bluuebunny/crossref_metadata_2025_split huggingface dataset:
Selective Ion Transport Layer for Stable Aqueous Zinc‐Ion Batteries
Authors: Lee Young‐Hoon , Jeoun Yunseo , Kim Ji Hwan , Shim Jaehyuk , Ahn Kwang‐Soon , Yu Seung‐Ho , Sung Yung‐Eun 
Published: November 2023

AbstractThe limited lifespan of aqueous zinc‐ion batteries (with vanadium‐oxide based cathodes) is constrained by practical applications due to corrosion accelerated by vanadium ions leaching from the cathode and uneven dendrite growth on the zinc metal anode. To address these issues, the difference in size between hydrated zinc ions (4.30 Å) in electrolyte and vanadium ions (8.34 Å) is considered. Uniformly coating the MOF‐801 nanoparticles (with a pore size of 6.0 Å) on the zinc foil formed a selective ion transport layer. The uniform zinc ion flux generated by the selective ion transport layer allows hydrated zinc ions to be transported evenly and promotes uniform zinc deposition, leading to a low overpotential (17.4 mV) and high cycle stability (1000 h) in the symmetric cell. Moreover, the selective ion transport layer, having pores smaller than vanadium ions, blocked vanadium ions from migrating toward the zinc anode, thereby reducing its corrosion and contributing to a capacity retention of 86% after 2000 cycles under full‐cell conditions. This study demonstrates that the pore size of the coating layer influences the long‐term stability of aqueous zinc‐ion batteries and may serve as a guide when selecting interface modification materials for various metal batteries.
Immunocompetent PDMS‐Free Organ‐on‐Chip Model of Cervical Cancer Integrating Patient‐Specific Cervical Fibroblasts and Neutrophils
Authors: Kromidas Elena , Geier Alicia , Weghofer Adrian , Liu Hui‐Yu , Weiss Martin , Loskill Peter 
Published: November 2023

AbstractDespite preventive measures and available treatments, cervical cancer still ranks as the fourth most prevalent cancer among women worldwide and remains the leading cause of cancer death in women in many developing countries. To gain further insights into pathogenesis and to develop novel (immuno)therapies, more sophisticated human models recreating patient heterogeneities and including aspects of the tumor microenvironment are urgently required. A novel polydimethylsiloxane‐free microfluidic platform, designed specifically for the generation and ccultivation of cervical cancerous tissue, is introduced. The microscale open‐top tissue chambers of the cervical cancer‐on‐chip (CCoC) enable facile generation and long‐term cultivation of SiHa spheroids in co‐culture with donor‐derived cervical fibroblasts. The resulting 3D tissue emulates physiological architecture and allows dissection of distinct effects of the stromal tissue on cancer viability and growth. Treatment with cisplatin at clinically‐relevant routes of administration and dosing highlights the platform's applicability for drug testing. Moreover, the model is amenable for integration and recruitment of donor‐derived neutrophils from the microvasculature‐like channel into the tissue, all while retaining their ability to produce neutrophil extracellular traps. In the future, the immunocompetent CCoC featuring donor‐specific primary cells and tumor spheroids has the potential to contribute to the development of new (immuno)therapeutic options.
Room‐Temperature, Current‐Induced Magnetization Self‐Switching in A Van Der Waals Ferromagnet
Authors: Zhang Hongrui , Chen Xiang , Wang Tianye , Huang Xiaoxi , Chen Xianzhe , Shao Yu‐Tsun , Meng Fanhao , Meisenheimer Peter , N'Diaye Alpha , Klewe Christoph , Shafer Padraic , Pan Hao , Jia Yanli , Crommie Michael F. , Martin Lane W. , Yao Jie , Qiu Ziqiang , Muller David A. , Birgeneau Robert J. , Ramesh Ramamoorthy 
Published: November 2023

Abstract2D layered materials with broken inversion symmetry are being extensively pursued as spin source layers to realize high‐efficiency magnetic switching. Such low‐symmetry layered systems are, however, scarce. In addition, most layered magnets with perpendicular magnetic anisotropy show a low Curie temperature. Here, the experimental observation of spin–orbit torque magnetization self‐switching at room temperature in a layered polar ferromagnetic metal, Fe2.5Co2.5GeTe2 is reported. The spin–orbit torque is generated from the broken inversion symmetry along the c‐axis of the crystal. These results provide a direct pathway toward applicable 2D spintronic devices.
Photothermal Fibrous Chitosan/Polydopamine Sponge for Intraoperative Hemostasis and Prevention of Tumor Recurrence in Hepatocellular Carcinoma Resection
Authors: Mu Lanxin , Qi Luhe , Long Haitao , Huang Jing , Zhong Zibiao , Shi Xiaowen , Chen Chaoji , Ye Qifa 
Published: November 2023

