bluuebunny/crossref_metadata_2025_split huggingface dataset:
Experimentelle Beobachtung eines terminalen Borylen‐Distickstoff‐Addukts durch Spaltung eines 1,2,3,4,5‐Diboratriazolins
Authors: Jayaraman Arumugam , Ritschel Benedikt , Arrowsmith Merle , Markl Christian , Jürgensen Malte , Halkić Anel , Konrad Yannick , Stoy Andreas , Radacki Krzysztof , Braunschweig Holger 
Published: August 2024

AbstractWährend Azide mit einfachen Alkenen nur unter harschen Bedingungen reagieren, reagiert ein Diboranalogon eines Alkens, das zweifach durch cyclische Alkyl(amino)carbene (CAAC) stabilisierte Dicyanodiboren 1, spontan mit organischen Aziden (7–10 Äq.) bei Raumtemperatur, um zwei Äquivalente stabiler CAAC‐stabilisierter Imino(cyano)borane (2‐R) zu ergeben. NMR‐spektroskopische Kontrollen der Reaktionsmischungen zeigen die anfängliche Bildung einer 1 : 1‐Mischung aus 2‐R und einem relativ langlebigen Zwischenprodukt (Int), welches in Gegenwart von überschüssigem Azid in ein zweites Äquivalent 2‐R umgewandelt wird. In Abwesenheit von überschüssigem Azid zersetzt sich Int jedoch zu 3, dem Produkt einer intramolekularen C−H‐Bindungsaktivierung durch eine mutmaßlich zweifach koordinierte Borylen‐Zwischenstufe, „(CAAC)B(CN)“. Mechanistische Erkenntnisse aus Abfangexperimenten, NMR‐spektroskopischen und hochauflösenden Massenspektrometrie‐Daten sowie DFT‐Berechnungen zeigen, dass Int das endständige Borylen‐Stickstoff‐Addukt [(CAAC)B(CN)(η1‐N2)] ist. Die Bildung der Iminoborane 2‐R aus Diboren 1 und RN3 erfolgt über eine Azid‐Diboren‐Huisgen‐[3+2]‐Cycloaddition, gefolgt von einer [3+2]‐Cycloreversion, wobei 2‐R und [(CAAC)B(CN)(η1‐N2)] entstehen. Letzteres durchläuft dann entweder eine N2‐Abspaltung und intramolekulare C−H‐Bindungsaktivierung zur Bildung von 3 oder eine Staudinger‐artige Reaktion mit einem zweiten Äquivalent Azid zur Bildung eines zweiten Äquivalents des Iminoborans 2‐R.
Temperature‐Dependent Left‐ and Right‐Twisted Conformational Changes in 1 : 1 Host‐Guest Systems: Theoretical Modeling and Chiroptical Simulations
Authors: Suzuki Nozomu , Taura Daisuke , Furuta Yusuke , Ono Yudai , Miyagi Senri , Kameda Ryota , Haino Takeharu 
Published: August 2024

AbstractAn efficient strategy for high‐performance chiral materials is to design and synthesize host molecules with left‐ and right‐ (M‐ and P‐)twisted conformations and to control their twisted conformations. For this, a quantitative analysis is required to describe the chiroptical inversion, chiral transfer, and chiral recognition in the host‐guest systems, which is generally performed using circular dichroism (CD) and/or proton nuclear magnetic resonance (1H NMR) spectroscopies. However, the mass‐balance model that considers the M‐ and P‐twisted conformations has not yet been established. In this study, we derived the novel equations based on the mass‐balance model for the 1 : 1 host‐guest systems. Then, we further applied them to analyze the 1 : 1 host‐guest systems for the achiral calixarene‐based capsule molecule, achiral dimeric zinc porphyrin tweezer molecule, and chiral pillar[5]arene with the chiral and/or achiral guest molecules by using the data obtained from the CD titration, variable temperature CD (VT−CD), and 1H NMR experiments. The thermodynamic parameters (ΔH and ΔS), equilibrium constants (K), and molar CD (Δϵ) in the 1 : 1 host‐guest systems could be successfully determined by the theoretical analyses using the derived equations.
Electrochemical Homo‐ and Crossannulation of Alkynes and Nitriles for the Regio‐ and Chemoselective Synthesis of 3,6‐Diarylpyridines
Authors: Ghosh Mangish , Mandal Tirtha , Lepori Mattia , Barham Joshua P. , Rehbein Julia , Reiser Oliver 
Published: August 2024

