bluuebunny/crossref_metadata_2025 huggingface dataset:
Paper without a Trail: Time‐Dependent Encryption using Pillar[5]arene‐Based Host–Guest Invisible Ink
Authors: Ju Huaqiang , Zhu Chao Nan , Wang Hu , Page Zachariah A. , Wu Zi Liang , Sessler Jonathan L. , Huang Feihe
Published: November 2021

A stimuli‐responsive invisible ink for time‐dependent encryption of information is reported. Consisting of a pillar[5]arene‐based supramolecular network grafted with spiropyran moieties, these materials display time‐dependent photochromic behavior with tailorable fading rates. Ultraviolet (UV) light results in isomerization of the colorless spiropyran to the corresponding colored merocyanine, while visible light or heat causes the reverse isomerization with a rate that is dependent on the density of host–guest crosslinks. The kinetics of discoloration are a function of merocyanine aggregation, which becomes more pronounced as the host–guest crosslink density is increased, leading to a reduced conversion rate and slower time‐dependent fading. The degree of crosslinking, and hence the fading rate, may be modulated via the addition of unbound pillar[5]arene host or nitrile guest as competitors. Time‐dependent information encryption is enabled by combining selective placement of host and guest competitors and UV patterning. UV patterning provides an initially “false” image that does not reveal the desired information, and it is only after a given time that the encrypted data appears. This work provides a unique approach to enhance the security of information storage associated with offline portable data encryption.
Recent Development of Liquid Metal‐Based Functional Materials Combined with Common Transition Metals
Authors: Wang Yang , Guo Jiarui , Xiao Wenlong , Sun Kang , Wang Hongzhang , Hu Liang
Published: November 2021

Gallium‐based liquid metals (LMs) are a group of metal materials that are in liquid state at room temperature. Their unique physiochemical properties such as fluidity, conductivity, and interfacial properties with other materials have presented great potentials and wide applications. Specifically, the interactions between gallium‐based LMs and some common but important transition metals (TMs) have not only enabled a series of intriguing phenomena but also provided valuable strategies or functional materials in soft robotics, devices, flexible electronics, addictive manufacturing, biomedical engineering and therapies, and other fields. The chemical mechanisms including the galvanic corrosion, infiltration, intermetallic compound formation should play vital roles within these interactions. Hereby the combining the LMs and TMs by alloying or physically mixing may offer a platform to develop novel and multifunctional materials system. To acquire a comprehensive understanding of those interactions as well as to inspire the researches for multifunctional materials design and applications, this article reviews the researches on the combination of LMs and TMs, discusses the characteristics, the mechanisms, and their applications especially in electronics, smart materials, and biomedicine. The main challenges and future research outlook are also discussed.
Carbon Nanotube Membranes in Water Treatment Applications
Authors: Barrejón Myriam , Prato Maurizio
Published: November 2021

Carbon nanotube (CNT)‐based membranes combine the promising properties of CNTs with the advantages of membrane separation technologies, offering enhanced membrane performance in terms of permeability and selectivity. This review looks at the existing membrane architectures based on CNTs and their main advantages and disadvantages for water treatment applications. The different types of CNT‐based membranes that are reported in the literature are highlighted, as well as their corresponding fabrication methods. Available methodologies for tailoring the final membrane properties and behavior are thoroughly discussed, making special emphasis in chemical modification of the CNT surface. Finally, the most common applications of CNT‐based membranes in water treatment are reviewed, including seawater or brine desalination, oil–water separation, removal of heavy metals, and organic pollutants. The main limitations and perspectives of CNT‐based membranes are also briefly outlined.
Quasistatic Equilibrium Chemical Vapor Deposition of Graphene
Authors: Ullah Sami , Ta Huy Q. , Yang Xiaoqin , Liu Yu , Hasan Maria , Bachmatiuk Alicja , Liu Lijun , Rümmeli Mark H.
Published: November 2021

This study reviews the majorly used chemical vapor deposition (CVD) with a focus on confined reaction configurations in which quasistatic equilibrium conditions are obtained for the fabrication of graphene with large size and high quality through controlled nucleation density, feedstock flux, and growth rates. The confinement configurations can also be used to tune the thickness, domain size and shape, and stacking order of the synthetic graphene. The confined CVD reaction configurations discussed include enclosure systems, inner‐tube setups, sandwiched substrates, as well as other types of configurations. The advantages and limitations of the different confinement configurations are presented, along ways to optimize the operational parameters for them.
Nucleophilic Etching Growth of Zeolite Materials with High Tunability
Authors: Dong Lei , Chen Yanpeng , Wang Ya , Wang Yanding , Gao Jinqiang , Zhu Rongshu , Hong Mei , Yang Shihe
Published: November 2021

Etching growth is widely employed for growing metal species, carving out some of the finest nanocrystals. However, such a general concept has so far evaded the growth of porous crystals. Herein, a novel nucleophilic etching growth mechanism that can be exploited to tune zeolite materials is uncovered. Most critical is the identification of mild etchant used in situ to successfully synthesize high‐quality hierarchically porous ZSM‐5 crystals. Time‐series sample characterizations allow to visualize and track the complex zeolite crystallization pathway involving initial nucleation, intermediate dissolution, and subsequent nanoparticle attachment regrowth. Competition and cooperation between framework growth and in situ dissolution lead to facile control over size, morphology, crystallinity, composition, and mesoporosity by varying the amount of etchant or nucleophilicity. The judicious use of this mechanism results in dramatically improved catalytic activity in methanol to hydrocarbon reactions owing to the simultaneously increased crystallinity, secondary mesopores, and proper acid properties.
A Magnetic‐Driven Switchable Adhesive Superhydrophobic Surface for In Situ Sliding Control of Superparamagnetic Microdroplets
Authors: Hu Dongdong , Lai Hua , Cheng Zhongjun , Song Yingbin , Luo Xin , Zhang Dongjie , Fan Zhimin , Xie Zhimin , Liu Yuyan
Published: November 2021

