bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modulating the Electronic Structure of MnNi2S3 Nanoelectrodes to Activate Pyroptosis for Electrocatalytic Hydrogen‐Immunotherapy
Authors: Li Jingrui , Wang Gang , Wen Zhaoyu , Sun Shumin , Han Zhihui , Yang Yuqi , Wu Jie , Pei Zifan , Liu Luyao , Chen Youdong , Cheng Liang 
Published: October 2024

AbstractHydrogen (H2) therapy has demonstrated antitumor effect, but the therapeutic efficacy is restricted by the low solubility and nontarget delivery of H2. Electrolysis of H2O by electrocatalysts sustainably releases enormous amounts of H2 and inspires the precise delivery of H2 for tumor therapy. Herein, manganese‐doped Ni2S3 nanoelectrodes (MnNi2S3 NEs) are designed for the electrocatalytic delivery of H2 and the activation of antitumor immunity to effectively potentiate H2‐immunotherapy. Ni atoms featuring empty 3d orbitals reduce the initial energy barrier of the hydrogen evolution reaction (HER) by promoting the adsorption of H2O. Moreover, Mn atoms with different electronegativity modulate the electronic structure of Ni atoms and facilitate the desorption of the generated H2, thus enhancing the HER activity of the MnNi2S3 NEs. Based on the high HER activity, controllable delivery of H2 for electrocatalytic hydrogen therapy (EHT) is achieved in a voltage‐dependent manner. Mechanistically, MnNi2S3 NE‐mediated EHT induces mitochondrial dysfunction and oxidative stress, which subsequently activates pyroptosis through the typical ROS/caspase‐1/GSDMD signaling pathway. Furthermore, MnNi2S3 NE‐mediated EHT enhances the infiltration of CD8+ T lymphocytes into tumors and reverses the immunosuppressive microenvironment. This work demonstrates an electrocatalyst with high HER activity for synergistic gas‐immunotherapy, which may spark electrocatalyst‐based tumor therapy strategies.
Interface Dependent Coexistence of Two‐Dimensional Electron and Hole Gases in Mn‐doped InAs/GaSb
Authors: Riney Logan , Bac Seul‐Ki , Zhukovskyi Maksym , Orlova Tatyana , Fields Shelby S. , Wang Jiashu , Kotte Tommy , Graf David , Bennett Steven P. , Liu Xinyu , Assaf Badih A. 
Published: October 2024

AbstractThe interface of common III‐V semiconductors InAs and GaSb can be utilized to realize a two‐dimensional (2D) topological insulator state. The 2D electronic gas at this interface can yield Hall quantization from coexisting electrons and holes. This anomaly is a determining factor in the fundamental origin of the topological state in InAs/GaSb. Here, the coexistence of electrons and holes in InAs/GaSb is tied to the chemical sharpness of the interface. Magnetotransport, in samples of Mn‐doped InAs/GaSb cleaved from wafers grown at a spatially inhomogeneous substrate temperature, is studied. It is reported that the observation of quantum oscillations and a quantized Hall effect whose behavior, exhibiting coexisting electrons and holes, is tuned by this spatial nonuniformity. Through transmission electron microscopy measurements, it is additionally found that samples that host this co‐existence exhibit a chemical intermixing between group III and group V atoms that extends over a larger thickness about the interface. The issue of intermixing at the interface is systematically overlooked in electronic transport studies of topological InAs/GaSb. These findings address this gap in knowledge and shed important light on the origin of the anomalous behavior of quantum oscillations seen in this 2D topological insulator.
Mapping Nanoscale‐To‐Single‐Cell Phosphoproteomic Landscape by Chip‐DIA
Authors: Muneer Gul , Gebreyesus Sofani Tafesse , Chen Ciao‐Syuan , Lee Tzu‐Tsung , Yu Fengchao , Lin Chih‐An , Hsieh Min‐Shu , Nesvizhskii Alexey I. , Ho Chao‐Chi , Yu Sung‐Liang , Tu Hsiung‐Lin , Chen Yu‐Ju 
Published: October 2024

