bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cobweb‐Inspired Microenvironment‐Targeting Nanosystem with Sequential Multiple‐Stage Stimulus‐Response Capacity for Ischaemic Tissue Repair
Authors: Ding Xiaoyu , Xing Xiaowen , Liu Jianfeng , Zhu Pengchong , Wang Cui , Bai Rui , Kong Bo , Zeng Chuyang , Zhang Wei , Yue Yin , Zhang Haitao , Xiang Jiajia , Yuan Zengqiang , Liu Zhiqiang 
Published: April 2023

AbstractMyocardial ischaemia is pathologically complicated; various changes in intracellular and extracellular microenvironments make it essential to develop a smart drug system with multiple stimulus responses to adapt to the complex process. Inspired by the cobweb, this study designs a microreticular nanosystem that adheres to tissue and is sequentially responsive to multiple stimuli in the ischaemic microenvironment. The nanosystem is fabricated from hyaluronic acid (HA), ROS‐responsive B‐PDEA, and hypoxia‐sensitive VEGF‐expressing plasmids (EPODNA) through electrostatic interactions. After intramyocardial injection, the tissue‐adhesive property of the nanosystem will significantly decrease its acute loss from the injection site. Extracellularly, the microreticular nanosystem first responds to activated hyaluronidase (hyal), releasing HA for microenvironment regulation and B‐PDEA/DNA nanoparticles (NP) with high transfection efficiency for cardiac cells. Intracellularly, ROS sequentially induced B‐PDEA/DNA NP dissociation, consuming some ROS to attenuate oxidative stress and releasing DNA to promote its expression. Meanwhile, local hypoxia significantly activates VEGF expression in plasmids for myocardial revascularization and repair. The function of the microreticular nanosystem is systematically evaluated in vitro. In a rat model of myocardial infarction, treatment with the microreticular nanosystem significantly promotes functional and structural improvements. Collectively, the study provides a promising smart nanosystem to promote tissue repair after complex damage.
Room Temperature Spin‐Phonon Coupling in Cr2O3Nanocrystals
Authors: Testa‐Anta Martín , Majcherkiewicz Julia N. , Xu Kai , Goñi Alejandro R. , Salgueiriño Verónica 
Published: April 2023

AbstractIn this study, nanocrystals of antiferromagnetic Cr2O3are shown via Raman spectroscopy to display peculiar lattice dynamics in terms of phonon softening and the occurrence of an exceptionally strong spin‐phonon coupling. This effect, which is observed to persist well above the onset of the antiferromagnetic ordering temperature, is ascribed to locally correlated spin fluctuations due to the modulation of the magnetic exchange interactions as the chromium atoms oscillate about their equilibrium position. It is found that the spin‐phonon coupling strength is governed by the competing antiferromagnetic and ferromagnetic interactions, where changes in the surface spin configuration can also play a crucial role. Overall, this work proves the size dependence of the interplay between the crystalline and magnetic structures in 3D antiferromagnets varying the surface‐to‐volume ratio and helps establish the fundamentals for a spin‐phonon coupling engineering at the nanoscale via a simple route in a very stable and easy to synthesize material. More importantly, it demonstrates the possibility of coupling phononic excitations with the magnetization dynamics at room temperature, offering a highly prospective nanomaterial for the design of novel magnonic devices.
The Interaction of Amines with Gold Nanoparticles
Authors: Lyu Yanchao , Becerril Lucia Morillas , Vanzan Mirko , Corni Stefano , Cattelan Mattia , Granozzi Gaetano , Frasconi Marco , Rajak Piu , Banerjee Pritam , Ciancio Regina , Mancin Fabrizio , Scrimin Paolo 
Published: April 2023

