bluuebunny/crossref_metadata_2025_split huggingface dataset:
Printed Four Key‐Device Units for Unified Platform of Wireless Anti‐Counterfeiting Label to Bridge in Blockchain
Authors: Sun Junfeng , Parajuli Sajjan , Shrestha Kiran , Park Jinhwa , Shrestha Sagar , Jung Younsu , Park Hyejin , Koirala Gyan Raj , Nasir Nadra , Kim Seongryeong , Truong Han , Jang Haesook , Lee Jinkwan , Lee Jongchan , Cho Gyoujin 
Published: October 2021

AbstractAs new authentic products are introduced into the market, counterfeiting has always been on the rise. In 2015, the global economic loss caused by counterfeiting is more than 1.7 trillion US dollars and has been increasing annually. Therefore, an inexpensive but efficient anti‐counterfeiting platform must be developed to end counterfeiting. Here, a wireless platform for the anti‐counterfeiting with an item‐tracking is developed by integrating printed four key‐device units, a 13.56 MHz rectenna (wireless power transmission), supercapacitors (power storage), 1‐bit code generator chip (logic code), and an electrophoretic based quick response code (memory). Our near‐field communication quick response code label platform is inexpensive and effective by utilizing blockchains and high throughput roll‐to‐roll printed devices. When practically applied, the near field communication quick response code label wirelessly operates through a near field communication carrier signal from a smartphone to demonstrate anti‐cloning and authentic item‐tracking through its interconnection with the blockchain.
Antimony‐Doped Lead‐Free Zero‐Dimensional Tin(IV)‐Based Organic–Inorganic Metal Halide Hybrids with High Photoluminescence Quantum Yield and Remarkable Stability
Authors: Zhang Guodong , Dang Peipei , Xiao Hui , Lian Hongzhou , Liang Shuang , Yang Ling , Cheng Ziyong , Li Guogang , Lin Jun 
Published: October 2021

AbstractLead‐free organic–inorganic metal halide perovskites have attracted wide attention owing to their outstanding photophysical properties. Herein, a new type of antimony‐doped 0D tin(IV)‐based organic–inorganic metal halide hybrid (C10H16N2)SnCl6:Sb with highly efficient luminescence and remarkable stability is reported. Upon photoexcitation, the prepared samples exhibit an ultrabroadband emission ranging from 400 to 900 nm with two centers at 500 and 660 nm, which originate from free excitons and self‐trapped excitons, respectively. Such 0D metal halide hybrids with ultrabroadband emission covering the entire visible spectrum are rare. Especially, the photoluminescence quantum yield (PLQY) of red emission is as high as 77% upon 345 nm ultraviolet excitation. More importantly, (C10H16N2)SnCl6:Sb exhibits relatively good stability. It can still maintain 90% photoluminescence intensity after one week of 365 nm ultraviolet irradiation. Simultaneously, its PL intensity still retains 61% of room temperature emission intensity at 400 K. This work provides a new direction for the development of 0D organic–inorganic metal halide hybrids with excellent performance.
Recent Advances in the Synthesis and Ring‐Opening Transformations of 2‐Oxazolidinones
Authors: Sun Feixiang , Van der Eycken Erik V. , Feng Huangdi 
Published: October 2021

AbstractOxazolidinone represents a class of most important five‐membered cyclic carbamates. They are of great significance for modern organic synthesis and are widespread as pharmacologically active compounds. This review summarizes recent advances in the chemistry of 2‐oxazolidinones, with an emphasis on their synthesis, employing different catalytic systems or catalyst‐free conditions, as well as on their ring‐opening transformations through decarboxylative coupling, covering the period from 2010 to early 2021. Detailed mechanistic aspects are highlighted, hoping to help researchers to explore the hidden opportunities for reaction discoveries.magnified image
Crossbar Array of Artificial Synapses Based on Ferroelectric Diodes
Authors: Seufert Laura , HassanpourAmiri Morteza , Gkoupidenis Paschalis , Asadi Kamal 
Published: October 2021