AbstractHepatectomy, a surgical procedure for liver cancer, is often plagued by high recurrence rates worldwide. The recurrence of liver cancer is primarily attributed to microlesions in the liver, changes in the immune microenvironment, and circulating tumor cells in the bloodstream. To address this issue, a novel intervention method that combines intraoperative hemostasis with mild photothermal therapy is proposed, which has the potential to ablate microlesions and improve the immune microenvironment simultaneously. Specifically, the integrated strategy is realized based on the fibrous chitosan/polydopamine sponge (CPDS), which is constructed from shearing‐flow‐induced oriented hybrid chitosan fibers and subsequent self‐assembly of polydopamine. The CPDS demonstrates high elasticity, excellent water absorption, and photothermal conversion performance. The results confirm the efficient hemostatic properties of the fibrous CPDS in various bleeding models. Notably, in subcutaneous and orthotopic postoperative recurrence and metastasis models of hepatocellular carcinoma, the fibrous CPDS significantly inhibits local tumor recurrence and distant metastasis. Moreover, the combination with lenvatinib can substantially enhance the antitumor effect. This comprehensive treatment strategy offers new insights into hepatectomy of liver cancer, representing a promising approach for clinical management.
High‐Density Artificial Synapse Array Consisting of Homogeneous Electrolyte‐Gated Transistors
Authors: Li Jun , Lei Yuxing , Wang Zexin , Meng Hu , Zhang Wenkui , Li Mengjiao , Tan Qiuyun , Li Zeyuan , Guo Wei , Wen Shengkai , Zhang Jianhua 
Published: November 2023

AbstractThe artificial synapse array with an electrolyte‐gated transistor (EGT) as an array unit presents considerable potential for neuromorphic computation. However, the integration of EGTs faces the drawback of the conflict between the polymer electrolytes and photo‐lithography. This study presents a scheme based on a lateral‐gate structure to realize high‐density integration of EGTs and proposes the integration of 100 × 100 EGTs into a 2.5 × 2.5 cm2 glass, with a unit density of up to 1600 devices cm−2. Furthermore, an electrolyte framework is developed to enhance the array performance, with ionic conductivity of up to 2.87 × 10−3 S cm−1 owing to the porosity of zeolitic imidazolate frameworks‐67. The artificial synapse array realizes image processing functions, and exhibits high performance and homogeneity. The handwriting recognition accuracy of a representative device reaches 92.80%, with the standard deviation of all the devices being limited to 9.69%. The integrated array and its high performance demonstrate the feasibility of the scheme and provide a solid reference for the integration of EGTs.
Fortifying Zinc Metal Anodes against Uncontrollable Side‐Reactions and Dendrite Growth for Practical Aqueous Zinc Ion Batteries: A Novel Composition of Anti‐Corrosive and Zn2+ Regulating Artificial Protective Layer
Authors: Park Jong Hyun , Choi Changhoon , Park Jung Been , Yu Seungho , Kim Dong‐Wan 
Published: November 2023

AbstractAqueous zinc‐ion batteries (AZIBs) have recently gained significant attention for grid‐scale energy storage applications owing to their high intrinsic energy density, low cost, and environmental benignity. Nevertheless, uncontrolled Zn dendrite accumulation, H2 gas generation, and inevitable corrosion resulting from intricate water‐induced side‐reactions remain the main hurdles to AZIB commercialization. To overcome these problems, it is imperative to develop easy‐to‐handle strategies for the construction of versatile artificial protective layers (APL) on Zn surfaces. Inspired by the suppressed HER and anti‐corrosive properties of zinc silicate (Zn2SiO4), this study rationally designed a novel APL consisting of Zn2SiO4 nanospheres and decorated surface‐modified carbon nanotube (CNT) to produce a stable and durable Zn anode (C‐ZSL@Zn). The C‐ZSL layer simultaneously improved Zn2+ transport kinetics and the Zn2+ de‐solvation effect, maintained electrically insulating properties, and uniformized Zn2+ flux on the Zn surface, synergistically enabling corrosion‐free and dendrite‐free Zn plating/stripping behavior on C‐ZSL@Zn. Consequently, the C‐ZSL@Zn achieved prolonged lifespans of ≈1600 (at 1 mA cm–2) and ≈1100 h (at a high depth of discharge of ≈51.24%) with ultralow voltage hysteresis in symmetric cells, together with improved cycling stability for coin‐ and pouch‐type Zn||α‐MnO2 full‐cells. This study creates a new avenue for constructing stable APL@Zn anodes for practical applications.
Tuning Dopant Distribution for Stabilizing the Surface of High‐Nickel Layered Oxide Cathodes for Lithium‐Ion Batteries
Authors: Liu Chen , Cui Zehao , Manthiram Arumugam 
Published: November 2023