AbstractUnderstanding the interactions between amines and the surface of gold nanoparticles is important because of their role in the stabilization of the nanosystems, in the formation of the protein corona, and in the preparation of semisynthetic nanozymes. By using fluorescence spectroscopy, electrochemistry, X‐ray photoelectron spectroscopy, high‐resolution transmission electron microscopy, and molecular simulation, a detailed picture of these interactions is obtained. Herein, it is shown that amines interact with surface Au(0) atoms of the nanoparticles with their lone electron pair with a strength linearly correlating with their basicity corrected for steric hindrance. The kinetics of binding depends on the position of the gold atoms (flat surfaces or edges) while the mode of binding involves a single Au(0) with nitrogen sitting on top of it. A small fraction of surface Au(I) atoms, still present, is reduced by the amines yielding a much stronger Au(0)–RN.+ (RN., after the loss of a proton) interaction. In this case, the mode of binding involves two Au(0) atoms with a bridging nitrogen placed between them. Stable Au nanoparticles, as those required for robust semisynthetic nanozymes preparation, are better obtained when the protein is involved (at least in part) in the reduction of the gold ions.
Gate‐Tunable Photovoltaic Efficiency in Graphene‐Sandwiched PdSe2 Photodetectors with Restrained Carrier Recombination
Authors: Chen Tianhong , Xiao Long , Liu Yuan , Wang Junzhuan , Wang Xinran , Wang Xiaomu , Yan Shancheng , Shi Yi 
Published: April 2023

AbstractThe exploration of various two‐dimensional (2D) materials provides a promising platform for constructing van der Waals heterojunction (vdWH) photovoltaic devices. The photovoltaic efficiency of such devices is still a challenge due to the recombination of photogenerated carriers resulting from the intrinsic doping property of materials. Here, PdSe2‐based graphene‐sandwiched vertical devices with high photovoltaic efficiency are constructed. As the graphene‐sandwiched structure limits the diffusion length to tens of nanometers, the carrier recombination during diffusion is spontaneously reduced. Moreover, due to the low‐resistance contact of graphene/PdSe2, the Fermi level and carrier density of PdSe2 can still be significantly tuned by gate voltage, which leads to a sharp enhancement of built‐in field and photovoltaic effect. As a result, the Gr/PdSe2/MoS2/Gr vdWH photovoltaic device shows a high power conversion efficiency of 3.9% and an open circuit voltage of 0.6 V under 650 nm laser illumination at room temperature. The present work provides an efficient scheme for the design of high‐efficiency 2D material photovoltaic devices.
TEMPO Mediated Cyclopropanols Ring Opening C−N Cross‐Coupling with Nitrogen Nucleophiles
Authors: Zhan Jun‐Long , Zhu Lin , Ren Wei , Wang Bing‐Jie , Zhao Xin‐Ming , Zhang Xin‐Ru , Zhang Xin‐Yu , Xie Yao‐Qiang 
Published: April 2023

AbstractA feasible and umpolung strategy for the synthesis of structurally diverse β‐amino ketones has been achieved through TEMPO mediated C−N coupling of cyclopropanols with nitrogen nucleophiles. Mechanism studies indicated that in situ generated enones derived from cyclopropanols are the key intermediates and TEMPO play multiple roles, including radical initiator, trapping reagent, a porter of β‐hydrogen and an in situ base. This protocol features broad substrate scope, good scalability and good to excellent yields and provides an alternative and complementary approach to the synthesis of structurally important β‐amino ketone scaffolds under metal and additive‐free conditions.magnified image
Composite Nanoplatforms Based on Nanocalcium Peroxide for Cancer Treatment: From Monotherapy to Combination Therapy
Authors: Hu Xinze , Liu Jiale , Wang Yuxin , Xu Boyu , Gongye Jingxian , Liu Yanduo , Sun Tiedong , Liu Liping , Wang Xijin 
Published: April 2023

