bluuebunny/crossref_metadata_2025_split huggingface dataset:
Sonochemically‐Induced Reduction of Alkenes to Alkanes with Ammonia
Authors: Humblot Anaelle , Chave Tony , Amaniampong Prince N. , Streiff Stéphane , Jérôme François 
Published: October 2022

AbstractWith the progressive defossilization of our industry, hydrogen (H2) has been identified as a central molecule to store renewable electricity. In this context, ammonia (NH3) is now rapidly emerging as a promising hydrogen carrier for the future. This game change indirectly impacts the field of fine chemistry where hydrogenation reactions are widely deployed. In particular, the possibility of performing hydrogenation reactions using ammonia directly instead of hydrogen has become highly desirable but it remains a very difficult scientific task, which we address in this communication. Here we show that the N−H bond of NH3 can be cleaved within cavitation bubbles, generated by ultrasonic irradiation at a high frequency, leading to the in situ formation of a diimide, which then induces the hydrogenation of alkenes. Advantageously, this work does not involve any transition metal and releases N2 as a sole co‐product.
Multicomponent Assembly of Complex Oxindoles by Enantioselective Cooperative Catalysis
Authors: Hua Ru‐Yu , Yu Si‐Fan , Jie Xiao‐Ting , Qiu Huang , Hu Wen‐Hao 
Published: October 2022

AbstractChiral oxindoles are important chemical scaffolds found in many natural products, and their enantioselective synthesis thus attracts considerable attention. Highly diastereo‐ and enantioselective synthetic methods for constructing C3 quaternary oxindoles have been well‐developed. However, the efficient synthesis of chiral 3‐substituted tertiary oxindoles has been rarely reported due to the ease of racemization of the tertiary stereocenter via enolization. Therefore, we herein report on the multicomponent assembly (from N‐aryl diazoamides, aldehydes, and enamines/indoles) of complex oxindoles by enantioselective cooperative catalysis. These reactions proceed under mild conditions and show broad substrate scope, affording the desired coupling products (>90 examples) with good to excellent stereocontrol. Additionally, this research also demonstrates the synthetic potential of this annulation by constructing the 6,6,5‐tricyclic lactone core structure of Speradine A.
Optimal Dihedral Angle in Twisted Donor–Acceptor Organic Emitters for Maximized Thermally Activated Delayed Fluorescence
Authors: Shi Yuhao , Ma Huili , Sun Zhiyu , Zhao Weijun , Sun Guangyan , Peng Qian 
Published: October 2022

AbstractThe twisted donor–acceptor (D‐A) organic formwork with a large dihedral angle (θDA) is usually adopted to narrow the singlet‐triplet energy gap for obtaining excellent thermally activated delayed fluorescence (TADF) emitters. However, the dependence of overall TADF properties on θDA has not been systematically investigated to this day. Taking new designed CzBP, CzBP‐1M and CzBP‐2M via introducing methyl as investigated models, it is found that (i) with increasing θDA, the charge transfer component in S1 is larger than that in T1 in varying degrees, leading to non‐monotonic spin‐orbit couplings; (ii) the electron‐vibration couplings between S1 and T1 states become the largest when θDA approaching 80°, facilitating phonon‐driven up‐conversion; (iii) the overall TADF rate reaches a peak at θDA≈80°. By this, the TADF on/off switching is realized via methyl moiety for regulating θDA from theoretical prediction to experimental confirmation. Importantly, the θDA near 80° would be a good descriptor for screening excellent D‐A type TADF emitters.
Ligand‐Controlled Regiodivergent Cyanoboration of Internal Allenes by Copper Catalysis
Authors: Hu Hui , Ji Guo‐Cui , Jiang Linjuan , Bi Siwei , Jiang Yuan‐Ye , Liu Yuanhong 
Published: October 2022

