bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bismuth as a Z‐Type Ligand: an Unsupported Pt−Bi Donor‐Acceptor Interaction and its Umpolung by Reaction with H2
Authors: Schwarzmann Johannes , Eskelinen Toni , Reith Sascha , Ramler Jacqueline , Karttunen Antti J. , Poater Jordi , Lichtenberg Crispin 
Published: July 2024

AbstractEstablishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2.
The impact of industrial methyl diethanolamine solution on the aging of cured ethylene‐propylene‐diene monomer and butyl rubber compounds, and associated blends with potential applications in rubber‐made sealants within gas refinery environments
Authors: Khani Zeynab , Movahed Saeed Ostad 
Published: July 2024

AbstractThis study investigates the impact of aging in methyl diethanolamine (MDEA) solution on cured rubber compounds comprising ethylene‐propylene‐diene monomer rubber (EPDM), butyl rubber (IIR), and blends, utilizing nano (nZnO) and conventional (ZnO) zinc oxides as curing activators. The analysis reveals that MDEA solution induces degradation in the rubber matrix by grafting amine and amide groups onto the rubber backbone, particularly affecting unsaturated units in diene monomers in EPDM and isoprene units in IIR. The Fourier‐transform infrared (FTIR) analysis validated the addition of these functional groups. Aging contributed to the formation of a thin rubber layer covering carbon black particles, likely due to un‐crosslinking and rubber chain scission, resulting in changes in bound rubber as observed in scanning electron microscopy (SEM) images. Tensile strength and elongation at break typically decreased with aging, with EPDM compounds exhibiting the highest initial tensile strength and IIR compounds demonstrating superior initial elongation. Hardness remains largely unaffected by aging. This study showed the detrimental effects of MDEA exposure on rubber compounds, emphasizing the critical importance of material selection and property tailoring for specific applications in MDEA‐rich environments, such as gas refineries.
Polybenzoxazine‐based PEMFC composite bipolar plates with three‐dimensional conductive skeleton
Authors: Xianwu Cao , Bin Liu , Qilong Huang , Bin Hu , Yizhang Tong , Zhitao Yang 
Published: July 2024

AbstractTo address the limitation of poor conductivity in composite bipolar plates (CBPs), a three‐dimensional (3D) conductive skeleton structure of graphite flakes (GF) is constructed using the sacrificial template method. This method prepares 3D polybenzoxazine/graphite flakes composite bipolar plates (3D‐PBA/GF CBPs) with high conductivity through vacuum impregnation of benzoxazine resin (BA). In this paper, the effect of the presence of a conductive network structure on the key properties of CBPs is analyzed, and the performance of GF randomly dispersed CBPs obtained through traditional solution dispersion is also compared. Thanks to the efficient conductive path within its 3D conductive skeleton structure, the 3D‐PBA/GF CBP achieves excellent conductivity meeting US Department of Energy (DOE) targets (in‐plane conductivity greater than 100 S/cm, area‐specific resistance less than 10 mΩ cm2) at a low filler content (50 wt%). In addition, CBPs with 3D conductive skeleton structures also exhibit qualified service performances to meet the requirements of proton exchange membrane fuel cells (PEMFCs). Compared with GF randomly dispersed CBPs, 3D‐PBA/GF CBPs exhibited higher power density in a single cell. This study demonstrates that constructing PBA/GF CBPs with a 3D conductive skeleton to achieve an accumulation distribution of conductive fillers is an efficient method for enhancing the conductivity of CBPs.
Engineering a 3‐dimensional tissue construct with adipose‐derived stem cells for healing bone defect: An ex vivo study with femur head
Authors: Mahajan Aditi , Sharma Siddhartha , Bhadada Sanjay Kumar , Aggarwal Aditya , Bhattacharyya Shalmoli 
Published: July 2024