Droplet manipulation plays an important role in many fields, and smart adhesion control on superhydrophobic surfaces is widely accepted as an effective strategy. However, some imperfections such as long response time and deformable elastic materials are still difficult to be avoided for existing methods. Herein, a new strategy is reported to reversibly control the surface adhesion and droplet's sliding without the change of surface chemistry and microstructure. A novel superhydrophobic surface is prepared by integrating a substrate with a certain size of NdFeB magnetic region and a hydrophobic SiO2 coating. The magnetic region on the surface is highly adhesive, which can pin a superparamagnetic droplet tightly. As an external magnet (EM) with opposite direction of magnetic flow to the NdFeB magnetic region is put above the droplet, the droplet rolls off as the surface is tilted, indicating that the high adhesive region has turned into the low adhesive state and in situ droplet's sliding control is realized. After removing the EM, the magnetic region on the surface can regain the high adhesion, demonstrating an excellent controllability. Finally, based on the smart controllability, the surface with several magnetic regions is designed and on‐demand storage/release control of different droplets is demonstrated.
Manifold Mechanical Deformations of Organic Crystals with Optical Waveguiding and Polarization Rotation Functions
Authors: Tang Baolei , Yu Xu , Ye Kaiqi , Zhang Hongyu
Published: November 2021

Although manifold flexible organic crystals with various kinds of mechanical properties have been reported recently, most of them only possess a single one that is either plastic or elastic. It is because different mechanical deformations require distinct packing structures and intermolecular interactions. Given that the organic crystal has an anisotropic physical nature it is possible but challenging to combine multiple mechanical deformation capabilities into one single crystal. Herein, based on a known organic molecule (Z)‐3‐(4‐(dimethylamino)phenyl)‐2‐phenylacrylonitrile (DPPC), a single crystal is obtained that exhibits three different mechanical properties, namely, elastic bending, thermoplastic bending and plastic twisting deformation. Notably, the unique DPPC crystal could serve as a quite good optical waveguiding medium in the straight, elastically bent and thermoplastic bent states. The crystals are also successfully applied for tuning the polarization direction of the light emitting from the crystal, and thus confirm the famous prediction that twisted crystals can tune polarization direction as liquid crystals do proposed by C. Mauguin in 1911. This study not only has scientific significance in guiding flexibility engineering but also provides a model of flexible organic crystals for multifunctional application in optical devices.
Fluorescence–Phosphorescence Manipulation and Atom Probe Observation of Fully Inorganic Silver Quantum Clusters: Imitating from and Behaving beyond Organic Hosts
Authors: Zheng Wenyan , Zhou Bo , Ren Zhijun , Xu Xiuxia , Yang Guang , Qiao Xvsheng , Yan Dongpeng , Qian Guodong , Fan Xianping
Published: November 2021

Silver quantum clusters (Ag QCs) have attracted great attention due to their unique electronic structure and molecule‐like photoluminescence (PL). Applications in catalysis, biology, and optoelectronics have already been realized, however, the understanding of PL mechanism and direct observation of Ag QCs still remain challenging. Here, fully inorganic Ag QCs well stabilized in the borate glass with simultaneous excellent chemical stability, tunable PL emission, and high quantum yield are prepared. And the PL properties of Ag QCs respond drastically to changes of the embedding environment, displaying pronounced fluorescence to phosphorescence (F‐P) switching. Combining the structural and spectral analysis, it is found that the F‐P switching is triggered by the Ag QCs aggregation and [BO3]→[BO4]− conversion of the borate network. Using atom probe tomography enables to quantitatively characterize the evolution of Ag QCs at an atomic level, which reveals that Ag QCs consisting of less than 20 atoms are responsible for the observed PL.
Triplet Exciton Enhanced Radioluminescence of Ga3+/Tb3+ Metallacrown Scintillators for X‐Ray Detection
Authors: Chen Zi , Lu Dongdong , Xie Hangqing , Yang Xiaolei , Li Yang , Bao Chenhao , Lei Lei , Xu Shiqing
Published: November 2021

The increasing demand for radiation detection in many applications has led to demanding requirements for scintillators. Realizing low‐dose, pollution‐free, and reliable X‐ray detection has become a key technical challenge. Here, a triplet‐enhanced lanthanide radioluminescence (RL) material Ga3+/Tb3+ metallacrowns (Tb‐1) is reported. This Tb‐1 crystal emits bright green luminescence under ultraviolet light or X‐ray excitation, and the emission intensity is 286 and 242 times that of Tb3+ in inorganic salt, respectively. Tb‐1 crystal is further passivated by trioctylphosphine oxide (TOPO), and the enhanced RL intensity is equivalent to that of commercial Tl‐doped cesium iodide scintillator. In addition, RL of Tb‐1–TOPO has an extremely narrow full width at half maximum and an excellent linear response to the X‐ray dose rate. The detection limit is calculated to be 0.146 μGy s−1, which is 38 times lower than typical medical imaging doses. Triplet‐enhanced lanthanide RL provides new ideas for replacing scintillators that require high temperature synthesis processes such as inorganic phosphors and ceramics, and provides a new alternative scintillator material for flexible X‐ray monitoring, bioimaging, radiotherapy, and other applications.
A Stable and Efficient Red‐Emitting Color Converter Based on K2SiF6:Mn4+ Phosphor‐in‐Glass Film for Next‐Generation Laser‐Excited Lighting and Display
Authors: Si Shuaichen , Huang Lin , Zhang Xuejie , Wang Jing
Published: November 2021

