bluuebunny/crossref_metadata_2025_split huggingface dataset:
Challenges and Recent Progress on Key Materials for Rechargeable Magnesium Batteries
Authors: Liu Fanfan , Wang Tiantian , Liu Xiaobin , Fan Li‐Zhen 
Published: May 2020

AbstractRechargeable magnesium batteries (RMBs), which have attracted tremendous attention in large‐scale energy storage applications beyond lithium ion batteries, have many advantages such as high volumetric capacity, low cost, and environmental friendliness. However, the strong polarization effect, slow kinetic de‐intercalation of Mg2+ ions, and the incompatibility between electrodes and electrolytes limit their commercial application. Thus, developing stable and high‐efficiency electrode materials and optimization of electrolytes are key to promoting the practical application of RMBs. In this review, a summary and discussion are provided regarding the recent progress in the development of the key materials for RMBs, including cathodes, anodes, and electrolytes. The cathode materials including intercalation type cathodes and conversion type cathodes are classified and introduced in detail by the reaction mechanism, the effects of structure on the kinetics of Mg2+ ion migration are clarified; the modification and interface issues of Mg anode materials are comprehensively stated, and the potential development prospects of RMB electrolytes are systematically analyzed. In addition, the main opportunities and challenges in this field are briefly elaborated and discussed. Finally, this review will provide a framework for the key materials for RMBs as a reference for future research.
Multiscale Understanding and Architecture Design of High Energy/Power Lithium‐Ion Battery Electrodes
Authors: Zhang Xiao , Ju Zhengyu , Zhu Yue , Takeuchi Kenneth J. , Takeuchi Esther S. , Marschilok Amy C. , Yu Guihua 
Published: May 2020

AbstractAmong various commercially available energy storage devices, lithium‐ion batteries (LIBs) stand out as the most compact and rapidly growing technology. This multicomponent system operates on coupled dynamics to reversibly store and release electricity. With the hierarchical electrode architectures inside LIBs, versatile functionality can be realized by design, while considerable difficulties remain to be solved to fully exploit the capability of each constituent. With the rapid electrification of the transportation sector and an urgent need to overhaul electric grids in the context of renewable energy penetration, demands for concomitant high energy and high power batteries are continuously increasing. Although building an ideal battery requires effort from multiple scientific and engineering aspects, it is imperative to gain insight into multiscale transport behaviors arising in both spatial and temporal dimensions, and enable their harmonic integration inside the whole battery system. In this progress report, recent research efforts on characterizing and understanding transport kinetics in LIBs are reviewed covering a broad range of electrode materials and length scales. To demonstrate the crucial role of such information in revolutionary electrode design, examples of innovative high energy/power electrodes are provided with their unique hierarchical porous architectures highlighted. To conclude, perspectives on further approaches toward advanced thick electrode designs with fast kinetics and tailored properties are discussed.
Implanting Isolated Ru Atoms into Edge‐Rich Carbon Matrix for Efficient Electrocatalytic Hydrogen Evolution
Authors: Zhang Huabin , Zhou Wei , Lu Xue Feng , Chen Tao , Lou Xiong Wen (David) 
Published: May 2020

AbstractAlthough the maximized dispersion of metal atoms has been realized in the single‐atom catalysts, further improving the intrinsic activity of the catalysts is of vital importance. Here, the decoration of isolated Ru atoms into an edge‐rich carbon matrix is reported for the electrocatalytic hydrogen evolution reaction. The developed catalyst displays high catalytic performance with low overpotentials of 63 and 102 mV for achieving the current densities of 10 and 50 mA cm−2, respectively. Its mass activity is about 9.6 times higher than that of the commercial Pt/C‐20% catalyst at an overpotential of 100 mV. Experimental results and density functional theory calculations suggest that the edges in the carbon matrix enhance the local electric field at the Ru site and accelerate the reaction kinetics for the hydrogen evolution. The present work may provide insights into electrocatalytic behavior and guide the design of advanced electrocatalysts.
The Impact of Atmosphere on Energetics of Lead Halide Perovskites
Authors: Hu Zhanhao , Liu Zonghao , Ono Luis K. , Jiang Maowei , He Sisi , Son Dae‐Yong , Qi Yabing 
Published: May 2020

