bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Gradient Engineering of Conductive and Hierarchically Potassiophilic Network for Highly Stable Potassium Metal Anode
Authors: Zhang Dongting , Liu Maocheng , Shi Wenjie , Qiu Yuping , Hu Yuxia , Yuan Zizhou , Xue Hongtao , Kong Lingbin , Zhao Kun , Ren Junqiang , Liu Bao 
Published: July 2024

AbstractPotassium (K) metal anodes are the most competitive candidates for low‐cost and high‐energy density rechargeable batteries. However, uncontrolled K dendrite growth strictly impedes the practical application of K metal anodes. Herein, a potassiophilic and conductive dual‐gradient free‐standing host (named TS‐PKS) composed of the bottom layer with Ti3CN and F doped SnO2 (F‐SnO2) and the top layer with perfluorinated sulfonic acid K (PFSA‐K) and ordered mesoporous silica (SBA15) is constructed to achieve dendrite‐free K deposition. The potassiophilicity and conductivity of the TS‐PKS host increase along with the depth direction to generate a bottom‐up dual‐gradient of K+ affinity and electroconductivity. Such bottom‐up dual‐gradient of K+ affinity and electroconductivity can synergistically manipulate uniform K metal deposition following the bottom‐up manner, preventing the notorious K dendrite growth. As a result, the TS‐PKS@K symmetric cell can stably cycle over 2800 h at 0.5 mA cm−2/0.5 mAh cm−2. Meanwhile, the TS‐PKS@K//PTCDA full battery also exhibits an initial specific capacity of 118.3 mAh g−1 at a high current density of 500 mA g−1 and maintains up to 81.1 mAh g−1 after 1000 cycles. This novel dual‐gradient strategy design offers a straightforward approach to effectively manipulate K metal deposition manner for achieving dendrite‐free K metal anodes.
Fine‐Tuned Pretrained Transformer for Amharic News Headline Generation
Authors: Degu Mizanu Zelalem , Meshesha Million 
Published: July 2024

ABSTRACTAmharic is one of the under‐resourced languages, making news headline generation particularly challenging due to the scarcity of high‐quality linguistic datasets necessary for training effective natural language processing models. In this study, we fine‐tuned the small check point of the T5v1.1 model (t5‐small) to perform Amharic news headline generation with an Amharic dataset that is comprised of over 70k news articles along with their headline. Fine‐tuning the model involves dataset collection from Amharic news websites, text cleaning, news article size optimization using the TF‐IDF algorithm, and tokenization. In addition, a tokenizer model is developed using the byte pair encoding (BPE) algorithm prior to feeding the dataset for feature extraction and summarization. Metrics including Rouge‐L, BLEU, and Meteor were used to evaluate the performance of the model and a score of 0.5, 0.24, and 0.71, respectively, was achieved on the test partition of the dataset that contains 7230 instances. The results were good relative to result of the t5 model without fine‐tuning, which are 0.1, 0.03, and 0.14, respectively. A postprocessing technique using a rule‐based approach was used for further improving summaries generated by the model. The addition of the postprocessing helped the system to achieve Rouge‐L, BLEU, and Meteor scores of 0.72, 0.52, and 0.81, respectively. The result value is relatively better than the result achieved by the nonfine‐tuned T5v1.1 model and the result of previous studies report on abstractive‐based text summarization for Amharic language, which had a 0.27 Rouge‐L score. This contributes a valuable insight for practical application and further improvement of the model in the future by increasing the article length, using more training data, using machine learning–based adaptive postprocessing techniques, and fine‐tuning other available pretrained models for text summarization.
Challenges and Applications of Supramolecular Metalate Chemistry
Authors: O'Connell‐Danes Joseph G. , Ngwenya Bryne T. , Morrison Carole A. , Love Jason B. 
Published: July 2024

AbstractWhile the supramolecular chemistry of simple anions is ubiquitous, the targeting and exploitation of their metal‐containing relatives, the metalates, is less well understood. This mini review highlights the latest advances in this emergent area by discussing the supramolecular chemistry of metalates thematically, with a focus on the exploitation of metalates in a diversity of applications, including medical imaging and therapy, environmental remediation, molecular magnetism, catalysis, perovskite materials, and metal separations. The unifying features of these systems are identified with a view to allow the supramolecular chemist to target the unique material properties of the metalates, even in areas that are currently relatively immature.
Controlled Protein‐Membrane Interactions Modulate Self‐Organization of Min Protein Patterns
Authors: Hasani Mergime , Esch Katharina , Zieske Katja 
Published: July 2024

