bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transition Metal Compounds Family for Li–S Batteries: The DFT‐Guide for Suppressing Polysulfides Shuttle
Authors: Liang Qi , Wang Sizhe , Yao Yao , Dong Peng , Song Haojie 
Published: April 2023

AbstractLithium–sulfur batteries (LSBs) are considered as one of the best candidates for the next generation of high‐energy‐density storage devices owing to their superior theoretical energy density, high specific capacity, and sufficient sulfur reservoirs. However, the shuttle effect of soluble polysulfides and sluggish LiPSs redox kinetics restrict the further application of LSBs. The polysulfides shuttle effect can be efficiently alleviated and LiPSs conversion kinetics be accelerated by designing optimal transition metal compounds (TMCs) as multifunctional catalyst materials. Herein, recent advances about TMCs in LSBs are systematically summarized and analyzed. First of all, the intrinsic structural characteristics of TMCs and relevant application on their works to the adsorption energies studies are described in detail. Second, the bonding manners and structural properties are analyzed by density functional theory (DFT)‐guided calculations, focusing on the adsorption and diffusion behavior between TMCs and LiPSs. Furthermore, the mechanism of LiPSs redox reaction conversion is studied from kinetics aspects, thus developing the continuous dynamic analysis on “adsorption–diffusion–conversion” toward LiPSs. Eventually, this study particularly highlights the importance of modification engineering and provides a forward‐looking overview for its further application prospects by introduction of the previous advanced studies in LSBs.
Progress and Perspectives of Lithium Aluminum Germanium Phosphate‐Based Solid Electrolytes for Lithium Batteries
Authors: Zhang Yue , Liu Hanshuo , Xie Zhong , Qu Wei , Freschi Donald J. , Liu Jian 
Published: April 2023

AbstractSolid‐state lithium batteries are considered promising energy storage devices due to their superior safety and higher energy density than conventional liquid electrolyte‐based batteries. Lithium aluminum germanium phosphate (LAGP), with excellent stability in air and good ionic conductivity, has gained tremendous attention over the past decades. However, the poor interface compatibility with Li anode, slow Li‐ion conduction in thick pellets, and high‐temperature sintering procedure limit the further development of LAGP solid electrolytes in practical applications. This review comprehensively summarizes the crystal structure, Li‐ion conducting mechanism, and various synthesis methods, especially the latest thin‐film preparation approach. The underlying reason for Li/LAGP interfacial instability is identified, followed by several advanced interface engineering strategies, for example, introducing a functional interlayer. The integration design of LAGP‐based solid electrolytes and cathode is also highlighted to enable high‐loading cathodes. Additionally, recent progress of lithium‐oxygen and lithium‐sulfur batteries with LAGP‐based solid electrolytes is discussed. Moreover, the different Li‐ion migration pathways, preparation procedures, and electrochemical performance of polymer‐LAGP composite solid electrolytes in Li‐ion batteries are introduced. Lastly, the remaining challenges and opportunities are proposed to encourage more efforts in this field. This review aims to provide fundamental insights and promising directions toward practical LAGP‐based solid‐state batteries.
Artificial Immunogenic Cell Death Lipid Nanoparticle Functions as a Therapeutic Vaccine for Cancer
Authors: Kim So‐Jung , Park Hae‐Bin , An Eun‐Koung , Eom Hee‐Yun , Zhang Wei , Kim Jihoe , Choi Inho , Kwak Minseok , Lee Peter C. W. , Jin Jun‐O 
Published: April 2023

AbstractAnticancer drug‐mediated induction of immunogenic cell death (ICD) blocks metastasis or recurrence in cancer cells by promoting specific immune activity against cancer antigens. However, this strategy has failed to afford adequate treatment efficiency. Overcoming the failure of ICD‐mediated cancer therapy, lipid nanoparticles (LNPs) containing cancer cell surface proteins are synthesized using sonication and extrusion without microfluidics. In addition, these LNPs are decorated with high‐mobility group box 1 protein and calreticulin, indicators of ICD, and named artificial ICD LNPs (AiLNPs). Administration of AiLNPs effectively targets dendritic cells (DCs) and induces DC activation in mice. Moreover, treating CT‐26 tumor‐bearing mice with AiLNPs inhibits tumor growth by inducing CT‐26 antigen‐specific T‐cell immunity. Furthermore, AiLNPs containing Lewis lung carcinoma (LLC1) membrane proteins can prevent metastatic LLC1 tumor growth in the lung via LLC1 antigen‐specific T‐cell activation. Finally, AiLNPs synthesized with human breast cancer membrane proteins activate DC‐mediated antigen‐specific T‐cell immunity, effectively killing tumor cells. Therefore, AiLNPs are expected to be developed as a patient‐specific cancer treatment to prevent cancer recurrence and metastasis.
Reduction‐Responsive Supramolecular Sheets for Selective Regulation of Facultative Anaerobe Agglutination
Authors: Lee Dawoon , Dong Longlong , Kim Ye Rim , Kim Jehan , Lee Myongsoo , Kim Yongju 
Published: April 2023

