bluuebunny/crossref_metadata_2025 huggingface dataset:
Photochemically Switchable Interconnected Microcavities for All‐Organic Optical Logic Gate
Authors: Hendra  , Takeuchi Akihide , Yamagishi Hiroshi , Oki Osamu , Morimoto Masakazu , Irie Masahiro , Yamamoto Yohei
Published: June 2021

Optical microcavities confine molecular luminescence and transfer it to a far longer distance than the conventional Förster resonant energy transfer process. Such cavity‐mediated energy transfer is advantageous for use in optical circuitry. However, to realize all‐organic optical circuits, optical gate operation with organic materials is indispensable. Here, all‐organic optical gates consisting of polymer whispering gallery mode (WGM) resonators that work as the optical source, drain, and gate, which are interconnected with polymer microfiber, are demonstrated. Photoirradiation of the source sphere, as an optical input, triggers the blue fluorescence that transmits to the gate sphere through the fiber. The fiber interconnection enhances both the light confinement efficiency in the individual spheres and the light transmission efficiency between distant spheres. The gate sphere contains photoisomerizable fluorescent dye that converts, in its closed state, the blue emission into green light, which is again transmitted to the drain sphere through the fiber and lets the sphere emit red light as an output. This optical cascade is switched on and off upon photoisomerization of the dye in the gate sphere. Furthermore, an energy cascade equipped with two gate spheres works as an OR‐type logic gate, demonstrating potential utility for the future all‐organic and all‐optical integrated devices.
Morphology Inversion of a Non‐Fullerene Acceptor Via Adhesion Controlled Decal‐Coating for Efficient Conversion and Detection in Organic Electronics
Authors: Kim Min Soo , Jang Woongsik , Nguyen Thuc‐Quyen , Wang Dong Hwan
Published: June 2021

In this study, a promising film formation technique is highlighted, named mold‐assisted decal‐coating, as a thin film transfer printing process using the polyurethane acrylate‐based stamping mold. By optimizing the surface energy of the mold with wetting coefficient theory, the mold‐assisted decal‐coating process is successfully demonstrated by transferring the photoactive layer composed of the polymer donor, poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)] and a narrow bandgap non‐fullerene acceptor (NFA), 2,2′‐[[4,4,9,9‐tetrakis(4‐hexylphenyl)‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl]bis[[4‐[(2‐ethylhexyl)oxy]‐5,2‐thiophenediyl]methylidyne(5,6‐difluoro‐3‐oxo‐1H‐indene‐2,1(3H)‐diylidene)]]bis[propanedinitrile]. This process induces a well‐ordered morphology of photoactive material, prevents damage to the underlying layer by suppressing the solvent penetration. Both photovoltaic cells and photodetectors prepared by the decal‐coated photoactive layers containing fluorinated NFAs showed higher performance (power conversion efficiency = 10.69% and specific detectivity = 1.27 × 1012 A cm Hz1/2 W−1, respectively) than those of cells prepared by the spin‐coating method owing to morphology inversion and smoother interface that led to suppressed internal resistance and enhanced charge flow in normal structure. Thus, the reproducible decal‐coating process using a customized elastomeric mediator is an important thin film coating technique for efficient next‐generation organic optoelectronic materials.
Grain Boundary Perfection Enabled by Pyridinic Nitrogen Doped Graphdiyne in Hybrid Perovskite
Authors: Fan Wenqiang , Zhang Suicai , Xu Chenzhe , Si Haonan , Xiong Zhaozhao , Zhao Yunqi , Ma Kaikai , Zhang Zheng , Liao Qingliang , Kang Zhuo , Zhang Yue
Published: June 2021

The solution processing in hybrid perovskite films inevitably results in the formation of detrimental defects at grain boundaries (GBs) that deteriorate the optoelectronic properties and bring about severe hysteresis as well as operational instability. Here, an effective scenario to alleviate the imperfection issue at perovskite GBs via incorporating pyridinic nitrogen‐doped graphdiyne (N‐GDY) is proposed. Taking full advantage of periodic acetylenic linkages and introduced pyridinic N atoms, the deep‐level trap states like Pb–I antisite defects and under‐coordinated Pb atoms are considerably passivated, thus diminishing the undesired non‐radiative recombination. Additionally, the spatial confinement coupling with electrostatic repulsion effect originated from the intrinsic 2D structure of N‐GDY, has been identified to deal with the halide ion migration behavior. Such contributions are further theoretically evidenced with the charge density delocalization as well as the ion migration energy barrier elevation. The authors unprecedentedly verified the superiorities based on the flexible chemical‐tailorability of atomic crystal GDY materials toward polycrystalline perovskite related energy conversion devices.
Tuning Superfast Curing Thiol‐Norbornene‐Functionalized Gelatin Hydrogels for 3D Bioprinting
Authors: Göckler Tobias , Haase Sonja , Kempter Xenia , Pfister Rebecca , Maciel Bruna R. , Grimm Alisa , Molitor Tamara , Willenbacher Norbert , Schepers Ute
Published: June 2021