AbstractSelf‐organizing protein patterns are crucial for living systems, governing important cellular processes such as polarization and division. While the field of protein self‐organization has reached a point where basic pattern‐forming mechanisms can be reconstituted in vitro using purified proteins, understanding how cells can dynamically switch and modulate these patterns, especially when transiently needed, remains an interesting frontier. Here, we demonstrate the efficient regulation of self‐organizing protein patterns through the modulation of simple biophysical membrane parameters. Our investigation focuses on the impact of membrane affinity changes on Min protein patterns at lipid membranes composed of Escherichia coli lipids or minimal lipid compositions, and we present three major results. First, we observed the emergence of a diverse array of pattern phenotypes, ranging from waves over flower‐shaped patterns to snowflake‐like structures. Second, we demonstrated the dependency of these patterns on the density of protein‐membrane linkers. Finally, we demonstrate that the shape of snowflake‐like patterns is fine‐tuned by membrane charge. Our results demonstrate the significant influence of membrane linkage as a straightforward biophysical parameter governing protein pattern formation. Our research points towards a simple yet intriguing mechanism by which cells can adeptly tune and switch protein patterns on the mesoscale.
Regulating Anode‐Electrolyte Interphasial Reactions by Zwitterionic Binder Chemistry in Lithium‐Ion Batteries with High‐Nickel Layered Oxide Cathodes and Silicon‐Graphite Anodes
Authors: Jin Biyu , Dolocan Andrei , Liu Chen , Cui Zehao , Manthiram Arumugam 
Published: July 2024

AbstractThe practical application of silicon (Si)‐based anodes faces challenges due to severe structural and interphasial degradations. These challenges are exacerbated in lithium‐ion batteries (LIBs) employing Si‐based anodes with high‐nickel layered oxide cathodes, as significant transition‐metal crossover catalyzes serious parasitic side reactions, leading to faster cell failure. While enhancing the mechanical properties of polymer binders has been acknowledged as an effective means of improving solid‐electrolyte interphase (SEI) stability on Si‐based anodes, an in‐depth understanding of how the binder chemistry influences the SEI is lacking. Herein, a zwitterionic binder with an ability to manipulate the chemical composition and spatial distribution of the SEI layer is designed for Si‐based anodes. It is evidenced that the electrically charged microenvironment created by the zwitterionic species alters the solvation environment on the Si‐based anode, featuring rich anions and weakened Li+‐solvent interactions. Such a binder‐regulated solvation environment induces a thin, uniform, robust SEI on Si‐based anodes, which is found to be the key to withstanding transition‐metal deposition and minimizing their detrimental impact on catalyzing electrolyte decomposition and devitalizing bulk Si. As a result, albeit possessing comparable mechanical properties to those of commercial binders, the zwitterionic binder enables superior cycling performances in high‐energy‐density LIBs under demanding operating conditions.
Constrained Catalytic Itinerary of a Retaining 3,6‐Anhydro‐D‐Galactosidase, a Key Enzyme in Red Algal Cell Wall Degradation
Authors: Wallace Michael D. , Cuxart Irene , Roret Thomas , Guée Laura , Debowski Aleksandra W. , Czjzek Mirjam , Rovira Carme , Stubbs Keith A. , Ficko‐Blean Elizabeth 
Published: July 2024