AbstractNano‐CaO2, with its multifunctional properties, has emerged as a promising candidate for tumor therapy. Its ability to release Ca2+ and H2O2 into the tumor microenvironment has positively modulated abnormal calcium signaling and kinetic therapy. Moreover, the indirectly produced O22− by CaO2 can alleviate hypoxic conditions. On the one hand, the accumulation of Ca2+ can lead to various tumor cell apoptosis events, such as calcium overload and tumor calcification. On the other hand, the released H2O2 can convert into more toxic reactive oxygen species (ROS) via exogenous stimulation and endogenous regulation, thereby making nano‐CaO2 a versatile tool in modern medicine, exhibiting its invaluable and irreplaceable medical value in tumor therapy. Hence, a comprehensive review of the recent advances in the nano‐CaO2 platform is imperative. This review provides an overview of the conventional synthesis strategies for nano‐CaO2. It elucidates the potential role of the nano‐CaO2 nanoplatforms in various tumor treatment strategies, including monotherapy and combination therapy, in detail. Given the remarkable outcomes achieved to date and the challenges that of future clinical translation, this work predicts the future research directions. This review will encourage further development of the metal oxide nanomedicine family, epitomized by nano‐CaO2.
Evacuation Simulation of a Passenger Ship Fire Based on a Modified Cellular Automaton
Authors: Liu Linfan , Zhang Huajun , Shi Jun , Geng Jianning 
Published: April 2023

AbstractThis study proposes a modified cellular automaton to simulate passenger ship fire evacuation. A fire dynamics simulator (FDS) is used to simulate the firing process for the passenger ship. The generated carbon monoxide (CO) concentration, temperature, and visibility are converted into equivalent lengths and input to the equivalent field of the modified cellular automaton. The fire field is applied to keep the evacuees away from the fire. And game theory is adopted to solve the conflict in the choice of route for evacuees. With or without fire on the passenger ship, three different evacuees’ densities are used to study the influence of different proportions of evacuees who are familiar with exits during the evacuation time. The positions of exits are also studied. The results show that when the fire release rate increases from 3000 to 8000 kW s−2 for the same evacuation scenario, the earliest time that evacuees are in danger is 50% earlier. The impact of fire on evacuees is greater than that of evacuees’ density. In the case of two close exits or exits close to the bulkheads, the congestion near exits is obvious and has the greatest effect on the evacuation time of the high evacuees’ density.
Focused Epicranial Brain Stimulation by Spatial Sculpting of Pulsed Electric Fields Using High Density Electrode Arrays
Authors: Jain Vishal , Forssell Mats , Tansel Derya Z. , Goswami Chaitanya , Fedder Gary K. , Grover Pulkit , Chamanzar Maysamreza 
Published: April 2023

AbstractTranscranial electrical neuromodulation of the central nervous system is used as a non‐invasive method to induce neural and behavioral responses, yet targeted non‐invasive electrical stimulation of the brain with high spatial resolution remains elusive. This work demonstrates a focused, steerable, high‐density epicranial current stimulation (HD‐ECS) approach to evoke neural activity. Custom‐designed high‐density (HD) flexible surface electrode arrays are employed to apply high‐resolution pulsed electric currents through skull to achieve localized stimulation of the intact mouse brain. The stimulation pattern is steered in real time without physical movement of the electrodes. Steerability and focality are validated at the behavioral, physiological, and cellular levels using motor evoked potentials (MEPs), intracortical recording, and c‐fos immunostaining. Whisker movement is also demonstrated to further corroborate the selectivity and steerability. Safety characterization confirmed no significant tissue damage following repetitive stimulation. This method can be used to design novel therapeutics and implement next‐generation brain interfaces.
Threshold Switching by Bipolar Avalanche Multiplication in Ovonic Chalcogenide Glasses
Authors: Fantini Paolo , Polino Nicola , Ghetti Andrea , Ielmini Daniele 
Published: April 2023

