bluuebunny/crossref_metadata_2025 huggingface dataset:
Hierarchically Macro–Microporous Covalent Organic Frameworks for Efficient Proton Conduction
Authors: Zou Wenwu , Jiang Guoxing , Zhang Weifeng , Zhang Longhai , Cui Zhiming , Song Huiyu , Liang Zhenxing , Du Li
Published: February 2023

Assembling molecular proton carriers into crosslinked networks is widely used to fabricate proton conductors, but they often suffer losses in conduction efficiency and stability accompanied by unclear causes. Covalent organic frameworks (COFs), with well‐defined crystal frameworks and excellent stability, offer a platform for exploring the proton transfer process. Herein, a strategy to construct proton conductors that induce conductivity and stability by introducing bottom‐up hierarchical structure, mass transport interfaces, and host–guest interactions into the COFs is proposed. The proton‐transport platforms are designed to possess hierarchically macro–microporous structure for proton storage and mass transport. The protic ionic liquids, with low proton dissociation energies investigated by DFT calculation, are installed at open channel walls for faster proton motion. As expected, the resultant proton conductors based on a covalent organic framework (PIL0.5@m‐TpPa‐SO3H) with hierarchical pores increase conductivity by approximately three orders of magnitude, achieving the value of 1.02 × 10−1 S cm−1 (90 °C, 100% RH), and maintain excellent stability. In addition, molecular dynamics simulations reveal the mechanism of “hydrogen‐bond network” for proton conduction. This work offers a fresh perspective on COF‐based material manufacturing for high‐performance proton conductors via a protocol of macro‐micropores.
Controlling Kinetic Quenching Depth Toward High‐Performance and Photo‐Stable Organic Solar Cells Printed from a Non‐Halogenated Solvent
Authors: Li Min , Zhang Kangning , Qiao Jiawei , Wang Qian , Wang Linghua , Sun Ming , Ying Lei , Li Ning , Lu Peng , Yin Hang , Du Xiaoyan , Hao Xiaotao
Published: February 2023

The investigation of drying dynamics and kinetic quenching depth related degradation of high‐performance photoactive materials with scalable coating techniques demands significant research attention. Herein, film formation kinetics regulated crystallinity, preferential orientation and vertical phase separation of the active layers is revealed, which then further affects exciton diffusion, dissociation, charge‐transport and recombination processes. By suppressing over aggregation/crystallization in slow drying process and overcoming quenching of disordered liquid phase in fast‐dried films, the optimized PM6:BTP‐eC9‐based organic solar cells  obtain power conversion efficiencies  up to 16.81%. In addition, photoluminescence lifetime distribution is found to be an alternative probe for kinetic quenching depth that governs the degradation rate. This study provides valuable insights into the control of thin film formation kinetics during scalable processing and develops an effective way to associate the kinetic quenching depth with morphological degradation for mechanistic understanding of long‐term stability.
A Synthetic Dynamic Polyvinyl Alcohol Photoresin for Fast Volumetric Bioprinting of Functional Ultrasoft Hydrogel Constructs
Authors: Qiu Wanwan , Gehlen Jenny , Bernero Margherita , Gehre Christian , Schädli Gian Nutal , Müller Ralph , Qin Xiao‐Hua
Published: February 2023

Tomographic volumetric bioprinting (VBP) enables fast photofabrication of cell‐laden hydrogel constructs in one step, addressing the limitations of conventional layer‐by‐layer additive manufacturing. However, existing biomaterials that fulfill the physicochemical requirements of VBP are limited to gelatin‐based photoresins of high polymer concentrations. The printed microenvironments are predominantly static and stiff, lacking sufficient capacity to support 3D cell growth. Here a dynamic resin based on thiol–ene photo‐clickable polyvinyl alcohol (PVA) and thermo‐sensitive sacrificial gelatin for fast VBP of functional ultrasoft cell‐laden hydrogel constructs within 7–15 s is reported. Using gelatin allows VBP of permissive hydrogels with low PVA contents of 1.5%, providing a stress‐relaxing environment for fast cell spreading, 3D osteogenic differentiation of embedded human mesenchymal stem cells and matrix mineralization. Additionally, site‐specific immobilization of molecules‐of‐interest inside a PVA hydrogel is achieved by 3D tomographic thiol–ene photopatterning. This technique may enable spatiotemporal control of cell‐material interactions and guides in vitro tissue formation using programmed cell‐friendly light. Altogether, this study introduces a synthetic dynamic photoresin enabling fast VBP of functional ultrasoft hydrogel constructs with well‐defined physicochemical properties and high efficiency.
Metal‐Coordinated Adsorption of Nanoparticles to Macrophages for Targeted Cancer Therapy
Authors: Zhu Mao‐Hua , Zhu Xin‐Di , Long Mei , Lai Xing , Yuan Yihang , Huang Yanhu , Zhang Lele , Gao Yuhao , Shi Jiangpei , Lu Qin , Sun Peng , Lovell Jonathan F. , Chen Hong‐Zhuan , Fang Chao
Published: February 2023