Laser diodes (LDs) are expected to be the next‐generation high luminance sources because of the unobvious “efficiency droop” phenomenon under high power. To achieve high‐quality white lighting, red emission is essential for white lighting devices. K2SiF6:Mn4+ (KSFM) is a highly suitable red phosphor for its strong broadband excitation in the UV and blue region and intense red emission at 631 nm. In addition, the ultranarrow emission makes it suitable for wide gamut displays. Herein, a stable and easily prepared red color converter, KSFM based phosphor‐in‐glass films on a coated sapphire substrate (CSA) is developed, which exhibits a high thermal conductivity of 32.02 W m−1 K−1. Compared with the KSFM phosphor, this KSFM–CSA composite shows an overall increase in thermal quenching and irradiation resistance abilities. A wide color gamut covering 128% of the National Television Standards Committee (NTSC) standard white LD (WLD) is fabricated by coupling a green‐emitting CsPbBr3 embedded glass plate and red‐emitting KSFM–CSA with blue LDs. Furthermore, a high‐quality WLD with a luminous flux (520 lm), luminous efficiency (93.0 lm W−1), and color rendering index (CRI, 81.4) is achieved. With its excellent properties, the KSFM–CSA has great potential in high‐power laser lighting and display.
Site‐Selective 1,4‐Difunctionalization of Nitrogen Heteroaromatics for Constructing Vinylidene Heterocycles
Authors: He Qianlin , Zhong Mingli , Chen Zhichao , Liao Chuyi , Xie Feng , Zhu Zhongzhi , Chen Xiuwen
Published: November 2021

A one‐pot protocol for constructing 1,4‐difunctionalized quinoline/pyridine derivatives via the reaction of N‐heteroaromatics, alkyl halides, and active methylene/methyl compounds was developed. The transformation involves dearomative functionalization of an in situ‐activated N‐heteroaromatic to construct new C−N and C=C bonds. This reaction has a broad substrate scope and functional group tolerance.

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Enantiodivergent Reaction of Ketimines with Malononitriles Using Single Cinchona Alkaloid Sulfonamide Catalysts
Authors: Nakamura Shuichi , Matsumoto Natsuki , Kibe Masato , Abe Kazuki , Takehara Tsunayoshi , Suzuki Takeyuki
Published: November 2021

We report the enantiodivergent reaction of ketimines derived from α‐ketoesters with malononitriles using a single chiral source. The reactions using an 8‐quinolinesulfonyl cinchona alkaloid catalyst in the presence and absence of Et2Zn gave both enantiomers in high yields with high enantioselectivities (53∼99% yield, 99:1∼3:97 er). The obtained malononitrile‐derived α‐amino acids were converted into various optically active compounds. A reaction mechanism is proposed to explain the observed enantiodivergency.

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Efficient Method to Catch Adsorption Behavior: Understanding the Effect of Sodium Ions on Benzene/Thiophene Adsorption in Na‐FAU
Authors: Zhou Xinming , Su Li , Si Fang , Wang Yajun , Zhang Tianhao , Wang Youhe , Yang Chaohe , Fu Hui
Published: November 2021

In this paper, grand canonical Monte Carlo simulations are applied to study the adsorption performance of thiophene and benzene. Pure adsorption and binary adsorption are performed in all silica faujasite (FAU) and Na‐FAU zeolite combined with density distributions and radial distribution functions (RDF). A new method to describe the adsorption mechanism in FAU has been proposed. One adsorbate is fixed in the center of 12 ring (12C) or the center of supercage (CSC) as the reference point. Then, RDFs represent the probability to find other adsorbates in a shell at the distance r of the reference point. Thus, the adsorption sites appeared are obtained as several ring shape areas. The intersection points, especially with high occurrence possibilities, is regarded as the main adsorption sites, showing good agreement with density distribution. Comparing RDFs of sorbate‐12C and the location of Na ions, the curve of thiophene‐12C and the curve of Na‐12C overlap can be found, which means thiophene prefers to adsorb around Na ions. On this point, the reason why the separation property of Na‐FAU zeolites is better than that of all silica FAU zeolites can be clearly explained.
Abnormal Electromechanical Property of Nonlinearly Graded Lead‐Free Ferroelectric Thin Films
Authors: Lich Le Van , Bui Tinh Quoc , Shimada Takahiro , Kitamura Takayuki , Hong Hue Dang Thi , Nguyen Trong‐Giang , Dinh Van‐Hai
Published: November 2021

A phase field model for nonlinearly graded ferroelectric thin films is developed based on the Ginzburg–Landau theory. The developed phase field model is validated by comparing simulated results and available experiment data. Via phase field simulations, effects of gradient index on polarization field and electromechanical response are systematically investigated. Anomalously large electromechanical responses are explored in nonlinearly graded ferroelectric thin films made of BaSrxTiO3, where SrTiO3 mole fraction varies across the film thickness according to power‐law relationships. In addition, a large gradient of polarization can be stabilized in graded ferroelectric thin films, where both magnitude and gradient of polarization can be manipulated by controlling the gradient index of thin films. The remarkable enhancement of electromechanical properties originates from the large gradient of polarization in thin films, which makes the polarization field more susceptible to external excitation. An optimal gradient index for maximizing the electromechanical response is also identified. Furthermore, a consideration of energy properties of graded thin films suggests that both energy storage density and charge–discharge efficiency increase with increasing gradient index of thin films.
Novel Li3VO4 Nanostructures Grown in Highly Efficient Microwave Irradiation Strategy and Their In‐Situ Lithium Storage Mechanism
Authors: Sun Yan , Li Chunsheng , Yang Chen , Dai Guoliang , Li Lin , Hu Zhe , Wang Didi , Liang Yaru , Li Yuanliang , Wang Yunxiao , Xu Yanfei , Zhao Yuzhen , Liu Huakun , Chou Shulei , Zhu Zhu , Wang Miaomiao , Zhu Jiahao
Published: November 2021

