bluuebunny/crossref_metadata_2025 huggingface dataset:
Performance Evaluation of Upper‐Level Ontologies in Developing Materials Science Ontologies and Knowledge Graphs
Authors: Beygi Nasrabadi Hossein , Norouzi Ebrahim , Sack Harald , Skrotzki Birgit
Published: October 2024

This study tackles a significant challenge in ontology development for materials science: selecting the most appropriate upper‐level ontologies for creating application‐level ontologies and knowledge graphs. Focusing on the use case of Brinell hardness testing, the research assesses the performance of various top‐level ontologies (TLOs)—basic formal ontology (BFO), elementary multiperspective material ontology (EMMO), and provenance ontology (PROVO)—in developing Brinell testing ontologies (BTOs). Consequently, three versions of BTOs are created using combinations of these TLOs along with their integrated mid‐ and domain‐level ontologies. The performance of these ontologies is evaluated based on ten parameters: semantic richness, domain coverage, extensibility, complexity, mapping efficiency, query efficiency, integration with other ontologies, adaptability to different data contexts, community acceptance, and documentation and maintainability. The results show that all candidate TLOs can effectively develop BTOs, each with its distinct advantages. BFO provides a well‐structured, understandable hierarchy, and excellent query efficiency, making it suitable for integration across various ontologies and applications. PROVO demonstrates balanced performance with strong integration capabilities. Meanwhile, EMMO offers high semantic richness and domain coverage, though its complex structure impacts query efficiency and integration with other ontologies.
A Surface‐Reconstructed Bilayer Heterojunction Enables Efficient and Stable Inverted Perovskite Solar Cells
Authors: Zhu Xueliang , Li Mubai , Mo Kangwei , Yang Man , Li Sheng , Yang Yujie , Wang Huijie , Li Ruiming , Liu Yong , Lin Qianqian , Wang Zhiping
Published: October 2024

The efficiency of perovskite photovoltaics remains distant from their theoretical limits, primarily due to high photovoltage losses. Here a strategy is reported to minimize voltage losses by reconstructing the perovskite surface into a bilayer heterojunction (BLH) structure. Unlike conventional low‐dimensional capping layers, typically constrained to a few nanometers to prevent low fill factors, this methodology facilitates a more comprehensive reaction with surface defects, allowing a more substantial capping layer (≈50 nanometers) without compromising charge transport integrity. Time‐resolved microwave conductivity analysis indicates a significant reduction in trap density at the top region of the perovskite film, showing an order of magnitude lower than that of the pristine sample. Incorporating this BLH in inverted cells results in a remarkably low photovoltage deficit of 325 mV, leading to a power conversion efficiency (PCE) of 26.1% (25.72% certified). The encapsulated device maintains 94% of its original efficiency after 1200 h of maximum power point tracking under one sun illumination at 65 °C.
Sequential Self‐Polymerization of Phenolic Compounds with Alkanedithiol Linkers as a Surface‐Independent and Solvent‐Resistant Surface Functionalization Strategy
Authors: Lim Jiwon , Lee Meng‐Hsun , Ahn Abigail , Kim Jinsang
Published: October 2024

A sequential self‐polymerization of phenolic compounds combined with alkanedithiol (ADT) crosslinkers is developed as a versatile surface‐independent coating and functionalization strategy. The resulting copolymer takes advantage of the diverse binding modes of catechol and gallol and the conformal substrate contact facilitated by the flexible aliphatic chain of ADT. Moreover, Michael addition and thiyl radical addition reactions between ADT and phenolic compounds produce crosslinked resulting polymer films, rendering solvent resistance to the surface coating. This approach is successfully employed using phenolic monomers, including dopamine, 3,4‐dihydroxybenzylamine, 4‐ethylcatechol, levodopa, tannic acid, caffeic acid, and 3,4‐dihydroxybenzylaldehyde, to functionalize glass (ceramic), aluminum (metal), polyethylene (polymer), and Teflon surfaces. The resulting copolymer prepared with a trifunctional thiol crosslinker demonstrated solvent resistance in NaOH (aq.), DMSO, and chloroform, overcoming the stability issues typically encountered by conventional surface coating from polydopamine derivatives.
One‐Pot Synthesis of Sulfonylated 5‐Aroyl‐2‐Arylpyridines via Ruthenium‐Catalyzed and K2S2O8‐Mediated Domino Annulation of β‐Ketosulfones with DMF
Authors: Chang Meng‐Yang , Yang Chi‐Ru , Chen Yeh‐Long
Published: October 2024

Ruthenium‐catalyzed and K2S2O8‐mediated synthesis of diverse sulfonylated 5‐aroyl‐2‐arylpyridines was developed through one‐pot stepwise annulation of two molecules of β‐ketosulfones and N,N‐dimethylformamide (DMF) under the sealed tube conditions. In the overall process, DMF acts as the synthon of one carbon and one imino moiety in the construction of pyridine skeleton via cascade formation of single (C−C/C−N) and double (C=C/C=N) bonds under refluxing DMF conditions. Plausible reaction mechanism is proposed and discussed.
Electronic Properties of Ultra‐Wide Bandgap BxAl1−xN Computed from First‐Principles Simulations
Authors: Milne Cody L. , Biswas Tathagata , Singh Arunima K.
Published: October 2024

