generation in Sulfide‐Based All‐Solid‐State Batteries and its Impact on High Energy Density
Authors: Yoshikawa Keisuke , Kato Takeshi , Suzuki Yasuhiro , Shiota Akihiro , Ohnishi Tsuyoshi , Amezawa Koji , Nakao Aiko , Yajima Takeshi , Iriyama Yasutoshi 
Published: July 2024

AbstractThe cathode surface of sulfide‐based all‐solid‐state batteries (SBs) is commonly coated with amorphous‐LiNbO3 in order to stabilize charge–discharge reactions. However, high‐voltage charging diminishes the advantages, which is caused by problems with the amorphous‐LiNbO3 coating layer. This study has investigated the degradation of amorphous‐LiNbO3 coating layer directly during the high‐voltage charging of SBs. O2 generation via Li extraction from the amorphous‐LiNbO3 coating layer is observed using electrochemical gas analysis and electrochemical X‐ray photoelectron spectroscopy. This O2 leads to the formation of an oxidative solid electrolyte (SE) around the coating layer and degrades the battery performance. On the other hand, elemental substitution (i.e., amorphous‐LiNbxP1‐xO3) reduces O2 release, leading to stable high‐voltage charge–discharge reactions of SBs. The results have emphasized that the suppression of O2 generation is a key factor in improving the energy density of SBs.
Hypoxia‐Preconditioned BMSC‐Derived Exosomes Induce Mitophagy via the BNIP3–ANAX2 Axis to Alleviate Intervertebral Disc Degeneration
Authors: Jin Yuxin , Wu Ouqiang , Chen Qizhu , Chen Linjie , Zhang Zhiguang , Tian Haijun , Zhou Hao , Zhang Kai , Gao Jianyuan , Wang Xinzhou , Guo Zhenyu , Sun Jing , Kwan Kenny Yat Hong , Jones Morgan , Li Yan Michael , Zare Ehsan Nazarzadeh , Makvandi Pooyan , Wang Xiangyang , Shen Shuying , Wu Aimin 
Published: July 2024

AbstractIntervertebral disc degeneration (IVDD) is a chronic degenerative disease involving the aging and loss of proliferative capacity of nucleus pulposus cells (NPCs), processes heavily dependent on mitochondrial dynamics and autophagic flux. This study finds that the absence of BCL2/adenovirus E1B 19 kDa interacting protein 3 (BNIP3) is associated with senescence‐related NPC degeneration, disrupting mitochondrial quality control. Bone marrow mesenchymal stem cells (BMSCs) have multidirectional differentiation potential and produce extracellular vesicles containing cellular activators. Therefore, in this study, BMSCs are induced under hypoxic stimulation to deliver BNIP3‐rich extracellular vesicles to NPCs, thereby alleviating aging‐associated mitochondrial autophagic flux, promoting damaged mitochondrial clearance, and restoring mitochondrial quality control. Mechanistically, BNIP3 is shown to interact with the membrane‐bound protein annexin A2 (ANXA2), enabling the liberation of the transcription factor EB (TFEB) from the ANXA2‐TFEB complex, promoting TFEB nuclear translocation, and regulating autophagy and lysosomal gene activation. Furthermore, a rat model of IVDD is established and verified the in vivo efficacy of the exosomes in repairing disc injuries, delaying NPC aging, and promoting extracellular matrix (ECM) synthesis. In summary, hypoxia‐induced BMSC exosomes deliver BNIP3‐rich vesicles to alleviate disc degeneration by activating the mitochondrial BNIP3/ANXA2/TFEB axis, providing a new target for IVDD treatment.
Modulating Electronic States of Cu in Metal‐Organic Frameworks for Emerging Controllable CH4/C2H4 Selectivity in CO2 Electroreduction
Authors: Sun Mingxu , Cheng Jiamin , Anzai Akihiko , Kobayashi Hirokazu , Yamauchi Miho 
Published: July 2024

