bluuebunny/crossref_metadata_2025_split huggingface dataset:
1D Crystalline Assemblies Exhibiting Large Second Harmonic Generation Susceptibilities and Stacking‐/Polarization‐Driven Tunability
Authors: Yang Jingyu , Pan Jinbo , Zhang Yan‐Fang , Wan Guolin , Zhu Yongqian , Wei Zixuan , Li Yuhui , Du Shixuan 
Published: November 2024

AbstractNonlinear optical (NLO) van der Waals (vdW) crystals containing 1D building blocks exhibit large NLO coefficients and birefringence that are crucial for their applications. In this work, 21 NLO 1D building blocks with large second harmonic generation (SHG) susceptibility from the Computational 1D Materials Database (C1DB) are screened. Among them, 14 are hitherto unreported and have SHG susceptibilities approaching theoretical upper limits. Forty‐five new vdW NLO crystals are then constructed by stacking one or two of the 21 building blocks. Eighteen of them inherit the large SHG susceptibilities of their corresponding 1D building blocks. Three stable crystals exhibit large SHG susceptibilities and birefringence, while one stable crystal possesses ferroelectricity. Interestingly, the SHG susceptibilities of the newly constructed NLO crystals are inversely proportional to the third power of their bandgaps. Further calculations show that the SHG susceptibilities of the vdW NLO crystals can be tuned either by stacking order or by reversing electric polarization, providing possibilities for their application in tunable nonlinear optics and NLO switches.
Room Temperature Strong Orbital Moments in Perpendicularly Magnetized Magnetic Insulator
Authors: Omar Ganesh Ji , Gargiani Pierluigi , Valvidares Manuel , Lim Zhi Shiuh , Prakash Saurav , Suraj T. S. , Ghosh Abhijit , Lim Sze Ter , Lourembam James , Ariando A. 
Published: November 2024

AbstractThe balance between the orbital and spin magnetic moments in a magnetic system is the heart of many intriguing phenomena. Here, experimental evidence of a large orbital moment is shown, which competes with its spin counterpart in a ferrimagnetic insulator thulium iron garnet, Tm3Fe5O12. Leveraging element‐specific X‐ray magnetic circular dichroism (XMCD), it is established that the dominant contribution to the orbital moment originates from 4f orbitals of Tm. Besides the large Tm orbital moment, intriguingly, the results also reveal a smaller but evident non‐zero XMCD signal in the O K edge, suggesting additional spin‐orbit coupling and exchange interactions with the nearest neighbor Fe atoms. The unquenched orbital moment is primarily responsible for a significant reduction in g‐factor, typically 2 in transition metals, as determined independently using ferromagnetic resonance spectroscopy. The findings reveal a non‐linear reduction in the g‐factor from 1.7 at 300 K to 1.56 at 200 K in Tm3Fe5O12 thin films. These results provide critical insights into the role of the f orbitals in long‐range magnetic order and stimulate further exploration in orbitronics.
Optimizing the Electrical Microenvironment Provided by 3D Micropillar Topography on a Piezoelectric BaTiO3 Substrate to Enhance Osseointegration
Authors: Sun Xiaowen , Guo Yaru , Zheng Xiaona , Bai Yunyang , Lu Yixuan , Yang Xue , Cai Ziming , Xu Erxiang , He Ying , Heng Boon Chin , Xu Mingming , Deng Xuliang , Zhang Xuehui 
Published: November 2024

AbstractThe electrical properties of bone implant scaffolds are a pivotal factor in regulating cellular behavior and promoting osteogenesis. The previous study shows that built‐in electric fields established between electropositive nanofilms and electronegative bone defect walls are beneficial for promoting bone defect healing. Considering that the physiological electrical microenvironment is spatially distributed in 3D, it is imperative to establish a 3D spatial charged microenvironment on bone scaffolds to optimize the efficacy of osseointegration. Nevertheless, this still poses a formidable challenge. Here, a bone repair strategy that utilizes micro‐scale 3D topography is developed on a piezoelectric BaTiO3 (BTO) substrate to provide 3D spatial electrical stimulation. The BTO micropillar arrays, especially with a height of 50 µm and positive‐charge distribution (50 µm positive), promote the spreading, cytoskeletal reorganization, focal adhesion maturation, and osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs). They enhanced the clustering of mechanosensing integrin α5 in BMSCs. The biomimetic 3D spatial electrical microenvironment accelerated bone repair and osseointegration in a rat femoral diaphysis defect repair model. The study thus reveals that implants with a 3D spatial electrical microenvironment can significantly enhance osseointegration, thereby providing a new strategy to optimize the performance of electroactive biomaterials for tissue regenerative therapies.
Spatial Isoforms Reveal the Mechanisms of Metastasis
Authors: Yin Yin , Wang Yuhao , Yu Xiao , Li Yang , Zhao Yahui , Wang Yanfeng , Liu Zhihua 
Published: November 2024