Ultra‐wide bandgap (UWBG) materials such as AlN and BN hold great promise for future power electronics due to their exceptional properties. They exhibit large bandgaps, high breakdown fields, high thermal conductivity, and high mechanical strengths. AlN and BN have been extensively researched, however, their alloys, BxAl1−xN, are much less studied despite their ability to offer tunable properties by adjusting x. In this article, the electronic properties of 17 recently predicted ground states of BxAl1−xN in the x = 0 − 1 range are predicted using first‐principles density functional theory and many‐body perturbation theory within GW approximation. All the BxAl1−xN structures are found to be UWBG materials and have bandgaps that vary linearly from that of wurtzite‐phase (w) AlN (6.19 eV) to that of w‐BN (7.47 eV). The bandstructures of BxAl1−xN show that a direct‐to‐indirect bandgap crossover occurs near x = 0.25. Furthermore, it is found that BxAl1−xN alloys have much larger dielectric constants than the constituent bulk materials (AlN = 9.3 ɛ0 or BN = 7.3 ɛ0), with values reaching as high as 12.1 ɛ0. These alloys are found to exhibit large dielectric breakdown fields in the range 9–35 MV cm−1 with a linear dependence on x. This work provides the much needed advancement in the understanding of the properties of BxAl1−xN to aid their application in next‐generation devices.
Use of Direct‐Fed Microbes to Enhance Shrimp Resistance to a Vibrio Parahaemolyticus Strain Causing Early Morality Syndrome (EMS)
Authors: Kuhn David D. , Smith Stephen A. , Williams Robert C. , Galagarza Óscar A. , Thompson Meaghan , Drahos David J. , Stevens Ann M.
Published: October 2024

Early mortality syndrome (EMS) or acute hepatopancreatic necrosis syndrome (AHPND) is an epizootic bacterial infection of shrimp that has had significant negative impact on the global shrimp aquaculture industry. This disease is largely attributed to pathogenic Vibrio parahaemolyticus EMS strains (VP‐EMS). Application of probiotics was examined for control of pathogenic VP‐EMS infections in Pacific white shrimp (Litopenaeus vannamei) under laboratory‐scale conditions. Two probiotic products, a single strain (O14VRQ) of Bacillus subtilis and a blend (Plus10) of five strains of Bacillus from four different species (Bacillus amyloliquifaciens, Bacillus megaterium, Bacillus brevis, and two distinct strains of Bacillus subtilis), were evaluated at various concentrations as feed additives (applied as a top coat on commercial feed) or dosed directly into the culture water. Two trials were conducted in which shrimp were fed either a control feed (no probiotics) or probiotic‐coated feed for 7 days prior to be being challenged with VP‐EMS. Shrimp were observed for clinical signs of disease and mortalities during the disease challenge study. These experiments demonstrated that while both Bacillus probiotic products were shown to significantly (p < 0.05) improve shrimp survival, the O14VRQ strain provided the most consistent protection across the trials in top‐coated feed. Overall, better efficacy was observed with probiotic‐coated feeds. Findings were directly and positively correlated with concentration for top‐coated and even more so for direct in‐tank applications. Collectively, these findings contribute to our understanding about how probiotic strains could be applied to enhance shrimp health in aquaculture.
Assessment of Adaptive Functioning and the Impact of Seizures in KBG Syndrome
Authors: Sarino Kathleen P. , Guo Lily , Yi Edward , Park Jiyeon , Kierzkowska Ola , Carter Drake , Marchi Elaine , Lyon Gholson J.
Published: October 2024

This study aimed to examine the adaptive functioning status and the impact of epileptic seizures on neurocognitive outcomes in KBG syndrome, a rare genetic neurodevelopmental disorder characterized by pathogenic variants in ANKRD11. A single clinician interviewed individuals and families with genetically confirmed cases of KBG syndrome. Trained professionals also conducted assessments using the Vineland–3 Adaptive Behavior Scales. The assessment covered the domains of communication, daily living skills, socialization, and maladaptive behaviors, and then compared individuals with and without epilepsy. Further comparisons were made with data from interviews and participants' medical records. Thirty‐nine individuals (22 males, 17 females) with KBG syndrome, confirmed through genetic analysis, were interviewed via videoconferencing, followed by Vineland–3 assessment by trained raters. Individuals with KBG syndrome came from 36 unique families spanning 11 countries. While the KBG cohort displayed lower overall adaptive behavior composite scores compared with the average population, several members displayed standard scores at or higher than average, as well as higher scores compared with those with the neurodevelopmental disorder Ogden syndrome. Within the KBG cohort, males consistently scored lower than females across all domains, but none of these categories reached statistical significance. While the group with epilepsy exhibited overall lower scores than the nonseizure group in every category, statistical significance was only reached in the written communication subdomain. Our research provides insights that can aid in epilepsy screening and inform assessment strategies for neurocognitive functioning in those with this condition. The cohort performed overall higher than expected, with outliers existing in both directions. Although our results suggest that seizures might influence the trajectory of KBG syndrome, the approaching but overall absence of statistical significance between study groups underscores the need for a more extensive cohort to discern subtle variations in functioning.
Modifications of Prenyl Side Chains in Natural Product Biosynthesis
Authors: Wang Huibin , Yang Yi , Abe Ikuro
Published: October 2024

