bluuebunny/crossref_metadata_2025_split huggingface dataset:
Copper‐Catalyzed Asymmetric 1,6‐Addition of Borylalkene‐Derived Nucleophiles to para‐Quinone Methides
Authors: Meng Deyuan , He Jing , Yoon Woojin , Yun Hoseop , Han Jung Tae , Yun Jaesook 
Published: November 2022

AbstractHerein, we report the catalytic 1,6‐addition of chiral alkyl copper nucleophiles, in‐situ generated from borylalkenes and a copper‐hydride catalyst under mild conditions. Chemo‐ and stereoselective control was crucial in this reductive coupling process of borylalkenes and para‐quinone methides, sequentially forming adjacent stereogenic centers with good diastereo‐ and enantioselectivity. Through the multicomponent and catalytic tandem reactions, asymmetric 1,6‐adducts of p‐quinone methides were efficiently synthesized.magnified image
Bias‐Free Solar‐Driven Syngas Production: A Fe2O3Photoanode Featuring Single‐Atom Cobalt Integrated with a Silver‐Palladium Cathode
Authors: Zhao Bin , Huang Xiaojuan , Ding Yong , Bi Yingpu 
Published: November 2022

AbstractPhotoelectrochemical syngas production from aqueous CO2is a promising technique for carbon capture and utilization. Herein, we demonstrate the efficient and tunable syngas production by integrating a single‐atom cobalt‐catalyst‐decorated α‐Fe2O3photoanode with a bimetallic Ag/Pd alloy cathode. A record syngas production activity of 81.9 μmol cm−2 h−1(CO/H2ratio: ≈1 : 1) was achieved under artificial sunlight (AM 1.5 G) with an excellent durability. Systematic studies reveal that the Co single atoms effectively extract the holes from Fe2O3photoanodes and serve as active sites for promoting oxygen evolution. Simultaneously, the Pd and Ag atoms in bimetallic cathodes selectively adsorb CO2and protons for facilitating CO production. Further incorporation with a photovoltaic, to allow solar light (>600 nm) to be utilized, yields a bias‐free CO2reduction device with solar‐to‐CO and solar‐to‐H2conversion efficiencies up to 1.33 and 1.36 %, respectively.
A Far‐Red Molecular Rotor Fluorogenic Trehalose Probe for Live Mycobacteria Detection and Drug‐Susceptibility Testing
Authors: Banahene Nicholas , Gepford Dana M. , Biegas Kyle J. , Swanson Daniel H. , Hsu Yen‐Pang , Murphy Brennan A. , Taylor Zachary E. , Lepori Irene , Siegrist M. Sloan , Obregón‐Henao Andrés , Van Nieuwenhze Michael S. , Swarts Benjamin M. 
Published: November 2022

AbstractIncreasing the speed, specificity, sensitivity, and accessibility of mycobacteria detection tools are important challenges for tuberculosis (TB) research and diagnosis. In this regard, previously reported fluorogenic trehalose analogues have shown potential, but their green‐emitting dyes may limit sensitivity and applications in complex settings. Here, we describe a trehalose‐based fluorogenic probe featuring a molecular rotor turn‐on fluorophore with bright far‐red emission (RMR‐Tre). RMR‐Tre, which exploits the unique biosynthetic enzymes and environment of the mycobacterial outer membrane to achieve fluorescence activation, enables fast, no‐wash, low‐background fluorescence detection of live mycobacteria. Aided by the red‐shifted molecular rotor fluorophore, RMR‐Tre exhibited up to a 100‐fold enhancement in M. tuberculosis labeling compared to existing fluorogenic trehalose probes. We show that RMR‐Tre reports on M. tuberculosis drug resistance in a facile assay, demonstrating its potential as a TB diagnostic tool.
Ordered Macro/Microporous Ionic Organic Framework for Efficient Separation of Toxic Pollutants from Water
Authors: Fajal Sahel , Hassan Atikur , Mandal Writakshi , Shirolkar Mandar M. , Let Sumanta , Das Neeladri , Ghosh Sujit K. 
Published: November 2022

