bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fully Encapsulated and Stable Black Phosphorus Field‐Effect Transistors
Authors: Arora Himani , Fekri Zahra , Vekariya Yagnika Nandlal , Chava Phanish , Watanabe Kenji , Taniguchi Takashi , Helm Manfred , Erbe Artur 
Published: October 2022

AbstractBlack phosphorus (BP) has quickly gained popularity in the scientific community owing to its interesting semiconducting properties, such as direct bandgap, high mobility, and intrinsic ambipolar behavior. However, its sensitivity to oxygen, moisture, and other air species has restricted its integration into active devices. Here, the lithography‐free via‐encapsulation scheme to fabricate fully‐encapsulated BP‐based field‐effect transistors (FETs) is employed. The full encapsulation is achieved by sandwiching the BP layers between the top and bottom hexagonal boron nitride (hBN) layers; top hBN passivating the BP layer from the environment and bottom hBN acting as a spacer and suppressing charge transfer to the BP layer from the SiO2 substrate. The embedded via‐metal electrodes allow the authors to perform reliable electrical measurements of the BP FETs. Based on these results, it is found that the electronic properties of the via‐encapsulated BP FETs are significantly improved compared to unencapsulated devices. This further establishes that the via‐contacting scheme leads to superior results compared to graphene‐hBN heterostructures and bare hBN layers combined with evaporated metal contacts (both use top and bottom hBN to encapsulate BP) by revealing higher mobility, lower hysteresis, and long‐term ambient‐stability in BP FETs.
Embedded 3D Printing of Thermally‐Cured Thermoset Elastomers and the Interdependence of Rheology and Machine Pathing
Authors: Stang Maria , Tashman Joshua , Shiwarski Daniel , Yang Humphrey , Yao Lining , Feinberg Adam 
Published: October 2022

AbstractThermoset elastomers are widely used high‐performance materials due to their thermal stability, chemical resistance, and mechanical properties. However, established casting and molding techniques limit the overall 3D complexity of parts that can be fabricated. Advanced manufacturing methods such as 3D printing have improved design flexibility and reduced development time but have proved challenging using thermally‐cured thermosets due to their viscosity, slow gelation kinetics, and high surface tension. To address this, freeform reversible embedding (FRE) 3D printing extrudes thermosets such as polydimethylsiloxane (PDMS) elastomer within a carbomer support bath, but due to the liquid‐like state of the prepolymer during extrusion has been limited to hollow structures. Here, FRE printing is significantly improved through rheological modification of PDMS with a thixotropic additive (1.0–10.0 wt.%) that imparts a yield stress (30–120 Pa) to help control filament morphology. Further, print process controls consisting of region‐specific slicing, filament retraction, and nonprint travel moves outside of the print to minimize the interaction of the nozzle with previously printed PDMS are implemented. The combined result is the FRE printing of PDMS in complex 3D parts with high fidelity, establishing a 3D printing methodology that can be used broadly with thermally‐cured thermoset elastomers and related polymers.
Automatic Snorkeling Electronic Equipment Enabled by Self‐Breathing Flexible Aqueous Aluminum‐Air Battery
Authors: He Ning , Ling Wei , Ji Xixi , Yu Chengrong , Liu Shang , Qin Bao , Zhang Xuan , Zhou Yexin , Mo Funian , Lei Hao , Zeng Lin , Lin Meng , Zhong Zheng , Yu Jie , Huang Yan 
Published: October 2022

AbstractSnorkeling equipments have played a vitally important role in various underwater operations, such as military, rescue activities, underwater research, archeology, and so on. However, existing snorkeling styles, represented by mechanical lifting system, artificial diving, and submarine mode (water storage and drainage), still face numerous challenges in the issues of large energy loss, complex structure, or environmental unfriendliness. Especially for small flexible equipments, an efficient and convenient way of snorkeling is of prime importance to various underwater explorations for a long time. Here, for the first time, an automatic snorkeling electronic equipment driven by a self‐breathing flexible aqueous aluminum‐air battery (Self‐BAAAB) which integrates functions of the snorkeling and the electric energy supply is designed. The self‐BAAAB battery consists of naturally inspired spongy sodium polyacrylate (PANa) hydrogel that acts as a flexible electrolyte and vertical N–O doped graphene fiber (NOGF) as an ORR/OER/HER trifunctional electrocatalyst. Benefited from the trifunctional catalytic properties and the aluminum metal stripping, the Self‐BAAAB consumes oxygen gas in the routine discharge process while the gas in turn is released during the charging process due to electrolysis of water in the super‐absorbing hydrogel, which triggers the sharp density variation of Self‐BAAAB, driving the “automatic snorkeling” feature of electronic equipment underwater. This work provides new insights into the design of the snorkeling electronic equipments and would promote the high efficiency of underwater operations, especially in a complex environment.
Genome‐Wide CRISPR/Cas9 Library Screening Revealed Dietary Restriction of Glutamine in Combination with Inhibition of Pyruvate Metabolism as Effective Liver Cancer Treatment
Authors: Yang Chunxue , Lee Derek , Zhang Misty Shuo , Tse Aki Pui‐Wah , Wei Lai , Bao Macus Hao‐Ran , Wong Bowie Po‐Yee , Chan Cerise Yuen‐Ki , Yuen Vincent Wai‐Hin , Chen Yiling , Wong Carmen Chak‐Lui 
Published: October 2022

