bluuebunny/crossref_metadata_2025 huggingface dataset:
Lithium Loaded Octa‐Poly(Ethylene Glycol) Based Adhesive Facilitates Axon Regeneration and Reconnection of Transected Peripheral Nerves
Authors: Bu Yazhong , Wang Xianghai , Li Lixia , Hu Xiaofang , Tan Dandan , Li Zhenlin , Lai Muhua , Qiu Xiaozhong , Sun Feifei , Wang Hufei , Yang Fei , Wu Decheng , Guo Jiasong
Published: May 2020

At present, reconnecting the transected nerve in clinic is still mainly reliant on surgery suture. This is a procedure that requires thorough training and is also time consuming. Here, an octa‐poly(ethylene glycol) (PEG)‐based adhesive for fast reconnecting of the transected peripheral nerve is reported. To enhance the therapeutic efficacy, a succinyl unit is applied to endow the controllably dissolvable property of the adhesive, and lithium is loaded in the adhesive to improve the axonal regeneration. Present data reveal that this adhesive possesses good cytocompatibility and can significantly shorten the reconnecting time of the transected nerve ends compared to that required for suture surgery. Histology, electrophysiological, and behavior assessments indicate that the adhesive reconnected nerves exhibit a low grade of fibrosis, inflammation response, and myoatrophy as well as robust axonal regeneration and functional recovery. Together, these results indicate that this octa‐PEG adhesive can act as an alternative to traditional nerve suture in peripheral nerve injury.
Ferroelectric Sr3Sn2O7:Nd3+: A New Multipiezo Material with Ultrasensitive and Sustainable Near‐Infrared Piezoluminescence
Authors: Tu Dong , Xu Chao‐Nan , Kamimura Sunao , Horibe Yoichi , Oshiro Hirotaka , Zhang Lu , Ishii Yoshiharu , Hyodo Koji , Marriott Gerard , Ueno Naohiro , Zheng Xu‐Guang
Published: May 2020

Ultrasensitive and sustainable near‐infrared (NIR)‐emitting piezoluminescence is observed from noncentrosymmetric and ferroelectric‐phase Sr3Sn2O7 doped with rare earth Nd3+ ions. Sr3Sn2O7:Nd3+ (SSN) with polar A21am structure is demonstrated to emit piezoluminescence of wavelength of 800–1500 nm at microstrain levels, which is enhanced by the ferroelectrically polarized charges in the multipiezo material. These discoveries provide new research opportunities to study luminescence properties of multipiezo and piezo‐photonic materials, and to explore their potential as novel ultrasensitive probes for deep‐imaging of stress distributions in diverse materials and structures including artificial bone and other implanted structures (in vivo, in situ, etc).
Strategies for High‐Performance Solid‐State Triplet–Triplet‐Annihilation‐Based Photon Upconversion
Authors: Lin Ting‐An , Perkinson Collin F. , Baldo Marc A.
Published: May 2020

Photon upconversion via triplet–triplet annihilation (TTA) has achieved high efficiencies in solution and within polymer matrices that support molecular migration systems. It has diverse potential applications including bioimaging, optical sensors, and photovoltaics. To date, however, the reported performance of TTA in rigid solid‐state systems is substantially inferior, which may complicate the integration of TTA in other solid‐state devices. Here, solid‐state loss mechanisms in a green‐to‐blue upconversion system are investigated, and three specific losses are identified: energy back transfer, sensitizer aggregation, and triplet–charge annihilation. Strategies are demonstrated to mitigate energy back transfer and sensitizer aggregation, and a completely dry‐processed solid‐state TTA upconversion system having an upconversion efficiency of ≈2.5% (by the convention of maximum efficiency being 100%) at a relatively low excitation intensity of 238 mW cm−2 is reported. This device is the first demonstration of dry‐processed solid‐state TTA comparable to solution‐processed solid‐state systems. The strategies reported here can be generalized to other upconversion systems and offer a route to achieving higher‐performance solid‐state TTA upconversion devices that are compatible with applications sensitive to solvent damage.
A Bottom‐Up Strategy for the Synthesis of Highly Siliceous Faujasite‐Type Zeolite
Authors: Zhu Dali , Wang Linying , Fan Dong , Yan Nana , Huang Shengjun , Xu Shutao , Guo Peng , Yang Miao , Zhang Jianming , Tian Peng , Liu Zhongmin
Published: May 2020

High‐silica zeolite Y is a desired catalytic material for oil refining and the petrochemical industry. However, its direct synthesis remains a symbolic challenge in the field of zeolite synthesis, with a limited improvement of the framework SiO2/Al2O3 ratio (SAR) from ≈5 to 9 over the past 60 years. Here, the synthesis of highly siliceous zeolite Y with tunable SAR up to 15.6 through a cooperative strategy is reported, which involves the use of FAU nuclei, a bulky organic structure‐directing agent (OSDA), and a gel system with low alkalinity (named NOA‐co strategy). A series of quaternary alkylammonium ions is discovered as effective OSDAs based on the NOA‐co strategy, and the relevant crystallization mechanism is elucidated. Moreover, the high‐silica products are demonstrated to have greatly improved (hydro)thermal stability, high concentration of strong acid sites, and uniform acid distribution, which lead to superior catalytic performance in the cracking of bulky hydrocarbons. It is anticipated that this synthetic strategy will benefit the synthesis and development of zeolitic catalysts in a wide range of reaction processes.
Bioinspired Soft Microrobots with Precise Magneto‐Collective Control for Microvascular Thrombolysis
Authors: Xie Meihua , Zhang Wei , Fan Chengying , Wu Chu , Feng Qishuai , Wu Jiaojiao , Li Yingze , Gao Rui , Li Zhenguang , Wang Qigang , Cheng Yu , He Bin
Published: May 2020

