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  1. Abstract

    Paired redox‐neutral electrolysis offers an attractive green platform for organic synthesis by avoiding sacrificial oxidants and reductants. Carboxylates are non‐toxic, stable, inexpensive, and widely available, making them ideal nucleophiles for C−C cross‐coupling reactions. Here, we report the electro/Ni dual‐catalyzed redox‐neutral decarboxylative C(sp3)−C(sp2) cross‐coupling reactions of pristine carboxylates with aryl bromides. At a cathode, a NiII(Ar)(Br) intermediate is formed through the activation of Ar−Br bond by a NiI‐bipyridine catalyst and subsequent reduction. At an anode, the carboxylates, including amino acid, benzyl carboxylic acid, and 2‐phenoxy propionic acid, undergo oxidative decarboxylation to form carbon‐based free radicals. The combination of NiII(Ar)(Br) intermediate and carbon radical results in the formation of C(sp3)−C(sp2) cross‐coupling products. The adaptation of this electrosynthesis method to flow synthesis and valuable molecule synthesis was demonstrated. The reaction mechanism was systematically studied through electrochemical voltammetry and density functional theory (DFT) computational studies. The relationships between the electrochemical properties of carboxylates and the reaction selectivity were revealed. The electro/Ni dual‐catalyzed cross‐coupling reactions described herein expand the chemical space of paired electrochemical C(sp3)−C(sp2) cross‐coupling and represent a promising method for the construction of the C(sp3)−C(sp2) bonds because of the ubiquitous carboxylate nucleophiles and the innate scalability and flexibility of electrochemical flow‐synthesis technology.

     
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  2. Tran, Duc ; Thai, My ; Krishnamachari, Bhaskar (Ed.)
    The security and performance of blockchain systems such as Bitcoin critically rely on the P2P network. This paper aims to investigate blockchain P2P networks. We explore the topologies, peer discovery, and data forwarding and examine the security and performance of the P2P network. Further, we formulate an optimization problem to study the theoretical limit of the performance and provide a solution to achieve optimal performance in a blockchain P2P network. 
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  3. Murphy, Beth (Ed.)
    This article briefly describes the design of the five Quander games and the game world in which the games are situated. It described the rational for the game design and includes brief descriptions of all 5 games and the reward system. 
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  4. Water soluble ferrocene (Fc) derivatives are promising cathode materials for aqueous organic redox flow batteries (AORFBs) towards scalable energy storage. However, their structure–performance relationship and degradation mechanism in aqueous electrolytes remain unclear. Herein, physicochemical and electrochemical properties, battery performance, and degradation mechanisms of three Fc catholytes, (ferrocenylmethyl)trimethylammonium chloride (C1-FcNCl), (2-ferrocenyl-ethyl)trimethylammonium chloride (C2-FcNCl), and (3-ferrocenyl-propyl)trimethylammonium chloride (C3-FcNCl) in pH neutral aqueous electrolytes were systemically investigated. UV-Vis and gas chromatography (GC) studies confirmed the thermal and photolytic C x -Cp − ligand dissociation decomposition pathways of both discharged and charged states of C1-FcNCl and C2-FcNCl catholytes. In contrast, in the case of the C3-FcNCl catholyte, the electron-donating 3-(trimethylammonium)propyl group strengthens the coordination between the C 3 -Cp − ligand and the Fe 3+ or Fe 2+ center and thus mitigates the ligand-dissociation degradation. Consistently, the Fc electrolytes displayed cycling stability in both half-cell and full-cell flow batteries in the order of C1-FcNCl < C2-FcNCl < C3-FcNCl. 
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  5. Abstract