The investigation of novel growth mechanisms for electrodes and the understanding of their in situ energy storage mechanisms remains major challenges in rechargeable lithium‐ion batteries. Herein, a novel mechanism for the growth of high‐purity diversified Li3VO4 nanostructures (including hollow nanospheres, uniform nanoflowers, dispersed hollow nanocubes, and ultrafine nanowires) has been developed via a microwave irradiation strategy. In situ synchrotron X‐ray diffraction and in situ transmission electron microscope observations are applied to gain deep insight into the intermediate Li3+xVO4 and Li3+yVO4 phases during the lithiation/delithiation mechanism. The first‐principle calculations show that lithium ions migrate into the nanosphere wall rapidly along the (100) plane. Furthermore, the Li3VO4 hollow nanospheres deliver an outstanding reversible capacity (299.6 mAh g−1 after 100 cycles) and excellent cycling stability (a capacity retention of 99.0% after 500 cycles) at 200 mA g−1. The unique nanostructure offers a high specific surface area and short diffusion path, leading to fast thermal/kinetic reaction behavior, and preventing undesirable volume expansion during long‐term cycling.
Elaborately Engineering a Self‐Indicating Dual‐Drug Nanoassembly for Site‐Specific Photothermal‐Potentiated Thrombus Penetration and Thrombolysis
Authors: Zhao Zhiqiang , Zhang Xuanbo , Zhang Hongyuan , Shan Xinzhu , Bai Meiyu , Wang Zhe , Yang Fujun , Zhang Haotian , Kan Qiming , Sun Bingjun , Sun Jin , He Zhonggui , Luo Cong
Published: November 2021

Thrombotic cardio‐cerebrovascular diseases seriously threaten human health. Currently, conventional thrombolytic treatments are challenged by the low utilization, inferior thrombus penetration, and high off‐target bleeding risks of most thrombolytic drugs, resulting in unsatisfactory treatment outcomes. Herein, it is proposed that these challenges can be overcome by precisely integrating the conventional thrombolytic strategy with photothermal therapy. After co‐assembly engineering optimization, a fibrin‐targeting peptide‐decorated nanoassembly of DiR (a photothermal probe) and ticagrelor (TGL, an antiplatelet drug) is prepared for thrombus‐homing delivery, abbreviated as FT‐DT NPs. The elaborately engineered nanoassembly shows multiple advantages, including simple preparation with high drug co‐loading capacity, synchronous delivery of two drugs with long systemic circulation, thrombus‐targeted accumulation with self‐indicating function, as well as photothermal‐potentiated thrombus penetration and thrombolysis with high therapeutic efficacy. As expected, FT‐DT NPs not only show bright fluorescence signals in the embolized vessels, but also perform photothermal/antiplatelet synergistic thrombolysis in vivo. This study offers a simple and versatile co‐delivery nanoplatform for imaging‐guided photothermal/antiplatelet dual‐modality thrombolysis.
WSe2 N‐Type Negative Capacitance Field‐Effect Transistor with Indium Low Schottky Barrier Contact
Authors: Dong Jianguo , Sheng Zhe , Yu Rui , Hu Wennan , Wang Yue , Sun Haoran , Zhang David Wei , Zhou Peng , Zhang Zengxing
Published: November 2021

In conventional metal‐oxide‐semiconductor field‐effect transistors, the subthreshold slope (SS) is limited by the Boltzmann distribution and the loss of gate control with the miniaturization of integrated circuits being an insurmountable ceiling for the huge demand of low‐power, high‐density electronic devices. Negative capacitance field‐effect transistors (NC‐FETs) may provide a promising solution to break the SS limit, and 2D semiconductors should give a possibility to prolong the miniaturization of the device size for the excellent gate control ability. Here, using indium as source/drain contact and ferroelectric hafnium zirconium oxide as gate dielectric, a WSe2 N‐type NC‐FET is achieved that is of a steep SS as low as 12.7 mV dec−1 and the current on/off ratio up to 109. The indium with low work function results in a pretty small Schottky barrier of 29.9 meV to the N‐type WSe2. An inverter is integrated based on the fabricated NC‐FET and a resistor load, which exhibited a high gain of ≈4.5 at VDD of 1.5 V. This device should complement the previously reported WSe2 P‐type NC‐FETs and offer a possible approach for homogeneously integrated CMOS circuits with ultralow power consumption.
Observation of the Pinch‐Off Effect during Electrostatically Gating the Metal‐Insulator Transition
Authors: Yajima Takeaki , Toriumi Akira
Published: November 2021