Living cell‐based drug delivery systems (LC‐DDSs) are limited by adverse interactions between drugs and carrier cells, typically drug‐induced toxicity to carrier cells and restriction of carrier cells on drug release. Here, a method is established to adsorb nanocarriers externally to living cells, thereby reducing cytotoxicity caused by drug uptake and realizing improved drug release at the disease site. It is found that a divalent metal ion‐phenolic network (MPN) affords adhesion of poly (lactic‐co‐glycolic acid) nanoparticles onto macrophage (Mφ) surfaces with minimized intracellular uptake and no negative effect on cell proliferation. On this basis, an Mφ‐DDS with doxorubicin‐loaded nanoparticles on cell surface (DOX‐NP@Mφ) is constructed. Compared to intracellular loading via endocytosis, this method well‐maintains bioactivity (viability and migration chemotaxis) of the carrier cell. By virtue of the photothermal effect of MPN at the tumor site, DOX‐NP‐associated vesicles are liberated for improved chemotherapy. This facile, benign, and efficient method (ice bath, 2 min) for extracellular nanoparticle attachment and minimizing intracellular uptake provides a platform technology for LC‐DDS development.
Understanding the Composition of Layer‐by‐Layer Deposited Active Layer at Buried Bottom Surface
Authors: Feng Kai , Chen Linya , Cheng Jingyu , Wei Wanxia , Liu Yang , Xie Cong , Lu Xin , Gu Honggang , Xiong Sixing , Zhou Yinhua
Published: February 2023

Layer‐by‐layer (LbL) coating is becoming a widely used method to fabricate nonfullerene active layer films for organic solar cells. However, the vertical compositional distribution of the LbL‐coated active layer, particularly at the buried bottom surface, is not clear yet. In common sense, it is believed that the LbL‐coating yields a donor–mixture–acceptor (D–m–A) vertical distribution in the active layer, i.e., a thin polymer donor layer at the bottom surface, a thin acceptor layer at the top surface and a donor‐acceptor mixture in the middle. In this study, it is shown that the LbL active layer vertically is an entire donor:acceptor mixture. A pure layer of polymer donor doesn't exist at the bottom surface. The LbL active layer delivers high performance in both conventional and inverted device structures. A thin polymer layer with different thicknesses (2, 6, 12 nm) is inserted at the bottom surface to study their effects on the device performance. Those inserted layers substantially deteriorate the device's performance. Furthermore, the assumption is further confirmed by X‐ray photoelectron spectroscopy measurement on the exposed “originally buried” surface. This study sheds light on understanding the vertical compositional distribution of active layer via layer‐by‐layer solution processing.
Rational Manipulation of Epitaxial Strains Enabled Valence Band Convergence and High Thermoelectric Performances in Mg3Sb2 Films
Authors: Xie Sen , Liu Wei , Wan Xiaolin , Lyu Jianan , Yan Fan , Ouyang Yujie , Li Xianda , Liu Yong , Wang Ziyu , Wang Rui , Wu Jinsong , Zhang Qingjie , Tang Xinfeng
Published: February 2023

Strain engineering is demonstrated to effectively regulate the functionality of materials, such as thermoelectric, ferroelectric, and photovoltaic properties. As the straightforward approach of strain engineering, epitaxial strain is usually proposed for rationally manipulating the electronic structure and performances of thermoelectric materials, but has rarely been verified experimentally. In this study, tunable and large epitaxial strains are demonstrated, as well as the resulting valence band convergence can be achieved in the Mg3Sb2 epi‐films with the choice of substrates. The large epitaxial strains up to 8% in Mg3Sb2 films represent one of the most striking results in strain engineering. The angle‐resolved photoemission spectroscopy measurements and the theoretical calculations reveal the vital role of epitaxial strain in tuning the crystal field splitting and the band structure of Mg3Sb2. Benefiting from the appropriate manipulation of the crystal field effect via in‐plane compressive strain, the valence band convergence is unambiguously discovered in the strained Mg3Sb2 film grown on InP(111) substrate. As a result, a state‐of‐the‐art thermoelectric power factor of 0.94 mWm−1K−2 is achieved in the strain‐engineered Mg3Sb2 film, well exceeding that of the strain‐relaxed Mg3Sb2. The work paves the way for effectively manipulating epitaxial strain and band convergence for Mg3Sb2 and other thermoelectric films.
Building K–C Anode with Ultrahigh Self‐Diffusion Coefficient for Solid State Potassium Metal Batteries Operating at −20 to 120 °C
Authors: Wu Jian‐Fang , Zhou Wang , Wang Zixing , Wang Wei‐Wei , Lan Xuexia , Yan Hanghang , Shi Tuo , Hu Renzong , Cui Xiangyang , Xu Chaohe , He Xiangming , Mao Bing‐Wei , Zhang Tao , Liu Jilei
Published: February 2023

Solid state potassium (K) metal batteries are intriguing in grid‐scale energy storage, benefiting from the low cost, safety, and high energy density. However, their practical applications are impeded by poor K/solid electrolyte (SE) interfacial contact and limited capacity caused by the low K self‐diffusion coefficient, dendrite growth, and intrinsically low melting point/soft features of metallic K. Herein, a fused‐modeling strategy using potassiophilic carbon allotropes molted with K is demonstrated that can enhance the electrochemical performance/stability of the system via promoting K diffusion kinetics (2.37 × 10−8 cm2 s−1), creating a low interfacial resistance (≈1.3 Ω cm2), suppressing dendrite growth, and maintaining mechanical/thermal stability at 200 °C. A homogeneous/stable K stripping/plating is consequently implemented with a high current density of 2.8 mA cm−2 (at 25 °C) and a record‐high areal capacity of 11.86 mAh cm−2 (at 0.2 mA cm−2). The enhanced K diffusion kinetics contribute to sustaining intimate interfacial contact, stabilizing the stripping/plating at high current densities. Full cells coupling ultrathin K–C composite anodes (≈50 µm) with Prussian blue cathodes and β/β″‐Al2O3 SEs deliver a high energy density of 389 Wh kg−1 with a retention of 94.4% after 150 cycles and fantastic performances at −20 to 120 °C.
An In Situ Fabricated Graphene/Bipolar Polymer Hybrid Material Delivers Ultralong Cycle Life over 15 000 Cycles as a High‐Performance Electrode Material
Authors: Zhao Yang , Xu Nuo , Ni Minghan , Wang Ziyuan , Zhu Jie , Liu Jie , Zhao Ruiqi , Zhang Hongtao , Ma Yanfeng , Li Chenxi , Chen Yongsheng
Published: February 2023