ABSTRACTThe compatibility of bone graft substitutes (BGS) with mesenchymal stem cells (MSCs) is an important parameter to consider for their use in repairing bone defects as it eventually affects the clinical outcome. In the present study, a few commercially available BGS – β‐tricalcium phosphate (β‐TCP), calcium sulfate, gelatin sponge, and different forms of hydroxyapatite (HAP) were screened for their interactions with MSCs from adipose tissue (ADSCs). It was demonstrated that HAP block favorably supported ADSC viability, morphology, migration, and differentiation compared to other scaffolds. The results strongly suggest the importance of preclinical evaluation of bone scaffolds for their cellular compatibility. Furthermore, the bone regenerative potential of HAP block with ADSCs was evaluated in an ex vivo bone defect model developed using patient derived trabecular bone explants. The explants were cultured for 45 days in vitro and bone formation was assessed by expression of osteogenic genes, ALP secretion, and high resolution computed tomography. Our findings confirmed active bone repair process in ex vivo settings. Addition of ADSCs significantly accelerated the repair process and improved bone microarchitecture. This ex vivo bone defect model can emerge as a viable alternative to animal experimentation and also as a potent tool to evaluate patient specific bone therapeutics under controlled conditions.
Transcranial direct current stimulation of the prefrontal and visual cortices diversely affects early and late perceptual learning
Authors: Wu Di , Zhu Yan , Wang Yifan , Liu Na , Zhang Pan 
Published: July 2024

AbstractBackgroundResearch has shown that visual perceptual learning (VPL) is related to modifying neural activity in higher level decision‐making regions. However, the causal roles of the prefrontal and visual cortexes in VPL are still unclear. Here, we investigated how anodal transcranial direct current stimulation (tDCS) of the prefrontal and visual cortices modulates VPL in the early and later phases and the role of multiple brain regions.MethodsPerceptual learning on the coherent motion direction identification task included early and later stages. After early training, participants needed to continuously train to reach a plateau; once the plateau was reached, participants entered a later stage. Sixty participants were randomly divided into five groups. Regardless of the training at the early and later stages, four groups received multitarget tDCS over the right dorsolateral prefrontal cortex (rDLPFC) and right middle temporal area (rMT), single‐target tDCS over the rDLPFC, and single‐target tDCS over the rMT or sham stimulation, and one group was stimulated at the ipsilateral brain region (i.e., left MT).ResultsCompared with sham stimulation, multitarget and two single‐target tDCS over the rDLPFC or rMT improved posttest performance and accelerated learning during the early period. However, multitarget tDCS and two single‐target tDCS led to equivalent benefits for VPL. Additionally, these beneficial effects were absent when anodal tDCS was applied to the ipsilateral brain region. For the later period, the above facilitating effects on VPL induced by multitarget or single‐target tDCS disappeared.ConclusionsThis study suggested the causal role of the prefrontal and visual cortices in visual motion perceptual learning by anodal tDCS but failed to find greater beneficial effects by simultaneously stimulating the prefrontal and visual cortices. Future research should investigate the functional associations between multiple brain regions to further promote VPL.
Exploring the synergy of problem‐based learning and computational fluid dynamics in university fluid mechanics instruction
Authors: Mora‐Melia Daniel , Gutiérrez‐Bahamondes Jimmy H. , Iglesias‐Rey Pedro L. , Martinez‐Solano Francisco Javier 
Published: July 2024

AbstractRecently, the growing demand for computational fluid dynamics (CFD) skills in industry has highlighted the importance of their incorporation into university academic programs at both the undergraduate and graduate levels. However, many academic programs treat CFD tools as a “black box” in which users simply enter data without fully understanding the inner workings of the software or its application in real‐world situations. Therefore, in the context of a civil engineering program in Chile, a novel approach combining problem‐based learning (PBL) with CFD was introduced into the curriculum of a fluid mechanics course to foster crucial competencies. This comprehensive methodology allows students to acquire fundamental theoretical knowledge that is directly related to specific problems in the classroom. Subsequently, students measure relevant variables in the laboratory, ultimately using these data to build computational models for comparing and contrasting reality with simulations. To gauge the effectiveness and impact of this PBL strategy, both quantitative analysis of student performance and qualitative analysis through surveys were conducted. The results reveal a significant improvement in student performance with the implementation of the PBL methodology, alongside a positive perception among students regarding its implementation. This underscores its benefits for learning, motivation, and academic performance. Additionally, the implementation of PBL was found to enhance both theoretical and practical understanding of concepts related to fluid dynamics and CFD simulation.
MCM8 promotes gastric cancer progression through RPS15A and predicts poor prognosis
Authors: Ding Lixian , Sun Mingjun , Sun Yanyan , Li Jinxing , Zhang Zhicheng , Dang Shuwei , Zhang Jinning , Yang Bang , Dai Youlin , Zhou Qinghao , Zhou Dazhi , Li Encheng , Peng Shuqi , Li Guodong 
Published: July 2024