In recent years, there has been a growing interest in understanding the enzymatic machinery responsible for the modifications of prenyl side chains and elucidating their roles in natural product biosynthesis. This interest stems from the pivotal role such modifications play in shaping the structural and functional diversity of natural products, as well as from their potential applications to synthetic biology and drug discovery. In addition to contributing to the diversity and complexity of natural products, unique modifications of prenyl side chains are represented by several novel biosynthetic mechanisms. Representative unique examples of epoxidation, dehydrogenation, oxidation of methyl groups to carboxyl groups, unusual C−C bond cleavage and oxidative cyclization are summarized and discussed. By revealing the intriguing chemistry and enzymology behind these transformations, this comprehensive and comparative review will guide future efforts in the discovery, characterization and application of modifications of prenyl side chains in natural product biosynthesis.
Experimental and Computational Evidence of a Stable RNA G‐Triplex Structure at Physiological Temperature in the SARS‐CoV‐2 Genome
Authors: Campanile Marco , Improta Roberto , Esposito Luciana , Platella Chiara , Oliva Rosario , Del Vecchio Pompea , Winter Roland , Petraccone Luigi
Published: October 2024

RG1 is a quadruplex‐forming sequence in the SARS‐CoV‐2 genome proposed as possible therapeutic target for COVID‐19. We demonstrate that the dominant conformation of RG1 under physiological conditions differs from the parallel quadruplex previously assumed. Through comprehensive investigations employing CD, UV, NMR, DSC, gel electrophoresis, MD simulations, in silico spectroscopy and the use of truncated RG1 sequences, we have identified this stable conformation as an RNA G‐triplex composed of two G‐triads. We believe this previously unreported RNA structure could serve as a novel therapeutic target. Our findings open new avenues for further studies on the presence and biological role of RNA G‐triplexes in vivo.
Planar Tetracoordinate Silicon in Si3Cu3− Cluster
Authors: Yin Xiao‐han , Zeng Hong‐lin , Liu Xin‐bo , Xu Xi‐Ling , Xu Hong‐Guang , Merino Gabriel , Zheng Wei‐jun , Cui Zhong‐hua
Published: October 2024

Photoelectron spectroscopy and theoretical calculations have identified the global minimum structure of the 16‐valence electron Si3Cu3− cluster, which features a planar tetracoordinate silicon (ptSi) in a rhombic arrangement. The Si3 and Cu3 triangles are interconnected by a Si2/Cu2 edge, forming an ordered chain‐like structure. Besides the conventional 2c–2e σ‐bond connecting Si3 and Cu3, the stability of this cluster is reinforced by a delocalized 3c–2e σ‐bond in Cu3 and a π‐bond in Si3. Our study provides experimental confirmation of a planar hypercoordinate heavier Group 14 element, opening possibilities for exploring similar structures in two‐dimensional materials.
Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles
Authors: Parrino Francesco , Gottuso Alessandro , Viganò Lorenzo , Mariani Pietro , Villa Irene , Cova Francesca , Callone Emanuela , Dirè Sandra , Palmisano Leonardo , Stredansky Matus , D'Arienzo Massimiliano
Published: October 2024

A commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid‐state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub‐surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster‐type energy transfer from excited sub‐surface Ti3+ centers.
When Metal Complexes Evolve, and a Minor Species is the Most Active: the Case of Bis(Phenanthroline)Copper in the Catalysis of Glutathione Oxidation and Hydroxyl Radical Generation
Authors: Falcone Enrico , Vigna Vincenzo , Schueffl Hemma , Stellato Francesco , Vileno Bertrand , Bouraguba Merwan , Mazzone Gloria , Proux Olivier , Morante Silvia , Heffeter Petra , Sicilia Emilia , Faller Peter
Published: October 2024

Several copper‐ligands, including 1,10‐phenanthroline (Phen), have been investigated for anticancer purposes based on their capacity to bind excess copper (Cu) in cancer tissues and form redox active complexes able to catalyse the formation of reactive oxygen species (ROS), ultimately leading to oxidative stress and cell death. Glutathione (GSH) is a critical compound as it is highly concentrated intracellularly and can reduce and dissociate copper(II) from the ligand forming poorly redox‐active copper(I)‐thiolate clusters. Here we report that Cu‐Phen2 speciation evolves in physiologically relevant GSH concentrations. Experimental and computational experiments suggest that at pH 7.4 mostly copper(I)‐GSH clusters are formed, but a minor species of copper(I) bound to one Phen and forming ternary complexes with GSH (GS−Cu‐Phen) is the redox active species, oxidizing quite efficiently GSH to GSSG and forming HO⋅ radicals. This minor active species becomes more populated at lower pH, such as typical lysosomal pH 5, resulting in faster GSH oxidation and HO⋅ production. Consistently, cell culture studies showed lower toxicity of Cu‐Phen2 upon inhibition of lysosomal acidification. Overall, this study underscores that sub‐cellular localisation can considerably influence the speciation of Cu‐based drugs and that minor species can be the most redox‐ and biologically‐active.
Endo‐Encapsulated Multi‐Resonance Dendrimers with Through‐Space Interactions for Efficient Narrowband Blue‐Emitting Solution‐Processed OLEDs
Authors: Chang Yufei , Zhang Kaiyuan , Zhao Lei , Wang Xingdong , Wang Shumeng , Shao Shiyang , Wang Lixiang
Published: October 2024

