bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Situ Engineering of a Cobalt‐free Perovskite Air Electrode Enabling Efficient Reversible Oxygen Reduction/Evolution Reactions
Authors: Hu Tong , Zhu Feng , Xia Jiaojiao , He Fan , Du Zhiwei , Zhou Yucun , Liu Ying , Wang Haobing , Chen Yu 
Published: June 2023

AbstractReversible protonic ceramic electrochemical cells (R‐PCECs) have received increasing focus for their good capability of converting and storing energy. However, the widely used cobalt‐based air electrodes are less thermomechanically compatible with the electrolyte and lack stability, which largely limits the development of R‐PCECs. Herein, a cobalt‐free perovskite with a nominal composition of PrBa0.8Ca0.2Fe1.8Ce0.2O6δ (PBCFC) is reported, which is in–situ engineered to a (Ba, Ce) deficient‐PBCFC phase, a BaCeO3, and a CeO2 phase under typical operating conditions, delivering a low area–specific resistance of 0.10 Ωcm2 at 700 oC. The generated BaCeO3 and CeO2 particles increase the conduction/transfer of protons and oxygen ions, thus providing extra active sites for the oxygen reactions. When utilized as an air electrode on a single cell, it achieves encouraging performance at 700 °C: a peak power density of 1.78 Wcm−2 and a current density of 5.00 Acm−2 at 1.3 V in the dual mode of the fuel cell (FC) and electrolysis (EL) mode with reasonable Faradaic efficiencies. In addition, the cells exhibit favorable operational durability of 65 h (FC mode), 95 h (EL mode), and promising cycling stability of 200 h.
Liquid Metal Actuators: A Comparative Analysis of Surface Tension Controlled Actuation
Authors: Liao Jiahe , Majidi Carmel , Sitti Metin 
Published: June 2023

AbstractLiquid metals, with their unique combination of electrical and mechanical properties, offer great opportunities for actuation based on surface tension modulation. Thanks to the scaling laws of surface tension, which can be electrochemically controlled at low voltages, liquid metal actuators stand out from other soft actuators for their remarkable characteristics such as high contractile strain rates and higher work densities at smaller length scales. This review summarizes the principles of liquid metal actuators and discusses their performance as well as theoretical pathways toward higher performances. The objective is to provide a comparative analysis of the ongoing development of liquid metal actuators. The design principles of the liquid metal actuators are analyzed, including low‐level elemental principles (kinematics and electrochemistry), mid‐level structural principles (reversibility, integrity, and scalability), and high‐level functionalities. A wide range of practical use cases of liquid metal actuators from robotic locomotion and object manipulation to logic and computation is reviewed. From an energy perspective, strategies are compared for coupling the liquid metal actuators with an energy source toward fully untethered robots. The review concludes by offering a roadmap of future research directions of liquid metal actuators.
Insight on the Intracellular Supramolecular Assembly of DTTO: A Peculiar Example of Cell‐Driven Polymorphism
Authors: Aloisio Ludovico , Moschetta Matteo , Boschi Alex , Fleitas Ariel García , Zangoli Mattia , Venturino Ilaria , Vurro Vito , Magni Arianna , Mazzaro Raffaello , Morandi Vittorio , Candini Andrea , D'Andrea Cosimo , Paternò Giuseppe Maria , Gazzano Massimo , Lanzani Guglielmo , Di Maria Francesca 
Published: June 2023

