bluuebunny/crossref_metadata_2025_split huggingface dataset:
Maackiain, a compound derived from Sophora flavescens, increases IL‐1β production by amplifying nigericin‐mediated inflammasome activation
Authors: Huh Jin‐Won , Lee Jung‐Hoon , Jeon Eekhyoung , Ryu Hyung Won , Oh Sei‐Ryang , Ahn Kyung‐Seop , Jun Hyun Sik , Ha Un‐Hwan 
Published: May 2020

Sophora flavescens is used as a traditional herbal medicine to modulate inflammatory responses. However, little is known about the impact of (‐)‐maackiain, a compound derived from S. flavescens, on the activation of inflammasome/caspase‐1, a key factor in interleukin‐1β (IL‐1β) processing. Here, we report that (‐)‐maackiain potently amplified caspase‐1 cleavage in macrophages in response to nigericin (Nig). In macrophages primed with either lipopolysaccharide or monophosphoryl lipid A, Nig‐mediated caspase‐1 cleavage was also markedly promoted by (‐)‐maackiain. Notably, (‐)‐maackiain induced the production of vimentin, an essential mediator for the activation of the NOD‐, LRR‐, and pyrin domain‐containing protein 3 inflammasome, thereby contributing to promotion of the formation of the inflammasome complex to activate caspase‐1. Taken together, our data suggest that (‐)‐maackiain exerts an immunostimulatory effect by promoting IL‐1β production via activation of the inflammasome/caspase‐1 pathway. Thus, the potent inflammasome‐activating effect of (‐)‐maackiain may be clinically useful as an acute immune‐stimulating agent.
Superior design solutions of section sizes in steel buildings for different lateral frame systems and column shapes
Authors: Takagi Jiro , Obana Ruka , Ohsaki Makoto 
Published: May 2020

AbstractSuperior design solutions of 7‐story steel buildings are obtained by the multiple start local search (MSLS) method, minimizing the steel volume for three types of structural systems: a space‐frame system with rectangular hollow structural section (HSS) columns (SFS), perimeter‐frame system (PFS) with I‐shaped columns (PFSH), and a PFS with rectangular HSS columns (PFSB). Most beam‐to‐column connections are moment connections in SFS, whereas they are limited in PFS. In terms of steel volume, PFSH is advantageous for moment‐frame buildings, and SFS and PFSB are suitable for braced frames with uniform column spacings. SFS is disadvantageous for mixed‐, moment‐, and braced‐frame buildings.
Pain Over Two Years After Start of Biologic Versus Conventional Combination Treatment in Early Rheumatoid Arthritis: Results From a Swedish Randomized Controlled Trial
Authors: Olofsson Tor , Wallman Johan K. , Jöud Anna , Schelin Maria E. C. , Ernestam Sofia , van Vollenhoven Ronald , Saevarsdottir Saedis , Lampa Jon 
Published: May 2020

ObjectiveTo compare the pain course between methotrexate (MTX)‐refractory early rheumatoid arthritis (RA) patients randomized to infliximab (IFX) versus sulfasalazine (SSZ) plus hydroxychloroquine (HCQ).MethodsThe randomized, controlled, open‐label Swedish Pharmacotherapy (SWEFOT) trial enrolled new‐onset RA patients from October 2002 to December 2005. After 3 months of receiving MTX, patients not reaching low disease activity (Disease Activity Score in 28 joints score ≤3.2) were randomized to adding IFX (n = 128) or SSZ plus HCQ (n = 130) and followed for 21 months. Here, outcomes included area under the curve (AUC) for visual analog scale (VAS) scores for pain, unacceptable pain (VAS pain score >40 mm [range 0–100]), and unacceptable pain despite inflammation control (refractory pain; VAS pain score >40 plus C‐reactive protein level <10 mg/liter). Between‐group differences were analyzed with multivariate regression models.ResultsOverall, 50% of randomized patients (n = 258) in the crude setting reported unacceptable pain at randomization, declining to 29% at 21 months (P < 0.001), when refractory pain constituted 82% of all unacceptable pain. Comparing randomized arms (intent‐to‐treat analysis), the AUC for VAS pain was lower in the MTX plus IFX group (P = 0.01), and at 21 months, 32% of patients receiving MTX plus IFX and 45% receiving MTX plus SSZ plus HCQ had unacceptable pain (adjusted relative risk 0.68 [95% confidence interval 0.51, 0.90]; P = 0.008). Regarding refractory pain, no between‐group differences were observed.ConclusionDespite active combination treatment, almost one‐third of new‐onset RA patients reported unacceptable pain after 21 months, and refractory pain constituted more than 4/5 of this pain load. Adding IFX versus SSZ plus HCQ to MTX reduced both cumulative pain and unacceptable pain at 21 months, suggesting less long‐term pain for the biologic therapy. These results display insufficient effects of current treatment strategies on inflammation‐independent pain components, warranting alternative approaches in affected patients.
Oxygen Vacancy Modulation of Bimetallic Oxynitride Anodes toward Advanced Li‐Ion Capacitors
Authors: Wang Shouzhi , Li Lili , He Weidong , Shao Yongliang , Li Yanlu , Wu Yongzhong , Hao Xiaopeng 
Published: May 2020