Different from conventional luminescent dendrimers with fluorophore tethered outside to dendron, here we first developed endo‐encapsulated luminescent dendrimers with multi‐resonance (MR) fluorophore embedded inside of carbazole dendrons by growing dendrons through 1,8‐positions of central carbazole moiety to create a cavity for accommodating the fluorophore. This endo‐encapsulated structure not only shields the fluorophore to fully resist aggregation‐caused spectral broadening, but also induce through‐space interactions between dendron and fluorophore via intramolecular π‐stacking, giving lowered singlet state energy and reduced singlet‐triplet energy splitting to accelerate reverse intersystem crossing (RISC) from triplet to singlet states. The resultant dendrimer containing 1,8‐linked second‐generation carbazole dendrons and boron, sulfur‐doped polycyclic MR fluorophore exhibits narrowband blue emission at 471 nm with FWHM kept at 34 nm even in neat film, together with ~4 times enhancement of RISC rate constant compared to its exo‐tethered counterpart. Solution‐processed OLEDs based on the endo‐encapsulated dendrimer reveal efficient narrowband blue emissions with maximum external quantum efficiency of 22.6 %, representing the best device efficiency for blue‐emitting multi‐resonance dendrimers so far.
The age and position of the southern boundary of prehistoric Polynesian dispersal
Authors: Anderson Atholl , Becerra‐Valdivia Lorena , Cadd Haidee , Marjo Christopher E. , Palmer Jonathan , Turney Chris , Wilmshurst Janet M.
Published: October 2024

Prehistoric Polynesian voyaging into high latitudes with landfall in Antarctica remains a widely credited proposition. We examine it through archaeological and environmental evidence from the Subantarctic region of the southwest Pacific, focussing upon an extensive archaeological site at Sandy Bay on Enderby Island. Combining a new set of radiocarbon ages with former, older, ages we show that the site is now within the same rapid expansion phase in which South Polynesia was first colonised. Radiocarbon ages across the site indicate a single continuous settlement, probably of some decades. Consideration of limiting factors in Subantarctic settlement, including of seafaring capability and critical resources, suggests that the site was about as far south as prehistoric habitation could be sustained and was probably vacated at the onset of the Little Ice age (LIA) in the late 14th century. An absence of prehistoric remains on islands further south also suggests that Polynesian exploration reached a boundary 2000 km short of Antarctica. The southern case is discussed briefly in the wider context of Polynesian expansion.
ZnO with Different Morphologies Sensitized by Metalloporphyrins as Catalysts for H2 Production by Water Splitting Under Sunlight
Authors: Stival João F. , Cechin Camila N. , Iglesias Bernardo A. , Lang Ernesto S. , Rebouças Júlio S. , Nakagaki Shirley
Published: October 2024

In this work, zinc oxide with different morphologies and textural properties were prepared and sensitized with metalloporphyrins (MPs) aiming to improve its solar energy harvesting capability for H2 production by water splitting under sunlight (a 300 W Xe/Hg lamp). An anionic iron(III)porphyrin and a cationic manganese(III)porphyrin were immobilized on different ZnO solids predominantly by electrostatic interactions. In general, the prepared MP‐free ZnO solid yielded modest catalytic results which had apparently no direct correlation with their textural properties or morphology. On the other hand, when these ZnO solids had iron or manganese porphyrin sensitizing them, their catalytic performances changed and a superior yield towards H2 production was observed in comparison to the pure ZnO solids, making evident the synergy achieved between these two components (ZnO and metalloporphyrins) for the prepared solids. It was also observed that the metalloporphyrins and the respective free‐base ligand suffered redox reactions when used as homogenous catalyst in this reaction, which could influence their performances as catalysts. The same was not observed in the solids containing immobilized MP, suggesting some protective effect of the ZnO solids on the MP complexes upon immobilization probably due to interaction of the complexes with the ZnO matrix.
Photometric and Kinematic Studies of Open Clusters Ruprecht 1 and Ruprecht 171
Authors: Çakmak Hikmet , Yontan Talar , Bilir Selçuk , Banks Timothy S. , Michel Raúl , Soydugan Esin , Koç Seliz , Erçay Hülya
Published: October 2024

This study outlines a detailed investigation using CCD UBV and Gaia DR3 data sets of the two open clusters Ruprecht 1 (Rup‐1) and Ruprecht 171 (Rup‐171). Fundamental astrophysical parameters such as color excesses, photometric metallicities, ages, and isochrone distances were based on UBV‐data analyses, whereas membership probability calculations, structural and astrophysical parameters, as well as the kinematic analyses were based on Gaia DR3‐data. We identified 74 and 596 stars as the most probable cluster members with membership probabilities over 50% for Rup‐1 and Rup‐171, respectively. The color excesses were obtained as and mag for Rup‐1 and Rup‐171, respectively. Photometric metallicity analyses were performed by considering F‐G type main‐sequence member stars and found to be and dex for Rup‐1 and Rup‐171, respectively. Ages and distances were based on both UBV and Gaia‐data analyses; according to isochrone‐fitting these values were estimated to be Myr, pc for Rup‐1 and Myr, pc for Rup‐171. The present‐day mass function slope of Rup‐1 was estimated as and Rup‐171 as . Galactic orbit integration analyses showed that both of the clusters might be formed outside the solar circle.
Dammarane‐Type Saponins from the Leaves of Vietnamese Ginseng (Panax vietnamensis Ha & Grushv.) and Their Acetylcholinesterase Inhibition In Vitro and In Silico
Authors: Vu Van Tuan , Hieu Nguyen Ngoc , Hiep Dang Hoang , Anh Nguyen Thi Hoang , Ngan Dang Thi , Tung Pham Ha Thanh , Thuong Phuong Thien , Tung Nguyen Huu
Published: October 2024

