bluuebunny/crossref_metadata_2025_split huggingface dataset:
Orbital Occupancy Modulation to Optimize Intermediate Absorption for Efficient Electrocatalysts in Water Electrolysis and Zinc–Ethanol–Air Battery
Authors: Ye Yanting , Xu Jinchang , Li Xiulan , Jian Yongqi , Xie Fangyan , Chen Jian , Jin Yanshuo , Yu Xiang , Lee Ming‐Hsien , Wang Nan , Sun Shuhui , Meng Hui 
Published: March 2024

AbstractSpin engineering is a promising way to modulate the interaction between the metal d‐orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o‐c‐CoSe2‐Ni is prepared as pre‐catalyst, then in situ electrochemical impedance spectroscopy (EIS) and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc–ethanol–air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co‐existence of four‐coordinated sites and six‐coordination sites in o‐c‐CoSe2‐Ni. The dz2 + dx2‐y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6‐Oh field with CoSe6‐Oh/CoSe4‐Td. This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc–ethanol–air battery.
Fast Li Replenishment Channels‐Assisted Recycling of Degraded Layered Cathodes with Enhanced Cycling Performance and Thermal Stability
Authors: Zhuang Zhaofeng , Li Junfeng , Ji Haocheng , Piao Zhihong , Wu Xinru , Ji Guanjun , Liu Song , Ma Jun , Tang Di , Zheng Nengzhan , Wang Junxiong , Zhou Guangmin 
Published: March 2024

AbstractThe direct recycling of cathode materials in lithium‐ion batteries is important for environmental protection and resource conservation. The key regeneration processes are composition replenishment and atom rearrangement, both of which depend on the migration and diffusion of atoms. However, for the direct recycling of degraded LiNi0.5Co0.2Mn0.3O2 (D‐NCM523) cathode, the irreversible phase transitions that accumulate during the long‐term cycles block the Li diffusion channels with a high diffusion energy barrier, making it difficult to fully repair the layered structure and resulting in rapid capacity decay. To address the challenge, fast Li replenishment channels are rebuilt to regulate the surface phase and effectively assist the regeneration process with a reduced energy barrier. This method reduces the amount of Li supplement by >75% and shortens the sintering time (only 2 h) to fully regenerate D‐NCM523, compared to general direct recycling methods. The regenerated NCM523 (LCMB‐NCM523) exhibits a satisfactory repaired specific capacity of 160 mAh g−1 and excellent cycling stability, retaining 78% of its capacity after 300 cycles. In addition, LCMB‐NCM523 is recycled with improved thermal decomposition peak temperature and enables 200 cycles even at 60 °C, greatly improving safety. This work proposes a promising way for the large‐scale direct regeneration of layered cathodes.
Synthesis of Quinine‐Inspired Antimalarials by Ni‐Catalysed Cross Electrophile Coupling
Authors: Lawer Aggie , Player Finlay P. , Avery Vicky M. , Foley Daniel J. 
Published: March 2024

AbstractWe describe the efficient synthesis of novel dehydroxyquinines by arylation of quincorine bromide using Ni‐catalysed cross electrophile coupling. The method demonstrates robust compatibility with (hetero)aryl bromides bearing diverse functional groups. Oxidation at C‐9 of the dehydroxyquinines expediently provided quinine‐inspired pseudo‐natural products (‘quinalogs’). Investigation of the compound collection against Plasmodium falciparum revealed a new insight into the structure activity relationship of quinine. Analogs bearing specifically functionalised pyridines, in place of the 6‐methoxyquinoline ring of quinine, retained activity at the same order of magnitude, albeit not exceeding the activity of the natural product. This synthetic strategy conveniently enables iteration of the aromatic component of quinine for the first time, and holds promise for the development of effective new antimalarials.
Photo‐Induced Synthesis of Functionalized γ‐Lactams via Iron‐Catalyzed LMCT Cascade
Authors: Song Zhuoheng , Bai Jinrui , Qi Dan , Guo Lin , Yang Chao , Xia Wujiong 
Published: March 2024