AbstractBinary metal oxides (such as NiCo2O4) are regarded as attractive electrode materials for advanced energy storage devices since they offer more electrochemical activity and higher capacity than monometal oxide. However, the volume expansion and low electronic conductivity are the main bottleneck seriously hindering their application. To overcome these barriers, a novel strategy that introduces a bimetallic oxynitride layer (NiCoON) with oxygen vacancy to the surface of NiCo2O4 nanowires as an anode for Li‐ion capacitors (LICs) is proposed. The oxygen vacancy on the surface and the modulation of multiple valence states are investigated by the electron paramagnetic resonance, X‐ray photoelectron spectroscopy characterization, and first‐principles calculation. Benefiting from the merits of substantially improved electrical conductivity and increased concentration of active sites, the optimized NiCoON electrode delivers remarkable capacity (1855 mAh g−1 at 0.2 A g−1) and rate performance. The LIC device assembled by NiCoON anodes and N‐doped carbon nanowire cathodes delivers excellent rate capability, high energy density (148.5 Wh kg−1), and outstanding power density (30 kW kg−1). This study provides a new pathway for developing bimetallic oxides with an improved performance in electrochemical energy storage, conversion fields, and beyond.
Efficient Blue Perovskite Light‐Emitting Diodes Boosted by 2D/3D Energy Cascade Channels
Authors: Zhang Fengjuan , Cai Bo , Song Jizhong , Han Boning , Zhang Baisong , Zeng Haibo 
Published: May 2020

AbstractLead halide perovskite, as an emerging semiconductor, provides a fire‐new opportunity for high‐definition display and solid‐state lighting. Earthshaking improvements are implemented in green, red, and near‐infrared perovskite light‐emitting diodes (PeLEDs). However, blue PeLEDs are still far behind in performance, which restricts the development of PeLEDs in practical applications. Herein, a facile energy cascade channel strategy via one‐step self‐organized and controllable 2D/3D perovskite preparation by introducing guanidine hydrobromide (GABr) is developed that greatly improves the efficiency of blue PeLEDs. The 2D/3D perovskite structure boosts the energy cascade to induce energy transfer from the wide into the narrow bandgap domains and inhibit free charge diffusion, which increases the density of electrons and holes, and enhances the radiative recombination. Profiting from this energy cascade channels, the external quantum efficiency of blue PeLEDs, emitting at 492 nm, is considerably enhanced from 1.5% of initial blue device to 8.2%. In addition, device operating stability under ambient conditions is also improved by 2.6‐fold. The one‐step self‐organized 2D/3D hybrid perovskites induced by GABr pave a new and simple route toward high‐performance blue emission PeLEDs.
Spin‐Selective Full‐Dimensional Manipulation of Optical Waves with Chiral Mirror
Authors: Li Zhancheng , Liu Wenwei , Cheng Hua , Choi Duk‐Yong , Chen Shuqi , Tian Jianguo 
Published: May 2020

