bluuebunny/crossref_metadata_2025 huggingface dataset:
Stereo‐Active Lone Pairs Induced Giant Polarization in a 2D Ge‐Based Halide Perovskite Antiferroelectric
Authors: Li Xiaoqi , Yue Zengshan , Zhang Fen , Wang Qianxi , Wei Qingyin , Sun Zhihua , Luo Junhua , Liu Xitao
Published: December 2023

Antiferroelectrics, characterized by electrically controlled antipolar‐polar phase transformation, have attracted tremendous attention as a class of promising electroactive materials for assembling electronic devices. The emerging two‐dimensional (2D) halide perovskites with superior compositional diversity offer an ideal platform for exploring electroactive materials, whereas lead‐free antiferroelectric counterparts are still scarcely reported. Herein, for the first time, a new lead‐free 2D germanium iodide perovskite antiferroelectric (i‐BA)2CsGe2I7 (1, i‐BA is iso‐butylammonium) has been presented, which exhibits a high Curie temperature (Tc) up to 403 K. Remarkably, benefiting from the lone pair stereochemical activity in Ge2+ induced large structural distortion and Cs+ ion off‐center displacement, 1 shows well‐defined double P–E hysteresis loops in a wide temperature range with a giant maximum polarization up to 18.8 µC cm−2, which achieves a new high record among molecular antiferroelectrics. Moreover, under a low external electric field of 22.5 kV cm−1, the antipolar‐polar phase transformation in 1 affords a recoverable energy storage density Wrec of 0.27 J cm−3 and high storage efficiency up to 79.76%. Such lead‐free halide perovskite antiferroelectric with intriguing antiferroelectric behaviors, including high Tc, large polarization and remarkable energy storage properties, is exciting, which provides an alternative candidate for high‐performance antiferroelectrics for environmentally friendly electronic devices.
Two‐Dimensional Conjugated Metal‐Organic Framework/Graphene π–π Stacked Heterostructures for Ultrafast Photonics
Authors: Chen Jiahao , Xu Yingtian , Liu Yang , Liu Heng , Zhang He , Jin Liang , Shi Linlin , Lan Yunping , Zou Yonggang , Fan Jie
Published: December 2023

2D conjugated metal‐organic frameworks (MOFs) with high in‐plane‐π‐conjugation are attracting significant attention in various fields owing to their outstanding electrical transport property, substantial specific surface areas, and tunable structures. However, their potential in ultrafast photonics has not been extensively explored. Herein, 2D conjugated Ni3(HITP)2 metal‐organic framework (MOF) and graphene (GR) π–π stacked vertical heterostructures (NG‐VHS) are synthesized using an ultrasound‐assisted method. Based on theoretical simulations and characterization analyses, the results suggest that the fast interface charge transfer and the extension of the π‐conjugated electron cloud will significantly enhance the electrical conductivity and the nonlinear optical properties, which is attributed to the π–π stacking interactions between Ni3(HITP)2 and GR. The charge transfer rate of NG‐VHS is given by 6.9 × 1011 s−1. Noticeably, NG‐VHS can serve as an excellent saturable absorber (SA) that can achieve fundamental mode‐locking with a pulse width of 451 fs, harmonic mode‐locking with repetition frequencies up to 1.205 GHz, and tunable dual‐wavelength mode‐locking. These results indicate the potential of NG‐VHS as a promising nonlinear optical material for ultrafast optical applications and a new platform for the design of advanced optoelectronic devices based on 2D conjugated MOFs.
PEDOT:PSS/Ketjenblack Holey Nanosheets with Ultrahigh Areal Capacitance for kHz AC Line‐Filtering Micro‐Supercapacitors
Authors: Zhao Miaomiao , Qin Yuchen , Wang Xinyang , Wang Lixia , Jin Qiu , Song Meirong , Wang Xiaopeng , Qu Liangti
Published: December 2023

Supercapacitors, with their superior capacity and lower space occupancy, offer inherent advantages over aluminum electrolytic capacitors (AECs) in meeting the demands of miniaturization and planarization of devices. However, the capacitive advantage of supercapacitors is often compromised by the limited availability of electrode materials under high‐frequency alternating current conditions. The development of electrode materials that possess both high‐frequency response and high capacity is undoubtedly critical. Herein, PEDOT:PSS/Ketjenblack holey nanosheets (PKHNs) prepared by a solvent thermal method are successfully developed as the electrode material to ensure rapid ion transport and abundant charge storage on the accessible nanosheet surfaces. The micro‐supercapacitors exhibit a high‐frequency capacitance (3089 µF cm−2 at 120 Hz, with a phase angle of −81.9°), achieved through an innovative structural design utilizing PKHNs materials. These micro‐supercapacitors demonstrate excellent frequency response with efficient 120 Hz filtering and offer volumetric advantages over the state‐of‐the‐art commercial ones during low‐voltage operations, making them an ideal choice for the next‐generation miniaturized filter capacitors.
Multiple Non‐Covalent Cross‐Linked Multifunctional Strong Hemostatic Agent for Dynamic Exposure Hemostasis
Authors: Ji Weijun , Li Sidi , Hou Xin , Zhao Jin , Yuan Xubo
Published: December 2023

