bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pure Shift NMR in Continuous Flow
Authors: Bazzoni Margherita , Régheasse Armand , Caytan Elsa , Felpin François‐Xavier , Giraudeau Patrick , Bernard Aurélie , Adams Ralph W. , Morris Gareth A. , Nilsson Mathias , Dumez Jean‐Nicolas 
Published: October 2024

AbstractFlow NMR is an expanding analytical approach with applications that include in‐line analysis for process control and optimisation, and real‐time reaction monitoring. The samples monitored by flow NMR are typically mixtures that yield complex 1D 1H spectra. “Pure shift” NMR is a powerful approach to simplifying 1H NMR spectra, but its standard implementation is not compatible with continuous flow because of interference between sample motion and the position‐dependent spin manipulations that are required in pure shift NMR. Here we show that pure shift NMR spectra can be successfully collected for continuously flowing samples, thanks to an adapted acquisition scheme, robust solvent suppression, and a velocity‐compensation strategy. The resulting method is used to collect ultrahigh resolution reaction monitoring data. Pure shift NMR spectra are expected to benefit many applications of flow NMR.
Regulatory Mechanisms and Synergistic Enhancement of the Diiron YtfE Protein in Nitric Oxide Reduction
Authors: Tsai Ruei‐Fong , Chen Hung‐Ying , Cheng Yang‐Chun , Lo Feng‐Chun , Lu Tsai‐Te , Liaw Wen‐Feng , Chiang Yun‐Wei 
Published: October 2024

AbstractThe diiron‐containing YtfE protein in Escherichia coli is pivotal in counteracting nitrosative stress, a critical barrier to bacterial viability. This study delves into the biochemical complexity governing YtfE's conversion of nitric oxide (NO) to nitrous oxide, a key process for alleviating nitrosative stress. Through site‐directed mutagenesis, we explored YtfE's molecular structure, with a particular focus on two internal transport tunnels important for its activity. Our findings illuminate Tunnel 1 as the primary conduit for substrate transport, regulated by conformational shifts within the N‐terminal domain that enable substrate access to the diiron core in the C‐terminal domain. Tunnel 2 emerges as a secondary, supportive route, activated when Tunnel 1 is compromised. This result challenges a previous model of distinct tunnels for substrate entry and product exit, suggesting both tunnels are capable of transporting substrates and products. Our engineering efforts enhanced the role of Tunnel 2, enabling a synergistic operation with Tunnel 1 and tripling YtfE's enzymatic activity compared to its wild‐type form. This research not only deepens our understanding of YtfE's regulatory mechanism for NO reduction but also introduces a strategy to amplify its enzymatic efficiency. The outcomes offer new ravenues for modulating bacterial stress responses.
Experimental and Computational Studies of Steric Factors in the Isomerization of Internal Alkynes within the Coordination Environment of Half‐Sandwich Metal Complexes
Authors: Korb Marcus , Ghazvini Seyed M. B. H. , Karton Amir , Low Paul J. 
Published: October 2024

AbstractThe isomerization of internal alkynes Ar1C≡CAr2 within the coordination environment of low‐valent half‐sandwich [Ru(dppe)Cp]+ complexes via a 1,2‐migration process affords vinylidene species [Ru{=C=C(Ar1)Ar2}(dppe)Cp]+. The rearrangement reactions of symmetrically and asymmetrically substituted substrates featuring different electron‐donating and ‐withdrawing groups and of varying steric bulk were modelled using density functional theory (DFT), and the conclusions supported by experimental observations. Examination of the reaction pathway and associated activation barriers reveal a high solvent dependency for the generation of the key intermediate species [Ru(dppe)Cp]+ from [RuCl(dppe)Cp] by halide dissociation in the presence of Na+ salts of weakly coordinating anions, with the lattice enthalpy of the NaCl by‐product playing a critical role in the overall thermochemical balance of the reaction. The activation barriers associated with the reaction of [Ru(dppe)Cp]+ with Ar1C≡CAr2, and the relative energies of the alkyne complexes [Ru(η2‐Ar1C≡CAr2)(dppe)Cp]+, are sensitive to the electron density of the alkyne and conformational changes associated with the ‘bend‐back’ of the substrate. The latter differs by up to 66.1 kJ/mol, which in turn impacts the barrier height of the subsequent 1,2‐migration step involved in the rearrangement process and ultimately the overall thermochemical nature of the complete reaction. The relative importance of these factors is evinced by the successful rearrangement of the very sterically congested 1(9‐anthryl)‐2(9‐phenanthryl) acetylene into the fully characterized diaryl vinylidene complex, which was isolated in 89 % yield.
LDL‐C and hs‐CRP Jointly Modify the Effect of Lp(a) on 5‐Year Death in Patients With Percutaneous Coronary Intervention
Authors: Li Jiawen , Yan Kailun , Zhu Pei , Tang Xiaofang , Yang Yuejin , Gao Runlin , Yuan Jinqing , Zhao Xueyan 
Published: October 2024