AbstractThe assembly of supramolecular structures within living systems is an innovative approach for introducing artificial constructs and developing biomaterials capable of influencing and/or regulating the biological responses of living organisms. By integrating chemical, photophysical, morphological, and structural characterizations, it is shown that the cell‐driven assembly of 2,6‐diphenyl‐3,5‐dimethyl‐dithieno[3,2‐b:2′,3′‐d]thiophene‐4,4‐dioxide (DTTO) molecules into fibers results in the formation of a “biologically assisted” polymorphic form, hence the term bio‐polymorph. Indeed, X‐ray diffraction reveals that cell‐grown DTTO fibers present a unique molecular packing leading to specific morphological, optical, and electrical properties. Monitoring the process of fiber formation in cells with time‐resolved photoluminescence, it is established that cellular machinery is necessary for fiber production and a non‐classical nucleation mechanism for their growth is postulated. These biomaterials may have disruptive applications in the stimulation and sense of living cells, but more crucially, the study of their genesis and properties broadens the understanding of life beyond the native components of cells.
PAF‐6 Doped with Phosphoric Acid through Alkaline Nitrogen Atoms Boosting High‐Temperature Proton‐Exchange Membranes for High Performance of Fuel Cells
Authors: Wang Liying , Wang Yuliang , Li Zhangnan , Li Tianyang , Zhang Ruyu , Li Jing , Liu Baijun , Lv Zhongyuan , Cai Weiwei , Sun Shuhui , Hu Wei , Lu Yunfeng , Zhu Guangshan 
Published: June 2023

AbstractHigh‐temperature proton‐exchange‐membrane fuel cells (HT‐PEMFCs) can offer improved energy efficiency and tolerance to fuel/air impurities. The high expense of the high‐temperature proton‐exchange membranes (HT‐PEMs) and their low durability at high temperature still impede their further practical applications. In this work, a phosphoric acid (PA)‐doped porous aromatic framework (PAF‐6‐PA) is incorporated into poly[2,2′‐(p‐oxydiphenylene)‐5,5′‐benzimidazole] (OPBI) to fabricate novel PAF‐6‐PA/OPBI composite HT‐PEMs through solution‐casting. The alkaline nitrogen structure in PAF‐6 can be protonated with PA to provide proton hopping sites, and its porous structure can enhance the PA retention in the membranes, thus creating fast pathways for proton transfer. The hydrogen bond interaction between the rigid PAF‐6 and OPBI can also enhance the mechanical properties and chemical stability of the composite membranes. Consequently, PAF‐6‐PA/OPBI exhibits an optimal proton conductivity of 0.089 S cm−1 at 200 °C, and peak power density of 437.7 mW cm−2 (Pt: 0.3 mg cm−2), which is significantly higher than that of the OPBI. The PAF‐6‐PA/OPBI provides a novel strategy for the practical application of PBI‐based HT‐PEMs.
Strong Magnetically‐Responsive Circularly Polarized Phosphorescence and X‐Ray Scintillation in Ultrarobust Mn(II)–Organic Helical Chains
Authors: Davydova Maria P. , Meng Lingqiang , Rakhmanova Mariana I. , Jia Zhenglin , Berezin Alexey S. , Bagryanskaya Irina Yu. , Lin Qianqian , Meng Hong , Artem'ev Alexander V. 
Published: June 2023

AbstractOver recent years, Mn(II)‐organic materials showing circularly polarized luminescence (CPL) have attracted great interest because of their eco‐friendliness, cheapness, and room temperature phosphorescence. Using the helicity design strategy, herein, chiral Mn(II)‐organic helical polymers are constructed featuring long‐lived circularly polarized phosphorescence with exceptionally high glum and ΦPL magnitudes of 0.021% and 89%, respectively, while remaining ultrarobust toward humidity, temperature, and X‐rays. Equally important, it is disclosed for the first time that the magnetic field has a remarkably high negative effect on CPL for Mn(II) materials, suppressing the CPL signal by 4.2‐times at = 1.6 T. Using the designed materials, UV‐pumped CPL light‐emitting diodes are fabricated, demonstrating enhanced optical selectivity under right‐ and left‐handed polarization conditions. On top of all this, the reported materials display bright triboluminescence and excellent X‐ray scintillation activity with a perfectly linear X‐ray dose rate response up to 174 µGyair s−1. Overall, these observations significantly contribute to the CPL phenomenon for multi‐spin compounds and promote the design of highly efficient and stable Mn(II)‐based CPL emitters.
Enhanced Multiwavelength Response of Flexible Synaptic Transistors for Human Sunburned Skin Simulation and Neuromorphic Computation
Authors: Wang Xin , Yang Shuting , Qin Zongze , Hu Bin , Bu Laju , Lu Guanghao 
Published: June 2023