Trauma requires immediate hemostasis during primary care, as well as durable hemostasis that can withstand dynamic wound exposure. Although current hemostatic materials can treat bleeding sites in emergency situations, their mechanical strength and storage conditions limit their practical application. The simultaneous combination of good mechanical properties, storage stability, biocompatibility, and rapid hemostasis of hemostatic materials remains a challenge. In this paper, a novel hemostatic material based on multiple non‐covalent bond crosslinking, which has excellent mechanical properties, good biocompatibility, storage stability, and rapid hemostasis ability, is reported. Under the drive of multiple non‐covalent bonds, the flowability of hydrogel micro‐modules (HM) decreases rapidly within 20 s after exposure to physiological saline. The HM form a gel barrier with a tensile strength of 62.10 kPa and an elongation at break of 1976% under multiple non‐covalent bonding. Furthermore, the mechanical properties do not change significantly after 30 days of storage. Cell viability is maintained at over 80% after 3 days of incubation with the cells, and the hemolysis test shows a very low hemolysis rate (2.08%). The hemostatic gel formed by HM effectively prevents secondary bleeding in dynamic hemostasis experiments simulating transportation. This work provides a hemostatic material with comprehensive properties for practical applications.
Exudate‐Induced Gelatinizable Nanofiber Membrane with High Exudate Absorption and Super Bactericidal Capacity for Bacteria‐Infected Wound Management
Authors: Wang Wenjie , Yu Qiao , Shao Zijian , Guo Yuxuan , Wang Yilin , Yang Ye , Zhao Weifeng , Zhao Changsheng
Published: December 2023

Invasion of bacteria and continuous oozing of exudate are significant causes of interference with the healing of infected wounds. Therefore, an exudate‐induced gelatinizable and near‐infrared (NIR)‐responsive nanofiber membrane composed of polyvinyl alcohol (PVA), carboxymethyl chitosan (CMC), and Fe‐doped phosphomolybdic acid (Fe‐PMA) with exceptional exudate absorption capacity and potent bactericidal efficacy is developed and denoted as the PVA‐FP‐CMC membrane. After absorbing exudate, the fiber membrane can transform into a hydrogel membrane, forming coordination bonds between the Fe‐PMA and CMC. The unique exudate‐induced gelation process imparts the membrane with high exudate absorption and retention capability, and the formed hydrogel also traps the bacteria that thrive in the exudate. Moreover, it is discovered for the first time that the Fe‐PMA exhibits an enhanced photothermal conversion capability and photocatalytic activity compared to the PMA. Therefore, the presence of Fe‐PMA provides the membrane with a photothermal and photodynamic therapeutic effect for killing bacteria. The PVA‐FP‐CMC membrane is proven with a liquid absorption ratio of 520.7%, a light‐heat conversion efficiency of 41.9%, high‐level generation of hydroxyl radical (•OH) and singlet oxygen (1O2), and a bacterial killing ratio of 100% for S. aureus and 99.6% for E. coli. The treatment of infected wounds on the backs of rats further confirms the promotion of wound healing by the PVA‐FP‐CMC membrane with NIR irradiation. Overall, this novel functional dressing for the synergistic management of bacteria‐infected wounds presents a promising therapeutic strategy for tissue repair and regeneration.
Distinguishing Molecular Mechanical Action from Photothermal and Photodynamic Behavior
Authors: Beckham Jacob L. , Bradford Thomas S. , Ayala‐Orozco Ciceron , Santos Ana L. , Arnold Dallin , van Venrooy Alexis R. , García‐López Víctor , Pal Robert , Tour James M.
Published: December 2023

Molecular motors (MM) are molecular machines, or nanomachines, that rotate unidirectionally upon photostimulation and perform mechanical work on their environment. In the last several years, it has been shown that the photomechanical action of MM can be used to permeabilize lipid bilayers, thereby killing cancer cells and pathogenic microorganisms and controlling cell signaling. The work contributes to a growing acknowledgement that the molecular actuation characteristic of these systems is useful for various applications in biology. However, the mechanical effects of molecular motion on biological materials are difficult to disentangle from photodynamic and photothermal action, which are also present when a light‐absorbing fluorophore is irradiated with light. Here, an overview of the key methods used by various research groups to distinguish the effects of photomechanical, photodynamic, and photothermal action is provided. It is anticipated that this discussion will be helpful to the community seeking to use MM to develop new and distinctive medical technologies that result from mechanical disruption of biological materials.
A Route to Complex Materials Consisting of Multiple Crystalline Phases Ir‐Ru‐IrxRu1‐xO2 as Multifunctional Electrocatalysts
Authors: Knani Sarra , Hajjar Perla , Lacour Marie‐Agnès , van der Lee Arie , Oliviero Erwan , Petit Eddy , Flaud Valerie , Cambedouzou Julien , Tingry Sophie , Napporn Teko W. , Cornu David , Holade Yaovi
Published: December 2023

The synthesis of catalytic materials containing active sites of various oxidation states (metal, oxide, etc.) for the dual use in reduction and oxidation reactions remains challenging because most of the reported methods for the metallic state are often incompatible with those for the oxide state. A new methodology is reported for the synthesis of a library of bimetallic metal‐oxide materials containing three crystalline phases Ir‐Ru‐IrxRu1‐xO2 by combining the calcination under air and the polymerization of aniline in the presence of IrCl3 and RuCl3 precursors. Morphology, structure, and surface oxidation state studies (XRD, SEM/EDX, S/TEM, XPS) confirm the hypothesis that IrCl3 evolves to Ir while RuCl3 evolves to RuO2 during the calcination under air. An Ir:Ru atomic ratio of 50:50 can be converted into a heterogeneous nanostructure composed of Ir, Ru, and IrxRu1‐xO2 to date, with remarkable catalytic activity for both hydrogen evolution reaction (HER) with a small overpotential of 40 mV and oxygen evolution reaction (OER) with a small overpotential of 290 mV at the metric current density of 10 mA cm−2 in 0.5 m H2SO4. The results can serve as a platform for the development of efficient multifunctional materials for practical use in both catalytic oxidation and reduction reactions.
Giant Superbunching Emission from Mesoscopic Perovskite Emitter Clusters
Authors: Qiang Gang , Cai Hongbing , Rasmita Abdullah , He Ruihua , Zhou Lei , Ru Shihao , Cai Xiangbin , Liu Xiaogang , Gao Weibo
Published: December 2023