Photocurable gelatin‐based hydrogels have established themselves as powerful bioinks in tissue engineering due to their excellent biocompatibility, biodegradability, light responsiveness, thermosensitivity and bioprinting properties. While gelatin methacryloyl (GelMA) has been the gold standard for many years, thiol‐ene hydrogel systems based on norbornene‐functionalized gelatin (GelNB) and a thiolated crosslinker have recently gained increasing importance. In this paper, a highly reproducible water‐based synthesis of GelNB is presented, avoiding the use of dimethyl sulfoxide (DMSO) as organic solvent and covering a broad range of degrees of functionalization (DoF: 20% to 97%). Mixing with thiolated gelatin (GelS) results in the superfast curing photoclick hydrogel GelNB/GelS. Its superior properties over GelMA, such as substantially reduced amounts of photoinitiator (0.03% (w/v)), superfast curing (1–2 s), higher network homogeneity, post‐polymerization functionalization ability, minimal cross‐reactivity with cellular components, and improved biocompatibility of hydrogel precursors and degradation products lead to increased survival of primary cells in 3D bioprinting. Post‐printing viability analysis revealed excellent survival rates of > 84% for GelNB/GelS bioinks of varying crosslinking density, while cell survival for GelMA bioinks is strongly dependent on the DoF. Hence, the semisynthetic and easily accessible GelNB/GelS hydrogel is a highly promising bioink for future medical applications and other light‐based biofabrication techniques.
Modulation of Spin–Orbit Torque from SrRuO3 by Epitaxial‐Strain‐Induced Octahedral Rotation
Authors: Zhou Jing , Shu Xinyu , Lin Weinan , Shao Ding Fu , Chen Shaohai , Liu Liang , Yang Ping , Tsymbal Evgeny Y. , Chen Jingsheng
Published: June 2021

Spin–orbit torque (SOT), which arises from the spin–orbit coupling of conduction electrons, is believed to be the key route for developing low‐power, high‐speed, and nonvolatile memory devices. Despite the theoretical prediction of pronounced Berry phase curvatures in certain transition‐metal perovskite oxides, which lead to considerable intrinsic spin Hall conductivity, SOT from this class of materials has rarely been reported until recently. Here, the SOT generated by epitaxial SrRuO3 of three different crystal structures is systematically studied. The results of both spin‐torque ferromagnetic resonance and in‐plane harmonic Hall voltage measurements concurrently reveal that the intrinsic SOT efficiency of SrRuO3 decreases when the epitaxial strain changes from tensile to compressive. The X‐ray diffraction data demonstrate a strong correlation between the magnitude of SOT and octahedral rotation around the in‐plane axes of SrRuO3, consistent with the theoretical prediction. This work offers new possibilities of tuning SOT with crystal structures and novel opportunities of integrating the unique properties of perovskite oxides with spintronic functionalities.
Engineering Fe–N Coordination Structures for Fast Redox Conversion in Lithium–Sulfur Batteries
Authors: Ma Cheng , Zhang Youquan , Feng Yiming , Wang Ning , Zhou Liangjun , Liang Chaoping , Chen Libao , Lai Yanqing , Ji Xiaobo , Yan Chenglin , Wei Weifeng
Published: June 2021

Critical drawbacks, including sluggish redox kinetics and undesirable shuttling of polysulfides (Li2Sn, n = 4–8), seriously deteriorate the electrochemical performance of high‐energy‐density lithium–sulfur (Li–S) batteries. Herein, these challenges are addressed by constructing an integrated catalyst with dual active sites, where single‐atom (SA)‐Fe and polar Fe2N are co‐embedded in nitrogen‐doped graphene (SA‐Fe/Fe2N@NG). The SA‐Fe, with plane‐symmetric Fe‐4N coordination, and Fe2N, with triangular pyramidal Fe‐3N coordination, in this well‐designed configuration exhibit synergistic adsorption of polysulfides and catalytic selectivity for Li2Sn lithiation and Li2S delithiation, respectively. These characteristics endow the SA‐Fe/Fe2N@NG‐modified separator with an optimal polysulfides confinement–catalysis ability, thus accelerating the bidirectional liquid–solid conversion (Li2Sn↔Li2S) and suppressing the shuttle effect. Consequently, a Li–S battery based on the SA‐Fe/Fe2N@NG separator achieves a high capacity retention of 84.1% over 500 cycles at 1 C (pure S cathode, S content: 70 wt%) and a high areal capacity of 5.02 mAh cm−2 at 0.1 C (SA‐Fe/Fe2N@NG‐supported S cathode, S loading = 5 mg cm−2). It is expected that the outcomes of the present study will facilitate the design of high‐efficiency catalysts for long‐lasting Li–S batteries.
Ce Doping Boosts the Thermo‐ and Photocatalytic Oxidation of CO at Low Temperature in TiZrO4 Solid Solutions
Authors: Tang Panjuan , Livraghi Stefano , Giamello Elio , Garroni Sebastiano , Malfatti Luca , Agnoli Stefano
Published: June 2021

Palladium nanoparticles supported on zirconium titanate with cerium doping up to 10% molar (Ce‐ZT) are prepared by a facile impregnation method and characterized by several techniques. Due to electronic effects, the amount of Ce cations in a reduced oxidation state, i.e., Ce(III), is surprisingly high, more than 50% of the total cerium amount. The Pd decorated Ce‐ZT nanoparticles exhibit excellent catalytic activity in the low temperature oxidation of CO. The amount of Pd and Ce concentration results to be the key parameters controlling the catalytic performance. The best activity is observed in the sample with the highest Ce doping (10% molar) and a nominal Pd loading of 2% w/w, which exhibits an outstanding turnover frequency of 0.1 s−1 at 45 °C. Moreover, the CO conversion remains unchanged at 100% for 24 h at 50 °C, or for several successive light‐off experiments up to 120 °C, demonstrating excellent long‐term stability. Light irradiation is shown to further improve the catalytic performance allowing to reach the same catalytic activity of dark conditions at a temperature that is 20–40 °C lower. Electron paramagnetic resonance spectroscopy experiments indicate that Pd nanoparticles and Ce(III) ions can trap electrons favoring charge separation and formation of superoxide species, therefore enabling photocatalysis.
Programmable 4D Printing of Bioinspired Solvent‐Driven Morphing Composites
Authors: Ren Luquan , Li Zhuoshi , Liu Qingping , Ren Lei , Wu Qian , Li Bingqian , Li Guiwei , Song Zhengyi , Zhou Xueli
Published: June 2021