AbstractSolar cells based on metal halide perovskites have emerged as a promising low‐cost photovoltaic technology. In contrast to inert atmospheres where most of the lab‐scale devices are made to date, large‐area low‐cost production of perovskite solar cells often involves processing of perovskites in various atmospheres including ambient air, nitrogen, and/or vacuum. Herein, the impact of atmosphere on the energy levels of methylammonium lead halide perovskite films is systematically investigated. The atmosphere is varied to simulate the typical fabrication process. Through a comprehensive analysis combining the Fermi level evolution, surface photovoltage, photoluminescence properties, photovoltaic performance, and device simulation, an overall landscape of the energy diagram of the perovskite layer is able to be determined. The findings have direct implications for real‐world devices under typical atmospheres, and provide insights into the fabrication‐process design and optimization. Furthermore, a universal Fermi level shift under vacuum for lead halide‐based perovskites revealed in this study, urges a refreshed view on the energetics studies conducted without considering the atmospheric effect.
Covalent Encapsulation of Sulfur in a MOF‐Derived S, N‐Doped Porous Carbon Host Realized via the Vapor‐Infiltration Method Results in Enhanced Sodium–Sulfur Battery Performance
Authors: Xiao Fengping , Yang Xuming , Wang Hongkang , Xu Jun , Liu Yulong , Yu Denis Y. W. , Rogach Andrey L. 
Published: May 2020

AbstractPractical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g−1 (1262 mAh g−1(sulfur)) at 0.1 A g−1, 270 mAh g−1 (730 mAh g−1(sulfur)) after 1000 cycles at 1 A g−1 and 201 mAh g−1 (543 mAh g−1(sulfur)) at 5.0 A g−1.
Entwicklung molekularer Sonden für die hyperpolarisierte NMR‐Bildgebung im biologischen Bereich
Authors: Kondo Yohei , Nonaka Hiroshi , Takakusagi Yoichi , Sando Shinsuke 
Published: May 2020

AbstractDie Hyperpolarisation von Atomkernen bietet einen Weg, die NMR‐Empfindlichkeit erheblich zu steigern. Durch Anwendung dieses leistungsstarken Hilfsmittels wurden niedermolekulare Verbindungen mit stabilen Isotopen für die hochempfindliche biomedizinische Bildgebung genutzt. Die jüngste Entwicklung molekularer Sonden für die hyperpolarisierte In‐vivo‐Analyse hat gezeigt, dass diese Technik in der Lage ist, einzigartige metabolische und physiologische Informationen zu liefern. Dieser Aufsatz bietet eine kurze Einführung in die Technik der Hyperpolarisation, Ansätze zum rationalen Design molekularer Sonden für die hyperpolarisierte NMR‐Bildgebung und Beispiele von Molekülen, die erfolgreich in vitro oder in vivo für diesen Zweck genutzt wurden.
A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes
Authors: Desnoyer Addison N. , Nicolay Amélie , Ziegler Micah S. , Torquato Nicole A. , Tilley T. Don 
Published: May 2020

AbstractReduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H2 and CO2.
Tuning the Properties of Graphdiyne by Introducing Electron‐Withdrawing/Donating Groups
Authors: Xie Chipeng , Hu Xiuli , Guan Zhaoyong , Li Xiaodong , Zhao Fuhua , Song Yuwei , Li Yuan , Li Xiaofang , Wang Ning , Huang Changshui 
Published: May 2020

AbstractThe properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron‐withdrawing/donating groups. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of GDY derivatives MeGDY, HGDY, and CNGDY. Cyano groups (electron‐withdrawing) and methyl groups (electron‐donating) decrease the band gap and increase the conductivity of the GDY network. The cyano and methyl groups affects the aggregation of GDY, providing a higher number of micropores and specific surface area. These groups also endow the original GDY additional advantages: the stronger electronegativity of cyano groups increase the affinity of GDY frameworks to lithium atoms, and the larger atomic volume of methyl groups increases the interlayer distance and provides more storage space and diffusion tunnels.
Synthesis and Localized Photoluminescence Blinking of Lead‐Free 2D Nanostructures of Cs3Bi2I6Cl3 Perovskite
Authors: Kundu Kaushik , Acharyya Paribesh , Maji Krishnendu , Sasmal Ranjan , Agasti Sarit S. , Biswas Kanishka 
Published: May 2020

AbstractTwo‐dimensional (2D) lead‐free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in‐depth understanding on their shape‐controlled charge‐carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single‐particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3Bi2I6Cl3, by solution‐based method. We applied fluorescence microscopy and super‐resolution optical imaging at single‐particle level to investigate their morphology‐dependent PL properties. Narrow emission line widths and passivation of non‐radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super‐resolution optical image of the NS from localization‐based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.
Protonation of CH3N3 and CF3N3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions
Authors: Saal Thomas , Blastik Zsófia E. , Haiges Ralf , Nirmalchandar Archith , Baxter Amanda F. , Christe Karl O. , Vasiliu Monica , Dixon David A. , Beier Petr , Prakash G. K. Surya 
Published: May 2020