AbstractBackgroundGastric cancer (GC) is the fourth leading cause of cancer‐related death worldwide. Minichromsome maintenance proteins family member 8 (MCM8) assists DNA repair and DNA replication. MCM8 exerts tumor promotor function in multiple digestive system tumors. MCM8 is also considered as a potential cancer therapeutic target.MethodsBioinformatics methods were used to analyze MCM8 expression and clinicopathological significance. MCM8 expression was detected by immunohistochemistry (IHC) staining and qRT‐PCR. MCM8 functions in GC cell were explored by Celigo cell counting, colony formation, wound‐healing, transwell, and annexin V‐APC staining assays. The target of MCM8 was determined by human gene expression profile microarray. Human phospho‐kinase array kit evaluated changes in key proteins after ribosomal protein S15A (RPS15A) knockdown. MCM8 functions were reassessed in xenograft mouse model. IHC detected related proteins expression in mouse tumor sections.ResultsMCM8 was significantly upregulated and predicted poor prognosis in GC. High expression of MCM8 was positively correlated with lymph node positive (p < 0.001), grade (p < 0.05), AJCC Stage (p < 0.001), pathologic T (p < 0.01), and pathologic N (p < 0.001). MCM8 knockdown inhibited proliferation, migration, and invasion while promoting apoptosis. RPS15A expression decreased significantly after MCM8 knockdown. It was also the only candidate target, which ranked among the top 10 downregulated differentially expressed genes (DEGs) in sh‐MCM8 group. RPS15A was identified as the target of MCM8 in GC. MCM8/RPS15A promoted phosphorylation of P38α, LYN, and p70S6K. Moreover, MCM8 knockdown inhibited tumor growth, RPS15A expression, and phosphorylation of P38α, LYN, and p70S6K in vivo.ConclusionsMCM8 is an oncogene and predicts poor prognosis in GC. MCM8/RPS15A facilitates GC progression.
Genome Mining Leads to the Identification of a Stable and Promiscuous Baeyer‐Villiger Monooxygenase from a Thermophilic Microorganism
Authors: Bunyat‐zada Amir R. , Ducharme Stephan E. , Cleveland Maria E. , Hoffman Esther R. , Howe Graeme W. 
Published: July 2024

AbstractBaeyer–Villiger monooxygenases (BVMOs) are NAD(P)H‐dependent flavoproteins that convert ketones to esters and lactones. While these enzymes offer an appealing alternative to traditional Baeyer‐Villiger oxidations, these proteins tend to be either too unstable or exhibit too narrow of a substrate scope for implementation as industrial biocatalysts. Here, sequence similarity networks were used to search for novel BVMOs that are both stable and promiscuous. Our genome mining led to the identification of an enzyme from Chloroflexota bacterium (strain G233) dubbed ssnBVMO that exhibits i) the highest melting temperature of any naturally sourced BVMO (62.5 °C), ii) a remarkable kinetic stability across a wide range of conditions, similar to those of PAMO and PockeMO, iii) optimal catalysis at 50 °C, and iv) a broad substrate scope that includes linear aliphatic, aromatic, and sterically bulky ketones. Subsequent quantitative assays using propiophenone demonstrated >95 % conversion. Several fusions were also constructed that linked ssnBVMO to a thermostable phosphite dehydrogenase. These fusions can recycle NADPH and catalyze oxidations with sub‐stoichiometric quantities of this expensive cofactor. Characterization of these fusions permitted identification of PTDH−L1‐ssnBVMO as the most promising protein that could have utility as a seed sequence for enzyme engineering campaigns aiming to develop biocatalysts for Baeyer‐Villiger oxidations.
Subdural hematoma due to skull base bone metastasis of epidermal growth factor receptor mutated non‐small cell lung cancer
Authors: Oka Tomohiko , Oda Naohiro , Daido Shigeru , Takata Ichiro 
Published: July 2024

Key Clinical MessageSubdural hematoma due to skull base bone metastasis of lung cancer is rare but are oncological emergency, necessitating prompt identification when a headache develops with the progression of the malignancy.
Successful endoscopic endonasal trans‐sphenoidal resection for pituitary macro adenoma with apoplexy in a twin pregnancy: A case report
Authors: Jha Ujjwal Kumar , Basnet Pragyan , Das Sunil Kumar 
Published: July 2024