AbstractThe intensive study of electrochemical CO2 reduction reaction (CO2RR) has resulted in numerous highly selective catalysts, however, most of these still exhibit uncontrollable selectivity. Here, it is reported for the first time the controllable CH4/C2H4 selectivity by modulating the electronic states of Cu incorporated in metal‐organic frameworks with different functional ligands, achieving a Faradaic efficiency of 58% for CH4 on Cu‐incorporated UiO‐66‐H (Ce) composite catalysts, Cu/UiO‐66‐H (Ce) and that of 44% for C2H4 on Cu/UiO‐66‐F (Ce). In situ measurements of Raman and X‐ray absorption spectra revealed that the electron‐withdrawing ability of the ligand side group controls the product selectivity on MOFs through the modulation of the electronic states of Cu. This work opens new prospects for the development of MOFs as a platform for the tailored tuning of selectivity in CO2RR.
Ferroelectric Polarization Dependent Piezoelectric Hardening in BiFeO3‐BaTiO3 Lead‐Free Ceramics
Authors: Lee Myang Hwan , Choi Hae In , Kim Da Jeong , Kim Ji Su , Lee Sang Woo , Park Yubin , Yang Sang Mo , Song Tae Kwon 
Published: July 2024

AbstractThe relation between the improvement of mechanical quality factor (Qm) and internal electric field (Ei) generated during the aging process in lead‐free piezoelectric BiFeO3‐BaTiO3 ceramics is investigated for hard piezoelectric application of power transducers. The change of built‐in Ei depends on the ferroelectric polarization (P) direction during the aging process. For the aging process with P parallel to Ei, Qm and Ei increases but Qm and Ei decreases with P antiparallel to Ei. These results are attributed to the migration of defects by depolarization fields and domain‐wall pinning. This work provides the systematic guidance to develop high‐power piezoelectric transducers with lead‐free ceramics.
Hydrogen Bonds and In situ Photoinduced Metallic Bi0/Ni0 Accelerating Z‐Scheme Charge Transfer of BiOBr@NiFe‐LDH for Highly Efficient Photocatalysis
Authors: Sun Rongjun , Zhu Zijian , Tian Na , Zhang Yihe , Huang Hongwei 
Published: July 2024

AbstractFor heterojunction system, the lack of stable interfacial driving force and definite charge transfer channel makes the charge separation and transfer efficiency unsatisfactory. The photoreaction mechanism occurring at the interface also receives less attention. Herein, a 2D/2D Z‐scheme junction BiOBr@NiFe‐LDH with large‐area contact featured by short interface hydrogen bonds and strong interfacial electric field (IEF) is synthesized, and in situ photoinduced metallic species assisting charge transfer mechanism is demonstrated. The hydrogen bonds between O atoms from BiOBr and H atoms from NiFe‐LDH induce a significant interfacial charge redistribution, establishing a robust IEF. Notably, during photocatalytic reaction, Bi0 and Ni0 are in situ performed in heterojunction, which separately act as electron transport mediator and electron trap to further accelerate charge transfer efficiency up to 71.2 %. Theoretical calculations further demonstrate that the existence of Bi0 strengthens the IEF. Therefore, high‐speed spatial charge separation is realized in Bi0/BiOBr@Ni0/NiFe‐LDH, leading to a prominent photocatalytic activity with a tetracycline removal ratio of 88.3 % within 7 min under visible‐light irradiation and the presence of persulfate, far exceeding majority of photocatalysts reported previously. This study provides valid insights for designing hydrogen bonding heterojunction systems, and advances mechanistic understanding on in situ photoreaction at interfaces.
Visible‐Light‐Driven Multicomponent Reactions for the Versatile Synthesis of Thioamides by Radical Thiocarbamoylation
Authors: Guo Hong‐Mei , Wang Jia‐Jin , Xiong Yanjiao , Wu Xuesong 
Published: July 2024