AbstractProtein phosphorylation plays a crucial role in regulating disease phenotypes and serves as a key target for drug development. Mapping nanoscale‐to‐single‐cell samples can unravel the heterogeneity of cellular signaling events. However, it remains a formidable analytical challenge due to the low detectability, abundance, and stoichiometry of phosphorylation sites. Here, we present a Chip‐DIA strategy, integrating a microfluidic‐based phosphoproteomic chip (iPhosChip) with data‐independent acquisition mass spectrometry (DIA‐MS) for ultrasensitive nanoscale‐to‐single‐cell phosphoproteomic profiling. The iPhosChip operates as an all‐in‐one station that accommodates both quantifiable cell capture/imaging and the entire phosphoproteomic workflow in a highly streamlined and multiplexed manner. Coupled with a sample size‐comparable library‐based DIA‐MS strategy, Chip‐DIA achieved ultra‐high sensitivity, detecting 1076±158 to 15869±1898 phosphopeptides from 10±0 to 1013±4 cells, and revealed the first single‐cell phosphoproteomic landscape comprising druggable sites and basal phosphorylation‐mediated networks in lung cancer. Notably, the sensitivity and coverage enabled the illumination of heterogeneous cytoskeleton remodeling and cytokeratin signatures in patient‐derived cells resistant to third‐generation EGFR therapy, stratifying mixed‐lineage adenocarcinoma‐squamous cell carcinoma subtypes, and identifying alternative targeted therapy for late‐stage patients. With flexibility in module design and functionalization, Chip‐DIA can be adapted to other PTM‐omics to explore dysregulated PTM landscapes, thereby guiding therapeutic strategies toward precision oncology.
PUMA: Deep Metric Imitation Learning for Stable Motion Primitives
Authors: Pérez‐Dattari Rodrigo , Della Santina Cosimo , Kober Jens 
Published: October 2024

Imitation learning (IL) facilitates intuitive robotic programming. However, ensuring the reliability of learned behaviors remains a challenge. In the context of reaching motions, a robot should consistently reach its goal, regardless of its initial conditions. To meet this requirement, IL methods often employ specialized function approximators that guarantee this property by construction. Although effective, these approaches come with some limitations: 1) they are typically restricted in the range of motions they can model, resulting in suboptimal IL capabilities, and 2) they require explicit extensions to account for the geometry of motions that consider orientations. To address these challenges, we introduce a novel stability loss function that does not constrain the function approximator's architecture and enables learning policies that yield accurate results. Furthermore, it is not restricted to a specific state space geometry; therefore, it can easily incorporate the geometry of the robot's state space. Proof of the stability properties induced by this loss is provided and the method is empirically validated in various settings. These settings include Euclidean and non‐Euclidean state spaces, as well as first‐order and second‐order motions, both in simulation and with real robots. More details about the experimental results can be found at https://youtu.be/ZWKLGntCI6w.
Advancing Equity in Rare Disease Research: Insights From the Undiagnosed Disease Network
Authors: Borja Nicholas A. , Tinker Rory J. , Bivona Stephanie A. , Smith Carson A. , Locker Theodore Krijnse , Fernandes Samuela ,   Undiagnosed Diseases Network, Phillips John A. , Stoler Justin , Taylor Herman , Zuchner Stephan , Tekin Mustafa 
Published: October 2024