ABSTRACTBackgroundRecent studies have suggested that adverse events associated with lipoprotein(a) [Lp(a)] might be modified by low‐density lipoprotein cholesterol (LDL‐C) or high‐sensitivity C‐reactive protein (hs‐CRP) levels, but whether LDL‐C and hs‐CRP jointly mediate the outcome of Lp(a) remains unknown in patients with coronary artery disease.Methods and ResultsA prospective study was conducted, enrolling consecutive 10 724 patients with percutaneous coronary intervention (PCI) in 2013. The endpoint event was all‐cause death. A total of 10 000 patients with complete baseline data were finally included. During a median follow‐up of 5.1 years, Lp(a) ≥ 30 mg/dL was an independent risk factor of all‐cause death in the overall population, LDL‐C ≥ 70 mg/dL, and hs‐CRP ≥ 2 mg/L population, respectively. According to concurrent LDL‐C (70 mg/dL) and hs‐CRP (2 mg/L) levels, further analysis revealed that when LDL‐C < 70 mg/dL regardless of hs‐CRP levels, Lp(a) ≥ 30 mg/dL was not an independent predictor of all‐cause death. However, when LDL‐C ≥ 70 mg/dL, Lp(a) ≥ 30 mg/dL was independently associated with a higher risk of all‐cause death in hs‐CRP ≥ 2 mg/L (HR: 1.488, 95% CI: 1.059‒2.092), but not in hs‐CRP < 2 mg/L (HR: 1.303, 95% CI: 0.914‒1.856).ConclusionAmong PCI patients, Lp(a)‐associated outcome was jointly affected by LDL‐C and hs‐CRP. As long as LDL‐C is well controlled, the adverse effects of increased Lp(a) on cardiovascular risk seem to be weakened, and only when LDL‐C and hs‐CRP increase at the same time, elevated Lp(a) is associated with poorer long‐term outcome.
Incorporating Inflammation Biomarker‐Driven Multivariate Predictive Model for Coronary Microcirculatory Dysfunction in Acute Myocardial Infarction Following Emergency Percutaneous Coronary Intervention
Authors: Yao Zhuoya , Ding Bin , Wang Jun , Qian Shaohuan , Song Xilong , Li Yao , Ding Siyu , Wang Hongju , Li Miaonan 
Published: October 2024

ABSTRACTBackgroundDespite patients with successful revascularization as evidenced by angiographic findings, inadequate clinical management of coronary microcirculatory dysfunction (CMD) may result in preventable adverse outcomes. Therefore, it is imperative to use a multimodal data‑driven predictive model for the occurrence of CMD in patients with acute myocardial infarction (AMI) following emergency percutaneous coronary intervention (PCI).MethodsA prospective case−control analysis was conducted on a cohort of 77 patients with AMI who underwent PCI. The most informative predictors were selected for the predictive model through the application of LASSO analysis and multi‐factor logistic regression. The diagnosis of CMD is based on findings from cardiac magnetic resonance (CMR).ResultsBased on the findings from LASSO analysis and multi‐factor logistic regression, variables including sex, neutrophil‐to‐lymphocyte ratio (NLR), Gensini score, and diabetes mellitus were identified as independent predictors for the development of CMD in AMI patients who underwent emergency PCI. The predictive model was evaluated using bootstrap self‐sampling 500 times. The resulting predictive model demonstrated an AUC value of 0.897 (95% CI: 0.827−0.958). The calibration curves exhibited good concordance between the predictions generated by the model and the CMR analysis. Furthermore, decision curve analysis revealed that the predictive model provided valuable clinical benefit in predicting CMD.ConclusionsThe multivariate predictive model, constructed using readily available clinical variables in patients with AMI who underwent PCI, demonstrates satisfactory predictability for identifying comorbid CMD, thereby facilitating the identification of high‐risk patients.
Insights into Molecular Interactions and Biological Effect of Natural Stilbenoids at the TRPA1 Ion Channel
Authors: Saadabadi Atefeh , Rantanen Marja , Marimuthu Parthiban , Koivisto Ari‐Pekka , Eklund Patrik C. , Salo‐Ahen Outi M. H. 
Published: October 2024

