bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hybrid Electrolyte with Dual‐Anion‐Aggregated Solvation Sheath for Stabilizing High‐Voltage Lithium‐Metal Batteries
Authors: Wang Xianshu , Wang Shuwei , Wang Huirong , Tu Wenqiang , Zhao Yun , Li Song , Liu Qi , Wu Junru , Fu Yongzhu , Han Cuiping , Kang Feiyu , Li Baohua 
Published: October 2021

AbstractLithium (Li)‐metal batteries (LMBs) with high‐voltage cathodes and limited Li‐metal anodes are crucial to realizing high‐energy storage. However, functional electrolytes that are compatible with both high‐voltage cathodes and Li anodes are required for their developments. In this study, the use of a moderate‐concentration LiPF6 and LiNO3 dual‐salt electrolyte composed of ester and ether co‐solvents (fluoroethylene carbonate/dimethoxyethane, FEC/DME), which forms a unique Li+ solvation with aggregated dual anions, that is, PF6− and NO3−, is proposed to stabilize high‐voltage LMBs. Mechanistic studies reveal that such a solvation sheath improves the Li plating/stripping kinetics and induces the generation of a solid electrolyte interphase (SEI) layer with gradient heterostructure and high Young's modulus on the anode, and a thin and robust cathode electrolyte interface (CEI) film. Therefore, this novel electrolyte enables colossal Li deposits with a high Coulombic efficiency (≈98.9%) for 450 cycles at 0.5 mA cm−2. The as‐assembled LiǁLiNi0.85Co0.10Al0.05O2 full batteries deliver an excellent lifespan and capacity retention at 4.3 V with a rigid negative‐to‐positive capacity ratio. This electrolyte system with a dual‐anion‐aggregated solvation structure provides insights into the interfacial chemistries through solvation regulation for high‐voltage LMBs.
Extracellular Matrix in Synthetic Hydrogel‐Based Prostate Cancer Organoids Regulate Therapeutic Response to EZH2 and DRD2 Inhibitors
Authors: Mosquera Matthew J. , Kim Sungwoong , Bareja Rohan , Fang Zhou , Cai Shuangyi , Pan Heng , Asad Muhammad , Martin Maria Laura , Sigouros Michael , Rowdo Florencia M. , Ackermann Sarah , Capuano Jared , Bernheim Jacob , Cheung Cynthia , Doane Ashley , Brady Nicholas , Singh Richa , Rickman David S. , Prabhu Varun , Allen Joshua E. , Puca Loredana , Coskun Ahmet F. , Rubin Mark A. , Beltran Himisha , Mosquera Juan Miguel , Elemento Olivier , Singh Ankur 
Published: October 2021

AbstractFollowing treatment with androgen receptor (AR) pathway inhibitors, ≈20% of prostate cancer patients progress by shedding their AR‐dependence. These tumors undergo epigenetic reprogramming turning castration‐resistant prostate cancer adenocarcinoma (CRPC‐Adeno) into neuroendocrine prostate cancer (CRPC‐NEPC). No targeted therapies are available for CRPC‐NEPCs, and there are minimal organoid models to discover new therapeutic targets against these aggressive tumors. Here, using a combination of patient tumor proteomics, RNA sequencing, spatial‐omics, and a synthetic hydrogel‐based organoid, putative extracellular matrix (ECM) cues that regulate the phenotypic, transcriptomic, and epigenetic underpinnings of CRPC‐NEPCs are defined. Short‐term culture in tumor‐expressed ECM differentially regulated DNA methylation and mobilized genes in CRPC‐NEPCs. The ECM type distinctly regulates the response to small‐molecule inhibitors of epigenetic targets and Dopamine Receptor D2 (DRD2), the latter being an understudied target in neuroendocrine tumors. In vivo patient‐derived xenograft in immunocompromised mice showed strong anti‐tumor response when treated with a DRD2 inhibitor. Finally, we demonstrate that therapeutic response in CRPC‐NEPCs under drug‐resistant ECM conditions can be overcome by first cellular reprogramming with epigenetic inhibitors, followed by DRD2 treatment. The synthetic organoids suggest the regulatory role of ECM in therapeutic response to targeted therapies in CRPC‐NEPCs and enable the discovery of therapies to overcome resistance.
A Dynamic and Self‐Adapting Interface Coating for Stable Zn‐Metal Anodes
Authors: Guo Zhikun , Fan Lishuang , Zhao Chenyang , Chen Aosai , Liu Nannan , Zhang Yu , Zhang Naiqing 
Published: October 2021