AbstractA base‐and‐additive‐free photo‐induced radical‐mediated cascade cyclization reaction of 1,6‐enyne compounds was presented. In this study, C(sp3)−H hydrocarbons, including various alkanes and ethers, were activated via Fe‐catalyzed photo‐induced conditions, providing a bunch of γ‐lactam products via hydrogen atom transfer and radical addition processes. Control experiments indicated that the reaction proceeded through photo‐induced ligand‐to‐metal charge transfer (LMCT) process. Gram scale experiment was also completed by using continuous‐flow‐photocatalytic‐device.
Enantioselective Syntheses of 3,4‐Dihydropyrans Employing Isochalcogenourea‐Catalyzed Formal (4+2)‐Cycloadditions of Allenoates
Authors: Piringer Magdalena , Hofer Mario , Vogl Lukas S. , Mayer Peter , Waser Mario 
Published: March 2024

AbstractWe herein successfully demonstrate the use of chiral isochalcogenoureas as Lewis Base catalysts for a variety of (4+2)‐cycloaddition reactions of allenoates and different Michael acceptors. In all cases the same structural key‐motive, a dihydropyran with a (Z)‐configurated exocyclic double bond could be accessed as the major regio‐ and diastereoisomer in an enantioselective manner. Furthermore, these chiral dihydropyrans were successfully engaged in different follow‐up transformations.
Evaluation of Bioprinted Autologous Cartilage Grafts in an Immunocompetent Rabbit Model
Authors: Gvaramia David , Fisch Philipp , Flégeau Killian , Huber Lena , Kern Johann , Jakob Yvonne , Hirsch Daniela , Rotter Nicole 
Published: March 2024

AbstractThe gold standard of auricular reconstruction involves manual graft assembly from autologous costal cartilage. The intervention may require multiple surgical procedures and lead to donor‐site morbidity, while the outcome is highly dependent on individual surgical skills. A tissue engineering approach provides the means to produce cartilage grafts of a defined shape from autologous chondrocytes. The use of autologous cells minimizes the risk of host immune response; however, factors such as biomaterial compatibility and in vitro maturation of the tissue‐engineered (TE) cartilage may influence the engraftment and shape‐stability of TE implants. Here, this work tests the biocompatibility of bioprinted autologous cartilage constructs in a rabbit model. The TE cartilage is produced by embedding autologous auricular chondrocytes into hyaluronan transglutaminase (HATG) based bioink, previously shown to support chondrogenesis in human auricular chondrocytes in vitro and in immunocompromised xenotransplantation models in vivo. A drastic softening and loss of cartilage markers, such as sulfated glycosaminoglycans (GAGs) and collagen type II are observed. Furthermore, fibrous encapsulation and partial degradation of the transplanted constructs are indicative of a strong host immune response to the autologous TE cartilage. The current study thus illustrates the crucial importance of immunocompetent autologous animal models for the evaluation of TE cartilage function and compatibility.
Hydrogels of Alginate Derivative‐Encased Nanodots Featuring Carbon‐Coated Manganese Ferrite Cores with Gold Shells to Offer Antiangiogenesis with Multimodal Imaging‐Based Theranostics
Authors: Gowtham Pemula , Girigoswami Koyeli , Prabhu Alex Daniel , Pallavi Pragya , Thirumalai Anbazhagan , Harini Karthick , Girigoswami Agnishwar 
Published: March 2024

AbstractThe investigation seeks to develop gold‐shelled carbon‐coated manganese ferrite nanodots enclosed within oxidized alginate polymeric hydrogels (MNF@C‐Au@OSA) to improve encapsulation efficiency, biocompatibility, and multimodal imaging capabilities. These engineered particles, MNF@C‐Au@OSA, are crafted through a hydrothermal synthesis, succeeded by the application of gold nanoparticle shelling and subsequent encapsulation within hydrogels derived from synthesized alginate derivatives, enhancing their overall appeal. Diverse characterization methodologies are employed in order to validate the multiple steps of the synthesis process. The resulting engineered nanoparticles exhibit dual‐mode (T1 and T2) magnetic resonance imaging (MRI) contrast capabilities and compatibility with computed tomography (CT) and fluorescence‐based imaging. To illustrate minimal toxicity, A375 cell lines are utilized for in vitro testing, whereas zebrafish embryos are employed for in vivo assessments. A Chorioallantoic Membrane Model (CAM) is used to establish the antiangiogenic characteristics of MNF@C‐Au@OSA, which is confirmed by histopathological observations. Taking these studies together, one can conclude that the engineered MNF@C‐Au@OSA possesses multimodal imaging capabilities and has demonstrated antiangiogenic properties, thereby establishing them as potential theranostic agents.
Transplantation of Neural Stem Cells Loaded in an IGF‐1 Bioactive Supramolecular Nanofiber Hydrogel for the Effective Treatment of Spinal Cord Injury
Authors: Song Peiwen , Han Tianyu , Wu Zuomeng , Fang Huang , Liu Yunlei , Ying Wang , Wang Xianwen , Shen Cailiang 
Published: March 2024