AbstractTwo terminal devices that exhibit resistance switching in response to an external voltage are interesting for neuromorphic computing applications. Owing to its simple device structure, a crossbar array of two‐terminal resistance switching devices is highly desired for application as artificial neural network weights. Here, ferroelectric diodes that show resistance switching in their forward bias are presented. The resistance can be set to a high‐ and a low‐resistance state or any state between these limits. It is demonstrated that the ferroelectric diodes can function as an artificial synapse. An array of the ferroelectric diodes with two bit and two row lines (2 × 2) is demonstrated. The resistance of every bit is independently tuned, and spike‐time‐dependent plasticity is shown for the array.
Bipolar membrane electrodialysis for clean production of L‐10‐camphorsulfonic acid: From laboratory to industrialization
Authors: Yan Junying , Yan Haiyang , Wang Huangying , Li Qiuhua , Zhang Hongjun , Jiang Chenxiao , Ye Bangjiao , Wang Yaoming , Xu Tongwen 
Published: October 2021

AbstractIn this study, bipolar membrane electrodialysis (BMED) was implemented for cleaner production of L‐10‐camphorsulfonic acid (L‐CSA) to lower the environmental impact. Under the current density of 300–400 A/m2 and feed salt concentration of 6–10 wt.%, the energy consumption and current efficiency were 2.24–2.70 kWh/kg and 20.89–29.5%, respectively. Positron annihilation lifetime spectroscopy, x‐ray photoelectron spectroscopy with ion beam etching, and other characterizations were used to elucidate the transport behaviors of large‐sized anions across the membranes. It was speculated that the large‐sized camphor sulfonate ions were more likely to deposit on the surface of the anion‐exchange membrane to form a deposition layer under a direct current electric field. The appearance of water splitting at this deposition layer would offset the water dissociation in the bipolar membrane. Nevertheless, the successful commissioning of industrial‐scale stack proved the feasibility and sustainability of BMED technique for a closed loop L‐CSA production.
Sex differences in adipose development in a hunter‐gatherer population
Authors: Kramer Karen L. , Campbell Benjamin C. , Achenbach Alan , Hackman Joseph V. 
Published: October 2021

AbstractObjectiveHumans are unusually sexually dimorphic in body composition, with adult females having on average nearly twice the fat mass as males. The development of adipose sex differences has been well characterized for children growing up in food‐abundant environments, with less known about cross‐cultural variation, particularly in populations without exposure to market foods, mechanized technologies, schooling, vaccination, or other medical interventions.MethodsTo add to the existing cross‐cultural data, we fit multiple growth curves to body composition and anthropometric data to describe adipose development for the Savanna Pumé, South American hunter‐gatherers.Results(1) Little evidence is found for an adiposity ‘rebound’ at the end of early childhood among either Savanna Pumé girls or boys. (2) Rather, fat deposition fluctuates during childhood, from age ~4 to ~9 years, with no appreciable accumulation until the onset of puberty, a pattern also observed among Congo Baka hunter‐gatherers. (3) Body fat fluctuations are more pronounced for girls than boys. (4) The age of peak skeletal, weight, and adipose gains are staggered to a much greater extent among the Savanna Pumé compared to the National Health and Nutrition Examination Survey (NHANES III) reference, suggesting this is an important developmental strategy in lean populations.ConclusionDocumenting growth patterns under diverse preindustrial energetic conditions provides an important baseline for understanding sex differences in body fat emerging today under food abundance.
Heritable disorders of oxygen sensing
Authors: Semenza Gregg L. 
Published: October 2021