AbstractIn case of pollutant segregation, fast mass diffusion is a fundamental criterion in order to achieve improved performance. The rapid mass transport through porous materials can be achieved by availing large open pores followed by easy and complete accessibility of functional sites. Inducing macroporosity into such materials could serve as ideal solution providing access to large macropores that offer unhindered transport of analyte and full exposure to interactive sites. Moreover, the challenge to configure the ionic‐functionality with macroporosity could emerge as an unparalleled avenue toward pollutants separation. Herein, we strategized a synthetic protocol for construction of a positively charged hierarchically‐porous ordered interconnected macro‐structure of organic framework where the size and number of macropores can easily be tuned. The ordered macropores with strong electrostatic interaction synergistically exhibited ultrafast removal efficiency towards various toxic pollutants.
Excitation‐Dependent Multicolour Luminescence of Organic Materials: Internal Mechanism and Potential Applications
Authors: Shen Yunxia , An Zhongfu , Liu Haichao , Yang Bing , Zhang Yujian 
Published: November 2022

AbstractExcitation‐dependent emission (Ex‐de) materials have been of considerable academic interest and have potential applications in real life. Such multicolour luminescence is a characteristic exception to the ubiquitously accepted Kasha's rule. This phenomenon has been increasingly presented in some studies on different luminescence systems; however, a systematic overview of the mechanisms underlying this phenomenon is currently absent. Herein, we resolve this issue by classifying multicolour luminescence from single chromophores and dual/ternary chromophores, as well as multiple emitting species. The underlying processes are described based on electronic and/or geometrical conditions under which the phenomenon occurs. Before we present it in categories, related photophysical and photochemical foundations are introduced. This systematic overview will provide a clear approach to designing multicolour luminescence materials for special applications.
Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers
Authors: McMullen Jacob S. , Huo Ryan , Vasko Petra , Edwards Alison J. , Hicks Jamie 
Published: November 2022

AbstractThe synthesis, characterisation and reactivity of two isostructural anionic magnesium and calcium complexes is reported. By X‐ray and neutron diffraction techniques, the anionic hydrides are shown to exist as dimers, held together by a range of interactions between the two anions and two bridging potassium cations. Unlike the vast proportion of previously reported dimeric group 2 hydrides, which have hydrides that bridge two group 2 centres, here the hydrides are shown to be “terminal”, but stabilised by interactions with the potassium cations. Both anionic hydrides were found to insert and couple CO under mild reaction conditions to give the corresponding group 2 cis‐ethenediolate complexes. These cis‐ethenediolate complexes were found to undergo salt elimination reactions with silyl chlorides, allowing access to small unsaturated disilyl ethers with a high percentage of their mass originating from the C1 source CO.
Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials
Authors: Thaggard Grace C. , Leith Gabrielle A. , Sosnin Daniil , Martin Corey R. , Park Kyoung Chul , McBride Margaret K. , Lim Jaewoong , Yarbrough Brandon J. , Maldeni Kankanamalage Buddhima K. P. , Wilson Gina R. , Hill Austin R. , Smith Mark D. , Garashchuk Sophya , Greytak Andrew B. , Aprahamian Ivan , Shustova Natalia B. 
Published: November 2022

AbstractConfinement‐imposed photophysics was probed for novel stimuli‐responsive hydrazone‐based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution‐like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady‐state and time‐resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone‐based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.
Highly Efficient Production of Nanoporous Block Copolymers with Arbitrary Structural Characteristics for Advanced Membranes
Authors: Guo Leiming , Ntetsikas Konstantinos , Zapsas Georgios , Thankamony Roshni , Lai Zhiping , Hadjichristidis Nikos 
Published: November 2022

AbstractThe great significance of boosting the design of percolating nanopore structures in block copolymers (BCPs) for various cases has been widely demonstrated in the past several decades. However, it still remains challenging to prepare the desired porous structures in a rapid, facile, and universal manner. Here we have developed an unconventional and benchtop strategy to rapidly generate the nanoporous polystyrene‐based BCPs with arbitrary structural characteristics regardless of the BCP bulk morphology. This universal pore‐forming strategy enables the sustainable CO2‐based BCPs to form advanced membranes after 1 s soaking for efficiently rejecting 94.2 % brilliant blue R (826 g mol−1). Meanwhile, the water permeance retains around 1020 L (m2 h bar)−1, which is 1–3 orders of magnitude higher than that of other membranes. This strategy may offer an excellent opportunity to introduce percolating pore structures in those newly developed BCPs with which the previously reported pore‐forming methods may not deal.
Phosphoric Acid‐Catalyzed Enantioselective Synthesis of Axially Chiral Anthrone‐based Compounds
Authors: He Shi‐Jiang , Zhu Shuai , Qiu Sheng‐Qi , Ding Wei‐Yi , Cheng Jun Kee , Xiang Shao‐Hua , Tan Bin 
Published: November 2022