AbstractThioamides are widely used structures in pharmaceuticals and agrochemicals, as well as important synthons for the construction of sulfur‐containing heterocycles. This report presents a series of visible‐light‐driven multicomponent reactions of amines, carbon disulfide, and olefins for the mild and versatile synthesis of linear thioamides and cyclic thiolactams. The use of inexpensive and readily available carbon disulfide as the thiocarbonyl source in a radical pathway enables the facile assembly of structurally diverse amine moieties with non‐nucleophilic carbon‐based reaction partners. Radical thiocarbamoylative cyclization provides a practical protocol that complements traditional approaches to thiolactams relying on deoxythionation. Mechanistic studies reveal that direct photoexcitation of in situ formed dithiocarbamate anions as well as versatile photoinduced electron transfer with diverse electron acceptors are key to the reactions.
Hexa‐atom Pt Catalyst Fabricated by a Ligand Engineering Strategy for Efficient Hydrogen Oxidation Reaction
Authors: Yan Li , Wang Dunchao , Li. Mengjiao , Lu Ruihu , Lu Mengge , Li Panpan , Wang Kaiyue , Jin Shao , Wang Ziyun , Tian Shubo 
Published: July 2024

AbstractAtomically precise supported nanocluster catalysts (APSNCs), which feature exact atomic composition, well‐defined structures, and unique catalytic properties, offer an exceptional platform for understanding the structure‐performance relationship at the atomic level. However, fabricating APSNCs with precisely controlled and uniform metal atom numbers, as well as maintaining a stable structure, remains a significant challenge due to uncontrollable dispersion and easy aggregation during synthetic and catalytic processes. Herein, we developed an effective ligand engineering strategy to construct a Pt6 nanocluster catalyst stabilized on oxidized carbon nanotubes (Pt6/OCNT). The structural analysis revealed that Pt6 nanoclusters in Pt6/OCNT were fully exposed and exhibited a planar structure. Furthermore, the obtained Pt6/OCNT exhibited outstanding acidic HOR performances with a high mass activity of 18.37 A ⋅ mgpt−1 along with excellent stability during a 24 h constant operation and good CO tolerance, surpassing those of the commercial Pt/C. Density functional theory (DFT) calculations demonstrated that the unique geometric and electronic structures of Pt6 nanoclusters on OCNT altered the hydrogen adsorption energies on catalytic sites and thus lowered the HOR theoretical overpotential. This work presents a new prospect for designing and synthesizing advanced APSNCs for efficient energy electrocatalysis.
Blade‐Coating (100)‐Oriented α‐FAPbI3 Perovskite Films via Crystal Surface Energy Regulation for Efficient and Stable Inverted Perovskite Photovoltaics
Authors: Feng Wenhuai , Liu Xudong , Liu Gengling , Yang Guo , Fang Yuxuan , Shen Jinliang , Jin Bowen , Chen Xi , Huang Yu‐Hua , Wang Xu‐Dong , Wu Congcong , Yang Shaopeng , Wu Wu‐Qiang 
Published: July 2024

AbstractPhotoactive black‐phase formamidinium lead triiodide (α‐FAPbI3) perovskite has dominated the prevailing high‐performance perovskite solar cells (PSCs), normally for those spin‐coated, conventional n‐i‐p structured devices. Unfortunately, α‐FAPbI3 has not been made full use of its advantages in inverted p‐i‐n structured PSCs fabricated via blade‐coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites during film formation. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol % of N‐aminoethylpiperazine hydroiodide (NAPI) additive into α‐FAPbI3 crystal‐derived perovskite ink, which enabled the formation of highly‐oriented α‐FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade‐coated α‐FAPbI3 perovskite films via combining a series of in‐situ characterizations and theoretical calculations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb−I framework help to reduce the surface energy of (100) crystal plane by 42 %, retard the crystallization rate and lower the formation energy of α‐FAPbI3. Benefited from multifaceted advantages of promoted charge extraction and suppressed non‐radiative recombination, the resultant blade‐coated inverted PSCs based on (100)‐oriented α‐FAPbI3 perovskite films realized promising efficiencies up to 24.16 % (~26.5 % higher than that of the randomly‐oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3‐based inverted PSCs fabricated via scalable deposition methods.
3D Lead‐Organoselenide‐Halide Perovskites and their Mixed‐Chalcogenide and Mixed‐Halide Alloys
Authors: Li Jiayi , Wang Yang , Saha Santanu , Chen Zhihengyu , Hofmann Jan , Misleh Jason , Chapman Karena W. , Reimer Jeffrey A. , Filip Marina R. , Karunadasa Hemamala I. 
Published: July 2024

