bluuebunny/crossref_metadata_2025_split huggingface dataset:
Digital Twin‐Assisted Degradation Diagnosis and Quantification of NMC Battery Aging Effects During Fast Charging
Authors: Guo Wendi , Sun Zhongchao , Guo Jia , Li Yaqi , Vilsen Søren Byg , Stroe Daniel Ioan 
Published: June 2024

AbstractA comprehensive understanding of aging mechanisms and degradation diagnosis under fast charging in battery electric vehicles is needed. However, there is a lack of tools to capture both macroscopic and microscopic parameters, still focusing on experiment results analysis. To get a comprehensive degradation insight for improved service life, this study explores aging mechanisms in LiNi0.5Co0.2Mn0.3O2 graphite batteries under different fast charging conditions (0.6C to 2C) for up to 1000 equivalent full cycles (EFCs). An improved digital twin is used to quantify aging effects and identify aging modes, combining electrochemical techniques with post‐mortem analysis for assessing chemical and structural degradation. After 1000 EFCs, the dominant aging modes are loss of active material (LAM) in the negative electrode and loss of lithium inventory (LLI), surpassing LAM in the positive electrode. Compared to constant current charging, multistep fast charging effectively mitigates Li plating effects and graphite cracking, resulting in a 13% reduction in LAM. Additionally, optimizing the depth of discharge leads to at least 4% reductions in LLI and 16% in LAMpos. This study proves the electrochemical digital twin's potential for quantifying aging effects and serves as a basis for future physics‐informed machine learning to predict aging behavior and modes.
Preoperative geniohyoid muscle mass in esophageal cancer patients is associated with swallowing function after esophagectomy
Authors: Kawata Sanshiro , Hiramatsu Yoshihiro , Honke Junko , Murakami Tomohiro , Booka Eisuke , Matsumoto Tomohiro , Morita Yoshifumi , Kikuchi Hirotoshi , Yamauchi Katsuya , Takeuchi Hiroya 
Published: June 2024

AbstractAimDysphagia often develops after esophagectomy. The geniohyoid muscle is involved in swallowing movements, but its significance in esophagectomy patients remains unclear. We investigated the relationship of preoperative geniohyoid muscle mass with post‐esophagectomy swallowing function.MethodsWe retrospectively analyzed 114 patients who underwent esophagectomy and gastric conduit reconstruction for esophageal malignancy. We evaluated preoperative geniohyoid muscle sagittal cross‐sectional areas (cm2) using computed tomography. Median values for each sex were considered as cutoff values. Dysphagia severity was assessed using the Penetration–Aspiration Scale (PAS) during video‐fluoroscopic swallowing studies performed 7–10 days postoperatively.ResultsThe cross‐sectional area was significantly larger in males than in females (3.2 ± 0.7 vs. 2.4 ± 0.5, p < 0.01: median in males: 3.2 cm2, and in females: 2.3 cm2). These values were used to define high and low cross‐sectional area groups. The cross‐sectional area correlated positively with grip strength (correlation coefficient (CC) = 0.530) and skeletal muscle index (CC = 0.541). Transthyretin levels (22.4 ± 6.8 vs. 25.4 ± 5.5, p = 0.03) and cross‐sectional area (2.6 ± 0.7 vs. 3.2 ± 0.8, p < 0.01) were significantly lower in patients with (PAS score ≥6; 20%) than in those without aspiration during fluoroscopic swallowing studies. Recurrent laryngeal nerve palsy was significantly more frequent in those with than in those without aspiration during fluoroscopic studies (22% vs. 5%, p = 0.03). In the multivariate analysis, low cross‐sectional area and recurrent laryngeal nerve palsy were both independent risk factors for aspiration during swallowing studies (odds ratio = 3.6, p = 0.03 and odds ratio = 6.6, p = 0.02, respectively).ConclusionPreoperative geniohyoid muscle mass, evaluated using neck computed tomography, can predict dysphagia after esophagectomy.
Hereditary chronic neutrophilic leukemia in a four‐generation family without transformation to acute leukemia
Authors: Lance Amanda , Chiad Zane , Seegers Sara L. , Paschall Sarah‐Catherine , Drummond Kendra , Steuerwald Nury M. , Yang Hsih‐Te , Chen Jenny , Voorhees Peter M. , Avalos Belinda R. , Druhan Lawrence J. 
Published: June 2024