ABSTRACTRare diseases affect 6%–8% of the population and present diagnostic challenges, particularly for historically marginalized ethnic and racial groups. The Undiagnosed Diseases Network (UDN) aims to enhance diagnosis rates and research participation among such minoritized groups. A retrospective review was conducted from 2015 to 2023, analyzing 2235 UDN participants to evaluate its progress toward this objective. Data on demographics, disease phenotypes, diagnostic outcomes, and socioeconomic factors were collected and statistical analyses assessed differences among ethnic and racial groups. This demonstrated that Hispanic and Black non‐Hispanic groups were underrepresented, while White non‐Hispanic participants were overrepresented in the UDN compared to the US population. Individuals whose primary language was not English were also significantly underrepresented. Diagnosis rates varied, with the highest rates among Asian non‐Hispanic (39.5%) and Hispanic (35.3%) groups and the lowest rate in the White non‐Hispanic group (26.8%) (p < 0.001). Binomial logistic regression found, however, that only participant age and disease phenotype predicted the likelihood of receiving a diagnosis (p < 0.001). Persistent ethnic and racial disparities in UDN participation appear to be associated with major differences in application rates. Under‐enrollment of historically marginalized ethnic and racial groups may be due to economic hardships and language barriers. No differences in the diagnostic yield among ethnic and racial groups were observed after controlling for other factors. This work highlights the value of comprehensive genetic evaluations for addressing healthcare disparities and suggests priorities for advancing inclusion in rare disease research.
An Electrochemical Route to Novel N‐benzoyl‐1,2,3‐triazoles and Protein Binding Studies of Selected Triazole Derivatives
Authors: Bandyopadhyay Manas , Goswami Upasi , Ghorai Shubhankar , Pathak Swastik , Ganguly Debabani , Escorihuela Jorge , Ganguly Jhuma , Bera Mrinal K. 
Published: October 2024

AbstractAn electrochemical, cost‐efficient and atom‐economic method for the synthesis of novel, structurally unique N‐benzoyl‐1,2,3‐triazole derivatives has been developed via cascade oxidation‐ 1,3‐dipolar cycloaddition reaction of readily available propargyl alcohol and benzoyl azide. The electro‐oxidation of propargyl alcohol and subsequent cycloaddition was performed in an undivided cell using graphite rod and stainless‐steel plate as inexpensive electrode materials. Numerous 4,5‐disubstituted N‐benzoyl‐1,2,3‐triazoles may be synthesized from milli to multi‐gram scale employing this protocol. The biological significance of few selected triazole derivatives were evaluated via protein binding studies.
Unravelling the Crucial of Spatial Al Distribution to Realize Precise Alkali‐Treatment for Target Acid‐Catalyzed Reactions
Authors: Li Junjie , Chen Huihui , Liu Wen , Zhi Yuchun , Ta Na , Xie Sujuan , Xu Longya , Li Xiujie , Zhu Xiangxue , Xu Shutao 
Published: October 2024

AbstractConstructing mesoporous structure within zeolites by alkali‐treatment is an effective protocol to improve their diffusion properties. However, undesirable changes in Brönsted acid site (BAS) densities always offset this advantage in acid‐catalyzed reactions. In this context, the crucial roles of spatial aluminum (Al) distribution were unraveled during alkali‐treatment of MFI zeolite and the desirable BAS density was achieved in obtained hierarchical samples for the target reactions. Various characterization methods, particularly the multiple one‐ and two‐dimensional magic‐angle spinning (MAS) NMR techniques, were performed to track the alkali‐treatment processes. For the sample with a more uniform spatial Al distribution, more tetrahedral Al sites would fall off and migrate around the Si‐OH in zeolite as Al(OH)4−. Those re‐deposited Al(OH)4− sites were easily transformed into NMR‐invisible Al sites during the calcination process, which contributed negligibly to both Brönsted and Lewis acidities, thus being referred to “acid‐free” Al species. While most tetrahedral Al sites were preserved after the alkali‐treatment of sample with non‐uniform Al distribution and the BAS density gradually increased with treatment time. According to the requirements of typical acid‐catalyzed reactions, such as catalytic cracking of 1,3,5‐triisopropylbenzene and methanol‐to‐olefins, the desired hierarchical zeolite catalysts were developed by matching the amounts of extracted Si and generated “acid‐free” Al during the precise alkali‐treatment.
A Turn‐On Fluorescence Probe Based on a New Salamo‐Co (II) Coordination Polymer for Tyrosine Detection and Its Application in Water Samples
Authors: Yuan Pei‐Lin , Chai Zhi‐Lei , Zhang Hai‐Wei , Tuo Na , Wang Li , Sun Chu‐Feng , Dong Wen‐Kui 
Published: October 2024

