bluuebunny/crossref_metadata_2025_split huggingface dataset:
Performance Degradation and Protective Effects of Atomic Layer Deposition for Mg‐based Thermoelectric Modules
Authors: Ying Pingjun , Villoro Ruben Bueno , Bahrami Amin , Wilkens Lennart , Reith Heiko , Mattlat Dominique Alexander , Pacheco Vicente , Scheu Christina , Zhang Siyuan , Nielsch Kornelius , He Ran 
Published: June 2024

AbstractThermoelectric technology has witnessed a resurgence in recent years due to increasing demands for sustainable energy sources and efficient cooling systems. Recently, the introduction of Te‐free thermoelectric modules using non‐toxic, abundant materials including p‐type MgAgSb and n‐type Mg3(Sb,Bi)2 marked a significant breakthrough. Despite promising performance, questions persist regarding long‐term robustness and stability, especially in harsh environments. In this study, a thorough exploration of thermoelectric modules is conducted, focusing on their performance degradation under various conditions. Through elemental mapping analysis, degradation mechanisms are identified within the modules during cycling in argon environments, where atomic migrations and the formation of complex oxides at contact regions are key factors. Furthermore, cycling tests in air reveal significant degradation, prompting the exploration of protective strategies. Surface coatings using atomic layer deposition (ALD) emerge as a promising solution, particularly by HfO2, demonstrating superior protective effects. Furthermore, re‐soldering effectively restores module performance is found, highlighting the importance of developing advanced soldering techniques to promote magnesium‐based thermoelectric technology as a sustainable alternative to Bi2Te3. These findings emphasize the importance of exploring novel contact materials and demonstrate the potential of ALD as a universal approach to enhancing module reliability and robustness.
Multifunctional and Electronically Conjugated Triazine Framework for Superior Electro‐Ionic Artificial Muscles
Authors: Garai Mousumi , Nguyen Van Hiep , Mahato Manmatha , Oh Saewoong , Saatchi Daniel , Yoo Hyunjoon , Ali Syed Sheraz , Van Lam Do , Taseer Ashhad Kamal , Oh Il‐Kwon 
Published: June 2024

AbstractElectro‐ionic artificial muscles, consisting of a configuration where an electrolyte membrane is flanked by two active electrodes, have emerged as transformative components in the field of soft robotics. Despite this, the current actuation performance falls short for many practical applications, because most existing electrode materials exhibit limitations in terms of their properties. Here, a multifunctional active electrode material is reported for an electro‐ionic artificial muscle, employing a triazine framework that incorporates 6,6′‐Dicyano‐2,2′‐bipyridyl (DCB‐TF). The multifunctional DCB‐TF boasts fully conjugated bonds, facilitating fast electron transfer, high porosity for ion accommodation, a substantial surface area of 1800 m2 g−1 for charge storage, numerous active sites for ion interactions, and complete aromatic rings contributing to stability. The application of DCB‐TF to the active electrodes in the electro‐ionic artificial muscles yields remarkable actuation performance, including a substantial bending displacement of 24 mm at 0.5 V and 0.2 Hz, a rapid response time of 2 s, and outstanding durability sustained over 3.4 million continuous cycles. Consequently, these soft actuators have enabled a dragonfly demonstration as a form of kinetic art.
T Cells Spatially Regulate B Cell Receptor Signaling in Lymphomas through H3K9me3 Modifications
Authors: Britto Lucy S. , Balasubramani Deepali , Desai Sona , Phillips Phunterion , Trehan Neev , Cesarman Ethel , Koff Jean L. , Singh Ankur 
Published: June 2024

