bluuebunny/crossref_metadata_2025_split huggingface dataset:
Doping Engineering to Modulate Lattice and Electronic Structure for Enhanced Piezocatalytic Therapy and Ferroptosis
Authors: Tian Boshi , Tian Ruixue , Liu Shaohua , Wang Yan , Gai Shili , Xie Ying , Yang Dan , He Fei , Yang Piaoping , Lin Jun 
Published: July 2023

AbstractPiezocatalytic therapy, which generates reactive oxygen species (ROS) under mechanical force, has garnered extensive attention for its use in cancer therapy owing to its deep tissue penetration depth and less O2‐dependence. However, the piezocatalytic therapeutic efficiency is limited owing to the poor piezoresponse, low separation of electron–hole pairs, and complicated tumor microenvironment (TME). Herein, a biodegradable, porous Mn‐doped ZnO (Mn–ZnO) nanocluster with enhanced piezoelectric effect is constructed via doping engineering. Mn‐doping not only induces lattice distortion to increase polarization but also creates rich oxygen vacancies (OV) for suppressing the recombination of electron–hole pairs, leading to high‐efficiency generation of ROS under ultrasound irradiation. Moreover, Mn‐doped ZnO shows TME‐responsive multienzyme‐mimicking activity and glutathione (GSH) depletion ability owing to the mixed valence of Mn (II/III), further aggravating oxidative stress. Density functional theory calculations show that Mn‐doping can improve the piezocatalytic performance and enzyme activity of Mn–ZnO due to the presence of OV. Benefiting from the boosting of ROS generation and GSH depletion ability, Mn–ZnO can significantly accelerate the accumulation of lipid peroxide and inactivate glutathione peroxidase 4 (GPX4) to induce ferroptosis. The work may provide new guidance for exploring novel piezoelectric sonosensitizers for tumor therapy.
The Oxygen Evolution Reaction Drives Passivity Breakdown for Ni–Cr–Mo Alloys
Authors: Larsson Alfred , Grespi Andrea , Abbondanza Giuseppe , Eidhagen Josefin , Gajdek Dorotea , Simonov Konstantin , Yue Xiaoqi , Lienert Ulrich , Hegedüs Zoltan , Jeromin Arno , Keller Thomas F. , Scardamaglia Mattia , Shavorskiy Andrey , Merte Lindsay R. , Pan Jinshan , Lundgren Edvin 
Published: July 2023

AbstractCorrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal–liquid interface governing passivity are notoriously challenging to study. In this work, a combination of synchrotron‐based techniques and electrochemical methods is used to investigate the passive film breakdown of a Ni–Cr–Mo alloy, which is used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo4+ sites in the oxide film to Mo6+ that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr‐containing alloys where Cr6+ is postulated to be dissolved at high anodic potentials, which is not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. The OER plays an important role in the mechanism of passivity breakdown of Ni–Cr–Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys.
A Sodiophilic Amyloid Fibril Modified Separator for Dendrite‐Free Sodium‐Metal Batteries
Authors: Wang Jinming , Gao Yan , Liu Di , Zou Guodong , Li Lanjie , Fernandez Carlos , Zhang Qingrui , Peng Qiuming 
Published: July 2023

AbstractSodium (Na) batteries are being considered as prospective candidates for the next generation of secondary batteries in contrast to lithium‐based batteries, due to their high raw‐material abundance, low cost, and sustainability. However, the unfavorable growth of Na‐metal deposition and severe interfacial reactions have prevented their large‐scale applications. Here, a vacuum filtration strategy, through amyloid‐fibril‐modified glass‐fiber separators, is proposed to address these issues. The modified symmetric cell can be cycled for 1800 h, surpassing the performance of previously reported Na‐based electrodes under an ester‐based electrolyte. Moreover, the Na/Na3V2(PO4)3 full cell with a sodiophilic amyloid‐fibril‐modified separator exhibits a capacity retention of 87.13% even after 1000 cycles. Both the experimental and the theoretical results show that the sodiophilic amyloid fibril homogenizes the electric field and Na‐ion concentration, fundamentally inhibiting dendrite formation. Simultaneously, the glutamine amino acids in the amyloid fibril have the highest adsorption energy for Na, resulting in the formation of a stable Na3N‐ and NaNxOy‐rich solid‐electrolyte‐interface film on the anode during cycling. This work provides not only a possible pathway to solve the dendrite problem in metal batteries using environmentally friendly biomacromolecular materials, but also a new direction for expanding biomaterial applications.
Lanthanide‐Functionalized Water‐Soluble Ionic Motors: Synergetically Regulated Rotary Motion by Allostery and Triplet Sensitization
Authors: Li Shaorui , Zhao Yuanmeng , Li Quan , Li Menglian , Zhang Xu , Xu Hai‐Bing 
Published: July 2023