AbstractHypoxia‐inducible factors (HIFs) activate gene transcription in response to reduced O2 availability and play critical roles in development, physiology, and disease pathogenesis. Mutations that dysregulate HIF activity are the genetic basis for tumor predisposition in the von Hippel–Lindau syndrome and excess red blood cell production in hereditary erythrocytosis.
A novel MBTPS2 variant associated with BRESHECK syndrome impairs sterol‐regulated transcription and the endoplasmic reticulum stress response
Authors: Strong Alanna , March Michael E. , Cardinale Christopher J. , Kim Sophia E. , Merves Jamie , Whitworth Hilary , Raffini Leslie , Larosa Christopher , Copelovitch Lawrence , Hou Cuiping , Slater Diana , Vaccaro Courtney , Watson Deborah , Zackai Elaine H. , Billheimer Jeffrey , Hakonarson Hakon 
Published: October 2021

AbstractIchthyosis follicularis, atrichia, and photophobia syndrome (IFAP syndrome) is a rare, X‐linked disorder caused by pathogenic variants in membrane‐bound transcription factor protease, site 2 (MBTPS2). Pathogenic MBTPS2 variants also cause BRESHECK syndrome, characterized by the IFAP triad plus intellectual disability and multiple congenital anomalies. Here we present a patient with ichthyosis, sparse hair, pulmonic stenosis, kidney dysplasia, hypospadias, growth failure, thrombocytopenia, anemia, bone marrow fibrosis, and chronic diarrhea found by research‐based exome sequencing to harbor a novel, maternally inherited MBTPS2 missense variant (c.766 G>A; (p.Val256Leu)). In vitro modeling supports variant pathogenicity, with impaired cell growth in cholesterol‐depleted media, attenuated activation of the sterol regulatory element‐binding protein pathway, and failure to activate the endoplasmic reticulum stress response pathway. Our case expands both the genetic and phenotypic spectrum of BRESHECK syndrome to include a novel MBTPS2 variant and cytopenias, bone marrow fibrosis, and chronic diarrhea.
Conformational Preferences of Allene Ketones in Lewis Base Catalysis: Synthesis of 4H‐Pyrans and 3,4‐Dihydro‐2H‐pyrans via α‐Regioselective [4+2] Annulations of γ‐Substituted Allene Ketones and Activated Alkenes
Authors: Hou Rongrong , Wang Ziyu , Peng Jia , Yuan Ye , Zhang Jingli , Wang Du , Sun Taolei 
Published: October 2021

AbstractA Lewis base‐catalyzed exclusively α‐regioselective [4+2] annulation of γ‐substituted allene ketones with 2‐arylidene‐1,3‐indanediones to construct highly functionalized 3,4‐dihydro‐2H‐pyran isomers have been developed. The annulation reaction initiates with addition of NR3/PR3 to s‐cis‐ or s‐trans‐allene ketone to generate two geometrically distinct zwitterionic isomers, and the ratio of the two zwitterionic isomers depends on catalyst‐controlled conformation preference of s‐cis/s‐trans‐allene ketone. By utilizing cinchonine as the catalyst, s‐trans‐allene ketone usually leads to preferential formation of (3S, 4S)‐3‐benzoyl‐4‐ phenyl‐3,4‐dihydro‐2H‐pyran isomer 3. In contrast, s‐cis‐allene ketone mainly favors the formation of (3R, 4S)‐3‐benzoyl‐4‐phenyl‐3,4‐dihydro‐2H‐pyran isomer 5 under the catalysis of R,S‐Josiphos‐1. It's worth noting that only (3S, 4S)‐3‐benzoyl‐4‐phenyl‐3,4‐dihydro‐2H‐pyran half‐chair isomer 3 can easily isomerize into 4H‐pyran. Density functional theory calculations elucidated the origin of considerable difference in isomerization between isomer 3 and isomer 5.
A Practical Synthesis of N‐aryl/N‐alkyl 4‐Pyridones under Continuous Flow Technology
Authors: Li Weiqiang , Wu Qin , Xu Genrui , Sun Yinjing , Huang Chao , Liu Teng 
Published: October 2021