AbstractThe zinc (Zn)‐ion battery has attracted much attention due to its high safety and environmental protection. At present, the critical issues of the generation of dendrites and the accumulation of dead Zn on the surface will lead to a sharp decline of the battery life. Zn dendrites can be inhibited to some extent by constructing an interface protective coating. However, the existing rigid coating method cannot maintain conformal contact with Zn due to the volume change of Zn deposition and will cause fracture irreversibly during the cycle. Here, a highly self‐adaptable poly(dimethylsiloxane) (PDMS)/TiO2−x coating is developed that can dynamically adapt to volume changes and inhibit dendrites growth. PDMS has high dynamic and self‐adaptability due to the crosslinking of the B–O bond. In addition, the rapid and uniform transfer of Zn2+ is induced by the oxygen‐vacancy‐rich TiO2−x. The assembled cells still achieve 99.6% coulombic efficiency after 700 cycles at a current density of 10 mA cm−2. The adaptive interface coating constructed provides a sufficient guarantee for the stable operation of the Zn anode.
Graphene‐Supported Atomically Dispersed Metals as Bifunctional Catalysts for Next‐Generation Batteries Based on Conversion Reactions
Authors: Chen Biao , Zhong Xiongwei , Zhou Guangmin , Zhao Naiqin , Cheng Hui‐Ming 
Published: October 2021

AbstractNext‐generation batteries based on conversion reactions, including aqueous metal–air batteries, nonaqueous alkali metal‐O2 and ‐CO2 batteries, alkali metal‐chalcogen batteries, and alkali metal‐ion batteries have attracted great interest. However, their use is restricted by inefficient reversible conversion of active agents. Developing bifunctional catalysts to accelerate the conversion reaction kinetics in both discharge and charge processes is urgently needed. Graphene‐, or graphene‐like carbon‐supported atomically dispersed metal catalysts (G‐ADMCs) have been demonstrated to show excellent activity in various electrocatalytic reactions, making them promising candidates. Different from G‐ADMCs for catalysis, which only require high activity in one direction, G‐ADMCs for rechargeable batteries should provide high activity in both discharging and charging. This review provides guidance for the design and fabrication of bifunctional G‐ADMCs for next‐generation rechargeable batteries based on conversion reactions. The key challenges that prevent their reversible conversion, the origin of the activity of bifunctional G‐ADMCs, and the current design principles of bifunctional G‐ADMCs for highly reversible conversion, have been analyzed and highlighted for each conversion‐type battery. Finally, a summary and outlook on the development of bifunctional G‐ADMC materials for next‐generation batteries with a high energy density and excellent energy efficiency are given.
Macrocycle‐Based Porous Organic Polymers for Separation, Sensing, and Catalysis
Authors: Li Zheng , Yang Ying‐Wei 
Published: October 2021