AbstractThe marine Bacteroidota Zobellia galactanivorans has a polysaccharide utilization locus dedicated to the catabolism of the red algal cell wall galactan carrageenan and its unique and industrially important α‐3,6‐anhydro‐D‐galactose (ADG) monosaccharide. Here we present the first analysis of the specific molecular interactions that the exo‐(α‐1,3)‐3,6‐anhydro‐D‐galactosidase ZgGH129 uses to cope with the strict steric restrictions imposed by its bicyclic ADG substrate — which is ring flipped relative to D‐galactose. Crystallographic snapshots of key catalytic states obtained with the natural substrate and novel chemical tools designed to mimic species along the reaction coordinate, together with quantum mechanics/molecular mechanics (QM/MM) metadynamics methods and kinetic studies, demonstrate a retaining mechanism where the second step is rate limiting. The conformational landscape of the constrained 3,6‐anhydro‐D‐galactopyranose ring proceeds through enzyme glycosylation B1,4→[E4]≠→E4/1C4 and deglycosylation E4/1C4→[E4]≠→B1,4 itineraries limited to the Southern Hemisphere of the Cremer–Pople sphere. These results demonstrate the conformational changes throughout catalysis in a non‐standard, sterically restrained, bicyclic monosaccharide, and provide a molecular framework for mechanism‐based inhibitor design for anhydro‐type carbohydrate‐processing enzymes and for future applications involving carrageenan degradation. In addition, our study provides a rare example of distinct niche‐based conformational itineraries within the same carbohydrate‐active enzyme family.
Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst
Authors: Xu Weici , Yamakawa Takeshi , Huang Meiling , Tian Peilin , Jiang Zhigen , Xu Ming‐Hua 
Published: July 2024

AbstractTransition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings in the reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our successful development of a novel cationic Rh(I)/chiral diene catalytic system capable of efficient enantioselective B−H and O−H insertions with diaryl diazomethanes, allowing the access to a broad range of gem‐diarylmethine boranes and gem‐diarylmethine ethers in good yields with high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into the O−H bond was achieved for the first time. A remarkable feature of this newly designed Rh(I)/diene catalyst bearing two ortho‐amidophenyl substitutents is that it can distinguish between two arene rings of the diaryl carbene through a stereochemically selective control of π–π stacking interactions. DFT calculations indicate that the rotation‐restricted conformation of Rh(I)/diene complex played an important role in the highly enantioselective carbene transformations. This work provides an interesting and unprecedented stereocontrol mode in diaryl metal carbene transformations.
Water soluble redox‐active polyurethanes as efficient corrosive inhibitors for mild steel
Authors: Prasad Paradhakshina Ermiya , Dhore Nikhil , Arukula Ravi , Rao Chepuri R. K. 
Published: July 2024

AbstractThere is a necessity for an eco‐friendly inhibitor technology to safeguard mild steel from corrosion. Redox‐active Oligoanilines, namely diamine‐capped trimer (DCTA) and tetramer (DCTAni) have been synthesized and incorporated into the polyurethane backbone derived from polyethylene glycols (PEG, Mw = 2050, 4000) and toluene diisocyanate (TDI). The four water‐soluble polyurethanes, resulting from PEG, TDI, and DCTA/DCTAni, were denoted as IH‐1, IH‐2, IH‐3, and IH‐4. The corresponding redox‐active polyurethanes were rationally characterized using FTIR, and UV–visible spectroscopies. Scanning electron microscopy (SEM) was employed to investigate the surface morphology. The electrochemical properties of these inhibitors were characterized by cyclic voltammetry (CV). All the inhibitors were studied for their corrosion inhibition efficiency using Tafel potentiodynamic polarization analysis and weight loss methods. These demonstrated high efficacy at a low concentration of 200–300 ppm. The absorptivity of polymers on the mild steel were confirmed by Langmuir adsorption isotherms with a well‐fitting (R2 = 99.9%). The SEM analysis showed the adsorption capacity of inhibitors as protective layers for the mild steel panels. Overall, this work paves the way for innovative ideas for producing more water‐soluble and electrochemically active polymer additives as excellent corrosive inhibitors for mild steel surfaces.
A genetic snapshot before extinction: Museomics reveals the phylogenetic position of a critically endangered freshwater gastropod
Authors: Stelbrink Björn , Kehlmaier Christian , Clewing Catharina , Wilke Thomas , Albrecht Christian 
Published: July 2024

AbstractIsland species are particularly vulnerable to various anthropogenic impacts. Because several island endemics are rare and not accessible, obtaining genetic information and reconstructing their biogeographical and evolutionary history becomes increasingly difficult. In the present study, we investigated the endangered freshwater gastropod Paludomus ajanensis (family Paludomidae) endemic to the Seychelles (Mahé and Silhouette) in the western Indian Ocean. By analysing historical DNA of this species, we were able to place this species in the family Paludomidae and to uncover its Asian affinity. The patchy distribution plus the documented recent population decline suggests this species should be considered ‘Critically Endangered’.
Integration of Genetic and Clinical Risk Factors for Risk Classification of Uveitis in Patients With Juvenile Idiopathic Arthritis
Authors: Tordoff Melissa , Smith Samantha L. , Lawson‐Tovey Saskia , Dick Andrew D. , Beresford Michael W. , Ramanan Athimalaipet V. , Hyrich Kimme L. , Morris Andrew P. , Eyre Stephen , Wedderburn Lucy R. , Bowes John ,   the CLUSTER Consortium
Published: July 2024

