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991.
Lipiao Bao Ying Li Pengyuan Yu Wangqiang Shen Peng Jin Xing Lu 《Angewandte Chemie (International ed. in English)》2020,59(13):5259-5262
Encapsulating one to three metal atoms or a metallic cluster inside fullerene cages affords endohedral metallofullerenes (EMFs) classified as mono‐, di‐, tri‐, and cluster‐EMFs, respectively. Although the coexistence of various EMF species in soot is common for rare‐earth metals, we herein report that europium tends to prefer the formation of mono‐EMFs. Mass spectroscopy reveals that mono‐EMFs (Eu@C2n) prevail in the Eu‐containing soot. Theoretical calculations demonstrate that the encapsulation energy of the endohedral metal accounts for the selective formation of mono‐EMFs and rationalize similar observations for EMFs containing other metals like Ca, Sr, Ba, or Yb. Consistently, all isolated Eu‐EMFs are mono‐EMFs, including Eu@D3h(1)‐C74, Eu@C2v(19138)‐C76, Eu@C2v(3)‐C78, Eu@C2v(3)‐C80, and Eu@D3d(19)‐C84, which are identified by crystallography. Remarkably, Eu@C2v(19138)‐C76 represents the first Eu‐containing EMF with a cage that violates the isolated‐pentagon‐rule, and Eu@C2v(3)‐C78 is the first C78‐based EMF stabilized by merely one metal atom. 相似文献
992.
Calcium batteries are a potentially sustainable, high‐energy‐density battery technology beyond Li ion batteries. Now the development of Ca batteries has become possible with a newly invented Ca electrolyte capable of reversible Ca deposition/stripping at room temperature. 相似文献
993.
Caiming Tang Jianhua Tan Peilin Zhang Yujuan Fan Zhiqiang Yu Xianzhi Peng 《Journal of mass spectrometry : JMS》2020,55(9)
Kinetic isotope effects (KIEs) occurring in mass spectrometry (MS) can provide in‐depth insights into the fragmentation behaviors of compounds of interest in MS. Yet, the fundamentals of KIEs in collision‐induced dissociation (CID) in tandem mass spectrometry (MS/MS) are unclear, and information about chlorine KIEs (Cl‐KIEs) of organochlorines in MS is particularly scarce. This study investigated the Cl‐KIEs of dichloromethane, trichloroethylene, and tetrachloroethylene during CID using gas chromatography‐electron ionization triple‐quadrupole MS/MS. Cl‐KIEs were evaluated with MS signal intensities. All the organochlorines presented large inverse Cl‐KIEs (<1, the departures of Cl‐KIEs from 1 denote the magnitudes of Cl‐KIEs), showing the largest magnitudes of 0.797, 0.910, and 0.892 at the highest collision energy (60 eV) for dichloromethane, trichloroethylene, and tetrachloroethylene, respectively. For dichloromethane, both intra‐ion and inter‐ion Cl‐KIEs were studied, within the ranges of 0.820–1.020 and 0.797–1.016, respectively, showing both normal and inverse Cl‐KIEs depending on collision energies. The observed Cl‐KIEs generally declined from large normal to extremely large inverse values with increasing collision energies from 0 to 60 eV but were inferred to be independent of MS signal intensities. The Cl‐KIEs are dominated by critical energies at low internal energies of precursor ions, resulting in normal Cl‐KIEs; while at high internal energies, the Cl‐KIEs are controlled by rotational barriers (or looseness/tightness of transition states), which lead to isotope‐competitive reactions in dechlorination and thereby inverse Cl‐KIEs. It is concluded that the Cl‐KIEs may depend on critical energies, bond strengths, available internal energies, and transition state looseness/tightness. The findings of this study yield new insights into the fundamentals of Cl‐KIEs of organochlorines during CID and may be conducive to elucidating the underlying mechanisms of KIEs in collision‐induced and photo‐induced reactions in the actual world. 相似文献
994.
Roberto Pestana-Nobles Jorge A. Leyva-Rojas Juvenal Yosa 《Molecules (Basel, Switzerland)》2020,25(22)
Biofilms are communities of microorganisms that can colonize biotic and abiotic surfaces and thus play a significant role in the persistence of bacterial infection and resistance to antimicrobial. About 65% and 80% of microbial and chronic infections are associated with biofilm formation, respectively. The increase in infections by multi-resistant bacteria instigates the need for the discovery of novel natural-based drugs that act as inhibitory molecules. The inhibition of diguanylate cyclases (DGCs), the enzyme implicated in the synthesis of the second messenger, cyclic diguanylate (c-di-GMP), involved in the biofilm formation, represents a potential approach for preventing the biofilm development. It has been extensively studied using PleD protein as a model of DGC for in silico studies as virtual screening and as a model for in vitro studies in biofilms formation. This study aimed to search for natural products capable of inhibiting the Caulobacter crescentus enzyme PleD. For this purpose, 224,205 molecules from the natural products ZINC15 database, have been evaluated through molecular docking and molecular dynamic simulation. Our results suggest trans-Aconitic acid (TAA) as a possible starting point for hit-to-lead methodologies to obtain new inhibitors of the PleD protein and hence blocking the biofilm formation. 相似文献
995.