Photon superbunching, as a crucial resource for photonic quantum technologies, is investigated in several systems. This phenomenon can be induced by both coherent collective spontaneous processes such as superfluorescence and superradiance, and cascaded emission. Although superbunching emission induced by superfluorescence and cascaded emission is demonstrated recently in perovskite quantum dot (QD) superlattice and single perovskite QD, the effect itself is not that strong, especially in the former case with a second‐order photon correlation g(2)(0) only slightly larger than 2. Here, the superbunching emission from mesoscopic CsPbBr3 emitter clusters is reported. The higher temperature and excitation power are found to suppress the superbunching effect significantly. Compared with the former results in the literature, under the same experimental conditions, that is, temperature and excitation power, much larger g(2)(0) with the maximum value of 21 being achieved at 1.6 K with an excitation power of 0.1 µW is observed. The discoveries here improve the understanding of superbunching emission in perovskite‐based materials and will enable their application in developing multi‐photon light sources for photonic quantum technologies.
The Faraday Effect and Phase Transition in the CH3NH3PbI3 Halide Perovskite Single Crystal
Authors: Shumitskaya Anastasia A. , Kozlov Vadim O. , Selivanov Nikita. I. , Stoumpos Constantinos C. , Zapasskii Valerii S. , Kapitonov Yury V. , Ryzhov Ivan I.
Published: December 2023

The spin degree of freedom of charge carriers in halide‐perovskite semiconductors can be highly useful for information photonics applications. The Faraday effect is known to be the best indicator of paramagnetism of the material and of the spin‐light interaction. In this work, the Faraday effect is demonstrated, for the first time, in a hybrid organic–inorganic halide perovskite MAPbI3 (MA+ = CH3NH). The Faraday rotation and birefringence are measured across the tetragonal‐cubic phase transition at 327 K. The Faraday rotation is strongly suppressed below the phase transition temperature due to anisotropy (linear birefringence) of the tetragonal crystal phase. The situation changes drastically above the phase transition temperature, when the crystal becomes optically isotropic. The emerging Faraday rotation obeys the Curie law, demonstrating its population‐related paramagnetic nature. This observation opens new prospects for application of these systems and for their investigations using methods of the polarization noise spectroscopy applicable to optically anisotropic materials.
Hybrid‐Phase Assisted Amplitude and Phase Control Using Full‐Space Metasurface
Authors: Wang Chaohui , Xu He‐Xiu , Liu Tong , Zhang Fan
Published: December 2023

Achieving independent control of phase and amplitude is pivotal yet challenging for electromagnetic (EM) wave manipulation. Metasurface provides an efficient recipe to this challenge, but most of the work reports so far are still confined in half space (transmission or reflection) and manipulation of linearly polarized EM waves, restricting itself from integrating more functionalities with complex wavefronts into one optoelectronic device. Here, a hybrid phase approach synthesizing propagation and geometric phases is proposed to achieve independent and arbitrary control of amplitude and phase response for circularly polarized (CP) wave in full space by using a non‐interleaved single‐celled metasurface. To validate the concept, a full‐space dual‐channel meta‐hologram is experimentally demonstrated, manifesting images of letters “T” and “R” at lower and upper frequencies (f1 and f2), respectively. The finding of full‐space metasurface opens new possibilities to control CP waves by simultaneous amplitude and phase modulations, which is important for high‐capacity wireless communications, as well as sophisticated functionality, and other advanced meta‐devices.
Enhancement‐Mode Phototransistors Based on β‐Ga2O3 Microflakes Fabricated by Focused Ion Beams
Authors: Yang Huarong , Cheng Tong‐Huai , Ouyang Huijia , Xin Qian , Liu Yiyuan , Meng Miao , Yu Feng Hua , Luo Feng , Mu Wenxiang , Jia Zhitai , Tao Xutang
Published: December 2023

This study introduces focused ion beam (FIB) processing for the first time to etch and thin β‐Ga2O3 microflakes, while exploring the effect of their thicknesses on the phototransistor performance. It is found that when the β‐Ga2O3 microflakes reach a certain thickness, the phototransistors switch from the depletion mode to the enhancement mode, exhibiting extremely low dark current without a gate voltage. The enhancement‐mode phototransistor prepared using this method demonstrates a photo‐dark current ratio as high as 2.3 × 105, a responsivity of 6.3 × 104 A W−1, and an external quantum efficiency of 3.1 × 107% when irradiated with incident light at a wavelength of 254 nm and a power density of 8 µW cm−2. Additionally, the device has a rise time of 43 ms and a fall time of 28 ms, respectively. By using FIB processing to etch and thin β‐Ga2O3 microflakes, this study effectively overcomes the poor controllability and low repeatability associated with the traditional mechanical exfoliation method, as well as the residual impurities from the plasma etching method. This opens up a new avenue for fabricating the high‐performance, low‐dimensional phototransistors based on β‐Ga2O3 with high repeatability and controllability.
Advances in Reversible Luminescence Modification and Applications of Inorganic Phosphors Based on Chromism Reaction
Authors: Haider Asif Ali , Zhao Heping , Zi Yinzhu , Xu Zan , Bai Xue , Cun Yangke , Liu Yue , Babeker Hassan , Saeed Abdul , Song Zhiguo , Qiu Jianbei , Huang Anjun , Liao Jiayan , Yang Zhengwen
Published: December 2023