ABSTRACTA novel salamo‐Co (II) coordination polymer probe CP was synthesized firstly, and its crystal structure, [Co3(L)2(PTA)(H2O)2]n·4nDMF, was determined by X‐ray diffraction analysis. The probe has a rare aggregation‐induced luminescence enhancement (AIEE) effect. When applied to amino acid detection, it was found to have a high selective recognition of tyrosine. With the increase of tyrosine, the fluorescent strength of the probe was enhanced in a short period of time. In addition, the binding ratio of probe to Tyr was determined by fluorescence titration experiment, and the detection limit LOD of probe CP for Tyr was calculated to be 2.57 × 10−9 M, and the binding constant Ka was 2.96 × 105 M−1. According to UV absorption spectrum, FT‐IR spectra, ESI mass spectrometry, and DFT calculation, it was speculated that Tyr can bind to the probe after adding Tyr into the probe solution, triggering FRET and ICT effects, resulting in increased fluorescence intensity and blue shift, and finally achieving the specific recognition of tyrosine by probe CP. Finally, the practical application of probe CP was studied. Through strip test and real water sample test, it was found that the probe can be used for qualitative and quantitative analysis of tyrosine.
Supported Nickel Nanoparticles as Catalyst in Direct sp3 C−H Alkylation of 9H‐Fluorene Using Alcohols as Alkylating Agent
Authors: M Vageesh , Joshi Harsh , A S Anupriya , Dey Raju 
Published: October 2024

AbstractHerein, we report an inexpensive first‐row transition metal Ni heterogeneous catalytic system for the Csp3‐mono alkylation of fluorene using alcohols as alkylating agents via borrowing hydrogen strategy. The catalytic protocol displayed versatility with high yields of the desired products using various types of primary alcohols, including aryl/hetero aryl methanols, and aliphatic alcohols as alkylating agents. The catalyst Ni NPs@N−C was synthesized via high‐temperature pyrolysis strategy, using ZIF‐8 as the sacrificial template. The Ni NPs@N−C catalyst was characterized by XPS, HR‐TEM, HAADF‐STEM, XRD and ICP‐MS. The catalyst is stable even in the air at room temperature, displayed excellent activity and could be recycled 5 times without appreciable loss of its activity.
Oxidative Amidation of Ferrocenyl Aldehydes with Amines Catalyzed by Chalcogenised Fe3Se2(CO)9 Cluster: Direct Transformation of Aldehyde to Amides
Authors: Sharma Deepak , Choudhary Aditya , Tomar Vijesh , Joshi Raj K. 
Published: October 2024

AbstractWith the interest and knowing the importance of ferrocenyl conjugates, a direct amidation of ferrocenyl aldehyde has been developed under feasible conditions. Varieties of amines has been oxidatively coupled with ferrocene aldehyde in the presence of highly economical and robustly stable iron chalcogenide ironcarbonyl clusters [Fe3E2(CO)9, E= S, Se, and Te] and TBHP. The reaction worked in greener solvent water at a moderate temperature of 70 °C and the ferrocenyl‐amides in just 30 minutes. All the varieties of amines were found to be well tolerated for the present method, and due to the high medicinal importance of ferrocenyl‐amides, sole focus of this report was concentrates on the synthesis of various new ferrocenyl‐amides in good to excellent amounts.
Rundum runder Holzbau
Authors: Jacob‐Freitag Susanne , Schmidt Jonas 
Published: October 2024