AbstractIn esophageal squamous cell carcinoma (ESCC), lymph node (LN) metastasis is associated with poor survival. Emerging evidence has demonstrated elevated CD8+ T‐cell levels in metastatic LNs following immunotherapy and increased chemoresistance. However, the underlying regulatory mechanisms of CD8+ T cells in chemoresistant/metastatic patients have not been elucidated. Given that metastasis is linked to aberrant splicing patterns, transcripts with alternative splicing forms also play a critical role. With spatial transcriptomics (ST), spatial isoform transcriptomics (SiT), single‐cell RNA sequencing (scRNA‐seq), and T‐cell receptor (TCR) sequencing, the spatial isoforms are analyzed quantitatively in human solid tumors and LNs. These isoforms are classified according to expression and spatial distribution patterns and proposed that the temporal heterogeneity in isoforms is attributed to isoform biogenesis dynamics. C1QC+ tumor‐associated macrophages (TAMs) contribute to the formation of metastases in the context of both immunotherapy and chemotherapy. Additionally, CD74 isoforms can be targeted by mRNA drugs, such as antisense oligonucleotides (ASOs) and RNA interference (RNAi), to prevent chemoresistance and metastasis. Overall, this work suggests that C1QC+ TAMs interact with CD8+ CXCL13+ Tex cells via enrichment with the CD74 isoform in the ESCC ‘s metastatic lymph node.
Emergent Self‐Adaptation in an Integrated Photonic Neural Network for Backpropagation‐Free Learning
Authors: Lugnan Alessio , Aggarwal Samarth , Brückerhoff‐Plückelmann Frank , Wright C. David , Pernice Wolfram H. P. , Bhaskaran Harish , Bienstman Peter 
Published: November 2024

AbstractPlastic self‐adaptation, nonlinear recurrent dynamics and multi‐scale memory are desired features in hardware implementations of neural networks, because they enable them to learn, adapt, and process information similarly to the way biological brains do. In this work, these properties occurring in arrays of photonic neurons are experimentally demonstrated. Importantly, this is realized autonomously in an emergent fashion, without the need for an external controller setting weights and without explicit feedback of a global reward signal. Using a hierarchy of such arrays coupled to a backpropagation‐free training algorithm based on simple logistic regression, a performance of 98.2% is achieved on the MNIST task, a popular benchmark task looking at classification of written digits. The plastic nodes consist of silicon photonics microring resonators covered by a patch of phase‐change material that implements nonvolatile memory. The system is compact, robust, and straightforward to scale up through the use of multiple wavelengths. Moreover, it constitutes a unique platform to test and efficiently implement biologically plausible learning schemes at a high processing speed.
Effect of Inhomogeneous Temperature in Chip‐Scale Infrared Thermal Sources: A Revisited Blackbody Radiation Formula with Experimental Validation
Authors: Labib Shady R. , Sabry Yasser M. , Elsayed Ahmed. A. , Marty Frédéric , Bourouina Tarik , Khalil Diaa 
Published: November 2024

AbstractMiniature and low‐cost light sources are highly desirable for numerous optical microsystems. Among these, devices based on blackbody radiation of a filament heated at a few hundred degrees, perfectly fit with the requirements of producing a broad spectral range falling in the infrared range, owing to Planck's law. These light sources are of primary interest for Fourier transform infrared (FTIR) spectroscopy. Although thermal light production is simple, achieving precise light intensity is not a trivial task. Herein, the impact of the inhomogeneous temperature on the emitted radiation is studied. Blackbody radiation formulae are revisited for miniature sources, taking into account the temperature distribution and using the principle of superposition of non‐coherent sources. A theoretical model is formulated by dividing the source into multiple annular elementary sources of different temperature. This results in effective, corrected blackbody emission. Analytical formulae are derived in the case of a quadratic temperature distribution. For the experimental validation, a silicon‐based source, made of a platinum resistive micro‐heater on top of heavily doped silicon, is fabricated and experimentally characterized at temperatures ranging from 300 to 520 K. The experimental results show good agreement with the model predictions in the explored wavelength range of (λ = 2.5–4.8 µm).
Community Diversity and Dynamics of Fish Assemblages in Lake Kanyaboli, Western Kenya
Authors: Kondowe Benjamin N. , Masese Frank O. , Raburu Phillip O. , Singini Wales , Sitati Augustine , Walumona Riziki Jacques 
Published: November 2024