AbstractChronic neutrophilic leukemia (CNL) is a rare myeloproliferative neoplasm (MPN) characterized by peripheral blood neutrophilia, marrow granulocyte hyperplasia, hepatosplenomegaly, and driver mutations in the colony‐stimulating factor 3 receptor (CSF3R). Designation of activating CSF3R mutations as a defining genomic abnormality for CNL has led to increased recognition of the disease. However, the natural history of CNL remains poorly understood with most patients reported being of older age, lacking germline data, and having poor survival, in part due to transformation to acute leukemia. CSF3R driver mutations in most patients with CNL have been reported to be acquired, although rare cases of germline mutations have been described. Here, we report the largest pedigree to date with familial CNL, spanning four generations with affected family members ranging in age from 4 to 53 years, none of whom have transformed to acute leukemia. A heterozygous T618I CSF3R mutation was identified in peripheral blood and mesenchymal stromal cells from the proband and in all affected living family members, while the unaffected family members tested were homozygous wild type. We show that the T618I mutation also confers a survival advantage to neutrophils in an MCL1‐dependent manner. Collectively, these data provide additional insights into the natural history of familial CNL arising from T618I CSF3R mutations and suggest that enhanced neutrophil survival also contributes to the high neutrophil count observed in patients with CNL.
An open‐label study of belumosudil, a selective ROCK2 inhibitor, as second or subsequent line of therapy for steroid‐dependent/steroid‐resistant chronic GVHD
Authors: Inamoto Yoshihiro , Kato Koji , Kawakita Toshiro , Onishi Yasushi , Matsuoka Ken‐ichi , Shiratori Soichi , Ikegame Kazuhiro , Hiramoto Nobuhiro , Toyosaki Masako , Katayama Yuta , Murayama Shun , Sasagawa Yuji , Maeda Yoshinobu , Hatake Kiyohiko , Teshima Takanori 
Published: June 2024

AbstractBelumosudil mesylate is a selective Rho‐associated coiled‐coil kinase 2 inhibitor with immunomodulatory and antifibrosis effects. This multicenter, open‐label, single‐arm study evaluated belumosudil 200 mg once daily as second or subsequent line of therapy (LOT) in 21 Japanese patients ≥12 years of age with steroid‐dependent/steroid‐resistant chronic graft‐versus‐host disease (cGVHD). The primary endpoint of best overall response rate (ORR) at 24 weeks after enrollment of the last patient was 85.7% (95% confidence interval [CI]: 63.7–97.0), and the lower limit of the 95% CI exceeded the pre‐defined threshold of 25%. The Kaplan–Meier estimate of duration of response rate at 24 weeks was 75% (95% CI: 46–90); 13/18 responders (72.2%) had a sustained response for ≥20 weeks. The median time to response was 4.1 weeks (range 3.90–8.10); ORR was 47.6% at 4 weeks and 75.0% at 24 weeks; best ORR was 80% for joints/fascia, 66.7% for the mouth, and 54.5% for skin. Overall, 57.1% of patients had clinically meaningful symptom improvement at least once; the median duration of symptom improvement was 22.2 weeks (range 4.0–51.3). Corticosteroid dose reductions were recorded for 57.1% of patients. Median failure‐free and overall survival were not reached. Treatment‐emergent adverse events occurred in 85.7% of patients (most commonly diarrhea, 19.0%), of which 38.1% were drug‐related. There were no drug‐related discontinuations or deaths. In summary, belumosudil 200 mg once daily as second or subsequent LOT in Japanese patients with steroid‐dependent/steroid‐resistant cGVHD was effective, with no new safety concerns.
A Quantum‐Chemical Study of the Mechanism of 1‐Azadienes Formation from Aldimines and Arylacetylenes in the KOtBu/DMSO Superbasic Medium
Authors: Orel Vladimir B. , Zubarev Andrey A. , Vitkovskaya Nadezhda M. , Schmidt Elena Yu. , Trofimov Boris A. 
Published: June 2024