Vietnamese ginseng (Panax vietnamensis Ha & Grushv.) represents one of the famous Panax spp. for valuable applications in both traditional and modern medicine; in which, its rhizome part has mainly been used as the medicinal materials based on the bioactive ginsenosides such as ginsenoside Rb1, ginsenoside Rg1, ginsenoside Rd, and majonoside R2. In modern medicine, the development of medicinal materials and utilization of medicinal plants are crucially based on standard bioactive ingredients, so this study to evaluate the leaves of Vietnamese ginseng as source of bioactive ginsenoside led to the identification of seven ginsenosides (1–7). Of them, ginsenoside Rd (2) and pseudoginsenoside RS1 (5) showed inhibitory effects on acetylcholinesterase in vitro with the IC50 values of 47.13 and 79.58 μM and supported by molecular docking analysis, in which ginsenoside Rd (2) and pseudoginsenoside RS1 (5) could play as allosteric inhibitors with high binding affinity (−8.5 and −9.4 kcal/mol) as evidenced by hydrogen bonding and hydrophobic interactions. The findings provided the scientific evidence for using the leaves of Vietnamese ginseng as an alternative source to the roots to enhance memory in traditional medicine as well as for further research on the anti‐dementia effects of 2 and 5.
In‐silico Screening and Synthesis of Benzo[c]Pyridazines Targeting N‐Methyl D‐Aspartate Glutamate Receptor for the Treatment of Seizures
Authors: Shankar Mishra Prem , Mishra Rakhi , Malik Abdul , Ali Khan Azmat
Published: October 2024

This study focuses on synthesizing novel benzopyridazine compounds with an evaluation of their anti‐epileptic activity by in‐silico screening and MES test. The compounds were synthesized under controlled conditions by the reaction of the substituted anilines with sodium nitrite, followed by the reaction with cyanoacetamide, substituted urea, ethanol, and water. The final compounds (5a–d; 6a–d) were tested for antiepileptic activity by in‐silico screening targeting N‐Methyl D‐Aspartate glutamate receptor (PDB ID:5IPV). The screened compounds are also evaluated by in vivo test (MES) by taking phenytoin as a standard drug. The results of the whole study were satisfactory with the yield of the compounds in the range of 88 % to 96 %. The results of in‐ silico, screening showed that compounds 6a and 6c have far more binding energy compared with standard phenytoin (6a −7.5 Kcal/mol. ; 6c −7.6 Kcal/mol. and Phenytoin −6.5 Kcal/mol.). The TD50 values of synthesized compounds (6a–6d) are observed to be significantly higher than those of standard phenytoin. The PI values of several synthetic compounds (6a and 6c) were found to be higher (55.8 % and 58.0 %) than the current antiepileptic medicine phenytoin (55.6 %), demonstrating the synthesized compound‘s safety potential.
Study on the Chemical Components and Anti‐Neuroinflammatory Activity of the Roots of Clausena excavate Burm. f.
Authors: Wang Yingjie , Sun Fuxin , Liang Yapeng , Yan Mi , Hou Yue , Hua Huiming , Zhou Di , Li Ning
Published: October 2024

The ethanol extract of the roots of Clausena excavata gave two previously undescribed coumarins, clauexcatin A (1) and clauexcatin B (2), as well as a pair of new isomers, trans/cis‐clauexcatin C (3a, 3b), along with thirty known compounds. Among these, compound 33 was isolated from this genus for the first time. The structures of these compounds were elucidated based on their physicochemical properties and spectroscopic data. The anti‐neuroinflammatory activities were assessed using LPS‐activated BV‐2 microglial cells. Compounds 6, 8, 17, 24, 29, and 30 exhibited significant inhibition of nitric oxide release in a dose‐dependent manner, with their inhibitory effects being 1.2 to 10.9 times greater than that of the positive control (minocycline).
Synthesis and Application of a Versatile Immunoproteasome Activity Probe
Authors: Halder Saayak , Loy Cody A. , Trader Darci J.
Published: October 2024

The immunoproteasome (iCP) has gained significant interest in recent years as it has been discovered to be significantly expressed under inflammatory conditions, as well as playing significant roles in several diseases, such as autoimmune disorders, viral infection, and cancer. Selective inhibitors have been generated as a method to overcome the off‐target effects of current proteasome inhibitor therapeutics. However, selective probes that allow for monitoring this protein complex remain limited, hindering our understanding of the iCP. Current probes are non‐selective, not commercially available, or require difficult synthesis. Here, we describe the modular synthesis and application of an iCP‐selective probe. The modular nature of the synthetic strategy can enable the incorporation of different fluorophores and covalent warheads, demonstrating the versatility of this probe.
Oxygen‐Doped Porous Ultrathin Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Evolution and Rhodamine B Degradation
Authors: Liu Tao , Zeng Yan , Ma Tao , Liang Feng
Published: October 2024