ABSTRACTAlthough Lake Kanyaboli provides a sanctuary for fish species that are considered extinct (e.g., Oreochromis esculentus, Oreochromis variabilis and Haplochromis spp.) in Lake Victoria, comprehensive data on species diversity and abundance are lacking. This study, conducted over a year (February 2020 to February 2021), addressed this gap by assessing the temporal variation in fish diversity, abundance and catch (biomass) in Lake Kanyaboli. The primary fish data collected in the lake were supplemented with secondary data, and physico‐chemical variables were used to correlate with fish assemblages. Fish catches decreased over time from 1981 to 2020, with the highest catch observed in 1981 (250 mt). Fish species composition data showed heterogeneity over the years, ranging from 9 to 15 species. O. esculentus, haplochromines, Oreochromis niloticus, Protopterus aethiopicus and Clarias sp. were present in all the reviewed years (from 1981 to 2020), whereas Coptodon zillii was non‐existent post‐1981 results. The February 2020 to February 2021 survey recorded 14 species dominated by Cichlidae (10 species), whereas Protopteridae and Anabantidae recorded one taxon each. Interestingly, Bagrus sp. was recorded in the current study, suggesting fish movement from the Yala River to the lake. The annual fish catch in the lake comprised tilapias (50%, O. esculentus, O. variabilis, O. niloticus and Oreochromis leucostictus), Clarias sp. (23%), P. aethiopicus (20%), haplochromines (7%), Cyprinids (0.03%) and Anabantidae (0.01%). There were no significant monthly differences in fish abundance and fish catches. The decline in fish catch in Lake Kanyaboli over the years is consistent with most tropical lakes and reservoirs in developing countries due to overexploitation. This study highlights the need for biomonitoring in Lake Kanyaboli to protect its fish population, including the endangered O. esculentus and O. variabilis, and ensure the long‐term sustainability of the ecosystem.
Synthesis of γ‐Alkenylated δ‐Sultones Via Brønsted Base‐Catalyzed Annulative SuFEx Reaction of Allyl Ketones and Ethenesulfonyl Fluorides
Authors: Zhang Qichao , Zhang Fang , Wei Zhihang , Shi Xiangyi , He Lin , Liu Jichang , Du Guangfen 
Published: November 2024

AbstractA tandem annulation reaction of allyl ketones and β‐aryl ethenesulfonyl fluorides has been described. Under the catalysis of Brønsted base, allyl ketones reacted with β‐aryl ethenesulfonyl fluorides through a tandem intermolecular Michael addition‐intramolecular SuFEx process to afford γ‐alkenylated δ‐sultones in good to excellent yields. In this reaction, no additional base was needed, and 4 Å molecular sieves were used as efficient HF scavenger to restrict the neutralization and deactivation of the Brønsted base catalyst.
Palladium‐Catalyzed, Regio‐/Stereo‐ and Enantiospecific Anti‐Carboxylation of Unactivated Internal Allenes
Authors: Jayadev Nagtilak Prajyot , Rajeshbhai Hirapara Deveen , Mane Manoj V. , Jain Akshat , Kapur Manmohan 
Published: November 2024

AbstractWe report herein a directing group‐controlled, palladium‐catalyzed, regio‐, stereo‐, and enantiospecific anti‐carboxylation of unactivated, internal allenes enabled via the synergistic interplay of a rationally designed bidentate directing group, palladium catalyst, and a multifunctional acetate ligand. The corresponding trans allyl ester was obtained in excellent yields with exclusive δ‐regioselectivity and anti‐carboxypalladation stereocontrol. The acetate ligand of the palladium catalyst controls the regio‐, stereo‐ and enantioselectivity in the desired transformation. The potential of this concept has been demonstrated by the development of the chiral version of this transformation by using axial‐to‐central chirality transfer with good yields and enantioselectivities. Detailed investigations, including kinetic studies, order studies, and DFT studies, were performed to validate the ligand‐assisted nucleopalladation process and the rationale behind the observed racemization of chiral allenes. The studies also indicated that the anti‐carboxypalladation step was the rate‐limiting as well as the stereo‐ and enantiodetermining step.
Screened d‐p Orbital Hybridization in Turing Structure of Confined Nickel for Sulfion Oxidation Accelerated Hydrogen Production
Authors: Zhu Yin , Wang Shao , Chen Yanxu , Zhang Yangyang , Feng Yafei , Zhang Genqiang 
Published: November 2024