The reversible luminescence modification of inorganic phosphors has emerged as a promising field, enabling innovative applications such as optical memory, multiple anti‐counterfeiting, and photoswitches. Traditional luminescence modulation techniques, such as core–shell structure design and energy transfer‐related luminescent ions regulation, face challenges in achieving reversible luminescence modification. Chromism induces reversible color changes in materials when stimulated by external fields such as electricity, heat, and light. Combining chromism with luminescence enables the creation of chromism‐driven reversible luminescence manipulation in a single material. This review summarizes recent advances in reversible luminescence modification of inorganic phosphors based on chromism reaction and highlights their potential applications in optical data storage, fingerprint acquisition, and anti‐counterfeiting areas. The potential prospective research directions are also discussed and the challenges and opportunities of chromism‐based reversible luminescent materials are presented for further extended applications.
Novel Cr3+‐Doped Garnet Phosphor with Broadband Efficient Far‐Red Emission for Photochrome Matching Plant‐Lighting
Authors: Dai Xiangyi , Zou Xikun , Zhang Haoran , Chen Weibin , Yang Chaowei , Molokeev Maxim S. , Xia Zhiguo , Liu Yingliang , Zhang Xuejie , Zheng Mingtao , Lei Bingfu
Published: December 2023

Cr3+‐doped phosphors are highly recognized in various fields for their remarkable luminous efficiency and spectral flexibility, including modern agriculture and horticulture. However, the shortage of suitable Cr3+‐doped phosphors for far‐red LED devices has inhibited their popularization in plant lighting. Herein, an innovative Cr3+‐doped phosphor Ca2YAl3Ge2O12:Cr3+ (CYAG:Cr3+), achieving a broad far‐red emission at 770 nm upon 450 nm blue light excitation is designed. The optimal CYAG:Cr3+ phosphor exhibits a high internal quantum yield of 78.2% and low thermal‐quenching behavior of 85%@373 K. Thus, the fabricated phosphor‐converted LEDs (pc‐LEDs) for plant far‐red lighting have a high output power of 33.3 mW and photovoltaic conversion efficiency of 11.5% at 100 mA. The potential of CYAG:Cr3+ in plant lighting is assessed by supplementing the far‐red lighting of Italian lettuce with fabricated pc‐LEDs, and the biomass of Italian lettuce is significantly increased by 33%. The successful development of CYAG:Cr3+ phosphors provides a high‐quality option for plant far‐red light devices and further stimulates the development of new Cr3+‐doped plant‐lighting phosphors.
Next‐Generation Vitrimers Design through Theoretical Understanding and Computational Simulations
Authors: Li Ke , Tran Nam Van , Pan Yuqing , Wang Sheng , Jin Zhicheng , Chen Guoliang , Li Shuzhou , Zheng Jianwei , Loh Xian Jun , Li Zibiao
Published: December 2023

Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end‐of‐life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation.
Enhanced Charge Separation in Nanoporous BiVO4 by External Electron Transport Layer Boosts Solar Water Splitting
Authors: Yang Xiaotian , Cui Jianpeng , Lin Luxue , Bian Ang , Dai Jun , Du Wei , Guo Shiying , Hu Jingguo , Xu Xiaoyong
Published: December 2023

The optimization of charge transport with electron‐hole separation directed toward specific redox reactions is a crucial mission for artificial photosynthesis. Bismuth vanadate (BiVO4, BVO) is a popular photoanode material for solar water splitting, but it faces tricky challenges in poor charge separation due to its modest charge transport properties. Here, a concept of the external electron transport layer (ETL) is first proposed and demonstrated its effectiveness in suppressing the charge recombination both in bulk and at surface. Specifically, a conformal carbon capsulation applied on BVO enables a remarkable increase in the charge separation efficiency, thanks to its critical roles in passivating surface charge‐trapping sites and building external conductance channels. Through decorated with an oxygen evolution catalyst to accelerate surface charge transfer, the carbon‐encased BVO (BVO@C) photoanode manifests durable water splitting over 120 h with a high current density of 5.9 mA cm−2 at 1.23 V versus the reversible hydrogen electrode (RHE) under 1 sun irradiation (100 mW cm−2, AM 1.5 G), which is an activity‐stability trade‐off record for single BVO light absorber. This work opens up a new avenue to steer charge separation via external ETL for solar fuel conversion.
Skin‐Inspired Capacitive Flexible Tactile Sensor with an Asymmetric Structure for Detecting Directional Shear Forces
Authors: Yu Haibo , Guo Hongji , Wang Jingang , Zhao Tianming , Zou Wuhao , Zhou Peilin , Xu Zhuang , Zhang Yuzhao , Zheng Jianchen , Zhong Ya , Wang Xiaoduo , Liu Lianqing
Published: December 2023

