bluuebunny/crossref_metadata_2025 huggingface dataset:
A Self‐Healing and Ionic Liquid Affiliative Polyurethane toward a Piezo 2 Protein Inspired Ionic Skin
Authors: Chen Chao , Ying Wu Bin , Li Jiayi , Kong Zhengyang , Li Fenglong , Hu Han , Tian Ying , Kim Do Hwan , Zhang Ruoyu , Zhu Jin
Published: October 2021

Ionic skin (I‐Skin) has the advantage of feasible compatibility with biological systems. Nevertheless, developing a stable and durable ionic skin is challenging. Here, an ionic polyurethane (i‐PU) is synthesized, which is capable of self‐healing and able to lock the ionic liquids (ILs). In detail, an ionic chain extender containing an ammonium cationic group is synthesized, followed by the polymerization to obtain the target i‐PU. Through electrostatic interaction and chain diffusion, the i‐PU can be fully self‐healed at room temperature within 400 min. Afterward, low contact angle (37°) of the i‐PU against IL and the density functional theory (DFT) calculation prove their good compatibility and strong interaction, originating from the electrostatic interaction. The Raman intensity map shows the reversible process of the enrichment and restoration of ionic concentration on the i‐PU/IL surface when external pressure is applied or released, proving stable binding of ions by ionic polymer chains. Lastly, the self‐healing I‐Skin based on the i‐PU/IL is fabricated with a wide range of pressures (0–120 kPa), fast response time (32 ms), excellent antifatigue property (2% attenuation after 1000 cycles), and remarkable sensitivity (52.4 kPa–1).
4D Printing of Engineered Living Materials
Authors: Rivera‐Tarazona Laura K. , Shukla Tarjani , Singh Kanwar Abhay , Gaharwar Akhilesh K. , Campbell Zachary T. , Ware Taylor H.
Published: October 2021

Herein, a method that uses direct‐ink‐write printing to fabricate engineering living materials (ELMs) that respond by undergoing a programmed shape change in response to specific molecules is reported. Stimuli‐responsiveness is imparted to ELMs by integrating genetically engineered yeast that only proliferate in the presence of specific biomolecules. This proliferation, in turn, leads to a shape change in the ELM in response to that biomolecule. These ELMs are fabricated by coprinting bioinks that contain multiple yeast strains. Locally, cellular proliferation leads to controllable shape change of the material resulting in up to a 370% increase in volume. Globally, the printed 3D structures contain regions of material that increase in volume and regions that do not under a given set of conditions, leading to programmable changes in form in response to target amino acids and nucleotides. Finally, this printing method is applied to design a reservoir‐based drug delivery system for the on‐demand delivery of a model drug in response to a specific biomolecule.
Amphipathic Binder Integrating Ultrathin and Highly Ion‐Conductive Sulfide Membrane for Cell‐Level High‐Energy‐Density All‐Solid‐State Batteries
Authors: Cao Daxian , Li Qiang , Sun Xiao , Wang Ying , Zhao Xianhui , Cakmak Ercan , Liang Wentao , Anderson Alexander , Ozcan Soydan , Zhu Hongli
Published: October 2021

Current sulfide solid‐state electrolyte (SE) membranes utilized in all‐solid‐state lithium batteries (ASLBs) have a high thickness (0.5–1.0 mm) and low ion conductance (<25 mS), which limit the cell‐level energy and power densities. Based on ethyl cellulose's unique amphipathic molecular structure, superior thermal stability, and excellent binding capability, this work fabricates a freestanding SE membrane with an ultralow thickness of 47 µm. With ethyl cellulose as an effective disperser and a binder, the Li6PS5Cl is uniformly dispersed in toluene and possesses superior film formability. In addition, an ultralow areal resistance of 4.32 Ω cm−2 and a remarkable ion conductance of 291 mS (one order higher than the state‐of‐the‐art sulfide SE membrane) are achieved. The ASLBs assembled with this SE membrane deliver cell‐level high gravimetric and volumetric energy densities of 175 Wh kg−1 and 675 Wh L−1, individually.
Modeling the Triboelectric Behaviors of Elastomeric Nonwoven Fabrics
Authors: Wang Yanan , Shim Eunkyoung , He Nanfei , Pourdeyhimi Behnam , Gao Wei
Published: October 2021