AbstractIn biological species, optogenetics and bioimaging work together to regulate the function of neurons. Similarly, the light‐controlled artificial synaptic system not only enhances computational speed but also simulates complex synaptic functions. However, reported synaptic properties are mainly limited to mimicking simple biological functions and single‐wavelength responses. Therefore, the development of flexible synaptic devices with multiwavelength optical signal response and multifunctional simulation remains a challenge. Here, flexible organic light‐stimulated synaptic transistors (LSSTs) enabled by alumina oxide (AlOX), with a simple fabrication process, are reported. By embedding AlOX nanoparticles, the excitons separation efficiency is improved, allowing for multiple wavelength responses. Optimized LSSTs can respond to multiple optical and electrical signals in a highly synaptic manner. Multiwavelength optical synaptic plasticity, electrical synaptic plasticity, sunburned skin simulation, learning efficiency model controlled by photoelectric cooperative stimulation, neural network computing, “deer” picture learning and memory functions are successfully proposed, which promote the development for future artificial intelligent systems. Furthermore, as prepared flexible transistors exhibit mechanical flexibility with bending radius down to 2.5 mm and improved photosynaptic plasticity, which facilitating development of neuromorphic computing and multifunction integration systems at the device‐level.
MoS2@Polyaniline for Aqueous Ammonium‐Ion Supercapacitors
Authors: Dai Juguo , Yang Chunying , Xu Yiting , Wang Xiaohong , Yang Siyu , Li Dongxu , Luo Lili , Xia Long , Li Junshan , Qi Xueqiang , Cabot Andreu , Dai Lizong 
Published: June 2023

AbstractAmmonium‐ion aqueous supercapacitors are raising notable attention owing to their cost, safety, and environmental advantages, but the development of optimized electrode materials for ammonium‐ion storage still lacks behind expectations. To overcome current challenges, here, a sulfide‐based composite electrode based on MoS2 and polyaniline (MoS2@PANI) is proposed as an ammonium‐ion host. The optimized composite possesses specific capacitances above 450 F g−1 at 1 A g−1, and 86.3% capacitance retention after 5000 cycles in a three‐electrode configuration. PANI not only contributes to the electrochemical performance but also plays a key role in defining the final MoS2 architecture. Symmetric supercapacitors assembled with such electrodes display energy densities above 60 Wh kg−1 at a power density of 725 W kg−1. Compared with Li+ and K+ ions, the surface capacitive contribution in NH4+‐based devices is lower at every scan rate, which points to an effective generation/breaking of H‐bonds as the mechanism controlling the rate of NH4+ insertion/de‐insertion. This result is supported by density functional theory calculations, which also show that sulfur vacancies effectively enhance the NH4+ adsorption energy and improve the electrical conductivity of the whole composite. Overall, this work demonstrates the great potential of composite engineering in optimizing the performance of ammonium‐ion insertion electrodes.
Integrating Enrichment, Reduction, and Oxidation Sites in One System for Artificial Photosynthetic Diluted CO2 Reduction
Authors: Yang Yan , Zhang Hong‐Yu , Wang Ya , Shao Lu‐Hua , Fang Liang , Dong Hong , Lu Meng , Dong Long‐Zhang , Lan Ya‐Qian , Zhang Feng‐Ming 
Published: June 2023