Organic electrode materials are promising for the future energy storage systems owing to their tunable structures, abundant resources, and environmental friendliness. Many advanced lithium‐ion batteries with organic electrodes have been developed and show excellent performance. However, developing organic materials with overall superior performance still faces great challenges, such as low capacity, poor stability, inferior conductivity, and low utilization of active sites. To address these issues, a bipolar polymer (Fc‐DAB) is designed and further polymerized in situ with three‐dimensional graphene (3DG), offering a hybrid material (Fc‐DAB@3DG) with a variety of merits. Fc‐DAB possesses stable polymer backbone and multiple redox‐active sites that can improve stability and capacity simultaneously. The embedded highly conductive 3DG network endows Fc‐DAB@3DG with stable conductive framework, large surface area, and porous morphology all together, so the fast diffusion of ions/electrons can be achieved, leading to high utilization of active sites and enhanced electrochemical performance. As a result, Fc‐DAB@3DG cathode delivers capacity of ≈260 mA h g−1 at 25 mA g−1, ultra‐long cycle life over 15 000 cycles at 2000 mA g−1 with retention of 99.999% per cycle, and remarkable rate performance. The quasi‐solid Li‐metal battery and full cell fabricated using this material also exhibit superior electrochemical performance.
Step‐Edge‐Induced Patterning and Orientation Control of Crystalline Organic Semiconductor Films
Authors: Wang Zhifang , Martin‐Jimenez Daniel , Zhong Qigang , Ebeling Daniel , Schirmeisen Andre , Wang Hong , Wang Wenchong , Chi Lifeng
Published: February 2023

Orientation control over micropatterned crystalline organic semiconductor film is crucial to achieve high device performance with small variation in organic electronics. Here, using Au patterned SiO2 substrates, a method is reported to realize high‐resolution patterning and orientation control of crystalline organic thin films simultaneously. The vacuum deposited N,N‐dioctyl‐3,4,9,10‐perylene tetracarboxylic diimide (PTCDI‐C8) molecules can selectively diffuse to and nucleate on prepatterned Au stripes, resulting in patterned crystalline films with a preferential orientation distribution. Scanning tunneling microscope and high‐resolution atomic force microscope images reveal that the PTCDI‐C8 molecules first assemble on Au with perylene diimide cores in a laying down configuration, providing nucleation sites at the step edges for directional growth along the a‐axis of the molecule crystal. Subsequent deposition of molecules leads to orientated crystalline films growth due to the π packing of the perylene diimide cores, resulting in orientation control on micropatterned crystalline films. The finding provides a new strategy to grow oriented crystalline films for high device performance uniformity.
Textile‐based Thermoelectric Generator Produced Via Electrochemical Polymerization
Authors: Serrano‐Claumarchirant José F. , Nasiri Mohammad A. , Cho Chungyeon , Cantarero Andrés , Culebras Mario , Gómez Clara M.
Published: February 2023

The recent development in the field of wearable electronics has increased the demand for batteries as power sources which are subjected to periodic recharging and replacement. Therefore, the next challenge is to design new systems for sustainable energy to power portable electronic devices that can be easily integrated into textiles such as thermoelectric generators that can convert waste heat into electricity. Looking at this scenario, this work shows a methodology to prepare thermoelectric textiles by electrochemical polymerization of poly(3,4‐ethylenedioxythiophene) (PEDOT) on felt fabrics. The polymerization of PEDOT is carried out utilizing three different counterions, LiClO4, 1‐butyl‐3‐methylimidazolium hexafluorophosphate (PF6), and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (BTFMSI) to provide a complete understanding of the role of the counterion in the thermoelectric properties. The electrical conductivity and Seebeck coefficient are dependent on the counterion, reaching the maximum ZT for PEDOT polymerized in presence of BTFMSI due to an improvement of carrier mobility. In addition, the manufactured textile thermoelectric device showed an outstanding power output (6.5 µW) compared to the previous devices reported to date.
Rough Surface Enhanced Interfacial Synthesis of Core‐Shell Magnetic Fluorescent Microspheres for Enhanced Latent Fingerprint Visualization
Authors: Yu Bingjie , Liu Shude , Zou Yidong , Deng Yonghui , Yue Qin
Published: February 2023

Developing latent fingerprints is extremely significant for personal identification and criminal investigation. Sub‐micrometer core‐shell structured magnetic fluorescent composite which combines the merits of noncontact magnetic responsiveness and strong fluorescence emission is highly desired for the visualization of latent fingerprint on various substrates with high resolutions. However, it remains a great challenge to synthesize uniform magnetic fluorescent composites with well‐defined structure and functionalities due to the uncontrollable heterogeneous growth. Herein, a urea‐assisted rough interface precipitation method is proposed to controllably synthesize uniform core‐shell structured magnetic fluorescent composite microspheres (Fe3O4@mesoSiO2@Y2O3:Eu3+). The composite microspheres with magnetic core and mesoporous silica shell (Fe3O4@mesoSiO2) possess huge guest‐host interface, numerous nucleation sites, and rough surface morphology, facilitating the efficient adsorption of Y3+/Eu3+ ions, and further controllable interface deposition of metal (Y, Eu) hydroxides induced by slow release of OH− and CO32− anions via the in‐solution decomposition of urea. After subsequent thermal annealing, the obtained Fe3O4@mesoSiO2@Y2O3:Eu3+ microspheres possess high magnetization for convenient magnetic manipulation, strong fluorescence intensity and negligible quenching effect, enabling a superior performance in latent fingerprint visualization with high contrast and resolution on various substrates.
Arbitrary Polarization Syntheses Based on Spin‐Momentum Locking in Spoof Surface Plasmon Polaritons
Authors: Liu Jun Feng , Wu Jun Wei , Fu Xiaojian , Tang Wenxuan , Cui Tie Jun
Published: February 2023