AbstractHepatocellular carcinoma (HCC) is the second most lethal cancer worldwide. Glutamine is an essential, extracellular nutrient which supports HCC growth. Dietary glutamine deficiency may be a potential therapeutic approach for HCC. HCC cells overcome metabolic challenges by rewiring their metabolic pathways for rapid adaptations. The efficiency of dietary glutamine deficiency as HCC treatment is examined and the adaptation machinery under glutamine depletion in HCC cells is unraveled. Using genome‐wide CRISPR/Cas9 knockout library screening, this study identifies that pyruvate dehydrogenase α (PDHA), pyruvate dehydrogenase β (PDHB), and pyruvate carboxylase (PC) in pyruvate metabolism are crucial to the adaptation of glutamine depletion in HCC cells. Knockout of either PDHA, PDHB or PC induced metabolic reprogramming of the tricarboxylic acid (TCA) cycle, disrupts mitochondrial function, leading to the suppression of HCC cell proliferation under glutamine depletion. Surprisingly, dietary glutamine restriction improves therapeutic responses of HCC to PDH or PC inhibitor in mouse HCC models. Stable isotope carbon tracing confirms that PDH or PC inhibitors further disrupt the metabolic rewiring of the TCA cycle induced by dietary glutamine depletion in HCC. In summary, the results demonstrate that pyruvate metabolism acts as novel targetable metabolic vulnerabilities for HCC treatment in combination with a glutamine‐deficient diet.
Engineering by Cuts: How Kirigami Principle Enables Unique Mechanical Properties and Functionalities
Authors: Tao Jiayue , Khosravi Hesameddin , Deshpande Vishrut , Li Suyi 
Published: October 2022

AbstractKirigami, the ancient art of paper cutting, has evolved into a design and fabrication framework to engineer multi‐functional materials and structures at vastly different scales. By slit cutting with carefully designed geometries, desirable mechanical behaviors—such as accurate shape morphing, tunable auxetics, super‐stretchability, buckling, and multistability—can be imparted to otherwise inflexible sheet materials. In addition, the kirigami sheet provides a versatile platform for embedding different electronic and responsive components, opening up avenues for building the next generations of metamaterials, sensors, and soft robotics. These promising potentials of kirigami‐based engineering have inspired vigorous research activities over the past few years, generating many academic publications. Therefore, this review aims to provide insights into the recent advance in this vibrant field. In particular, this paper offers the first comprehensive survey of unique mechanical properties induced by kirigami cutting, their underlying physical principles, and their corresponding applications. The synergies between design methodologies, mechanics modeling, advanced fabrication, and material science will continue to mature this promising discipline.
Interfacial 2D Montmorillonite Nanocoatings Enable Sandwiched Polymer Nanocomposites to Exhibit Ultrahigh Capacitive Energy Storage Performance at Elevated Temperatures
Authors: Wang Yifei , Li Zongze , Moran Thomas J. , Ortiz Luis A. , Wu Chao , Konstantinou Antigoni C. , Nguyen Hiep , Zhou Jierui , Huo Jindong , Davis‐Amendola Kerry , Zhou Peinan , Huey Bryan D. , Cao Yang 
Published: October 2022