AbstractMolecular motors, based on overcrowded alkenes (L) serving as ligands to chelate lanthanide nitrate, afford the first lanthanide‐functionalized water‐soluble ionic compound [L2‐Ln(NO3)2(H2O)2]·NO3 (LnL2). Benefitting from the “pull–push” feature of L together with 3LMCT from L to LnIII, irradiation with visible light not only drives photochemical isomerization but also induces energy transfer from L to LnIII, decreasing their intensity of low‐energy 3LMCT (ligand‐to‐metal triplet energy transfer) absorptions and sensitizing the Ln‐based luminescence. Thus, the typical EuIII‐based luminescence of EuL2 favors tracing its movement by time‐resolved luminescence, and temperature‐dependent luminescence renders it possibly to be used as potential luminescent thermometers. Very excitingly, besides a contraction of the stator by Ln–L interactions on decreasing the steric hindrance on the “fjord region,” the efficiency of intramolecular 3LMCT sensitization synergetically regulates the rotary motion of lanthanide‐complexed motors in thermal helix inversion steps.
Polyoxazoline‐Based Nanovaccine Synergizes with Tumor‐Associated Macrophage Targeting and Anti‐PD‐1 Immunotherapy against Solid Tumors
Authors: Matos Ana I. , Peres Carina , Carreira Barbara , Moura Liane I. F. , Acúrcio Rita C. , Vogel Theresa , Wegener Erik , Ribeiro Filipa , Afonso Marta B. , Santos Fábio M. F. , Martínez‐Barriocanal Águeda , Arango Diego , Viana Ana S. , Góis Pedro M. P. , Silva Liana C. , Rodrigues Cecília M. P. , Graca Luis , Jordan Rainer , Satchi‐Fainaro Ronit , Florindo Helena F. 
Published: July 2023

AbstractImmune checkpoint blockade reaches remarkable clinical responses. However, even in the most favorable cases, half of these patients do not benefit from these therapies in the long term. It is hypothesized that the activation of host immunity by co‐delivering peptide antigens, adjuvants, and regulators of the transforming growth factor (TGF)‐β expression using a polyoxazoline (POx)‐poly(lactic‐co‐glycolic) acid (PLGA) nanovaccine, while modulating the tumor‐associated macrophages (TAM) function within the tumor microenvironment (TME) and blocking the anti‐programmed cell death protein 1 (PD‐1) can constitute an alternative approach for cancer immunotherapy. POx‐Mannose (Man) nanovaccines generate antigen‐specific T‐cell responses that control tumor growth to a higher extent than poly(ethylene glycol) (PEG)‐Man nanovaccines. This anti‐tumor effect induced by the POx‐Man nanovaccines is mediated by a CD8+‐T cell‐dependent mechanism, in contrast to the PEG‐Man nanovaccines. POx‐Man nanovaccine combines with pexidartinib, a modulator of the TAM function, restricts the MC38 tumor growth, and synergizes with PD‐1 blockade, controlling MC38 and CT26 tumor growth and survival. This data is further validated in the highly aggressive and poorly immunogenic B16F10 melanoma mouse model. Therefore, the synergistic anti‐tumor effect induced by the combination of nanovaccines with the inhibition of both TAM‐ and PD‐1‐inducing immunosuppression, holds great potential for improving immunotherapy outcomes in solid cancer patients.
Recyclable Thin‐Film Soft Electronics for Smart Packaging and E‐Skins
Authors: Reis Carneiro Manuel , de Almeida Aníbal T. , Tavakoli Mahmoud , Majidi Carmel 
Published: July 2023

AbstractDespite advances in soft, sticker‐like electronics, few efforts have dealt with the challenge of electronic waste. Here, this is addressed by introducing an eco‐friendly conductive ink for thin‐film circuitry composed of silver flakes and a water‐based polyurethane dispersion. This ink uniquely combines high electrical conductivity (1.6 × 105S m−1), high resolution digital printability, robust adhesion for microchip integration, mechanical resilience, and recyclability. Recycling is achieved with an ecologically‐friendly processing method to decompose the circuits into constituent elements and recover the conductive ink with a decrease of only 2.4% in conductivity. Moreover, adding liquid metal enables stretchability of up to 200% strain, although this introduces the need for more complex recycling steps. Finally, on‐skin electrophysiological monitoring biostickers along with a recyclable smart package with integrated sensors for monitoring safe storage of perishable foods are demonstrated.
Field‐Induced Transparent Electrode‐Integrated Transparent Solar Cells and Heater for Active Energy Windows: Broadband Energy Harvester
Authors: Patel Malkeshkumar , Kim Sangho , Kim Joondong 
Published: July 2023