AbstractActivated B cell‐like diffuse large B‐cell lymphoma (ABC‐DLBCL) is a subtype associated with poor survival outcomes. Despite identifying therapeutic targets through molecular characterization, targeted therapies have limited success. New strategies using immune‐competent tissue models are needed to understand how DLBCL cells evade treatment. Here, synthetic hydrogel‐based lymphoma organoids are used to demonstrate how signals in the lymphoid tumor microenvironment (Ly‐TME) can alter B cell receptor (BCR) signaling and specific histone modifications, tri‐methylation of histone 3 at lysine 9 (H3K9me3), dampening the effects of BCR pathway inhibition. Using imaging modalities, T cells increase DNA methyltransferase 3A expression and cytoskeleton formation in proximal ABC‐DLBCL cells, regulated by H3K9me3. Expansion microscopy on lymphoma organoids reveals T cells increase the size and quantity of segregated H3K9me3 clusters in ABC‐DLBCL cells. Findings suggest the re‐organization of higher‐order chromatin structures that may contribute to evasion or resistance to therapy via the emergence of novel transcriptional states. Treating ABC‐DLBCL cells with a G9α histone methyltransferase inhibitor reverses T cell‐mediated modulation of H3K9me3 and overcomes T cell‐mediated attenuation of treatment response to BCR pathway inhibition. This study emphasizes the Ly‐TME's role in altering DLBCL fate and suggests targeting aberrant signaling and microenvironmental cross‐talk that can benefit high‐risk patients.
Large‐Scale Fabrication of Stable Silicon Anode in Air for Sulfide Solid State Batteries via Ionic‐Electronic Dual Conductive Binder
Authors: Wang Zhilu , Shen Xuefeng , Chen Shengjie , Qiao Rui , Sun Baoyu , Deng Junkai , Song Jiangxuan 
Published: June 2024

AbstractThe construction of a continuous ionic/electronic pathway is critical for Si‐based sulfide all‐solid‐state batteries (ASSBs) with the advantages of high‐energy density and high‐cycle stability. However, a significant impediment arises from the parasitic reaction occurring between the ionic sulfide solid‐state electrolyte and electronic carbon additive, posing a formidable challenge. Additionally, the fabrication of electrodes necessitates stringent operational conditions, further limiting practical applicability. Herein, an ionic–electronic dual conductive binder for the fabrication of robust silicon anode under ambient air conditions in the absence of high‐cost and air‐sensitive sulfide solid‐state electrolyte for ASSBs is reported. This binder incorporates in situ reduced silver nanoparticles into a high‐strength polymer rich in ether bonds, establishing a conductive pathway for lithium ions and electrons. With the binder‐composited Si anode, the half‐cell exhibits a remarkable capacity of 1906.9 mAh g−1 and stable cycling for 500 cycles at a current density of 2 C (4.4 mA cm−2) under a low stack pressure of 5 MPa. The full cell using Ni0.9Co0.075Mn0.025O2 (NCM90) exhibits a remark cycling stability within 2000 cycles at 5 C (8 mA cm−2). This work presents an inspired design of functional binders for large‐scale manufacture and mild operation in a low‐cost way for Si anodes in ASSBs.
Ceria‐Optimized Oxygen‐Species Exchange in Hierarchical Bimetallic Hydroxide for Electrocatalytic Water Oxidation
Authors: Guo Linchuan , Zhang Zhuang , Mu Zhaori , Da Pengfei , An Li , Shen Wei , Hou Yichao , Xi Pinxian , Yan Chun‐Hua 
Published: June 2024

AbstractThe utilization of rare earth elements to regulate the interaction between catalysts and oxygen‐containing species holds promising prospects in the field of oxygen electrocatalysis. Through structural engineering and adsorption regulation, it is possible to achieve high‐performance catalytic sites with a broken activity‐stability tradeoff. Herein, this work fabricates a hierarchical CeO2/NiCo hydroxide for electrocatalytic oxygen evolution reaction (OER). This material exhibits superior overpotentials and enhanced stability. Multiple potential‐dependent experiments reveal that CeO2 promotes oxygen‐species exchange, especially OH− ions, between catalyst and environment, thereby optimizing the redox transformation of hydroxide and the adsorption of oxygen‐containing intermediates during OER. This is attributed to the reduction in the adsorption energy barrier of Ni to *OH facilitated by CeO2, particularly the near‐interfacial Ni sites. The less‐damaging adsorbate evolution mechanism and the CeO2 hierarchical shell significantly enhance the structural robustness, leading to exceptional stability. Additionally, the observed “self‐healing” phenomenon provides further substantiation for the accelerated oxygen exchange. This work provides a neat strategy for the synthesis of ceria‐based complex hollow electrocatalysts, as well as an in‐depth insight into the co‐catalytic role of CeO2 in terms of oxygen transfer.
Monodentate Phosphinoamine Nickel Complex Supported on a Metal–Organic Framework for High‐Performance Ethylene Dimerization
Authors: Chen Wenmiao , Elumalai Palani , Mamlouk Hind , Rentería‐Gómez Ángel , Veeranna Yempally , Shetty Sharan , Kumar Dharmesh , Al‐Rawashdeh Ma'moun , Gupta Somil S. , Gutierrez Osvaldo , Zhou Hong‐Cai , Madrahimov Sherzod T. 
Published: June 2024