AbstractThe mechanism of 1‐azadienes formation from aldimines and arylacetylenes in the KOtBu/DMSO superbasic medium has been explored theoretically using a DFT approach [B2PLYP(D2)/6‐311+G(d,p)//B3LYP/6‐31+G(d)] and a sophisticated model taking the potassium tert‐butoxide and the nearest solvation shell of the potassium cation explicitly into account. The main focus is placed on (i) a detailed analysis of the kinetic and thermodynamic characteristics of the isomerization of intermediate propargylamine into 1‐azadienes, and (ii) the factors determining the isomeric composition of 1‐azadienes with different substituents in the starting arylaldimines and arylacetylenes. Our findings clearly indicate that the mild experimental conditions of 1‐azadienes formation are accounted for by the relatively small activation barrier (ΔG≠≤16.2 kcal/mol) of the limiting step (ethynylation of aldimine with arylacetylenes). The rapid isomerization of propargylamine to 1‐azadiene is found to be due to low activation barriers (ΔG≠≤9.1 kcal/mol) related to the protons transfer. The isomeric composition in the case of various substituted 1‐azadienes is determined solely by the difference in the thermodynamic stability of the 1E,2E‐ and 1Z,2E‐forms.
Contemporary practice patterns for chronic rhinosinusitis with nasal polyps
Authors: Ayoub Noel F. , Sbeih Firas , Bleier Benjamin S. 
Published: June 2024

Key points
Data on current practice patterns for the management of chronic rhinosinusitis with nasal polyps, including which medications are deemed by otolaryngologists to better manage patient symptoms, are limited.
This study demonstrated that contemporary practice patterns are largely consistent with published clinical consensus statements.
Off‐label nasal steroid irrigations and dupilumab are the most commonly used topical and systemic therapies for chronic rhinosinusitis with nasal polyps, respectively.
Suppression of eEF2 phosphorylation alleviates synaptic failure and cognitive deficits in mouse models of Down syndrome
Authors: Wang Xin , Yang Qian , Zhou Xueyan , Keene C. Dirk , Ryazanov Alexey G. , Ma Tao 
Published: June 2024

AbstractINTRODUCTIONCognitive impairment is a core feature of Down syndrome (DS), and the underlying neurobiological mechanisms remain unclear. Translation dysregulation is linked to multiple neurological disorders characterized by cognitive impairments. Phosphorylation of the translational factor eukaryotic elongation factor 2 (eEF2) by its kinase eEF2K results in inhibition of general protein synthesis.METHODSWe used genetic and pharmacological methods to suppress eEF2K in two lines of DS mouse models. We further applied multiple approaches to evaluate the effects of eEF2K inhibition on DS pathophysiology.RESULTSWe found that eEF2K signaling was overactive in the brain of patients with DS and DS mouse models. Inhibition of eEF2 phosphorylation through suppression of eEF2K in DS model mice improved multiple aspects of DS‐associated pathophysiology including de novo protein synthesis deficiency, synaptic morphological defects, long‐term synaptic plasticity failure, and cognitive impairments.DISCUSSIONOur data suggested that eEF2K signaling dysregulation mediates DS‐associated synaptic and cognitive impairments.Highlights
Phosphorylation of the translational factor eukaryotic elongation factor 2 (eEF2) is increased in the Down syndrome (DS) brain.
Suppression of the eEF2 kinase (eEF2K) alleviates cognitive deficits in DS models.
Suppression of eEF2K improves synaptic dysregulation in DS models.
Cognitive and synaptic impairments in DS models are rescued by eEF2K inhibitors.
Allenamides as a Powerful Tool to Incorporate Diversity: Thia‐Michael Lipidation of Semisynthetic Peptides and Access to β‐Keto Amides
Authors: Na Tae‐Ung , Sander Veronika , Davidson Alan J. , Lin Rolland , Hermant Yann O. , Hardie Boys Madeleine T. , Pletzer Daniel , Campbell Georgia , Ferguson Scott A. , Cook Gregory M. , Allison Jane R. , Brimble Margaret A. , Northrop Brian H. , Cameron Alan J. 
Published: June 2024