AbstractStimuli‐responsive supramolecular materials have promising biological applications because of their ability to rapidly undergo significant structural changes in response to diverse stimuli. Herein, supramolecular sheets assembled via charge‐transfer interactions between the pyrene moiety of a d‐mannose‐containing amphiphile and 7,7,8,8‐tetracyanoquinodimethane (TCNQ) are reported. The supramolecular sheets show reduction‐responsive behavior, in which their disassembly is triggered by the reduction of TCNQ by sodium sulfide. In an anaerobic environment, the sheet structure remains intact and the exposed d‐mannose moieties induce the agglutination of facultative anaerobes, thereby inhibiting bacterial growth. In contrast, in an aerobic environment, the reduction of TCNQ by the hydrogen sulfide generated by facultative anaerobes causes sheet disassembly. This enables continuous bacterial growth, because the collapsed sheets cannot induce agglutination. Thus, this study presents a novel supramolecular material for the selective regulation of facultative anaerobe growth according to the external environment.
In Situ Grown Silver–Polymer Framework with Coordination Complexes for Functional Artificial Tissues
Authors: Zhang Songlin , Deng Yibing , Libanori Alberto , Zhou Yihao , Yang Jiachen , Tat Trinny , Yang Lin , Sun Wanxin , Zheng Peng , Zhu You‐Liang , Chen Jun , Tan Swee Ching 
Published: April 2023

AbstractSelf‐sensing actuators are critical to artificial robots with biomimetic proprio‐/exteroception properties of biological neuromuscular systems. Existing add‐on approaches, which physically blend heterogeneous sensor/actuator components, fall short of yielding satisfactory solutions, considering their suboptimal interfaces, poor adhesion, and electronic/mechanical property mismatches. Here, a single homogeneous material platform is reported by creating a silver–polymer framework (SPF), thus realizing the seamless sensing–actuation unification. The SPF‐enabled elastomer is highly stretchable (1200%), conductive (0.076 S m−1), and strong (0.76 MPa in‐strength), where the stretchable polymer matrix synthesis and in situ silver nanoparticles reduction are accomplished simultaneously. Benefiting from the multimodal sensing capability from its architecture itself (mechanical and thermal cues), self‐sensing actuation (proprio‐deformations and external stimuli perceptions) is achieved for the SPF‐based pneumatic actuator, alongside an excellent load‐lifting attribute (up to 3700 times its own weight), substantiating its advantage of the unified sensing–actuation feature in a single homogenous material. In view of its human somatosensitive muscular systems imitative functionality, the reported SPF bodes well for use with next‐generation functional tissues, including artificial skins, human–machine interfaces, self‐sensing robots, and otherwise dynamic materials.
Engineered Extracellular Vesicles Derived from Dermal Fibroblasts Attenuate Inflammation in a Murine Model of Acute Lung Injury
Authors: Salazar‐Puerta Ana I. , Rincon‐Benavides María A. , Cuellar‐Gaviria Tatiana Z. , Aldana Julian , Vasquez Martinez Gabriela , Ortega‐Pineda Lilibeth , Das Devleena , Dodd Daniel , Spencer Charles A. , Deng Binbin , McComb David W. , Englert Joshua A. , Ghadiali Samir , Zepeda‐Orozco Diana , Wold Loren E. , Gallego‐Perez Daniel , Higuita‐Castro Natalia 
Published: April 2023