AbstractLayered oxide cathodes with a high‐nickel (Ni ≥ 0.9) content exhibit great potential for enabling high‐energy‐density lithium‐ion batteries. However, their practical feasibility and cycle life are hampered by severe surface reactivity with the electrolyte. A LiNi0.90Co0.05Al0.05O2 cathode is presented enriched with Al on the surface (S‐NCA) and benchmark it against a LiNi0.90Co0.05Al0.05O2 cathode obtained by a conventional co‐precipitation method that has a uniform Al distribution throughout the bulk (B‐NCA). The S‐NCA cathode greatly outperform with an impressive capacity retention of 84% after 1000 cycles in pouch full cells with graphite anode compared to 62% retention for B‐NCA. Advanced surface characterization methodologies, including time‐of‐flight secondary‐ion mass spectrometry, reveal that the Al‐enriched surface morphology facilitates the formation of a robust, thin electrode‐electrolyte interphase (EEI), effectively suppressing the oxidative decomposition of the electrolyte, gas generation, and metallic dead lithium formation on graphite anode. The results illustrate that surface reactivity with the electrolyte is the primary factor limiting the cycle of cells with high‐Ni cathodes. The work provides valuable insights toward the practical viability of ultrahigh‐Ni cathodes in lithium‐ion batteries.
Timing of conceptions in Phayre's leaf monkeys: Energy and phytochemical intake
Authors: Borries Carola , Lu Amy , Ossi‐Lupo Kerry , Koenig Andreas 
Published: November 2023

AbstractObjectivesRaising offspring imposes energetic costs, especially for female mammals. Consequently, seasons favoring high energy intake and sustained positive energy balance often result in a conception peak. Factors that may weaken this coordinated effect include premature offspring loss and adolescent subfertility. Furthermore, seasonal ingestion of phytochemicals may facilitate conception peaks. We examined these factors and potential benefits of a conception peak (infant survival and interbirth interval) in Phayre's leaf monkeys (Trachypithecus phayrei crepusculus).Materials and MethodsData were collected at Phu Khieo Wildlife Sanctuary, Thailand (78 conceptions). We estimated periods of high energy intake based on fruit and young leaf feeding and via monthly energy intake rates. Phytochemical intake was based on fecal progestin. We examined seasonality (circular statistics and cox proportional hazard models) and compared consequences of timing (infant survival and interbirth intervals, t‐test, and Fisher exact test).ResultsConceptions occurred in all months but peaked from May to August. This peak coincided with high fecal progestin rather than presumed positive energy balance. Primipara conceived significantly later than multipara. Neither infant survival nor interbirth intervals were related to the timing of conception.DiscussionPeriods of high energy intake may not exist and would not explain the conception peak in this population. However, the presumed high intake of phytochemicals was tightly linked to the conception peak. Timing conceptions to the peak season did not provide benefits, suggesting that the clustering of conceptions may be a mere by‐product of phytochemical intake. To confirm this conclusion, seasonal changes in phytochemical intake and hormone levels need to be studied more directly.
Structure of Staphylococcus aureus ClpP Bound to the Covalent Active‐Site Inhibitor Cystargolide A
Authors: Illigmann Astrid , Vielberg Marie‐Theres , Lakemeyer Markus , Wolf Felix , Dema Taulant , Stange Patrik , Kuttenlochner Wolfgang , Liebhart Elisa , Kulik Andreas , Staudt Nicole D. , Malik Imran , Grond Stephanie , Sieber Stephan A. , Kaysser Leonard , Groll Michael , Brötz‐Oesterhelt Heike 
Published: November 2023