AbstractLipopeptides are an important class of biomolecules for drug development. Compared with conventional acylation, a chemoselective lipidation strategy offers a more efficient strategy for late‐stage structural derivatisation of a peptide scaffold. It provides access to chemically diverse compounds possessing intriguing and non‐native moieties. Utilising an allenamide, we report the first semisynthesis of antimicrobial lipopeptides leveraging a highly efficient thia‐Michael addition of chemically diverse lipophilic thiols. Using chemoenzymatically prepared polymyxin B nonapeptide (PMBN) as a model scaffold, an optimised allenamide‐mediated thia‐Michael addition effected rapid and near quantitative lipidation, affording vinyl sulfide‐linked lipopeptide derivatives. Harnessing the utility of this new methodology, 22 lipophilic thiols of unprecedented chemical diversity were introduced to the PMBN framework. These included alkyl thiols, substituted aromatic thiols, heterocyclic thiols and those bearing additional functional groups (e.g., amines), ultimately yielding analogues with potent Gram‐negative antimicrobial activity and substantially attenuated nephrotoxicity. Furthermore, we report facile routes to transform the allenamide into a β‐keto amide on unprotected peptides, offering a powerful “jack‐of‐all‐trades” synthetic intermediate to enable further peptide modification.
Interface Engineering via Manipulating Solvation Chemistry for Liquid Lithium‐Ion Batteries Operated≥100 °C
Authors: Gao Hongjing , Chen Yufang , Teng Tao , Yun Xiaoru , Lu Di , Zhou Guangmin , Zhao Yun , Li Baohua , Zhou Xing , Zheng Chunman , Xiao Peitao 
Published: June 2024

AbstractHigh‐performance and temperature‐resistant lithium‐ion batteries (LIBs), which are able to operate at elevated temperatures (i.e., >60 °C) are highly demanded in various fields, especially in military or aerospace exploration. However, their applications were largely impeded by the poor electrochemical performance and unsatisfying safety issues, which were induced by the severe side reactions between electrolytes and electrodes at high temperatures. Herein, with the synergetic effects of solvation chemistry and functional additive in the elaborately designed weakly solvating electrolyte, a unique robust organic/inorganic hetero‐interphase, composed of gradient F, B‐rich inorganic components and homogeneously distributed Si‐rich organic components, was successfully constructed on both cathodes and anodes, which would effectively inhibit the constant decomposition of electrolytes and dissolution of transition metal ions, thus highly enhancing the high‐temperature electrochemical performance. As a result, both cathodes and anodes, without compromising their low‐temperature performance, can operate at temperatures ≥100 °C, with excellent capacity retentions of 96.1 % after 500 cycles and 93.5 % after ≥200 cycles, respectively, at 80 °C. Ah‐level LiCoO2||graphite full cells with a cut‐off voltage of 4.3 V also exhibited superior temperature‐resistance with a capacity retention of 89.9 % at temperature as high as 120 °C. Moreover, the fully charged pouch cells exhibited highly enhanced safety, demonstrating their potentials in practical applications at ultrahigh temperatures.
Aggregation of One‐Dimensional Wires: The Case of Long Oligoynes
Authors: Gordillo‐Gámez Fernando , Gao Yueze , Aragó Juan , Ortí Enrique , Aranda Daniel , Kertesz Miklos , Tykwinski Rik R. , Casado Juan 
Published: June 2024