New‐era soft microrobots for biomedical applications need to mimic the essential structures and collective functions of creatures from nature. Biocompatible interfaces, intelligent functionalities, and precise locomotion control in a collective manner are the key parameters to design soft microrobots for the complex bio‐environment. In this work, a biomimetic magnetic microrobot (BMM) inspired by magnetotactic bacteria (MTB) with speedy motion response and accurate positioning is developed for targeted thrombolysis. Similar to the magnetosome structure in MTB, the BMM is composed of aligned iron oxide nanoparticle (MNP) chains embedded in a non‐swelling microgel shell. Linear chains in BMMs are achieved due to the interparticle dipolar interactions of MNPs under a static magnetic field. Simulation results show that, the degree and speed of assembly is proportional to the field strength. The BMM achieves the maximum speed of 161.7 µm s−1 and accurate positioning control under a rotating magnetic field with less than 4% deviation. Importantly, the locomotion analyses of BMMs demonstrate the frequency‐dependent synchronization under 8 Hz and asynchronization at higher frequencies due to the increased drag torque. The BMMs can deliver and release thrombolytic drugs via magneto‐collective control, which is promising for ultra‐minimal invasive thrombolysis.
Bismuth Oxychalcogenide Nanosheet: Facile Synthesis, Characterization, and Photodetector Application
Authors: Li Meng‐Qiu , Dang Le‐Yang , Wang Gui‐Gen , Li Fei , Han Mao , Wu Zhi‐Peng , Li Gui‐Zhong , Liu Zheng , Han Jie‐Cai
Published: May 2020

New 2D bismuth oxychalcogenide nanosheets have excellent theoretical properties such as high electronic mobility and excellent oxidation resistance, which have good application prospective for optoelectronic devices. In this paper, during the synthesis process via mild hydrothermal route, ammonium bismuth citrate (C6H13BiN2O7·H2O) is selected as Bi source. Both Bi2O2S and Bi2O2Se nanosheets (lateral size: over 2.0 µm, thickness: ≈ 5.0 nm) are synthesized successfully using thiourea (CH4N2S) as S source, and sodium selenite (Na2O3Se) as Se source, respectively. The as‐synthesized Bi2O2S and Bi2O2Se materials have desirable nanosheet‐like morphologies. After adding C6H13BiN2O7·H2O, [(NH3)2C6H7O7]3‐ can intercalate between the interlayers of Bi2O2S or Bi2O2Se, limiting the growth along c‐axis direction, so that 2D sheets can be obtained. Finally, the photodetectors are fabricated based on Bi2O2S and Bi2O2Se films coated by thermal spraying. The experimental results show that the maximum responsivity and detectivity of Bi2O2S‐based photodetector are 0.059 A W‐1 and 6.77 × 109 Jones, respectively. As to Bi2O2Se‐based photodetector, the maximum responsivity and detectivity can reach 75.14 A W‐1 and 3.95 × 1012 Jones, respectively. The mild hydrothermal synthesis using ammonium bismuth citrate as Bi source is a universal and facile method to obtain Bi2O2S and Bi2O2Se nanosheets for optoelectronic applications.
Efficient Trap Passivation of MAPbI3 via Multifunctional Anchoring for High‐Performance and Stable Perovskite Solar Cells
Authors: Garai Rabindranath , Afroz Mohammad Adil , Gupta Ritesh Kant , Iyer Parameswar Krishnan
Published: May 2020

Chemical passivation of ionic defects in perovskite materials is an effective strategy to reduce charge recombination in perovskite solar cells (PSCs). Although several additives have been used for this purpose, the passivation mechanisms of different functional groups have remained unclear. Herein, the effect of molecules possessing multiple functional anchoring is systematically investigated. Three different multifunctional molecules namely 5‐aminoisophthalic acid (AIA), 5‐hydroxyisophthalic acid (HIA), and chelidamic acid (CA) are strategically chosen. These molecules not only take part in the crystallization process but also passivate the trap states effectively. CA shows superior passivation capacity among all with a better dipolar electron density distribution. The passivated films have considerably improved morphology with fewer pin holes, larger grains, and lower trap states in comparison to the pristine film. CA‐passivated p–i–n structured photovoltaic devices demonstrate the best power conversion efficiency (PCE) of 19.06% with an impressive open circuit voltage (VOC) of 1.097 V, whereas pristine devices show a PCE of 13.60% and VOC of 0.972 V. Moreover, the modified device reveals notable thermal and ambient stability in comparison to the pristine device due to lower defect states and reduced ion migration.
Shaping Nanoparticles for Interface Catalysis: Concave Hollow Spheres via Deflation–Inflation Asymmetric Growth
Authors: Yu Rongtai , Huang Xiaodan , Liu Yang , Kong Yueqi , Gu Zhengying , Yang Yang , Wang Yue , Ban Wenhuang , Song Hao , Yu Chengzhong
Published: May 2020