AbstractWe incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se−), which occupies both the X− and A+ sites in the prototypical ABX3 perovskite. The new organoselenide‐halide perovskites: (SeCYS)PbX2 (X=Cl, Br) expand upon the recently discovered organosulfide‐halide perovskites. Single‐crystal X‐ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide‐halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid‐state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV–straddling the ideal range for tandem solar cells or visible‐light photocatalysis. The comprehensive description of the average and local structures, and how they can fine‐tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid‐state and organo‐main‐group chemistry.
Functional Group‐Driven Competing Mechanism in Electrochemical Reaction and Adsorption/Desorption Processes toward High‐Capacity Aluminum‐Porphyrin Batteries
Authors: Jiao Shuqiang , Han Xue , Jiang Li‐Li , Du Xueyan , Huang Zheng , Li Shijie , Wang Wei , Wang Mingyong , Liu Yunpeng , Song Wei‐Li 
Published: July 2024

AbstractNonaqueous organic aluminum batteries are considered as promising high‐safety energy storage devices due to stable ionic liquid electrolytes and Al metals. However, the stability and capacity of organic positive electrodes are limited by their inherent high solubility and low active organic molecules. To address such issues, here porphyrin compounds with rigid molecular structures present stable and reversible capability in electrochemically storing AlCl2+. Comparison between the porphyrin molecules with electron‐donating groups (TPP‐EDG) and with electron‐withdrawing groups (TPP‐EWG) suggests that EDG is responsible for increasing both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, resulting in decreased redox potentials. On the other hand, EWG is associated with decreasing both HOMO and LUMO energy levels, leading to promoted redox potentials. EDG and EWG play critical roles in regulating electron density of porphyrin π bond and electrochemical energy storage kinetics behavior. The competitive mechanism between electrochemical redox reaction and de/adsorption processes suggests that TPP‐OCH3 delivers the highest specific capacity ~171.8 mAh g−1, approaching a record in the organic Al batteries.
p–d Orbital Hybridization in Ag‐based Electrocatalysts for Enhanced Nitrate‐to‐Ammonia Conversion
Authors: Wu Guanzheng , Zhang Wuyong , Yu Rui , Yang Yidong , Jiang Jiadi , Sun Mengmiao , Du Aijun , He Wenhui , Dai Lei , Mao Xin , Chen Zhening , Qin Qing 
Published: July 2024

AbstractConsidering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate‐to‐ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p–d orbital hybridization via doping p‐block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn‐doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH3 at −0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3±14.1 mg h−1 mgcat.−1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere‐level current density of 1.1 A cm−2 with an NH3 yield of 78.6 mg h−1 cm−2, during which NH3 can be further extracted to prepare struvite as high‐quality fertilizer. A mechanistic study reveals that a strong p–d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate‐determining step for NH3 synthesis, which as a general principle, can be further extended to Bi‐ and In‐doped Ag catalysts. Moreover, when integrated into a Zn‐nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L−1, high power density of 18.1 mW cm−2, and continuous NH3 production.
Catalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes via Sequential Povarov Reaction and Aromatizations
Authors: Yu Shaoze , Yuan Mengyao , Xie Wansen , Ye Zidan , Qin Tianren , Yu Na , Yang Xiaoyu 
Published: July 2024