AbstractAcute respiratory distress syndrome (ARDS) represents a significant burden to the healthcare system, with ≈200 000 cases diagnosed annually in the USA. ARDS patients suffer from severe refractory hypoxemia, alveolar‐capillary barrier dysfunction, impaired surfactant function, and abnormal upregulation of inflammatory pathways that lead to intensive care unit admission, prolonged hospitalization, and increased disability‐adjusted life years. Currently, there is no cure or FDA‐approved therapy for ARDS. This work describes the implementation of engineered extracellular vesicle (eEV)‐based nanocarriers for targeted nonviral delivery of anti‐inflammatory payloads to the inflamed/injured lung. The results show the ability of surfactant protein A (SPA)‐functionalized IL‐4‐ and IL‐10‐loaded eEVs to promote intrapulmonary retention and reduce inflammation, both in vitro and in vivo. Significant attenuation is observed in tissue damage, proinflammatory cytokine secretion, macrophage activation, influx of protein‐rich fluid, and neutrophil infiltration into the alveolar space as early as 6 h post‐eEVs treatment. Additionally, metabolomics analyses show that eEV treatment causes significant changes in the metabolic profile of inflamed lungs, driving the secretion of key anti‐inflammatory metabolites. Altogether, these results establish the potential of eEVs derived from dermal fibroblasts to reduce inflammation, tissue damage, and the prevalence/progression of injury during ARDS via nonviral delivery of anti‐inflammatory genes/transcripts.
Degeneracy Removal of Spin Bands in Collinear Antiferromagnets with Non‐Interconvertible Spin‐Structure Motif Pair
Authors: Yuan Lin‐Ding , Zunger Alex 
Published: April 2023

AbstractEnergy bands in antiferromagnets are supposed to be spin degenerate in the absence of spin–orbit coupling (SOC). Recent studies have identified formal symmetry conditions for antiferromagnetic crystals in which this degeneracy can be lifted, spin splitting,even in the vanishing SOC (i.e., non‐relativistic) limit. Materials having such symmetries could enable spin‐split antiferromagnetic spintronics without the burden of using heavy‐atom compounds. However, the symmetry conditions that involve spin and magnetic symmetry are not always effective as practical material selection filters. Furthermore, these symmetry conditions do not readily disclose trends in the magnitude and momentum dependence of the spin‐splitting energy. Here, it is shown that the formal symmetry conditions enabling spin‐split antiferromagnets can be interpreted in terms of local motif pairs, such as octahedra or tetrahedra, each carrying opposite magnetic moments. Collinear antiferromagnets with such a spin‐structure motif pair, whose components interconvert by neither translation nor spatial inversion, will show spin splitting. Such a real‐space motif‐based approach enables an easy way to identify and design materials (illustrated in real example materials) having spin splitting without the need for SOC, and offers insights into the momentum dependence and magnitude of the spin splitting.
Sono‐Driven STING Activation using Semiconducting Polymeric Nanoagonists for Precision Sono‐Immunotherapy of Head and Neck Squamous Cell Carcinoma
Authors: Jiang Jianli , Zhang Miaomiao , Lyu Tao , Chen Linrong , Wu Min , Li Ruowei , Li Haoze , Wang Xiang , Jiang Xiqun , Zhen Xu 
Published: April 2023

AbstractImmunotherapy has offered new opportunities to treat head and neck squamous cell carcinoma (HNSCC); however, its clinical applications are hindered by modest therapeutic outcomes and the “always‐on” pharmacological activity of immunomodulatory agents. Strategies for precise spatiotemporal activation of antitumor immunity can tackle these issues but remain challenging. Herein, a semiconducting polymeric nanoagonist (SPNM) with in situ sono‐activatable immunotherapeutic effects for precision sono‐immunotherapy of HNSCC is reported. SPNM is self‐assembled from a sonodynamic semiconducting polymer core conjugated with a stimulator of interferon genes (STING) agonist (MSA‐2) via a singlet oxygen cleavable linker. Under sono‐irradiation, SPNM produces singlet oxygen not only to eradicate tumor cells to trigger immunogenic cell death but also to unleash caged STING agonists via the cleavage of diphenoxyethene bonds for in situ activation of the STING pathway in the tumor region. Such sono‐driven STING activation mediated by SPNM promotes effector T cell infiltration and potentiates systemic antitumor immunity, eventually leading to tumor growth inhibition and long‐term immunological memory. This study thus presents a promising strategy for the precise spatiotemporal activation of cancer immunotherapy.
An Artificial Olfactory System Based on a Chemi‐Memristive Device
Authors: Chun Suk Yeop , Song Young Geun , Kim Ji Eun , Kwon Jae Uk , Soh Keunho , Kwon Ju Young , Kang Chong‐Yun , Yoon Jung Ho 
Published: April 2023