Hollow spheres are charming objects in nature. In this work, an unexpected deflation–inflation asymmetric growth (DIAG) strategy is reported, generating hollow nanoparticles with tailored concave geometry for interface catalysis. Starting from aminophenol‐formaldehyde (APF) nanospheres where the interior crosslinking degree is low, fully deflated nanobowls are obtained after etching by acetone. Due to APF etching and repolymerization reactions occuring asymmetrically within a single particle, an autonomous inflation process is observed similar to a deflated basketball that inflates back to a “normal” ball, which is rare at the nanoscale. A nucleophilic addition reaction between acetone and APF is elucidated to explain the chemistry origin of the DIAG process. Interestingly, the deflated APF hollow spheres enable preferential immobilization of lipase in the concave domain, which facilitates the stabilization of Pickering emulsion droplets for enhanced enzymatic catalysis at the oil–water interface. The study provides new understandings in the designable synthesis of hollow nanoparticles and paves the way toward a wide range of applications of asymmetric architectures.
The Application of a High‐κ Polymer Dielectric in Graphene Transistors
Authors: Wen Jiamin , Yan Chengyuan , Sun Zhenhua
Published: May 2020

The high‐κ polymer P(VDF‐TrFE‐CFE) is applied in the dielectric layer of a thin film transistor based on graphene, inducing a considerable overall performance improvement compared with conventional SiO2 or ordinary polymer PMMA dielectrics. A systematical study reveals the reason for this improvement to be the strong screening effect on the Coulomb scattering in the dielectric‐semiconductor interface, which originates from the high‐κ value of P(VDF‐TrFE‐CFE). This positive effect is dominant enough to compensate for the adverse effects induced by the application of P(VDF‐TrFE‐CFE), including the large surface roughness and strong phonon scattering. A prototype transistor fabricated on a plastic substrate shows similar superior performance and sustainability upon bending operation, testifying the adaptability of P(VDF‐TrFE‐CFE) in a flexible graphene transistor. This study proposes a high‐κ polymer dielectric that is valid for high‐performing transistors based on 2D semiconductor materials.
Elastic, Conductive Coating Layer for Self‐Standing Sulfur Cathode Achieving Long Lifespan Li–S Batteries
Authors: Wang Wenqiang , Wang Dongya , Wang Guiyou , Zheng Mengyao , Wang Gengchao
Published: May 2020

The shuttle of polysulfide and severe volume change of sulfur cathodes, are the bottlenecks in the practical application of lithium–sulfur batteries, and need to be solved through further exploration of simple and scalable strategies. Herein, an elastic and conductive coating layer is designed and synthesized, by combining water soluble conducting polymer modified carbon nanotubes (PASANTs) with crosslinked waterborne polyurethane (cWPU). It shows high electronic conductivity and excellent resilience. As a result, a lithium–sulfur battery with cWPU/PASANTs coated cathode is able to achieve an outstanding cycle stability with a capacity of 70.8% after 500 cycles at 0.5C and an excellent rate performance (specific capacity of 1130 mAh g−1 at 0.1C and maintain 68.2% at 2C). This work embodies a systematic design concept, which shows the application prospects of large‐scale production, and is expected to be further applied to other easily pulverized high‐specific‐capacity materials such as silicon and tin.
Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries
Authors: Zhou Aijun , Cheng Weijie , Wang Wei , Zhao Qiang , Xie Jian , Zhang Wuxing , Gao Hongcai , Xue Leigang , Li Jingze
Published: May 2020

Na‐ion batteries (NIBs) and K‐ion batteries (KIBs) are promising candidates for next‐generation electric energy storage applications due to their low costs and appreciable energy/power density compared to Li‐ion batteries. In the search for viable electrode materials for NIBs and KIBs, Prussian blue analogs (PBAs) with inherent rigid and open frameworks and large interstitial voids have shown an impressive ability to accommodate big alkali‐metal ions without structure collapse. In particular, hexacyanoferrates (HCFs) utilizing abundant Fe(CN)6 resources are the most interesting subgroup of PBAs, being able to deliver a specific capacity of 70–170 mAh g‒1 and a voltage of 2.5‒3.8 V in NIBs/KIBs. In this Review, a comprehensive discussion of the HCF‐type cathode materials in terms of their structural features, redox mechanisms, synthesis control, and modification strategies based on research advances over the last ten years. The methodologies and achievements in improving the material properties of HCFs including the compositional stoichiometry, crystal water, crystallinity, morphology, and electrical conductivity are outlined, with the aim to promote understanding of these materials and provide new insights into future design of PBAs for advanced rechargeable batteries.
Exploiting the Spinel Structure for Li‐ion Battery Applications: A Tribute to John B. Goodenough
Authors: Thackeray Michael M.
Published: May 2020

This review provides a personal account of career‐long efforts, interwoven with the contributions of others, to exploit the [B2]O4 framework of an A[B2]O4 spinel structure for lithium‐ion battery applications, where A = Li, and B is one or more metal cations. The narrative starts at the Council for Scientific and Industrial Research (CSIR) in South Africa in the mid‐1970s when, in response to the Middle East oil crisis, worldwide efforts were turned to develop high‐temperature sodium and lithium batteries to power electric vehicles. In 1981, results in CSIR's program on a high‐temperature lithium battery led to a collaborative project on room‐temperature lithium cells with Prof. John B. Goodenough at Oxford University, where studies of Fe3O4, Mn3O4, and LiMn2O4 cathodes led to the recognition of the broad utility of the [B2]O4 spinel framework as an anode, cathode, or solid electrolyte for rechargeable lithium cells. This finding has had a profound and lasting impact, influencing further ideas and discoveries at the CSIR, Argonne National Laboratory, and elsewhere. The narrative emphasizes the compositional versatility of the spinel structure and the opportunities to tailor the electrochemical potential and stability of a Li‐ion cell.
Shade stress decreased maize grain yield, dry matter, and nitrogen accumulation
Authors: Gao Jia , Liu Zheng , Zhao Bin , Dong Shuting , Liu Peng , Zhang Jiwang
Published: May 2020