In this article, we propose a bioinspired programmed 4D printing method. A combination of magnetic orientation process and grayscale 3D printing is used to achieve site‐specific orientation of the reinforcing fibers and gradient crosslinking of the matrix resin in the thickness direction within 2D composite films. After solventization and desolventization, 2D thin film structures can be transformed into complex 3D architectures, and the transformed 3D architectures can be permanently preserved without stimulation sources. Thus, the method can also be considered as an efficient 3D printing process. Then, the influences of crosslinking density, sample geometry, formulation, and fiber architecture on the deformation of the printed objects are investigated. Finally, as a proof of concept, various samples, including a hand, snowflake, and leaf, are printed to verify the feasibility of the proposed 4D printing strategy. This programmed 4D printing method provides a simple and effective reversible strategy, taking the full advantages of 4D printing and expanding the design space of 4D printing.
Switchable Electrically Driven Optical Antenna Based on Ultrathin Amorphous Silica
Authors: Tang Jibo , Hu Huatian , He Xiaobo , Xu Yuhao , Zhang Yuan , Guan Zhiqiang , Zhang Shunping , Xu Hongxing
Published: June 2021

Electrically driven optical antenna (EDOA) attracts considerable interest thanks to its capability of converting electronic signal to light within an ultrafast timescale and on a highly compact dimension. However, active control of EDOA, such as its emission wavelength, is still challenging because of the lack of an efficient way to reversibly change the size, gap, or dielectric environment of a nanoscale device. Here, an emission wavelength switchable EDOA is developed by applying a bias on Au@SiO2 core–shell nanoparticle bridged on two gold electrodes. The tuning of the light emission is based on the formation and elimination of conductive filaments within the ultrathin amorphous silica shell, which allows a reversible switching of the conductivity in the junction. This leads to the modifications of both the inelastic electron tunneling and the plasmonic response of the EDOA, resulting in an emission wavelength shift as large as 115 nm. The results offer new opportunities for developing switchable EDOA toward integrated optoelectronic circuits, nanoscale sensing, and high‐resolution display.
Shape‐Dependent Kinetics of Halide Vacancy Filling in Organolead Halide Perovskites
Authors: Okamoto Takuya , Shahjahan Md. , Biju Vasudevanpillai
Published: June 2021

Halide perovskites show high photoluminescence quantum yields and tunable bandgap. While perovskites’ optical properties significantly degrade due to the ionic and electronic defects, a correlation among their structure, size, defects, and degradation rate remains concealed. The authors report the crystal shape‐ and halide vacancy‐dependent stability of methylammonium lead bromide single crystals. The vacancies are filled in the cubic‐, plate‐, and rod‐shaped crystals by the halide‐soaking and light‐soaking processes. The differences in the stability, photoluminescence intensity, lifetime, and vacancy filling rates in these geometrical shapes derive from their specific surface‐to‐volume ratios. The shape‐dependent vacancy filling helps to correlate the electron microscope images, elemental compositions, and the photoluminescence intensity and lifetime.
A Light‐Emitting Liquid Crystal Display Device without Polarizers and Alignment Layers
Authors: Zhao Dongyu , Bi Weihua , Tang Ben Zhong
Published: June 2021

Light‐emitting displays become the future direction of display technology for the radical requirement of reducing energy consumption. Here, an approach of fabricating a luminescent liquid crystal (LE‐LC) display device without polarizers and alignment layers is reported, achieved by using an aggregation‐induced emission (AIE)‐active LE‐LC mixture. Through studying the relationship between emission of the LE‐LC at several orientation modes and the concentration of the AIE‐featured fluorescent dye, the difference of fluorescence at aggregation state is revealed. When the concentration of the fluorescent dye is high enough, the emission of the planar‐aligned LE‐LCs is ≈4 times of the vertical‐aligned LE‐LCs. An electronically controlled LE‐LC cell is thus constructed, in which the homeotropic alignment of liquid crystals is induced by doping of CuInS2 nanoparticles. Therefore, this simple LE‐LC display avoids the use of polarizers and alignment layers, raising the exciting possibility of development of high efficiency and low energy‐consumption LE‐LC devices.
Highly Efficient Gradient Solid Immersion Lens with Large Numerical Aperture for Broadband Achromatic Deep Subwavelength Focusing and Magnified Far Field
Authors: Chen Jin , Zhou Yang Yang , Chu Hong Chen , Lai Yun , Chen Huan Yang , Chen Mingji , Fang Daining
Published: June 2021

Achromatic deep subwavelength lens with large numerical aperture (NA) is in urgent need in several fields, from optical imaging, photolithography, spectroscopy, nanophotonics to microwave engineering and sensing. However, the previous proposed approaches to achieve deep subwavelength lens suffer from severe chromatic aberrations, limited bandwidth, and limited efficiency. In this paper, enlightened by Maxwell's fish‐eye lens, a semicircular gradient solid immersion lens is proposed and manufactured by gradient isotropic dielectrics. Highly efficient (above 85%) achromatic (7–13 GHz) deep subwavelength focusing with full width at half maximum around 0.15λ and large NA of 2.4 as well as magnified far‐field radiation (4–12 GHz) with high recognition are achieved. Theoretical analysis reveals that electric field enhancement at the lens/air interface and magnification of high spatial frequency deep subwavelength information contribute to deep subwavelength focusing and magnified far‐field radiation, respectively. Measured results of near field and far field agree well with those of theoretical predictions, which makes the presented lens having the potential to be applied in deep subwavelength engineering systems.
Metasurface Based on Inverse Design for Maximizing Solar Spectral Absorption
Authors: Jiang Xinpeng , Yuan Huan , Chen Dingbo , Zhang Zhaojian , Du Te , Ma Hansi , Yang Junbo
Published: June 2021