AbstractTechnologies based on the fusion of gas sensors and neuromorphic computing to mimic the olfactory system have immense potential. However, the implementation of neuromorphic olfactory systems remains in a state of infancy because conventional gas sensors lack the necessary functions. Therefore, this study proposes a hysteretic “chemi‐memristive gas sensor” based on oxygen vacancy chemi‐memristive dynamics that differ from that of conventional gas sensors. After the memristive switching operation, the redox reaction with the external gas molecules is enhanced, resulting in the generation and elimination of oxygen vacancies that induce rapid current changes. In addition, the pre‐generated oxygen vacancies enhance the post‐sensing properties. Therefore, fast responses, short recovery times, and hysteretic gas response are achieved by the proposed sensor at room temperature. Based on the advantageous functionality of the sensor, device‐level olfactory systems that can monitor the history of input gas stimuli are experimentally demonstrated as a potential application. Moreover, analog conductance modulation induced by oxidizing and reducing gases enables the conversion of external gas stimuli into synaptic weights and hence the realization of typical synaptic functionalities without an additional device or circuit. The proposed chemi‐memristive device represents an advance in the bioinspired technology adopted in creating artificial intelligence systems.
Tetraphenylethene‐Based Multicomponent Platinum (II) Metallacages with Tunable Luminescence and Aggregation‐Induced Electrochemiluminescence Properties
Authors: Wang Yu , Liu Jiani , Niu Yibo , He Linli , Wang Yujie , Ma Ying , Yao Yao , Ye Jianshan 
Published: April 2023

AbstractMetallacages (MCs) are one kind of functional 3D supramolecular complexes with controllable structures, their special cage structures lead to diverse photophysical properties, enabling their wide application in catalysis, bio‐imaging, and organic light‐emitting devices. Herein, a series of tetraphenylene (TPE)‐based MCs with tunable structures is reported via the coordination‐driven self‐assembly strategy. The resulting MCs demonstrate tunable fluorescence (FL) and electrochemiluminescence (ECL) due to their size‐dependent energy gaps. More importantly, their aggregation‐induced ECL (AIECL) property is observed, and the corresponding self‐catalytic ECL enhancement mechanism is proposed. In addition, a sensitive ECL sensor toward iodide ions (I−) is developed based on the competitive coordination of I− with the pyridine group of ligands. This study may promote the design of MCs materials and broaden their applications in the ECL study.
Concentration‐Induced Hetero‐Valent Partial‐Inverse Occupation of Infrared Phosphor
Authors: Hsu Jia‐Yu , Chung Ren‐Jei , Kuo Yen‐Ling , Lin Chun Che , Majewska Natalia , Kreft Dominik , Mahlik Sebastian , Fang Mu‐Huai 
Published: April 2023

AbstractInfrared luminescent materials have evoked much attention from chemists and material scientists. Although substantial progress is made in materials design, the luminescent mechanism remains ambiguous in the complex structures, presenting major barriers to developing novel infrared luminescent materials. Herein, this study aims to deliberate a complete discussion on infrared phosphors with concentration‐induced hetero‐valent partial‐inverse occupation. High‐resolution synchrotron X‐ray diffraction and Raman spectroscopy reveal the subtle structural change in LiGa5(1−x)O8:5xCr3+. Besides, Cr K‐edge wavelet analysis and extended X‐ray absorption fine structure illustrate the impact of Cr in the second shell of another Cr ion and the practical coordination of Ga and Cr ions. Furthermore, unexpected two‐center Cr3+emissions and the Cr–Cr pair emission are observed at high Cr concentrations. Variation between the zero‐phonon line and N‐line at different temperatures is demonstrated. Finally, the structural and luminescent properties are comprehensively discussed, providing the origin of the unexpected Cr2 emission. This study not only provides insight into the hetero‐valent partial‐inverse occupation process in inorganic materials but also sheds light on developing novel infrared luminescent materials.
Merger of Visible Light‐Driven Chiral Organocatalysis and Continuous Flow Chemistry: An Accelerated and Scalable Access into Enantioselective α‐Alkylation of Aldehydes
Authors: Molnár Márk , Kappe C. Oliver , Ötvös Sándor B. 
Published: April 2023