AbstractThe caseinolytic protease is a highly conserved serine protease, crucial to prokaryotic and eukaryotic protein homeostasis, and a promising antibacterial and anticancer drug target. Herein, we describe the potent cystargolides as the first natural β‐lactone inhibitors of the proteolytic core ClpP. Based on the discovery of two clpP genes next to the cystargolide biosynthetic gene cluster in Kitasatospora cystarginea, we explored ClpP as a potential cystargolide target. We show the inhibition of Staphylococcus aureus ClpP by cystargolide A and B by different biochemical methods in vitro. Synthesis of semisynthetic derivatives and probes with improved cell penetration allowed us to confirm ClpP as a specific target in S. aureus cells and to demonstrate the anti‐virulence activity of this natural product class. Crystal structures show cystargolide A covalently bound to all 14 active sites of ClpP from S. aureus, Aquifex aeolicus, and Photorhabdus laumondii, and reveal the molecular mechanism of ClpP inhibition by β‐lactones, the predominant class of ClpP inhibitors.
Crystalline, Porous Helicene Covalent Organic Frameworks
Authors: Yan Qianqian , Tao Shanshan , Liu Ruoyang , Zhi Yongfeng , Jiang Donglin 
Published: November 2023

AbstractHelicenes are a class of fascinating chiral helical molecules with rich chemistry developed continuously over the past 100 years. Their helical, conjugated, and twisted structures make them attractive for constructing molecular systems. However, studies over the past century are mainly focused on synthesizing helicenes with increased numbers of aromatic rings and complex heterostructures, while research on inorganic, organic, and polymeric helicene materials is still embryonic. Herein, we report the first examples of helicene covalent organic frameworks, i.e., [7]Helicene sp2c‐COF‐1, by condensing [7]Helicene dialdehyde with trimethyl triazine via the C=C bond formation reaction under solvothermal conditions. The resultant [7]Helicene sp2c‐COF‐1 exhibits prominent X‐ray diffraction peaks and assumes a highly ordered 2D lattice structure originated from the twisted configuration of [7]Helicene unit. The C=C linked [7]Helicene sp2c‐COF‐1 materials exhibited extended π conjugation and broadly tuned their absorption, emission, redox activity, photoconductivity, and light‐emitting activity, demonstrating rich multifunctionalities and great potentials in developing various applications. This work opens a way to a new family of COFs as well as helicene materials, enabling the exploration of unprecedented π architectures and properties.
Halogen‐Modulated 2D Coordination Polymers for Efficient Hydrogen Peroxide Photosynthesis under Air and Pure Water Conditions
Authors: Zhang Jieping , Lei Hang , Li Zhijia , Jiang Feilong , Chen Lian , Hong Maochun 
Published: November 2023

AbstractH2O2 is a widely used eco‐friendly oxidant and a potential energy carrier. Photocatalytic H2O2 production from water and O2 is an ideal approach with the potential to address the current energy crisis and environmental issues. Three zig‐zag two‐dimensional coordination polymers (2D CPs), named CuX‐dptz, were synthesized by a rapid and facile method at room temperature, showing preeminent H2O2 photoproduction performance under pure water and open air without any additives. CuBr‐dptz exhibits a H2O2 production rate high up to 1874 μmol g−1 h−1, exceeding most reported photocatalysts under this condition, even comparable to those supported by sacrificial agents and O2. The coordination environment of Cu can be modulated by halogen atoms (X=Cl, Br, I), which in turn affects the electron transfer process and finally determines the reaction activity. This is the first time that 2D CPs have been used for photocatalytic H2O2 production in such challenging conditions, which provides a new pathway for the development of portable in situ H2O2 photosynthesis devices.
Exploring the impact of cellulose nanocrystals and annealing treatment on the interlayer bond strength of polylactic acid 3D printed composites
Authors: Zhang Ying , Lu Jia , Wu Junjun , Gao Xueqin 
Published: November 2023

AbstractThe extrusion‐based 3D printing process offers advantages, such as high precision, low cost, high speed, simplicity, and the ability to deposit multiple materials simultaneously. However, using 3D printing composite materials with orthogonal anisotropy can limit the interlayer bonding strength of printed parts. In this study, the interlayer tensile strength of 3D‐printed polylactic acid (PLA) was affected by adding 0.5 wt% cellulose nanocrystals (CNC) and 1.2 wt% di‐cumyl peroxide (DCP) to PLA, and annealing at low temperature (373 K, 1 h). The effects of annealing and CNC were determined by mechanical testing, scanning electron microscopy, differential scanning calorimetry, expansion testing, rheological testing, and x‐ray diffraction analysis. After annealing, the interlayer gap increased due to crystal shrinkage, leading to a 25.9% decrease in tensile strength. However, the addition of CNC and DCP significantly improved the flow properties of the sample, resulting in better interlayer bonding and a 52.7% increase in tensile strength.
Survey of freshwater mussels using high‐resolution acoustic imaging sonar and deep learning‐based object detection in Lake Izunuma, Japan
Authors: Zhao Fan , Mizuno Katsunori , Tabeta Shigeru , Hayami Hiroki , Fujimoto Yasufumi , Shimada Tetsuo 
Published: November 2023