AbstractInvisible power generation by natural and artificial light enables sustainability by onsite‐power deployment, lower cost, and minimal burden on the built environment. However, dark, opaque photovoltaics limit light utilization in a transparent way. Herein, it is proposed that the active energy window (AEW) invisibly features power production, providing higher freedom for onsite power generators in window objects without limiting human vision. The AEW has a transparent photovoltaic (TPV) for onsite power and a transparent heater (TH) to remove the effects of shadows from snow and recover the power lost. Moreover, a heating function is applied to remove the effects of weathering related to snow. The proposed prototype integrates a TPV‐TH, offering ultraviolet (UV)‐blocking, daylighting, thermal comfort, and onsite power with a power conversion efficiency of 3% (AM1.5G). Field‐induced transparent electrodes are applied to the TPV‐TH and designed considering the AEW. Owing to these electrodes, the AEW ensure a wide field‐of‐view without optical dead zones, ensuring see‐through vision. The first TPV‐TH integration is performed into a 2 cm2‐window that generates onsite power of 6 mW and has an average visible transmittance of ≈39%. It is believed that light can be utilized with comfort through the AEW in self‐sustainable buildings and vehicles.
Measured task load in directed observers versus active participants undergoing high‐fidelity simulation education in a critical care setting
Authors: Devlin‐Hegedus Jessica , Miller Matthew , Cooke Sean , Ware Sandra , Richmond Clare 
Published: July 2023

AbstractObjectivesThe use of directed observers in high‐fidelity simulation education is increasingly common. While evidence suggests similar educational outcomes for directed observers compared to active participants in technical skills, it remains uncertain if this benefit also exists for senior clinicians, especially in mental workload. We sought to compare the workload between active participants and directed observers using an objective measure.MethodsWe performed a prospective, repeated‐measures observational study during the New South Wales Ambulance Aeromedical Operations induction training from 2019 to 2020. Participants included senior critical care doctors, paramedics, and nurses undergoing high‐fidelity simulation of prehospital and interhospital aeromedical missions. Task load was measured using the National Aeronautics and Space Administration task load index (NASA‐TLX) administered following each simulation debrief. Prehospital and interhospital simulations were compared separately by building a multilevel model for complete case and all study data. Post hoc comparisons of NASA‐TLX score for each group were performed using estimated marginal means (EMMs).ResultsWe enrolled 70 participants, comprising 49 physicians (70%), 19 paramedics (27%), and two flight nurses (3%). From the complete case analysis, statistically significant differences were observed for total NASA‐TLX scores between active participants and directed observers in both prehospital (participant EMM 78, observer EMM 65, estimated difference −13, 95% confidence interval [CI] −20 to −7) and interhospital simulations (participant EMM 69, observer EMM 59, estimated difference −10, 95% CI −16 to −3). When all available data were included, the pattern of results did not change.ConclusionsIn our sample of senior clinicians, the task load experienced by both active participants and directed observers in high‐fidelity simulation education was high for both prehospital and interhospital simulation exercises. The statistically significant differences we report are unlikely to be practically significant. Our results support the use of directed observers when resource limitations do not allow all course attendees to participate in every simulation.
Efficient CO2 photoreduction enabled by the energy transfer pathway in metal‐organic framework
Authors: Liu Hai‐Xiong , Si Duan‐Hui , Smith Mallory F. , Li Ren‐Fu , Li Xi‐Ya , Li Lan , Huang Hai‐Bo , Fang Zhi‐Bin , Zhou Hong‐Cai , Liu Tian‐Fu 
Published: July 2023