Flexible pressure sensors based on micro‐/nanostructures can be integrated into robots to achieve sensitive tactile perception. However, conventional symmetric structures, such as pyramids or hemispheres, can sense only the magnitude of a force and not its direction. In this study, a capacitive flexible tactile sensor inspired by skin structures and based on an asymmetric microhair structure array to perceive directional shear force is designed. Asymmetric microhair structures are obtained by two‐photon polymerization (TPP) and replication. Owing to the features of asymmetric microhair structures, different shear force directions result in different deformations. The designed device can determine the directions of both static and dynamic shear forces. Additionally, it exhibits large response scales ranging from 30 Pa to 300 kPa and maintains high stability even after 5000 cycles; the final relative capacitive change (ΔC/C0) is <2.5%. This flexible tactile sensor has the potential to improve the perception and manipulation ability of dexterous hands and enhance the intelligence of robots.
BHLHE40 Inhibits Ferroptosis in Pancreatic Cancer Cells via Upregulating SREBF1
Authors: Cao Yizhi , Wang Xuelong , Liu Yang , Liu Pengyi , Qin Jiejie , Zhu Youwei , Zhai Shuyu , Jiang Yongsheng , Liu Yihao , Han Lijie , Luo Jiaxin , Zhang Ronghao , Shi Minmin , Wang Liwen , Tang Xiaomei , Xue Meilin , Liu Jia , Wang Weishen , Wen Chenlei , Deng Xiaxing , Peng Chenghong , Chen Hao , Cheng Dongfeng , Jiang Lingxi , Shen Baiyong
Published: December 2023

Pancreatic cancer (PCa) is one of the most fatal human malignancies. The enhanced infiltration of stromal tissue into the PCa tumor microenvironment limits the identification of key tumor‐specific transcription factors and epigenomic abnormalities in malignant epithelial cells. Integrated transcriptome and epigenetic multiomics analyses of the paired PCa organoids indicate that the basic helix‐loop‐helix transcription factor 40 (BHLHE40) is significantly upregulated in tumor samples. Increased chromatin accessibility at the promoter region and enhanced mTOR pathway activity contribute to the elevated expression of BHLHE40. Integrated analysis of chromatin immunoprecipitation‐seq, RNA‐seq, and high‐throughput chromosome conformation capture data, together with chromosome conformation capture assays, indicate that BHLHE40 not only regulates sterol regulatory element‐binding factor 1 (SREBF1) transcription as a classic transcription factor but also links the enhancer and promoter regions of SREBF1. It is found that the BHLHE40‐SREBF1‐stearoyl‐CoA desaturase axis protects PCa cells from ferroptosis, resulting in the reduced accumulation of lipid peroxidation. Moreover, fatostatin, an SREBF1 inhibitor, significantly suppresses the growth of PCa tumors with high expressions of BHLHE40. This study highlights the important roles of BHLHE40‐mediated lipid peroxidation in inducing ferroptosis in PCa cells and provides a novel mechanism underlying SREBF1 overexpression in PCa.
Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2− Constructed from Twisted Cu13 Units
Authors: Zhou Huimin , Duan Tengfei , Lin Zidong , Yang Tao , Deng Huijuan , Jin Shan , Pei Yong , Zhu Manzhou
Published: December 2023

Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper‐hydride nanocluster, [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2− via a mild one‐pot reaction is presented. Through X‐ray crystallography analysis, it is revealed that [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2− exhibits a unique shell–core–shell structure. The inner Cu29 kernel is composed of three twisted Cu13 units, connected through Cu4 face sharing. Surrounding the metal core, two Cu6 metal shells, resembling a protective sandwich structure are observed. This arrangement, along with intracluster π···π interactions and intercluster C─H···F─C interactions, contributes to the enhanced stability of [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2−. The presence, number, and location of hydrides within the nanocluster are established through a combination of experimental and density functional theory investigations. Notably, the addition of a phosphine ligand triggers a fascinating nanocluster‐to‐nanocluster transformation in [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2−, resulting in the generation of two nanoclusters, [Cu14(SC6H3F2)3(PPh3)8H10]+ and [Cu13(SC6H3F2)3(P(PhF)3)7H10]0. Furthermore, it is demonstrated that [Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2− exhibits catalytic activity in the hydrogenation of nitroarenes. This intriguing nanocluster provides a unique opportunity to explore the assembly of M13 units, similar to other coinage metal nanoclusters, and investigate the nanocluster‐to‐nanocluster transformation in phosphine and thiol ligand co‐protected copper nanoclusters.
Observation of the Anomalous Hall Effect in a Layered Polar Semiconductor
Authors: Kim Seo‐Jin , Zhu Jihang , Piva Mario M. , Schmidt Marcus , Fartab Dorsa , Mackenzie Andrew P. , Baenitz Michael , Nicklas Michael , Rosner Helge , Cook Ashley M. , González‐Hernández Rafael , Šmejkal Libor , Zhang Haijing
Published: December 2023

Progress in magnetoelectric materials is hindered by apparently contradictory requirements for time‐reversal symmetry broken and polar ferroelectric electronic structure in common ferromagnets and antiferromagnets. Alternative routes can be provided by recent discoveries of a time‐reversal symmetry breaking anomalous Hall effect (AHE) in noncollinear magnets and altermagnets, but hitherto reported bulk materials are not polar. Here, the authors report the observation of a spontaneous AHE in doped AgCrSe2, a layered polar semiconductor with an antiferromagnetic coupling between Cr spins in adjacent layers. The anomalous Hall resistivity 3 is comparable to the largest observed in compensated magnetic systems to date, and is rapidly switched off when the angle of an applied magnetic field is rotated to ≈80° from the crystalline c‐axis. The ionic gating experiments show that the anomalous Hall conductivity magnitude can be enhanced by modulating the p‐type carrier density. They also present theoretical results that suggest the AHE is driven by Berry curvature due to noncollinear antiferromagnetic correlations among Cr spins, which are consistent with the previously suggested magnetic ordering in AgCrSe2. The results open the possibility to study the interplay of magnetic and ferroelectric‐like responses in this fascinating class of materials.
Study on Growth of Tungsten Bronze Phase from Niobate Perovskite Ceramics in Controlled Atmosphere for Photoferroelectric Applications
Authors: Shi Xi , Bai Yang , Wichmann Christoph , Moritz Michael , Kuhfuß Michel , Papp Christian , Khansur Neamul H
Published: December 2023

