bluuebunny/crossref_metadata_2025_split huggingface dataset:
Beating the Responsivity‐Speed Trade‐Off in Asymmetric GaN‐Based UV Photodetectors: A Novel van der Waals Metal Contact Approach
Authors: Li Fang , Liu Xin , Wang Danhao , Kang Yang , Zhang Jiahao , Luo Dongyang , Sun Xiyu , Zhang Haochen , Chen Wei , Luo Yuanmin , Yu Huabin , Memon Muhammad Hunain , Sun Haiding 
Published: April 2024

AbstractAsymmetric‐type UV photodetectors have attracted extensive interest for their applications in modern optoelectronics. Conventional fabrication approaches for asymmetric metal contacts typically cause damage at the metal‐semiconductor interface, leading to Fermi level pinning and further limiting barrier height adjustability and functionality. Herein, for the first time, van der Waals (vdW) asymmetric metal contact on wide bandgap semiconductor gallium‐nitride (GaN) is successfully fabricated and achieve the mitigation of Fermi level pinning effect through the formation of a damage‐free metal‐semiconductor interface. Scanning transmission electron microscopy reveals an atomically clean and sharp interface with a distinct vdW gap between the semiconductor and metal electrode. More importantly, the absence of interface damage effectively suppresses charge recombination and results in substantial enhancement in photoresponse characteristics, demonstrating an increased responsivity from 1.8 to 56.7 A W−1 along with a significantly improved response/recovery time from 545/115 to 420/20 ms and an ultralow dark current at the picoampere‐level compared to that of the photodetector with electrodes fabricated with traditional e‐beam evaporated technique. Such simultaneously enhanced responsivity and response speed overcome the responsivity‐speed trade‐off in asymmetric photodetectors and mark a milestone in integrating asymmetric metal contacts with semiconductors through a non‐destructive manner, offering unparalleled opportunities for developing high‐performance asymmetric optoelectronic systems.
Generation of High‐Purity Full Poincaré Beam Arrays via Metasurface Integrated Degenerate Cavity
Authors: Ma Siyuan , Xu Mingfeng , Pu Mingbo , Zheng Yuhan , Zeng Qingji , Luo Xin , Zhang Fei , Guo Yinghui , Li Xiong , Ma Xiaoliang , Luo Xiangang 
Published: April 2024

AbstractRecently, full Poincaré beams (FPBs) with spatially variant polarization states spanning the entire surface of the Poincaré sphere have attracted considerable interests. Expanding the FPBs into an array way has the promising applications from multiparticle manipulation to optical communication. However, how to efficiently generate a high‐purity FPB array with intracavity method remains elusive. Here, a metasurface‐integrated degenerate cavity laser is proposed for efficient generation of 10 × 10 FPB array, where a pair of metasurfaces are adopted to independently modulate the circular polarization state while compensating the mode discrepancies within the cavity. Such a design strategy enables a self‐reproducing intracavity optical field, concurrently ensuring the stabilization of intracavity oscillation. It is numerically demonstrated that the purity of orbital angular momentum (OAM) in the first‐order FPB array can approach to 92.89%, with a root‐mean‐square error (RMSE) of polarization ellipse parameters below 8.17%. This work provides a compact and efficient design platform for the generation of a variety of vector beam arrays and may find promising applications in free space communication and multiple particle manipulation.
Phospholanes via Twofold C‐H‐Addition to Phospholes
Authors: Getfert K. , Roesler F. , Bruhn C. , Pietschnig R. 
Published: April 2024

AbstractA synthetic route towards phospholanes via twofold C−H‐addition of a DMSO molecule to β‐H substituted phospholes is described. The resulting fused phospholane oxothiolane system in case of symmetric α‐substitution possesses four stereogenic centers or rather six in case of asymmetric α‐substitution. The reaction conditions are shown to be applicable for a variety of phospholes with different P‐ or α‐substituents always leading to stereoselective formation of the fused heterocyclic ring system. All phospholane derivatives with one exception are sufficiently air stable for purification with column chromatography and are fully characterized by NMR and elemental analysis and mass spectrometry. With the help of X‐ray crystallography, the different configurations of the isomers could be demonstrated. For one model system derivatization reactions are presented. When oxidizing or reducing the sulfoxide group only a single diastereomer is observed.
2D Semiconductor Nanostructures for Solar‐Driven Photocatalysis: Unveiling Challenges and Prospects in Air Purification, Sustainable Energy Harvesting, and Water Treatment
Authors: Boukhvalov Danil W. , Politano Grazia Giuseppina , D'Olimpio Gianluca , Politano Antonio 
Published: April 2024