AbstractNatural stilbenoids, polyphenolic compounds notably found in Scots pine and Norway spruce, have been shown to exhibit analgesic and anti‐inflammatory effects through the TRPA1 channel, making them promising hits for the development of novel agents to treat inflammatory diseases and pain. In this study, we computationally investigated the putative binding sites of natural stilbenoids at the TRPA1 channel. Specifically, we employed molecular docking and MD simulation approaches to explore three known ligand binding sites at TRPA1. Furthermore, the biological effect of the studied compounds on TRPA1 was assessed in vitro using a fluorescent imaging plate reader (FLIPR™) calcium assay. Our modeling results suggest the stilbenoids exhibit higher affinity to the two agonist binding sites than the antagonistic site. Consistent with this, the in vitro results showed that the stilbenoids act as moderate TRPA1 channel agonists and likely inhibit the channel through a desensitization mechanism rather than act as pure TRPA1 antagonists. Additionally, our bias‐force pulling simulations proposed an additional binding pocket for the natural stilbenoids that is distinct from the known ligand binding sites at TRPA1. The results of the study give useful insights into structure‐based design and development of novel therapeutic TRPA1 modulators.
Aerobic exercise and CogniTIVe functioning in women with breAsT cancEr (ACTIVATE): A randomized controlled trial
Authors: Brunet Jennifer , Sharma Sitara , Zadravec Kendra , Taljaard Monica , LeVasseur Nathalie , Srikanthan Amirrtha , Bland Kelcey A. , Sabri Elham , Collins Barbara , Hayden Sherri , Simmons Christine , Smith Andra M. , Campbell Kristin L. 
Published: October 2024

AbstractBackgroundAs the prevalence of chemotherapy‐related cognitive impairment rises, investigation into treatment options is critical. The objectives of this study were to test the effects of an aerobic exercise intervention initiated during chemotherapy compared to usual care (wait list control condition) on (1) objectively measured cognitive function and self‐reported cognitive function, as well as on (2) the impact of cognitive impairment on quality of life (QOL) postintervention (commensurate with chemotherapy completion).MethodsThe Aerobic exercise and CogniTIVe functioning in women with breAsT cancEr (ACTIVATE) trial was a two‐arm, two‐center randomized controlled trial conducted in Ottawa and Vancouver (Canada). Fifty‐seven women (Mage, 48.8 ± 10 years) diagnosed with stage I–III breast cancer and awaiting chemotherapy were randomized to aerobic exercise initiated with chemotherapy (nEX = 28) or usual care during chemotherapy with aerobic exercise after chemotherapy completion (nUC = 29). The intervention lasted 12–24 weeks and consisted of supervised aerobic training and at‐home exercise. The primary outcome was objective cognitive function measured via 13 neuropsychological tests (standardized to M ± SD, 0 ± 1); secondary outcomes of self‐reported cognitive function and its impact on QOL were assessed via questionnaires. Data collected pre‐ and postintervention (the primary end point) were analyzed.ResultsAlthough no significant differences between groups were found for objective cognitive function outcomes postintervention after accounting for multiple testing, four of six self‐reported cognitive function outcomes showed significant differences favoring the aerobic exercise group.ConclusionsAmong women initiating chemotherapy for breast cancer, aerobic exercise did not result in significant differences in objective cognitive function postintervention after chemotherapy completion; however, the results do support the use of this intervention for improving self‐reported cognitive function and its impact on QOL.
Hydrogen Evolution Reaction of Electrodeposited Ni‐W Films in Acidic Medium and Performance Optimization Using Machine Learning
Authors: de Paz‐Castany Roger , Eiler Konrad , Nicolenco Aliona , Lekka Maria , García‐Lecina Eva , Brunin Guillaume , Rignanese Gian‐Marco , Waroquiers David , Collet Thomas , Hubin Annick , Pellicer Eva 
Published: October 2024