AbstractSpinal cord injury (SCI) leads to massive cell death, disruption, and demyelination of axons, resulting in permanent motor and sensory dysfunctions. Stem cell transplantation is a promising therapy for SCI. However, owing to the poor microenvironment that develops following SCI, the bioactivities of these grafted stem cells are limited. Cell implantation combined with biomaterial therapies is widely studied for the development of tissue engineering technology. Herein, an insulin‐like growth factor‐1 (IGF‐1)‐bioactive supramolecular nanofiber hydrogel (IGF‐1 gel) is synthesized that can activate IGF‐1 downstream signaling, prevent the apoptosis of neural stem cells (NSCs), improve their proliferation, and induce their differentiation into neurons and oligodendrocytes. Moreover, implantation of NSCs carried out with IGF‐1 gels promotes neurite outgrowth and myelin sheath regeneration at lesion sites following SCI. In addition, IGF‐1 gels can enrich extracellular vesicles (EVs) derived from NSCs or from nerve cells differentiated from these NSCs via miRNAs related to axonal regeneration and remyelination, even in an inflammatory environment. These EVs are taken up by autologous endogenous NSCs and regulate their differentiation. This study provides adequate evidence that combined treatment with NSCs and IGF‐1 gels is a potential therapeutic strategy for treating SCI.
Complete Selective Switching of Ferroelastic Domain Stripes in Multiferroic Thin Films by Tip Scanning
Authors: Wu Mengjun , Wang Xintong , Sun Fei , Zhang Xiaoyue , Zhang Yi , Liu Linjie , Chen Weijin , Zheng Yue 
Published: March 2024

AbstractBiFeO3 is a rare single‐phase multiferroic which shows coupled ferroelectricity, ferroelasticity and antiferromagnetism at room temperature. Many fantastic properties of BiFeO3 are regulated by its domain structure. While (001) rhombohedral BiFeO3 thin films can possibly develop up‐to eight degenerate states of two‐variant 71° ferroelastic domain stripes, complete selective control of all possible switching paths between these states has not yet been achieved. Here, combining phase field simulations and scanning probe microscopy experiments, we demonstrated such a complete selective control. The tip bias and the built‐in field were shown to affect the volume fraction of the 71°, 109° and 180° switched domains in rhombohedral BiFeO3 thin films under single‐point loading. Meanwhile, tip scanning further broke the symmetry of the nucleated domains, leading to different switched domain patterns. We then grew BiFeO3 thin films with a specific two‐variant 71° ferroelastic domain state and showed that such a state could be deterministically switched into the other seven two‐variant domain states by collaborative controlling tip scanning and tip bias in scanning probe microscopy experiments. These results should deepen our current understanding on the domain switching kinetics in BiFeO3 thin films and indicate they are promising platforms for developing configurable electronic and spintronic devices.
Role of Ether‐Based Electrolytes in Enhancing Potential of Potassium‐ion Batteries
Authors: Jo Chang‐Heum , Myung Seung‐Taek 
Published: March 2024

AbstractPotassium‐ion batteries are a promising advancement in secondary batteries, offering the potential to surpass even sodium‐ion batteries in replacing lithium‐ion batteries. Although the technology has the potential for high energy density, unresolved technical difficulties pose a challenge. Fortunately, progress is made in improving electrode materials, with studies demonstrating that controlling the fundamental cause of electrolyte degradation can significantly enhance the performance of potassium‐ion batteries. However, the ability of ether‐based electrolytes to improve battery performance is overlooked despite their inherent characteristics. This work explores the role and principles of ether‐based electrolytes in enhancing the potential of potassium‐ion batteries, highlighting various controversies and prospects in this area arising from insufficient research.
Hairy cell leukemia 2024: Update on diagnosis, risk‐stratification, and treatment—Annual updates in hematological malignancies
Authors: Troussard Xavier , Maître Elsa , Paillassa Jérôme 
Published: March 2024