Shade stress severely limits plant growth and crop productivity. This study investigated the relationship between shade stress and nitrogen (N) accumulation in maize at different growth stages. Field experiments were conducted in 2015 and 2016 with three shading treatments: from emergence stage (VE) to physiological maturity (R6) (whole‐season shade), from six‐leaf (V6) to tassel stage (VT) (midseason shade), and from VT to R6 (late‐season shade). Ambient sunlight was used as control (CK). Two hybrids, Zhengdan958 (ZD958) and Denghai 605 (DH605), were used. This study focused on accumulation and partition of dry matter (DM) and N based on the above treatments. Shading reduced DM and N accumulation of maize, which decreased yield. In addition, 15N stable isotope tracing revealed that shading disrupted N accumulation, partitioning, and remobilization in different organs. The contents of grain 15N in whole‐season shade, midseason shade, and late‐season shade from ZD958 decreased by 60, 28, and 50%, respectively, compared with those in CK, and DH605 decreased by 70, 32, and 51%, respectively. Our results indicate that yield decline can be mainly attributed to DM and that N accumulation and remobilization were disrupted by shading at different maize growth stages. Shading during the vegetative stage and reproductive stage reduced N accumulation, and shading during the reproductive stage mainly promoted N transport from other organs to grain, which mitigated some of the effects of reduced N absorption.
Seeding rate effects on organic rice growth, yield, and economic returns
Authors: Li Xiufen , Dou Fugen , Watkins Kenton B. , Wang Shu , Chen Kun , Zhou Xin‐Gen , McClung Anna , Storlien Joseph O. , Hons Frank M.
Published: May 2020

Seeding rate is an important factor in optimizing yield components and thus grain yield of conventional rice (Oryza sativa L.), yet limited information on its effect on organic rice production is available. A field study was conducted under organic management over 2 yr to comprehensively evaluate the effects of seeding rate (108, 161, 215, 269, 323, 376, and 431 seeds m−2) and rice cultivar (Presidio [inbred] and XP753 [hybrid]) on yield components, grain yield, milling quality, weed density, and economic returns. Seeding rate had significant effects on seedling stand density and dry biomass with positive linear correlations. Yield linearly increased with increasing seeding rate with the greatest yields of 3,462 kg ha−1 for Presidio and 7,508 kg ha−1 for XP753 at the highest seeding rate tested. Panicle number was positively correlated with seeding rate, while milling quality was not affected by seeding rate. The linear‐plateau (LP) model fit best for Presidio and the quadratic‐plateau (QP) model fit best for XP753 to estimate the ex ante economic optimum seeding rate (EOSR). The EOSR was 87 kg ha−1 (340 seeds m−2) for Presidio and 48 kg ha−1 (192 seeds m−2) for XP753. Using the EOSR, producers could expect a yield of 3053 kg ha−1 and an economic return of US$1,288−$1,346 ha−1 for Presidio, and a yield of 5,835−6,092 kg ha−1 and an economic return of $1,986−$2,686 ha−1 for XP753.
Unobtrusive, Low‐Cost Out‐of‐Hospital, and In‐Hospital Measurement and Monitoring System
Authors: Vuorinen Tiina , Noponen Kai , Jeyhani Vala , Aslam Muhammad Awais , Junttila Matti Juhani , Tulppo Mikko Paavo , Kaikkonen Kari Sakari , Huikuri Heikki Veli , Seppänen Tapio , Mäntysalo Matti , Vehkaoja Antti
Published: May 2020

Continuous monitoring of vital signs can be a life‐saving matter for different patient groups. The development is going toward more intelligent and unobtrusive systems to improve the usability of body‐worn monitoring devices. Body‐worn devices can be skin‐conformable, patch‐type monitoring systems that are comfortable to use even for prolonged periods of time. Herein, an intelligent and wearable, out‐of‐hospital, and in‐hospital four‐electrode electrocardiography (ECG) and respiration measurement and monitoring system is proposed. The system consists of a conformable screen‐printed disposable patch, a measurement unit, gateway unit, and cloud‐based analysis tools with reconfigurable signal processing pipelines. The performance of the ECG patch and the measurement unit was tested with cardiac patients and compared with a Holter monitoring device and discrete, single‐site electrodes.
In‐Memory Eigenvector Computation in Time O(1)
Authors: Sun Zhong , Pedretti Giacomo , Ambrosi Elia , Bricalli Alessandro , Ielmini Daniele
Published: May 2020

In‐memory computing with cross‐point resistive memory arrays has gained enormous attention to accelerate the matrix‐vector multiplication in the computation of data‐centric applications. By combining a cross‐point array and feedback amplifiers, it is possible to compute matrix eigenvectors in one step without algorithmic iterations. Herein, time complexity of the eigenvector computation is investigated, based on the feedback analysis of the cross‐point circuit. The results show that the computing time of the circuit is determined by the mismatch degree of the eigenvalues implemented in the circuit, which controls the rising speed of output voltages. For a dataset of random matrices, the time for computing the dominant eigenvector in the circuit is constant for various matrix sizes; namely, the time complexity is O(1). The O(1) time complexity is also supported by simulations of PageRank of real‐world datasets. This work paves the way for fast, energy‐efficient accelerators for eigenvector computation in a wide range of practical applications.
Synthesis of C1−C9 and C10−C21 Fragments of (−)‐Dolabriferol
Authors: Bandaru Anandaraju , Si Debjani , Kaliappan Krishna P.
Published: May 2020