Broadband absorption of sunlight plays a crucial role in applying solar energy. However, despite being a decade‐old technology, there are only a handful of simple metasurfaces designed by conventional methods. This work theoretically combines inverse design with broadband absorption of sunlight to optimize a metasurface that exhibits triple coupling mode resonance for maximizing solar spectral absorption. The metasurface consists of dual‐layer titanium nitride (TiN) cylinder grating arrays, TiN dielectric layers, and silicon nitride layers. The simulation results reveal the high absorptivity of 93% in the range of 250–2450 nm, which covers almost the entire solar spectrum. The advantages of genetic algorithm (GA) including less computational cost and high performance of populations are compared with conventional method. Based on mode analysis, the origin of the observed triple coupling mode resonances is revealed. In addition, the GA‐based metasurface has a high solar–thermal efficiency that includes not only the high absorptivity of 93% in solar spectrum, but also the low emissivity of 21% in infrared band without restriction of polarization and incident angle. The design, which highlights the potential impact on maximizing broadband absorption using simple method to optimize complex coupling, opens a novel approach to study solar–thermal energy harvesting and manipulation.
Multichannel High‐Efficiency Metasurfaces Based on Tri‐Band Single‐Cell Meta‐Atoms with Independent Complex‐Amplitude Modulations
Authors: Xie Rensheng , Zhang Dajun , Wang Xiong , An Sensong , Zheng Bowen , Zhang Hualiang , Zhai Guohua , Li Lin , Ding Jun
Published: June 2021

Achieving multitasking wavefront manipulations at multiple frequencies within a planar meta‐device is pivotal for increasing data density and functionality diversity yet still challenging in integrated devices. Considering both high efficiency and compactness, herein, a high‐efficiency reflective metasurface based on single‐cell meta‐atoms with independent complex‐amplitude modulations at three distinct frequencies under the circularly polarized incidence is demonstrated, which can facilitate the formation of three mutually orthogonal channels with three distinctive functionalities. As a proof‐of‐concept demonstration, a tri‐channel metasurface is designed and verified through both numerical simulation and experiment, where channels 1, 2, and 3 implement a dual‐vortex‐beam generator, a quad‐focus metalens, and a meta‐hologram at three different frequencies, respectively. The simulated results and the measured results have very good agreements, validating the proposed tri‐band single‐cell metasurface design strategy. The proposed method can open new opportunities to improve the information density and has promising prospects in image displays, communication systems, and optical storage.
Argyrin F Treatment‐Induced Vulnerabilities Lead to a Novel Combination Therapy in Experimental Glioma
Authors: Walter Bianca , Canjuga Denis , Yüz Simge G. , Ghosh Michael , Bozko Przemyslaw , Przystal Justyna M. , Govindarajan Parameswari , Anderle Nicole , Keller Anna‐Lena , Tatagiba Marcos , Schenke‐Layland Katja , Rammensee Hans‐Georg , Stevanovic Stefan , Malek Nisar P. , Schmees Christian , Tabatabai Ghazaleh
Published: June 2021

Glioblastoma are incurable primary tumors of the central nervous system that frequently harbor molecular alterations in the retinoblastoma pathway with subsequent cell cycle abnormalities. It is aimed to investigate the anti‐glioma activity of the novel cell cycle‐stabilizing compound Argyrin F and its potential treatment‐induced vulnerabilities to exploit possibilities for novel rational combination therapies. Human and murine glioma cells are used, cytotoxicity and clonogenic survival assays, cell cycle analyses, and immunoblots are performed. Residual freshly resected tissue is used for a preclinical glioma model ex vivo, i.e., patient‐derived microtumors (PDMs) for co‐culture experiments with autologous tumor‐infiltrating lymphocytes (TILs). Mass spectrometry‐based immunopeptidomics are performed and the orthotopic syngeneic SMA560/VM/Dk glioma mouse model is used. Argyrin F‐induced cell cycle arrest and reduced clonogenic survival is observed. Argyrin F‐treated experimental glioma in vivo displays 4.6‐fold more glioma‐infiltrating CD8+ T cells. A distinctive treatment‐induced immunopeptidome is discovered. The combination of Argyrin F plus PD‐1 antibody increases cellular toxicity in PDM/TILs co‐cultures ex vivo and prolonged overall survival compared with monotherapies in vivo. Thus, Argyrin F leads to anti‐glioma effects and increases the immunogenicity, paving the way for a novel combination therapy of Argyrin F plus PD‐1 blockade.
Electron–Phonon Coupling and Electron–Phonon Scattering in SrVO3
Authors: Mirjolet Mathieu , Rivadulla Francisco , Marsik Premysl , Borisov Vladislav , Valentí Roser , Fontcuberta Josep
Published: June 2021

Understanding the physics of strongly correlated electronic systems has been a central issue in condensed matter physics for decades. In transition metal oxides, strong correlations characteristic of narrow d bands are at the origin of remarkable properties such as the opening of Mott gap, enhanced effective mass, and anomalous vibronic coupling, to mention a few. SrVO3 with V4+ in a 3d1 electronic configuration is the simplest example of a 3D correlated metallic electronic system. Here, the authors' focus on the observation of a (roughly) quadratic temperature dependence of the inverse electron mobility of this seemingly simple system, which is an intriguing property shared by other metallic oxides. The systematic analysis of electronic transport in SrVO3 thin films discloses the limitations of the simplest picture of e–e correlations in a Fermi liquid (FL); instead, it is shown show that the quasi‐2D topology of the Fermi surface (FS) and a strong electron–phonon coupling, contributing to dress carriers with a phonon cloud, play a pivotal role on the reported electron spectroscopic, optical, thermodynamic, and transport data. The picture that emerges is not restricted to SrVO3 but can be shared with other 3d and 4d metallic oxides.
Improvement of Synaptic Properties in Oxygen‐Based Synaptic Transistors Due to the Accelerated Ion Migration in Sub‐Stoichiometric Channels
Authors: Lee Jongwon , Nikam Revannath Dnyandeo , Kwak Myonghoon , Kwak Hyunjeong , Kim Seyoung , Hwang Hyunsang
Published: June 2021