ObjectiveJuvenile idiopathic arthritis (JIA)–associated uveitis (JIAU) is a serious JIA comorbidity that can result in vision impairment. This study aimed to identify genetic risk factors within the major histocompatibility complex for JIAU and evaluate their contribution for improving risk classification when combined with clinical risk factors.MethodsData on single nucleotide polymorphisms, amino acids, and classical HLA alleles were available for 2,497 patients with JIA without uveitis and 579 patients with JIAU (female 2,060, male 1,015). Analysis was restricted to patients with inferred European ancestry. Forward conditional logistic regression identified genetic markers exceeding a Bonferroni‐corrected significance (6 × 10−6). Multivariable logistic regression estimated the effects of clinical and genetic risk factors, and a likelihood ratio test calculated the improvement in model fit when adding genetic factors. Uveitis risk classification performance of a model integrating genetic and clinical risk factors was estimated using area under the receiver operator characteristic curve and compared with a model of clinical risk factors alone.ResultsThree genetic risk factors were identified, mapping to HLA‐DRB1, HLA‐DPB1, and HLA‐A. These markers were statistically independent from clinical risk factors and significantly improved the fit of a model when included with clinical risk factors (P = 3.3 × 10−23). The addition of genetic markers improved the classification of JIAU compared with a model of clinical risk factors alone (area under the curve 0.75 vs 0.71).ConclusionIntegration of a genetic and clinical risk prediction model outperforms a model based solely on clinical risk factors. Future JIAU risk prediction models should include genetic risk factors.
White Light Emission from Zn(II) and DMSO‐Induced Copper Nanocluster Assembly
Authors: Barnwal Neha , Nandi Nilanjana , Sarkar Priyanka , Sahu Kalyanasis 
Published: July 2024

AbstractAn assembly of metal nanoclusters driven by appropriate surface ligands and solvent environment may engender entirely new photoluminescence (PL). Herein, we first synthesize histidine (His) stabilized copper nanoparticles (CuNPs) and, subsequently, copper nanoclusters (CuNCs) from it using 3‐mercaptopropionic acid (MPA) as an etchant. The CuNCs originally emit bluish‐green (λem=470 nm) PL with a low quantum yield (QY∼1.8 %). However, it transformed into a dual‐emissive nanocluster assembly (Zn‐CuNCs) in the presence of Zn(II) salt, having a distinct blue emission band (λem=420 nm) and a red emission band (λem=615 nm) with eight times QY (∼9.1 %) enhancement. The temperature‐dependent emission spectra of Zn‐CuNCs depicted that the blue emission band persists for all the temperature ranges (0–80 °C) while the red emission band vanishes at high temperatures (70–80 °C). Thus, the blue emission may originate from the locally excited state (LES) emission of the nanoclusters, while the red emission originates from through‐space interaction (TSI) and Cu(I)…Cu(I) interaction within the assembly. Adding dimethyl sulfoxide (DMSO) further modifies the emission intensities; the red band was amplified four times, while the blue band was diminished by 2.5 times. The transmission electron microscopy (TEM) images unveiled that the Zn‐CuNCs are a large assembly of tiny nanoclusters, which become more compact in DMSO. The blue emission possesses steady‐state fluorescence anisotropy, while the red emission shows no anisotropy. Further, near‐perfect white light emission(WLE) was rendered with CIE coordinates of (0.33, 0.32) by combining the dual emission of the Zn‐CuNCs with the original green emission of the CuNCs.
Concentration‐dependent luminescence characterization of terbium‐doped strontium aluminate nanophosphors
Authors: Thomas Neenu Mary , Safeera Thevaruparambil Abdul Basheer , Vanchipurackal Ison Varkey , Anila Edathottiyil Issac 
Published: July 2024