AbstractThe use of solar light to accelerate chemical processes (photocatalysis) has the potential to alleviate the pollution and energy crises. Thanks to their large surface area, unusual electronic structure, and abundance of low‐coordinate surface atoms, 2D semiconductors have shown enormous promise in photocatalytic applications. The synthesis, photoexcitation processes, design, and development of 2D semiconductor photocatalysts are thoroughly examined in this perspective, as well as their possible applications in air purification, solar energy conversion, organic synthesis, carbon capture and storage, and water treatment. This work highlights ongoing research efforts focused on improving the selectivity and efficiency of photocatalytic applications based on 2D semiconductors by means of hybrid systems, heterostructures, doping, and computational methodologies, together with open challenges. Finally, the integration of 2D semiconductor photocatalysts into indoor and outdoor environments is discussed, thereby facilitating the purification of air and water and generating clean energy, which assists in the pursuit of sustainable development objectives.
The Electrochemical Hydrogen Evolution Reaction Based on Helical Chain Stacked 2D Tellurium Nanoflakes
Authors: Yu Jing , Wang Yingying , Liu Wenjun , Fan Xiaofeng , Duang Yuhao , Zhang Fan , Jiang Yanxiao 
Published: April 2024

AbstractA crucial factor in advancing the broad utilization of electrocatalytic hydrogen evolution reaction (HER) is the development of efficient catalysts with sufficient active sites. Herein, a hydrothermal approach is utilized to fabricate helical chain stacked two‐dimensional (2D) tellurium (Te) nanoflakes, whose HER performance hasn't been systematically studied yet. It is found that Te nanoflakes transferred on carbon fiber paper (CFP) exhibit impressive HER properties and show a load dependence. The overpotential required for HER is significantly reduced to 279 mV under a load condition of 0.86 mg cm−2 at a current density of 10 mA cm−2. Density functional theory (DFT) calculations are further systematically carried out on Te catalytic sites along the helical chain at [0001] direction with a threefold screw symmetry. It is found that the Gibbs free energy of adsorbed hydrogen atom (ΔGH*) on Te sites is significantly lower than that of molybdenum disulfide (MoS2). Besides, the active sites based on surface atom density calculation reveal that Te provides more adsorption sites than layered MoS2. The decreased adsorption energy and efficient adsorption sites in Te may highlight the promising application of elemental crystal Te in electrocatalytic hydrogen production and pave the way for developing new types of electrocatalysts.
Self‐Powered Biomimetic Pressure Sensor Based on Mn–Ag Electrochemical Reaction for Monitoring Rehabilitation Training of Athletes
Authors: Yang Ziyan , Wang Qingzhou , Yu Huixin , Xu Qing , Li Yuanyue , Cao Minghui , Dhakal Rajendra , Li Yang , Yao Zhao 
Published: April 2024

AbstractSelf‐powered pressure detection using smart wearable devices is the subject of intense research attention, which is intended to address the critical need for prolonged and uninterrupted operations. Current piezoelectric and triboelectric sensors well respond to dynamic stimuli while overlooking static stimuli. This study proposes a dual‐response potentiometric pressure sensor that responds to both dynamic and static stimuli. The proposed sensor utilizes interdigital electrodes with MnO2/carbon/polyvinyl alcohol (PVA) as the cathode and conductive silver paste as the anode. The electrolyte layer incorporates a mixed hydrogel of PVA and phosphoric acid. The optimized interdigital electrodes and sandpaper‐like microstructured surface of the hydrogel electrolyte contribute to enhanced performance by facilitating an increased contact area between the electrolyte and electrodes. The sensor features an open‐circuit voltage of 0.927 V, a short‐circuit current of 6 µA, a higher sensitivity of 14 mV/kPa, and outstanding cycling performance (>5000 cycles). It can accurately recognize letter writing and enable capacitor charging and LED lighting. Additionally, a data acquisition and display system employing the proposed sensor, which facilitates the monitoring of athletes’ rehabilitation training, and machine learning algorithms that effectively guide rehabilitation actions are presented. This study offers novel solutions for the future development of smart wearable devices.
Photoexcitation Altered Reaction Pathway Greatly Facilitate Ammonia Synthesis Over Isolated Ru Sites
Authors: Feng Chengyang , Raziq Fazal , Hu Miao , Huang Huawei , Wu Zhi‐Peng , Zuo Shouwei , Luo Jun , Ren Yuanfu , Chang Bin , Cha Dongkyu , Ayirala Subhash , Al‐Yousef Ali , Dao Thang Duy , Zhang Huabin 
Published: April 2024