Spin‐momentum locking is universal and an inherent property of evanescent electromagnetic (EM) waves, which transfers the spinning or handedness of electromagnetic waves onto their propagation direction. This motivates an approach to investigate the polarization‐controlled directional transmission or emission. Here, the spin‐momentum locking is demonstrated in spoof surface plasmon polariton (SSPP) waveguides, and momentum‐controlled radiation is further realized in SSPP‐patch antennas. The study shows that the circular polarization of the SSPP‐patch antennas originates from the spin‐momentum locking in the SSPP waveguides and hence is determined by the propagation direction of the SSPP modes. Two examples are presented to achieve ±45° dual‐polarizations and vertical/horizontal dual‐polarizations by combining the SSPP‐patch antenna with hybrid couplers. Finally, a straightforward method is proposed for synthesizing the polarization emitted by the SSPP‐patch antenna, allowing access to arbitrary polarization states on the Poincare sphere. The SSPP‐patch antenna is polarization responsive, shedding light on chiral sensors, Stokes polarimetry, and polarization measurement. Hence, the spin‐momentum locking and the related momentum‐controlled radiations provide additional freedom to regulate the EM waves by engineering the helicity in the SSPP waveguide.
Expanded Potential Stem Cells from Human Embryos Have an Open Chromatin Configuration with Enhanced Trophoblast Differentiation Ability
Authors: Chen Andy Chun Hang , Lee Yin Lau , Ruan Hanzhang , Huang Wen , Fong Sze Wan , Tian Siyu , Lee Kai Chuen , Wu Genie Minju , Tan Yongqi , Wong Timothy Chun Hin , Wu Jian , Zhang Weiyu , Cao Dandan , Chow Judy Fung Cheung , Liu Pengtao , Yeung William Shu Biu
Published: February 2023

Human expanded potential stem cells (hEPSC) have been derived from human embryonic stem cells and induced pluripotent stem cells. Here direct derivation of hEPSC from human pre‐implantation embryos is reported. Like the reported hEPSC, the embryo‐derived hEPSC (hEPSC‐em) exhibit a transcriptome similar to morula, comparable differentiation potency, and high genome editing efficiency. Interestingly, the hEPSC‐em show a unique H3 lysine‐4 trimethylation (H3K4me3) open chromatin conformation; they possess a higher proportion of H3K4me3 bound broad domain (>5 kb) than the reported hEPSC, naive, and primed embryonic stem cells. The open conformation is associated with enhanced trophoblast differentiation potency with increased trophoblast gene expression upon induction of differentiation and success in derivation of trophoblast stem cells with bona fide characteristics. Hippo signaling is specifically enriched in the H3K4me3 broad domains of the hEPSC‐. Knockout of the Hippo signaling gene, YAP1 abolishes the ability of the embryo‐derived EPSC to form trophoblast stem cells.
Biomimetic Convex Implant for Corneal Regeneration Through 3D Printing
Authors: Xu Yingni , Liu Jia , Song Wenjing , Wang Qianchun , Sun Xiaomin , Zhao Qi , Huang Yongrui , Li Haochen , Peng Yuehai , Yuan Jin , Ji Baohua , Ren Li
Published: February 2023

Blindness caused by corneal damage affects millions of people worldwide, and this number continues to rise. However, rapid epithelization and a stable epithelium process are the two biggest challenges for traditional corneal materials. These processes are related to corneal curvature, which is an important factor in determination of the corneal healing process and epithelial behavior during corneal damage. In this study, smooth 3D‐printed convex corneal implants based on gelatin methacrylate and collagen are generated. As epithelium distribution and adhesion vary in different regions of the natural cornea, this work separates the surfaces into four regions and studies how cells sense topological cues on curvature. It is found that rabbit corneal epithelial cells (RCECs) seeded on steeper slope gradient surfaces on convex structures result in more aligned cell organization and tighter cell‐substrate adhesion, which can also be verified through finite element simulation and signaling pathway analysis. In vivo transplantation of convex implants result in a better fit with adjacent tissue and stronger cell adhesion than flat implants, thereby accelerating corneal epithelialization and promoting collagen fibers and neural regeneration within 180 days. Taken together, printed convex corneal implants that facilitate corneal regeneration may offer a translational strategy for the treatment of corneal damage.
A CPG‐Based Versatile Control Framework for Metameric Earthworm‐Like Robotic Locomotion
Authors: Zhou Qinyan , Xu Jian , Fang Hongbin
Published: February 2023