AbstractWe disclose a mediated electrochemical [2+2+2] annulation of alkynes with nitriles, forming substituted pyridines in a single step from low‐cost, readily available starting materials. The combination of electrochemistry and a triarylamine redox mediator obviates the requirements of transition metals and additional oxidants. Besides the formation of diarylpyridine moieties via the homocoupling of two identical alkynes, the heterocoupling of two different alkynes depending on their electronic nature is possible, highlighting the unprecedented control of chemoselectivity in this catalytic [2+2+2] process. Mechanistic investigations like cyclic voltammetry and crossover experiments combined with DFT calculations indicate the initial oxidation of an alkyne as the key step leading to the formation of a vinyl radical cation intermediate. The utilization of continuous flow technology proved instrumental for an efficient process scale‐up. The utility of the products is exemplified by the synthesis of π‐extended molecules, being relevant for material or drug synthesis.
Synthesis, Structural Characterization, Anticancer, Antimicrobial, Antioxidant, and Computational Assessments of Zinc(II), Iron(II), and Copper(II) Chelates Derived From Selenated Schiff Base
Authors: Shaaban Saad , Abdullah Khalid Tuama , Shalabi Kamal , Yousef Tarek A. , Al Duaij Omar K. , Alsulaim Ghayah M. , Althikrallah Hanan A. , Alaasar Mohamed , Al‐Janabi Ahmed S. M. , Abu‐Dief Ahmed M. 
Published: August 2024

ABSTRACTNovel selenated azomethine ligand (MSeOH) and its Zn(II), Fe(II), and Cu(II) chelates were synthesized. Their chemical structures were confirmed by molar conductivity, thermal analysis, X‐ray diffraction, IR, NMR, and MS spectroscopic techniques. The antitumor and antimicrobial properties were evaluated against various mammalian cells and pathogenic strains. Furthermore, the antioxidant activities were also assessed using DPPH and SOD bioassays. To gain a deeper understanding of the molecular structure and electronic properties of these complexes, a density functional theory (DFT) study was conducted. The parameters examined in this study provide valuable insight into the bonding, electronic properties, reactivity, and polarity of the compounds under investigation. The biological and theoretical results point to promising activities of the selenated ligand and its complexes.
Genome‐wide identification and coexpression network analysis of heat shock protein superfamily in Apolygus lucorum
Authors: Li Yuan‐Yuan , Deligeer  , Liu Jing , Shi Kai 
Published: August 2024

AbstractHeat shock proteins (Hsp) function as crucial molecular chaperones, playing pivotal roles in insects' response to stress stimuli. Apolygus lucorum, known for its broad spectrum of host plants and significant crop damage potential, presents a compelling subject for understanding stress response mechanisms. Hsp is important for A. lucorum to tolerate temperature and insecticide stress and may be involved in the formation of resistance to the interactive effects of temperature and insecticide. Here, we employed comprehensive genomic approaches to identify Hsp superfamily members in its genome. In total, we identified 42 Hsp genes, including 3 Hsp90, 16 Hsp70, 13 Hsp60, and 10 Hsp20. Notably, we conducted motif analysis and gene structures for Hsp members, which suggested the same families are relatively conserved. Furthermore, leveraging the weighted gene coexpression network analysis, we observed diverse expression patterns of different Hsp types across various tissues, with certain Hsp70 showing tissue‐specific bias. Noteworthy among the highly expressed Hsp genes was testis‐specific, which may serve as a pivotal hub gene regulating the gene network. Our findings shed light on the molecular evolutionary dynamics and temperature stress response mechanisms of Hsp genes in A. lucorum, offering insights into its adaptive strategies and potential targets for pest management.
Alginate‐derived carbon dots for “turn off–on” anti‐neoplastic 5‐fluorouracil sensing in biological samples
Authors: Majd Sasan Abbasi , Kashanian Soheila , Babaei Mahsa , Shekarbeygi Zahra 
Published: August 2024