AbstractMit dem in 2023 fertiggestellten Globe Theater hat Coburg ein neues Highlight der besonderen Art. Das neue Theater ist nicht nur ein viergeschossiger Rundbau, sondern auch fast ein purer Holzbau. Es dient als Übergangslösung für die Zeit der Generalsanierung des altehrwürdigen Landestheaters im historischen Stadtzentrum. Das Gebäudeensemble liegt zentrumsnah auf dem Areal des ehemaligen Güterbahnhofs und besteht aus einem Haupt‐ und drei Nebengebäuden in Holzbauweise. Dabei ragt der eigentliche Theaterbau als Rundbau markant in die Höhe. Die drei Nebengebäude schließen an das Hauptgebäude hintereinander an und sind durch einen verglasten Verbindungsgang miteinander verbunden. Der Rundbau aus Brettsperrholz, Brettschichtholz und Geschossdecken in Holz‐Beton‐Verbund‐Trockenbauweise war für alle Planer und Bauausführenden eine Herausforderung. Gerade auch bei der Werkplanung, Fertigung, Anlieferung und Montage der Holz‐Beton‐Verbunddecken galt es, einen optimalen Ablauf zu gewährleisten, den ZÜBLIN Timber aus Aichach verantwortete. Die neue Interimsspielstätte findet seit Eröffnung großen Zuspruch und soll auch nach Wiedereröffnung des Landestheaters für Veranstaltungen genutzt werden.
Relationship of PSC to embryos: Extending and refining capture of PSC lines from mammalian embryos
Authors: Ying Qi‐Long , Nichols Jennifer 
Published: October 2024

AbstractPluripotent stem cell lines derived from preimplantation mouse embryos have opened opportunities for the study of early mammalian development and generation of genetically uncompromised material for differentiation into specific cell types. Murine embryonic stem cells are highly versatile and can be engineered and introduced into host embryos, transferred to recipient females, and gestated to investigate gene function at multiple levels as well as developmental mechanisms, including lineage segregation and cell competition. In this review, we summarize the biomedical motivation driving the incremental modification to culture regimes and analyses that have advanced stem cell research to its current state. Ongoing investigation into divergent mechanisms of early developmental processes adopted by other species, such as agriculturally beneficial mammals and birds, will continue to enrich knowledge and inform strategies for future in vitro models.
In Vitro Inhibitory Effect of Berberine Against Rotavirus
Authors: Nguyen Hue Thi , Hoa‐Tran Thi Nguyen , Tran Huy Quang , Nguyen Thuy Thi Thu 
Published: October 2024

AbstractAlthough berberine (BBR) is well known as an active constituent in traditional medicines used in the treatment of gastrointestinal diseases, its potential against viral gastroenteritis has not been specifically reported. This study aims to investigate the antiviral activity of BBR against rotavirus and evaluate its cytotoxicity and pharmacological efficacies, including antioxidant and anti‐inflammatory activities in vitro. Using ultraviolet‐visible absorption spectroscopy, the saturation concentration of BBR was determined as 2261 μg/mL, indicating that BBR is a poor water‐soluble compound. The inhibition rate of nitric oxide (NO) production of BBR solution at a concentration of 283 μg/mL was similar to that of Cardamonin 0.3 μM with a cell viability of 92.46±0.35 %, revealing the anti‐inflammatory activity of BBR. The cytotoxicity of the BBR solution depended on its concentration, whereby the 50 % cytotoxicity concentration (CC50) of BBR after 96 h exposure was 664 μg/mL. Investigation of cytopathic effects (CPEs) of MA104 cells treated with BBR and BBR‐incubated rotavirus indicates that BBR could effectively inhibit the replication of rotavirus. CPEs were not observed in the cells inoculated with rotavirus (100TCID50) which was pre‐incubated with BBR for 96 hours at a BBR concentration of 283 μg/mL. Therefore, the study provides reliable results to demonstrate the ability of BBR to inhibit the replication of rotavirus.
Bacterial Acyl Homoserine Lactones Triggered Non‐Native Substrate Hydroxylation Catalyzed by Directed‐Evolution‐Derived Cytochrome P450BM3 Mutants
Authors: Yokoyama Yuya , Ariyasu Shinya , Karasawa Masayuki , Kasai Chie , Aiba Yuichiro , Sugimoto Hiroshi , Shoji Osami 
Published: October 2024