AbstractEthylene dimerization is an efficient industrial chemical process to produce 1‐butene, with demanding selectivity and activity requirements on new catalytic systems. Herein, a series of monodentate phosphinoamine‐nickel complexes immobilized on UiO‐66 are described for ethylene dimerization. These catalysts display extensive molecular tunability of the ligand similar to organometallic catalysis, while maintaining the high stability attributed to the metal–organic framework (MOF) scaffold. The highly flexible postsynthetic modification method enables this study to prepare MOFs functionalized with five different substituted phosphines and 3 N‐containing ligands and identify the optimal catalyst UiO‐66‐L5‐NiCl2 with isopropyl substituted nickel mono‐phosphinoamine complex. This catalyst shows a remarkable activity and selectivity with a TOF of 29 000 (molethyl/molNi/h) and 99% selectivity for 1‐butene under ethylene pressure of 15 bar. The catalyst is also applicable for continuous production in the packed column micro‐reactor with a TON of 72 000 (molethyl/molNi). The mechanistic insight for the ethylene oligomerization has been examined by density functional theory (DFT) calculations. The calculated energy profiles for homogeneous complexes and truncated MOF models reveal varying rate‐determining step as β‐hydrogen elimination and migratory insertion, respectively. The activation barrier of UiO‐66‐L5‐NiCl2 is lower than other systems, possibly due to the restriction effect caused by clusters and ligands. A comprehensive analysis of the structural parameters of catalysts shows that the cone angle as steric descriptor and butene desorption energy as thermodynamic descriptor can be applied to estimate the reactivity turnover frequency (TOF) with the optimum for UiO‐66‐L5‐NiCl2. This work represents the systematic optimization of ligand effect through combination of experimental and theoretical data and presents a proof‐of‐concept for ethylene dimerization catalyst through simple heterogenization of organometallic catalyst on MOF.
Computational Polarization Imaging In Vivo through Surgical Smoke Using Refined Polarization Difference
Authors: Wang Daqian , Song Jiawei , Gao Jun , Qi Ji , Elson Daniel S. 
Published: June 2024

AbstractIn surgery, the surgical smoke generated during tissue dissection and hemostasis can degrade the image quality, affecting tissue visibility and interfering with the further image processing. Developing reliable and interpretable computational imaging methods for restoring smoke‐affected surgical images is crucial, as typical image restoration methods relying on color‐texture information are insufficient. Here a computational polarization imaging method through surgical smoke is demonstrated, including a refined polarization difference estimation based on the discrete electric field direction, and a corresponding prior‐based estimation method, for better parameter estimation and image restoration performance. Results and analyses for ex vivo, the first in vivo animal experiments, and human oral cavity tests show that the proposed method achieves visibility restoration and color recovery of higher quality, and exhibits good generalization across diverse imaging scenarios with interpretability. The method is expected to enhance the precision, safety, and efficiency of advanced image‐guided and robotic surgery.
In Silico Screening Accelerates Nanocarrier Design for Efficient mRNA Delivery
Authors: Henser‐Brownhill Tristan , Martin Liam , Samangouei Parisa , Ladak Aaqib , Apostolidou Marina , Nagel Benita , Kwok Albert 
Published: June 2024

AbstractLipidic nanocarriers are a broad class of lipid‐based vectors with proven potential for packaging and delivering emerging nucleic acid therapeutics. An important early step in the clinical development cycle is large‐scale screening of diverse formulation libraries to assess particle quality and payload delivery efficiency. Due to the size of the screening space, this process can be both costly and time‐consuming. To address this, computational models capable of predicting clinically relevant physio‐chemical properties of dendrimer‐lipid nanocarriers, along with their mRNA payload delivery efficiency in human cells are developed. The models are then deployed on a large theoretical nanocarrier pool consisting of over 4.5 million formulations. Top predictions are synthesised for validation using cell‐based assays, leading to the discovery of a high quality, high performing, candidate. The methods reported here enable rapid, high‐throughput, in silico pre‐screening for high‐quality candidates, and have great potential to reduce the cost and time required to bring mRNA therapies to the clinic.
Phase behavior of ionic fluid in charged confinement: An associating polymer density functional theory study
Authors: Cheng Jin , Xu Jipeng , Wang Sijie , Chen Xueqian , Lian Cheng , Liu Honglai 
Published: June 2024