Electrostatically controlling material phases has been a long‐standing challenge. While it is partially achieved by electrostatic gating with ionic liquid, it often involves unintended chemical reactions. In this sense, it has recently attracted tremendous attention that a solid‐state electrostatic gating is successfully applied to insulator‐metal transition by using ultrahigh‐permittivity gate dielectrics. However, the detailed characteristics of this new class of device are totally unknown. Here, systematic studies are performed on the three‐terminal device using VO2 insulator‐metal transition and TiO2 gate dielectrics, and for the first time the pinch‐off effect in phase transition devices is observed, a clear sign of electrostatic gating. Furthermore, the increase in the drain voltage has a “catalytic effect” of drastically sharpening the gate‐induced transition, demonstrating a 0.1 V gate control. The characteristics are simulated by a quasi‐equilibrium model, providing the firm ground for electrical control of material phases with high speed and high resolution.
Position‐Induced Efficient Doping for Highly Doped Organic Thermoelectric Materials
Authors: Min Jiwoo , Kim Daegun , Han Se Gyo , Park Chaneui , Lim Hyungsub , Sung Woong , Cho Kilwon
Published: November 2021

Electrical doping is essentially required for high‐performance organic thermoelectric (TE) materials; however, the doping efficiency ηd has not been extensively investigated in highly doped organic semiconductors (OSCs). Here, it is demonstrated that the distribution of dopant molecules in a specific position in highly doped OSCs affects the ηd, which is critically related to the Seebeck coefficient S and the electrical conductivity σ. Poly(2,5‐bis(3‐hexadecylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT) films are p‐doped with 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) by either solution‐sequential (SSq) doping or vapor doping. SSq doping deposited F4TCNQ only in the amorphous domains of PBTTT films, whereas vapor doping deposited it in both the amorphous and crystalline domains. F4TCNQ molecules in the crystalline domains exhibited a high ηd and led to a rapid increase of the power factor with increasing σ: S2σ ∝ σ0.76. These results provide guidance for the efficient doping of highly doped OSCs and emphasize the importance of doping efficiency in obtaining high‐performance organic TE materials.
Passive Perching with Energy Storage for Winged Aerial Robots
Authors: Stewart William , Guarino Luca , Piskarev Yegor , Floreano Dario
Published: November 2021

Perching in unmanned aerial vehicles (UAVs) offers the possibility of extending the range of aerial robots beyond the limits of their batteries. It has been a topic of intense study for multirotor UAVs. Perching in winged UAVs is harder because a kinetic energy balance has to be struck. Reducing too much energy results in the vehicle stalling and falling. Too much kinetic energy at touchdown could damage the vehicle. Most studies used dangerous pitch‐up maneuvers to manage this balance. This work presents a system that eliminates the pitch‐up maneuver by mechanically capturing and storing kinetic energy at impact. It is validated using a passive mechanical system consisting of a storage mechanism for energy recuperation and a claw for perching on a horizontal rod. The energy stored in the mechanism is then used to unperch. The mathematical model for the recuperation strategy is presented and perching success at various approach attitudes are characterized. The proof‐of‐concept claw recaptures 5% of the kinetic energy during perching. Experiments indicate that the device can successfully perch at a wide range of yaw angles, but requires more precision in roll. We show that our perching mechanism enables the fastest UAV perching to date (7.4 m s−1).
An infant with congenital respiratory insufficiency and diaphragmatic paralysis: A novel BICD2 phenotype?
Authors: Chin Hui‐Lin , Huynh Stephanie , Ashkani Jahanshah , Castaldo Michael , Dixon Katherine , Selby Kathryn , Shen Yaoqing , Wright Marie , Boerkoel Cornelius F. , Hendson Glenda , Jones Steven J. M.
Published: November 2021

Monoallelic pathogenic variants in BICD2 are associated with autosomal dominant Spinal Muscular Atrophy Lower Extremity Predominant 2A and 2B (SMALED2A, SMALED2B). As part of the cellular vesicular transport, complex BICD2 facilitates the flow of constitutive secretory cargoes from the trans‐Golgi network, and its dysfunction results in motor neuron loss. The reported phenotypes among patients with SMALED2A and SMALED2B range from a congenital onset disorder of respiratory insufficiency, arthrogryposis, and proximal or distal limb weakness to an adult‐onset disorder of limb weakness and contractures. We report an infant with congenital respiratory insufficiency requiring mechanical ventilation, congenital diaphragmatic paralysis, decreased lung volume, and single finger camptodactyly. The infant displayed appropriate antigravity limb movements but had radiological, electrophysiological, and histopathological evidence of myopathy. Exome sequencing and long‐read whole‐genome sequencing detected a novel de novo BICD2 variant (NM_001003800.1:c.[1543G>A];[=]). This is predicted to encode p.(Glu515Lys); p.Glu515 is located in the coiled‐coil 2 mutation hotspot. We hypothesize that this novel phenotype of diaphragmatic paralysis without clear appendicular muscle weakness and contractures of large joints is a presentation of BICD2‐related disease.
Exploring the genetic overlap of suicide‐related behaviors and substance use disorders
Authors: Colbert Sarah M. C. , Hatoum Alexander S. , Shabalin Andrey , Li Qingqin S. , Coon Hilary , Nelson Elliot C. , Agrawal Arpana , Docherty Anna R. , Johnson Emma C.
Published: November 2021