AbstractAn ovonic threshold switch (OTS) based on chalcogenide glasses finds application as a selecting device in storage class memory (SCM) arrays. The OTS operation relies on the threshold switching, where the device switches from the off to the on state without phase transition, then the device turns off almost immediately as the voltage is reduced below a certain holding value. The physics behind the switching phenomenon has attracted wide interest due to the complicated interplay between electronic transport, joule heating and phase transition. In this work, it is shown that the current‐voltage characteristic close to the switching point carries the fingerprint of carrier multiplication. The physical mechanism of threshold switching is then explained by bipolar impact ionization leading to avalanche multiplication, which in turn gives rise to the typical S‐shaped characteristic. Numerical simulations by this physics‐based model account for the measured switching properties, namely threshold voltage and current, at various chalcogenide thicknesses and compositions. These results provide the theoretical framework for future design and optimization of OTS in memory and computing applications.
Intravenous Thrombolysis 4.5–9 Hours After Stroke Onset: A Cohort Study from the TRISP Collaboration
Authors: Altersberger Valerian L. , Sibolt Gerli , Enz Lukas S. , Hametner Christian , Scheitz Jan F. , Henon Hilde , Bigliardi Guido , Strambo Davide , Martinez‐Majander Nicolas , Stolze Lotte J. , Heldner Mirjam R. , Grisendi Ilaria , Jovanovic Dejana R. , Bejot Yannick , Pezzini Alessandro , Leker Ronen R. , Kägi Georg , Wegener Susanne , Cereda Carlo W. , Ntaios Georges , De Marchis Gian Marco , Bonati Leo H. , Psychogios Marios , Lyrer Philippe , Räty Silja , Tiainen Marjaana , Wouters Anke , Caparros François , Heyse Miriam , Erdur Hebun , Padjen Visnja , Zedde Marialuisa , Arnold Marcel , Nederkoorn Paul J. , Michel Patrik , Zini Andrea , Cordonnier Charlotte , Nolte Christian H. , Ringleb Peter A. , Curtze Sami , Engelter Stefan T. , Gensicke Henrik ,   the TRISP collaborators
Published: April 2023

ObjectiveTo investigate the safety and effectiveness of intravenous thrombolysis (IVT) >4.5–9 hours after stroke onset, and the relevance of advanced neuroimaging for patient selection.MethodsProspective multicenter cohort study from the ThRombolysis in Ischemic Stroke Patients (TRISP) collaboration. Outcomes were symptomatic intracranial hemorrhage, poor 3‐month functional outcome (modified Rankin scale 3–6) and mortality. We compared: (i) IVT >4.5–9 hours versus 0–4.5 hours after stroke onset and (ii) within the >4.5–9 hours group baseline advanced neuroimaging (computed tomography perfusion, magnetic resonance perfusion or magnetic resonance diffusion‐weighted imaging fluid‐attenuated inversion recovery) versus non‐advanced neuroimaging.ResultsOf 15,827 patients, 663 (4.2%) received IVT >4.5–9 hours and 15,164 (95.8%) within 4.5 hours after stroke onset. The main baseline characteristics were evenly distributed between both groups. Time of stroke onset was known in 74.9% of patients treated between >4.5 and 9 hours. Using propensity score weighted binary logistic regression analysis (onset‐to‐treatment time >4.5–9 hours vs onset‐to‐treatment time 0–4.5 hours), the probability of symptomatic intracranial hemorrhage (ORadjusted 0.80, 95% CI 0.53–1.17), poor functional outcome (ORadjusted 1.01, 95% CI 0.83–1.22), and mortality (ORadjusted 0.80, 95% CI 0.61–1.04) did not differ significantly between both groups. In patients treated between >4.5 and 9 hours, the use of advanced neuroimaging was associated with a 50% lower mortality compared with non‐advanced imaging only (9.9% vs 19.7%; ORadjusted 0.51, 95% CI 0.33–0.79).InterpretationThis study showed no evidence in difference of symptomatic intracranial hemorrhage, poor outcome, and mortality in selected stroke patients treated with IVT between >4.5 and 9 hours after stroke onset compared with those treated within 4.5 hours. Advanced neuroimaging for patient selection was associated with lower mortality. ANN NEUROL 2023;94:309–320
Discovery and Biosynthesis of Cihunamides, Macrocyclic Antibacterial RiPPs with a Unique C−N Linkage Formed by CYP450 Catalysis
Authors: An Joon Soo , Lee Hyunbin , Kim Hyungyu , Woo Seungyeon , Nam Hyunsung , Lee Jayho , Lee Ji Yun , Nam Sang‐Jip , Lee Sang Kook , Oh Ki‐Bong , Kim Seokhee , Oh Dong‐Chan 
Published: April 2023