Graphite phase carbon nitride (g−C3N4) is a highly promising metal‐free photocatalyst, but its low activity, due to limited quantum efficiency and small specific surface area, restricts its practical application. While exfoliating bulk crystals into porous thin‐layer nanosheets and incorporating dopants have been shown to improve photocatalytic efficiency, these methods are typically complex, time‐consuming, and costly processes. In this study, we developed a simple approach to synthesize oxygen‐doped porous g−C3N4 (OCN) nanosheets. The resulting OCN exhibited significantly enhanced light absorption and visible‐light photocatalytic activity compared to bulk g−C3N4 (BCN) and g−C3N4 (CN). The OCN achieved an impressive hydrogen evolution reaction (HER) rate of 8.02 mmol g−1 h−1, eight times greater than BCN, and demonstrated a high Rhodamine B (RhB) degradation rate of 97.3 % owing to the generation of abundant singlet oxygen. These improvements in photocatalytic performance are attributed to the narrow band gap and enhanced electron transfer properties, suggesting a promising route for the efficient design of g−C3N4‐based photocatalysts.
Negative Flashforward Imagery in Adolescent Social Anxiety Disorder: A Pilot Study of Imagery Reports and a Short EMDR Intervention
Authors: Thunnissen Marjolein R. , de Jong Peter J. , Weijermans Jiska , Vet Leonieke J. J. , Rijkeboer Marleen M. , Nauta Maaike H.
Published: October 2024

Psychological treatments for social anxiety disorder (SAD) in adolescents have shown poorer outcomes than for other anxiety disorders. A relevant factor to consider for improving outcomes may be negative imagery. In this pilot study, we examined negative ‘flashforward’ imagery of feared catastrophic outcomes in adolescents with SAD and evaluated the feasibility and preliminary outcomes of a short eye movement desensitization and reprocessing (EMDR) intervention targeting this imagery. We used a case series design with a 1‐week baseline period. Outcomes included symptoms of social anxiety and avoidance related to selected social situations and features of associated flashforward imagery as the proposed mechanism of change during the intervention. We found that six out of seven assessed adolescents reported to experience flashforwards and rated image distress, vividness and threat appraisal as high. In these six participants (aged 14–17 years old), the short EMDR flashforward intervention appeared feasible and was followed by a decrease in social anxiety and avoidance in five participants, while no notable changes were observed during the baseline period. Furthermore, we observed a decrease in flashforward imagery features in at least five participants. Nonparametric tests of the overall (group‐based) changes during the intervention period partially supported these findings. Limitations include the small sample size and the lack of a control group. Results suggest that vivid and distressing flashforward imagery is a common experience and that targeting flashforwards with EMDR may be beneficial in treating social anxiety in youth. Further experimental research on effects and added value to current treatments is necessary.

Trial Registration: Dutch Clinical Trial Register (National Trial Register [NTR]): NL8974
Simulated exploration of parameter space and resource allocation for strategic creation of neo‐domestication breeding programs
Authors: Fumia Nathan , Zenil‐Ferguson Rosana , Wolfe Marnin , Kantar Michael
Published: October 2024

Modern domestication efforts have occurred in a wide range of species. These efforts have led to different levels of change from the initial wild populations and market success. In this study, we explore different breeding cycle parameters to understand the rate of change in different potential starting points of neo‐domestication breeding programs. The design of a program that will bring a new crop to market requires consideration of cost efficiency and resource allocation. More crop diversity on the market creates an opportunity to design different types of food systems that can be tailored toward regional and local food security. Stochastic simulation of the rate of gain and variance is applied to different parameter combinations through the breeding cycle—crossing, evaluation, and selection—to identify population level changes along the continuum of wild to semi‐domestic plant species. The simulated breeding schemes differ in phenotypic gain and variance depending on selection strategy and population type, discovering the largest phenotypic gain of oligogenic traits occurring using phenotypic recurrent selection for landrace and orphan populations while choosing genomic selection for wild populations. There were also differences based on selection strategy, with maximum avoidance consistently leading to lower gains but higher additive variance. Overall, when looking to domesticate a new species, our simulations find phenotypic recurrent selection to be the most cost‐effective option and lead to the most gain in early generations of selection, with marker technology being most useful once initial gains have plateaued.
Deciphering Electrocatalytic Hydrogen Production in Water Through a Bioinspired Water‐Stable Copper(II) Complex Adorned with (N2S2)‐Donor Sites
Authors: Diyali Sangharaj , Saha Subhajit , Diyali Nilankar , Bhattacharjee Avantika , Mallick Abhishek , Agrawalla Suraj Kumar , Purohit Chandra Shekhar , Biswas Bhaskar
Published: October 2024

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase‐like active sites in sustainable H2 generation, a meticulously designed and water‐stable copper(II) complex, [Cl−Cu−LN2S2]ClO4, featuring the N,S‐type ligand, LN2S2 (2,2′‐((butane‐2,3‐diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes ‐Cl substitution by H2O during electrochemical conditions yielding [H2O−Cu−LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s−1 for hydrogen generation. Controlled potential electrolysis at −1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2 %. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post‐CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton‐electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.
Mechanistic Study of the Electrochemical Reduction of CO2 in Aprotic Ionic Liquid in Air
Authors: Iijima Go , Sugiura Kyosuke , Morishita Kenichi , Shingai Hajime , Naruse Junichi , Yamamoto Atsushi , Fujita Yuki , Yoto Hiroaki
Published: October 2024