Suicide‐related behaviors are heterogeneous and transdiagnostic, and may demonstrate varying levels of genetic overlap with different substance use disorders (SUDs). We used linkage disequilibrium score regression, genomic structural equation models, and Mendelian randomization to examine the genetic relationships between several SUDs and suicide‐related behaviors. Our analyses incorporated summary statistics from the largest genome‐wide association studies (GWAS) of problematic alcohol use, the Fagerström test for nicotine dependence, cannabis use disorder, and opioid use disorder (Ns ranging from 46,213–435,563) and GWAS of ever self‐harmed, suicide attempt, and suicide death (Ns ranging from 18,223–117,733). We also accounted for genetic liability to depression (N = 500,199) and risk tolerance (N = 315,894). Suicide‐related behaviors were significantly genetically correlated with each other and each SUD, but there was little evidence of causal relationships between the traits. Simultaneously correlating a common SUD factor with each specific suicide indicator while controlling for depression and risk tolerance revealed significant, positive genetic correlations between the SUD factor and suicide‐related behaviors (rg = 0.26–0.45, SE = 0.08–0.09). In the model, depression's association with suicide death (β = 0.42, SE = 0.06) was weaker compared to ever‐self harmed and suicide attempt (β = 0.58, SE = 0.05 and β = 0.50, SE = 0.06, respectively). We identify a general level of genetic overlap between SUDs and suicide‐related behaviors, which is independent of depression and risk tolerance. Additionally, our findings suggest that genetic and behavioral contributions to suicide death may somewhat differ from nonlethal suicide‐related behaviors.
Three‐Component Vicinal Sulfonamination of Alkynes toward 3‐Sulfonylindoles via the Insertion of Sulfur Dioxide
Authors: Zhang Jie , Chen Jian , Zhai Yongheng , Yu Jin‐Tao , Pan Changduo
Published: November 2021

A convenient and efficient three‐component transformation of 2‐alkynyl arylazides, aryldiazonium tetrafluoroborates and sodium metabisulfite has been developed under mild and transition‐metal‐free conditions. Sodium metabisulfite which is cheap, easily available and abundant in nature is successfully utilized as SO2 surrogate, leading to a series of 3‐sulfonylindole derivatives in moderate to good yields. Cascade radical addition/cyclization was involved in this protocol with the formation of two C−S bonds and one C−N bond in one‐pot.
The diet at the onset of the Andean Civilization: New stable isotope data from Caral and Áspero, North‐Central Coast of Peru
Authors: Pezo‐Lanfranco Luis , Machacuay Marco , Novoa Pedro , Peralta Rodolfo , Mayer Elver , Eggers Sabine , Shady Ruth
Published: November 2021

Objectives

The subsistence system of the first urban centers with monumental architecture from the North‐Central Coast of Peru, the core area for the social complexity process of Central Andes, has been debated since the late 1960s. To shed light on this aspect, we report paleodietary data from the two most important sites of the Supe Valley: Caral (3000–200 BC), the major settlement of the middle valley, and Áspero (3000–1800 BC), a notable coastal settlement. Our main objective was to test the Maritime Foundations of Andean Civilization hypothesis.

Materials and Methods

Stable isotope values (δ13Ccol, δ13Cap, and δ15N) from 52 individuals (70 samples: 44 bones and 26 teeth) were analyzed using conventional methods and Bayesian Mixing Models to address the role of marine products and plants in people's diet at both sites over time.

Results

Our results suggest high C3 carbohydrate consumption (55%–68% total calories in Áspero and >70% in Caral). The consumption of marine resources was stable for Áspero between 3300 and 1800 BC, but it decreased for Caral between 2550 and 200 BC.

Discussion

Marine protein was more important in Áspero than in Caral over time. C3 plants, possibly tubers, formed the foundation of the diet in both sites during the Formative period (~3000–200 BC). Maize was a marginal food (<12% of calories) at least until 800 BC (29% of calories). The Maritime Foundations hypothesis does not completely account for these findings. Our results suggest the predominance of crop‐focused agriculture during the evaluated period.
Exploring physical activity in Central Chile during the Early Ceramic Period and Late Intermediate Period (200–1450 CE)
Authors: Abarca‐Labra Violeta , Herrera‐Soto María‐José , Flores‐Alvarado Sandra , Ulloa‐Velásquez Carolina , Urrutia‐Álvarez Constanza , Falabella‐Gellona Fernanda , Sanhueza‐Riquelme Lorena
Published: November 2021

Objectives

We explore physical activity in early farming societies of Central Chile during the Early Ceramic and Late Intermediate Periods (200–1450 CE), a time of technological changes and intensification of food production. The existence of differences in entheseal changes (EC) between females and males is evaluated in two periods with different subsistence strategies.

Material and methods

EC were recorded with method in the upper and lower limbs of 56 male and female adult individuals from the Early Ceramic Period (ECP) and Late Intermediate Period (LIP). Hierarchical multiple factor analysis and hierarchical clustering on principal components were performed using an exploratory approach.

Results

In all the analyzed limbs, the EC scores are higher in males than females, which may be explained by sexual dimorphism. A constant overlap in the variability of the EC among males and females is observed. However, the EC scores show a different pattern of variability when comparing ECP females with LIP females. The results show that the scores increase in the latter. In contrast, when comparing ECP males with LIP males scores decrease in the later period.