AbstractRealizing arbitrary manipulation of optical waves, which still remains a challenge, plays a key role in the implementation of optical devices with on‐demand functionalities. However, it is hard to independently manipulate multiple dimensions of optical waves because the optical dimensions are basically associated with each other when adjusting the optical response of the devices. Here, the concise design principle of a chiral mirror is utilized to realize the full‐dimensional independent manipulation of circular‐polarized waves. By simply changing three structural variables of the chiral mirror, the proposed design principle can arbitrarily and independently empower the spin‐selective manipulation of amplitude, phase, and operation wavelength of circular‐polarized waves with a large modulation depth. This approach provides a simple solution for the realization of spin‐selective full‐dimensional manipulation of optical waves and shows ample application possibilities in the areas of optical encryption, imaging, and detection.
Concurrently Approaching Volumetric and Specific Capacity Limits of Lithium Battery Cathodes via Conformal Pickering Emulsion Graphene Coatings
Authors: Park Kyu‐Young , Lim Jin‐Myoung , Luu Norman S. , Downing Julia R. , Wallace Shay G. , Chaney Lindsay E. , Yoo Hocheon , Hyun Woo Jin , Kim Hyeong‐U , Hersam Mark C. 
Published: May 2020

AbstractTo achieve the high energy densities demanded by emerging technologies, lithium battery electrodes need to approach the volumetric and specific capacity limits of their electrochemically active constituents, which requires minimization of the inactive components of the electrode. However, a reduction in the percentage of inactive conductive additives limits charge transport within the battery electrode, which results in compromised electrochemical performance. Here, an electrode design that achieves efficient electron and lithium‐ion transport kinetics at exceptionally low conductive additive levels and industrially relevant active material areal loadings is introduced. Using a scalable Pickering emulsion approach, Ni‐rich LiNi0.8Co0.15Al0.05O2 (NCA) cathode powders are conformally coated using only 0.5 wt% of solution‐processed graphene, resulting in an electrical conductivity that is comparable to 5 wt% carbon black. Moreover, the conformal graphene coating mitigates degradation at the cathode surface, thus providing improved electrochemical cycle life. The morphology of the electrodes also facilitates rapid lithium‐ion transport kinetics, which provides superlative rate capability. Overall, this electrode design concurrently approaches theoretical volumetric and specific capacity limits without tradeoffs in cycle life, rate capability, or active material areal loading.
Cycling a Lithium Metal Anode at 90 °C in a Liquid Electrolyte
Authors: Hou Li‐Peng , Zhang Xue‐Qiang , Li Bo‐Quan , Zhang Qiang 
Published: May 2020

AbstractStable operation at elevated temperature is necessary for lithium metal anode. However, Li metal anode generally has poor performance and safety concerns at high temperature (>55 °C) owing to the thermal instability of the electrolyte and solid electrolyte interphase in a routine liquid electrolyte. Herein a Li metal anode working at an elevated temperature (90 °C) is demonstrated in a thermotolerant electrolyte. In a Li|LiFePO4battery working at 90 °C, the anode undergoes 100 cycles compared with 10 cycles in a practical carbonate electrolyte. During the formation of the solid electrolyte interphase, independent and incomplete decomposition of Li salts and solvents aggravate. Some unstable intermediates emerge at 90 °C, degenerating the uniformity of Li deposition. This work not only demonstrates a working Li metal anode at 90 °C, but also provides fundamental understanding of solid electrolyte interphase and Li deposition at elevated temperature for rechargeable batteries.
Reactions between Diazo Compounds and Hypervalent Iodine(III) Reagents
Authors: Zhao Rong , Shi Lei 
Published: May 2020

AbstractSite‐selective “cut and sew” transformations employing diazo compounds and hypervalent iodine(III) compounds involve the departure of leaving groups, a “cut” process, followed by a reorganization of the fragments by bond formation, a “sew” process. Bearing controllable cleavage sites, diazo compounds and hypervalent iodine(III) compounds play a critical role as versatile reagents in a wide range of organic transformations because their excellent nucleofugality allows for a large number of unusual reactions to occur. In recent years, the combination of diazo compounds and hypervalent iodine(III) reagents has emerged as a promising tool for developing new and valuable approaches, and has met considerable success. In this Minireview, this combination is systematically illustrated with recent advances in the field, with the aim of elaborating the synthetic utility and potential of this concept as a powerful strategy in organic synthesis.
A Macrocycle Based on a Heptagon‐Containing Hexa‐peri‐hexabenzocoronene
Authors: Jiménez Vicente G. , David Arthur H. G. , Cuerva Juan M. , Blanco Victor , Campaña Araceli G. 
Published: May 2020