Annelids such as earthworms are considered to have central pattern generators (CPGs) that generate rhythms in neural circuits to coordinate the deformation of body segments for effective locomotion. At present, the states of earthworm‐like robot segments are often assigned holistically and artificially by mimicking the earthworms’ retrograde peristalsis wave, which is unable to adapt their gaits for variable environments and tasks. This motivates the authors to extend the bioinspired research from morphology to neurobiology by mimicking the CPG to build a versatile framework for spontaneous motion control. Here, the spatiotemporal dynamics is exploited from the coupled Hopf oscillators to not only unify the two existing gait generators for restoring temporal‐symmetric phase‐coordinated gaits and discrete gaits but also generate novel temporal‐asymmetric phase‐coordinated gaits. Theoretical and experimental tests consistently confirm that the introduction of temporal asymmetry improves the robot's locomotion performance. The CPG‐based controller also enables seamless online switching of locomotion gaits to avoid abrupt changes, sharp stops, and starts, thus improving the robot's adaptability in variable working scenarios.
Versatile Hydrogel Dressing with Skin Adaptiveness and Mild Photothermal Antibacterial Activity for Methicillin‐Resistant Staphylococcus Aureus‐Infected Dynamic Wound Healing
Authors: Zhao Peng , Zhang Yu , Chen Xiaoai , Xu Chang , Guo Jingzhe , Deng Meigui , Qu Xiongwei , Huang Pingsheng , Feng Zujian , Zhang Jimin
Published: February 2023

Bacterial infection often induces chronic repair of wound healing owing to aggravated inflammation. Hydrogel dressing exhibiting intrinsic antibacterial activity may substantially reduce the use of antibiotics for infected wound management. Hence, a versatile hydrogel dressing (rGB/QCS/PDA–PAM) exhibiting skin adaptiveness on dynamic wounds and  mild photothermal antibacterial activity is developed for safe and efficient infected wound treatment. Phenylboronic acid‐functionalized graphene (rGB) and oxadiazole‐decorated quaternary carboxymethyl chitosan (QCS) are incorporated into a polydopamine–polyacrylamide (PDA–PAM) network with multiple covalent and noncovalent bonds, which conferred the hydrogel with flexible mechanical properties, strong tissue adhesion and excellent self‐healing ability on the dynamic wounds. Moreover, the glycocalyx‐mimicking phenylboronic acid on the surface of rGB enables the hydrogel to specifically capture bacteria. The enhanced membrane permeability of QCS enhanced bacterial vulnerability to photothermal therapy（PTT）, which is demonstrated by efficient mild PTT antibacteria against methicillin‐resistant Staphylococcus aureus in vitro and in vivo at temperatures of <49.6 °C. Consequently, the hydrogel demonstrate accelerated tissue regeneration on MRSA‐infected wound in vivo, with an intact epidermis, abundant collagen deposition and prominent angiogenesis. Therefore, rGB/QCS/PDA–PAM is a versatile hydrogel dressing exhibiting inherent antibacterial activity and has considerable potential in treating wounds infected with drug‐resistant bacteria.
Functionalized Cortical Bone‐Inspired Composites Adapt to the Mechanical and Biological Properties of the Edentulous Area to Resist Fretting Wear
Authors: Wang ZhongYi , Xiang QianRong , Tan Xin , Zhang YaDong , Zhu HaoQi , Pu Jian , Sun JiKui , Sun ManLin , Wang YingKai , Wei Qiang , Yu HaiYang
Published: February 2023

Dental implants with long‐term success of osseointegration have always been the goal, however, difficulties exist. The accumulation of fretting damage at the implant–bone interface often gets overlooked. Commonly used titanium is approximately 7‐fold harder and stiffer than cortical bone. Stress shielding caused by the mismatching of the elastic modulus aggravates fretting at the interface, which is accompanied by the risk of the formation of proinflammatory metal debris and implant loosening. Thus, the authors explore functionalized cortical bone‐inspired composites (FCBIC) with a hierarchical structure at multiple scales, that exhibit good mechanical and biological adaptivity with cortical bone. The design is inspired by nature, combining brittle minerals with organic molecules to maintain machinability, which helps to acquire excellent energy‐dissipating capability. It therefore has the comparable hardness and elastic modulus, strength, and elastic‐plastic deformation to cortical bone. Meanwhile, this cortical bone analogy exhibits excellent osteoinduction and osseointegration abilities. These two properties also facilitate each other to resist fretting wear, and therefore improve the success rate of implantation. Based on these results, the biological–mechanical co‐operation coefficient is proposed to describe the coupling between these two factors for designing the optimized dental implants.
Recruiting Unicellular Algae for the Mass Production of Nanostructured Perovskites
Authors: Kuhrts Lucas , Helmbrecht Lukas , Noorduin Willem L. , Pohl Darius , Sun Xiaoxiao , Palatnik Alexander , Wetzker Cornelia , Jantschke Anne , Schlierf Michael , Zlotnikov Igor
Published: February 2023

Functional capacities of lead halide perovskites are strongly dependent on their morphology, crystallographic texture, and internal ultrastructure on the nano‐ and the meso‐scale. In the last decade, significant efforts are directed towards the development of novel synthesis routes that would overcome the morphological constraints provided by the physical and crystallographic properties of these materials. In contrast, various living organisms, such as unicellular algae, have the ability to mold biogenic crystals into a vast variety of intricate nano‐architectured shapes while keeping their single crystalline nature. Here, using the cell wall of the dinoflagellate L. granifera as a model, sustainably harvested biogenic calcite is successfully transformed into nano‐structured perovskites. Three variants of lead halide perovskites CH3NH3PbX3 are generated with X = Cl−, Br− and I−; exhibiting emission peak‐wavelength ranging from blue, to green, to near‐infrared, respectively. The approach can be used for the mass production of nano‐architectured perovskites with desired morphological, textural and, consequently, physical properties exploiting the numerous templates provided by calcite forming unicellular organisms.
Cropping systems with perennial vegetation and livestock integration promote soil health
Authors: Augarten Abigail J. , Malone Lindsay Chamberlain , Richardson Gregory S. , Jackson Randall D. , Wattiaux Michel A. , Conley Shawn P. , Radatz Amber M. , Cooley Eric T. , Ruark Matthew D.
Published: February 2023