AbstractThe electron donor‐acceptor complex‐enabled asymmetric photochemical alkylation strategy holds potential to attain elusive chiral α‐alkylated aldehydes without an external photoredox catalyst. The photosensitizer‐free conditions are beneficial concerning process costs and sustainability. However, lengthy organocatalyst preparation steps as well as limited productivity and difficult scalability render the current approaches unsuitable for synthesis on enlarged scales. Inspired by these limitations, a protocol was developed for the enantioselective α‐alkylation of aldehydes based on the synergistic combination of visible light‐driven asymmetric organocatalysis and a controlled continuous flow reaction environment. With the aim to reduce process costs, a commercially available chiral catalyst has been exploited to achieve photosensitizer‐free enantioselective α‐alkylations using phenacyl bromide derivates as alkylating agents. As a result of elaborate optimization and process development, the present flow strategy furnishes an accelerated and inherently scalable entry into enantioenriched α‐alkylated aldehydes including a chiral key intermediate of the antirheumatic esonarimod.magnified image
Nerve‐on‐a‐Chip Derived Biomimicking Microfibers for Peripheral Nerve Regeneration
Authors: Yu Yunru , Jin Binghui , Chen Jinghao , Lou Chenghao , Guo Jiahui , Yang Chaoyu , Zhao Yuanjin 
Published: April 2023

AbstractFibrous scaffolds have shown their advantages in tissue engineering, such as peripheral nerve regeneration, while most of the existing fiber‐shaped scaffolds are with simple structures, and the in vitro performance for nerve regeneration lacks systematic analysis. Here, novel nerve‐on‐a‐chip derived biomimicking microfibers for peripheral nerve regeneration are presented. The microfibers with controllable core–shell structures and functionalities are generated through capillary microfluidic devices. By integrating these microfibers into a multitrack‐architectured chip, and coculturing them with nerve cells as well as gradient bioactive elements, the nerve‐on‐a‐chip with the capabilities of systematically assessing the performances of nerve fiber formation in the hollow microfibers at in vitro level is constructed. Based on a rat sciatic nerve injury model, the rapid promotion ability is demonstrated of optimized microfibers in nerve regeneration and function recovery in vivo, which implies the credibility of the nerve‐on‐a‐chip on biomimicking microfibers evaluation for peripheral nerve regeneration. Thus, it is convinced that the organ‐on‐a‐chip will undoubtedly open up a new chapter in evaluating biological scaffolds for in vivo tissue engineering.
Surface‐Confined Ultra‐Low Scale Pd Engineered Layered Co(OH)2 toward High‐Performance Hydrazine Electrooxidation in Alkaline Saline Water
Authors: Sarker Swagotom , Choi Ji Hoon , Lee Hak Hyeon , Kim Dong Su , Cho Hyung Koun 
Published: April 2023

AbstractApplications of abundant seawater in electrochemical energy conversion are constrained due to the sluggish oxygen evolution reaction and the corrosive chlorine oxidation reaction. Hence, it is imperative to develop an efficient anodic reaction alternative suitable for coupling with the cathodic counterpart. Due to a low thermodynamic oxidation potential, hydrazine oxidation reaction (HzOR) offers a unique pathway to overcome these challenges. Herein, spontaneously in situ reduced atomic scale Pd surface‐confined to electrochemically prepared layered Co(OH)2 on carbon cloth is synthesized. This study reveals the hydrazine and Pd‐dependent morphological evolution of Co(OH)2 and its Pd hybrids into nanoparticulate form. Unlike various layered double hydroxides, Pd integrated Co(OH)2 benefits from the contribution of Co(OH)2 as an active HzOR catalyst and the reductive support to host Pd, resulting in synergistically improved performances. Mass activities of Pd in alkaline and alkaline saline electrolyte are 11.24 and 9.83 A mgPd−1 at 200 mV, respectively, corresponding to the highest HzOR activities among noble metals. The optimized Pd hybrid demonstrates ≈6.5 times the current density relative to PtC (14.91 mA cm−2 at 200 mV) in alkaline saline water with hydrazine. These findings would be beneficial to realize high overpotential anodic alternatives and reduce over‐dependence on freshwater for electrocatalysis.