AbstractThe present investigation describes the synthesis of luminescent terbium‐doped strontium aluminate nanoparticles emitting bright green light, which were synthesized through a solid‐state reaction method assisted by microwave radiation. Various samples containing different concentrations of Tb were synthesized, and an analysis of their structural and morphological features was conducted using powder x‐ray diffraction, Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The band gaps of the samples were determined utilizing the Kubelka–Munk method. The quenching mechanism observed was identified to be due to dipole–dipole interaction using the Dexter theory. The optimized sample with a terbium concentration of 4 at.% has a luminescence lifetime of 1.05 ms with 20.62% quantum efficiency. The results of this study indicate that the terbium‐doped strontium aluminate fluorescent nanoparticles exhibit promising potential for a wide range of applications, including bioimaging, sensing and solid‐state lighting.
Magnetic resonance imaging‐based radiomics nomogram for the evaluation of therapeutic responses to neoadjuvant chemohormonal therapy in high‐risk non‐metastatic prostate cancer
Authors: Wu Xiao‐Hui , Ruan Zhong‐Tian , Ke Zhi‐Bin , Lin Fei , Chen Jia‐Yin , Xue Yu‐Ting , Lin Bin , Chen Shao‐Hao , Chen Dong‐Ning , Zheng Qing‐Shui , Xue Xue‐Yi , Wei Yong , Xu Ning 
Published: July 2024

AbstractPurposeThe aim of this study was to assess the potential application of a radiomics features‐based nomogram for predicting therapeutic responses to neoadjuvant chemohormonal therapy (NCHT) in patients with high‐risk non‐metastatic prostate cancer (PCa).MethodsClinicopathologic information was retrospectively collected from 162 patients with high‐risk non‐metastatic PCa receiving NCHT and radical prostatectomy at our center. The postoperative pathological findings were used as the gold standard for evaluating the efficacy of NCHT. The least absolute shrinkage and selection operator (LASSO) was conducted to develop radiomics signature. Multivariate logistic regression analyses were conducted to identify the predictors of a positive pathological response to NCHT, and a nomogram was constructed based on these predictors.ResultsSixty‐three patients (38.89%) experienced positive pathological response to NCHT. Receiver operating characteristic analyses showed that the area under the curve (AUC) of periprostatic fat (PPF) radiomics signature was 0.835 (95% CI, 0.754–0.898), while the AUC of intratumoral radiomics signature was 0.822 (95% CI, 0.739–0.888). Multivariate logistic regression analysis revealed that PSA level, PPF radiomics signature and intratumoral radiomics signature were independent predictors of positive pathological response. A nomogram based on these three predictors was constructed. The AUC was 0.908 (95% CI, 0.839–0.954). The Hosmer–Lemeshow goodness‐of‐fit test showed that the nomogram was well calibrated. Decision curve analysis revealed the favorable clinical practicability of the nomogram. The nomogram was successfully validated in the validation cohort. Kaplan–Meier analyses showed that nomogram and positive pathological response were significantly related with survival of PCa.ConclusionThe radiomics–clinical nomogram based on mpMRI radiomics features exhibited superior predictive ability for positive pathological response to NCHT in high‐risk non‐metastatic PCa.
Alpha‐Glucosidase Inhibitory Effects of Flavonoids, Phenolic Acids and Iridoids Isolated From Vinca Soneri: In Vitro and In Silico Perspectives
Authors: Uyanır Eliz , Šoral Michal , Seyhan Gökçe , Akkaya Didem , Barut Burak , Sari Suat , Duman Hayri , Renda Gülin , Şöhretoğlu Didem 
Published: July 2024

AbstractVarious Vinca species have been traditionally used for their antihypertensive, sedative, and hemostatic properties, as well as for treating diabetes. In this study, some flavonoids, phenolic acids and iridoids were isolated from an endemic Vinca species, Vinca soneri for the first time. α‐Glucosidase inhibitory effects of the isolates were tested and kaempferol‐3‐O‐α‐rhamnopyranosyl (1→6) β‐galactopyranoside (1) was found to be the most active one with an IC50 value of 285.73 ±7.35 μM. Enzyme kinetic assay revealed that it inhibited α‐glucosidase in competitive manner. Molecular geometry of 1 was predicted and Frontier molecular orbital analysis was performed using Density Functional Theory (DFT) calculations. Molecular docking and MM‐GBSA calculations predicted good fit for 1 in the enzyme active site and key interactions with the catalytic residues. As a result, current study identifies 1 as a promising competitive α‐glucosidase inhibitor to be developed as a potential antidiabetic drug candidate.