AbstractWith the rapid development of materials science, porous organic polymers (POPs) have received remarkable attentions because of their unique properties such as the exceptionally high surface area and flexible molecular design. The ability to incorporate specific functions in a precise manner makes POPs promising platforms for a myriad of applications in molecular adsorption, separation, and catalysis. Therefore, many different types of POPs have been rationally designed and synthesized to expand the scope of advanced materials, endowing them with distinct structures and properties. Recently, supramolecular macrocycles with excellent host–guest complexation abilities are emerging as powerful crosslinkers for developing novel POPs with hierarchical structures and improved performance, which can be well‐organized at different spatial scales. Macrocycle‐based POPs could have unusual porous, adsorptive, and optical properties when compared to their nonmacrocycle‐incorporated counterparts. This cooperation provides valuable insights for the molecular‐level understanding of skeletal complexity and diversity. Here, the research advances of macrocycle‐based POPs are aptly summarized by showing their syntheses, properties, and applications in terms of separation, sensing, and catalysis. Finally, the current challenging issues in this exciting research field are delineated and a comprehensive outlook is offered for their future directions.
High‐Performance Tin–Lead Mixed‐Perovskite Solar Cells with Vertical Compositional Gradient
Authors: Cao Jiupeng , Loi Hok‐Leung , Xu Yang , Guo Xuyun , Wang Naixiang , Liu Chun‐ki , Wang Tianyue , Cheng Haiyang , Zhu Ye , Li Mitch Guijun , Wong Wai‐Yeung , Yan Feng 
Published: October 2021

AbstractSn–Pb mixed perovskites with bandgaps in the range of 1.1–1.4 eV are ideal candidates for single‐junction solar cells to approach the Shockley–Queisser limit. However, the efficiency and stability of Sn–Pb mixed‐perovskite solar cells (PSCs) still lag far behind those of Pb‐based counterparts due to the easy oxidation of Sn2+. Here, a reducing agent 4‐hydrazinobenzoic acid is introduced as an additive along with SnF2 to suppress the oxidation of Sn2+. Meanwhile, a vertical Pb/Sn compositional gradient is formed spontaneously after an antisolvent treatment due to different solubility and crystallization kinetics of Sn‐ and Pb‐based perovskites and it can be finely tuned by controlling the antisolvent temperature. Because the band structure of a perovskite is dependent on its composition, graded vertical heterojunctions are constructed in the perovskite films with a compositional gradient, which can enhance photocarrier separation and suppress carrier recombination in the resultant PSCs. Under optimal fabrication conditions, the Sn–Pb mixed PSCs show power conversion efficiency up to 22% along with excellent stability during light soaking.
High Carrier Mobility and High Figure of Merit in the CuBiSe2 Alloyed GeTe
Authors: Yin Liang‐Cao , Liu Wei‐Di , Li Meng , Sun Qiang , Gao Han , Wang De‐Zhuang , Wu Hao , Wang Yi‐Feng , Shi Xiao‐Lei , Liu Qingfeng , Chen Zhi‐Gang 
Published: October 2021

AbstractAccording to the Mott's relation, the figure‐of‐merit of a thermoelectric material depends on the charge carrier concentration and carrier mobility. This explains the observation that low thermoelectric properties of GeTe‐based materials suffer from the degraded carrier mobility, on account of the fluctuation of electronegativity and ionicity of various elements. Here, high‐performance CuBiSe2 alloyed GeTe with high carrier mobility due to the small electronegativity difference between Cu and Ge atoms and the weak ionicity of CuTe and BiTe bonds, is developed. Density functional theory calculations indicate that CuBiSe2 alloying increases the formation energy of Ge vacancies and correspondingly reduces the amount of Ge vacancies, leading to an optimized carrier concentration and a high power factor of ≈37.4 µW cm−1 K−2 at 723 K. Moreover, CuBiSe2 alloying induces dense point defects and triggers ubiquitous lattice distortions, leading to a reduced lattice thermal conductivity of 0.39 W m−1 K−1 at 723 K. These synergistic effects result in an optimization of the carrier mobility, the carrier concentration, and the lattice thermal conductivity, which favors an enhanced peak figure‐of‐merit of ≈2.2 at 723 K in (GeTe)0.94(CuBiSe2)0.06. This study provides guidance for the screening of GeTe‐based thermoelectric materials with high carrier mobility.
4‐Hydroxycoumarin: A Versatile Substrate for Transition‐metal‐free Multicomponent Synthesis of Bioactive Heterocycles
Authors: Borah Biplob , Dhar Dwivedi Kartikey , Chowhan L. Raju 
Published: October 2021