Our efforts on the synthesis of C1−C9 and C10−C21 subunits of dolabriferol, a non‐contiguous polypropionate marine natural product, from a common intermediate using two non‐aldol variants is reported. i) Shimizu reaction, a Pd(0) mediated stereoselective epoxy‐ring opening of alkenyl oxiranes, has been employed for the stereoselective installation of methyl groups at C4 and C13 and ii) Bode's protocol, a NHC‐mediated reaction on β‐epoxy aldehydes, has been utilized for stereoselective construction of methyl and hydroxyl groups in anti‐fashion at C6−C7 and C15−C16 in the natural product.
Redox‐Active Hybrid Polyoxometalate‐Stabilised Gold Nanoparticles
Authors: Martin Carmen , Kastner Katharina , Cameron Jamie M. , Hampson Elizabeth , Alves Fernandes Jesum , Gibson Emma K. , Walsh Darren A. , Sans Victor , Newton Graham N.
Published: May 2020

We report the design and preparation of multifunctional hybrid nanomaterials through the stabilization of gold nanoparticles with thiol‐functionalised hybrid organic–inorganic polyoxometalates (POMs). The covalent attachment of the hybrid POM forms new nanocomposites that are stable at temperatures and pH values which destroy analogous electrostatically functionalised nanocomposites. Photoelectrochemical analysis revealed the unique photochemical and redox properties of these systems.
Emergence of a Radical‐Stabilizing Metal–Organic Framework as a Radio‐photoluminescence Dosimeter
Authors: Liu Hanzhou , Qin Haoming , Shen Nannan , Yan Siqi , Wang Yaxing , Yin Xuemiao , Chen Xinjian , Zhang Chao , Dai Xing , Zhou Ruhong , Ouyang Xiaoping , Chai Zhifang , Wang Shuao
Published: May 2020

Radio‐photoluminescence (RPL) materials display a distinct radiation‐induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal‐ion‐doped inorganic materials. Here we document the RPL of a metal–organic framework (MOF) for the first time: X‐ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X‐ray attenuator. These radicals afford new emission features in both UV‐excited and X‐ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF‐based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated.
Magnesium tetraorganyl derivatives of group 13 metals as intermediate products in the synthesis of group 13 metal alkyls and aryls
Authors: Basiak Dariusz , Wojciechowski Tomasz , Rzepiński Patryk , Dobrzycki Łukasz , Wojewódzka Anna , Monikowska Dorota , Zygadło‐Monikowska Ewa , Ziemkowska Wanda
Published: May 2020

Reactions of organomagnesium halides with group 13 metal halides lead to the formation of R3M type compounds (R = alkyl, aryl; M = Al, Ga, In) and are considered as the simplest methods of R3M compound syntheses. These seemingly simple reactions reveal a much more complex chemistry involving mixed magnesium‐group 13 metal compounds. To elucidate the reaction course of reactions of organomagnesium halides with group 13 metal halides, we have studied reactions of R3M with organomagnesium halides. The interaction of Et3M with R1MgX led to the formation of following products being mixtures of crystalline ionic complexes with the general composition of [Et4‐nR1nM]−[XMg (thf)5]+·(thf): [Et2.2Al(CH=CH2)1.8]−[BrMg (thf)5]+·(thf) (1), [Et3Ga(CH=CH2)]−[BrMg (thf)5]+·(thf) (2), [Et4Al]−[BrMg (thf)5]+·(thf) (3), [Et4Ga]−[BrMg (thf)5]+·(thf) (4), [Et2.9Al(C6H5)1.1]−[BrMg (thf)5]+·(thf) (5), [Et2.9Ga(C6H5)1.1]−[BrMg (thf)5]+·(thf) (6), [Et3.4GaMe0.6]−[IMg (thf)5]+·(thf) (7) and [Et4In]−[BrMg (thf)5]+·(thf) (8). A comparison of the production course of group 13 metal trialkyls R3M with a thermal decomposition of 1–8 products showed that reactions of MX3 with RMgX (X = Br, I; R = alkyl, aryl) yield initially intermediate ionic compounds, which must then be thermally decomposed to obtain pure R3M compounds. If group 13 metal bromides and iodides, and alkyl (aryl)magnesium bromides and iodides in thf are used, only intermediate products with the [R4M]−[XMg (thf)5]+·(thf) structure are formed.
Structural, DFT/B3LYP and molecular docking studies of binuclear thiosemicarbazide Copper (II) complexes and their biological investigations
Authors: Fayed Tarek A. , Gaber Mohamed , Abu El‐Reash Gaber M. , El‐Gamil Mohammed M.
Published: May 2020