AbstractIn this report, a practical synthetic approach to access N‐aryl/N‐alkyl 4‐pyridones via a two‐step continuous flow process has been developed. In comparison to batch conditions, this [3+2+1] cycloaddition involving a three‐components cascade reaction of aniline, dialkyl ethoxymethyl enemalonate and dialkyl acetylenedicarboxylate under mild conditions, which can provide N‐aryl/N‐alkyl 4‐pyridone derivatives with a wider substrate scope and good to excellent yields.
Portal Venous Pulsatility Index as a predictor of fibrosis in patients with non‐alcoholic fatty liver disease
Authors: Lu Shisheng , Archard Robyn , Mcleod Linda , Banh Angus , Con Danny , Ardalan Zaid , Kutaiba Numan 
Published: October 2021

AbstractIntroductionNon‐alcoholic fatty liver disease (NAFLD) is a growing public health issue. Non‐invasive methods to assess the fibrosis stage are limited, and biopsy remains the gold standard. The objective of our study was to assess whether the portal venous pulsatility index (VPI) can be used as a predictor of high‐risk NAFLD at a tertiary referral centre for liver transplantation.MethodsWe retrospectively reviewed patients with biopsy‐proved NAFLD who had undergone a liver ultrasound scan within 1 year of biopsy at our centre from 2011 to 2019.ResultsWe did not find a significant correlation between the VPI and the NAFLD risk category or correlation between the VPI and degree of steatosis (P > 0.05 for both).ConclusionSince VPI can be easily obtained on routine liver ultrasound and since other studies do report a positive association with significant fibrosis, more studies are needed before it can be recommended or not in risk‐stratifying NAFLD patients into high‐ vs. low‐risk NAFLD.
Nitrene Photochemistry of Manganese N‐Haloamides**
Authors: Van Trieste Gerard P. , Reid Kaleb A. , Hicks Madeline H. , Das Anuvab , Figgins Matthew T. , Bhuvanesh Nattamai , Ozarowski Andrew , Telser Joshua , Powers David C. 
Published: October 2021

AbstractManganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C−H amination and olefin aziridination catalysis. The reactivity of the transient high‐valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N‐haloamide complexes. The S=2 N‐haloamide complexes are characterized by 1H NMR, UV‐vis, IR, high‐frequency and ‐field EPR (HFEPR) spectroscopies, and single‐crystal X‐ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C−H bonds, such as the α‐C−H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low‐temperature spectroscopy and analysis of kinetic isotope effects for C−H amination indicate halogen‐dependent photoreactivity: Photolysis of N‐chloroamides proceeds via initial cleavage of the Mn−N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N‐iodoamides proceeds via N−I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N‐haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group‐transfer catalysis.
Discovery and Mechanism of Action of Small Molecule Inhibitors of Ceramidases**
Authors: Healey Robert D. , Saied Essa M. , Cong Xiaojing , Karsai Gergely , Gabellier Ludovic , Saint‐Paul Julie , Del Nero Elise , Jeannot Sylvain , Drapeau Marion , Fontanel Simon , Maurel Damien , Basu Shibom , Leyrat Cedric , Golebiowski Jérôme , Bossis Guillaume , Bechara Cherine , Hornemann Thorsten , Arenz Christoph , Granier Sebastien 
Published: October 2021