Discussion

Physical activity in the societies of Central Chile with incipient agriculture did not vary by sex or during the timeframe studied. Nevertheless, the interaction between sex‐period and the variability pattern of the EC from one period to another suggests different ways of doing similar physical activities or different emphases for similar biomechanical actions.
Redox‐Active Heteroatom‐Functionalized Polyacetylenes
Authors: Luppi Bruno T. , Muralidharan Abhishek V. , Ostermann Nils , Cheong I T. , Ferguson Michael J. , Siewert Inke , Rivard Eric
Published: November 2021

The discovery of metallic conductivity in polyacetylene [‐HC=CH‐]n upon doping represents a landmark achievement. However, the insolubility of polyacetylene and a dearth of methods for its chemical modification have limited its widespread use. Here, we employ a ring‐opening metathesis polymerization (ROMP) protocol to prepare functionalized polyacetylenes (fPAs) bearing: (1) electron‐deficient boryl (‐BR2) and phosphoryl (‐P(O)R2) side chains; (2) electron‐donating amino (‐NR2) groups, and (3) ring‐fused 1,2,3‐triazolium units via strain‐promoted Click chemistry. These functional groups render most of the fPAs soluble and can lead to intense light absorption across the visible to near‐IR region. Also, the presence of redox‐active boryl and amino groups leads to opposing near‐IR optical responses upon (electro)chemical reduction or oxidation. Some of the resulting fPAs show greatly enhanced air stability when compared to known polyacetylenes. Lastly, these fPAs can be cross‐linked to yield network materials with the full retention of optical properties.
Vectorial Catalysis in Surface‐Anchored Nanometer‐Sized Metal–Organic Frameworks‐Based Microfluidic Devices
Authors: Semrau Anna Lisa , Stanley Philip M. , Huber Dominik , Schuster Michael , Albada Bauke , Zuilhof Han , Cokoja Mirza , Fischer Roland A.
Published: November 2021

Vectorial catalysis—controlling multi‐step reactions in a programmed sequence and by defined spatial localization in a microscale device—is an enticing goal in bio‐inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface‐anchored nanometer‐sized metal–organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. Catalyst immobilization at defined sections along the microchannel and a two‐step cascade reaction was conducted with full conversion after 30 seconds and high turnover frequencies (TOF≈105 h−1).
Synthesis and biological evaluation of novel tetranuclear cyclopalladated complex bearing thiosemicarbazone scaffold ligand: Interactions with double‐strand DNA, coronavirus, and molecular modeling studies
Authors: Lighvan Zohreh Mehri , Khonakdar Hossein Ali , Akbari Ali , Jahromi Maryam Dehdashti , Ramezanpour Azar , Kermagoret Anthony , Heydari Abolfazl , Jabbari Esmaiel
Published: November 2021

Threading intercalators are a novel class of materials that carry two substituents along the diagonal positions of an aromatic ring. When bound to DNA, these substituents project out in DNA grooves. Tetranuclear complexes appear to be promising threading intercalators for developing therapeutics against cancer and viral infections that require high nucleic acid binding affinity. The objective of this work was to prepare the thiosemicarbazone scaffold ligand [4‐ClC6H4CHN=NC(S)NHPh] and tetranuclear cyclopalladated complex [Pd(4‐ClC6H4CHN=NC(S)NHPh)4] and to characterize the compounds by elemental analysis, 1D and 2D NMR, HRMS, and IR spectroscopy. The calf thymus DNA (CT‐DNA) binding properties of the compounds were investigated in vitro under simulated physiological conditions using UV–vis spectroscopy, emission spectral titration, methylene blue competitive binding, circular dichroism, DNA thermal denaturation, DNA binding, and coronavirus interactions using molecular simulation. The compounds showed cytotoxic effect against both human breast (MCF‐7) and colorectal (HCT116) cancer cells in a dose‐dependent manner. We demonstrated that the compounds are promising for DNA threading intercalation binders with large DNA binding constants on the order of 107 M−1magnitude.
A nine‐coordinated bismuth(III) Schiff‐base complex: Design, synthesis, computational studies, and antimicrobial activity
Authors: Lei Yan‐Hua , Jiang Jian‐Hong , Li Xu , Li Qiang‐Guo , Li Chuan‐Hua
Published: November 2021

A new bismuth(III) Schiff‐base complex [Bi2(HL)2(NO3)4] was synthesized by using equivalent molar of Schiff‐base ligand [H2L = (E)‐N′‐(2‐hydroxy‐3‐methoxybenzylidene)isonicotinohydrazide] and Bi(NO3)3•5H2O with the assistance of Mannitol. The complex was structurally characterized by elemental analysis, spectroscopic methods, and single crystal X‐ray diffraction. The experimental and theoretical vibrational bands (infrared and Raman spectra) have been discussed. The antimicrobial activity of the complex against Schizosaccharomyces pombe was evaluated by bio‐microcalorimetry at 32°C. Some thermokinetic parameters (k, Pmax, tG, and Qtotal) were obtained from the metabolic power–time curves of S. pombe, and their quantitative relationships with the concentration (c) were discussed. The half inhibition concentrations (IC50) of isoniazid, Schiff base, and the complex were calculated. The complex showed the strongest inhibition effect among three compounds.
Quantitative assessment of damage evolution of carbon fiber‐reinforced polymer laminates embedded with different nanoparticles using acoustic emission
Authors: Zhou Wei , Yang Sa , Ji Xiao‐long , Xu Han‐qing , Ding Zhen‐jun , Liu Ran , Zhang Peng‐fei
Published: November 2021

Nanoparticles can be used to optimize the interface structure and improve the mechanical properties of fiber‐reinforced composites. Herein, the damage evolution of carbon fiber‐reinforced composites embedded with different nanoparticles has been investigated using acoustic emission (AE) technology. Principal component analysis is used to reduce the dimension of AE parameters. Combining fuzzy C‐means (FCM) clustering with hierarchical clustering can improve the clustering quality, which is helpful to apply FCM results to the quantitative evaluation of damage. For multiwalled carbon nanotubes, graphene, and cellulose nanofibres, the cumulative AE energy of matrix cracking increases by 39.29%, 51.12%, and 53.69%, respectively, that of fiber/matrix debonding increases by 13.5%, 118.5% and 56.58%, and that of fiber breakage decreases by 97.9%, 94.32%, and 87.6%, respectively. The addition of nanoparticles helps to improve the stiffness and toughness of epoxy resin, and restricts crack propagation, thus enhancing the interfacial properties. AE technology can successfully help quantitatively evaluate the damage behavior and the mechanism of different multiscale reinforced composites. AE characteristic responses within the composites are consistent with scanning electron microscopy results.
The neuroanatomy of Zulmasuchus querejazus (Crocodylomorpha, Sebecidae) and its implications for the paleoecology of sebecosuchians
Authors: Pochat‐Cottilloux Yohan , Martin Jeremy E. , Jouve Stéphane , Perrichon Gwendal , Adrien Jérome , Salaviale Céline , de Muizon Christian , Cespedes Ricardo , Amiot Romain
Published: November 2021