AbstractArtificial photosynthetic diluted CO2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon‐resources recycling utilization. Herein, a three‐in‐one photocatalytic system of CO2 enrichment, CO2 reduction and H2O oxidation sites is designed for diluted CO2 reduction. A Zn‐Salen‐based covalent organic framework (Zn‐S‐COF) with oxidation and reductive sites is synthesized; then, ionic liquids (ILs) are loaded into the pores. As a result, [Emim]BF4@Zn‐S‐COF shows a visible‐light‐driven CO2‐to‐CO conversion rate of 105.88 µmol g−1 h−1 under diluted CO2 (15%) atmosphere, even superior than most photocatalysts in high concentrations CO2. Moreover, natural sunlight driven diluted CO2 reduction rate also reaches 126.51 µmol g−1 in 5 h. Further experiments and theoretical calculations reveal that the triazine ring in the Zn‐S‐COF promotes the activity of H2O oxidation and CO2 reduction sites, and the loaded ILs provide an enriched CO2 atmosphere, realizing the efficient photocatalytic activity in diluted CO2 reduction.
An All‐Printed, Fast‐Response Flexible Humidity Sensor Based on Hexagonal‐WO3 Nanowires for Multifunctional Applications
Authors: Guo Panwang , Tian Bin , Liang Jing , Yang Xiuping , Tang Guilin , Li Quancai , Liu Qun , Zheng Ke , Chen Xiong , Wu Wei 
Published: June 2023

AbstractThe utilization of printing techniques for the development of high‐performance humidity sensors holds immense significance for various applications in the fields of the Internet of Things, agriculture, human healthcare, and storage environments. However, the long response time and low sensitivity of current printed humidity sensors limit their practical applications. Herein, a series of high‐sensing‐performance flexible resistive‐type humidity sensors is fabricated by the screen‐printing method, and hexagonal tungsten oxide (h‐WO3) is employed as the humidity‐sensing material due to its low cost, strong chemical adsorption ability, and excellent humidity‐sensing ability. The as‐prepared printed sensors exhibit high sensitivity, good repeatability, outstanding flexibility, low hysteresis, and fast response (1.5 s) in a wide relative humidity (RH) range (11–95% RH). Furthermore, the sensitivity of humidity sensors can be easily adjusted by altering the manufacturing parameters of the sensing layer and interdigital electrode to meet the diverse requirements of specific applications. The printed flexible humidity sensors possess immense potential in various applications, including wearable devices, non‐contact measurements, and packaging opening state monitoring.
Macrophage‐Hitchhiked Orally Administered β‐Glucans‐Functionalized Nanoparticles as “Precision‐Guided Stealth Missiles” for Targeted Pancreatic Cancer Therapy
Authors: Chen Kuan‐Hung , Nguyen Nhien , Huang Tun‐Yu , Lin Yu‐Jung , Yu Yu‐Tzu , Song Hsiang‐Lin , Wang Jui‐To , Nguyen Van Khanh , Chen Hsin‐Lung , Chu Li‐An , Chiang Hui‐Hua Kenny , Sung Hsing‐Wen 
Published: June 2023

AbstractThe prognosis in cases of pancreatic ductal adenocarcinoma (PDAC) with current treatment modalities is poor owing to the highly desmoplastic tumor microenvironment (TME). Herein, a β‐glucans‐functionalized zinc–doxorubicin nanoparticle system (βGlus‐ZnD NPs) that can be orally administered, is developed for targeted PDAC therapy. Following oral administration in PDAC‐bearing mice, βGlus‐ZnD NPs actively target/transpass microfold cells, overcome the intestinal epithelial barrier, and then undergo subsequent phagocytosis by endogenous macrophages (βGlus‐ZnD@Mϕ). As hitchhiking cellular vehicles, βGlus‐ZnD@Mϕ transits through the intestinal lymphatic system and enters systemic circulation, ultimately accumulating in the tumor tissue as a result of the tumor‐homing and “stealth” properties that are conferred by endogenous Mϕ. Meanwhile, the Mϕ that hitchhikes βGlus‐ZnD NPs is activated to produce matrix metalloproteinases, destroying the desmoplastic stromal barrier, and differentiates toward the M1‐like phenotype, modulating the TME and recruiting effector T cells, ultimately inducing apoptosis of the tumor cells. The combination of βGlus‐ZnD@Mϕ and immune checkpoint blockade effectively inhibits the growth of the primary tumor and suppresses the development of metastasis. It thus represents an appealing approach to targeted PDAC therapy.
Kirigami Makes a Soft Magnetic Sheet Crawl
Authors: Duhr Pierre , Meier Yuki A. , Damanpack Alireza , Carpenter Julia , Studart André R. , Rafsanjani Ahmad , Demirörs Ahmet F. 
Published: June 2023