Key Clinical MessagePituitary apoplexy is a medical and surgical emergency requiring prompt diagnosis and often urgent treatment to manage symptoms and prevent further complications.AbstractThis report describes the successful management of a 37‐year‐old pregnant woman with a history of pituitary macroadenoma and apoplexy during a twin pregnancy. Presenting with bitemporal vision loss, a common pituitary adenoma symptom, she showed no other alarming signs despite a twin pregnancy. Successful endoscopic resection improved her vision, and postoperative recovery was uneventful. The discussion underscores significance of the diagnostic utility of contrast MRI. The patient's favorable outcome supports endoscopic resection feasibility in pregnant individuals with pituitary apoplexy.
Modular Synthesis of Azines Bearing a Guanidine Core from N‐Heterocyclic Carbene (NHC)‐Derived Selenoureas and Diazo Reagents
Authors: Tonis Efstathios , Tzouras Nikolaos V. , Bracho Pozsoni Nestor , Saab Marina , Bhandary Subhrajyoti , Van Hecke Kristof , Nelson David J. , Nahra Fady , Nolan Steven P. , Vougioukalakis Georgios C. 
Published: July 2024

AbstractN‐Heterocyclic carbene (NHC)‐derived selenoureas comprise a fundamentally important class of NHC derivatives, with key applications in coordination chemistry and the determination of NHC electronic properties. Considering the broad reactivity of chalcogen‐containing compounds, it is surprising to note that the use of NHC‐derived selenoureas as organic synthons remains essentially unexplored. The present contribution introduces a novel, straightforward transformation leading to azines bearing a guanidine moiety, through the reaction of a wide range of NHC‐derived selenoureas with commercially available diazo compounds, in the presence of triphenylphosphine. This transformation offers a new approach to such products, having biological, materials chemistry, and organic synthesis applications. The guanidine‐bearing azines are obtained in excellent yields, with all manipulations taking place in air. A reaction mechanism is proposed, based on both experimental mechanistic findings and density functional theory (DFT) calculations. A one‐pot, multicomponent transesterification reaction between selenoureas, α‐diazoesters, alcohols, and triphenylphosphine was also developed, providing highly functionalized azines.
Catalyst development for the tri‐reforming of methane (TRM) process by integrated singular machine learning models
Authors: de Souza Paulo A. L. , Afzal Raja Muhammad , Camacho Felipe Gomes , Mahinpey Nader 
Published: July 2024

AbstractTri‐reforming of methane (TRM) is a promising technology for the simultaneous production of hydrogen and syngas with high energy efficiency (above 70%). However, catalyst design for TRM is challenging due to complex reaction kinetics and the need for catalyst materials with great stability and activity. Machine learning, particularly artificial neural networks (ANNs), has emerged as a powerful tool in catalyst development for the TRM process. More than 6000 data points were selected to build individual models for each reaction and later coupled into an ensembled model used to make predictions considering TRM experimental conditions. The reaction temperature input parameter was found to be the one with major relative importance (61.4%), contributing the most to changes in the CH4 conversion %. Dry reforming of methane (DRM), steam reforming of methane (SRM), and partial oxidation of methane (POX) models observed errors (RMSE) of 3.44%, 2.20%, 1.61%, respectively, with the ensembled model having a maximum error of 4.48%. The newly devised artificial neural network (ANN) model demonstrates remarkable capability in accurately predicting CH4 conversion for novel catalyst formulations in the TRM process, exhibiting minimal error deviation.
The liquefaction characteristics of poplar under CuMgAlOx catalysis in supercritical methanol
Authors: Li Li , Wang Jiayi , Lian Zihe , Chen Hongtao , Li Jian 
Published: July 2024