AbstractInherently chiral calix[4]arenes represent a unique type of chiral molecules with significant applications, yet their catalytic enantioselective synthesis remains largely underexplored. We report herein the catalytic enantioselective synthesis of inherently chiral calix[4]arenes through the sequential organocatalyzed enantioselective Povarov reaction and aromatizations. The chiral phosphoric acid catalyzed three‐component Povarov reaction involving amino group‐substituted calix[4]arenes, aldehydes and (di)enamides desymmetrized the prochiral calix[4]arene substrates, which was followed by various aromatization methods, resulting in a diverse array of novel quinoline‐containing calix[4]arenes with good yields and high enantioselectivities (up to 75 % yield, 99 % ee). The large‐scale enantioselective synthesis and diverse derivatizations of the chiral calix[4]arene products highlight the value of this method. Furthermore, preliminary exploration into their photophysical and chiroptical properties demonstrate the potential applications of these novel calix[4]arene molecules.
Development of biobased, sustainable and environmentally friendly glycerol ester rosins for the production of thermoplastic road marking paint
Authors: Yılmaz Bilge , Deniz İlhan , Fazlı Hilal , Bekircan Olcay , Gültekin Ergün , Pranovich Andrey 
Published: July 2024

AbstractIn recent years, natural rosin derivatives have gained significant importance in the production of sustainable bio‐based materials, including thermoplastic road marking paint (TRMP). This study evaluates the use of sustainable natural glycerol ester rosins as bio‐based binders in TRMP formulations, specifically focusing on pine, wood, and tall oil rosins. Various analytical techniques, such as FT‐IR, TGA, MALDI‐TOF‐MS and GPC‐HPLC, were utilized to analyze both unmodified and glycerol ester rosins. Standard tests, including acid number (mg KOH/g) ASTM D 465‐05 and softening point (°C) ASTM E 28‐99, were also conducted on the samples. The optimum synthesis conditions for glycerol ester rosins (GER) were determined as follows: a rosin/glycerol molar ratio of 2.54, catalyst/rosin weight ratio of 0.5%, and antioxidant/rosin weight ratio of 1.0%. GPC‐HPLC analysis revealed average esterification reaction yields of over 90.85%. Furthermore, TRMPs underwent various tests, including gloss factor (β), chromaticity coordinates (x, y), UVB aging, and softening point (°C). The results demonstrated that GERs exhibited superior performance, especially in the UVB aging test, with all TRMPs classified as UV1 type. These findings highlight the promising potential of GERs derived from different types of rosins in producing sustainable, environmentally friendly, and bio‐based next‐generation TRMPs.
Genetically Proxied Interleukin‐13 Inhibition Is Associated With Risk of Psoriatic Disease: A Mendelian Randomization Study
Authors: Zhao Sizheng Steven , Hyrich Kimme , Yiu Zenas , Barton Anne , Bowes John 
Published: July 2024

ObjectiveInhibitors of the interleukin 13 (IL‐13) pathway, such as dupilumab, are licensed for atopic dermatitis and asthma. Adverse events resembling psoriatic disease after dupilumab initiation have been reported, but evidence is limited to case reports with uncertain causality. We aimed to investigate whether genetically mimicked IL‐13 inhibition (IL‐13i) is associated with risk of psoriatic arthritis (PsA) and psoriasis.MethodsWe instrumented IL‐13i using a protein‐coding variant in the IL13 gene, rs20541, that is associated with circulating eosinophil count (biomarker of IL‐13i) at genome‐wide significance in a study of 563,946 individuals. Outcome genetic data were taken from studies of PsA, psoriasis, and related spondyloarthritis traits in up to 10,588 cases and 209,287 controls. Colocalization analysis was performed to examine genetic confounding. We additionally used circulating IgE as a biomarker to test whether associations were replicated, both in the test and in an independent genetic dataset. We also replicated analyses using individual‐level data from the UK Biobank.ResultsGenetically proxied IL‐13i was associated with increased risk of PsA (odds ratio [OR] 37.39; 95% confidence interval [95% CI] 11.52–121.34; P = 1.64 × 10−9) and psoriasis (OR 20.08; 95% CI 4.38–92.01; P = 1.12 × 10−4). No consistent associations were found for Crohn disease, ulcerative colitis, ankylosing spondylitis, or iritis. Colocalization showed no strong evidence of genetic confounding for psoriatic disease. Results were replicated using circulating IgE for the exposure, using independent outcome data and using individual‐level data.ConclusionWe provide supportive genetic evidence that IL‐13i is linked to increased risk of PsA and psoriasis. Physicians prescribing IL‐13 inhibitors should be vigilant for these adverse events.image