Thiosemicarbazide copper (II) complexes; [Cu2(HL1)2(H2O)2Cl2].H2O (1) and [Cu2(HL2)2(H2O)2Cl2].2H2O (2) (where H2L1 = 2‐picolinoyl‐N‐(pyridin‐2‐yl)hydrazine‐1‐carbothioamide and H2L2 = 2‐(2‐(2‐aminothiazol‐4‐yl)acetyl)‐N‐(pyridin‐2‐yl)hydrazine‐1‐carbothioamide) have been synthesized and characterized. Analytical and spectroscopic data revealed that ligands behaves as monobasic tetradentate with octahedral geometry. In addition, the optimized geometry of the ligands and their complexes was approved with the Jaguar 9.1 program in the Schrödinger set using DFT (density functional theory) to predict chemical processes and to estimate the properties of the material made by the hybrid functional density system B3LYP. Furthermore, the thermal degradation curves of complexes were discussed in order to determine the kinetic and thermodynamic parameters by various approaches. Additionally, the antioxidant (using the DPPH and SOD methods) and the antibacterial potency of the compounds were examined. Also, docking study of ligands and their complexes was carried out against Staphylococcus aureus gram +ve, gram ‐ve bacterial strains of Escherichia coli and Candida albicans using the XP glide protocol of Schrödinger suite.
Free Fatty Acids in Commercial Krill Oils: Concentrations, Compositions, and Implications for Oxidative Stability
Authors: Fuller Ioan D. , Cumming Adam H. , Card Asli , Burgess Elaine J. , Barrow Colin J. , Perry Nigel B. , Killeen Daniel P.
Published: May 2020

The concentrations and pro‐oxidative effects of free fatty acids in commercial krill oil are not well defined. We now report that krill oil free fatty acids account for 2–13% of total lipids in commercial krill oil (n = 8) that these compounds are enriched in eicosapentaenoic acid (+7.1%) and docosahexaenoic acid (+6.3%) relative to whole oils; and that this composition make them highly pro‐oxidizing in marine triacylglycerol oils, but not in krill oil, which derives oxidative stability from both its phospholipids, and neutral lipids (the latter because of astaxanthin). Specific fatty acid esterification patterns showed that krill oil free fatty acids predominantly (88–93%) originated from phospholipids, mainly from the sn‐2 position, which was eight‐fold more hydrolyzed than the sn‐1 position. Lipolysis was not ongoing in stored oils. Adding small amounts of krill oil (1–5%) to marine triacylglycerol oils significantly increased their oxidative stability and also their resistance to free fatty acid‐mediated pro‐oxidative effects.
Synthesis of the C1‐C10 Fragment of Muamvatin
Authors: Bandaru Anandaraju , Kaliappan Krishna P.
Published: May 2020

This report delineates our efforts towards the synthesis of a stereochemically well‐defined ketone, the C1−C10 fragment of muamvatin, the first example of a 2, 4, 6‐trioxaadamantane ring skeletal polypropionate marine natural product, using two non‐aldol variants. i) The Shimizu reaction, a Pd(0) mediated stereoselective epoxy‐ring opening of alkenyl oxiranes, was employed for the stereoselective installation of methyl groups in syn‐fashion and ii) Bode's protocol, a NHC‐mediated reaction on β‐epoxy aldehydes, was utilized for stereoselective construction of methyl and hydroxyl groups in anti‐fashion.
Techno‐economic evaluation of a natural deep eutectic solvent‐based biorefinery: Exploring different design scenarios
Authors: Kumar Adepu K. , Sharma Shaishav , Dixit Gaurav , Shah Ekta , Patel Aesha , Boczkaj Grzegorz
Published: May 2020

This paper presents a comprehensive techno‐economic evaluation of an integrated natural deep eutectic solvent (NADES)‐based biorefinery – a 1 ton day−1 capacity design plant. The key parameters include payback period, net present value (NPV), and internal rate of return (IRR). These were compared with the parameters of conventional biorefineries. The ‘nth plant’ results clearly revealed that the single product‐based biorefinery is not a sustainable approach. Hence, value‐added products viz., cellulose, lignin, xylan, silica, etc., play a vital role in the cost‐effectiveness of bio‐based biorefineries. Based on ‘base‐case’ experimental results, a pilot‐scale plant design scenario is most feasible, with a NPV of 1.4 million USD, >100% IRR, and a payback period of <2 years. Sensitivity analysis revealed that lignin has the greatest impact on revenue. This report proves that multi‐product biorefineries provide better sustainability. The concepts of solvent recycling and reuse, and key challenges to the commercialization of this design approach, were also discussed. The application of NADES in biorefineries, has several advantages, making the implementation of NADES a key feature for increased sustainability in this industry. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd
A systematic review of evidence for and against routine surveillance imaging after completing treatment for childhood extracranial solid tumors
Authors: Morgan Jessica E. , Walker Ruth , Harden Melissa , Phillips Robert S.
Published: May 2020

Background

Regular off‐treatment imaging is often used to assess for recurrence of disease after childhood cancer treatment. It is unclear if this increases survival, or what burden surveillance places on patients, families, or health‐care services. This systematic review examines the impact of routine surveillance imaging after treatment of pediatric extracranial solid tumors.

Methods

Collaborative patient and public involvement informed the design and interpretation of this work. Thirteen electronic databases, conference proceedings, and trial registries were searched alongside reference list checking and forward citation searching from 1990 onwards. Studies were screened and data were extracted by two researchers. Risk of bias was assessed using a modified ROBINS‐I tool. Relevant outcomes were overall survival, psychological distress indicators, number of imaging tests, cost‐effectiveness, and qualitative data regarding experiences of surveillance programs. PROSPERO (CRD42018103764).

Results

Of 17 727 records identified, 55 studies of 10 207 patients were included. All studies used observational methods. Risk of bias for all except one study was moderate, serious, or critical. Data were too few to conduct meta‐analysis; however, narrative synthesis was performed. Surveillance strategies varied, and poorly reported, involving many scans and substantial radiation exposure (eg, neuroblastoma, median 133.5 mSv). For most diseases, surveillance imaging was not associated with increased overall survival, with the probable exception of Wilms tumor. No qualitative or psychological distress data were identified.