AbstractPolymer dielectrics are essential for advanced electrical and electronic power systems due to their ultrafast charge–discharge rate. However, a long‐standing challenge is to maintain their dielectric performance at high temperatures. Here, a layered barium titanate/polyamideimide nanocomposite reinforced with rationally designed interfaces is reported for high‐temperature high‐energy‐density dielectrics. Nanocoatings composed of 2D montmorillonite nanosheets with anisotropic conductivities are interposed at two kinds of macroscopic interfaces: 1) the interfaces between adjacent layers in the nanocomposites (inside) and 2) the interfaces between the surface of the nanocomposite and the electrode (outside). By revealing the charge transport behavior with Kelvin probe force microscope, surface potential decay, and finite element simulation, it is demonstrated that the outside nanocoatings are observed to diminish charge injection from the electrode, while the inside nanocoatings can suppress the kinetic energy of hot carriers by redirecting their transport. In this interface‐reinforced nanocomposite, an ultrahigh energy density of 2.48 J cm−3, as well as a remarkable charge–discharge efficiency >80%, is achieved at 200 °C, six times higher than that of the nanocomposite without interfacial nanocoatings. This research unveils a novel approach for the structural design of polymer nanocomposites based on engineered interfaces to achieve high‐efficient and high‐temperature capacitive energy storage.
Defect‐Induced Dense Amorphous/Crystalline Heterophase Enables High‐Rate and Ultrastable Sodium Storage
Authors: Osman Sahar , Peng Chao , Li Fangkun , Chen Haoliang , Shen Jiadong , Zhong Zeming , Huang Wenjie , Xue Dongfeng , Liu Jun 
Published: October 2022

AbstractCurrently, the construction of amorphous/crystalline (A/C) heterophase has become an advanced strategy to modulate electronic and/or ionic behaviors and promote structural stability due to their concerted advantages. However, their different kinetics limit the synergistic effect. Further, their interaction functions and underlying mechanisms remain unclear. Here, a unique engineered defect‐rich V2O3 heterophase structure (donated as A/C‐V2O3−x@C‐HMCS) composed of mesoporous oxygen‐deficient amorphous − hollow core (A‐V2O3−x/HMC) and lattice‐distorted crystalline shell (C‐V2O3/S) encapsulated by carbon is rationally designed via a facile approach. Comprehensive density functional theory (DFT) calculations disclose that the lattice distortion enlarges the porous channels for Na+ diffusion in the crystalline phase, thereby optimizing its kinetics to be compatible with the oxygen‐vacancy‐rich amorphous phase. This significantly reduces the high contrast of the kinetic properties between the crystalline and amorphous phases in A/C‐V2O3−x@C‐HMCS and induces the formation of highly dense A/C interfaces with a strong synergistic effect. As a result, the dense heterointerface effectively optimizes the Na+ adsorption energy and lowers the diffusion barrier, thus accelerating the overall kinetics of A/C‐V2O3−x@C‐HMCS. In contrast, the perfect heterophase (defects‐free) A/C‐V2O3@C‐HCS demonstrates sparse A/C interfacial sites with limited synergistic effect and sluggish kinetics. As expected, the A/C‐V2O3−x@C‐HMCS achieves a high rate and ultrastable performance (192 mAh g−1 over 6000 cycles at 10 A g−1) when employed for the first time as a cathode for sodium‐ion batteries (SIBs). This work provides general guidance for realizing dense heterophase cathode design for high‐performance SIBs and beyond.
Progress and Prospects of Emerging Potassium–Sulfur Batteries
Authors: Lei Yao‐Jie , Yang Hui‐Ling , Liang Yaru , Liu Han‐Wen , Zhang Binwei , Wang Liang , Lai Wei‐Hong , Wang Yun‐Xiao , Liu Hua‐Kun , Dou Shi‐Xue 
Published: October 2022

AbstractThe potassium–sulfur battery (K–S battery) as an innovative battery technology is a promising candidate for large‐scale applications, due to its high energy density and the low cost of both K and S. The development of the K–S technology is, however, inhibited by its low reversible capacity and the safety issues related to the K metal anode. Here, the review starts by discussing the mechanism of the redox reactions for the K–S batteries and emphasizes the challenges for this battery system based on its current research status. Furthermore, the current improvement strategies for the K–S system in terms of the sulfur cathode, electrolyte, separator, and K metal anode are summarized. Finally, future perspectives on the development of the K–S system are proposed.
Atroposelective Synthesis of Triaryl α‐Pyranones with 1,2‐Diaxes by N‐Heterocyclic Carbene Organocatalysis
Authors: Zhang Simiao , Wang Xiaoxue , Han Li‐Li , Li Jibin , Liang Zheng , Wei Donghui , Du Ding 
Published: October 2022