AbstractWe show an unexpected aggregation phenomenon of a long oligoyne (Py[16]) with 16 contiguous triple bonds and endcapped with bulky 3,5‐bi(3,5‐bis‐tert‐butylphenyl)pyridine groups. Aggregation of 1D π‐conjugated oligoyne chains is rare given the minimal π–π intermolecular interactions as well as its flexibility that works against self‐assembly. In dilute solutions, the reversible aggregation of Py[16] initiates at low temperature in the range of 140–180 K, and is not observed for shorter oligoynes in this series. Cryogenic UV/Vis electronic absorption spectra and vibrational Raman spectra with different laser wavelength lines tuning from in‐resonance to off‐resonance conditions have been used to extract the vibrational features characterizing the monomer and aggregate species. Theoretical calculations complement the spectroscopic findings.
Function Switch of a Fungal Sesterterpene Synthase through Molecular Dynamics Simulation Assisted Alteration of an Aromatic Residue Cluster in the Active Pocket of PfNS
Authors: Zhang Weiyan , Wang Xinye , Zhu Guoliang , Zhu Bin , Peng Kaitong , Hsiang Tom , Zhang Lixin , Liu Xueting 
Published: June 2024

AbstractTerpene synthases (TPSs) play pivotal roles in generating diverse terpenoids through complex cyclization pathways. Protein engineering of TPSs offers a crucial approach to expanding terpene diversity. However, significant potential remains untapped due to limited understanding of the structure‐function relationships of TPSs. In this investigation, using a joint approach of molecular dynamics simulations‐assisted engineering and site‐directed mutagenesis, we manipulated the aromatic residue cluster (ARC) of a bifunctional terpene synthase (BFTPS), Pestalotiopsis fici nigtetraene synthase (PfNS). This led to the discovery of previously unreported catalytic functions yielding different cyclization patterns of sesterterpenes. Specifically, a quadruple variant (F89A/Y113F/W193L/T194W) completely altered PfNS′s function, converting it from producing the bicyclic sesterterpene nigtetraene to the tricyclic ophiobolin F. Additionally, analysis of catalytic profiles by double, triple, and quadruple variants demonstrated that the ARC functions as a switch, unprecedently redirecting the production of 5/11 bicyclic (Type B) sesterterpenes to 5/15 bicyclic (Type A) ones. Molecular dynamics simulations and theozyme calculations further elucidated that, in addition to cation‐π interactions, C−H⋅⋅⋅π interactions also play a key role in the cyclization patterns. This study offers a feasible strategy in protein engineering of TPSs for various industrial applications.
Accelerating the Discovery of Oxygen Reduction Electrocatalysts: High‐Throughput Screening of Element Combinations in Pt‐Based High‐Entropy Alloys
Authors: Pan Yiyang , Shan Xiangyi , Cai Furong , Gao Han , Xu Jianan , Zhou Min 
Published: June 2024

AbstractThe vast number of element combinations and the explosive growth of composition space pose significant challenges to the development of high‐entropy alloys (HEAs). Here, we propose a procedural research method aimed at accelerating the discovery of efficient electrocatalysts for oxygen reduction reaction (ORR) based on Pt‐based quinary HEAs. The method begins with an element library provided by a large language model (LLM), combined with microscale precursor printing and pulse high‐temperature synthesis techniques to prepare multi‐element combination HEA array in one step. Through high‐throughput measurement using scanning electrochemical cell microscopy (SECCM), precise identification of highly active HEA element combinations and exploration of composition space for a specific combination are achieved. Advantageous element combinations are further validated in practical electrocatalytic evaluations. The contributions of individual element sites and the synergistic effects among elements of such HEAs in enhancing reaction activity are elucidated via density functional theory (DFT) calculations. This method integrates high‐throughput experiments, practical catalyst validation, and DFT calculations, providing a new pathway for accelerating the discovery of efficient multi‐element materials in the field of energy catalysis.
exo‐6b2‐Methyl‐Substituted Pentabenzocorannulene: Synthesis, Structural Analysis, and Properties
Authors: Wu Guan‐Yi , Huang Chun‐Lin , Kang Hao‐Wen , Ou Wei‐Ting , Ho Yeu‐Shiuan , Cheng Mu‐Jeng , Wu Yao‐Ting 
Published: June 2024