Theoretical modeling of triboelectric nanogenerators (TENGs) is fundamental to their performance optimization, since it can provide useful guidance on the material selection, structure design, and parameter control of relevant systems. Built on the theoretical model of film‐based TENGs, here, an analytical model is introduced for conductor‐to‐dielectric contact‐mode nonwoven‐based TENGs, which copes with the unique hierarchical structure of nonwovens and details the correlation between the triboelectric output (maximum transferred charge density) and nonwoven structural parameters (thickness, solidity, and average fiber diameter). A series of styrene–ethylene–butylene–styrene nonwoven samples are fabricated through a melt‐blowing process to map nonwoven structural features within certain ranges, while an ion‐injection protocol is adopted to quantify the triboelectric output with superior consistency and reproducibility. With a database containing structural features and triboelectric output of 43 nonwoven samples, a good model fitting is achieved via nonlinear regression analysis in Python, which also shows good predictive power and suggests the existing of tribo‐output maxima at a specific thickness, solidity, or average fiber diameter when other structural parameters are fixed. The model is also successfully applied to a group of polypropylene meltblown nonwovens, which verifies its universality on meltblown‐nonwoven‐based TENGs.
2D Piezoelectric Bi2MoO6 Nanoribbons for GSH‐Enhanced Sonodynamic Therapy
Authors: Dong Yushan , Dong Shuming , Liu Bin , Yu Chenghao , Liu Jing , Yang Dan , Yang Piaoping , Lin Jun
Published: October 2021

Reducing the scavenging capacity of reactive oxygen species (ROS) and elevating ROS production are two primary goals of developing novel sonosensitizers for sonodynamic therapy (SDT). Hence, ultrathin 2D Bi2MoO6–poly(ethylene glycol) nanoribbons (BMO NRs) are designed as piezoelectric sonosensitizers for glutathione (GSH)‐enhanced SDT. In cancer cells, BMO NRs can consume endogenous GSH to disrupt redox homeostasis, and the GSH‐activated BMO NRs (GBMO) exhibit an oxygen‐deficient structure, which can promote the separation of electron–hole pairs, thereby enhancing the efficiency of ROS production in SDT. The ultrathin GBMO NRs are piezoelectric, in which ultrasonic waves introduce mechanical strain to the nanoribbons, resulting in piezoelectric polarization and band tilting, thus accelerating toxic ROS production. The as‐synthesized BMO NRs enable excellent computed tomography imaging of tumors and significant tumor suppression in vitro and in vivo. A piezoelectric Bi2MoO6 sonosensitizer‐mediated two‐step enhancement SDT process, which is activated by endogenous GSH and amplified by exogenous ultrasound, is proposed. This process not only provides new options for improving SDT but also broadens the application of 2D piezoelectric materials as sonosensitizers in SDT.
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

As 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

Lead‐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

Oxazolidinone 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

Two 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

In 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.
Large‐Area Piezoresistive Tactile Sensor Developed by Training a Super‐Simple Single‐Layer Carbon Nanotube‐Dispersed Polydimethylsiloxane Pad
Authors: Cho Min-Young , Lee Jin-Woong , Park Chaewon , Lee Byung Do , Kyeong Joon Seok , Park Eun Jeong , Lee Kee Yang , Sohn Kee-Sun
Published: October 2021