AbstractThe sulfion oxidation reaction (SOR) could offer an energy‐efficient and tech‐economically favorable alternative to the oxygen evolution reaction (OER) for H2 production. Transition metal (TM) based catalysts have been considered promising candidates for SOR but suffer from limited activity due to the excessive bond strength from TM‐S2− d‐p orbit coupling. Herein, we propose a feasible strategy of screening direct d‐p orbit hybridization between TM and S2− by constructing the Turing structure composed of lamellar stacking carbon‐confined nickel nanosheets. The optimized p‐p orbit coupling between electron‐injected carbon and S2− enables exceptional catalytic activity and stability for sulfion degradation and energy‐efficient yet value‐added H2 production. Specifically, it achieves a current density of 500 mA cm−2 at an ultralow potential of 0.67 V vs. RHE for alkaline SOR. Theoretical calculations indicate that the electron transfer from Ni imparts metallicity and a higher p‐band center to carbon shells, thereby contributing to optimized p‐p orbit hybridization and a thermodynamically favorable stepwise sulfion degradation. Practically, a two‐electrode flow cell achieves an industrial current density of 1 A cm−2 at an unprecedented low voltage of 0.91 V while maintaining stability for over 300 hours, and exhibits high productivities of 3.83 and 0.32 kg h−1 m−2 for sulfur and H2, respectively.
Stabilization Strategies of Buried Interface for Efficient SAM‐Based Inverted Perovskite Solar Cells
Authors: Yu Xinyu , Sun Xianglang , Zhu Zonglong , Li Zhong'an 
Published: November 2024

AbstractIn recent years, self‐assembled monolayers (SAMs) anchored on metal oxides (MO) have greatly boosted the performance of inverted (p‐i‐n) perovskite solar cells (PVSCs) by serving as hole‐selective contacts due to their distinct advantages in transparency, hole‐selectivity, passivation, cost‐effectiveness, and processing efficiency. While the intrinsic monolayer nature of SAMs provides unique advantages, it also makes them highly sensitive to external pressure, posing a significant challenge for long‐term device stability. At present, the stability issue of SAM‐based PVSCs is gradually attracting attention. In this minireview, we discuss the fundamental stability issues arising from the structural characteristics, operating mechanisms, and roles of SAMs, and highlight representative works on improving their stability. We identify the buried interface stability concerns in three key aspects: 1) SAM/MO interface, 2) SAM inner layer, and 3) SAM/perovskite interface, corresponding to the anchoring group, linker group, and terminal group in the SAMs, respectively. Finally, we have proposed potential strategies for achieving excellent stability in SAM‐based buried interfaces, particularly for large‐scale and flexible applications. We believe this review will deepen understanding of the relationship between SAM structure and their device performance, thereby facilitating the design of novel SAMs and advancing their eventual commercialization in high‐efficiency and stable inverted PVSCs.
Applicable Descriptors under Weak Metal‐Oxygen d–p Interaction for the Oxygen Evolution Reaction
Authors: Fan Fangshi , Lei Bohan , Song Xiaomin , Liang Jiayuan , Cai Weiwei , Zhong Yu , Wu Yongjun , Bao Ningzhong , Zhang Lingjie 
Published: November 2024

AbstractThe oxygen evolution reaction (OER) plays a crucial role in water electrolysis and renewable energy conversion processes. Descriptors are utilized to elucidate the structure‐performance relationships of OER catalytic materials, yet each descriptor exhibits specificity to particular systems. Currently, there is a lack of effective descriptors to describe the relationship between electronic structure and OER performance in ionic systems. This study reveals for the first time that widely used OER descriptors, the d‐band center and charge transfer energy, are limited in their effectiveness for oxide systems dominated by ionic bonds, in which ionic interactions significantly enhance or suppress the catalytic activity. Furthermore, composite descriptors tailored for ionic systems are proposed, with findings extended to complex multi‐component and high‐entropy oxides. The results indicate that the metal d‐band unoccupied states parameter and the active states parameter can serve as effective OER descriptors for ionic catalytic materials. This work addresses the gap in OER descriptors for ionic systems, offering a new theoretical foundation and guidance for the development of efficient OER catalytic materials.
Azopyridine Polymers in Organic Phase Change Materials for High Energy Density Photothermal Storage and Controlled Release
Authors: Liang Rihui , Yuan Bo , Zhang Fei , Feng Wei 
Published: November 2024