AbstractCihunamides A–D (1–4), novel antibacterial RiPPs, were isolated from volcanic‐island‐derived Streptomyces sp. The structures of 1–4 were elucidated by 1H, 13C, and 15N NMR, MS, and chemical derivatization; they contain a tetrapeptide core composed of WNIW, cyclized by a unique C−N linkage between two Trp units. Genome mining of the producer strain revealed two biosynthetic genes encoding a cytochrome P450 enzyme and a precursor peptide. Heterologous co‐expression of the core genes demonstrated the biosynthesis of cihunamides through P450‐mediated oxidative Trp‐Trp cross‐linking. Further bioinformatic analysis uncovered 252 homologous gene clusters, including that of tryptorubins, which possess a distinct Trp‐Trp linkage. Cihunamides do not display the non‐canonical atropisomerism shown in tryptorubins, which are the founding members of the “atropitide” family. Therefore, we propose to use a new RiPP family name, “bitryptides”, for cihunamides, tryptorubins, and their congeners, wherein the Trp‐Trp linkages define the structural class rather than non‐canonical atropisomerism.
Self‐Polarization Triggered Multiple Polar Units Toward Electrochemical Reduction of CO2 to Ethanol with High Selectivity
Authors: Zhang Yangyang , Chen Yanxu , Wang Xiaowen , Feng Yafei , Zhang Huaikun , Zhang Genqiang 
Published: April 2023

AbstractElectrochemical conversion of CO2 to highly valuable ethanol has been considered a intriguring strategy for carbon neutruality. However, the slow kinetics of coupling carbon‐carbon (C−C) bonds, especially the low selectivity ethanol than ethylene in neutral conditions, is a significant challenge. Herein, the asymmetrical refinement structure with enhanced charge polarization is built in the vertically oriented bimetallic organic frameworks (NiCu‐MOF) nanorod array with encapsulated Cu2O (Cu2O@MOF/CF), which can induce an intensive internal electric field to increase the C−C coupling for producing ethanol in neutral electrolyte. Particularly, when directly employed Cu2O@MOF/CF as the self‐supporting electrode, the ethanol faradaic efficiency (FEethanol) could reach maximum 44.3 % with an energy efficiency of 27 % at a low working‐potential of −0.615 V versus the reversible hydrogen electrode (vs. RHE) using CO2‐saturated 0.5 M KHCO3 as the electrolyte. Experimental and theoretical studies suggest that the polarization of atomically localized electric fields derived from the asymmetric electron distribution can tune the moderate adsorption of *CO to assist the C−C coupling and reduce the formation energy of H2CCHO*‐to‐*OCHCH3 for the generation of ethanol. Our research offers a reference for the design of highly active and selective electrocatalysts for reducing CO2 to multicarbon chemicals.
Sodium Carbazolide and Derivatives as Solid‐State Electrolytes for Sodium‐Ion Batteries
Authors: Yu Yang , Wang Jintao , Qin Zhaoxian , Lv Yingtong , Pei Qijun , Chen Tan Khai , Zhang Tengfei , Wu Anan , He Teng , Wu Hui , Lipton Andrew S. , Chen Ping 
Published: April 2023