    Ferrocyanide, such as K4[Fe(CN)6], is one of the most popular cathode electrolyte (catholyte) materials in redox flow batteries. However, its chemical stability in alkaline redox flow batteries is debated. Mechanistic understandings at the molecular level are necessary to elucidate the cycling stability of K4[Fe(CN)6] and its oxidized state (K3[Fe(CN)6]) based electrolytes and guide their proper use in flow batteries for energy storage. Herein, a suite of battery tests and spectroscopic studies are presented to understand the chemical stability of K4[Fe(CN)6] and its charged state, K3[Fe(CN)6], at a variety of conditions. In a strong alkaline solution (pH 14), it is found that the balanced K4[Fe(CN)6]/K3[Fe(CN)6] half‐cell experiences a fast capacity decay under dark conditions. The studies reveal that the chemical reduction of K3[Fe(CN)6] by a graphite electrode leads to the charge imbalance in the half‐cell cycling and is the major cause of the observed capacity decay. In addition, at pH 14, K3[Fe(CN)6] undergoes a slow CN/OHexchange reaction. The dissociated CNligand can chemically reduce K3[Fe(CN)6] to K4[Fe(CN)6] and it is converted to cyanate (OCN) and further, decomposes into CO32‐and NH3. Ultimately, the irreversible chemical conversion of CNto OCNleads to the irreversible decomposition of K4/K3[Fe(CN)6] at pH 14.

     
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  6. Context. The role of large-scale magnetic fields in the evolution of star-forming regions remains elusive. Its investigation requires the observational characterization of well-constrained molecular clouds. The Monoceros OB 1 molecular cloud is a large complex containing several structures that have been shown to be engaged in an active interaction and to have a rich star formation history. However, the magnetic fields in this region have only been studied on small scales. Aims. We study the large-scale magnetic field structure and its interplay with the gas dynamics in the Monoceros OB 1 east molecular cloud. Methods. We combined observations of dust polarized emission from the Planck telescope and CO molecular line emission observations from the Taeduk Radio Astronomy Observatory 14-metre telescope. We calculated the strength of the plane-of-sky magnetic field using a modified Chandrasekhar-Fermi method and estimated the mass-over-flux ratios in different regions of the cloud. We used the comparison of the velocity and intensity gradients of the molecular line observations with the polarimetric observations to trace dynamically active regions. Results. The molecular complex shows an ordered large-scale plane-of-sky magnetic field structure. In the northern part, it is mostly orientated along the filamentary structures, while the southern part shows at least two regions with distinct magnetic field orientations. Our analysis reveals a shock region in the northern part right between two filamentary clouds that, in previous studies, were suggested to be involved in a collision. The magnetic properties of the north-main and north-eastern filaments suggest that these filaments once formed a single one, and that the magnetic field evolved together with the material and did not undergo major changes during the evolution of the cloud. In the southern part, we find that either the magnetic field guides the accretion of interstellar matter towards the cloud or it is dragged by the matter falling towards the main cloud. Conclusions. The large-scale magnetic field in the Monoceros OB 1 east molecular cloud is tightly connected to the global structure of the complex. In the northern part, it seems to serve a dynamically important role by possibly providing support against gravity in the direction perpendicular to the field and to the filament. In the southern part, it is probably the most influential factor governing the morphological structure by guiding possible gas inflow. A study of the whole Monoceros OB 1 molecular complex at large scales is necessary to form a global picture of the formation and evolution of the Monoceros OB 1 east cloud and the role of the magnetic field in this process. 
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  7. Aqueous redox flow batteries could provide viable grid-scale electrochemical energy storage for renewable energy because of their high-power performance, scalability, and safe operation ( 1 , 2 ). Redox-active organic molecules serve as the energy storage materials ( 2 , 3 ), but only very few organic molecules, such as viologen ( 4 , 5 ) and anthraquinone molecules ( 6 ), have demonstrated promising energy storage performance ( 2 ). Efforts continue to develop other families of organic molecules for flow battery applications that would have dense charge capacities and be chemically robust. On page 836 of this issue, Feng et al. ( 7 ) report a class of ingeniously designed 9-fluorenone (FL) molecules as high-performance, potentially low-cost organic anode electrolytes (anolytes) in aqueous organic redox flow batteries (see the figure, top). These FL anolytes not only display exceptional energy storage performance but also exhibit an unprecedented two-electron storage mechanism. 
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