AbstractAs a chemotherapy drug, 5‐fluorouracil (5‐FU) has been used for colon cancer for decades. Excessive levels of 5‐FU in the human body can lead to notable adverse effects, including severe diarrhea, infection, mouth sores, skin peeling, skin inflammation, and ulcers, which are important and relatively common digestive side effects. In addition, 5‐FU is an analog of uracil and also has similarities to pyrimidines. Therefore, it is not easy to separate them. This research presented a sensor capable of detecting drugs in minimal amounts. An alginate‐derived carbon dot (CD) was synthesized by unique optical properties that obey an on–off fluorescence mechanism for 5‐FU sensing. Introducing copper (Cu(I)) to CDs results in fluorescence quenching through electron transfer. However, when 5‐FU is added to the system as an oxidizing agent, a redox reaction occurs on the surface of the CDs, which leads to the restoration of fluorescence as Cu(I) is altered to Cu(II). Experimental results showed a strong linear correlation (R2 = 0.99) in the concentration range of 1.00–45.00 nM, with the following linear regression, and revealed the relative standard deviation (RSD%) and detection limit of 2.57%, and 1.00 nM, respectively. These results validated the excellent detection capability of the proposed method even at low concentrations of 5‐FU and in the presence of other drugs and interfering substances. Also, the recovery of 5‐FU (varies from 100.46% to 113.7%, with RSD equal to 1.89–3.63) in serum samples indicates the absence of matrix interference in the determination of 5‐FU. In summary, this novel approach to developing a cost‐effective and sensitive sensor holds great potential for future applications in healthcare and related fields.
Nonlinearities and timescales in neural models of temporal interference stimulation
Authors: Plovie Tom , Schoeters Ruben , Tarnaud Thomas , Joseph Wout , Tanghe Emmeric 
Published: August 2024

AbstractIn temporal interference (TI) stimulation, neuronal cells react to two interfering sinusoidal electric fields with a slightly different frequency (, in the range of about 1–4 kHz, in the range of about 1–100 Hz). It has been previously observed that for the same input intensity, the neurons do not react to a purely sinusoidal signal at or . This study seeks a better understanding of the largely unknown mechanisms underlying TI neuromodulation. To this end, single‐compartment models are used to simulate computationally the response of neurons to the sinusoidal and TI waveform. This study compares five different neuron models: Hodgkin‐Huxley (HH), Frankenhaeuser–Huxley (FH), along with leaky, exponential, and adaptive‐exponential integrate‐and‐fire (IF). It was found that IF models do not entirely reflect the experimental behavior while the HH and FH model did qualitatively replicate the observed neural responses. Changing the time constants and steady state values of the ion gates in the FH model alters the response to both the sinusoidal and TI signal, possibly reducing the firing threshold of the sinusoidal input below that of the TI input. The results show that in the modified (simplified) model, TI stimulation is not qualitatively impacted by nonlinearities in the current–voltage relation. In contrast, ion channels have a significant impact on the neuronal response. This paper offers insights into neuronal biophysics and computational models of TI stimulation.
The “healthy = (un)tasty” intuition concerning colour in organic wine labels
Authors: Petit Olivia , Wang Qian Janice , Spence Charles 
Published: August 2024

AbstractOrganic labels certify a product's commitment to ecological balance. However, the association between organic products and health benefits can inadvertently promote overconsumption, particularly in the case of alcoholic beverages such as red wine. In research conducted with participants from the United States, we demonstrate that consumers implicitly link organic wine with health and pleasure, which is explicitly reflected in heightened purchase intentions and anticipated consumption volume. Interestingly, our findings indicate that these effects are moderated by label colour. Implicitly, red organic labels are associated with a less healthy but tastier drink than green labels. Explicitly, organic labels overall stimulate higher purchase intentions regardless of their colour. Nevertheless, our results highlight a moderating role of label colour. Compared to green labels, red organic labels elicit increased purchase intentions, driven by greater expectations of tastiness associated with the red label. Additionally, red labels convey a perception of higher alcohol strength and an intention to consume wine in smaller quantities versus green labels. Thus, the use of a red label may signal both pleasure and potential danger, facilitating organic wine sales without necessarily increasing consumption. These findings have implications for marketers and policymakers interested in supporting responsible wine consumption.
Transition‐Metal‐Free Radical Relay Cascade Annulation of Amides: Access to Antitumor Active Benzo[b]azepine and Oxindole Derivatives
Authors: Sheng Xia‐xin , Qiu Chao‐ying , Wang Li‐na , Du Yu‐jia , Tang Lu‐ning , Chen Jia‐ming , Liu Guo‐ying , Yang Sen , Zheng Peng‐fei , Chen Ming 
Published: August 2024

AbstractEfficient transition‐metal‐free synthesis of benzo[b]azepines and oxindoles is achieved via a radical relay cascade strategy employing halogen atom transfer (XAT) for aryl radical generation followed by intramolecular hydrogen atom transfer (HAT). Optimization yielded moderate to substantial yields under visible light irradiation. Preliminary biological assessments revealed promising anti‐tumor activity for select compounds. This study underscores the potential of XAT‐mediated radical relay cascades in medicinal chemistry and anticancer drug discovery.
Overriding Cage Effect in Electron Donor‐Acceptor Photoactivation of Diaryliodonium Reagents: Synthesis of Chalcogenides
Authors: Meher Prahallad , Parida Sushanta Kumar , Mahapatra Sanat Kumar , Roy Lisa , Murarka Sandip 
Published: August 2024