AbstractAmmonia, poised as a carbon‐neutral energy carrier, holds immense promise in reshaping the future energy landscape. Despite the enduring importance of the Haber–Bosch process in ammonia production, its substantial carbon emissions and energy demands necessitate more sustainable pathways. Here, an advanced ammonia synthesis route, enhanced by photoexcitation is demonstrated, which fundamentally modifies the activation pathways of N2 molecules. This alteration significantly lowers the reaction activation energy, resulting in remarkably improved reaction efficiency. The impact of light excitation culminates in an unprecedented ammonia synthesis rate of 18 mmol g−1 h−1, surpassing the traditional thermal catalytic process by 2.57‐fold. More importantly, light assistance reduces the thermal energy input by ≈16%, making it comparable to thermal catalysis while substantially improving energy utilization. This work introduces a greener strategy for ammonia synthesis, pushing the century‐old fossil‐fueled Haber–Bosch process to a new frontier.
In Situ Polymerization Inhibiting Electron Localization in Hybrid Electrolyte for Room‐Temperature Solid‐State Lithium Metal Batteries
Authors: Shen Chunli , Feng Wencong , Yu Yongkun , Wang Hanxiao , Cheng Yu , Dong Chenxu , Gu Jiapei , Zheng Aqian , Liao Xiaobin , Xu Xu , Mai Liqiang 
Published: April 2024

AbstractHybrid solid electrolytes (HSEs) have attracted much attention due to their advantages as both inorganic and organic polymer electrolytes. However, the organic/inorganic interfacial space charge layer has a great barrier to the transport of Li+ in the HSE. Here, an in situ polymerization layer is proposed on garnet‐type particles, working as the coherent region to eliminate the space charge layer at the organic/inorganic interfaces by inhibiting electron localization. The conjugate hybridization of fillers weakens the aggregation of particles, induces the dissociation of Li salt, and provides high‐throughput Li+ transport pathways at the ceramics/polymer interface. Furthermore, the continuous Li+ conduction networks are connected by the coherent region between inorganic fillers and polymer chains. The fabricated HSE exhibits a high ionic conductivity of 0.47 mS cm−1 and ion migration numbers of 0.78 at room temperature. The 3D Li//Li systematic battery assembled with the HSE delivers a high critical current density (CCD) of 2.0 mA cm−2. Meanwhile, the 4.5 V NCM811//Li batteries achieve a prolonged operation of 500 cycles at 0.5 C. The Li//LiFePO4 batteries demonstrate superior capacity retention of 96.4% at 1 C after 500 cycles.
Crystallographic Manipulation Strategies toward Reversible Zn Anode with Orientational Deposition
Authors: Yang Xianzhong , Dong Zixing , Weng Gao , Su Yiwen , Huang Jiawen , Chai Hong , Zhang Ying , Wu Kuan , Baek Jong‐Beom , Sun Jingyu , Chao Dongliang , Liu Huakun , Dou Shixue , Wu Chao 
Published: April 2024

AbstractThe reversibility and sustainability of Zn anode are greatly hampered by the dendrite growth and side reactions. Orientational deposition, which allows the assembly of Zn deposits in a highly ordered and compact manner, offers a solution to these issues by enabling dendrite‐free Zn anodes. Moreover, Zn orientational deposition can effectively inhibit side reaction by reducing the exposed surface area of the electrode. Despite significant progress in the field of Zn orientational deposition, there is still a lack of clear guidelines for regulating the orientation, and the underlying mechanisms remain rather elusive. Therefore, a comprehensive review is urgently needed to provide a mechanistic insight into Zn orientational deposition. This review summarizes the burgeoning strategies for steering Zn orientational deposition, categorizing the corresponding mechanisms into five aspects: heteroepitaxial deposition, homoepitaxial deposition, interfacial cultivation, crystal facet anchoring, and current density regulation. The distinct advantages and limitations of each mechanism in controlling the growth orientation are discussed in detail. Finally, the challenges and future trends pertaining to Zn orientational deposition are envisaged, aiming in essence to realize highly reversible Zn anodes and ultimately bridge the gap between reality and ideal in aqueous Zn‐ion batteries.
Manipulating noncovalent conformational lock via side‐chain engineering for luminescence at aggregate level
Authors: Lian Mingbing , Mu Yingxiao , Ye Zecong , Lu Ziying , Xiao Jingping , Zhang Jianyu , Ji Shaomin , Zhang Haoke , Huo Yanping , Tang Ben Zhong 
Published: April 2024