Grzegorz Greczynski Lars Hultman 《Angewandte Chemie (International ed. in English)》2020,59(13):5002-5006
X‐ray photoelectron spectroscopy (XPS) is an indispensable technique in modern materials science for the determination of chemical bonding as evidenced by more than 10 000 XPS papers published annually. A literature survey reveals that in the vast majority of cases an incorrect referencing of the binding energy scale is used, neglecting warnings that have been formulated from the early days of the technique. Consequences for the data reliability are disastrous and decades of XPS work require revisiting. The purpose of this Viewpoint is to highlight the existing problems, review the criticism and suggest ways forward. 相似文献
996.
Hui Duan Wan‐Ping Chen Min Fan Wen‐Peng Wang Le Yu Shuang‐Jie Tan Xiang Chen Qiang Zhang Sen Xin Li‐Jun Wan Yu‐Guo Guo 《Angewandte Chemie (International ed. in English)》2020,59(29):12069-12075
Garnet‐type electrolytes suffer from unstable chemistry against air exposure, which generates contaminants on electrolyte surface and accounts for poor interfacial contact with the Li metal. Thermal treatment of the garnet at >700 °C could remove the surface contaminants, yet it regenerates the contaminants in the air, and aggravates the Li dendrite issue as more electron‐conducting defective sites are exposed. In a departure from the removal approach, here we report a new surface chemistry that converts the contaminants into a fluorinated interface at moderate temperature <180 °C. The modified interface shows a high electron tunneling barrier and a low energy barrier for Li+ surface diffusion, so that it enables dendrite‐proof Li plating/stripping at a high critical current density of 1.4 mA cm?2. Moreover, the modified interface exhibits high chemical and electrochemical stability against air exposure, which prevents regeneration of contaminants and keeps high critical current density of 1.1 mA cm?2. The new chemistry presents a practical solution for realization of high‐energy solid‐state Li metal batteries. 相似文献
997.
Ying Liu Ximing Rong Mingze Li Maxim S. Molokeev Jing Zhao Zhiguo Xia 《Angewandte Chemie (International ed. in English)》2020,59(28):11634-11640
The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs2AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5D4→7F6‐3) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+. By controlling Tb3+ ions concentration, the emission colors of Bi‐doped Cs2Ag(In1?xTbx)Cl6 NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications. 相似文献
998.
Mingyue Zhou Yan Chen Manohar Salla Hang Zhang Xun Wang Srinivasa Reddy Mothe Qing Wang 《Angewandte Chemie (International ed. in English)》2020,59(34):14286-14291
Aqueous organic redox flow batteries (AORFBs) have received considerable attention for large‐scale energy storage. Quinone derivatives, such as 9,10‐anthraquinone‐2,7‐disulphonic acid (2,7‐AQDS), have been explored intensively owing to potentially low cost and swift reaction kinetics. However, the low solubility in pH‐neutral electrolytes restricts their application to corrosive acidic or caustic systems. Herein, the single molecule redox‐targeting reactions of 2,7‐AQDS anolyte are presented to circumvent its solubility limit in pH‐neutral electrolytes. Polyimide was employed as a low‐cost high‐capacity solid material to boost the capacity of 2,7‐AQDS electrolyte to 97 Ah L?1. Through in situ FTIR spectroscopy, a hydrogen‐bonding mediated reaction mechanism was disclosed. In conjunction with NaI as catholyte and nickel hexacyanoferrate as the catholyte capacity booster, a single‐molecule redox‐targeting reaction‐based full cell with energy density up to 39 Wh L?1 was demonstrated. 相似文献
999.
Tao Zhang Jingxiang Low Jiaguo Yu Alexei M. Tyryshkin Elika Mikmekov Tewodros Asefa 《Angewandte Chemie (International ed. in English)》2020,59(35):15000-15007
A mesoporous TiO2?x material comprised of small, crystalline, vacancy‐rich anatase nanoparticles (NPs) shows unique optical, thermal, and electronic properties. It is synthesized using polymer‐derived mesoporous carbon (PDMC) as a template. The PDMC pores serve as physical barriers during the condensation and pyrolysis of a titania precursor, preventing the titania NPs from growing beyond 10 nm in size. Unlike most titania nanomaterials, during pyrolysis the NPs undergo no transition from the anatase to rutile phase and they become catalytically active reduced TiO2?x. When exposed to a slow electron beam, the NPs exhibit a charge/discharge behavior, lighting up and fading away for an average period of 15 s for an extended period of time. The NPs also show a 50 nm red‐shift in their UV/Vis absorption and long‐lived charge carriers (electrons and holes) at room temperature in the dark, even long after UV irradiation. The NPs as photocatalysts show a good activity for CO2 reduction. 相似文献
1000.
Ryan P. Jansonius Phil A. Schauer David J. Dvorak Benjamin P. MacLeod David K. Fork Curtis P. Berlinguette 《Angewandte Chemie (International ed. in English)》2020,59(29):12192-12198
Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst. When the electrodes were subjected to mechanically‐applied tensile strain, the amount of hydrogen that absorbed into the palladium decreased, and HER electrocatalytic activity increased. This study showcases how strain can be used to modulate the hydrogen absorption capacity and HER activity of palladium. 相似文献