AbstractAnthrones and analogues are structural cores shared by diverse pharmacologically active natural and synthetic compounds. The sp2‐rich nature imposes inherent obstruction to introduce stereogenic element onto the tricyclic aromatic backbone. In our pursuit to expand the chemical space of axial chirality, a novel type of axially chiral anthrone‐derived skeleton was discovered. This work establishes oxime ether as suitable functionality to furnish axial chirality on symmetric anthrone skeletons through stereoselective condensation of the carbonyl entity with long‐range chirality control. The enantioenriched anthrones could be elaborated into dibenzo‐fused seven‐membered N‐heterocycles containing well‐defined stereogenic center via Beckmann rearrangement with axial‐to‐point chirality conversion.
Proton‐Reservoir Hydrogel Electrolyte for Long‐Term Cycling Zn/PANI Batteries in Wide Temperature Range
Authors: Feng Doudou , Jiao Yucong , Wu Peiyi 
Published: November 2022

AbstractAdvanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO4)2 was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm−2, and the Zn/PANI battery can provide ultra‐high stable specific capacity of 79.6 mAh g−1 for more than 70 000 cycles at 15 A g−1. This can be mainly ascribed to the −SO3−H+ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton‐supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.
Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion
Authors: Díaz‐Jiménez Àlex , Monreal‐Corona Roger , Poater Albert , Álvarez María , Borrego Elena , Pérez Pedro J. , Caballero Ana , Roglans Anna , Pla‐Quintana Anna 
Published: November 2022

AbstractThe trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp3)−H bond has been achieved for the first time during a silver‐catalyzed carbene/alkyne metathesis (CAM) process. A Tpx‐containing silver complex first promotes the generation of a donor‐acceptor silver carbene which triggers CAM, generating a subsequent donor‐donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp3)−H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C−H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step.
α‐Synuclein as a Target for Metallo‐Anti‐Neurodegenerative Agents
Authors: Cao Kaiming , Zhu Yang , Hou Zhuanghao , Liu Manman , Yang Yanyan , Hu Hongze , Dai Yi , Wang Yu , Yuan Siming , Huang Guangming , Mei Jiaming , Sadler Peter J. , Liu Yangzhong 
Published: November 2022

AbstractThe unique thermodynamic and kinetic coordination chemistry of ruthenium allows it to modulate key adverse aggregation and membrane interactions of α‐synuclein (α‐syn) associated with Parkinson's disease. We show that the low‐toxic RuIII complex trans‐[ImH][RuCl4(Me2SO)(Im)] (NAMI‐A) has dual inhibitory effects on both aggregation and membrane interactions of α‐syn with submicromolar affinity, and disassembles pre‐formed fibrils. NAMI‐A abolishes the cytotoxicity of α‐syn towards neuronal cells and mitigates neurodegeneration and motor impairments in a rat model of Parkinson's. Multinuclear NMR and MS analyses show that NAMI‐A binds to residues involved in protein aggregation and membrane binding. NMR studies reveal the key steps in pro‐drug activation and the effect of activated NAMI‐A species on protein folding. Our findings provide a new basis for designing ruthenium complexes which could mitigate α‐syn‐induced Parkinson's pathology differently from organic agents.
Nitrenoid from Oxime: A Practical Synthesis of Planar Chiral Ferrocenyl Phenanthridines via Nitrene‐Involved Ring‐Expansion Reaction
Authors: Li Na , Hong Biqiong , Zhao Jinbo , Gu Zhenhua 
Published: November 2022