AbstractMany studies in metal‐organic frameworks (MOFs) aiming for high photocatalytic activity resort to self‐assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer, which, however, usually needs tedious synthetic procedure and design of a new MOF. In this work, we demonstrated that building a Förster resonance energy transfer (FRET) pathway can be realized through suitable molecular doping in a given MOF structure without altering the original porous structure, presenting an alternative strategy to design efficient photocatalysts for CO2 reduction. In situ electron spin resonance, ultrafast transient absorption spectroscopy, and computational studies reveal that the FRET‐induced excitation has dramatically altered the exciton transfer pathway in structure and facilitated electron‐hole separation. As a result, the molecular doped MOFs synthesized through one‐pot reaction show outstanding selectivity (96%) and activity (1314 μmol·g−1·h−1) for CO production versus almost no activity for the pristine MOFs, and this result stands out from existing competitors. Furthermore, the reaction mechanism was proposed and the intermediate signals were detected by in situ diffuse reflectance infrared Fourier transform spectroscopies. This study presents a clear picture of building FRET process in MOFs through molecular doping and provides a new design strategy for MOF‐based photocatalysts.
Facile Directed Synthesis of (Z)‐1‐(Aryl(arylimino)methyl)piperidine‐2,6‐diones from C,N‐Diarylformamidines
Authors: Trukhanova Yulia A. , Spiridonova Dar'ya V. , Kuvaeva Elena V. , Chernov Nikita M. , Alekseeva Galina M. , Sopova Marina V. , Fedorova Elena V. , Yakovlev Igor P. 
Published: July 2023

AbstractA simple methodology has been developed for the synthesis of previously unstudied N‐substituted glutarimide derivatives – (Z)‐1‐(aryl(arylimino)methyl)piperidine‐2,6‐diones 4 a–p obtained in one step from C,N‐diarylformamidines 1 a–p and glutaric anhydride 6 with product yields from 46 up to 88 % and chromatographic purity from 94 to 99 %. The structures of the obtained compounds were proved using NMR spectroscopy 1H, 13C, X‐ray diffraction analysis, mass spectroscopy, and elemental analysis. An in vivo study of the analgesic activity of a representative of series 4 a was carried out.
Updated Bounds on Axion‐Like Particle Dark Matter with the Optical MUSE‐Faint Survey
Authors: Todarello Elisa 
Published: July 2023

AbstractBounds are derived on the axion‐like particle (ALP) to two‐photon coupling in the mass range 2.65 − 5.27 eV. The bounds are obtained by searching for the signal from ALP decay in the Multi Unit Spectroscopic Explorer (MUSE) observations of five dwarf spheroidal galaxies, under the assumption that ALPs constitute the dark matter component of the haloes. These bounds are of the same order and improve on the robustness of those of Regis et al., (2021), and currently represent the strongest bounds within the considered mass range.
Triazinium Ligation: Bioorthogonal Reaction of N1‐Alkyl 1,2,4‐Triazinium Salts**
Authors: Šlachtová Veronika , Bellová Simona , La‐Venia Agustina , Galeta Juraj , Dračínský Martin , Chalupský Karel , Dvořáková Alexandra , Mertlíková‐Kaiserová Helena , Rukovanský Peter , Dzijak Rastislav , Vrabel Milan 
Published: July 2023

AbstractThe development of reagents that can selectively react in complex biological media is an important challenge. Here we show that N1‐alkylation of 1,2,4‐triazines yields the corresponding triazinium salts, which are three orders of magnitude more reactive in reactions with strained alkynes than the parent 1,2,4‐triazines. This powerful bioorthogonal ligation enables efficient modification of peptides and proteins. The positively charged N1‐alkyl triazinium salts exhibit favorable cell permeability, which makes them superior for intracellular fluorescent labeling applications when compared to analogous 1,2,4,5‐tetrazines. Due to their high reactivity, stability, synthetic accessibility and improved water solubility, the new ionic heterodienes represent a valuable addition to the repertoire of existing modern bioorthogonal reagents.
Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**
Authors: Jiang Yuhan , Kibune Masato , Tosaka Masatoshi , Yamago Shigeru 
Published: July 2023

AbstractThe practical synthesis of structurally controlled hyperbranched polymers (HBPs) by organotellurium‐mediated radical polymerization (TERP) in water under emulsion conditions is reported. Copolymerization of vinyltelluride named evolmer, which induces controlled branch structure, and acrylates with TERP chain transfer agent (CTA) in water afforded HBPs having dendron structure. The molecular weight, dispersity, branch number, and branch length of the HBPs were controlled by changing the amount of CTA, evolmer, and acrylate monomers. HB‐poly(butyl acrylate)s (HBPBAs) with up to the 8th generation having an average of 255 branches were successfully synthesized. As the monomer conversion reached nearly quantitative and the obtained polymer particles were well dispersed in water, the method is highly suitable for synthesizing topological block polymers, block polymers consisting of different topologies. Thus, linear‐block‐HB, HB‐block‐linear, and HB‐block‐HB‐PBAs with the controlled structure were successfully synthesized by adding the second monomer(s) to the macro‐CTA. The intrinsic viscosity of the resulting homo‐ and topological block PBAs was systematically controlled by the degree of the branch, the branch length, and the topology. Therefore, the method opens the possibility of obtaining various HBPs with diverse branch structures and tuning the polymer properties by the polymer topology.
Triphosphat‐Pronucleotid (TriPPPro)‐Reporter mit Optimierten Zellpermeablen Farbstoffen zum Metabolischen Labeling von Zellulärer und Viraler DNA in Lebenden Zellen
Authors: Sterrenberg Vincente T. , Stalling Dörte , Knaack J. Iven H. , Soh Timothy K. , Bosse Jens B. , Meier Chris 
Published: July 2023