AbstractOne‐pot multi‐component reactions especially under transition‐metal‐free catalysis served as an efficient, and environmentally friendly method for the construction of value‐added compounds. Their importance in organic synthesis has drastically increased due to their operational simplicity, cost‐effectiveness, step‐ and pot‐economic nature. On the other hand, the molecular hybridization concept has recently emerged as a key fascinating area in medicinal and organic chemistry for the design of new drugs. Owing to the widespread occurrence in natural products, and pharmaceutical agents, the incorporation of another heterocycle either as substituents or as a fused material into 4‐hydroxycoumarin moiety offers new opportunities for the broad application of the targeted coumarin‐heterocycles into many branches of chemistry. Considering the importance of both the topics, here we have reviewed the developments achieved in the synthesis of diverse medicinally privileged oxygen, and nitrogen‐containing heterocycles as well as spiro‐heterocycles either linked or fused with coumarin moiety by using readily accessible 4‐hydroxycoumarin as the starting material via one‐pot multi‐component reaction under transition‐metal‐free conditions.
Moderate Surface Segregation Promotes Selective Ethanol Production in CO2Hydrogenation Reaction over CoCu Catalysts
Authors: Liu Sihang , Yang Chengsheng , Zha Shenjun , Sharapa Dmitry , Studt Felix , Zhao Zhi‐Jian , Gong Jinlong 
Published: October 2021

AbstractCobalt‐copper (CoCu) catalysts have industrial potential in CO/CO2hydrogenation reactions, and CoCu alloy has been elucidated as a major active phase during reactions. However, due to elemental surface segregation and dealloying phenomena, the actual surface morphology of CoCu alloy is still unclear. Combining theory and experiment, the dual effect of surface segregation and varied CO coverage over the CoCu(111) surface on the reactivity in CO2hydrogenation reactions is explored. The relationship between C−O bond scission and further hydrogenation of intermediate *CH2O was discovered to be a key step to promote ethanol production. The theoretical investigation suggests that moderate Co segregation provides a suitable surface Co ensemble with lateral interactions of co‐adsorbed *CO, leading to promoted selectivity to ethanol, in agreement with theory‐inspired experiments.
Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration
Authors: Mi Ruijie , Chen Haohua , Zhou Xukai , Li Nan , Ji Danqing , Wang Fen , Lan Yu , Li Xingwei 
Published: October 2021

AbstractAxially chiral open‐chain olefins represent an underexplored class of chiral platform. In this report, two classes of tetrasubstituted axially chiral acyclic olefins have been accessed in excellent enantioselectivity and regioselectivity via C−H activation of (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The coupling of indoles bearing an N‐aminocarbonyl directing group afforded C–N axially chiral acrylamides with the assistance of a racemic zinc carboxylate additive. DFT studies suggest a β‐nitrogen elimination–reinsertion pathway for the directing group migration. Meanwhile, the employment of N‐phenoxycarboxamide delivered C−C axially chiral enamides via migration of the oxidizing directing group. Experiments suggest that in both cases the (hetero)arene substrate adopts a well‐defined orientation during the C−H activation, which in turn determines the disposition of the alkyne in migratory insertion. Synthetic applications of representative chiral olefins are demonstrated.
Enhancing Dye‐Triplet‐Sensitized Upconversion Emission Through the Heavy‐Atom Effect in CsLu2F7:Yb/Er Nanoprobes
Authors: Zhang Peng , Ke Jianxi , Tu Datao , Li Jiayao , Pei Yifan , Wang Le , Shang Xiaoying , Guan Tianyong , Lu Shan , Chen Zhuo , Chen Xueyuan 
Published: October 2021