AbstractNitrenes and nitrenoids are highly reactive species and the proposed key intermediates in nitrogen‐containing heterocyclic compound synthesis. In this work, we developed a practical method for the synthesis of phenanthridines by the reaction of oximes and Grignard reagents (with or without diethylzinc) via ring‐expansion of magnesium coordinated nitrenoid complex as the key step. The method has been used to synthesize optically active planar chiral ferrocenyl phenanthridines.
Palmitoylated cellulose nanocrystal/polycarbonate composite with high mechanical performance and good transparency
Authors: Xie Zhongyuan , Wang Xingjuan , Chen Zhangyun , Jiang Hua 
Published: November 2022

AbstractTo fabricate polycarbonate (PC) composites with high mechanical and optical properties, PC composite films reinforced by cellulose nanocrystals esterified using palmitoyl chloride (palmitoylated cellulose nanocrystal [PAL‐CNCs]) were fabricated by casting‐evaporation and characterized by several techniques. It was shown that the PAL‐CNCs with a substitution degree of 0.43 and the crystalline index of 53.3% were better dispersed in chloroform and tetrahydrofuran, and achieved a water contact angle of 81.0°. The crystallite size and crystalline index of the PC in the composite film significantly increased to more than 5.2 nm and 51.5%, respectively, after the incorporation of the PAL‐CNCs. The PC composite film had an increase of 91.4% in tensile strength, 84.1% in Young's modulus, and a decrease of 5% in impact strength. Meanwhile, its UV–Vis‐light transmittance was above 90%. Therefore, the palmitoylated ‐CNCs were a better candidate for engineering PC composites with high mechanical performance and transparency.
Synthesis of fluorine contained hyperbranched polysiloxane and their effect on the thermal conductivity of epoxy resins
Authors: Jia Yuan , Yang Juxiang , Liu Zhen , Li Beibei 
Published: November 2022

AbstractTo improve the thermostability properties of epoxy (EP) resin, two kinds of novel hyperbranched polysiloxanes containing fluorine were prepared via the sol–gel process and the convenient transesterification process, respectively (F‐HBPSi‐1 and F‐HBPSi‐2). These two prepared F‐HBPSi were then used as modifier phased to blend with EP to obtain two new series polymer alloys F‐HBPSi‐1/EP and F‐HBPSi‐2/EP. The dielectric properties and thermal conductivities of the cured F‐HBPSi/EP resins were measured, while their thermal properties were also investigated by thermogravimetry (TG). The results showed that both the thermal conductivities and the thermostability properties of these two F‐HBPSi/EP were increased effectively, without further damaging their dielectric properties. Meanwhile, the F‐HBPSi‐2/EP exhibits better thermal conductivities and thermostability properties than that of F‐HBPSi‐1/EP. The improved overall performance of F‐HBPSi‐2/EP can be attributed to the low viscosity and excellent compatibility of F‐HBPSi‐2, as well as the good synergism between fluorine and silicon.
Synthesis and performance evaluation of carboxyl‐rich low phosphorus copolymer scale inhibitor
Authors: Ma Wentao , Zhang Yu , Li Huan 
Published: November 2022

AbstractA novel low phosphorus terpolymer scale inhibitor P(IA‐MA‐SHP) was prepared by aqueous free radical polymerization using itaconic acid (IA), maleic acid (MA), and sodium hypophosphite (SHP) as raw materials. It was mainly used as an efficient scale inhibitor to inhibit CaCO3. The structures of the copolymers were characterized by Fourier transform infrared,1H‐NMR, and13C‐NMR, and the thermal properties, and scale sample crystal structure morphology of the copolymers were analyzed by thermogravimetric analysis, x‐ray diffraction (XRD), and scanning electron microscope (SEM). The effects of dosage, monomer ratio, temperature, and reaction time on the scale inhibition effect were investigated, and the optimal synthesis conditions were determined. The results show that: when the monomer ratio isn(IA):n(MA) = 1.0:1.0, the mass fraction of SHP is 10%, the amount of ammonium persulfate initiator is 12%, the reaction temperature is 90°C, and the reaction time is 4 h, when the dosage of the agent is 20 mg L−1, the scale inhibition rate of CaCO3is 94.30%, while it also has a favorable inhibitory effect on CaSO4. The results of SEM and XRD show that the copolymer scale inhibitor can distort the lattice and has a favorable adsorption and dispersion effect. In addition, it has a positive effect on controlling the scale.
Tail approach synthesis of triazolylthiazolotriazole bearing benzenesulfonamides as carbonic anhydrase inhibitors capable of inducing apoptosis
Authors: Vats Lalit , Siwach Kiran , Angeli Andrea , Bikal Prerna , Bhardwaj Jitender Kumar , Supuran Claudiu T. , Sharma Pawan K. 
Published: November 2022