AbstractSphingolipid metabolism is tightly controlled by enzymes to regulate essential processes in human physiology. The central metabolite is ceramide, a pro‐apoptotic lipid catabolized by ceramidase enzymes to produce pro‐proliferative sphingosine‐1‐phosphate. Alkaline ceramidases are transmembrane enzymes that recently attracted attention for drug development in fatty liver diseases. However, due to their hydrophobic nature, no specific small molecule inhibitors have been reported. We present the discovery and mechanism of action of the first drug‐like inhibitors of alkaline ceramidase 3 (ACER3). In particular, we chemically engineered novel fluorescent ceramide substrates enabling screening of large compound libraries and characterized enzyme:inhibitor interactions using mass spectrometry and MD simulations. In addition to revealing a new paradigm for inhibition of lipid metabolising enzymes with non‐lipidic small molecules, our data lay the ground for targeting ACER3 in drug discovery efforts.
A Striking Mode of Activation of Carbon Disulfide with a Cooperative Bis(silylene)
Authors: Luecke Marcel‐Philip , Giarrana Luisa , Kostenko Arseni , Gensch Tobias , Yao Shenglai , Driess Matthias 
Published: October 2021

AbstractThe reactivity of the 1,4‐substituted bis(silylenyl)terphenylene 1, 1,4‐[ortho‐(LSi)C6H4]2C6H4, (L=RC(NtBu)2, R=Ph, Mes) towards CS2 is reported. It results in a dearomatization of the phenylene ring, affording the 1,3‐substituted cyclohexadiene derivative 2. According to DFT calculations, a transient silene containing a Si=C bond capable of π(C=C) addition at the aromatic phenylene ring is a key intermediate. In contrast, addition of CS2 to the biphenyl‐substituted mono‐silylene ortho‐(LSi)C6H4‐C6H5 3 leaves the aromatic π‐system intact and forms, in a [1+2] cycloaddition reaction, the corresponding thiasilirane 4 with a three‐membered SiSC ring. Further experimental studies led to the isolation of the novel mesoionic five‐membered Si2S2C heterocycle 6, which reacts with CS2 under C−C bond formation. All isolated new compounds were fully characterized and their molecular structures determined by single‐crystal X‐ray diffraction analyses.
Installing a Green Engine To Drive an Enzyme Cascade: A Light‐Powered In Vitro Biosystem for Poly(3‐hydroxybutyrate) Synthesis
Authors: Li Fei , Wei Xinlei , Zhang Lin , Liu Cheng , You Chun , Zhu Zhiguang 
Published: October 2021

AbstractMany existing in vitro biosystems harness power from the chemical energy contained in substrates and co‐substrates, and light or electric energy provided from abiotic parts, leading to a compromise in atom economy, incompatibility between biological and abiotic parts, and most importantly, incapability to spatiotemporally co‐regenerate ATP and NADPH. In this study, we developed a light‐powered in vitro biosystem for poly(3‐hydroxybutyrate) (PHB) synthesis using natural thylakoid membranes (TMs) to regenerate ATP and NADPH for a five‐enzyme cascade. Through effective coupling of cofactor regeneration and mass conversion, 20 mM PHB was yielded from 50 mM sodium acetate with a molar conversion efficiency of carbon of 80.0 % and a light‐energy conversion efficiency of 3.04 %, which are much higher than the efficiencies of similar in vitro PHB synthesis biosystems. This suggests the promise of installing TMs as a green engine to drive more enzyme cascades.
Cation‐Deficiency‐Dependent CO2 Electroreduction over Copper‐Based Ruddlesden–Popper Perovskite Oxides
Authors: Zhu Jiawei , Wang Yanying , Zhi Aomiao , Chen Zitao , Shi Lei , Zhang Zhenbao , Zhang Yu , Zhu Yinlong , Qiu Xiaoyu , Tian Xuezeng , Bai Xuedong , Zhang Ying , Zhu Yongfa 
Published: October 2021