Soil health can differ across cropping systems because of variation in edaphic and management factors. We evaluated how biological indicators of soil health (soil organic matter [SOM], permanganate oxidizable carbon [POXC], mineralizable carbon [MinC], autoclaved‐citrate‐extractable [ACE] protein, and potentially mineralizable nitrogen [PMN]) compared across four common Wisconsin cropping systems: grazed cool‐season pastures, forage‐based rotations that included perennial legumes or grasses, annual rotations receiving manure, and annual rotations receiving synthetic fertilizers. Biological indicators of soil health were up to 195% greater in pastures than other cropping systems. MinC, POXC and PMN were 10%–90% greater in forage‐based rotations than annual cropping systems, but only MinC and POXC were greater in annual systems with manure compared to those without manure by 35% and 7%, respectively. Perennial vegetation and livestock integration offer the greatest potential to increase biological indicators of soil health in agricultural lands.
PbI6 Octahedra Stabilization Strategy Based on π‐π Stacking Small Molecule Toward Highly Efficient and Stable Perovskite Solar Cells
Authors: Wang Xianzhao , Liu Dachang , Liu Ruichen , Du Xiaofan , Zhang Bingqian , Sun Xiuhong , Chen Chen , Li Zhipeng , Zhao Qiangqiang , Shao Zhipeng , Wang Xiao , Cui Guanglei , Pang Shuping
Published: February 2023

The unavoidable iodine loss in the perovskite layer is closely related to carrier non‐radiative and device degradation. During the post‐annealing process, the fragile PbI bond is easy to break, leading to the formation of iodine vacancies and inducing stress‐driven structure collapse. Herein, a PbI6 octahedra stabilization strategy via building robust grain boundary modification networks is developed. The introduction of conjugated structure into amides can significantly enhance their anchoring ability with PbI units, while the π–π stacking effect of benzamide enables a passivation network with polymer‐like effect. This is well evidenced by the excellent properties in eliminated iodine loss and stabilized perovskite lattice. Therefore, benzamide modification not only transform the perovskite films from n‐type to p‐type by suppressing the iodine vacancy‐doping effect, but also reduces defect density, ultimately bringing the perovskite layer longer carrier diffusion length and better charge injection efficiency. Finally, the benzamide modified devices realize both high power conversion efficiency of 24.78% and excellent operating stability. Of particular note, the module efficiency with 14 cm2 active area is over 21%.
Designing Bidirectionally Functional Polymer Electrolytes for Stable Solid Lithium Metal Batteries
Authors: Ma Qiang , Fu Sha , Wu An‐Jun , Deng Qi , Li Wei‐Dong , Yue Dan , Zhang Bing , Wu Xiong‐Wei , Wang Zhen‐Ling , Guo Yu‐Guo
Published: February 2023

The development of high energy density lithium metal batteries has been retarded by the uncontrolled lithium dendrite formation and unstable Ni‐rich cathode–electrolyte interface (CEI). Herein, the bidirectionally functional polymer electrolytes (BDFPE) are designed via direct UV solidification of functional polymer species on electrode surfaces to simultaneously handle the interface issues faced by anodes and cathodes. By constructing the BDFPE, a smooth and dendrite‐free lithium deposition is enabled for Li||Li symmetry cells after 1800 h ultralong cycling at 1 mA cm−2 and 1 mAh cm−2, which are attributed to the fast ion conductivity (5.84 × 10−4 S cm−1), high Li+ transfer number (0.69) of BDFPE and low interfacial resistance between electrode and solid electrolytes. Furthermore, Li||LiNi0.6Co0.2Mn0.2O2 batteries demonstrate a favorable cycling and rate capability, and a stable and phosphate‐based CEI layer is constructed in situ. DFT studies reveal that the functional additives FEC and TEP participate in the interface formation. The finding provides a promising design strategy to accommodate the anode and cathode interfaces for high energy density lithium metal batteries.
High‐Entropy‐Nanofibers Enhanced Polymer Nanocomposites for High‐Performance Energy Storage
Authors: Dou Lvye , Yang Bingbing , Lan Shun , Liu Yiqian , Liu Yiqun , Nan Ce‐Wen , Lin Yuan‐Hua
Published: February 2023

Polymer composite dielectrics capable of high energy density, high efficiency, and high‐temperature stability are in high demand for application in various electronic vehicles and power systems. A major challenge, however, is the reasonable design of high‐performance nanofillers that are beneficial to the polarization and breakdown strength simultaneously. Here, high‐entropy‐induced ceramic nanofibers with a stable Bi2Ti2O7‐type pyrochlore phase are developed as effective nanofillers to enhance the energy storage performance of polyetherimide (PEI) composites. Benefiting from the linear pyrochlore phase, refined grain size, and increased amorphous fraction of the high‐entropy nanofillers, the resultant PEI composites exhibit significantly improved energy storage performance over a wide temperature range of 25–150 °C. Notably, a high energy density of 6.46 J cm−3 under an electric field of 590 MV m−1 is achieved at 150 °C, which outperforms most of the reported PEI composites. This study provides a guideline for the development of dielectric fillers with tunable dielectric properties and microstructures, thus promoting the development of high‐performance polymer composites.
Graphene‐Like Monoelemental 2D Materials for Perovskite Solar Cells
Authors: Suragtkhuu Selengesuren , Sunderiya Suvdanchimeg , Myagmarsereejid Purevlkham , Purevdorj Solongo , Bati Abdulaziz S. R. , Bold Bujinlkham , Zhong Yu Lin , Davaasambuu Sarangerel , Batmunkh Munkhbayar
Published: February 2023