AbstractNi−W alloy films were electrodeposited from a gluconate aqueous bath at pH=5.0, at varying current densities and temperatures. While there is little to no difference in composition, i. e., all films possess ~12 at.% W, their activity at hydrogen evolution reaction (HER) in acidic medium is greatly influenced by differences in surface morphology. The kinetics of HER in 0.5 M H2SO4 indicates that the best performing film was obtained at a current density of −4.8 mA/cm2 and 50 °C. The Tafel slopes (b) and the overpotentials at a geometric current density of −10 mA/cm2 (η10) obtained for 200 cycles of linear sweep voltammetry (LSV) from a set of films deposited using different parameters were fed into a machine learning algorithm to predict optimum deposition conditions to minimize b, η10, and the degradation of samples over time. The optimum deposition conditions predicted by the machine learning model led to the electrodeposition of Ni−W films with superior performance, exhibiting b of 33–45 mV/dec and an η10 of 0.09–0.10 V after 200 LSVs.
Bifunctional MoNi4/Nickel Foam Electro‐Catalyst for Ultra‐Efficient Oxidation of High‐Concentration 5‐Hydroxymethylfurfural and HER
Authors: Liu Hao , Xia Jie , Liu Xiaohui , Hu Yongfeng , Shakouri Mohsen , Wu Haoran , Zhu Minghui , Guo Yong , Chen Jingye , Wang Haifeng , Wang Yanqin 
Published: October 2024

AbstractThe electro‐catalytic oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) provides an attractive route to produce 2, 5‐furandicarboxylic acid (FDCA) as a substitute for terephthalic acid used in the plastics industry. Herein, we prepared MoNi4 alloy on nickel foam (NF) using a simple hydrothermal method followed by hydrogen reduction. Applied MoNi4/NF as the bifunctional electrodes for the electro‐catalytic HMF oxidation reaction (HMFOR) and HER, 98.7 % FDCA yield and 97.3 % Faraday efficiency (FE) can be achieved even with HMF concentration as high as 200 mM. Notably, no obvious deactivation was observed after ten consecutive cycles. In‐situ Raman, XANES and EXAFS results show that the nickel species of MoNi4/NF is first oxidized to Ni3+ species under the applied voltage, and after undergoing the electro‐catalytic HMFOR, then reduced to Ni2−δ state (with a valence between 0 and +2) due to the electron‐donating effect from Mo. MoNi4/NF with more than one electron transfer between Ni3+ and Ni2−δ during the HMFOR enables it to have excellent electro‐catalytic oxidation ability toward HMFOR.
Unleashing the Synergistic Potential of 2D‐2D Nanosheet Based S‐Scheme Heterojunction: Cooperative Boosting of CO2 Reduction to Solar Fuel and Biomass Valorization
Authors: Dhingra Shivali , Jain Ayushi , Jaryal Arpna , Bera Chandan , Kailasam Kamalakannan 
Published: October 2024

AbstractHarnessing inexhaustible solar energy for CO2 valorization is a substantial step toward achieving a carbon‐neutral energy cycle. However, CO2 conversion often exhibits slow kinetics, necessitating the utilization of sacrificial agents making the process economically unfeasible. In the ongoing quest for sustainable and economically feasible CO2 valorization, herein the photoreduction of CO2 to CO coupled with biomass‐based alcohol oxidation to fine chemicals is reported via Bi2WO6/g‐C3N4 (BWO/g‐CN) 2D‐2D nanosheet based S‐scheme heterojunction. Importantly, BWO/g‐CN‐60 exhibits highest photocatalytic activity with CO production rate of 6.87 mmol g−1 h−1, accompanied by >98 % selectivity and selective oxidation of veratryl alcohol to veratraldehyde, with notable yield of 42 % in 6 h under simulated solar light. The apparent quantum yield (AQY) of 14.3 % is achieved for CO production at the wavelength of 420 nm. Additionally, the formed heterostructure results in enhanced charge separation and accelerated charge transfer kinetics as validated by PL, EIS, and photocurrent studies. EPR, 13CO2 labeling, DFT studies, and various controlled experiments provided a deeper insight into the mechanism of underlying photo‐redox process. Thus, the current study presents a sustainable paradigm for CO2 mitigation by converting it into solar fuel, while synergistically producing the fine chemicals through effectively harnessing the full potential of charge carriers.
Ni‐Metalized Covalent Organic Cage as a Photocatalyst for Selective Photoreduction of CO2 to CO
Authors: Miao Rongbin , Niu Qing , Li Liuyi , Yu Yan 
Published: October 2024