AbstractThe first copper‐catalyzed regiodivergent cyanoboration of internal allenes with B2pin2 (bis(pinacolato)diboron) and NCTS (N‐cyano‐N‐phenyl‐p‐toluenesulfonamide) derivatives is reported. The β,γ‐ and α,β‐cyanoborylated products were synthesized with high regio‐ and stereo‐selectivity. Computational studies revealed that nucleophilic addition of allylcopper or related intermediates on cyanation reagent is the regio‐ and stereo‐determining step, while transmetalation with B2pin2 is the rate‐determining step. The nucleophilic addition step proceeds via inner‐sphere mechanism in the CuI/P(o‐tol)3 and CuI/Xantphos (P(o‐tol)3=tris(o‐methylphenyl)phosphine, Xantphos=4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene) catalytic systems and via outer‐sphere mechanism in the CuII/Xantphos catalytic system, respectively.
Circularly Polarized Luminescence from Zero‐Dimensional Hybrid Lead‐Tin Bromide with Near‐Unity Photoluminescence Quantum Yield
Authors: Wei Yi , Li Chen , Li Yawen , Luo Zhishan , Wu Xiaoyu , Liu Yulian , Zhang Liming , He Xin , Wang Wei , Quan Zewei 
Published: October 2022

AbstractZero‐dimensional (0D) hybrid metal halides with perfect host‐guest structures are promising candidates to construct circularly polarized luminescence (CPL)‐active materials. However, it still remains challenging to obtain 0D chiral metal halides with simultaneously strong CPL and high photoluminescence quantum yield. Here, a new enantiomeric pair of 0D hybrid lead‐tin bromides, (RR/SS‐C6N2H16)2Pb0.968Sn0.032Br6 ⋅ 2H2O (R/S‐PbSnBr ⋅ H2O), is reported. TheR/S‐PbSnBr ⋅ H2O compounds not only show intriguing self‐trapped exciton emissions with near‐unity quantum yield, but also present intense CPL with a dissymmetry factorglumof ±3.0×10−3. Such CPL activities originate from the asymmetric [SnBr6]4−luminophores inR/S‐PbSnBr ⋅ H2O, due to the induced structural chirality by the organic ligands via N−H⋅⋅⋅Br hydrogen bonds. Furthermore, CPL emissions with tunable colors fromR/S‐PbSnBr ⋅ H2O and dehydrated compounds are reversibly observed, which extends their chiroptical applications.
Electrical Pulse Induced One‐step Formation of Atomically Dispersed Pt on Oxide Clusters for Ultra‐Low‐Temperature Zinc‐Air Battery
Authors: Ye Chenliang , Zheng Meng , Li Zhiming , Fan Qikui , Ma Haiqing , Fu Xianzhu , Wang Dingsheng , Wang Jin , Li Yadong 
Published: October 2022

AbstractAtomically dispersed sites anchored on small oxide clusters are attractive new catalytic materials. Herein, we demonstrate an electrical pulse approach to synthesize atomically dispersed Pt on various oxide clusters in one step with nitrogen‐doped carbon as the support (Pt1−MOx/CN). As a proof‐of‐concept application, Pt1−FeOx/CN is shown to exhibit high activity for oxygen reduction reaction (ORR) with a half‐wave potential of 0.94 V vs RHE, in contrast to the poor catalytic performance of atomically dispersed Pt on large Fe2O3nanoparticles. Our work has revealed that, by tuning the size of the iron oxide down to the cluster regime, an optimal OH* adsorption strength for ORR is achieved on Pt1−FeOx/CN due to the regulation of Pt−O bonds. The unique structure and high catalytic performance of Pt1−FeOx/CN enable the Zinc‐Air batteries an excellent performance at ultralow temperature of −40 °C with a high peak power density of 45.1 mW cm−2and remarkable cycling stability up to 120 h.
Preparation of high‐performance deproteinized natural rubber/chitosan composite films via a green and sulfur‐free method
Authors: Yuan Changcheng , Sun Jinyu , Tian Xiaohui , Yuan Yizhong 
Published: October 2022

AbstractTo solve the environment and health issues arose from the sulfur vulcanization, a facile and completely eco‐friendly method of latex‐assembly and in situ cross‐linking is developed to prepare fully bio‐based and high‐performance rubber films. The films are featured by a “reinforced concrete” structure composed of dynamically cross‐linked chitosan framework and unvulcanized deproteinized natural rubber (DPNR) matrix. The self‐assembly of DPNR latex particles and chitosan, as well as the in situ cross‐linking of chitosan in the film forming process are confirmed by transmission electron microscope and dynamic light scattering. As green rubbers without vulcanization, the as‐designed composite films possess excellent mechanic properties comparable to those of the sulfur vulcanized DPNR film, whose tensile strength and toughness reach 15.2 MPa and 77.6 MJ m−3 respectively. Moreover, the films exhibited appropriate permeability to moisture and achievable reprocessing, which have potential applications in wearable devices.
Synthesis of reactive copolymers with peroxide functionality for cross‐linking water‐soluble polymers
Authors: Serdiuk Vitalii , Shevchuk Oleh , Tetiana Kovalenko , Bukartyk Natalya , Tokarev Viktor 
Published: October 2022