AbstractA cyclophane is reported incorporating two units of a heptagon‐containing extended polycyclic aromatic hydrocarbon (PAH) analogue of the hexa‐peri‐hexabenzocoronene (HBC) moiety (hept‐HBC). This cyclophane represents a new class of macrocyclic structures that incorporate for the first time seven‐membered rings within extended PAH frameworks. The saddle curvature of the hept‐HBC macrocycle units induced by the presence of the nonhexagonal ring along with the flexible alkyl linkers generate a cavity with shape complementarity and appropriate size to enable π interactions with fullerenes. Therefore, the cyclophane forms host–guest complexes with C60 and C70 with estimated binding constants of Ka=420±2 m−1 and Ka=(6.49±0.23)×103 m−1, respectively. As a result, the macrocycle can selectively bind C70 in the presence of an excess of a mixture of C60 and C70.
Beute für das Proteasom: Gezielter Proteinabbau aus medizinalchemischer Perspektive
Authors: Luh Laura M. , Scheib Ulrike , Juenemann Katrin , Wortmann Lars , Brands Michael , Cromm Philipp M. 
Published: May 2020

AbstractDer gezielte Proteinabbau (targeted protein degradation, TPD), die Fähigkeit, das Schicksal eines Proteins durch Auslösen seines Abbaus auf hoch selektive und effiziente Weise kontrollieren zu können, hat in den letzten Jahrzehnten für ein enormes Interesse in der chemischen Biologie und der Wirkstoffentwicklung gesorgt. Führende Konzepte im TPD‐Gebiet sind der niedermolekular‐induzierte Proteinabbau mittels “Molekularer Kleber” (molecular glue) und PROTACs (proteolysis targeting chimeras), die den Weg für die Erweiterung des wirkstofftauglichen (druggable) Strukturraums ebnen und ein neues Paradigma der Wirkstoffentwicklung erschaffen haben. Zudem wurde eine Fülle neuer Techniken entwickelt, um die zellulären Proteinlevel zu modulieren und zu kontrollieren, was ein besseres Verständnis der Proteinfunktionen sowie die Erkennung und Verifizierung neuer therapeutischer Targets ermöglicht. Dieser Artikel bietet einen umfassenden Überblick über chemisch‐biologische Techniken zur Induktion von TPD. Er erläutert die Stärken und Schwächen dieser Methoden im Kontext der Wirkstoffentwicklung und erörtert ihr zukünftiges Potenzial aus der Perspektive eines Medizinalchemikers.
Studying Natural Buckyballs and Buckybowls in Fossil Materials
Authors: Farmani Zahra , Vetere Alessandro , Poidevin Corentin , Auer Alexander A. , Schrader Wolfgang 
Published: May 2020

AbstractBuckyballs (fullerenes) were first reported over 30 years ago, but still little is known regarding their natural occurrence, since they have so far only been found at sites of high‐energy incidents, such as lightning strikes or meteor impacts, but have not been reported in low‐energy materials like fossil fuels. Using ultrahigh‐resolution mass spectrometry, a wide range of fullerenes from C30 to C114 was detected in the asphaltene fraction of a heavy crude oil, together with their building blocks of C10nH10 stoichiometry. High‐level DLPNO‐CCSD(T) calculations corroborate their stability as spherical and hemispherical species. Interestingly, the maximum intensity of the fullerenes was found at C40 instead of the major fullerene C60. Hence, experimental evidence supported by calculations show the existence of not only buckyballs but also buckybowls as 3‐dimensional polyaromatic compounds in fossil materials.
Observation of Transition‐Metal–Boron Triple Bonds in IrB2O− and ReB2O−
Authors: Chen Teng‐Teng , Cheung Ling Fung , Chen Wei‐Jia , Cavanagh Joseph , Wang Lai‐Sheng 
Published: May 2020

AbstractMultiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal dπ→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB2O− [Bi≡B−B≡O]− in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]− fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB2O− and ReB2O− and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB2O− has a closed‐shell bent structure (Cs, 1A′) with BO− coordinated to an Ir≡B unit, (−OB)Ir≡B, whereas ReB2O− is linear (C∞v, 3Σ−) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]−. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems.
Prey for the Proteasome: Targeted Protein Degradation—A Medicinal Chemist's Perspective
Authors: Luh Laura M. , Scheib Ulrike , Juenemann Katrin , Wortmann Lars , Brands Michael , Cromm Philipp M. 
Published: May 2020