The revolutionary concept of creating a large‐area tactile sensor by training a simple, bulky material through deep learning (DL) is proposed. This enables the replacement of the conventional tactile sensor comprising a patterned array structure with a super‐simple, single‐layer, large‐area tactile sensor pad. A crude carbon nanotube‐dispersed polydimethylsiloxane pad—with a bias applied to the center and the resultant piezoresistive current detected at several electrodes located on the pad edge—plays a smart sensory role without the need for complicated fabrication of microengineered structures. The piezoresistive current while recording the indented location and the pressure thereon is measured, and then various DL models (a multimodel arrangement is necessary due to the viscoelasticity of the pad) using the collected data are trained. The proposed concept is realized using a tandem model comprising a combination of algorithms selected from deep neural networks, convolutional neural networks, long short‐term memory networks, and 16 state‐of‐the‐art machine learning algorithms. The hold‐out dataset test accuracy for the indented location identification reaches 98.89%, and the goodness of fit for pressure prediction is evaluated with mean squared error of 2.5 × 10−3and coefficient of determination of 98.05%.
Fabrication of Soft and Wearable Electrostatic Generator Based on Streaming Electrification
Authors: Kamiyauchi Shota , Yokoyama Yuki , Kuwajima Yu , Seki Yumeta , Awaki Satoshi , Maeda Shingo , Shigemune Hiroki
Published: October 2021

Electrostatic actuators, which are characterized by low weight, power consumption, noise, and remaining heat, have been studied widely and are expected to find use in wearable devices. However, they require high‐voltage control and safety circuits, which may increase their bulk. Herein, a soft electrostatic generator is proposed for use in wearable devices. Specifically, streaming electrification is used, wherein electric charge is generated through the interactions between a fluid and a solid material (the developed system is named a “streaming electrification generator”). The contact area with the insulating fluid is increased by using a porous material, and the amount of charge generated is increased to the level needed to drive electrostatic actuators using materials with different dielectric characteristics. Moreover, the generator is made of soft materials and therefore can adapt to the shape of the human body and not interfere with its movement. Finally, it is ideal for wearables because it does not use materials that are harmful to the human body. Thus, the developed system, which is made of soft materials, is a novel power generator and should be suitable for electrostatic actuators used in wearable devices.
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

Objective

Humans 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.

Methods

To 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.

Conclusion

Documenting 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

Hypoxia‐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

Ichthyosis 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

A 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

In 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

Introduction

Non‐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.

Methods

We 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.

Results

We 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).

Conclusion

Since 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

Manganese 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

Sphingolipid 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

The 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

Many 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

We 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

We 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

High‐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

While 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.
Eutectic Crystallization Activates Solid‐State Zinc‐Ion Conduction
Authors: Qiu Huayu , Hu Rongxiang , Du Xiaofan , Chen Zhou , Zhao Jingwen , Lu Guoli , Jiang Meifang , Kong Qingyu , Yan Yiyuan , Du Junzhe , Zhou Xinhong , Cui Guanglei
Published: October 2021

Solid‐state zinc (Zn) batteries offer a new candidate for emerging applications sensitive to volume, safety and cost. However, current solid polymeric or ceramic electrolyte structures remain poorly conductive for the divalent Zn2+, especially at room temperature. Constructing a heterogeneous interface which allows Zn2+ percolation is a viable option, but this is rarely involved in multivalent systems. Herein, we construct a solid Zn2+‐ion conductor by inducing crystallization of tailored eutectic liquids formed by organic Zn salts and bipolar ligands. High‐entropy eutectic‐networks weaken the ion‐association and form interfacial Zn2+‐percolated channels on the nucleator surfaces, resulting in a solid crystal with exceptional selectivity for Zn2+ transport (t
=0.64) and appreciable Zn2+ conductivity (σ
=3.78×10−5 S cm−1 at 30 °C, over 2 orders of magnitude higher than conventional polymers), and finally enabling practical ambient‐temperature Zn/V2O5 metal solid cells. This design principle leveraged by the eutectic solidification affords new insights on the multivalent solid electrochemistry suffering from slow ion migration.
A Molecular Compound for Highly Selective Purification of Ethylene
Authors: Noonikara‐Poyil Anurag , Cui Hui , Yakovenko Andrey A. , Stephens Peter W. , Lin Rui‐Biao , Wang Bin , Chen Banglin , Dias H. V. Rasika
Published: October 2021