Perovskite solar cells (PSCs) have attracted a great deal of attention from the photovoltaic (PV) community because of their remarkable performance, low production cost, and high potential to be integrated into other optoelectronic applications. Despite their promise, the challenges associated with their operational stability have drawn increasing attention over the past decade. Owing to their unique structure and fascinating properties such as high charge mobility, excellent conductivity, tunable bandgap, good optical transparency, and optimal surface functionalization, nanostructured materials, in particular monoelemental 2D materials, have recently been demonstrated to play versatile functions in suppressing the degradation of PSCs and enhancing the PV performance of the devices. In this review, recent advances in perovskite solar cells employing monoelemental 2D materials are presented. A brief overview of perovskite light absorbers based PV devices is first introduced, followed by critical discussions on the use of various elemental 2D materials including graphene, phosphorene, antimonene, borophene, bismuthene, and their derivatives for different components of the perovskite solar cells. Finally, the challenges in this cutting‐edge research area are highlighted, and the authors express their own perspectives on addressing these key issues.
Initiating Jahn–Teller Effect in Vanadium Diselenide for High Performance Magnesium‐Based Batteries Operated at −40 °C
Authors: Xu Xin , Ye Chao , Chao Dongliang , Davey Kenneth , Qiao Shi‐Zhang
Published: February 2023

Poor electronic and ionic conductivity of electrode materials at low temperatures of −20 °C and below has significantly impeded development of batteries for cold conditions. However, for the first time, layer‐structured metallic vanadium diselenide (1T‐VSe2) is reported as a cathode material for low‐temperature Mg2+/Li+ hybrid batteries. A high electronic conductivity and fast ion diffusion kinetics for 1T‐VSe2 are demonstrated at selected temperatures, and a very safe 1T‐VSe2/Mg battery for operation at temperatures to −40 °C. The battery exhibits 97% capacity retention over 500 cycles, which is better performance than reported Mg‐based batteries. The Jahn–Teller effect in compressed configuration is initiated in 1T‐VSe2 with the change of electronic state occurring on electrochemical intercalation of alkali metal ions. Using combined experiment and theory via operando synchrotron X‐ray diffraction, ex situ X‐ray absorption spectroscopy and DFT computation, it is confirmed that the weak Jahn–Teller distortion contributes significantly to fast‐overall kinetics, structural stability, and high electronic conductivity of the electrode. Understanding at an atomic level of the mechanism is demonstrated, that provides valuable guidance in designing high‐performance electrode materials for low‐temperature batteries.
An in‐depth investigation of cryptic taxonomic diversity in the rare endemic mustard Draba maguirei
Authors: Windham Michael D. , Picard Kathryn T. , Pryer Kathleen M.
Published: February 2023

Premise

Previously published evidence suggests that Draba maguirei, a mustard endemic to a few localities in the Bear River, Wellsville, and Wasatch Mountains of northern Utah, may represent a cryptic species complex rather than a single species. Conservation concerns prompted an in‐depth systematic study of this taxon and its putative relatives.

Methods

Sampling most known populations of D. maguirei s.l. (D. maguirei var. maguirei and D. maguirei var. burkei), we integrate data from geography, ecology, morphology, cytogenetics and pollen, enzyme electrophoresis, and the phylogenetic analysis of nuclear internal transcribed spacer sequences to explore potential taxonomic diversity in the species complex.

Results

Draba maguirei var. burkei is shown here to be a distinct species (D. burkei) most closely related to D. globosa, rather than to D. maguirei. Within D. maguirei s.s., the northern (high elevation) and southern (low elevation) population clusters are genetically isolated and morphologically distinguishable, leading to the recognition here of the southern taxon as D. maguirei subsp. stonei.

Conclusions

Our study reveals that plants traditionally assigned to D. maguirei comprise three genetically divergent lineages (D. burkei and two newly recognized subspecies of D. maguirei), each exhibiting a different chromosome number and occupying a discrete portion of the geographic range. Although previously overlooked and underappreciated taxonomically, the three taxa are morphologically recognizable based on the distribution and types of trichomes present on the leaves, stems, and fruit. Our clarification of the diversity and distribution of these taxa provides an improved framework for conservation efforts.
Nosology of genetic skeletal disorders: 2023 revision
Authors: Unger Sheila , Ferreira Carlos R. , Mortier Geert R. , Ali Houda , Bertola Débora R. , Calder Alistair , Cohn Daniel H. , Cormier‐Daire Valerie , Girisha Katta M. , Hall Christine , Krakow Deborah , Makitie Outi , Mundlos Stefan , Nishimura Gen , Robertson Stephen P. , Savarirayan Ravi , Sillence David , Simon Marleen , Sutton V. Reid , Warman Matthew L. , Superti‐Furga Andrea
Published: February 2023