AbstractThe methylamino diazonium cations [CH3N(H)N2]+ and [CF3N(H)N2]+ were prepared as their low‐temperature stable [AsF6]− salts by protonation of azidomethane and azidotrifluoromethane in superacidic systems. They were characterized by NMR and Raman spectroscopy. Unequivocal proof of the protonation site was obtained by the crystal structures of both salts, confirming the formation of alkylamino diazonium ions. The Lewis adducts CH3N3⋅AsF5 and CF3N3⋅AsF5 were also prepared and characterized by low‐temperature NMR and Raman spectroscopy, and also by X‐ray structure determination for CH3N3⋅AsF5. Electronic structure calculations were performed to provide additional insights. Attempted electrophilic amination of aromatics such as benzene and toluene with methyl‐ and trifluoromethylamino diazonium ions were unsuccessful.
Homogeneous Molecular Iron Catalysts for Direct Photocatalytic Conversion of Formic Acid to Syngas (CO+H2)
Authors: Irfan Rana Muhammad , Wang Taotao , Jiang Daochuan , Yue Qiudi , Zhang Lei , Cao Hongyun , Pan Yang , Du Pingwu 
Published: May 2020

AbstractThe catalytic decomposition of formic acid to generate syngas (a mixture of H2 and CO) is a highly valuable strategy for energy conversion. Syngas can be used directly in internal combustion engines or can be converted to liquid fuels, meeting future energy challenges in a sustainable manner. Herein, we report the use of homogeneous molecular iron catalysts combined with a CdS nanorods (NRs) semiconductor to construct a highly efficient photocatalytic system for direct conversion of formic acid to syngas at room temperature and atmospheric pressure. Under optimal conditions, the photocatalytic system presents an activity of 150 mmol gcatalyst−1 h−1 towards H2, and an apparent quantum yield (AQY) of 16.8 %, making it among the most active noble‐metal‐free photocatalytic systems for H2 evolution from formic acid under visible light. Meanwhile, these iron‐based molecular catalysts also demonstrate remarkable enhancement in CO evolution with robust stability. The mechanistic role of the molecular catalyst is further investigated by using cyclic voltammetry, which suggests the formation of FeI species as the key step in the catalytic conversion of formic acid to syngas.
Two‐Plateau Li‐Se Chemistry for High Volumetric Capacity Se Cathodes
Authors: Qi Xiaoqun , Yang Ying , Jin Qiang , Yang Fengyi , Xie Yong , Sang Pengfei , Liu Kun , Zhao Wenbin , Xu Xiaobin , Fu Yongzhu , Zhou Jian , Qie Long , Huang Yunhui 
Published: May 2020

AbstractFor Li‐Se batteries, ether‐ and carbonate‐based electrolytes are commonly used. However, because of the “shuttle effect” of the highly dissoluble long‐chain lithium polyselenides (LPSes, Li2Sen, 4≤n≤8) in the ether electrolytes and the sluggish one‐step solid‐solid conversion between Se and Li2Se in the carbonate electrolytes, a large amount of porous carbon (>40 wt % in the electrode) is always needed for the Se cathodes, which seriously counteracts the advantage of Se electrodes in terms of volumetric capacity. Herein an acetonitrile‐based electrolyte is introduced for the Li‐Se system, and a two‐plateau conversion mechanism is proposed. This new Li‐Se chemistry not only avoids the shuttle effect but also facilitates the conversion between Se and Li2Se, enabling an efficient Se cathode with high Se utilization (97 %) and enhanced Coulombic efficiency. Moreover, with such a designed electrolyte, a highly compact Se electrode (2.35 gSe cm−3) with a record‐breaking Se content (80 wt %) and high Se loading (8 mg cm−2) is demonstrated to have a superhigh volumetric energy density of up to 2502 Wh L−1, surpassing that of LiCoO2.
Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes
Authors: Zhang Qun‐Liang , Xiong Qin , Li Miao‐Miao , Xiong Wei , Shi Bin , Lan Yu , Lu Liang‐Qiu , Xiao Wen‐Jing 
Published: May 2020

AbstractHigher‐order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium‐sized architectures. Typically, configuration‐restrained conjugated systems are utilized as 8π‐components for higher‐order concerted cycloadditions. However, for this reason, 10‐membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri‐ and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible‐light activation and asymmetric palladium catalysis. This protocol provides a new route to 10‐membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo‐, peri‐, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd‐containing 1,8‐dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo‐Wolff rearrangement.
(E)‐2‐(2‐Allylidenehydrazinyl)thiazole derivatives: Design, green synthesis, in silico and in vitro antimycobacterial and radical scavenging studies
Authors: Hublikar Mahesh , Kadu Vikas , Dublad Jitender Kumar , Raut Dattatraya , Shirame Sachin , Makam Parameshwar , Bhosale Raghunath 
Published: May 2020