Recent research has found that by introducing A‐site deficiency into Ba/Ni co‐doped (K,Na)NbO3 ABO3‐type perovskite, a beneficial interface for photoferroelectric applications is formed between the perovskite and tungsten bronze (TB) phases. To date, such an interface is formed only spontaneously, and the growth mechanism of the TB phase in the perovskite phase is unclear. This work investigates controlled interface formation using KNBNNO (K0.50Na0.44Ba0.04Ni0.02Nb0.98O2.98) annealed at different temperatures for different durations, and in various atmospheres. Structural, microstructural, and chemical analyses suggest that vacuum, N2, and O2 atmospheres promote the growth of the TB phase from the sample surface, of which the thickness increases with annealing temperature and duration. In contrast, annealing in air does not promote such growth due to lower evaporation of K and Na. Among all atmospheres, the growth starts the earliest, i.e., at 800 °C, in vacuum compared to that as late as 1000 °C in O2. The association of growth of the TB phase with the degree of alkali volatilization that is dependent on the atmosphere, and that with the resultant variation in diffusion rate, uncovers the formation mechanism of the beneficial interface that may also be applicable to other KNN‐based materials for advanced photoferroelectric applications.
Multivalent Cation Transport in Polymer Electrolytes – Reflections on an Old Problem
Authors: Jeschull Fabian , Hub Cornelius , Kolesnikov Timofey I. , Sundermann David , Hernández Guiomar , Voll Dominik , Mindemark Jonas , Théato Patrick
Published: December 2023

Today an unprecedented diversification is witnessed in battery technologies towards so‐called post‐Li batteries, which include both other monovalent (Na+ or K+) and multivalent ions (e.g., Mg2+ or Ca2+). This development is driven, among other factors, by goals to establish more sustainable and cheaper raw material platforms, using more abundant raw material, while maintaining high energy densities. For these new technologies a decisive role falls to the electrolyte, that ultimately needs to form stable electrode‐electrolyte interfaces and provide sufficient ionic conductivity, while guaranteeing high safety. The transport of metal‐ions in a polymer matrix is studied extensively as solid electrolytes for battery applications, particularly for Li‐ion batteries and are now also considered for multivalent systems. This poses a great challenge as ion transport in the solid becomes increasingly difficult for multivalent ions. Interestingly, this topic is a subject of interest for many years in the 80s and 90s and many of the problems then are still causing issues today. Owing to recent progress in this field new possibilities arise for multivalent ion transport in solid polymer electrolytes. For this reason, in this perspective a stroll down memory lane is taken, discuss current advancements and dare a peek into the future.
Nonconventional aggregation‐induced emission polysiloxanes: Structures, characteristics, and applications
Authors: Zhao Yan , Xu Lei , He Yanyun , Feng Zhixuan , Feng Weixu , Yan Hongxia
Published: December 2023

Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics, including water‐solubility, biocompatibility, and environmental friendliness and have shown potential applications in diverse fields. As an indispensable branch of nonconventional luminescent materials, polysiloxanes, which consist of electron‐rich auxochromic groups, have exhibited outstanding photophysical properties due to the unique silicon atoms. The flexible Si‐O bonds benefit the aggregation, and the empty 3d orbitals of Si atoms can generate coordination bonds including N → Si and O → Si, altering the electron delocalization of the material and improving the luminescent purity. Herein, we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives. With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions, the role of Si atoms played in the nonconventional luminophores is highlighted. This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing, biomedicine, lighting devices, etc.
Fluorescent pH‐sensing bandage for point‐of‐care wound diagnostics
Authors: Al‐Hawat Marie‐Lynn , Cherifi Katia , Tricou Léo‐Paul , Lamontagne Stéphanie , Tran Minh , Ngu Amy Ching Yie , Manrique Gabriela , Guirguis Natalie , Machuca‐Parra Arturo Israel , Matoori Simon
Published: December 2023

Diabetic foot ulcers (DFUs) are a serious and prevalent complication of diabetes. Current diagnostic options are limited to macroscopic wound analysis such as wound size, depth, and infection. Molecular diagnostics promise to improve DFU diagnosis, staging, and assessment of treatment response. Here, we developed a rapid and easy‐to‐use fluorescent pH‐sensing bandage for wound diagnostics. In a fluorescent dye screen, we identified pyranine as the lead compound due to its suitable pH‐sensing properties in the clinically relevant pH range of 6–9. To minimize the release of this dye into the wound bed, we screened a library of ionic microparticles and found a strong adhesion of the anionic dye to a cationic polymeric microparticle. These dye‐loaded microparticles showed a strong fluorescence response in the clinically relevant pH range of 6–9 and a dye release below 1% after 1 day in biological media. The dye‐loaded microparticles were subsequently encapsulated in a calcium alginate hydrogel to minimize the interaction of the microparticles with the wound tissue. This pH‐sensing diagnostic wound dressing was tested on full thickness dorsal wounds of mice, and a linear fluorescence response (R2 = 0.9909) to clinically relevant pH values was observed. These findings encourage further development of this pH‐sensing system for molecular diagnostics in DFUs.
What explains the high island endemicity of Philippine Rafflesia? A species distribution modeling analysis of three threatened parasitic plant species and their hosts
Authors: Obico Jasper J. A. , Lapuz R. Sedricke C. , Barcelona Julie F. , Pelser Pieter B.
Published: December 2023

Premise

Rafflesia are rare holoparasitic plants. In the Philippines, all but one species are found only on single islands. This study aimed to better understand the factors contributing to this distributional pattern. Specifically, we sought to determine whether narrow environmental tolerances of host and/or parasite species might explain their island endemicity.