The oxygen ion‐based synaptic transistor (OIST) is a promising candidate for next‐generation synaptic devices for neuromorphic computing. However, the key process parameters that control synaptic characteristics have not yet been studied. In this study, the authors report near‐ideal synaptic characteristics by adopting oxygen‐deficient transition metal‐oxide (TMO) channels and yttria‐stabilized zirconia electrolytes. With decreasing oxygen stoichiometry in the TMO channel by controlling the O2 flow rate during reactive sputtering, the oxygen ion supply and migration are accelerated by lowering the migration barrier. The reduced barrier energy and improved ion diffusivity characteristic in the oxygen‐deficient TMO channels are confirmed experimentally through cyclic voltammetry analysis. As a result, improved weight‐update linearity and wide conductance range can be achieved in OIST devices with an oxygen‐deficient TMO (WO2.7, TiO1.7) channel. The authors confirm the excellent pattern recognition accuracy, which can be explained by the improved synaptic characteristics of the OIST synapse array.
Artificial Synapse Based on Organic–Inorganic Hybrid Perovskite with Electric and Optical Modulation
Authors: Lao Jie , Xu Wen , Jiang Chunli , Zhong Ni , Tian Bobo , Lin Hechun , Luo Chunhua , Travas‐Sejdic Jadranka , Peng Hui , Duan Chun‐Gang
Published: June 2021

Artificial synapse of neuromorphic computing has been attracting significant attention as an alternative concept for next‐generation computing. Here, a two‐terminal synaptic device based on potassium iodide (KI) and CH3NH3PbI3 (MAPbI3) hybrid film (KI–MAPbI3) is reported. The use of KI as an additive in the film preparation process greatly reduces grain boundaries, facilitating the improvement of device performance. The prepared synaptic device exhibits dual response to electric and light stimuli due to the unique properties of MAPbI3. Besides the successful simulation of biological synaptic functionalities such as paired‐pulse facilitation (PPF), plasticity in long‐term potentiation (LTP), and long‐term depression (LTD), the learning behavior of human under different moods and Pavlov's dog experiment are also simulated by combining electric and light stimuli. For image recognition, the simulation result shows that the device achieves an accuracy of 84.2% under light illumination after only 1500 learning phases.
Lattice Location Studies of the Amphoteric Nature of Implanted Mg in GaN
Authors: Wahl Ulrich , Correia João Guilherme , Costa Ângelo R. G. , David‐Bosne Eric , Kappers Menno J. , da Silva Manuel Ribeiro , Lippertz Gertjan , Lima Tiago A. L. , Villarreal Renan , Vantomme André , Pereira Lino M. C.
Published: June 2021

Despite the renewed interest in ion implantation doping of GaN, efficient electrical activation remains a challenge. The lattice location of 27Mg is investigated in GaN of different doping types as a function of implantation temperature and fluence at CERN's ISOLDE facility. The amphoteric nature of Mg is elucidated, i.e., the concurrent occupation of substitutional Ga and interstitial sites: following room temperature ultra‐low fluence (≈2 × 1010 cm−2) implantation, the interstitial fraction of Mg is highest (20–24%) in GaN pre‐doped with stable Mg during growth, and lowest (2–6%) in n‐GaN:Si, while undoped GaN shows an intermediate interstitial fraction of 10–12%. Both for p‐ and n‐GaN prolonged implantations cause interstitial 27Mg to approach the levels found for undoped GaN. Implanting above 400 °C progressively converts interstitial Mg to substitutional Ga sites due to the onset of Mg interstitial migration (estimated activation energy 1.5–2.3 eV) and combination with Ga vacancies. In all sample types, implantations above a fluence of 1014 cm−2 result in >95% substitutional Mg. Ion implantation is hence a very efficient method to introduce Mg into substitutional Ga sites, i.e., challenges toward high electrical activation of implanted Mg are not related to lack of substitutional incorporation.
Metal‐Ligand π Interactions in Lithium‐Rich Li2RhO3 Cathode Material Activate Bimodal Anionic Redox
Authors: Zhang Kun , Jiang Zewen , Ning Fanghua , Li Biao , Shang Huaifang , Song Jin , Zuo Yuxuan , Yang Tonghuan , Feng Guang , Ai Xinping , Xia Dingguo
Published: June 2021

Li‐rich oxide (LRO) cathodes that exhibit anionic redox activity can boost the energy density of Li‐ion batteries. Oxygen redox in LROs can originate from the charge compensation of pure O 2p nonbonding (NB) states; however, the high charging voltages cause much safety concerns in practical applications. Exploiting new anionic redox modes that can be used at low voltages is thus imperative. In view of this, a further understanding of the anionic redox behavior with respect to metal‐ligand interactions in LROs is highly desired. In this study, by analyzing the orbital combinations of transition metals (TMs) and O in LROs, the prevalence of π‐type, σ‐type, and NB states is investigated. Highly covalent Li2RhO3 with strong π‐type interactions is selected as a model material. Owing to the closer energy levels of O and Rh and the orbital vacancy of Rh4+, oxygen acts as a π‐electron donor to central Rh and exhibits high reactivity in the occupied anti‐bonding state, showing a novel low‐voltage O redox which is distinct from high‐voltage NB O redox. This π‐type oxygen redox mode expands the fundamental theories of anionic redox and provides a new design route to achieve high‐capacity Li‐rich cathode materials.
Acidic Water Oxidation on Quantum Dots of IrOx/Graphdiyne
Authors: Wang Zhongqiang , Zheng Zhiqiang , Xue Yurui , He Feng , Li Yuliang
Published: June 2021