The endocranial structures of the sebecid crocodylomorph Zulmasuchus querejazus (MHNC 6672) from the Lower Paleocene of Bolivia are described in this article. Using computed tomography scanning, the cranial endocast, associated nerves and arteries, endosseous labyrinths, and cranial pneumatization are reconstructed and compared with those of extant and fossil crocodylomorphs, representative of different ecomorphological adaptations. Z. querejazus exhibits an unusual flexure of the brain, pericerebral spines, semicircular canals with a narrow diameter, as well as enlarged pharyngotympanic sinuses. First, those structures allow to estimate the alert head posture and hearing capabilities of Zulmasuchus. Then, functional comparisons are proposed between this purportedly terrestrial taxon, semi‐aquatic, and aquatic forms (extant crocodylians, thalattosuchians, and dyrosaurids). The narrow diameter of the semicircular canals but expanded morphology of the endosseous labyrinths and the enlarged pneumatization of the skull compared to other forms indeed tend to indicate a terrestrial lifestyle for Zulmasuchus. Our results highlight the need to gather new data, especially from altirostral forms in order to further our understanding of the evolution of endocranial structures in crocodylomorphs with different ecomorphological adaptations.
Activating endogenous resolution pathways by soluble epoxide hydrolase inhibitors for the management of COVID‐19
Authors: Manickam Manoj , Meenakshisundaram Sangeetha , Pillaiyar Thanigaimalai
Published: November 2021

Anti‐inflammatory, specialized proresolving mediators such as resolvins, protectins, maresins, and lipoxins derived from polyunsaturated acids may play a potential role in lung diseases as they protect different organs in animal disease models. Polyunsaturated fatty acids are an important resource for epoxy fatty acids (EET, EEQ, and EDP) that mediate a broad array of anti‐inflammatory and proresolving mechanisms, such as mitigation of the cytokine storm. However, epoxy fatty acids are rapidly metabolized by soluble epoxide hydrolase (sEH). In animal studies, administration of sEH inhibitors (sEHIs) increases epoxy fatty acid levels, reduces lung inflammation, and improves lung function, making it a viable COVID‐19 treatment approach. Thus, using sEHIs to activate endogenous resolution pathways might be a novel method to minimize organ damage in severe cases and improve outcomes in COVID‐19 patients. This review focuses on the use of sEH inhibitors to activate endogenous resolution mechanisms for the treatment of COVID‐19.
Cyclopentadienyl Complexes of the Alkaline Earths in Light of the Periodic Trends
Authors: Baguli Sudip , Mondal Sumana , Mandal Chhotan , Goswami Santu , Mukherjee Debabrata
Published: November 2021

The electron‐rich cyclopentadienyl and the analogous indenyl and fluorenyl ligands (collectively denoted here as Cp’) have been impactful in stabilizing electron‐deficient metal centers including the highly electropositive alkaline earths. Being in the s‐block, the group 2 metals follow a major periodic variation in their atomic and ionic properties which is reflected in those Cp’ compounds. This article presents an overview of this class of compounds for all the five metals from beryllium to barium (radium is excluded for its radioactivity), highlighting their systematic variation.
Powerful quasars with young jets in multi‐epoch radio surveys
Authors: Nyland Kristina , Dong Dillon Z. , Patil Pallavi , Lacy Mark , van Velzen Sjoert , Kimball Amy E. , Sarbadhicary Sumit K. , Hallinan Gregg , Baldassare Vivienne , Clarke Tracy E. , Goulding Andy D. , Greene Jenny , Hughes Andrew , Kassim Namir , Kunert‐Bajraszewska Magdalena , Maccarone Thomas J. , Mooley Kunal , Mukherjee Dipanjan , Peters Wendy , Petrov Leonid , Polisensky Emil , Rujopakarn Wiphu , Whittle Mark , Vaccari Mattia
Published: November 2021

Energetic feedback driven by the large‐scale (100's of kpc) lobes of classical radio galaxies is known to play an important role in shaping galaxy evolution. However, the prevalence of young and compact jets – and their impact on the interstellar medium – remains an open question. Multi‐epoch radio surveys with cadences of years to decades offer a promising means of identifying even faint (mJy‐level) jets that are compact and potentially young on the basis of variability. Recently, a comparison of images from the Very Large Array Sky Survey (VLASS) and the Faint Images of the Radio Sky at Twenty Centimeters (FIRST) survey has revealed a population of distant () quasars that have brightened dramatically in the past 1–2 decades. These quasars appear to have transitioned from “radio‐quiet” nondetections in FIRST to “radio‐loud” detections in VLASS. Extensive multiband follow‐up observations with the VLA from 1 to 18 GHz have revealed compact (sub‐kpc) radio sources that are consistent with young jets that were recently triggered. Here, we summarize the status of our on‐going study of quasars with newborn jets identified in the radio time domain.