AbstractBy understanding the rampant infections of Mycobacterium tuberculosis (Mtb) and inflammations caused due to the generation of radical species during the Mtb infection, a series of (E)‐2‐(2‐allylidenehydrazinyl)thiazole derivatives, with dual‐action properties, was designed. The molecules were designed with a considerable variation in LogP, one of the critical parameters in physicochemical properties, and analyzed for their drug‐likeness. For the synthesis, a simple, green, and multicomponent one‐pot synthesis method was developed. The in vitro inhibition potentials were evaluated against Mtb H37Rv by the microplate Alamar Blue assay. The results reveal that compound 6 was potent, with a MIC value of 6.5 µg/ml, and showed better interactions with the KasA protein with binding free energy (ΔG) of −9.4 kcal/mol. Also, the radical scavenging properties were studied to establish the dual‐action properties of the molecules. Compound 9 exhibited promising antioxidant and nitric oxide radical scavenging activities, with 81.7% and 81.0%, respectively, at 1,000‐μg/ml concentration.
Off‐target glycans encountered along the synthetic biology route toward humanizedN‐glycans inPichia pastoris
Authors: Laukens Bram , Jacobs Pieter P. , Geysens Katelijne , Martins Jose , De Wachter Charlot , Ameloot Paul , Morelle Willy , Haustraete Jurgen , Renauld Jean‐Christophe , Samyn Bart , Contreras Roland , Devos Simon , Callewaert Nico 
Published: May 2020

AbstractThe glycosylation pathways of several eukaryotic protein expression hosts are being engineered to enable the production of therapeutic glycoproteins with humanized application‐customized glycan structures. In several expression hosts, this has been quite successful, but one caveat is that the newN‐glycan structures inadvertently might be substrates for one or more of the multitude of endogenous glycosyltransferases in such heterologous background. This then results in the formation of novel, undesired glycan structures, which often remain insufficiently characterized. When expressing mouse interleukin‐22 in aPichia pastoris(syn.Komagataella phaffii) GlycoSwitchM5 strain, which had been optimized to produce Man5GlcNAc2N‐glycans, glycan profiling revealed two major species: Man5GlcNAc2and an unexpected, partially α‐mannosidase‐resistant structure. A detailed structural analysis using exoglycosidase sequencing, mass spectrometry, linkage analysis, and nuclear magnetic resonance revealed that this novel glycan was Man5GlcNAc2modified with a Glcα‐1,2‐Manβ‐1,2‐Manβ‐1,3‐Glcα‐1,3‐R tetrasaccharide. Expression of a Golgi‐targeted GlcNAc transferase‐I strongly inhibited the formation of this novel modification, resulting in more homogeneous modification with the targeted GlcNAcMan5GlcNAc2structure. Our findings reinforce accumulating evidence that robustly customizing theN‐glycosylation pathway inP. pastoristo produce particular human‐type structures is still an incompletely solved synthetic biology challenge, which will require further innovation to enable safe glycoprotein pharmaceutical production.
Clinical outcomes of patients with advanced synovial sarcoma or myxoid/round cell liposarcoma treated at major cancer centers in the United States
Authors: Pollack Seth M. , Somaiah Neeta , Araujo Dejka M. , Druta Mihaela , Van Tine Brian A. , Burgess Melissa A. , Chawla Sant P. , Seetharam Mahesh , Okuno Scott H. , Bohac Chet , Chen Michael , Yurasov Sergey , Attia Steven 
Published: May 2020

AbstractBackgroundOutcomes data regarding advanced synovial sarcoma (SS) and myxoid/round cell liposarcoma (MRCL) are limited, consisting primarily of retrospective series and post hoc analyses of clinical trials.MethodsIn this multi‐center retrospective study, data were abstracted from the medical records of 350 patients from nine sarcoma centers throughout the United States and combined into a registry. Patients with advanced/unresectable or metastatic SS (n = 249) or MRCL (n = 101) who received first‐line systemic anticancer therapy and had records of tumor imaging were included. Overall survival (OS), time to next treatment, time to distant metastasis, and progression‐free survival (PFS) were evaluated using the Kaplan‐Meier method and Cox regression.ResultsAt start of first‐line systemic anticancer therapy, 92.4% of patients with SS and 91.1% of patients with MRCL had metastatic lesions. However, 74.7% of patients with SS and 72.3% of patients with MRCL had ≥2 lines of systemic therapy. Median OS and median PFS from first‐line therapy for SS was 24.7 months (95% CI, 20.9‐29.4) and 7.5 months, respectively (95% CI, 6.4‐8.4). Median OS and median PFS from start of first‐line therapy for MRCL was 29.9 months (95% CI, 27‐44.6) and 8.9 months (95% CI 4.5‐12.0).ConclusionsTo the best of our knowledge, this is the largest retrospective study of patients with SS and MRCL. It provides an analysis of real‐world clinical outcomes among patients treated at major sarcoma cancer centers and could inform treatment decisions and design of clinical trials. In general, the survival outcomes for this selected population appear more favorable than in published literature.