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a “live” picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented.
Divergent Synthesis of Skeletally Distinct Arboridinine and Arborisidine
Authors: Wang Cheng , Pang Yubing , Wu Yuecheng , Zhang Nanping , Yang Rui , Li Ying , Chen Pengquan , Jiang Huanfeng , Xu Xue‐Tao , Kam Toh‐Seok , Fan Ting , Ma Zhiqiang
Published: October 2021

A divergent synthesis of skeletally distinct arboridinine and arborisidine was achieved. The central divergent strategy was inspired by the divergent biosynthetic cyclization mode of arboridinine and arborisidine and their hidden topological connection. The branch point was reached through a Michael and Mannich cascade process. A site‐selective intramolecular Mannich reaction was developed to construct the tetracyclic core of arboridinine, while a site‐selective intramolecular α‐amination of ketone was used to access the tetracyclic core of arborisidine. A strategic Peterson olefination through intramolecular nucleophile delivery was able to set up the exocyclic olefin of arboridinine.
Dual Nanoislands on Ni/C Hybrid Nanosheet Activate Superior Hydrazine Oxidation‐Assisted High‐Efficiency H2 Production
Authors: Zhu Yin , Zhang Jihua , Qian Qizhu , Li Yapeng , Li Ziyun , Liu Yi , Xiao Chong , Zhang Genqiang , Xie Yi
Published: October 2021

Clean hydrogen evolution through electrochemical water splitting underpins various innovative approaches to the pursuit of sustainable energy conversion technologies, but it is blocked by the sluggish anodic oxygen evolution reaction (OER). The hydrazine oxidation reaction (HzOR) has been considered as one of the most promising substitute for OER to improve the efficiency of hydrogen evolution reaction (HER). Herein, we construct novel dual nanoislands on Ni/C hybrid nanosheet array: one kind of island represents the part of bare Ni particle surface, while the other stands for the part of core–shell Ni@C structure (denoted as Ni‐C HNSA), in which exposed Ni atoms and Ni‐decorated carbon shell perform as active sites for HzOR and HER respectively. As a result, when the current density reaches 10 mA cm−2, the working potentials are merely −37 mV for HER and ‐20 mV for HzOR. A two‐electrode electrolyzer exhibits superb activity that only requires an ultrasmall cell voltage of 0.14 V to achieve 50 mA cm−2.
Macrocyclic Donor–Acceptor Dyads Composed of a Perylene Bisimide Dye Surrounded by Oligothiophene Bridges
Authors: Bold Kevin , Stolte Matthias , Shoyama Kazutaka , Holzapfel Marco , Schmiedel Alexander , Lambert Christoph , Würthner Frank
Published: October 2021

Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide (PBI) dye have been synthesized via a platinum‐mediated cross‐coupling strategy. The crystal structure of the double bridged PBI reveals allsyn‐arranged thiophene units that completely enclose the planar PBI chromophore via a 12‐membered macrocycle. The target structures were characterized by steady‐state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Both donor–acceptor dyads show ultrafast Förster Resonance Energy Transfer and photoinduced electron transfer, thereby leading to extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent.
UV‐induced oxygenation of toluene enhanced by Co (acac)2/9‐mesityl‐10‐methylacridinium ion/N‐hydroxyphthalimide tandem
Authors: Pokutsa Alexander , Ohkubo Kei , Zaborovski Andriy , Bloniarz Pawel
Published: October 2021