AbstractReplacing widely used organic liquid electrolytes with solid‐state electrolytes (SSEs) could effectively solve the safety issues in sodium‐ion batteries. Efforts on seeking novel solid‐state electrolytes have been continued for decades. However, issues about SSEs still exist, such as low ionic conductivity at ambient temperature, difficulty in manufacturing, low electrochemical stability, poor compatibility with electrodes, etc. Here, sodium carbazolide (Na‐CZ) and its THF‐coordinated derivatives are rationally fabricated as Na+ conductors, and two of their crystal structures are successfully solved. Among these materials, THF‐coordinated complexes exhibit fast Na+ conductivities, i.e., 1.20×10−4 S cm−1 and 1.95×10−3 S cm−1 at 90 °C for Na‐CZ‐1THF and Na‐CZ‐2THF, respectively, which are among the top Na+ conductors under the same condition. Furthermore, stable Na plating/stripping is observed even over 400 h cycling, showing outstanding interfacial stability and compatibility against Na electrode. More advantages such as ease of synthesis, low‐cost, and cold pressing for molding can be obtained. In situ NMR results revealed that the evaporation of THF may play an essential role in the Na+ migration, where the movement of THF creates defects/vacancies and facilitates the migration of Na+.
Who Binds Better? Let Alphafold2 Decide!
Authors: Varga Julia K. , Schueler‐Furman Ora 
Published: April 2023

AbstractDeep learning is revolutionizing structural biology to an unprecedented extent. Spearheaded by DeepMind's Alphafold2, structural models of high quality can be generated, and are now available for most known proteins and many protein interactions. The next challenge will be to leverage this rich structural corpus to learn about binding: which protein can contact which partner(s), and at what affinity? In a recent study, Chang and Perez have presented an elegant approach towards this challenging goal for interactions that involve a short peptide binding to its receptor. The basic idea is straightforward: given a receptor that binds to two peptides, if the receptor sequence is presented with both peptides together at the same time, AlphaFold2 should model the tighter binding peptide into the binding site, while excluding the second. A simple idea that works!
Influence of the Time Scale on the Reaction Mechanism of CO Oxidation over a Au/TiO2 Catalyst
Authors: Wang Xianwei , Bürgi Thomas 
Published: April 2023

AbstractKnowledge of the reaction mechanism is key for rational catalyst improvement. Traditionally mechanistic studies focus on structure and the reaction conditions like temperature, pH, pressure, etc., whereas the time dimension is often overlooked. Here, we demonstrate the influence of time on the mechanism of a catalytic reaction. A dual catalytic mechanism was identified for the CO oxidation over Au/TiO2 by time‐resolved infrared spectroscopy coupled with modulation excitation spectroscopy. During the first seconds, CO on the gold particles is the only reactive species. As the reaction proceeds, the redox properties of TiO2 dominate the catalytic activity through electronic metal‐support interaction (EMSI). CO induces the reduction and reconstruction of TiO2 whereas oxygen leads to its oxidation. The activity of the catalyst follows the spectroscopic signature of the EMSI. These findings demonstrate the power of studying short‐time kinetics for mechanistic studies.
Pore Size Modulation in Flexible Metal‐Organic Framework Enabling High Performance Gas Sensing
Authors: Wang Chuan‐Zhe , Chen Jie , Li Qiao‐Hong , Wang Guan‐E , Ye Xiao‐Liang , Lv Jia , Xu Gang 
Published: April 2023

AbstractPore size plays a critical role in determining the performance of metal‐organic frameworks (MOFs) in catalysis, sensing, and gas storage or separation. However, revealing the pore‐size/property relationship remains extremely challenging because ideal structure models possessing different pore sizes but having the same components are lacking. In this work, a solvent‐coordination directed structure swelling method was developed for modulating the ratio between the large and narrow pore phases of a flexible MOF, MIL‐88B. Pore‐size‐dependent gas sensitivity and selectivity were studied for the first time in the MIL‐88B samples. The optimized MIL‐88B‐20 % sample showed one of the best sensing performances among all the reported MOF‐based H2S‐sensing materials. This work not only provides a method to synthesize ideal structure models for revealing the relationship between pore‐size and properties, but also may inspire the development of high‐performance gas sensing materials.