AbstractAzo‐compounds molecules and phase change materials offer potential applications for sustainable energy systems through the storage and controllable release photochemical and phase change energy. Developing novel and highly efficient Azo‐based solar thermal fuels (STFs) for photothermal energy storage and synergistic cooperation with organic phase change materials present significant challenges. Herein, three types of (ortho‐, meta‐, and para‐) azopyridine polymers hinged with flexible alkyl chain are synthesized, in which meta‐azopyridine polymer exhibits striking photothermal storage capacity of 430 J/g, providing a feasibility solution for developing high energy density Azo‐based STFs. Furthermore, a stable two‐phase hybrid system was innovatively constructed by combining the meta‐azopyridine polymer with organic phase change materials leveraging hydrogen bonds and van der Waals interactions to collectively harness phase change energy and photothermal energy. The organic phase change material not only supplies additional phase change latent heat but also serves as a solvent, offering abundant free volume for the photo‐induced isomerization of the azopyridine chromophores, which successfully circumvents the low charging efficiency in the condensed state and reliance on solvent‐assisted charging in traditional Azo‐based STFs. This study demonstrates the energy distribution and utilization for household consumers and the photothermal‐assisted insulation strategy, achieving more extensive potential implementation for STFs.
Flexible ZSM‐5 Zeolite Membrane for High‐Performance Helium Separation
Authors: Deng Yongyan , Qiu Fuxin , Wu Jiaxing , Li Jialu , Li Ziyi , Huang Qinglin , Zhu Guangshan , Zou Xiaoqin 
Published: November 2024

AbstractFlexible zeolite membranes are promising for scalable and adaptable separation of critical gases such as helium; however, the synthesis of such membranes remains a significant challenge. In this study, we report the successful fabrication of crack‐free ZSM‐5 zeolite membranes on polytetrafluoroethylene (PTFE) supports using a seeded growth method. PTFE‐supported membranes exhibit unprecedented helium permeance of over 6.7×10−7 mol m−2 s−1 Pa−1 and high He/N2 and He/CH4 separation factors of 17 and 83 respectively, surpassing current state‐of‐the‐art membranes. These flexible membranes maintain excellent separation performance even after bending and stretching. Furthermore, large‐scale membranes demonstrate stable helium separation from multicomponent gas mixtures, showcasing their significant potential for practical helium extraction from natural gas.
Interface‐Engineering‐Induced C−C Coupling for C2H4 Photosynthesis from Atmospheric‐Concentration CO2 Reduction
Authors: Du Peijin , Ding Jinyu , Liu Chengyuan , Li Peipei , Liu Wenxiu , Yan Wensheng , Pan Yang , Hu Jun , Zhu Junfa , Li Xiaodong , Chen Qingxia , Jiao Xingchen 
Published: November 2024

AbstractProducing ethylene (C2H4) from carbon dioxide (CO2) photoreduction under mild conditions is primarily restricted by the difficulty of C−C coupling. Herein, we designed highly active metal atom clusters anchored on semiconductor nanosheets, which established heteroatom sites on the interface to steer C−C coupling, realizing air‐concentration CO2 photoreduction into C2H4 in pure water. As an example, the Pd nanoclusters loaded on ZnO nanosheets are prepared, demonstrated by the X‐ray photoelectron spectroscopy and high‐angle annular dark‐field image. In situ Fourier transform infrared spectroscopy confirms the C−C coupling step over the Pd‐ZnO nanosheets, while quasi in situ X‐ray photoelectron spectroscopy illustrates the active sites of Pd and Zn atoms on the Pd‐ZnO nanosheets during CO2 photoreduction. Density functional theoretical calculations unveil the transition state energy barrier of C−C coupling of CO* and COH* intermediates are only 0.998 eV, hinting the easy C−C coupling to produce C2 fuels. Therefore, the Pd‐ZnO nanosheets realize C2H4 photosynthesis by atmospheric‐concentration CO2 reduction with the formation rate of 1.03 μmol g−1 h−1, while the ZnO nanosheets only acquired the carbon monoxide product.