Efficient acidic water oxidation utilization in the oxygen evolution reaction (OER) is still an important bottleneck for hydrogen production. From fundamental principles, a controllable graphdiyne (GDY) induced growth strategy is established; highly uniform size distribution of oxidized iridium quantum dots is prepared on the surface of graphdiyne (IrOxQD/GDY). The result shows that, the catalyst exhibits excellent activity and durability for acidic OER, with a current density of 10 mA cm−2 at a small overpotential of 236 mV versus the reversible hydrogen electrode (RHE) and a Tafel slope of 70 mV dec−1. The performance is greatly superior to previously reported electrocatalysts. Remarkably, the acidic electrolyzer using IrOxQD/GDY as both cathode and anode electrodes can reach 10 mA cm−2 only at a much low cell voltage of 1.49 V (vs RHE). The results show the superior advantages of graphdiyne in effectively increasing numbers of the catalytically active sites for improving the charge transfer behavior and protecting the metal catalysts from corrosion.
Mechanistic Insights of Mg2+‐Electrolyte Additive for High‐Energy and Long‐Life Zinc‐Ion Hybrid Capacitors
Authors: Wang Pinji , Xie Xuesong , Xing Zhenyue , Chen Xianhong , Fang Guozhao , Lu Bingan , Zhou Jiang , Liang Shuquan , Fan Hong Jin
Published: June 2021

An electrolyte cation additive strategy provides a versatile route for developing high‐energy and long‐life aqueous zinc‐ion hybrid capacitors. However, the mechanisms of energy storage and Zn anode protection are still unclear in Zn‐based systems with dual‐ion electrolytes. Here, a dual charge storage mechanism for zinc‐ion hybrid capacitors with both cations and anions adsorption/desorption and the reversible formation of Zn4SO4(OH)6·xH2O enabled by the Mg2+ additive in the common aqueous ZnSO4 electrolyte are proposed. Theoretical calculations verify that the self‐healing electrostatic shield effect and the solvation‐sheath structure regulation rendered by the Mg2+ additive account for the observed uniform Zn deposition and dendrite suppression. As a result, an additional energy storage capacity of ≈50% compared to that in a pure 2 m ZnSO4 electrolyte and an extended cycle life with capacity retention of 98.7% after 10 000 cycles are achieved. This work highlights the effectiveness of electrolyte design for dual‐ion carrier storage mechanism in aqueous devices toward high energy density and long cycle life.
Stepping Out of Transition Metals: Activating the Dual Atomic Catalyst through Main Group Elements
Authors: Sun Mingzi , Wong Hon Ho , Wu Tong , Dougherty Alan William , Huang Bolong
Published: June 2021

In recent years, investigations into atomic catalysts has accelerated significantly. Although different atomic catalysts have been developed, the introduction of main group elements is rarely considered. In this work, the possibility of introducing alkaline/alkaline earth metals (AAEM), post‐transition metal (Post‐TM), and metalloids to form stable graphdiyne‐based dual atomic catalysts (GDY‐DAC) is revealed. The main group elements not only act as a promising separator to improve the loading of DACs but also activate the alkyl chains to facilitate the electroactivity of GDY‐DAC. Most importantly, the main group elements in the GDY‐DAC do not affect the electroactivity of transition or lanthanide metals and even enable subtle modulations on the electronic structures. The p band center is a significant descriptor to modulate the electroactivity in oxides while their applications in the atomic catalysts are unclear. With the further evaluations of machine learning, it is found that the involvements of s‐orbitals and p‐orbitals perturb the prediction accuracies of both formation energies and p‐band center, especially for the AAEM. This work supplies insights that are expected to aid progress in designing main group elements‐based atomic catalysts, which opens a new avenue in designing advanced electrocatalysts.
Physical therapy treatment of hypermobile Ehlers–Danlos syndrome: A systematic review
Authors: Reychler Gregory , De Backer Maya‐Mafalda , Piraux Elise , Poncin William , Caty Gilles
Published: June 2021

Physiotherapy techniques are regularly prescribed in the hypermobile type Ehlers–Danlos syndrome (hEDS) and they are appreciated by the patients. The objective of this systematic review was to investigate the effect of the different physiotherapy techniques related to the children and adult patients with hEDS. PubMed, SPORTDiscus, Cochrane Library, PEDro, Scopus, and Embase databases were analyzed from inception to April 2020. Characteristics of the studies (authors), patients (sample size, sex, age, Beighton score), and nonpharmacological treatment (length of the program, number of session, duration of the session, and type of intervention), and the results with the dropout rate were extracted. From the 1045 retrieved references, 6 randomized controlled trial with a sample size ranging from 20 to 57 patients were included in the systematic review. There was a huge heterogeneity in the interventions. The durations of the program were from 4 to 8 weeks. Pain or proprioception demonstrated significant improvements in the intervention group regardless of the type of intervention. A benefit of the inspiratory muscle training was observed on functional exercise capacity. The quality of life was systematically improved. Physiotherapy benefits on proprioception and pain in patients with hEDS even if robust randomized control studies are missing.
Homozygous WNT9B variants in two families with bilateral renal agenesis/hypoplasia/dysplasia
Authors: Lemire Gabrielle , Zheng Bixia , Ediae Grace U. , Zou Ruobing , Bhola Priya T. , Chisholm Caitlin , de Nanassy Joseph , Lo Bryan , Wang Chunyan , Shril Shirlee , El Desoky Sherif , Shalaby Mohammed , Kari Jameela A. , Wang Xueqi ,   Care4Rare Canada Consortium, Kernohan Kristin D. , Boycott Kym M. , Hildebrandt Friedhelm , Sawyer Sarah L.
Published: June 2021