AbstractWith the rapid advancement of the new energy industry, porous electrode materials and complex electrolytes have gained widespread usage. Electrolytes exhibit distinctive phase behavior when subjected to the combined influence of confined space and electric fields. However, the measurement and prediction of such phase behavior encounter significant challenges. Consequently, numerous theoretical tools have been employed to establish models for phase equilibrium calculations. Nevertheless, current research in this field has notable limitations and fails to address the confinement of space or complex polymer electrolytes. Considering these shortcomings, an associating polymer density functional theory (PDFT) was developed by modifying excess free energy. This study examines the phase behavior of electrolytes with various chain lengths within diverse confined slits, revealing that the confinement effect and fluid tail chains can narrow the phase diagram. Additionally, a linear correlation between the electric field strength and the phase equilibrium offset has been identified, and a quantitative relationship is derived. The results of this investigation contribute to a deeper comprehension of complex fluid phase behavior and guide the design of electrochemical devices.
Thermoeconomic analysis of sCO2 power cycles
Authors: Chen Duoli , O'Connell John P. , Seider Warren D. 
Published: June 2024

AbstractThe second‐law analysis evaluates the irreversibilities of a process. Systematic study of the relationship between thermodynamic efficiency and process modifications enhances process synthesis. The Allam cycle is an oxy‐fuel combustion cycle with nearly complete carbon capture that offers greater efficiency than current electricity generating systems. This study applies lost work analysis to the original Allam cycle and three modifications to obtain the distribution of irreversibilities and the effects of different configurations among potential process improvements for more sustainable power generation. The major inefficiencies are from the combustors and heat exchangers. We also examine the economic profitability of the alternatives. The largest equipment costs are for the turbines, compressors, and recuperators. We find that improving efficiency leads to less economic return; a configuration with partial compression has the highest efficiency, while the original Allam cycle has the highest profitability. We discuss how to resolve this apparent conflict between sustainability and profitability.
Steering Geometric Reconstruction of Bismuth with Accelerated Dynamics for CO2 Electroreduction
Authors: Wang Xiaowen , Zhang Yangyang , Wang Shao , Li Yifan , Feng Yafei , Dai Zechuan , Chen Yanxu , Meng Xiangmin , Xia Jing , Zhang Genqiang 
Published: June 2024

AbstractBismuth‐based materials have emerged as promising catalysts in the electrocatalytic reduction of CO2 to formate. However, the reasons for the reconstruction of Bi‐based precursors to form bismuth nanosheets are still puzzling, especially the formation of defective bismuth sites. Herein, we prepare bismuth nanosheets with vacancy‐rich defects (V‐Bi NS) by rapidly reconstructing Bi19Cl3S27 under negative potential. Theoretical analysis reveals that the introduction of chlorine induces the generation of intrinsic electric field in the precursor, thereby increasing the electron transfer rate and further promoting the metallization of trivalent bismuth. Meanwhile, experimental tests verify that Bi19Cl3S27 has a faster reconstruction rate than Bi2S3. The formed V‐Bi NS exhibits up to 96 % HCOO− Faraday efficiency and 400 mA cm−2 HCOO− partial current densities, and its electrochemical active surface area normalized formate current density and yield are 2.2 times higher than those of intact bismuth nanosheets (I‐Bi NS). Density functional theory calculations indicate that bismuth vacancies with electron‐rich aggregation reduce the activation energy of CO2 to *CO2− radicals and stabilize the adsorption of the key intermediate *OCHO, thus facilitating the reaction kinetics of formate production.
Skeletal and Mechanistic Diversity in Ir‐Catalyzed Cycloisomerizations of Allene‐Tethered Pyrroles and Indoles
Authors: Arribas Andrés , Calvelo Martín , Rey Alejandro , Mascareñas José L. , López Fernando 
Published: June 2024

AbstractPyrroles and indoles bearing N‐allenyl tethers participate in a variety of iridium‐catalyzed cycloisomerization processes initiated by a C−H activation step, to deliver a diversity of synthetically relevant azaheterocyclic products. By appropriate selection of the ancillary ligand and the substitution pattern of the allene, the reactions can diverge from simple intramolecular hydrocarbonations to tandem processes involving intriguing mechanistic issues. Accordingly, a wide range of heterocyclic structures ranging from dihydro‐indolizines and pyridoindoles to tetrahydroindolizines, as well as cyclopropane‐fused tetrahydroindolizines can be obtained. Moreover, by using chiral ligands, these cascade processes can be carried out in an enantioselective manner. DFT studies provide insights into the underlying mechanisms and justify the observed chemo‐ regio‐ and stereoselectivities.
Kopplung von Arylchloriden mit Lithium‐Nukleophilen, an molekular definierten Alkynyllithium‐Palladium‐Katalysatoren
Authors: Goebel Jonas F. , Stemmer Johanna , Krüger Nele , Sakhaee Nader , Gooßen Lukas J. 
Published: June 2024