AbstractIn recent times, diaryliodonium reagents (DAIRs) have witnessed a resurgence as arylating reagents, especially under photoinduced conditions. However, reactions proceeding through electron donor‐acceptor (EDA) complex formation with DAIRs are restricted to electron‐rich reacting partners serving as donors due to the well‐known cage effect. We discovered a practical and high‐yielding visible‐light‐induced EDA platform to generate aryl radicals from the corresponding DAIRs and use them to synthesize key chalcogenides. In this process, an array of DAIRs and dichalcogenides react in the presence of 1,4 diazabicyclo[2.2.2]octane (DABCO) as a cheap and readily available donor, furnishing a variety of di(hetero)aryl and aryl/alkyl chalcogenides in good yields. The method is scalable, features a broad scope with good yields, and operates under open‐to‐air conditions. The photoinduced chalcogenation technology is suitable for late‐stage functionalizations and disulfide bioconjugations and facilitates access to biologically relevant thioesters, dithiocarbamates, sulfoximines, and sulfones. Moreover, the method applies to synthesizing diverse pharmaceuticals, such as vortioxetine, promazine, mequitazine, and dapsone, under amenable conditions.
Free‐Radical Polymerization Induced Grafting‐to of Polymer Chains onto Aluminum Nanoparticles†
Authors: Sun Panqi , Yang Chenggong , Peng Fei , Dang Junbo , Wang Wentao , Deng Daiwu , Zhang Ning‐Ning , Yang Yang , Liu Kun 
Published: August 2024

Comprehensive SummaryAluminum nanoparticles (Al NPs) have significant potential applications in various fields due to their unique LSPR. Significant advancements have been achieved in controlling the size and morphology of Al NPs. However, the efficient modification of Al NPs with polymers has not been implemented. Herein, we report a facile and efficient free‐radical polymerization induced grafting‐to (FRPIGt) method for grafting polymer chains onto Al NPs. By optimizing polymerization conditions, we were able to achieve a polymer brush layer with a weight loss fraction of up to 43.3%, which was higher than those of other polymers with carboxyl or primary amine end groups. Moreover, a broad range of vinyl monomers, including styrene, methacrylate, and methyl methacrylate, can be applied using the FRPIGt method to modify Al NPs. In addition, the FRPIGt method can be extended to photoinduced organocatalyzed atom‐transfer‐radical polymerization. This work paves a new path for the preparation of a wide range of polymer‐functionalized Al NPs and their polymer composites to be utilized in various fields.
Noise‐robust neural networks for medical image segmentation by dual‐strategy sample selection
Authors: Shi Jialin , Yang Youquan , Zhang Kailai 
Published: August 2024

SummaryDeep neural networks for medical image segmentation often face the problem of insufficient clean labeled data. Although non‐expert annotations are more readily accessible, these low‐quality annotations lead to significant performance degradation of existing neural network methods. In this paper, we focus on robust learning of medical image segmentation with noisy annotations and propose a novel noise‐tolerant framework based on dual‐strategy sample selection, which selects the informative samples to provide effective supervision information. First, we propose the first round of sample selection by designing a novel joint loss, which includes conventional supervised loss and regularization loss. To further select information‐rich samples, we propose confidence‐based pseudo‐label sample selection from a novel perspective as the complement. The dual strategies are used in a collaborative manner and the network is optimized with mined informative samples. We conducted extensive experiments on datasets with both simulated noisy labels and real‐world noisy labels. For instance, on a simulated dataset with 25% noise ratio, our method achieves segmentation Dice value with 90.56% 0.03%. Furthermore, increasing the noise ratio to 95%, our method still maintains a high Dice value of 73.85% 0.28% compared to other baselines. Extensive results have demonstrated that our method can weaken the effects of noisy labels on medical image segmentation.
Towards Sustainable Direct Recycling: Unraveling Structural Degradation Induced by Thermal Pretreatment of Lithium‐Ion Battery Electrodes
Authors: Liu Shuaiwei , Dolotko Oleksandr , Bergfeldt Thomas , Knapp Michael , Ehrenberg Helmut 
Published: August 2024