AbstractTargeted protein degradation (TPD), the ability to control a proteins fate by triggering its degradation in a highly selective and effective manner, has created tremendous excitement in chemical biology and drug discovery within the past decades. The TPD field is spearheaded by small molecule induced protein degradation with molecular glues and proteolysis targeting chimeras (PROTACs) paving the way to expand the druggable space and to create a new paradigm in drug discovery. However, besides the therapeutic angle of TPD a plethora of novel techniques to modulate and control protein levels have been developed. This enables chemical biologists to better understand protein function and to discover and verify new therapeutic targets. This Review gives a comprehensive overview of chemical biology techniques inducing TPD. It explains the strengths and weaknesses of these methods in the context of drug discovery and discusses their future potential from a medicinal chemist's perspective.
A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers
Authors: Caló Fabio P. , Fürstner Alois 
Published: May 2020

AbstractThe heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α‐diazo‐α‐trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent complex [Rh2((R)‐TPCP)4] (5), it is shown that the protic acetamidate ligand is quintessential for rendering 7 highly enantioselective. The ‐NH group is thought to lock the ensuing metal carbene in place via interligand hydrogen bonding. The resulting stannylated cyclopropanes undergo “stereoretentive” cross coupling, which shows for the first time that even chiral quarternary carbon centers can be made by the Stille–Migita reaction.
Emissive Metallacycle‐Crosslinked Supramolecular Networks with Tunable Crosslinking Densities for Bacterial Imaging and Killing
Authors: Jeyakkumar Ponmani , Liang Yongping , Guo Mengying , Lu Shuai , Xu Donghua , Li Xiaopeng , Guo Baolin , He Gang , Chu Dake , Zhang Mingming 
Published: May 2020

AbstractThe chemical structures and topologies of the crosslinks in supramolecular networks play a crucial role in their properties and functions. Herein, the preparation of a type of poly(N‐isopropylacrylamide) (PNIPAAM)‐based supramolecular networks crosslinked by emissive hexagonal metallacycles is presented. The topological connections in these networks greatly affect their properties, as evidenced by their differences in absorption, emission, lower critical solution temperature, and modulus along with the variation of crosslinking densities. The integration of PNIPAAM and metallacycles in the networks benefits them improved bioavailability, making them serve as reagents for bacterial imaging and killing. This study provides a strategy to prepare cavity‐crosslinked polymer networks for antibacterial applications.
Enantiomeric Discrimination by Surface‐Enhanced Raman Scattering–Chiral Anisotropy of Chiral Nanostructured Gold Films
Authors: Liu Zexi , Ai Jing , Kumar Prashant , You Enming , Zhou Xiong , Liu Xi , Tian Zhongqun , Bouř Petr , Duan Yingying , Han Lu , Kotov Nicholas A. , Ding Songyuan , Che Shunai 
Published: May 2020

AbstractA surface‐enhanced Raman scattering‐chiral anisotropy (SERS‐ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS‐ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs.
Synthesis, reactivity,in vitroboron neutron capture therapy assay, and molecular docking of fluorocyclocarboxyboranylamine
Authors: Zhu Yinghuai , Cai Jianghong , Zheng Chong , Narayan S Hosmane , Masao Takagaki 
Published: May 2020

AbstractThe one‐pot reaction of Me3NBH2CN with Et3O+BF4−followed by addition of BF3·Et2O and water produces a trimethylamine derivative of fluorocyclocarboxyboranylamine, Me3NBH2C(O2BF2NH2) (1) in 36.0% yield. Compound1undergoes exchange reaction between the exo‐Me3N moiety and piperidine or pyridine to produce the corresponding piperidine‐substituted fluorocyclocarboxyboranylamine (2) or pyridine‐substituted fluorocyclocarboxyboranylamine (3) in 51.2% or 42.4% yields, respectively. The new compounds were characterized by1H,13C,11B, and19F nuclear magnetic resonance spectroscopy; Fourier‐transform infrared spectroscopy; and elemental analyses and the crystal structure of1was determined to confirm its molecular geometry. Thein vitrokilling effects of1, along with its toxicity measurements and molecular docking interactions with matrix metalloproteinases showed a potential promise of such species as both boron neutron capture therapy and boron neutron capture synovectomy agents in the treatment of tumors and rheumatoid arthritis, respectively, in the presence of slow neutrons.