WNT9B plays a key role in the development of the mammalian urogenital system. It is essential for the induction of mesonephric and metanephric tubules, the regulation of renal tubule morphogenesis, and the regulation of renal progenitor cell expansion and differentiation. To our knowledge, WNT9B has not been associated with renal defects in humans; however, WNT9B−/− mice have renal agenesis/hypoplasia and reproductive tract abnormalities. We report four individuals from two unrelated consanguineous families with bilateral renal agenesis/hypoplasia/dysplasia and homozygous variants in WNT9B. The proband from Family 1 has bilateral renal cystic dysplasia and chronic kidney disease. He has two deceased siblings who presented with bilateral renal hypoplasia/agenesis. The three affected family members were homozygous for a missense variant in WNT9B (NM_003396.2: c.949G>A/p.(Gly317Arg)). The proband from Family 2 has renal hypoplasia/dysplasia, chronic kidney disease, and is homozygous for a nonsense variant in WNT9B (NM_003396.2: c.11dupC/p.(Pro5Alafs*52)). Two of her siblings died in the neonatal period, one confirmed to be in the context of oligohydramnios. The proband's unaffected brother is also homozygous for the nonsense variant in WNT9B, suggesting nonpenetrance. We propose a novel association of WNT9B and renal anomalies in humans. Further study is needed to delineate the contribution of WNT9B to genitourinary anomalies in humans.
A novel truncating variant in the FGD1 gene associated with Aarskog–Scott syndrome in a family previously diagnosed with Tel Hashomer camptodactyly
Authors: Kessel Irena , German Alina , Peleg Amir ,   Regeneron Genetics Center, Gonzaga‐Jauregui Claudia , Paperna Tamar , Ekhilevitch Nina , Kurolap Alina , Baris Feldman Hagit , Sagi‐Dain Lena
Published: June 2021

Tel Hashomer camptodactyly syndrome is a long‐known entity characterized by camptodactyly with muscular hypoplasia, skeletal dysplasia, and abnormal palmar creases. Currently, the genetic basis for this disorder is unknown, thus there is a possibility that this clinical presentation may be contained within another genetic diagnosis. Here, we present a multiplex family with a previous clinical diagnosis of Tel Hashomer camptodactyly syndrome. Whole exome sequencing and pedigree‐based analysis revealed a novel hemizygous truncating variant c.269_270dup (p.Phe91Alafs*34) in the FGD1 gene (NM_004463.3) in all three symptomatic patients, congruous with a diagnosis of Aarskog–Scott syndrome. Our report adds to the limited data on Aarskog–Scott syndrome, and emphasizes the importance of unbiased comprehensive molecular testing toward establishing a diagnosis for genetic syndromes with unknown genetic basis.
Access to and Reactivity of Fe0, Fe−I, FeI, and FeII PCcarbeneP Pincer Complexes
Authors: Wang Qingyang , Manzano Richard A. , Tinnermann Hendrik , Sung Simon , Leforestier Baptiste , Krämer Tobias , Young Rowan D.
Published: June 2021

Despite their promising metal–ligand cooperative reactivity, PCcarbeneP pincer ligands are rarely reported for first‐row transition‐metal centres. Using a dehydration methodology, we report access to an Fe0 PCcarbeneP pincer complex (1) that proceeds via an isolated α‐hydroxylalkyl hydrido complex (3). Reversible carbonyl migration to the carbene position in 1 is found to allow coordination chemistry and E−H bond addition (E=H, B, Cl) across the iron–carbene linkage, representing a unique mechanism for metal–ligand cooperativity. The PCcarbeneP pincer ligand is also found to stabilize formal FeII, FeI, and Fe−I oxidation states, as demonstrated with synthesis and characterization of the complexes [11‐X][BArF20] (X=Br, I), 12, and K[13]. Compound K[13] is found to be highly reactive, and abstracts hydrogen from a range of aliphatic C−H sources. Computational analysis by DFT suggests that the formal FeI and Fe−I complexes contain significant carbene radical character. The ability of the PCcarbeneP ligand scaffold to partake in metal–ligand cooperativity and to support a range of iron oxidation states renders it as potentially useful in many catalytic applications.
Copper‐Catalyzed Highly Selective Protoboration of CF3‐Containing 1,3‐Dienes
Authors: Wu Juanjuan , Wu Hongli , Li Xinzhi , Liu Xinyu , Zhao Qian , Huang Genping , Zhang Chun
Published: June 2021

The copper‐catalyzed highly selective protoboration of CF3‐containing conjugated diene with proton source and B2Pin2 has been developed. This chemistry could suppress the well‐known defluorination and provide borated reagents with an intact CF3‐group. Further studies indicated that the functional group tolerance of this chemistry is very well, and the products could be used as versatile precursors for different types of transformations. Importantly, using chiral diphosphine ligand, we have developed the first example for using such starting material to synthesis allylic boron‐reagents which bearing a CF3‐containing chiral center. Notably, the reaction mechanism was intensively studied by DFT calculations, which could reveal the reason that defluorination was inhibited.
Twofold C−H Activation‐Based Enantio‐ and Diastereoselective C−H Arylation Using Diarylacetylenes as Rare Arylating Reagents
Authors: Hu Panjie , Kong Lingheng , Wang Fen , Zhu Xiaolin , Li Xingwei
Published: June 2021