AbstractAs the demand for lithium‐ion batteries (LIBs) continues to increase, there is a growing focus on recycling these battery wastes. Among the existing recycling methods, direct recycling is considered a promising approach, because it allows waste to be returned directly to production. One crucial step in this process is the pretreatment, which involves separating the active materials from the current collector. Thermal treatment provides a feasible and effective approach for achieving this separation. Nonetheless, concerns persist regarding the potential impacts of this process on the structure. This study aims to examine the effects of thermal treatment on the separation efficiency and crystal structure of fresh and cycled NMC (LiNi0.6Co0.2Mn0.2O2) cathodes and graphitic anodes, under various atmospheres and temperatures. The results reveal that an air/oxygen atmosphere facilitates complete separation of cathode materials from aluminum with minimal structural degradation and at lower temperatures compared to other atmospheres. For graphite, thermal treatment under argon, nitrogen and hydrogen demonstrates good structural stability. However, for cycled anodes, the desired separation is not achieved due to the possible interface adhesion that occurs during cycling and heating. Additionally, compared to fresh materials, cycled materials experience more pronounced structural degradation during thermal treatment.
Pulse Charge Suppressing Dendrite Growth at Low Temperature by Rapidly Replenishing Lithium Ion on Anode Surface
Authors: Ren Ke‐Feng , Liu He , Guo Jia‐Xin , Sun Xin , Guo Cong , Bao Weizhai , Yu Feng , Cheng Xin‐Bing , Li Jingfa 
Published: August 2024

AbstractDendrite growth of lithium (Li) metal anodes is considered as one of the most tough issues for Li metal batteries with a theoretically high energy density. This is attributed to the rapid exhaustion of Li ions at the electrode/electrolyte interface, which is even worse at low temperatures with poor diffusion kinetics of Li ions. Here, pulse charge with intermittent rest time during battery charging is proposed to handle the dendrite growth issue of Li metal anodes at low temperatures. The depleted Li ions near the interfaces can be rapidly replenished during the rest time, thus effectively suppressing the dendrites growth. Further investigation found that the large dendrites can be suppressed at the Li ion nucleation stage. The equivalent lifespan considering the rest time is proposed. At −10 °C, the lifespan of Li||Li batteries cycled under 3 mA cm−2 and 1 mAh cm−2 is increased from 24 h to equivalent 64 h. Li||LiNi0.5Co0.2Mn0.3O2 batteries with 80% capacity retention can be stably operated from 39 cycles to 56 cycles. This design presents an efficient and convenient strategy to regulate the deposition behaviors of Li metal anodes with a dendrite‐free morphology.
Multi‐omics integration reveals the oncogenic role of eccDNAs in diffuse large B‐cell lymphoma through STING signalling
Authors: Wu Zijuan , Zhang Wei , Wang Luqiao , Leng Jiayan , Li Yongle , Fan Zhou , Zhan Mengtao , Cao Lei , Jiang Yongning , Jiang Yan , Sun Bing , Fu Jianxin , Li Jianyong , Shi Wenyu , Jin Hui 
Published: August 2024

AbstractBackgroundExtrachromosomal circular DNAs (eccDNAs), a type of double‐stranded DNAs (dsDNAs) that facilitate the activation of the DNA sensing machinery, have been implicated in the progression and prognosis of various diseases. While the roles of eccDNAs remain contentious, their significance in diffuse large B‐cell lymphoma (DLBCL) has not been reported.MethodsCircular DNA sequencing (circle‐seq) was used to demonstrate the expression profile of eccDNAs in DLBCL, and atomic force microscopy to validate the presence of eccDNAs. CCK‐8 and scRNA‐seq techniques were employed to uncover the activation of eccDNA in the STING pathway, leading to enhanced cell proliferation. Chemotherapeutic drugs were used to test the hypothesis that DNA damage induces the production of eccDNA, thereby activating the STING pathway independent of cGAS. GEO databases were used for verification of the prognosis of the eccDNA‐related genes, and animal models were used to investigate the synergistic effects of DNA damage therapy in combination with STING inhibitors on anti‐tumour responses.ResultsEccDNAs were widely expressed in DLBCL and associated with the prognosis of patients. Elevated abundance of eccDNAs promoted the progression of DLBCL. Chemotherapeutic drugs‐induced DNA damage triggered the generation of eccDNAs, resulting in the activation of the STING signalling in a cGAS‐independent manner. Moreover, inhibition of STING exerted a synergistic anti‐tumour effect with cisplatin.ConclusionsEccDNAs induced by DNA damage exert an oncogenic role in DLBCL via activating the STING signalling independently of cGAS. This finding offers a rational therapeutic strategy combining chemotherapy with targeting STING.Highlights
EccDNAs induced by DNA damage exert an oncogenic role in DLBCL via activating the STING signalling independently of cGAS.
The combined treatment of chemotherapeutic drugs with STING inhibitor significantly delayed the tumor progression, providing new insights into the therapeutic strategy for patients with DLBCL, particularly the relapsed and/or refractory (R/R) ones.