Abstractexo‐6b2‐Methyl‐substituted pentabenzocorannulene (exo‐PBC‐Me) was synthesized by the palladium‐catalyzed cyclization of 1,2,3‐triaryl‐1H‐cyclopenta[l]phenanthrene. Its bowl‐shaped geometry with an sp3 carbon atom in the backbone and a methyl group located at the convex (exo) face was verified by X‐ray crystallography. According to DFT calculations, the observed conformer is energetically more favorable than the endo one by 39.9 kcal/mol. Compared to the nitrogen‐doped analogs with intact π‐conjugated backbones (see the main text), exo‐PBC‐Me displayed a deeper bowl depth (avg. 1.93 Å), redshifted and broader absorption (250–620 nm) and emission (from 585 to more than 850 nm) bands and a smaller optical HOMO–LUMO gap (2.01 eV). exo‐PBC‐Me formed polar crystals where all bowl‐in‐bowl stacking with close π ⋅ ⋅ ⋅ π contacts is arranged unidirectionally, providing the potential for applications as organic semiconductors and pyroelectric materials. This unusual structural feature, molecular packing, and properties are most likely associated with the assistance of the methyl group and the sp3 carbon atom in the backbone.
Cucurbit[8]uril‐Mediated Supramolecular Heterodimerisation and Photoinduced [2+2] Heterocycloaddition to Generate Unexpected [2]Rotaxanes
Authors: Zhang Shu , Zhang Liyan , Chen Aocheng , An Yi , Chen Xu‐Man , Yang Hong , Li Quan 
Published: June 2024

AbstractIn contrast to the self‐assembly of homosupramolecules, the self‐assembly of heterosupramolecules is more challenging and significant in various fields. Herein, we design and investigate a cucurbit[8]uril‐mediated heterodimerisation based on an arene‐fluoroarene strategy. Furthermore, the heteroternary complex is found to be able to undergo a photoinduced [2+2] heterocycloaddition, resulting in the formation of an unexpected [2]rotaxane. This work demonstrates a novel supramolecular heterodimerisation system that not only contributes to the development of photoisomerisation systems, but also enriches synthetic methods for mechanically interlocked molecules.
5‐(4′‐carboxylphenoxy) isophthalic acid and 1, 4‐bis(1‐imidazolyl)benzene appended Co(II)‐based MOF as efficient photocatalyst for nitrofurantoin degradation
Authors: Wang Jia‐Jia , Pu Cui‐Ying , Lu Lu , Muddassir Mohd. , Srivastava Shreya , Jayswal Madhav Raj , Wang Xiaoxiong , Kumar Abhinav 
Published: June 2024

A new Cobalt(II)‐based metal–organic framework (MOF) with composition [Co2(μ2‐OH)(L)(bib)·H2O·2DMA]n (1) (H3L = 5‐[4′‐carboxylphenoxy] isophthalic acid, bib = 1, 4‐bis[1‐imidazolyl]benzene, DMA = dimethylacetamide) has been solvothermally synthesized and characterized. The MOF exhibits unprecedented topology with Schläfli symbol (43)2(4.66.1686) and display optical band gap of 3.68 eV and hence utilized as photocatalyst to photodegrade antibiotics such as metronidazole, tinidazole, nitrofurantoin, and dimetridazole. Among these antibiotics, it displays exceptional photocatalytic degradation of nitrofurantoin. Additional studies suggest that at pH 5 and 5 mg/L dosage of 1, 99.66% of nitrofurantoin decomposes at its 40 ppm concentration. Further, mechanistic pathway for light‐driven nitrofurantoin decomposition has been explored by utilizing experimental, namely, radical trapping experiments and computational techniques employing density of states and Hirshfeld surface analyses.