Methods

We used Maxent species distribution modeling to identify areas with suitable habitat for R. lagascae, R. lobata, and R. speciosa and their Tetrastigma host species. These analyses were carried out for current climate conditions and two future climate change scenarios.

Results

Although species distribution models indicated suitable environmental conditions for the Tetrastigma host species in many parts of the Philippines, considerably fewer areas were inferred to have suitable conditions for the three Rafflesia species. Some of these areas are on islands from which they have not been reported. All three species will face significant threats as a result of climate change.

Conclusions

Our results suggest that limited inter‐island dispersibility and/or specific environmental requirements are likely responsible for the current pattern of island endemicity of the three Rafflesia species, rather than environmental requirements of their Tetrastigma host species.
Role of Basal Forebrain Neurons in Adrenomyeloneuropathy in Mice and Humans
Authors: Gong Yi , Laheji Fiza , Berenson Anna , Li Yedda , Moser Ann , Qian April , Frosch Matthew , Sadjadi Reza , Hahn Ryan , Maguire Casey A. , Eichler Florian
Published: December 2023

Objective

X‐linked adrenoleukodystrophy is caused by mutations in the peroxisomal half‐transporter ABCD1. The most common manifestation is adrenomyeloneuropathy, a hereditary spastic paraplegia of adulthood. The present study set out to understand the role of neuronal ABCD1 in mice and humans with adrenomyeloneuropathy.

Methods

Neuronal expression of ABCD1 during development was assessed in mice and humans. ABCD1‐deficient mice and human brain tissues were examined for corresponding pathology. Next, we silenced ABCD1 in cholinergic Sh‐sy5y neurons to investigate its impact on neuronal function. Finally, we tested adeno‐associated virus vector‐mediated ABCD1 delivery to the brain in mice with adrenomyeloneuropathy.

Results

ABCD1 is highly expressed in neurons located in the periaqueductal gray matter, basal forebrain and hypothalamus. In ABCD1‐deficient mice (Abcd1−/y), these structures showed mild accumulations of α‐synuclein. Similarly, healthy human controls had high expression of ABCD1 in deep gray nuclei, whereas X‐ALD patients showed increased levels of phosphorylated tau, gliosis, and complement activation in those same regions, albeit not to the degree seen in neurodegenerative tauopathies. Silencing ABCD1 in Sh‐sy5y neurons impaired expression of functional proteins and decreased acetylcholine levels, similar to observations in plasma of Abcd1−/y mice. Notably, hind limb clasping in Abcd1−/y mice was corrected through transduction of ABCD1 in basal forebrain neurons following intracerebroventricular gene delivery.

Interpretation

Our study suggests that the basal forebrain–cortical cholinergic pathway may contribute to dysfunction in adrenomyeloneuropathy. Rescuing peroxisomal transport activity in basal forebrain neurons and supporting glial cells might represent a viable therapeutic strategy. ANN NEUROL 2024;95:442–458
Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes
Authors: Fang Tongchang , Wang Liwei , Wu Miaomiao , Qi Xiaotian , Liu Chao
Published: December 2023

The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis of diborodichloromethane (DBDCM) through the reaction of trichloromethyllithium with bis(pinacolato)diboron (B2pin2). The resulting DBDCM reagent serves as a basic synthetic unit for the construction of various structurally diverse gem‐diborylalkanes through controllable C−Cl functionalizations. Moreover, we have developed consecutive tetra‐functionalizations of DBDCM for the construction of diverse tertiary and quaternary carbon containing molecules. The use of isotopically enriched 13C‐chloroform and 10B2pin2 enables the synthesis of isotopically enriched 13C‐DBDCM and 10B‐DBDCM reagents, which are beneficial for the convenient synthesis of carbon‐13 and boron‐10 molecules.
Vacancy‐induced catalytic mechanism for alcohol electrooxidation on nickel‐based electrocatalyst
Authors: Chen Wei , Shi Jianqiao , Wu Yandong , Jiang Yimin , Huang Yu‐Cheng , Zhou Wang , Liu Jilei , Dong Chung‐Li , Zou Yuqin , Wang Shuangyin
Published: December 2023

Owing to outstanding performances, nickel‐based electrocatalysts are commonly used in electrochemical alcohol oxidation reactions (AORs), and the active phase is usually vacancy‐rich nickel oxide/hydroxide (NiOxHy) species. However, researchers are not aware of the catalytic role of atom vacancy in AORs. Here, we study vacancy‐induced catalytic mechanisms for AORs on NiOxHy species. As to AORs on oxygen‐vacancy‐poor β‐Ni(OH)2, the only redox mediator is electrooxidation‐induced electrophilic lattice oxygen species, which can only catalyze the dehydrogenation process (e.g., the electrooxidation of primary alcohol to carboxylic acid) instead of the C−C bond cleavage. Hence, vicinal diol electrooxidation reaction involving the C−C bond cleavage is not feasible with oxygen‐vacancy‐poor β‐Ni(OH)2. Only through oxygen vacancy‐induced adsorbed oxygen‐mediated mechanism, can oxygen‐vacancy‐rich NiOxHy species catalyze the electrooxidation of vicinal diol to carboxylic acid and formic acid accompanied with the C−C bond cleavage. Crucially, we examine how vacancies and vacancy‐induced catalytic mechanisms work during AORs on NiOxHy species.
Influence of dielectric properties of polybutylene terephthalate and respective foam beads on process behavior in radio‐frequency welding
Authors: Dippold Marcel , Töpfer Christian , Ruckdäschel Holger
Published: December 2023