AbstractLimbless crawling on land requires breaking symmetry of the friction with the ground and exploiting an actuation mechanism to generate propulsive forces. Here, kirigami cuts are introduced into a soft magnetic sheet that allow to achieve effective crawling of untethered soft robots upon application of a rotating magnetic field. Bidirectional locomotion is achieved under clockwise and counterclockwise rotating magnetic fields with distinct locomotion patterns and crawling speed in forward and backward propulsions. The crawling and deformation profiles of the robot are experimentally characterized and combined with detailed multiphysics numerical simulations to extract locomotion mechanisms in both directions. It is shown that by changing the shape of the cuts and orientation of the magnet the robot can be steered, and if combined with translational motion of the magnet, complex crawling paths are programed. The proposed magnetic kirigami robot offers a simple approach to developing untethered soft robots with programmable motion.
3D Printing of Ionogels with Complementary Functionalities Enabled by Self‐Regulating Ink
Authors: Huang Jiahui , Yu Zhenchuan , Wu Peiyi 
Published: June 2023

AbstractShaping soft and conductive materials into sophisticated architectures through 3D printing is driving innovation in myriad applications, such as robotic counterparts that emulate the synergic functions of biological systems. Although recently developed multi‐material 3D printing has enabled on‐demand creation of intricate artificial counterparts from a wide range of functional viscoelastic materials. However, directly achieving complementary functionalities in one ink design remains largely unexplored, given the issues of printability and synergy among ink components. In this study, an easily accessible and self‐regulating tricomponent ionogel‐based ink design to address these challenges is reported. The resultant 3D printed objects, based on the same component but with varying ratios of ink formulations, exhibit distinct yet complementary properties. For example, their Young's modulus can differ by three orders of magnitude, and some structures are rigid while others are ductile and viscous. A theoretical model is also employed for predicting and controlling the printing resolution. By integrating complementary functionalities, one further demonstrates a representative bioinspired prototype of spiderweb, which mimics the sophisticated structure and multiple functions of a natural spiderweb, even working and camouflaging underwater. This ink design strategy greatly extends the material choice and can provide valuable guidance in constructing diverse artificial systems by 3D printing.
Magnetic‐Electric Metamirror and Polarizing Beam Splitter Composed of Anisotropic Nanoparticles
Authors: Tuz Vladimir R. , Prokhorov Alexei V. , Shesterikov Alexander V. , Volkov Valentyn S. , Chichkov Boris N. , Evlyukhin Andrey B. 
Published: June 2023

AbstractThe emergence of new materials and fabrication techniques provides progress in the development of advanced photonic and communication devices. Transition metal dichalcogenides (e.g., molybdenum disulfide, MoS2) are novel materials possessing unique physical and chemical properties promising for optical applications. In this paper, a metasurface composed of particles made of bulk MoS2 is proposed and numerically studied considering its operation in the near‐infrared range. In the bulk configuration, MoS2 has a layered structure being a uniaxial anisotropic crystal demonstrating an optical birefringence property. It is supposed that the large‐scale and uniform MoS2 layers are synthesized in a vertical‐standing morphology, and then they are patterned into a regular 2D array of disks to form a metasurface. The natural anisotropy of MoS2 is utilized to realize the splitting of electric and magnetic dipole modes of the disks while optimizing their geometric parameters to bring the desired modes into overlap. At the corresponding resonant frequencies, the metasurface behaves as either an electric or a magnetic mirror, depending on the polarization of incident light. Based on the extraordinary reflection characteristics of the proposed metasurface, it can be considered an alternative to traditional mirrors and optical splitters when designing compact and highly efficient metadevices, which provide polarization and phase manipulation of electromagnetic waves on a subwavelength scale.
Kooperative Lewis‐Säure‐1,2,3‐Triazolium‐Aryloxid‐Katalyse: Addition von Pyrazolonen an Nitroolefine als Zugang zu Diaminoamiden
Authors: Wanner Daniel M. , Becker Patrick M. , Suhr Simon , Wannenmacher Nick , Ziegler Slava , Herrmann Justin , Willig Felix , Gabler Julia , Jangid Khushbu , Schmid Juliane , Hans Andreas C. , Frey Wolfgang , Sarkar Biprajit , Kästner Johannes , Peters René 
Published: June 2023