AbstractInhibition of human carbonic anhydrase (hCA) isoform IX with concurrent induction of apoptosis is a promising approach for targeting cancer in humans. Prompted by the scope, novel benzenesulfonamides containing the 1,2,3‐triazolylthiazolotriazole tail were synthesized and screened as inhibitors of hCA isoforms I, II, IV, and IX. The tumor‐associated isoform hCA IX was strongly inhibited by the sulfonamides reported here with KI values ranging from 45 nM to 1.882 μM. Overall, nine compounds showed hCA IX inhibition with KI < 250 nM. The glaucoma‐associated isoform hCA II was moderately inhibited while the cytosolic isoform hCA I and membrane‐bound isoform hCA IV were weakly inhibited by the synthesized sulfonamides. Compound 6Ac (KI = 3.6 nM) was found to be an almost three times more potent inhibitor of hCA II as compared to the standard drug acetazolamide (KI = 12.1 nM). The selective hCA IX inhibitors were further studied for their apoptotic efficacy in goat ovarian cells and showed better results as compared to the control. A comparative study of previously synthesized compounds and molecular docking study of representative compounds revealed some important generalizations that could prove beneficial in further investigations of isoform‐selective hCA inhibitors.
Health behaviors, psychosocial factors, and academic engagement in youth with autism spectrum disorder: A latent class analysis
Authors: Garcia Jeanette M. , Hahs‐Vaughn Debbie , Shurack Riley 
Published: November 2022

AbstractThe purpose of this study was to identify behavioral and health‐related profiles of children with autism spectrum disorder (ASD), based on the 2016 National Survey of Children's Health. A sample of 894 children with ASD (weighted sample N = 768,181) were included in the analysis. All data were parent‐reported and included measures on current diagnosis of ASD, general child health, weight status, physical activity (PA), screen time (ST), sleep duration, academic engagement, and social engagement. Latent class analysis, estimated with Mplus v. 8.4, was used to identify latent profiles of children with ASD. A three‐profile solution was the best fitting model, per model fit criteria. Children in profile 1 had overall more positive attributes (better health and weight, PA, more engaged in school, little difficulty in making friends, and modest ST) relative to children in either profiles 2 or 3. Children in profile 2 had distinctly increased ST and more difficulty in making friends when compared with children in either other profile. A greater proportion of children in profiles 2 and 3 were receiving behavioral treatment compared to profile 1; however, no differences were observed among profiles according to ASD severity, medication status, or additional health conditions. Studies should examine causal mechanisms among health behaviors, academic achievement, and social engagement in youth with ASD.
Die gewebte Membran des Al Bayt Stadions
Authors: Stockhusen Knut , Paech Christoph 
Published: November 2022

AbstractIn der zeitgenössischen Architektur bieten textile Membranen vielfältige Anwendungsmöglichkeiten. Üblicherweise bestehen solche Membranen aus einem regulären Gewebe, das beidseitig mit einer Deckschicht versehen ist, um es vor Umwelteinflüssen zu schützen. Meist verliert die Membran dabei ihr textiles Aussehen und büßt hinsichtlich ihrer Haptik ein. Aber genau diese Sicht‐ und Fühlbarkeit der Textur kombiniert mit einem traditionellen, identitätsstiftenden Farbmuster war ein zentraler Entwurfsparameter für die 71.000 m2 große Untermembran im Al Bayt Stadion. Um dem entwurfsprägenden Leitgedanken gerecht zu werden, wurde eine neuartige Membran entwickelt, für die einzelne PVC‐beschichtete Polyesterfäden in unterschiedlichen Farben verwoben werden. Durch die Verwendung eines Jacquard‐Webstuhls ist es möglich, das Gewebe mit unterschiedlichen Mustern zu versehen. Die mechanischen Materialeigenschaften der Membran variieren dabei nicht nur in Kett‐ und Schussrichtung, sondern auch innerhalb einer Richtung mit dem entsprechenden eingewebten Muster.