AbstractWe report the directed evolution of cytochrome P450BM3 to efficiently utilize the bacterial quorum sensing signalling molecule N‐decanoyl homoserine lactone (C10‐HSL) as an effective decoy molecule. This represents the first important step in our endeavor to develop of a self‐sufficient decoy‐molecule system in whole‐cells that only necessitates the addition of culture medium and substrate to realize the hydroxylation of non‐native substrates. Following five rounds of directed evolution, mutant P450BM3, in the presence of C10‐HSL, catalyzed the hydroxylation of benzene at a rate of 475 min−1, the highest turnover rate recorded for any P450 enzyme, and achieving a 46% yield in a whole‐cell reaction system. High‐resolution X‐ray crystal structure analysis of a series of mutants narrates the directed evolution process, revealing how C10‐HSL is fixed in the binding pocket to permit binding of non‐native substrates. Finally, introduction of the C10‐HSL synthase gene ExpI into Escherichia coli, enabled the in situ production of C10‐HSL, realizing, for the first time, the hydroxylation of non‐native substrates without the need for the laborious synthesis and addition of decoy molecules.
3’‐Dehydroxypurpurogallin‐4‐Carboxamides as Influenza A Endonuclease Inhibitors: Synthesis, Structure‐Activity Relationship Analysis, and Structural Characterization of Protein Complex
Authors: Kráľ Michal , Kotačka Tomáš , Reiberger Róbert , Panýrková Gabriela , Radilová Kateřina , Osifová Zuzana , Flieger Miroslav , Konvalinka Jan , Majer Pavel , Kožíšek Milan , Machara Aleš 
Published: October 2024

AbstractThe influenza RNA‐dependent RNA polymerase harbours an endonuclease subunit characterized by a catalytic site housing two divalent metal ions. By effectively chelating both Mg2+ and Mn2+ ions, a small‐molecule inhibitor with a metal‐binding pharmacophore can halt endonuclease activity. Herein, two 3’‐dehydroxypurpurogallin‐4‐carboxamide series, namely twelve C‐4’ unsubstituted and twelve C‐4’ phenyl substituted congeners were designed and prepared to be tested as inhibitors of the metal‐dependent viral enzyme. These inhibitors were accessed through the chemoenzymatic reaction of gallic acid with either pyrocatechol or phenylpyrocatechol moderated by laccase, followed by amidation. Experimental IC50 values were determined using AlphaScreen technology, with the most potent inhibitors exhibiting IC50 values around 0.35 μM. Using X‐ray crystallography, we analyzed structure of the endonuclease in complex with one potent 3’‐dehydroxypurpurogallin‐carboxamide at 2.0 Å resolution, revealing the coordination of the compound's triad of oxygen atoms with the two metal ions in the influenza A endonuclease active site.
Insights into the Hydration Layer of Reduced Graphene Oxides: A Computational Study
Authors: Savazzi Filippo , Risplendi Francesca , Cicero Giancarlo 
Published: October 2024

AbstractReduced graphene oxide (rGO) has emerged as a versatile material with diverse applications, particularly in aqueous environments. Understanding its interactions with water molecules is crucial for various fields, ranging from energy storage to sensing. In this study, we investigate the behavior of graphene and rGO in water, focusing on elucidating their wetting properties and the influence of oxygen‐containing functional groups. Through extensive molecular dynamics simulations, we analyze the orientation and electrostatic dipole of water molecules near the rGO interface, revealing a direct correlation between rGO hydrophilicity and oxidation level. Specifically, we observe stronger hydrogen bonding networks near higher coverage rGO monolayers, indicating enhanced hydrophilicity. Furthermore, by studying water confined between rGO layers, we find uniform water transport with lateral self‐diffusion coefficients comparable to bulk water, highlighting the potential of rGO membranes in various applications. Our findings provide insights into the atomic‐scale interactions governing rGO‐water interfaces, paving the way for the rational design of graphene‐based materials for application in aqueous environments.