AbstractThe unfavorable photochemical processes at the molecular level have become a barrier limiting the use of aromatic amides as high‐performance luminescent materials. Herein, we propose a reliable strategy for manipulating noncovalent conformational lock (NCL) via side‐chain engineering to burst out eye‐catching luminescence at the aggregate level. Contrary to the invisible emission in dilute solutions, dyad OO with a three‐centered H‐bond gave the wondrous crystallization‐induced emission with a quantum yield of 66.8% and clusterization‐triggered emission, which were much brighter than those of isomers. Theoretical calculations demonstrate that crystallization‐induced planarized intramolecular charge transfer (PICT), conformation rigidification, and through‐space conjugation (TSC) are responsible for aggregate‐state luminescence. Robust NCL composed of intramolecular N‐H···O interactions could boost molecular rigidity and planarity, thus greatly facilitating PICT and TSC. This study would inspire researchers to design efficient luminescent materials at the aggregate level via rational conformational control.
Rethinking pathways to the dioecy–polyploidy association: Genera with many dioecious species have fewer polyploids
Authors: Osterman Wilhelm H. A. , Hill Adrian , Hagan James G. , Whitton Jeannette , Bacon Christine D. , Bjorkman Anne D. 
Published: April 2024

AbstractPremiseNumerous studies have found a positive association between dioecy and polyploidy; however, this association presents a theoretical conflict: While polyploids are predicted to benefit from self‐reproduction for successful establishment, dioecious species cannot self‐reproduce. We propose a theoretical framework to resolve this apparent conflict. We hypothesize that the inability of dioecious species to self‐reproduce hinders their establishment as polyploids. We therefore expect that genera with many dioecious species have fewer polyploids, leading to a negative association between polyploidy and dioecy across genera.MethodsWe used three publicly available databases to determine ploidy and sexual systems for 131 genera and 546 species. We quantified (1) the relationship between the frequency of polyploid species and the frequency of dioecious species across genera, and (2) the proportion of polyploids with hermaphroditism and dioecy across species, adjusting for phylogenetic history.ResultsAcross genera, we found a negative relationship between the proportion of polyploids and the proportion of dioecious species, a consistent trend across clades. Across all species, we found that sexual system (dioecious or not) was not associated with polyploidy.ConclusionsPolyploids are rare in genera in which the majority of species are dioecious, consistent with the theory that self‐reproduction favors polyploid establishment. The low frequency of polyploidy among dioecious species indicates the association is not as widespread as previously suggested. Our findings are consistent with previous studies identifying a positive relationship between the two traits, but only if polyploidy promotes a transition to dioecy, and not the reverse.
The Role of Hydrogen Bonds in Thermally Responsive Crystallization‐Driven Template Autocatalysis
Authors: Wu Huimin , Chen Qing‐Xuan , Su Yang , Chen Zhen 
Published: April 2024

AbstractAutocatalysis has been recognized to be involved in the emergence of life and intrinsic to biomolecular replication. Recently, an efficient template autocatalysis driven by solvent‐free crystallization has been reported. Herein, we unveil the role of intermolecular hydrogen bonds formed by amides in crystallization‐driven template autocatalysis (CDTA), which involves the autocatalytic activity, template selectivity, and thermal responsiveness. We found that the thermal‐induced cis‐trans isomerization of amides possibly affects the H‐bonding‐mediated template ability of products for autocatalytic transformation. As a result, CDTA can be reversibly inhibited and activated by tuning the reaction temperatures. Our work sheds light on the significance of noncovalent H‐bonding interactions in artificial self‐replicators.
Assembly of Glycopeptides in Living Cells Resembling Viral Infection for Cargo Delivery
Authors: Tian Feng , Guo Ruo‐Chen , Wu Chunxia , Liu Xin , Zhang Zeyu , Wang Yamei , Wang Hao , Li Gongyu , Yu Zhilin 
Published: April 2024