The “Nosology of genetic skeletal disorders” has undergone its 11th revision and now contains 771 entries associated with 552 genes reflecting advances in molecular delineation of new disorders thanks to advances in DNA sequencing technology. The most significant change as compared to previous versions is the adoption of the dyadic naming system, systematically associating a phenotypic entity with the gene it arises from. We consider this a significant step forward as dyadic naming is more informative and less prone to errors than the traditional use of list numberings and eponyms. Despite the adoption of dyadic naming, efforts have been made to maintain strong ties to the MIM catalog and its historical data. As with the previous versions, the list of disorders and genes in the Nosology may be useful in considering the differential diagnosis in the clinic, directing bioinformatic analysis of next‐generation sequencing results, and providing a basis for novel advances in biology and medicine.
Tuning Local Coordination Environments of Manganese Single‐Atom Nanozymes with Multi‐Enzyme Properties for Selective Colorimetric Biosensing
Authors: Wang Ying , Cho Ara , Jia Guangri , Cui Xiaoqiang , Shin Junhyeop , Nam Inho , Noh Kyung‐Jong , Park Byoung Joon , Huang Rui , Han Jeong Woo
Published: February 2023

Single‐atom nanozymes (SAzymes) are promising in next‐generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi‐enzyme properties is still challenging. Herein, we systematically investigate the relationship between atomic configuration and multi‐enzymatic performances. The constructed MnSA−N3‐coordinated SAzymes (MnSA−N3−C) exhibits much more remarkable oxidase‐, peroxidase‐, and glutathione oxidase‐like activities than that of MnSA−N4−C. Based on experimental and theoretical results, these multi‐enzyme‐like behaviors are highly dependent on the coordination number of single atomic Mn sites by local charge polarization. As a consequence, a series of colorimetric biosensing platforms based on MnSA−N3−C SAzymes is successfully built for specific recognition of biological molecules. These findings provide atomic‐level insight into the microenvironment of nanozymes, promoting rational design of other demanding biocatalysts.
Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites
Authors: Chai Congcong , Zhou Junyan , Hao Munan , Li Qi , Lu Jiali , Jin Shifeng , Chen Xiaolong
Published: February 2023

The nanostructuring of single‐molecule magnets (SMMs) on substrates, in nanotubes and periodic frameworks is highly desired for the future magnetic recording devices. However, the ability to organize SMMs into long‐range ordered arrays in these systems is still lacking. Here, we report the incorporation of magnetic (RECl2(H2O)6)+ (RE=rare earths) molecular groups into the framework of an organic metal halide perovskite (OMHP)—(H2dabco)CsCl3. Intriguingly, we show the incorporated rare‐earth groups self‐organized into long‐range ordered arrays that uniformly and periodically distributed in the A sites of OMHP. The ordered (RECl2(H2O)6)+ groups serve as SMMs in the perovskite frameworks, exhibiting large effective magnetic moment, moderate magnetic anisotropy and two‐step relaxation behavior. With the additional merit of great structural flexibility and multifunction of OMHPs, the preparation of the first SMMs@OMHP magnetic materials furthers the development of molecular spintronics.
Diazadiboraacenes: Synthesis, Spectroscopy and Computations
Authors: Ruhl Julia , Oberhof Nils , Dreuw Andreas , Wegner Hermann A.
Published: February 2023

The incorporation of heteroatoms into hydrocarbon compounds greatly expands the chemical space of molecular materials. In this context, B−N doping takes a center stage due to its isosterism with a C=C‐bond. Herein, we present a new and modular synthetic concept to access novel diazadiborabenzo[b]triphenylenes7 a–husing the B−N doped biradical16as intermediate. Characterization of the photophysical properties revealed the emission spectra of the diazadibora benzo[b]triphenylenes7 a–hcan conveniently be tuned by small changes of the substitution on the boron‐atom. All of the diazadibora compounds show a short life‐time phosphorescence. Additionally, we were able to rationalize the excited‐state relaxation of the diazadiboraacene7 avia intersystem crossing by quantum chemical calculations. The new synthetic strategy provides an elegant route to various novel B−N doped acenes with great potential for applications in molecular materials.
Activating Bi p‐orbitals in Dispersed Clusters of Amorphous BiOx for Electrocatalytic Nitrogen Reduction
Authors: Kang Jianxin , Chen Xiangyu , Si Rutong , Gao Xiang , Zhang Shuo , Teobaldi Gilberto , Selloni Annabella , Liu Li‐Min , Guo Lin
Published: February 2023

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiOx. Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half‐occupied pz orbitals of the Bi2+ ions being highly efficient toward electron injection into the inert N2 molecule. With sufficient catalytic sites to adsorb and activate N2, the bonding between N2 and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 μg h−1 mg−1cat) in NH3 production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p‐block elements for catalysis of multi‐electron reactions.
Post‐curing and structural relaxation of epoxy networks during early stages of aging for civil engineering applications
Authors: Oumnas Sanaa , Quelennec Blandine , Richaud Emmanuel , Duthoit Alexis , Delpouve Nicolas , Delbreilh Laurent
Published: February 2023

In this work, epoxy networks used for civil engineering constructions are aged at ambient temperature, and the impact of the early stages of aging on mechanical properties is analyzed. It is observed that Young's modulus and the yield stress increase with the aging time whereas the strain at break and the toughness decrease. The structural causes for these variations are investigated by swelling experiments, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. By combining experimental results, it is deduced that the aging process occurs in two stages. During the first 7 days of aging, the change in mechanical properties should essentially be attributed to the postcuring, which results in additional crosslinking reactions. When increasing the aging time to 21 days, the crosslinking density reaches a plateau, but a second stage emerges, in which the mechanical properties continue evolving in the same way, with variations of the mechanical parameters being of comparable amplitude. This second stage is attributed to the evolution of the thermodynamic state of the glass, leading to a densification of the epoxy network through minimization of the free volume, and favoring the creation of physical interactions between polymer segments. Therefore, structural relaxation is shown to have a significant impact on the mechanical properties.