AbstractIn an effort to explore the potential energy of biomass and reduce industrial reliance on fossil fuels, this study investigates the liquefaction of poplar wood using supercritical methanol and a CuMgAlOx catalyst. It assesses the composition of liquefied products and performs a comprehensive life‐cycle assessment. Results display that at 360°C, with 1 h of CuMgAlOx, poplar wood's conversion rate reached 98.4%. The proportion of alcoholic compounds in the liquefaction products increased dramatically from 7.99% without a catalyst to 70.81% with it, a rise of 786.23%. Moreover, the process's global warming potential (GWP) intensity is significantly lower at 0.886 gCO2eq/MJ compared to the 93 gCO2eq/MJ from conventional petroleum refining, underscoring its substantial emission reduction potential.
Magnetic adsorbents from co‐pyrolysis of non‐woody biomass and red mud for water decontamination
Authors: Loebsack Griffin , Kang Kang , Yeung Ken K.‐C. , Bartoli Mattia , Berruti Franco , Klinghoffer Naomi B. 
Published: July 2024

AbstractRed mud (RM) and non‐woody biomass are both underutilized resources for renewable composite materials, which could be used in environmental decontamination processes. This study aims to investigate the efficacy of co‐pyrolyzing non‐woody biomass with RM to produce a magnetic biochar composite. When pyrolyzed, RM is reduced to magnetic iron while the non‐woody biochar is responsible for the adsorption of organic compounds. Ibuprofen, acetaminophen, methyl orange, and methylene blue were used as test compounds to investigate the overall adsorptive capacity of the composite and to determine the possible adsorption mechanisms of biochar produced from RM pyrolyzed with switch grass, phragmites, rice husk, and miscanthus. The composite produced from a 1 to 1 mixture of RM and miscanthus showed the highest adsorption capacity with 13.8 and 8.34 mg/g of ibuprofen and acetaminophen adsorbed, respectively, which is attributed to its greater ‐interactions as a result of lower surface oxygen sites. Different ratios of RM to biomass were also tested for the production of the miscanthus composite, where it was found that the 1:2 ratio showed the best overall adsorption with 25.9 mg/g removal of acetaminophen, surpassing the miscanthus biochar's at 17.9 mg/g.
Assembling 2D Ni‐Co nanosheets onto Mo2C Nanorod towards Efficient Electrocatalytic Hydrogen Evolution†
Authors: Zhang Xiao , Diao Yanan , Cai Huizhu , Fang Jiancong , Chen Bingbing , Bi Mingshu , Shi Chuan 
Published: July 2024

Comprehensive SummaryA novel electrocatalyst, Ni‐Co/β‐Mo2C@C, was rationally designed to enhance the efficiency of the hydrogen evolution reaction (HER) in this work. Assembled with two‐dimensional Ni‐Co nanosheets onto Mo2C nanorods coated with a thin carbon shell, the catalyst demonstrates remarkable performance, including low overpotential (η10 = 57 mV) and reduced Tafel slope (63 mV·dec–1) in 0.5 mol·L–1 H2SO4 electrolyte. This innovative design strategy provides abundant active sites and efficient electron/ion transport pathways, effectively shortening reactant diffusion distances and enhancing electrocatalytic activity. Additionally, the carbon shell coating protects the catalyst from etching and agglomeration, ensuring its durability. This work presents a promising approach for engineering highly efficient metal carbide‐based HER catalysts through tailored composition and nanostructure design.
In Situ Liquid Cell Transmission Electron Microscopy Observations of Growth and Anticorrosion Behaviors of AuCl3 Shell on Au Nanobipyramids
Authors: Wei Wei , Sun Jun , Zhang Songtao , Sun Litao , Xu Feng 
Published: July 2024

Comprehensive SummaryDesigning new materials and architectures to maintain activity and stability requires a better understanding on the anticorrosion dynamics of nanoparticles. Under‐coordinated atoms on the surface of nanoparticles can be protected by deposited shells. Real‐time observation on how protective shells grow and play a role is challenging but worthwhile. Here, protective effects of AuCl3 shells on Au nanobipyramids (NBPs) are studied in HAuCl4 aqueous solutions by in‐situ liquid cell transmission electron microscopy (LCTEM). This study is the first to observe the formation of Au‐AuCl3 core‐shell nanostructure and the corresponding anticorrosion behaviors of AuCl3 deposited shell. The presence of CTAB can substantially influence the growth mode and structure of AuCl3 shell, by a direct or indirect way, intervene the dissolution of Au NBP. These growth or dissolution kinetics here revealed at the nanoscale provide insights towards engineering of the surface anticorrosion to pursue Au nanoparticles with improved stability in acidic environment.