The capture and electrochemical conversion of dilute CO2 in air is a promising approach to mitigate global warming. Aiming to increase the efficiency of the electrochemical reduction of CO2, we fabricated electrodes and developed a custom‐designed sealed electrochemical reaction system to study the mechanism of this conversion. The performance of three metal electrodes, Ag, Cu, and SUS 316 L, was compared in an aprotic ionic liquid as the electrolyte to monitor the CO2 concentration and chemical reactions using a CO2 sensor and diffuse reflectance infrared Fourier transform spectroscopy and Raman spectroscopy in CO2/N2 (400 ppm CO2 and 99.96 % N2) or synthetic air (400 ppm CO2, 21 % O2, and 79 % N2). The CO2 concentration decreased at negative potentials and was more drastic in synthetic air than in CO2/N2. At negative potential in synthetic air, IR revealed carbon monoxide, carbonate, or peroxydicarbonate on the Ag, Cu, or SUS 316L electrodes, respectively. Reaction intermediates were identified using Raman spectroscopy. Superoxide (O2⋅−), produced by the reduction of O2 on each electrode, promotes the electrochemical reduction of CO2 whose reduction potential is higher on the negative side than that of O2. This research deepens our understanding of the electrochemical capture/release and conversion of dilute CO2.
Eniluracil blocks AREG signalling‐induced pro‐inflammatory fibroblasts of melanoma in heart failure
Authors: Ran Qin , Chen Long
Published: October 2024

Aims

Heart failure (HF) is characterized by a heightened risk of melanoma, which often metastasizes to the heart. The overlap pathology between HF and melanoma includes chronic low‐grade inflammation and dysregulation of inflammatory cancer‐associated fibroblasts (iCAFs). The impact of HF on iCAF‐driven tumour inflammation remains obscure.

Methods and Results

To identify critical genes for HF development, transcriptomic data (GSE57338) containing 313 clinical HF samples [136 healthy controls, 95 ischaemia (ISCH) and 82 dilated cardiomyopathy (DCM)] were analysed to screen differentially expressed genes (DEGs) and perform enrichment analysis. Fifty‐one DEGs in ISCH and 62 DEGs in DCM were identified with log2|fold change (FC)| ≥ 1 and P value ≤0.05. All these genes are involved in extracellular matrix organization, immune/inflammatory responses and Wnt signalling pathways. Then, the overall survival curves and prognostic models of DEGs in melanoma were evaluated. The correlation of gene expression with lymphocyte infiltration levels was assessed. Only aldehyde oxidase 1 (AOX1) and amphiregulin (AREG) maintained the same trend in melanoma as in HF, negatively affecting prognosis by regulating lymphocyte infiltration (log‐rank P value = 0.0017 and 0.0019). The potential drug molecules were screened, and the binding energies were calculated via molecular docking. Eniluracil, a known AOX1 targeting drug, was found to stably bind with AREG (hydrogen bond binding energies: −65.633, −63.592 and −62.813 kcal/mol).

Conclusions

The increased prevalence of melanoma in HF patients and its propensity for cardiac metastasis may be due to AREG‐mediated systemic low‐grade inflammation. Eniluracil holds promise as a therapeutic agent that may block AREG signalling, inhibiting the activation of iCAF mediated by regulatory T cell (Treg) and neutrophil.
Subclinical Hyperthyroidism Enhances Gonadotropin‐Lowering Effects of Metformin in Postmenopausal Women
Authors: Krysiak Robert , Kowalcze Karolina , Okopień Bogusław
Published: October 2024

Metformin treatment decreases elevated concentrations of anterior pituitary hormones. The aim of this prospective, cohort study was to investigate whether hyperthyroidism modulates the impact of metformin on gonadotroph secretory function. The study population included 48 postmenopausal women with untreated type 2 diabetes or prediabetes, 24 of whom had coexisting grade 1 subclinical hyperthyroidism. Both groups were matched for age, insulin sensitivity, and gonadotropin levels. Over the entire study period, all participants were treated with metformin (2.55–3 g daily). Plasma glucose, insulin, thyroid‐stimulating hormone (TSH), total and free thyroid hormones, follicle‐stimulating hormone (FSH), luteinizing hormone (LH), estradiol, prolactin, adrenocorticotropic hormone (ACTH), and insulin‐like growth factor‐1 (IGF‐1) were assayed at entry and 6 months later. At baseline, the study groups differed in levels of TSH and thyroid hormones but not in body mass index, blood pressure, glucose homeostasis markers (fasting glucose, homeostatic model assessment 1 of insulin resistance ratio [HOMA1‐IR], and glycated hemoglobin [HbA1c]), and the remaining hormones. There were no differences between both groups in the degree of reduction in plasma glucose and HbA1c in response to metformin treatment. Although metformin decreased HOMA1‐IR in both groups, this effect was stronger in women with hyperthyroidism than with normal thyroid function (−50 ± 20% vs −30 ± 15%). Similar relationships were observed for FSH (−43 ± 21% vs −21 ± 12%). Only in hyperthyroid women did the drug reduce LH concentration (by 35 ± 17%). Metformin did not affect circulating levels of TSH, total and free thyroxine, total and free triiodothyronine, estradiol, prolactin, ACTH, and IGF‐1. The obtained results indicate that hyperthyroidism enhances the gonadotropin‐lowering effects of metformin, as well as the fact that this agent has a neutral effect on the hypothalamic–pituitary–thyroid axis in case of its overactivity.
Assessing postural stability in flatfoot using a time‐in‐boundary method during single‐leg standing
Authors: Sung Paul S. , Lee Dongchul
Published: October 2024