AbstractDisease OverviewHairy cell leukemia (HCL) and HCL‐like disorders, including HCL variant (HCL‐V) and splenic diffuse red pulp lymphoma (SDRPL), are a very heterogenous group of mature lymphoid B‐cell disorders characterized by the identification of hairy cells, a specific genetic profile, a different clinical course and the need for appropriate treatment.DiagnosisDiagnosis of HCL is based on morphological evidence of hairy cells, an HCL immunologic score of 3 or 4 based on the CD11c, CD103, CD123, and CD25 expression, the trephine biopsy which makes it possible to specify the degree of tumoral bone marrow infiltration and the presence of BRAFV600E somatic mutation.Risk StratificationProgression of patients with HCL is based on a large splenomegaly, leukocytosis, a high number of hairy cells in the peripheral blood, and the immunoglobulin heavy chain variable region gene mutational status. VH4‐34 positive HCL cases are associated with a poor prognosis, as well as HCL with TP53 mutations and HCL‐V.TreatmentPatients should be treated only if HCL is symptomatic. Chemotherapy with risk‐adapted therapy purine analogs (PNAs) are indicated in first‐line HCL patients. The use of chemo‐immunotherapy combining cladribine (CDA) and rituximab (R) represents an increasingly used therapeutic approach. Management of relapsed/refractory disease is based on the use of BRAF inhibitors (BRAFi) plus R, MEK inhibitors (MEKi), recombinant immunoconjugates targeting CD22, Bruton tyrosine kinase inhibitors (BTKi), and Bcl‐2 inhibitors (Bcl‐2i). However, the optimal sequence of the different treatments remains to be determined.
Regulating Charge Transport Dynamics at the Buried Interface and Bulk of Perovskites by Tailored‐phase Two‐dimensional Crystal Seed Layer
Authors: Li Dengxue , Xing Zhi , Wang Yajun , Li Jianlin , Hu Biao , Hu Xiaotian , Hu Ting , Chen Yiwang 
Published: March 2024

AbstractTargeting the trap‐assisted non‐radiative recombination losses and photochemical degradation occurring at the interface and bulk of perovskite, especially the overlooked buried bottom interface, a strategy of tailored‐phase two‐dimensional (TP‐2D) crystal seed layer has been developed to improve the charge transport dynamics at the buried interface and bulk of perovskite films. Using this approach, TP‐2D layer constructed by TP‐2D crystal seeds at the buried interface can induce the formation of homogeneous interface electric field, which effectively suppress the accumulation of charge carriers at the buried interface. Additionally, the presence of TP‐2D crystal seed has a positive effect on the crystallization process of the upper perovskite film, leading to optimized crystal quality and thus promoted charge transport inside bulk perovskites. Ultimately, the best performing PSCs based on TP‐2D layer deliver a power conversion efficiency of 24.58 %. The devices exhibit an improved photostability with 88.4 % of their initial PCEs being retained after aging under continuous 0.8‐sun illumination for 2000 h in air. Our findings reveal how to regulate the charge transport dynamics of perovskite bulk and interface by introducing homogeneous components.
Bimodal Oxidation Electrochemiluminescence Mechanism of Coreactant‐Embedded Covalent Organic Frameworks via Postsynthetic Modification
Authors: Meng Xiaoxiao , Zheng Lifeng , Luo Rengan , Kong Weisu , Xu Zhiyuan , Dong Pengfei , Ma Jing , Lei Jianping 
Published: March 2024

AbstractElectrochemiluminescence (ECL) efficiency is determined by charge transfer between coreactants and emitters in coreactant systems, which are usually limited by their slow intermolecular charge transfer. In this study, a covalent organic framework (COF) with aldehyde residue was synthesized, and then coreactants were covalently integrated into the skeleton through the postsynthetic modification strategy, resulting in a crystalline coreactant‐embedded COF nanoemitter (C–COF). Compared to the pristine COF with an equivalent external coreactant, C–COF exhibited an extraordinary 1008‐fold enhancement of ECL intensity due to the rapid intrareticular charge transfer. Significantly, with the pH increase, C–COF shows protonation‐induced ECL enhancement for the first ECL peaked at +1.1 V and an opposite trend for the second ECL at +1.4 V, which were attributed to the antedating oxidation of coreactant in framework and COF self‐oxidation, respectively. The resulting bimodal oxidation ECL mechanism was rationalized by spectral characterization and density functional theory calculations. The postsynthetic coreactant‐embedded nanoemitters present innovative and universal avenues for advancing ECL systems.
A Triply‐Periodic‐Minimal‐Surface Structured Interphase based on Fluorinated Polymers Strengthening High‐energy Lithium Metal Batteries
Authors: Ma Cong , Zou Shihui , Wu Yuxuan , Yue Ke , Cai Xiaohan , Wang Yao , Nai Jianwei , Guo Tianqi , Tao Xinyong , Liu Yujing 
Published: March 2024