AbstractAtropisomers bearing multiple stereogenic axes are of increasing importance to the field of material science, pharmaceuticals, and catalysis. However, the atroposelective construction of multi‐axis atropisomers remains rare and challenging, due to the intrinsical difficulties in the stereo‐control of the multiple stereogenic axes. Herein, we demonstrate a single‐step construction of a new class of 1,2‐diaxially chiral triaryl α‐pyranones by an N‐heterocyclic carbene organocatalytic asymmetric [3+3] annulation of well‐designed alkynyl acylazolium precursors and enolizable sterically hindered 2‐aryl ketones. The protocol features broad substrate scope (>50 examples), excellent stereo‐control (most cases >20 : 1 dr, up to 99.5 : 0.5 er), and potentially useful synthetic applications. The success of this reaction relies on the rational design of structurally matched reaction partners and the careful selection of the asymmetric catalytic system. DFT calculations have also been performed to discover and rationalize the origin of the high stereoselectivity of this reaction.
Deaminative Arylation and Alkenyaltion of Aliphatic Tertiary Amines with Aryl and Alkenylboronic Acids via Nitrogen Ylides
Authors: Su Jianke , Li Chengbo , Hu Xinyuan , Guo Yu , Song Qiuling 
Published: October 2022

AbstractTransition‐metal‐catalyzed Suzuki–Miyaura coupling has significantly advanced C−C bond formation and has been well recognized in organic synthesis, pharmaceuticals, materials science and other fields. In this rapid development, cross coupling without transition metal catalyst is a big challenge in this field, and using widely existing tertiary amines as electrophiles to directly couple with boronic acids has great hurdles yet significant application prospects. Herein, we report an efficient and general deaminative arylation and alkenylation of tertiary amines (propargyl amines, allyl amines and 1H‐indol‐3‐yl methane amines) with ary and alkenylboronic acids enabled by difluorocarbene under transition‐metal‐free conditions. Preliminary mechanism experiments suggest that in situ formed difluoromethyl quaternary amine salt, nitrogen ylide and tetracoordinate boron species are the key intermediates, the subsequent 1,2‐metallate shift and protodeboronation complete the new coupling reaction.
The Role of Cytochrome P450 AbyV in the Final Stages of Abyssomicin C Biosynthesis
Authors: Devine Andrew J. , Parnell Alice E. , Back Catherine R. , Lees Nicholas R. , Johns Samuel T. , Zulkepli Ainul Z. , Barringer Rob , Zorn Katja , Stach James E. M. , Crump Matthew P. , Hayes Martin A. , van der Kamp Marc W. , Race Paul R. , Willis Christine L. 
Published: October 2022

AbstractAbyssomicin C and its atropisomer are potent inhibitors of bacterial folate metabolism. They possess complex polycyclic structures, and their biosynthesis has been shown to involve several unusual enzymatic transformations. Using a combination of synthesis and in vitro assays we reveal that AbyV, a cytochrome P450 enzyme from the aby gene cluster, catalyses a key late‐stage epoxidation required for the installation of the characteristic ether‐bridged core of abyssomicin C. The X‐ray crystal structure of AbyV has been determined, which in combination with molecular dynamics simulations provides a structural framework for our functional data. This work demonstrates the power of combining selective carbon‐13 labelling with NMR spectroscopy as a sensitive tool to interrogate enzyme‐catalysed reactions in vitro with no need for purification.
Site‐Selective Pyridine C−H Alkylation with Alcohols and Thiols via Single‐Electron Transfer of Frustrated Lewis Pairs
Authors: Tan Chang‐Yin , Kim Myojeong , Park Inyoung , Kim Yuhyun , Hong Sungwoo 
Published: October 2022

AbstractA unified strategy for the deoxygenative or desulfurative pyridylation of various alcohols and thiols has been developed through a single‐electron transfer (SET) process of frustrated Lewis pairs (FLPs) derived from pyridinium salts and PtBu3. Mechanistic studies revealed that N‐amidopyridinium salts serve as effective Lewis acids for the formation of FLPs with PtBu3, and the generated phosphine radical cation ionically couples with the in situ generated xanthate, eventually affording the alkyl radical through facile β‐scission under photocatalyst‐free conditions. The reaction efficiency was further accelerated by visible‐light irradiation. This method is conceptually appealing by using encounter complexes in FLP chemistry to promote SET, which provides a previously unrecognized opportunity for the selective heteroarylation of a diverse range of alcohols and thiols with various functional groups, even in complex settings under mild reaction conditions.
A Sulfoxide Reagent for One‐Pot, Three‐Component Syntheses of Sulfoxides and Sulfinamides**
Authors: Saito Fumito 
Published: October 2022