The effect of near‐UV irradiation on the oxygenation of toluene dissolved in MeCN was studied in a stainless‐steel reactor upon O2 bubbling at 80°C and 100°C and 10 atm using Co (acac)2 and 9‐mesityl‐2,7,10‐trimethylacridinium perchlorate (Me2Acr+–Mes ClO4−) as the catalyst and photocatalyst, respectively. In the absence of the process mediator N‐hydroxyphthalimide (NHPI), the rate of PhCH3 oxidation was extremely low, leading to trace amounts of the products formed. The presence of NHPI and the irradiation with UV light enhanced the substrate oxygenation and benzyl alcohol, benzaldehyde, and benzoic acid yield substantially by three to four times. The relative content of the last product was lowest at the beginning of the process as well as in light‐excited oxygenation. In this report, we highlight the mechanism of catalyst, photocatalyst, and mediator combined effect on product yield and composition.
Experimental study on an oil‐based polymer gel for lost circulation control in high‐temperature fractured formation
Authors: Qiu Jiaxian , Bai Yingrui , Sun Jinsheng , Dai Liyao , Lei Shaofei , Liu Fan
Published: October 2021

Aiming at the lack of plugging agent for oil‐based drilling fluid leakage in fractured formation, an oil‐based gel‐plugging agent with high structural strength and strong thermal stability was synthesized based on monomer polymerization and crosslinking. According to the preparation experiment, when the total concentration of methyl methacrylate (MMA) and butyl acrylate (BA) is 30% and the ratio is 6:4, the oil‐based gel solution can be completely gelatinized from 80 to 200°C, which has high gel strength and controllable gelation time. The effects of total concentration of BA and MMA, the ratio of BA and MMA, synthesis temperature, oil‐based drilling fluid invasion, shear effect, and fiber concentration on gelling performance were systematically studied. Fourier transform infrared molecular structure analysis showed that the oil‐based gel contained benzene ring group and ester characteristic group. From the rheological properties of oil‐based gel with 30% gelling agent at 160°C, it could be seen that the elastic modulus G′ of 10 Hz is 232 kPa, which is much larger than the storage modulus G″ is 99 kPa, which reflects the solid properties and has good elasticity and high strength. The displacement experiment of sand filling pipe and dynamic and static plugging experiment of high temperature and high pressure shows that the oil‐based gel has high bearing capacity in fractures and sand filling pipe. The bearing pressure is 3.01 MPa in 6 mm fractures, and the bearing pressure gradient is 0.602 MPa/cm.
Cross‐dehydrogenative Coupling of N‐Aryl Tetrahydroisoquinolines Catalyzed by an Anthraquinone‐containing Polymeric Photosensitizer
Authors: Wang Fei , Yu Dan , Chen Yang , Sun Jing , Wang Jing‐Yun , Zhou Ming‐Dong
Published: October 2021

This work reports the photocatalytic application of an anthraquinone‐containing polymeric photosensitizer (AQ‐PHEMA) in the visible light‐induced cross‐dehydrogenative‐coupling of N‐aryl tetrahydroisoquinolines with several nucleophiles, including nitromethane, 1‐methyl‐2‐alkyl ketone and dialkyl (aryl) phosphine oxide. The results revealed that the reaction could be catalyzed by AQ‐PHEMA efficiently to afford a series of 1‐substituted‐2‐aryl‐1,2,3,4‐tetrahydroisoquinolines in good to excellent yields with nice substrate tolerance under aerobic conditions at room temperature. The practical application potential was also showcased by a gram‐scale synthesis. More importantly, the utilization of AQ‐PHEMA as a heterogeneous photosensitizer also showed nice recyclability and reusability of the catalyst, whereas AQ‐PHEMA can be easily separated and reused for at least 8 times without significant loss of photocatalytic activity.
Human neutrophil peptide 1 promotes immune sterilization in vivo by reducing the virulence of multidrug‐resistant Klebsiella pneumoniae and increasing the ability of macrophages
Authors: Wang Hui‐Yun , Chen Xiao‐chun , Yan Zhi‐han , Tu Fan , He Tian , Gopinath Subash C. B. , Rui Xiao‐hong , Cao Fu‐tao
Published: October 2021