C−H bond activation has been established as an attractive strategy to access axially chiral biaryls, and the most straightforward method is direct C−H arylation of arenes. However, the arylating source has been limited to several classes of reactive and bulky reagents. Reported herein is rhodium‐catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes for enantio‐ and diastereoselective construction of biaryls with both central and axial chirality. This twofold C−H activation reaction stays contrast to the previously explored Miura–Satoh type 1:2 coupling of arenes and alkynes in terms of chemoselectivity and proceeded under mild conditions with the alkyne acting as a rare arylating reagent. Both C−H activation events are stereo‐determining and are under catalyst control, with the 2ndC−H activation being diastereo‐determining in a remote fashion. Analysis of the stereochemistry of the major and side products suggests moderate enantioselectivity of the initial C−H activation–desymmetrization process. However, the minor (R) rhodium vinyl intermediate is consumed more readily in undesired protonolysis, eventually resulting in high enantio‐ and diastereoselectivity of the major product.
Monitoring Metabolites Using an NAD(P)H‐sensitive Polymer Dot and a Metabolite‐Specific Enzyme
Authors: Chen Haobin , Yu Jiangbo , Zhang Jicheng , Sun Kai , Ding Zhaoyang , Jiang Yifei , Hu Qiongzheng , Wu Changfeng , Chiu Daniel T.
Published: June 2021

We introduce an NAD(P)H‐sensitive polymer dot (Pdot) biosensor for point‐of‐care monitoring of metabolites. The Pdot is combined with a metabolite‐specific NAD(P)H‐dependent enzyme that catalyzes the oxidation of the metabolite, generating NAD(P)H. Upon UV illumination, the NAD(P)H quenches the fluorescence emission of Pdot at 627 nm via electron transfer, and also fluoresces at 458 nm, resulting in a shift from red to blue emission at higher NAD(P)H concentrations. Metabolite concentration is quantified ratiometrically‐based on the ratio of blue‐to‐red channel emission intensities, with a digital camera‐with high sensitivity and specificity. We demonstrate phenylalanine biosensing in human plasma for a phenylketonuria screening test, quantifying several other disease‐related metabolites (lactate, glucose, glutamate, and β‐hydroxybutyrate), and a paper‐based assay with smartphore imaging for point‐of‐care use.
Wiggling Mesopores Kinetically Amplify the Adsorptive Separation of Propylene/Propane
Authors: Yuan Ya‐Fei , Wang Yong‐Sheng , Zhang Xue‐Liang , Li Wen‐Cui , Hao Guang‐Ping , Han Lu , Lu An‐Hui
Published: June 2021

Adsorptive separation is an appealing technology for propylene and propane separation; however, the challenge lies in the design of efficient adsorbents which can distinguish the two molecules having very similar properties. Here we report a kinetically amplified separation by creating wiggling mesopores in structurally robust carbon monoliths. The wiggling mesopores with alternating wide and narrow segments afford a surface area of 413 m2 g−1and a tri‐modal pore size distribution centered at 1.5, 4.2 and 6.6 nm, respectively. The synergistically kinetic and equilibrium effects were observed and quantitatively assessed, which together ensured a remarkable propylene/propane selectivity up to 39. This selectivity outperformed not only the available carbon adsorbents but also highly competitive among the dominated crystalline porous adsorbents. In addition, the wiggling mesoporous carbon adsorbent showed excellent dynamical separation stability, which ensured its great potential in practical molecular separations.
Endothelial ontogeny and the establishment of vascular heterogeneity
Authors: Stone Oliver A. , Zhou Bin , Red‐Horse Kristy , Stainier Didier Y.R.
Published: June 2021

The establishment of distinct cellular identities was pivotal during the evolution of Metazoa, enabling the emergence of an array of specialized tissues with different functions. In most animals including vertebrates, cell specialization occurs in response to a combination of intrinsic (e.g., cellular ontogeny) and extrinsic (e.g., local environment) factors that drive the acquisition of unique characteristics at the single‐cell level. The first functional organ system to form in vertebrates is the cardiovascular system, which is lined by a network of endothelial cells whose organ‐specific characteristics have long been recognized. Recent genetic analyses at the single‐cell level have revealed that heterogeneity exists not only at the organ level but also between neighboring endothelial cells. Thus, how endothelial heterogeneity is established has become a key question in vascular biology. Drawing upon evidence from multiple organ systems, here we will discuss the role that lineage history may play in establishing endothelial heterogeneity.
Tailoring of thermoluminescent properties and assessment of trapping parameters of natural fluorite samples from Dogargaon fluorite mines, India
Authors: Randive Kirtikumar , Jawadand Sanjeevani , Dora M. L. , Kadam Abhijeet R. , Dhoble S. J.
Published: June 2021

Mineral fluorite or fluorspar (CaF2) can host significant quantities of trivalent REE3+ (rare earth element) by substitution with divalent Ca2+. The fluorites associated with carbonatites are often REE‐rich compared to those derived from sedimentary, hydrothermal, or Mississippi Valley‐type (MVT) fluorites. The naturally occurring fluorites have several industrial applications one of which is for luminescence. Whether or not REE enriched, the fluorite makes an ideal host for REEs, which are very important phosphors. The naturally occurring fluorites are available in sufficient quantities to cater to the industrial demand. Investigations have been carried out on the fluorites from active fluorite mines at Dongargaon in central India. Thermoluminescence behavior of a natural fluorite sample was investigated using a Nucleonix TL 1009I thermoluminescence reader. Multiple traps formed in the broad thermoluminescent (TL) glow curve were found by TL anal deconvolution software. Trapping parameters for all multiple traps formed on deconvoluting broad TL glow curve were found by different methods like Initial rise method, Chen's Peak shape method and Ilich method.