AbstractA series of reactive copolymers with peroxide functionality (RCPFs) were synthesized via radical copolymerization of monomer mixtures in an organic solvent comprised of a peroxide monomer 5‐(tert‐butyl peroxy)‐5‐methylhex‐1‐en‐3‐yne, acrylamide, maleic anhydride, and butyl methacrylate. Peroxide functionality allows the RCPFs to initiate a variety of radical processes, including cross‐linking of organic polymers. Hydrophilic monomer subunits (acrylamide and maleic anhydride) within the RCPF macromolecules promote cross‐linking of water‐soluble polymers. We aimed to investigate RCPF comonomer ratio and its effects on copolymerization kinetics and composition, as well as physico‐chemical and colloidal properties. We also evaluated and characterized the kinetic parameters of the thermal decomposition of peroxide moieties in the synthesized RCPF. Findings revealed that RCPF possessed surface‐active properties and reduced surface tension at its aqueous solution–air interface. The data indicated that the decomposition process complied with the first‐order kinetics, and complex thermal analysis confirmed the presence of peroxide moieties. RCPFs' ability to cross‐link water‐soluble polymers was demonstrated on poly(acrylamide) and poly(vinyl alcohol).
Tailoring Permanent Charge Carrier Densities in Epitaxial Graphene on SiC by Functionalization with F4‐TCNQ
Authors: Yin Yefei , Chatterjee Atasi , Momeni Davood , Kruskopf Mattias , Götz Martin , Wundrack Stefan , Hohls Frank , Pierz Klaus , Schumacher Hans W. 
Published: October 2022

AbstractThe outstanding properties and the potential for large‐scale fabrication open a wide field for electronic applications of epitaxial graphene on silicon carbide substrates. However, reliable doping methods to permanently control and tailor the carrier concentration to the desired value without applying an electrostatic gate are challenging and still under investigation. In this study, a post‐growth molecular doping technique is investigated that compensates for the high electron density of pristine epitaxial graphene by using the acceptor F4‐TCNQ. By precise adjustment of the dopant concentration, the carrier density can be tuned in a wide range from intrinsicn‐ to thep‐type regime. The fabricated quantum Hall devices are ready‐to‐use, and no further treatments are required. High‐precision resistance measurements of graphene‐based devices with different doping levels show a quantization accuracy of 10−9that underlines the high quality of the fabricated devices and the suitability of this method for device applications. The experimentally observed correlation between the carrier density and the onset of the quantum Hall plateau gives a reliable criterion for the choice of devices in quantum resistance metrology.
An Intramolecular Cycloetherification of Unactivated Olefinic Substrates Bearing endo‐Alcohol: Access to Diversely Alkylated Oxa‐Cage Derivatives Useful for Olefin‐Metathesis
Authors: Kotha Sambasivarao , Keesari Ramakrishna Reddy 
Published: October 2022

AbstractHerein, we report an efficient and rapid synthetic methodology to access diversely substituted oxa‐cages from unactivated olefinic substrates derived from endo‐norbornenes by employing Lewis acid‐ (BF3 ⋅ OEt2) or base (NaH)‐promoted intramolecular etherification. Although both BF3 ⋅ OEt2 and NaH are found to be efficient for this transformation, slightly better yields and less reaction times are achieved with NaH/DMF (0.25–1 h at 100 °C) as compared to BF3 ⋅ OEt2/DCM (2–3 h at 0 °C to rt). The evolution of this intramolecular cyclization was studied by time‐dependent NMR studies in CDCl3 solvent. Further, these observations are supported by infrared (IR) spectral data. It is worth mentioning that the present methodology enables a new route to assemble highly fused oxa‐cage systems by choosing suitably substituted oxa‐cage compounds for the olefin‐metathesis sequence. The highly fused oxa‐cage systems may have potential applications in high‐energy‐density materials (HEDMs) and supramolecular chemistry.
Retrieving Spent Cathodes from Lithium‐Ion Batteries through Flourishing Technologies
Authors: Raj Benjamin , Sahoo Manoj Kumar , Nikoloski Aleksandar , Singh Pritam , Basu Suddhasatwa , Mohapatra Mamata 
Published: October 2022