AbstractPalladiumkatalysierte Kreuzkupplungen von Arylchloriden erfordern zumeist sterisch anspruchsvolle, elektronenreiche Liganden wie Phosphine oder heterocyclische Carbene. Die Reaktion von Palladiumsalzen mit Alkinyllithium‐Reagenzien liefert jedoch ähnlich leistungsfähige Kreuzkupplungskatalysatoren. Dabei werden zunächst Dilithium‐Tetraalkinylpalladat‐Komplexe gebildet. Diese katalysieren die Kupplung von Arylchloriden mit Lithiumsalzen diverser terminaler Alkine unter Bildung von Alkinylarenen. Isolierte Li‐Alkinyl‐Pd‐Komplexe vermitteln auch Kupplungen von Aryl‐ und Allylchloriden mit (Hetero)aryl‐, Alkyl‐ und Allyllithiumverbindungen sowie mit Lithiumamiden. Keine dieser Reaktionen läuft in Gegenwart unmodifizierter Palladiumsalze ab. Der präparative Nutzen dieses Ansatzes wurde durch die Synthese von 49 Molekülen nachgewiesen, darunter pharmazeutisch relevante Verbindungen.
Interfacially Ordered NiCoMoS Nanosheets Arrays on Hierarchical Ti3C2Tx MXene for High‐Energy‐Density Fiber‐Shaped Supercapacitors with Accelerated Pseudocapacitive Kinetics
Authors: Mei Xiaotong , Yang Chao , Chen Fangyuan , Wang Yuting , Zhang Yang , Man Zengming , Lu Wangyang , Xu Jianhong , Wu Guan 
Published: June 2024

AbstractBalancing electrochemical activity and structural reversibility of fibrous electrodes with accelerated Faradaic charge transfer kinetics and pseudocapacitive storage are highly crucial for fiber‐shaped supercapacitors (FSCs). Herein, we report novel core–shell hierarchical fibers for high‐performance FSCs, in which the ordered NiCoMoS nanosheets arrays are chemically anchored on Ti3C2Tx fibers. Beneficial from architecting stable polymetallic sulfide arrays and conductive networks, the NiCoMoS−Ti3C2Tx fiber maintains fast charge transfer, low diffusion and OH− adsorption barrier, and stabilized multi‐electronic reaction kinetics of polymetallic sulfide. Consequently, the NiCoMoS−Ti3C2Tx fiber exhibits a large volumetric capacitance (2472.3 F cm−3) and reversible cycling performance (20,000 cycles). In addition, the solid‐state symmetric FSCs deliver a high energy density of 50.6 mWh cm−3 and bending stability, which can significantly power electronic devices and offer sensitive detection for dopamine.
Discovery, Total Synthesis, and Anti‐Inflammatory Evaluation of Naturally Occurring Naphthopyrone‐Macrolide Hybrids as Potent NLRP3 Inflammasome Inhibitors
Authors: Sun Chunxiao , Jiang Yuqi , Li Changlong , Sun Simin , Lin Jiaqi , Wang Wenxue , Zhou Luning , Li Liping , Shah Mudassir , Che Qian , Zhang Guojian , Wang De , Zhu Tianjiao , Li Dehai 
Published: June 2024

AbstractNumerous clinical disorders have been linked to the etiology of dysregulated NLRP3 (NACHT, LRR, and PYD domain‐containing protein 3) inflammasome activation. Despite its potential as a pharmacological target, modulation of NLRP3 activity remains challenging. Only a sparse number of compounds have been reported that can modulate NLRP3 and none of them have been developed into a commercially available drug. In this research, we identified three potent NLRP3 inflammasome inhibitors, gymnoasins A‐C (1–3), with unprecedented pentacyclic scaffolds, from an Antarctic fungus Pseudogymnoascus sp. HDN17‐895, which represent the first naturally occurring naphthopyrone‐macrolide hybrids. Additionally, biomimetic synthesis of gymnoasin A (1) was also achieved validating the chemical structure and affording ample amounts of material for exhaustive bioactivity assessments. Biological assays indicated that 1 could significantly inhibited in vitro NLRP3 inflammasome activation and in vivo pro‐inflammatory cytokine IL‐1β release, representing a valuable new lead compound for the development of novel therapeutics with the potential to inhibit the NLRP3 inflammasome.