Conclusions

At present, there is insufficient evidence to evaluate the effects of routine surveillance imaging on survival in most pediatric extracranial solid tumors. More high‐quality data are required, preferably through randomized controlled trials with well‐conducted qualitative elements.
Impact of perceived value on casual mobile game loyalty: The moderating effect of intensity of playing
Authors: Molinillo Sebastian , Japutra Arnold , Liébana‐Cabanillas Francisco
Published: May 2020

The retention rate of mobile game players is one of the subjects that spark most interest in the industry, as many abandon the games only a few hours after downloading them. This study examines the antecedents of loyalty towards mobile games from the perspective of perceived value and explores the moderating effect of intensity of playing. The results revealed that hedonic value (i.e., perceived enjoyment and perceived attractiveness) and, to a lesser extent, utilitarian value (i.e., effort expectancy and perceived usefulness) are crucial in the loyalty that players feel towards mobile games. Intensity of playing weakens the relationship between perceived usefulness, perceived enjoyment and loyalty intention. Based on the findings, theoretical and practical implications are provided.
Nucleophilic RhI Catalyzed Selective Isomerization of Terminal Aziridines to Enamides
Authors: Tian Yingying , Kunz Doris
Published: May 2020

The selective isomerization of various terminal N‐Boc protected aziridines to enamides was realized using the highly reactive nucleophilic rhodium catalyst C with the Lewis acid LiNTf2 as co‐catalyst under moderate conditions. The reaction proceeds smoothly with only 1 mol% catalyst loading and excellent yields were achieved. An intermediate containing an enamide with a non‐conjugated terminal C=C double bond was detected during the course of the reaction, which isomerizes to form the thermodynamically favored 2‐amido styrene. Mechanistic insight is gained based on these observations.
Chemical Functionalization of 2D Materials
Authors: Martín Nazario , Tagmatarchis Nikos , Wang Qing Hua , Zhang Xiaoyan
Published: May 2020

This Special Issue of Chemistry–A European Journal is dedicated to the Chemical Functionalization of 2D Materials, and features some great contributions from experts in the field of 2D materials. This issue was originally assembled to support the Symposium G “Chemical Functionalization of 2D Materials” at the European Materials Research Society (E‐MRS) 2020 Spring Meeting, which was originally scheduled to be held in Strasbourg, France, from May 25th to 29th, 2020. Although the E‐MRS 2020 Spring Meeting has been cancelled due to the COVID‐19 outbreak, the publication of this Special Issue has proceeded and has become even more important as the contributors discuss diverse and timely research themes related to 2D materials. In this Editorial, a brief overview of the different types of 2D materials is given, together with the chemical functionalization schemes that can be applied to them to achieve new properties as well as enable improved performance in applications. Some of the articles featured in this Special Issue are also highlighted, with the hope that they will inspire readers and further advance the field.
The Underlying Chemistry to the Formation of PO2 Radicals from Organophosphorus Compounds: A Missing Puzzle Piece in Flame Chemistry
Authors: Liang Shuyu , Hemberger Patrick , Steglich Mathias , Simonetti Pietro , Levalois‐Grützmacher Joëlle , Grützmacher Hansjörg , Gaan Sabyasachi
Published: May 2020

Reactive species, such as .PO2 and HOPO, are considered of upmost importance in flame inhibition and catalytic combustion processes of fuels. However, the underlying chemistry of their formation remains speculative due to the unavailability of suitable analytical techniques that can be used to identify the transient species which lead to their formation. This study elucidates the reaction mechanisms of the formation of phosphoryl species from dimethyl methyl phosphonate (DMMP) and dimethyl methyl phosphoramidate (DMPR) under well‐defined oxidative conditions. Photoelectron photoion coincidence techniques that utilized vacuum ultraviolet synchrotron radiation were applied to isomer‐selectively detect the elusive key intermediates and stable products. With the help of in situ recorded spectral fingerprints, different transient species, such as PO2 and triplet O radicals, have been exclusively identified from their isomeric components, which has helped to piece together the formation mechanisms of phosphoryl species under various conditions. It was found that .PO2 formation required oxidative conditions above 1070 K. The combined presence of O2 and H2 led to significant changes in the decomposition chemistry of both model phosphorus compounds, leading to the formation of .PO2. The reaction .PO+O2→.PO2+O: was identified as the key step in the formation of .PO2. Interestingly, the presence of O2 in DMPR thermolysis suppresses the formation of PN‐containing species. In a previous study, PN species were identified as the major species formed during the pyrolysis of DMPR. Thus, the findings of this study has shed light onto the decomposition pathways of organophosphorus compounds, which are beneficial for their fuel additive and fire suppressant applications.
Brønsted Acid‐Catalyzed General Petasis Allylation and Isoprenylation of Unactivated Ketones
Authors: Zhou Yang , Zhao Zhen‐Ni , Zhang Yu‐Long , Liu Jun , Yuan Quan , Schneider Uwe , Huang Yi‐Yong
Published: May 2020