AbstractThe inherent advancement of lithium‐ion batteries (LIBs) in electronic gadgets is expanding exponentially, and the ongoing surge of electric vehicles (EVS) in the near future will result in an unprecedented amount of lithium waste. Used cathode materials contain hazardous metal toxic, polymer binder, and electrolytes, posing a serious risk to the environment and public health. For socio‐environmental reasons, it is required to recover all valuable metals or to immediately relithiate the used cathode materials by adding suitable salts in the stoichiometric ratio. As the consumption of batteries increases over time in daily life, recycling LIBs will become more and more crucial. Compared to the traditional hydrometallurgical and pyrometallurgical routes, direct recycling technologies can regenerate electrodes without using an intensive energy or chemicals, which saves money and reduces secondary waste. As a result, the authors emphasise direct relithiation methods for spent cathode relithiation, such as hydrothermal, ionothermal, electrochemical, and molten salts. In‐depth analysis and discussion are also given to the aforementioned approaches. The deactivation, disintegration, and separation processes used in the physical processing of black mass and other constituents are discussed. We reviewed the obstacles, possible commercialization of technology, and recommendations to the reviewer for the developing ecologically friendly recycling technology in the near future toward the circular economy.
NetCellMatch: Multiscale Network‐Based Matching of Cancer Cell Lines to Patients Using Graphical Wavelets
Authors: Desai Neel , Morris Jeffrey S. , Baladandayuthapani Veerabhadran 
Published: October 2022

AbstractCancer cell lines serve as model in vitro systems for investigating therapeutic interventions. Recent advances in high‐throughput genomic profiling have enabled the systematic comparison between cell lines and patient tumor samples. The highly interconnected nature of biological data, however, presents a challenge when mapping patient tumors to cell lines. Standard clustering methods can be particularly susceptible to the high level of noise present in these datasets and only output clusters at one unknown scale of the data. In light of these challenges, we present NetCellMatch, a robust framework for network‐based matching of cell lines to patient tumors. NetCellMatch first constructs a global network across all cell line‐patient samples using their genomic similarity. Then, a multi‐scale community detection algorithm integrates information across topologically meaningful (clustering) scales to obtain Network‐Based Matching Scores (NBMS). NBMS are measures of cluster robustness which map patient tumors to cell lines. We use NBMS to determine representative “avatar” cell lines for subgroups of patients. We apply NetCellMatch to reverse‐phase protein array data obtained from The Cancer Genome Atlas for patients and the MD Anderson Cell Line Project for cell lines. Along with avatar cell line identification, we evaluate connectivity patterns for breast, lung, and colon cancer and explore the proteomic profiles of avatars and their corresponding top matching patients. Our results demonstrate our framework's ability to identify both patient‐cell line matches and potential proteomic drivers of similarity. Our methods are general and can be easily adapted to other'omic datasets.
The Insertion of EII and EIV Chlorides (E=Si, Ge) into the Si−Si Bond of Disilylene
Authors: Baradzenka Aliona G. , Vyboishchikov Sergei F. , Pilkington Melanie , Dmitrienko Anton , Nikonov Georgii I. 
Published: October 2022