AbstractPyrazolone repräsentieren ein strukturell wichtiges Motiv in vielen Wirkstoffen. Ihre asymmetrische Synthese ist daher gut untersucht. Trotzdem ist eine enantio‐ sowie diastereoselektive 1,4‐Addition an Nitroolefine, die Produkte mit benachbarten Stereozentren bildet, kaum bekannt. In diesem Artikel wird ein neuartiger, polyfunktioneller CuII‐1,2,3‐Triazolium‐Aryloxid‐Katalysator vorgestellt, der diese Reaktion mit hoher Stereokontrolle ermöglicht. DFT‐Studien zeigen hierbei, dass die Triazolium‐Einheit den Übergangszustand durch eine Wasserstoffbrücke des C(5)−H zum Nitroolefin stabilisiert, was die polyfunktionelle Aktivierung durch dieses System belegt. Weiterhin zeigt sich, dass der Katalysator durch eine intramolekulare Wasserstoffbrücke eine starre Käfig‐/ Poren‐Struktur ausbildet, wodurch Stereokontrolle erlangt wird. Kontrollsysteme in der Katalyse bestätigen hierbei die essenzielle Rolle des Triazoliums, Aryloxids sowie CuII, welche eine ausgeklügelte strukturelle Orchestrierung benötigen, um hoch effizient zu arbeiten. Die Additionsprodukte wurden verwendet um Pyrazolidinone durch chemoselektive C=N‐Reduktion zu bilden. Diese Heterozyklen konnten als Vorstufen zur Synthese von β,γ’‐Diaminoamiden durch chemoselektive Nitro‐ und N,N‐Bindungsreduktion genutzt werden. Morphologisches Profiling mittels Cell Painting Assay konnte die biologische Aktivität der Pyrazolidinone aufzeigen, wobei die Regulierung der DNA‐Synthese als potenzielle Wirkungsweise identifiziert wurde. Ein Produkt zeigte hierbei biologische Ähnlichkeit zu Camptothecin, einer Leitstruktur in der Krebstherapie.
Redox Reorganization: Aluminium Promoted 1,5‐Hydride Shifts Allow the Controlled Synthesis of Multisubstituted Cyclohexenes
Authors: Smith Lewis B. , Armstrong Roly J. , Hou Jingyan , Smith Edward , Sze Ming , Sterling Alistair J. , Smith Alex , Duarte Fernanda , Donohoe Timothy J. 
Published: June 2023

AbstractAn efficient synthesis of cyclohexenes has been achieved from easily accessible tetrahydropyrans via a tandem 1,5‐hydride shift–aldol condensation. We discovered that readily available aluminium reagents, e.g. Al2O3 or Al(OtBu)3 are essential for this process, promoting the 1,5‐hydride shift with complete regio‐ and enantiospecificity (in stark contrast to results obtained under basic conditions). The mild conditions, coupled with multiple methods available to access the tetrahydropyran starting materials makes this a versatile method with exceptional functional group tolerance. A wide range of cyclohexenes (>40 examples) have been prepared, many in enantiopure form, showing our ability to selectively install a substituent at each position around the newly forged cyclohexene ring. Experimental and computational studies revealed that aluminium serves a dual role in facilitating the hydride shift, activating both the alkoxide nucleophile and the electrophilic carbonyl group.