AbstractDas metabolische Labeling von Nucleinsäuren in lebenden Zellen ist von äußerstem Interesse, um die Dynamik des Nucleinsäure‐Stoffwechsels in Echtzeit zu verfolgen und hat somit das Potenzial, neue Einblicke in die Zellbiologie sowie in Pathogen‐Wirtszell‐Interaktionen zu liefern. Eine katalysatorfreie Diels–Alder‐Reaktion mit inversem Elektronenbedarf (iEDDA) mit Nucleosiden, die eine hochreaktive Gruppe wie das axiale 2‐trans‐Cycloocten (2TCOa) tragen, ist ideal geeignet, um die intrazelluläre Markierung von DNA zu ermöglichen. Da Triphosphate von Nucleosiden nicht membranpermeabel sind, ist, nach der Aufnahme in die Zelle, die Phosphorylierung der modifizierten Nucleoside durch zelluläre Kinasen erforderlich. Leider schränkt dabei das enge Substratfenster der meisten endogenen Kinasen die Verwendung von Nucleosid‐Analoga mit hochreaktiven Gruppen ein. Hier wenden wir unseren TriPPPro‐ (Triphosphat‐Pronucleotid) Ansatz an, um einen hoch reaktiven 2TCOa‐modifizierten 2′‐Desoxycytidintriphosphat‐Reporter direkt in lebenden Zellen freizusetzen. Wir zeigen, dass dieses Nucleosidtriphosphat metabolisch in de novo synthetisierte zelluläre und virale DNA eingebaut wird und mit hochreaktiven und zellpermeablen Fluoreszenzfarbstoff‐Tetrazin‐Konjugaten via iEDDA markiert werden kann, um DNA in lebenden Zellen direkt sichtbar zu machen. Damit stellen wir die erste umfassende Methode zur Visualisierung zellulärer und viraler Nucleinsäuren in lebenden Zellen vor.
Mehrere Triplett‐Metall‐zentrierte Jahn–Teller‐Isomere bestimmen die temperaturabhängigen Lumineszenzlebensdauern in [Ru(bpy)3]2+
Authors: Hernández‐Castillo David , Nau Roland E. P. , Schmid Marie‐Ann , Tschierlei Stefanie , Rau Sven , González Leticia 
Published: July 2023

AbstractEin genaues Verständnis der Faktoren, welche die Lumineszenzlebensdauer von Übergangsmetallverbindungen bestimmen, ist für Anwendungen in der Photokatalyse und der photodynamischen Therapie von entscheidender Bedeutung. Die im Falle von [Ru(bpy)3]2+ (bpy=2,2’‐Bipyridin) allgemein akzeptierte Theorie besagt, dass die Emissionslebensdauer durch Optimierung der Energiebarriere zwischen dem emittierenden Triplett‐Zustand des Metall‐Liganden‐Ladungstransfers (3MLCT) und dem thermisch aktivierten Triplett‐Zustand des Metall‐Zentrums (3MC), oder der Energielücke zwischen beiden Zuständen gesteuert werden kann. Hier zeigen wir, dass dies nicht allgemeingültig ist. Darüber hinaus demonstrieren wir, dass die Betrachtung eines einzelnen Relaxationspfades, der vom energetisch niedrigsten Minimum aus bestimmt wird, zu falschen Vorhersagen der temperaturabhängigen Emissionslebensdauer führt. Stattdessen erhalten wir eine ausgezeichnete Übereinstimmung mit den experimentellen temperaturabhängigen Lebensdauern, wenn ein erweitertes kinetisches Modell herangezogen wird, welches alle Pfade im Zusammenhang mit mehreren Jahn–Teller‐Isomeren und ihren effektiven Reaktionsbarrieren beinhaltet. Diese Konzepte sind für das Design weiterer lumineszierender Übergangsmetallkomplexe mit individuell angepassten Emissionslebensdauern auf der Grundlage theoretischer Vorhersagen unerlässlich.