AbstractReactions of silicon and germanium dichlorides L⋅ECl2 (E=Si, L=IPr; E=Ge, L=dioxane) with the phosphinoamidinato‐supported disilylene ({κ2(N,P)‐NNP}Si)2 resulted in formal tetrylene insertions into the Si−Si bond. In the case of the reaction with silylene, two products were isolated. The first product ({κ2(N,P)‐NNP}Si)2SiCl2, is the formal product of direct SiCl2 insertion into the Si−Si bond of ({κ2(N,P)‐NNP}Si)2 and thus features two separated silylamido silylene centers. Over time, migration of the SiCl2 group to a lateral position afforded the second product, the disilylene {κ2(Si,P)−SiCl2NNP}Si−Si{κ2(N,P)‐NNP}. In contrast, insertion of GeCl2 resulted only in the isolation of the germanium analogue of {κ2(Si,P)−SiCl2NNP}Si−Si{κ2(N,P)‐NNP}, containing a Ge atom in the central position namely, compound {κ2(Si,P)−SiCl2NNP}Ge−Si{κ2(N,P)‐NNP}, which is a rare example of a silylene‐germylene. Finally, reaction of disilylene ({κ2(N,P)−NNP}Si)2 with SiCl4 and SiHCl3 led to the formation of the new bis(silyl)silylene, ({NNP}SiCl2)2Si:. All four new products from these insertion reactions have been characterized by multinuclear NMR and single‐crystal X‐ray diffraction studies.
Recycling of Cofactors in Crude Enzyme Hydrogels as Co‐immobilized Heterogeneous Biocatalysts for Continuous‐Flow Asymmetric Reduction of Ketones
Authors: Chen Qiang , Wang Yujun , Luo Guangsheng 
Published: October 2022

AbstractFlow biocatalysis involving oxidoreductase is limited by the difficulty in recycling expensive cofactors. In this study, an enzyme‐rich hydrogel monolithic microreactor was developed via in situ microfluidic assembly of inexpensive crude enzymes. This porous gel biocatalyst exhibited good tethering functions to nicotinamide cofactors; thus, they were retained by the hydrogel to controllably form a novel heterogeneous biocatalyst with self‐sufficient cofactors. The flow asymmetric production of a chiral alcohol in this cofactor‐entrapped gel microreactor achieved >99 % enantioselectivity and a high space‐time yield of 46.3 g L−1 h−1 at 94.8 % conversion. Moreover, the turnover number of cofactors reached as high as 4800 after continuous operation of 160 reactor volumes, realizing significantly higher utilization of the cofactors compared with many reported strategies. Furthermore, this engineered heterogeneous biocatalyst exhibited improved performance in terms of product tolerance and storage stability, paving the way for a green, cost‐effective, and sustainable continuous‐flow production of enantiopure alcohols.
Experimental water hyacinth invasion and destructive management increase human schistosome transmission potential
Authors: Desautels Daniel J. , Hartman Rachel B. , Weber Maggie E. , Jacob Nathan , Sun Andrew , Civitello David J. 
Published: October 2022

AbstractInvasive species cause environmental degradation, decrease biodiversity, and alter ecosystem function. Invasions can also drive changes in vector‐borne and zoonotic diseases by altering important traits of wildlife hosts or disease vectors. Managing invasive species can restore biodiversity and ecosystem function, but it may have cascading effects on hosts, parasites, and human risk of infection. Water hyacinth,Eichhornia crassipes, is an extremely detrimental invader in many sites of human schistosome transmission, especially in Lake Victoria, where hyacinth is correlated with high snail abundance and hotspots of human schistosome infection. Hyacinth is often managed via removal or in situ destruction, but the effects of these strategies on snail intermediate hosts and schistosomes are not known. We evaluated the effects of water hyacinth invasion and these management strategies on the dynamics of human schistosomes,Schistosoma mansoni, and snails,Biomphalaria glabrata, in experimental mesocosms over 17 weeks. We hypothesized that hyacinth, which is inedible to snails, would affect snail growth, reproduction, and cercariae production through the balance of its competitive effects on edible algae and its production of edible detritus. We predicted that destruction would create a pulse of edible detrital resources, thereby increasing snail growth, reproduction, and parasite production. Conversely, we predicted that removal would have small or negligible effects on snails and schistosomes, because it would alleviate competition on edible algae without generating a resource pulse. We found that hyacinth invasion suppressed algae, changed the timing of peak snail abundance, and increased total production of human‐infectious cercariae ~6‐fold relative to uninvaded controls. Hyacinth management had complex effects on algae, snails, and schistosomes. Removal increased algal growth and snail abundance (but not biomass), and slightly reduced schistosome production. In contrast, destruction increased snail biomass (but not abundance), indicating increases in body size. Destruction caused the greatest schistosome production (10‐fold more than the control), consistent with evidence that larger snails with greater access to food are most infectious. Our results highlight the dynamic effects of invasion and management on a globally impactful human parasite and its intermediate host. Ultimately, preventing or removing hyacinth invasions would simultaneously benefit human and environmental health outcomes.