Radio‐frequency welding shows great potential for a more sustainable manufacturing of lightweight bead foam products based on local dielectric heating of the part. This study provides the first insight into the material‐process interactions required to enable interdiffusion between foam particles and thus adhesion. The complex relative permittivity is analyzed by impedance spectroscopy of the bulk polymer and foam beads using specially designed measurement cells. Due to the increased flexibility of the polymer chains at elevated temperatures, the relaxation mechanisms are promoted, resulting in a shift of the curves to higher frequencies. At a fixed frequency, a peak in the imaginary part is observed above temperature, revealing the superposition of these two parameters. The foamed beads show similar trends with an attenuated signal due to the high volumetric fraction of air within the multiphase system. The linear dependence between and volumetric power as direct process feedback due to dielectric heating was observed during welding. Compared to the delayed signals from the shielded temperature sensors, the analysis of power consumption allows for higher quality real‐time monitoring throughout the process cycle. The correlation also allows prediction of power levels at defined temperatures.
African swine fever virus E120R inhibited cGAS‐STING‐mediated IFN‐β and NF‐κB pathways
Authors: Cui Shuai , Wang Yang , Chen Shiyu , Fang Lichun , Jiang Yajun , Pang Zhongbao , Jiang Yitong , Guo Xiaoyu , Zhu Hongfei , Jia Hong
Published: December 2023

African swine fever (ASF) is an acute and severe contagious disease triggered by the African swine fever virus (ASFV), which severely threatens the global swine industry. At present, no safe and efficacious vaccine has been provided to prevent and control this disease. The pathogenesis and immune evasion mechanism of ASFV are still unknown, which seriously hinders the development of safe and effective ASF vaccines. Certain proteins of ASFV involved in immunosuppression helped to evade the host innate immune response. The cGAS‐STING signaling pathway is important to the innate immune system. It induces the production of type I interferons (IFNs) and other cytokines by recognizing cytoplasmic DNA, mediating antimicrobial innate immunity through type I IFN, and nuclear factor‐κB (NF‐κB) pathways. In the present study, E120R, a late‐phase expression protein and a key virulent factor of ASFV inhibited cGAS‐STING mediated promoter activities of IFN‐β and NF‐κB in HEK293T cells. The ectopic expression of E120R down‐regulated IFN‐β pathway by targeting interferon regulatory factor 3 (IRF3) and p65, inhibited the phosphorylation of STING, and further inhibited the phosphorylation of TANK‐binding kinase 1 (TBK1) and IRF3, with no significant effects on p65 phosphorylation. Additionally, E120R also inhibited the NF‐κB pathways by inhibiting the nuclear translocation of p50 and p65, which was mediated by Sendai virus (SeV). Further, the study showed that the 61–80 amino acids sites in the C‐terminal domain of E120R were crucial for these functions. In conclusion, our work preliminarily elucidated a novel mechanism of inhibiting host innate immune response by ASFV E120R, which will provide a new target for the ASFV live gene deletion vaccine development and the theoretical basis for ASFV prevention.
Lipase‐catalyzed production of biodiesel: a critical review on feedstock, enzyme carrier and process factors
Authors: Xia Shuaibo , Lin Jiale , Sayanjali Sara , Shen Cai , Cheong Ling‐Zhi
Published: December 2023

Biodiesel is a green and renewable alternative energy source which can be produced through lipase‐catalyzed transesterification process. Enzymatic biodiesel production has generated much interest owing to its environmentally friendly process, low wastewater treatment requirements and easy product separation. In this work, we attempt to review some of the recent patents and state‐of‐the‐art technology in lipase‐catalyzed transesterification for biodiesel production including feedstock, lipases, novel carriers and process factors. This work will provide useful guidance for researchers to develop cost efficient process for production of biodiesels.
DREAM a little dREAM of DRM: Model organisms and conservation of DREAM‐like complexes
Authors: Hoareau Marion , Rincheval‐Arnold Aurore , Gaumer Sébastien , Guénal Isabelle
Published: December 2023

DREAM complexes are transcriptional regulators that control the expression of hundreds to thousands of target genes involved in the cell cycle, quiescence, differentiation, and apoptosis. These complexes contain many subunits that can vary according to the considered target genes. Depending on their composition and the nature of the partners they recruit, DREAM complexes control gene expression through diverse mechanisms, including chromatin remodeling, transcription cofactor and factor recruitment at various genomic binding sites. This complexity is particularly high in mammals. Since the discovery of the first dREAM complex (drosophila Rb, E2F, and Myb) in Drosophila melanogaster, model organisms such as Caenorhabditis elegans, and plants allowed a deeper understanding of the processes regulated by DREAM‐like complexes. Here, we review the conservation of these complexes. We discuss the contribution of model organisms to the study of DREAM‐mediated transcriptional regulatory mechanisms and their relevance in characterizing novel activities of DREAM complexes.