Flatfoot, a foot deformity characterized by the collapse of the arch, significantly impacts an individual's balance and stability. This study explored postural adjustments and sway excursions in individuals with and without flatfoot using the Time‐in‐Boundary method. This method assessed relative stability by exploring various center of pressure radius thresholds during three trials of single‐leg stance. We observed significant interactions in threshold levels (F = 4.37, p = 0.04) and normalized relative stable times (F = 7.64, p = 0.01), particularly in the initial trials. Initially, the flatfoot group showed marked decreases in stable times at 10 mm, 15 mm, and 20 mm thresholds, which expanded to 25 mm and 30 mm in subsequent trials. Despite a significant decrease in stability at the 30 mm threshold in early trials, participants exhibited improved stability control as trials progressed. This enhancement likely reflects a combination of a learning effect and an increased understanding of the task requirements, underscoring the adaptability of postural control systems to the biomechanical challenges posed by flatfoot. The Time‐in‐Boundary method has proven to be an effective tool for clinicians to assess postural control, playing a vital role in developing customized rehabilitation strategies for individuals with flatfoot.
When the attention control condition works: A systematic review of attention control training for posttraumatic stress disorder
Authors: Clauss Kate , Cheney Tamara , Somohano Vanessa C. , Hannon Sara , DeGutis Joseph , Esterman Michael , Constans Joseph , O'Neil Maya
Published: October 2024

Attentional bias and deficits in attentional control are associated with posttraumatic stress disorder (PTSD) symptoms. Attention control training (ACT) may address these factors. We reviewed randomized controlled trials (RCTs) of ACT for PTSD to address unanswered questions about ACT's effectiveness, tolerability, and implementation. Studies were included if they were an RCT that used an adult sample, recruited participants with a PTSD diagnosis, and had ACT as at least one treatment arm. The PTSD Trials Standardized Data Repository (PTSD‐Repository) and additional databases were searched to identify PTSD RCTs published through May 2024. Seven studies met the inclusion criteria (N = 407). The effect size for ACT versus a comparison condition on PTSD symptoms was large, but the confidence interval (CI) overlapped with 0, g = 0.75, 95% CI [‐0.63, 2.12]. The same pattern was observed for attention bias variability, g = 1.04, 95% CI [‐0.90, 2.98]. There was a significant within‐group effect of ACT on self‐reported PTSD symptoms, g = ‐1.43, 95% CI [‐2.83, ‐0.03]. Risk of bias varied, with high risk of bias being primarily due to bias in the measurement of the outcome. These effects should be interpreted cautiously given the significant heterogeneity and wide confidence intervals observed. It remains unclear for whom and under what conditions ACT may be most effective. Future studies should move beyond response time measures, employ an inactive comparator, and examine the mechanism of action to determine whether ACT could be a viable intervention for PTSD.
Development of Machine Learning Copilot to Assist Novices in Learning Flexible Laryngoscopy
Authors: Miller Mattea E. , Witte Dan , Lina Ioan , Walsh Jonathan , Rameau Anaïs , Bhatti Nasir I.
Published: October 2024

Objectives

Here we describe the development and pilot testing of the first artificial intelligence (AI) software “copilot” to help train novices to competently perform flexible fiberoptic laryngoscopy (FFL) on a mannikin and improve their uptake of FFL skills.

Methods

Supervised machine learning was used to develop an image classifier model, dubbed the “anatomical region classifier,” responsible for predicting the location of camera in the upper aerodigestive tract and an object detection model, dubbed the “anatomical structure detector,” responsible for locating and identifying key anatomical structures in images. Training data were collected by performing FFL on an AirSim Combo Bronchi X mannikin (United Kingdom, TruCorp Ltd) using an Ambu aScope 4 RhinoLaryngo Slim connected to an Ambu® aView™ 2 Advance Displaying Unit (Ballerup, Ambu A/S). Medical students were prospectively recruited to try the FFL copilot and rate its ease of use and self‐rate their skills with and without the copilot.

Results

This model classified anatomical regions with an overall accuracy of 91.9% on the validation set and 80.1% on the test set. The model detected anatomical structures with overall mean average precision of 0.642. Through various optimizations, we were able to run the AI copilot at approximately 28 frames per second (FPS), which is imperceptible from real time and nearly matches the video frame rate of 30 FPS. Sixty‐four novice medical students were recruited for feedback on the copilot. Although 90.9% strongly agreed/agreed that the AI copilot was easy to use, their self‐rating of FFL skills following use of the copilot were overall equivocal to their self‐rating without the copilot.

Conclusions

The AI copilot tracked successful capture of diagnosable views of key anatomical structures effectively guiding users through FFL to ensure all anatomical structures are sufficiently captured. This tool has the potential to assist novices in efficiently gaining competence in FFL.

Level of Evidence

NA Laryngoscope, 135:1046–1053, 2025