Brønsted acid‐catalyzed general Petasis allylation and isoprenylation of unactivated ketones were developed by using o‐hydroxyaniline and the corresponding pinacolyl boronic esters. This robust methodology provided access to a broad variety of quaternary homoallylic amines and dienyl amines in high yields, proved to be applicable to a gram‐scale synthesis, and allowed the synthesis of a potentially bioactive quaternary homoallylic aminodiol.
Anthranoxides as Highly Reactive Arynophiles for the Synthesis of Triptycenes
Authors: Iwata Takayuki , Hyodo Mizuki , Fukami Takuto , Shiota Yoshihito , Yoshizawa Kazunari , Shindo Mitsuru
Published: May 2020

We report herein an efficient method to synthesize triptycenes by the reaction of benzynes and anthranoxides, which are electron‐rich and readily prepared from the corresponding anthrones. Using this method, 1,9‐syn‐substituted triptycenes were regioselectively obtained employing 3‐methoxybenzynes. This method was also applied to synthesize pentiptycenes. A DFT study revealed that the cycloaddition of lithium anthranoxide and benzyne proceeds stepwise.
Hollow‐Structured Electrode Materials: Self‐Templated Synthesis and Their Potential in Secondary Batteries
Authors: Lu Si‐Qi , Sun Yong‐Gang , Xu Yan‐Song , Guo Si‐Jie , Cao An‐Min , Wan Li‐Jun
Published: May 2020

Hollow‐structured electrode materials have found broad applications in secondary batteries. The built‐in cavity of the prepared materials shows favorable features such as structural stability against volumetric deformation, good reservoir for electrolyte, and fast charge transport kinetics, which are highly efficient to improve the electrochemical performance of the electrode materials, particularly their cycling stability and high rate capability. However, the full potential of hollow‐structured materials is restrained by their limited synthesis capability, which currently relies on template‐based protocols with well‐known challenges in both product yield and operational convenience. In this review, the recent progress on different synthetic methodologies for the creation of hollow structures without the use of extra templates is summarized. Starting from solid precursors, focus is laid on the formation mechanisms for the creation of a cavity inside the electrode materials, and subsequently different driving forces such as Ostwald ripening, Kirkendall effect, and selective etching of an inhomogeneous particle are discussed, highlighting the self‐templated processes as designable and scalable ones with good control on the key structural characters. Furthermore, the applications of hollow structures in different kinds of battery systems are discussed in terms of building up a clear structure‐performance relationship of the electrode materials. Finally, we provide a perspective on the development trends of self‐templated construction of hollow structures.
T Cell Receptor Engineered Lymphocytes for Cancer Therapy
Authors: Rollins Meagan R. , Spartz Ellen J. , Stromnes Ingunn M.
Published: May 2020

T lymphocytes are capable of specific recognition and elimination of target cells. Physiological antigen recognition is mediated by the T cell receptor (TCR), which is an alpha beta heterodimer comprising the products of randomly rearranged V, D, and J genes. The exquisite specificity and functionality of T cells can be leveraged for cancer therapy: specifically, the adoptive transfer of T cells that express tumor‐reactive TCRs can induce regression of solid tumors in patients with advanced cancer. However, the isolation and expression of a tumor antigen‐specific TCRs is a highly involved process that requires identifying an immunogenic epitope, ensuring human cells are of the correct haplotype, performing a laborious T cell expansion process, and carrying out downstream TCR sequencing and cloning. Recent advances in single‐cell sequencing have begun to streamline this process. This protocol synthesizes and expands upon methodologies to generate, isolate, and engineer human T cells with tumor‐reactive TCRs for adoptive cell therapy. Though this process is perhaps more arduous than the alternative strategy of using chimeric antigen receptors (CARs) for engineering, the ability to target intracellular proteins using TCRs substantially increases the types of antigens that can be safely targeted. © 2020 Wiley Periodicals LLC.

Basic Protocol 1: Generation of human autologous dendritic cells from monocytes

Basic Protocol 2: In vitro priming and expansion of human antigen‐specific T cells

Basic Protocol 3: Cloning of antigen‐specific T cell receptors based on single‐cell VDJ sequencing data

Basic Protocol 4: Validation of T cell receptor expression and functionality in vitro

Basic Protocol 5: Rapid expansion of T cell receptor–transduced T cells and human T cell clones
Increased seedlings per hill compensates yield loss due to zero tillage in machine‐transplanted fragrant rice
Authors: He Longxin , Ashraf Umair , Du Bin , Lai Rifang , Luo Haowen , Abrar Muhammad , Tang Xiangru
Published: May 2020

Zero tillage is a soil conservation technique. However, reduction in grain yield might be caused without the effects caused by tillage at the beginning of planting. Present study was conducted in order to test the hypothesis that increased seedlings number per hill could compensate for yield decrement under zero tillage. A two‐year field experiment was conducted between 2018 and 2019 with two fragrant rice cultivars and three treatments: convention tillage with normal seedlings number per hill (CTNS); zero tillage with normal seedlings number per hill (ZTNS) and zero tillage with high seedlings number per hill (ZTHS). The results showed that lower leaf area index, dry matter accumulation, accumulation of nitrogen, phosphorus and potassium were observed in ZTNS treatment than CTNS treatment. Compared with CTNS treatment, ZTNS treatment significantly decreased the grain yield by 11.80‐26.65%. However, the differences between ZTHS and CTNS for yield attributes (effective panicle number, grain number per panicle, seed‐setting rate and 1000‐grain weight) and grain yield were generally small during both seasons and at both sites for both cultivars. Therefore, our study indicates that increasing seedlings number per hill could be an effective strategy to compensate the potential negative effects on yield formation and grain yield of fragrant rice under zero tillage.