By studying the expression in patients and cell modeling in vitro, antimicrobial peptides for Klebsiella were screened. Killing curve and membrane permeability experiments are used to study the antibacterial effect of antimicrobial peptides in vitro. Cytotoxicity‐related indicators including lipopolysaccharide (LPS), capsule polysaccharide (CPS), and outer membrane protein expression were measured. Intranasal inoculation of pneumoconiosis was used to construct a mouse infection model, and the survival rate and cytokine expression level were tested. Human neutrophil peptide 1 (HNP‐1) showed a significant antibacterial effect, which improved the permeability of the outer membrane of K. pneumoniae. Moreover, HNP‐1 decreased LPS, CPS content, and outer membrane proteins. K. pneumoniae infection decreased antimicrobial peptide, oxidative stress, and autophagy‐related genes, while HNP‐1 increased these genes. After coculture with macrophages, the endocytosis of macrophages is enhanced and the bacterial load is greater in the K. pneumoniae + peptide group. Besides, higher levels of pp38 and pp65 in the K. pneumoniae + peptide group. HNP‐1 rescued the cytotoxicity induced by K. pneumoniae. The survival rate is significantly improved after K. pneumoniae is treated by HNP‐1. All cytokines in the peptide group were significantly higher. HNP‐1 promotes immune sterilization by reducing the virulence of multidrug‐resistant K. pneumoniae and increasing the ability of macrophages.
Active learning tools improve the learning outcomes, scientific attitude, and critical thinking in higher education: Experiences in an online course during the COVID‐19 pandemic
Authors: Rossi Izadora Volpato , de Lima Jordana Dinorá , Sabatke Bruna , Nunes Maria Alice Ferreira , Ramirez Graciela Evans , Ramirez Marcel Ivan
Published: October 2021

Active teaching methodologies have been placed as a hope for changing education at different levels, transiting from passive lecture‐centered to student‐centered learning. With the health measures of social distance, the COVID‐19 pandemic forced a strong shift to remote education. With the challenge of delivering quality education through a computer screen, we validated and applied an online course model using active teaching tools for higher education. We incorporated published active‐learning strategies into an online construct, with problem‐based inquiry and design of inquiry research projects to serve as our core active learning tool. The gains related to students' science learning experiences and their attitudes toward science were assessed by applying questionnaires before, during, and after the course. The course counted on the participation of 83 students, most of them (60.8%) from postgraduate students. Our results show that engagement provided by active learning methods can improve performance both in hard and soft skills. Students' participation seems to be more relevant when activities require the interaction of information, prediction, and reasoning, such as open‐ended questions and design of research projects. Therefore, our data show that, in pandemic, active learning tools benefit students and improve their critical thinking and their motivation and positive positioning in science.
Neuroanatomical differences in the memory systems of intellectual giftedness and typical development
Authors: Kuhn Taylor , Blades Robin , Gottlieb Lev , Knudsen Kendra , Ashdown Christopher , Martin‐Harris Laurel , Ghahremani Dara , Dang Bianca H. , Bilder Robert M. , Bookheimer Susan Y.
Published: October 2021

Introduction

Studying neuro‐structural markers of intellectual giftedness (IG) will inform scientific understanding of the processes helping children excel academically.

Methods

Structural and diffusion‐weighted MRI was used to compare regional brain shape and connectivity of 12 children with average to high average IQ and 18 IG children, defined as having IQ greater than 145.

Results

IG had larger subcortical structures and more robust white matter microstructural organization between those structures in regions associated with explicit memory. TD had more connected, larger subcortical structures in regions associated with implicit memory.

Conclusions

It was found that the memory systems within brains of children with exceptional intellectual abilities are differently sized and connected compared to the brains of typically developing children. These different neurodevelopmental trajectories suggest different learning strategies. A spectrum of intelligence types is envisioned, facilitated by different ratios of implicit and explicit system, which was validated using a large external dataset.