AbstractThe challenge of constructing a mechanically robust yet lightweight artificial solid‐electrolyte interphase layer on lithium (Li) anodes highlights a trade‐off between high battery safety and high energy density. Inspired by the intricate microstructure of the white sea urchin, we first develop a polyvinyl fluoride‐hexafluoropropylene (PVDF‐HFP) interfacial layer with a triple periodic minimal surface structure (TPMS) that could offer maximal modulus with minimal weight. This design endows high mechanical strength to an ordered porous structure, effectively reduces local current density, polarization, and internal resistance, and stabilizes the anode interface. At a low N/P ratio of ~3, using LiFePO4 as the cathode, Li anodes protected by TPMS‐structured PVDF‐HFP achieve an extremely low capacity‐fading‐rate of approximately 0.002 % per cycle over 200 cycles at 1 C, with an average discharge capacity of 142 mAh g−1. Meanwhile, the TPMS porous structure saves 50 wt % of the interfacial layer mass, thereby enhancing the energy density of the battery. The TPMS structure is conducive to large‐scale additive manufacturing, which will provide a reference for the future development of lightweight, high‐energy‐density secondary batteries.
Conformer‐Selective Photoelectron Circular Dichroism
Authors: Rouquet Etienne , Dupont Jennifer , Lepere Valeria , Garcia Gustavo A. , Nahon Laurent , Zehnacker Anne 
Published: March 2024

AbstractConformational flexibility and chirality both play a key role in molecular recognition. It is therefore very useful to develop spectroscopic methods that simultaneously probe both properties. It has been theoretically predicted that photoelectron circular dichroism (PECD) should be very sensitive to conformational isomerism. However, experimental proof has been less forthcoming and only exists for a very few favorable cases. Here, we present a new PECD scheme based on resonance‐enhanced two‐photon ionization (RE2PI) using UV/Vis nanosecond laser excitations. The spectral resolution obtained thereby guarantees conformer‐selectivity by inducing resonant conformer‐specific ππ* S1←S0 transitions. We apply this experimental scheme to the study of chiral 1‐indanol, which exists in two conformers linked by a ring inversion and defined by the position of the hydroxyl group, namely axial and equatorial. We show that the PECD of the equatorial and axial forms considerably differ in sign, magnitude and shape. We also discuss the influence of the total ionization energy, vibronic excitation of intermediate and final states, and relative polarization of the excitation and ionization lasers. Conformer‐specificity adds a new dimension to the applications of PECD in analytical chemistry addressing now the general case of floppy systems.
A decade's overview of 2‐aminothiophenes and their fused analogs as promising anticancer agents
Authors: Darwish Donia G. , El‐Sherief Hany A. M. , Abdel‐Aziz Salah A. , Abuo‐Rahma Gamal El‐Din A. 
Published: March 2024

AbstractOver the past decades, cancer has been a challenging domain for medicinal chemists as it is an international health concern. In association, small molecules such as 2‐aminothiophenes and their derivatives showed significant antitumor activity through variable modes of action. Therefore, this article aims to review the advances regarding these core scaffolds over the past 10 years, where 2‐aminothiophenes and their fused analogs are classified and discussed according to their biological activity and mode of action, in the interest of boosting new design pathways for medicinal chemists to develop targeted antitumor candidates.
Controllable Chemoselectivity Cascade Reactions for the Synthesis of Phenanthrenols via Palladium‐Catalyzed‐Suzuki/Heck Reaction and Michael Addition
Authors: Yongpanich Phornphan , Chatrangsan Kamonlak , Tummatorn Jumreang , Thongsornkleeb Charnsak , Ruchirawat Somsak 
Published: March 2024

AbstractPalladium serves as a multi‐functional catalyst which is controllable by tuning reaction conditions. This work demonstrated the utilization of a palladium catalyst for the synthesis of phenanthrenols by cascade palladium‐catalyzed Suzuki/Heck reaction between chalcone and 2‐bromophenylboronic acid, followed by Michael addition. The sequential reaction could be controlled by reactivity of the palladium catalyst in different solvents and concentrations of reagents. This protocol could be applied to a broad range of substrates to give products in low to good yields.