AbstractSulfoxides and sulfinamides represent versatile sulfur functional groups found in ligands, chiral auxiliaries, and bioactive molecules. Canonical two‐component syntheses, however, rely on substrates with a preinstalled C−S bond and impede efficient and modular access to these sulfur motifs. Herein is presented the application of an easily prepared, bench‐stable sulfoxide reagent for one‐pot, three‐component syntheses of sulfoxides and sulfinamides. The sulfoxide reagent donates the SO unit upon the reaction with a Grignard reagent (RMgX) as a sulfenate anion (RSO−). While subsequent trapping reactions of this key intermediate with carbon electrophiles provide sulfoxides, a range of tertiary, secondary, and primary sulfinamides can be prepared by substitution reactions with electrophilic amines. The syntheses of sulfinamide analogs of amide‐ and sulfonamide‐containing drugs illustrate the utility of the method for the rapid preparation of medicinally relevant molecules.
The Anionic Chemistry in Regulating the Reductive Stability of Electrolytes for Lithium Metal Batteries
Authors: Yao Nan , Sun Shu‐Yu , Chen Xiang , Zhang Xue‐Qiang , Shen Xin , Fu Zhong‐Heng , Zhang Rui , Zhang Qiang 
Published: October 2022

AbstractAdvanced electrolyte design is essential for building high‐energy‐density lithium (Li) batteries, and introducing anions into the Li+ solvation sheaths has been widely demonstrated as a promising strategy. However, a fundamental understanding of the critical role of anions in such electrolytes is very lacking. Herein, the anionic chemistry in regulating the electrolyte structure and stability is probed by combining computational and experimental approaches. Based on a comprehensive analysis of the lowest unoccupied molecular orbitals, the solvents and anions in Li+ solvation sheaths exhibit enhanced and decreased reductive stability compared with free counterparts, respectively, which agrees with both calculated and experimental results of reduction potentials. Accordingly, new strategies are proposed to build stable electrolytes based on the established anionic chemistry. This work unveils the mysterious anionic chemistry in regulating the structure–function relationship of electrolytes and contributes to a rational design of advanced electrolytes for practical Li metal batteries.
Self‐assembled Ru(bda) Coordination Oligomers as Efficient Catalysts for Visible Light‐Driven Water Oxidation in Pure Water
Authors: Schlossarek Tim , Stepanenko Vladimir , Beuerle Florian , Würthner Frank 
Published: October 2022

AbstractWater‐soluble multinuclear complexes based on ruthenium 2,2′‐bipyridine‐6,6′‐dicarboxylate (bda) and ditopic bipyridine linker units are investigated in three‐component visible light‐driven water oxidation catalysis. Systematic studies revealed a strong enhancement of the catalytic efficiency in the absence of organic co‐solvents and with increasing oligomer length. In‐depth kinetic and morphological investigations suggest that the enhanced performance is induced by the self‐assembly of linear Ru(bda) oligomers into aggregated superstructures. The obtained turnover frequencies (up to 14.9 s−1) and turnover numbers (more than 1000) per ruthenium center are the highest reported so far for Ru(bda)‐based photocatalytic water oxidation systems.
Preparation of laminated safety glass based on high strength polyurethane film by solution annealing
Authors: Ding Wenhe , Zhan Siqi , Liu Hongyan , Bo Yanyan , Sun Zhongliang , Wang Shiwei , Zhang Mingyao 
Published: October 2022

AbstractCompared with the traditional polyvinyl butyral (PVB) laminated glass, the polyurethane (PU) based laminated glass has the advantages of higher impact strength and longer service life. Thus, aromatic polyurethane films have attracted more attentions in recent years due to their high light transmittance, adhesion and functionality. In this paper, the tensile strength of polyurethane films based on bis(4‐isocyanatocyclohexyl)‐methane (HMDI) have been increased from 27 to 51 MPa and their elongation at break have been increased from 330% to 525% after solvent annealing in toluene. It is attributed to molecular segments with high crystallization and hydrogen bond formation of PU, which are confirmed by FT‐IR and XRD characterization. Based on this, laminated glasses with higher impact strength based on the thermoplastic polyurethane films are constructed successfully.
Fabrication of Highly Resistive NiO Thin Films for Nanoelectronic Applications
Authors: Mohr Johannes , Hennen Tyler , Bedau Daniel , Nag Joyeeta , Waser Rainer , Wouters Dirk J. 
Published: October 2022

AbstractThin films of the prototypical charge transfer insulator nickel oxide appear to be a promising material for novel nanoelectronic devices. The fabrication of the material is challenging, however, and mostly a p‐type semiconducting phase is reported. Here, the results of a factorial experiment are presented that allow optimization of the properties of thin films deposited using sputtering. A cluster analysis is performed, and four main types of films are found. Among them, the desired insulating phase is identified. From this material, nanoscale devices are fabricated, which demonstrate that the results carry over to relevant length scales. Initial switching results are reported.