AbstractLanthanide (Ln3+)‐doped upconversion (UC) nanoprobes, which have drawn extensive attention for various bioapplications, usually suffer from small absorption cross‐sections and weak luminescence intensity of Ln3+ ions. Herein, we report the controlled synthesis of a new class of Ln3+‐doped UC nanoprobes based on CsLu2F7:Yb/Er nanocrystals (NCs), which can effectively increase the intersystem crossing (ISC) efficiency from singlet excited state to triplet excited state of IR808 up to 99.3 % through the heavy atom effect. By virtue of the efficient triplet sensitization of IR808, the optimal UC luminescence (UCL) intensity of IR808‐modified CsLu2F7:Yb/Er NCs is enhanced by 1309 times upon excitation at 808 nm. Benefiting from the intense dye‐triplet‐sensitized UCL, the nanoprobes are demonstrated for sensitive assay of extracellular and intracellular hypochlorite with an 808‐nm/980‐nm dual excited ratiometric strategy.
A Modular Approach to the Antifungal Sphingofungin Family: Concise Total Synthesis of Sphingofungin A and C
Authors: Raguž Luka , Peng Chia‐Chi , Kaiser Marcel , Görls Helmar , Beemelmanns Christine 
Published: October 2021

AbstractSphingofungins are fungal natural products known to inhibit the biosynthesis of sphingolipids which play pivotal roles in various cell functions. Here, we report a short and flexible synthetic approach towards the sphingofungin family. Key step of the synthesis was a decarboxylative cross‐coupling reaction of chiral sulfinyl imines with a functionalized tartaric acid derivative, which yielded the core motif of sphingofungins carrying four consecutive stereocenters and a terminal double bond. Subsequent metathesis reaction allowed for the introduction of different side chains of choice resulting in a total of eight sphingofungins, including for the first time sphingofungin C (eight steps from commercially available protected tartaric acid with an overall yield of 6 %) and sphingofungin A (ten steps). All newly synthesized derivatives were tested for their antifungal, cell‐proliferative and antiparasitic activity unraveling their structure–activity relations.
Labile Photo‐Induced Free Radical in α‐Ketoglutaric Acid: a Universal Endogenous Polarizing Agent for In Vivo Hyperpolarized 13C Magnetic Resonance
Authors: Gaunt Adam P. , Lewis Jennifer S. , Hesse Friederike , Cheng Tian , Marco‐Rius Irene , Brindle Kevin M. , Comment Arnaud 
Published: October 2021

AbstractHyperpolarized (HP) 13C magnetic resonance enables non‐invasive probing of metabolism in vivo. To date, only 13C‐molecules hyperpolarized with persistent trityl radicals have been injected in humans. We show here that the free radical photo‐induced in alpha‐ketoglutaric acid (α‐KG) can be used to hyperpolarize photo‐inactive 13C‐molecules such as [1‐13C]lactate. α‐KG is an endogenous molecule with an exceptionally high radical yield under photo‐irradiation, up to 50 %, and its breakdown product, succinic acid, is also endogenous. This radical precursor therefore exhibits an excellent safety profile for translation to human studies. The labile nature of the radical means that no filtration is required prior to injection while also offering the opportunity to extend the 13C relaxation time in frozen HP 13C‐molecules for storage and transport. The potential for in vivo metabolic studies is demonstrated in the rat liver following the injection of a physiological dose of HP [1‐13C]lactate.
Rationally Designed Mn2O3–ZnMn2O4 Hollow Heterostructures from Metal–Organic Frameworks for Stable Zn‐Ion Storage
Authors: Zeng Yinxiang , Wang Yan , Jin Qi , Pei Zhihao , Luan Deyan , Zhang Xitian , Lou Xiong Wen (David) 
Published: October 2021