AbstractSelf‐assembly in living cells represents one versatile strategy for drug delivery; however, it suffers from the limited precision and efficiency. Inspired by viral traits, we here report a cascade targeting‐hydrolysis‐transformation (THT) assembly of glycosylated peptides in living cells holistically resembling viral infection for efficient cargo delivery and combined tumor therapy. We design a glycosylated peptide via incorporating a β‐galactose‐serine residue into bola‐amphiphilic sequences. Co‐assembling of the glycosylated peptide with two counterparts containing irinotecan (IRI) or ligand TSFAEYWNLLSP (PMI) results in formation of the glycosylated co‐assemblies SgVEIP, which target cancer cells via β‐galactose‐galectin‐1 association and undergo galactosidase‐induced morphological transformation. While GSH‐reduction causes release of IRI from the co‐assemblies, the PMI moieties release p53 and facilitate cell death via binding with protein MDM2. Cellular experiments show membrane targeting, endo‐/lysosome‐mediated internalization and in situ formation of nanofibers in cytoplasm by SgVEIP. This cascade THT process enables efficient delivery of IRI and PMI into cancer cells secreting Gal‐1 and overexpressing β‐galactosidase. In vivo studies illustrate enhanced tumor accumulation and retention of the glycosylated co‐assemblies, thereby suppressing tumor growth. Our findings demonstrate an in situ assembly strategy mimicking viral infection, thus providing a new route for drug delivery and cancer therapy in the future.
Mass capture fishing in the Marquesas Islands
Authors: Nims Reno , Pillay Patricia , Allen Melinda S. 
Published: April 2024

ABSTRACTMass capture of small fishes with a variety of nets, traps, and weirs was widely practiced and economically important across East Polynesia at western contact. Archaeological research, however, has suggested these technologies were less important during the early settlement period and gained prominence over time. Several explanations have been proposed, including resource depression, changes in marine environments, and/or social and economic reorientations. In the Marquesas Islands, pelagic and offshore fishes were historically well represented in early assemblages relative to most Polynesian islands. Here we report on fishbone assemblages from Nuku Hiva Island that were recovered with fine mesh screens, identified using a wide range of skeletal elements, and analysed with morphometric methods. The Hakaea Beach results demonstrate that mass capture of small fishes was especially important at this locality and sustained over three early, successive occupations. These patterns may reflect the nature of the local fisheries, preferential use of high‐return capture strategies in this reef‐limited setting, and/or purposeful avoidance of ciguatera‐prone fishes and a preference for less vulnerable fishes. Overall, our findings highlight geographic variation in early Marquesan fisheries and provide archaeological evidence that mass capture technologies had an important place in the maritime toolkits of the earliest East Polynesian fishers.
Electrochemical Testing and Benchmarking of Compositionally Complex Lithium Argyrodite Electrolytes for All‐Solid‐State Battery Application
Authors: Du Jianxuan , Lin Jing , Zhang Ruizhuo , Wang Shuo , Indris Sylvio , Ehrenberg Helmut , Kondrakov Aleksandr , Brezesinski Torsten , Strauss Florian 
Published: April 2024

AbstractCeramic ion conductors play a pivotal role as electrolytes in solid‐state batteries (SSBs). Aside from the ionic conductivity, their (electro)chemical stability has a profound effect on the performance. Lithium thiophosphates represent a widely used class of superionic materials, yet they suffer from limited stability and are known to undergo interfacial degradation upon battery cycling. Knowledge of composition‐dependent properties is essential to improving upon the stability of thiophosphate solid electrolytes (SEs). In recent years, compositionally complex (multicomponent) and high‐entropy lithium argyrodite SEs have been reported, having room‐temperature ionic conductivities of σion>10 mS cm−1. In this work, various multi‐cationic and ‐anionic substituted argyrodite SEs are electrochemically tested via cyclic voltammetry and impedance spectroscopy, as well as under operating conditions in SSB cells with layered Ni‐rich oxide cathode and indium‐lithium anode. Cation substitution is found to negatively affect the electrochemical stability, while anion substitution (introducing Cl−/Br− and increasing halide content) has a beneficial effect on the cyclability, especially at high current rates.