Abstract

The use of traditional in situ methods for underwater surveys to map freshwater mussel habitats is limited by challenges such as water transparency, depth and high labour demands. In this study, adaptive resolution imaging sonar (ARIS) was applied to monitor mussel distribution and abundance.
In contrast to conventional quadrat surveys, this acoustic survey is non‐invasive and enables direct observation of mussels to allow their survival status to be determined in turbid water. ARIS produces high‐quality acoustic images that facilitate the creation of a distribution map for broader‐scale monitoring, especially if paired with deep learning methods such as the YOLOv4 algorithm for automatic mussel detection and classification.
ARIS was successfully applied to surveying over 2000 m2 of Lake Izunuma in Miyagi, Japan. In one site, a high mussel abundance of ~0.6 individuals/m2 was detected, while other sites had low densities. The detection model achieved a mean average precision of 0.97.
The survey results were used to generate a distribution map of living mussels. This study illustrates the feasibility of using an acoustic video camera with an open‐source deep learning algorithm to monitor mussels and other benthos in turbid water.
Electronic and steric substituent effects on the fluorescence emission of 2‐pyrazoline derivatives
Authors: Memarian Hamid Reza , Rejali Narges , Soltani Marzieh 
Published: November 2023

AbstractA series of substituted 2‐pyrazolines were synthesized, and the steric and electronic effects of substituents on the C3‐ and C5‐positions of the heterocyclic ring on their fluorescent ability were investigated. Two different conjugative intramolecular charge transfer (ICT) and intramolecular charge transfer through space (spiro‐conjugation) affect the fluorescence intensity of these compounds. The extent of the ICT process and spiro‐conjugation depends on the electronic nature of the additional substitution and its position on the attached aryl rings. In addition, the effects of the concentration and the solvent polarity on the fluorescence emission were studied. Density functional theory (DFT) calculations were carried out to gain insight into the geometric, electronic, and spectroscopic properties of the pyrazoline derivatives. The results of both experimental and computational studies explain the effects of the geometrical orientation of the C3‐ and C5‐aryl rings toward the heterocyclic ring and also the electronic nature of their additional substitutions on the fluorescence intensity.
Photoexcitation dynamics of azide ion bound ferric myoglobin probed by femtosecond infrared spectroscopy
Authors: Park Seongchul , Kim Jooyoung , Lim Manho 
Published: November 2023

AbstractThe photoexcitation dynamics of N3−‐bound ferric myoglobin (MbN3) were investigated after exciting MbN3 in D2O at 283 K with a 575 nm pulse by probing the anti‐symmetric stretching mode of the azide. Global fitting of the overall time‐resolved spectra revealed that thermal relaxation of two stretching bands proceeded with a time constant of 6 ps, and that a new absorption band formed and decayed with time constants of 0.6 and 23 ps, respectively. The new absorption near 2040 cm−1 was attributed to the high‐spin species 2.4 kJ/mol above the low‐spin species, as the excited low‐spin relaxes thermally via the high‐spin species. However, this absorption could also arise from deligated N3̄ remaining within the protein. The decay of this absorption can be interpreted as either spin transition of the high‐spin species into the low‐spin species or geminate recombination of the dissociated N3̄. The implications of both interpretations are discussed.
Data‐Driven Protein Engineering for Improving Catalytic Activity and Selectivity
Authors: Ao Yu‐Fei , Dörr Mark , Menke Marian J. , Born Stefan , Heuson Egon , Bornscheuer Uwe T. 
Published: November 2023

AbstractProtein engineering is essential for altering the substrate scope, catalytic activity and selectivity of enzymes for applications in biocatalysis. However, traditional approaches, such as directed evolution and rational design, encounter the challenge in dealing with the experimental screening process of a large protein mutation space. Machine learning methods allow the approximation of protein fitness landscapes and the identification of catalytic patterns using limited experimental data, thus providing a new avenue to guide protein engineering campaigns. In this concept article, we review machine learning models that have been developed to assess enzyme‐substrate‐catalysis performance relationships aiming to improve enzymes through data‐driven protein engineering. Furthermore, we prospect the future development of this field to provide additional strategies and tools for achieving desired activities and selectivities.