AbstractMn‐based oxides have sparked extensive scientific interest for aqueous Zn‐ion batteries due to the rich abundance, plentiful oxidation states, and high output voltage. However, the further development of Mn‐based oxides is severely hindered by the rapid capacity decay during cycling. Herein, a two‐step metal–organic framework (MOF)‐engaged templating strategy has been developed to rationally synthesize heterostructured Mn2O3–ZnMn2O4 hollow octahedrons (MO–ZMO HOs) for stable zinc ion storage. The distinctive composition and hollow heterostructure endow MO–ZMO HOs with abundant active sites, enhanced electric conductivity, and superior structural stability. By virtue of these advantages, the MO–ZMO HOs electrode shows high reversible capacity, impressive rate performance, and outstanding electrochemical stability. Furthermore, ex situ characterizations reveal that the charge storage of MO–ZMO HOs mainly originates from the highly reversible Zn2+ insertion/extraction reactions.
A Dual‐Targeting Circular Aptamer Strategy Enables the Recognition of Different Leukemia Cells with Enhanced Binding Ability
Authors: Ai Lili , Peng Tianhuan , Li Yingying , Kuai Hailan , Sima Yingyu , Su Minhui , Wang Dan , Yang Qiuxia , Wang Xue‐Qiang , Tan Weihong 
Published: October 2021

AbstractCurrently, the broad use of monovalent aptamers in oncology faces challenges, including insufficient recognition and internalization caused by a finite number of receptors on the cell surface, as well as a confined recognition spectrum. Herein, we describe the development of a dual‐targeting circular aptamer (DTCA) that can recognize two different biomarkers on living cells to augment aptamer–receptor interactions, thus enhancing recognition of the target cells. This improvement not only boosts binding and internalization abilities, but also expands the recognition spectrum of these aptamers to different leukemia cells. Moreover, the stability of DTCA in serum can be significantly improved by an enzyme‐promoted terminal ligation strategy. The chemical incorporation of 5‐fluorodeoxyuridine into DTCA resulted in a pharmaceutically functional aptamer that exhibited excellent selectivity, as demonstrated by its high cytotoxicity against target cancer cells, but not to normal cells. The superiority of our newly developed strategy was further highlighted by its precise tumor‐imaging capability.
Macrocycle Dynamics in a Branched [8]Catenane Controlled by Three Different Stimuli in Three Different Regions
Authors: Ng Antony Wing Hung , Lai Samuel Kin‐Man , Yee Chi‐Chung , Au‐Yeung Ho Yu 
Published: October 2021

AbstractA branched [8]catenane from an efficient one‐pot synthesis (72 % HPLC yield, 59 % isolated yield) featuring the simultaneous use of three kinds of templates and cucurbit[6]uril‐mediated azide–alkyne cycloaddition (CBAAC) for ring‐closing is reported. Design and assembly of the [8]catenane precursors are unexpectedly complex that can involve cooperating, competing and non‐influencing interactions. Due to the branched structure, dynamics of the [8]catenane can be modulated in different extent by rigidifying/loosening the mechanical bonds at different regions by using solvent polarity, acid‐base and metal ions as the stimuli. This work not only highlights the importance of understanding the delicate interplay of the weak and non‐obvious supramolecular interactions in the synthesis of high‐order [n]catenane, but also demonstrates a complex control of dynamics and flexibility for exploiting [n]catenanes applications.
Chiroptical Switching and Quantitative Chirality Sensing with (Pseudo)halogenated Quinones
Authors: Formen Jeffrey S. S. K. , Wolf Christian 
Published: October 2021

Abstract(Pseudo)halogenated quinones react smoothly with chiral amines, amino alcohols, and amino acids toward push–pull conjugates with optical sensing and switching applications. The chiroptically active conjugates serve as redox switches between two reversibly interconverting states with remarkably different UV and CD signatures. Addition of sodium borohydride generates a hydroquinone derivative that is quantitatively re‐oxidized to the original quinone upon exposure to air. This chiroptical quinone/hydroquinone redox switch system combines several attractive features such as simple set‐up, use of inexpensive chemicals, short response time, and thermal and photochemical stability. A conceptually new sensing approach that is based on integrated chiroptical amplification and redox switching enables on‐the‐fly deconvolution of otherwise overlapping CD spectra and is used for quantitative er analysis of challenging samples containing constitutional isomers in varying enantiomeric compositions.