AbstractWe report an effective strategy to enhance CO2 electroreduction (CER) properties of Cu‐based Ruddlesden–Popper (RP) perovskite oxides by engineering their A‐site cation deficiencies. With La2−xCuO4‐δ (L2−xC, x=0, 0.1, 0.2, and 0.3) as proof‐of‐concept catalysts, we demonstrate that their CER activity and selectivity (to C2+ or CH4) show either a volcano‐type or an inverted volcano‐type dependence on the x values, with the extreme point at x=0.1. Among them, at −1.4 V, the L1.9C delivers the optimal activity (51.3 mA cm−2) and selectivity (41.5 %) for C2+, comparable to or better than those of most reported Cu‐based oxides, while the L1.7C exhibits the best activity (25.1 mA cm−2) and selectivity (22.1 %) for CH4. Such optimized CER properties could be ascribed to the favorable merits brought by the cation‐deficiency‐induced oxygen vacancies and/or CuO/RP hybrids, including the facilitated adsorption/activation of key reaction species and thus the manipulated reaction pathways.
The Formal Cross‐Coupling of Amines and Carboxylic Acids to Form sp3–sp3 Carbon–Carbon Bonds
Authors: Zhang Zirong , Cernak Tim 
Published: October 2021

AbstractWe have developed a deaminative–decarboxylative protocol to form new carbon(sp3)–carbon(sp3) bonds from activated amines and carboxylic acids. Amines and carboxylic acids are ubiquitous building blocks, available in broad chemical diversity and at lower cost than typical C−C coupling partners. To leverage amines and acids for C−C coupling, we developed a reductive nickel‐catalyzed cross‐coupling utilizing building block activation as pyridinium salts and redox‐active esters, respectively. Miniaturized high‐throughput experimentation studies were critical to our reaction optimization, with subtle experimental changes such as order of reagent addition, composition of a binary solvent system, and ligand identity having a significant impact on reaction performance. The developed protocol is used in the late‐stage diversification of pharmaceuticals while more than one thousand systematically captured and machine‐readable reaction datapoints are reposited.
Tailoring Co3d and O2p Band Centers to Inhibit Oxygen Escape for Stable 4.6 V LiCoO2 Cathodes
Authors: Kong Weijin , Zhang Jicheng , Wong Deniz , Yang Wenyun , Yang Jinbo , Schulz Christian , Liu Xiangfeng 
Published: October 2021

AbstractHigh‐voltage LiCoO2 delivers a high capacity but sharp fading is a critical issue, and the capacity decay mechanism is also poorly understood. Herein, we clarify that the escape of surface oxygen and Li‐insulator Co3O4 formation are the main causes for the capacity fading of 4.6 V LiCoO2. We propose the inhibition of the oxygen escape for achieving stable 4.6 V LiCoO2 by tailoring the Co3d and O2p band center and enlarging their band gap with MgF2 doping. This enhances the ionicity of the Co−O bond and the redox activity of Co and improves cation migration reversibility. The inhibition of oxygen escape suppresses the formation of Li‐insulator Co3O4 and maintains the surface structure integrity. Mg acts as a pillar, providing a stable and enlarged channel for fast Li+ intercalation/extraction. The modulated LiCoO2 shows almost zero strain and achieves a record capacity retention at 4.6 V: 92 % after 100 cycles at 1C and 86.4 % after 1000 cycles at 5C.
Chiral Heterogeneous Scandium Lewis Acid Catalysts for Continuous‐Flow Enantioselective Friedel–Crafts Carbon–Carbon Bond‐Forming Reactions
Authors: Saito Yuki , Kobayashi Shū 
Published: October 2021

AbstractWhile continuous‐flow reactions with chiral heterogeneous catalysts provide a highly efficient method to synthesize optically active compounds, chiral heterogeneous Lewis acid catalysis has been less extensively explored. We have developed the first example of chiral heterogeneous Sc catalysts, which demonstrated excellent activity and selectivity for continuous‐flow enantioselective Friedel–Crafts reactions of isatins with indoles. Noncovalent interactions between chiral Sc complexes and heteropoly acid‐anchored amine‐functionalized SiO2 as support were utilized for the synthesis. The heteropoly acid was found to be crucial for the preparation, activity, and selectivity of the catalysts. The chiral ligand could be easily tuned without chemical modification and the continuous‐flow synthesis of a biologically active compound was achieved.