AbstractMetal complex‐based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2‐to‐CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis.
RuCo@C Hollow Nanoprisms Derived from ZIF‐67 for Enhanced Hydrogen and Oxygen Evolution Reactions
Authors: Salah Abdulwahab , Ren Hong‐Da , Al‐Ansi Nabilah , Al‐Salihy Adel , Mahyoub Samah A. , Qaraah Fahim A. , Hezam Abdo , Drmosh Qasem A. 
Published: October 2024

AbstractZeolitic imidazolate frameworks (ZIFs) are commonly used to create complex hollow structures for energy applications. This study presents a simple method to produce a novel hollow nanoprism Co@C hierarchical composite from ZIF‐67 through high‐temperature treatment at 800 °C. This composite serves as a platform for Ru nanoparticle deposition, forming RuCo@C hollow nanoprism (RuCo@C HNP). As an electrocatalyst in 1 M KOH, RuCo@C HNP exhibits excellent hydrogen evolution reaction (HER) performance, with a low overpotential of 32 mV to reach 10 mA cm−2, a Tafel slope of 39.67 mV dec−1, a high turnover frequency (TOF) of 3.83 s−1 at η200, and stable performance over 50 h. It also achieves a low η10 of 266 mV for the oxygen evolution reaction (OER) with a Tafel slope of 45.22 mV dec−1. Density functional theory (DFT) calculations reveal that Ru doping in Ni/Co maintains a low water dissociation barrier, reduces the energy barrier for the OER rate‐determining step, and creates active sites for H*, enhancing adsorption/desorption abilities. These results are attributed to the synergy between Co and Ru and the hollow prism structure′s increased surface area. This method for synthesizing hollow structures using ZIF composites shows promise for applications in the energy sector.
Distillery‐Waste‐Derived C−SiO2 Catalyst Support Reinforces Phenol Adsorption and Selective Hydrogenation
Authors: Xu Xiuzhen , Feng Weiqin , Liu Xudong , Jiang Zhicheng , Shi Bi 
Published: October 2024

AbstractSelective hydrogenation of lignin‐derived phenolic compounds is an essential process for developing the sustainable chemical industry and reducing dependence on nonrenewable resources. Herein, a composite C−SiO2 material (DGC) was prepared via the stepwise pyrolysis and steam activation of the distiller′s grains, a fermentation solid waste from the Chinese liquor industry. After Ru loading, Ru/DGC was used for the catalytic hydrogenation of phenol to cyclohexanol. Steam activation remarkably increased the hydrophilicity and specific surface area of DGC, introducing oxygen‐containing functional groups on the surface of DGC, thereby promoting the adsorption of Ru3+ and phenol. Additionally, the large specific surface area facilitated the dispersion of the active metal. Furthermore, the steam activation of DGC promoted the graphitization of the carbon matrix and formed Si−H/Si−OH bonds on the SiO2 surface. The benzene ring of phenol interacted with the carbon matrix via π–π stacking, and the hydroxyl group of phenol interacted with SiO2 via hydrogen bonding. The synergistic interactions of phenol at the C−SiO2 interface enhanced phenol adsorption to promote the hydrogenation. Consequently, 100 % of phenol was hydrogenated to cyclohexanol at 60 °C within 30 min. Furthermore, the optimized catalyst exhibited high activity for phenol hydrogenation even after four reuse cycles. The outstanding stability of the catalyst and its requirement for mild reaction conditions favor its large‐scale industrial applications.
Prospective associations of interleukin‐6 and APOE allele with cognitive decline in biracial community‐dwelling older adults: The Chicago Health and Aging Project (CHAP)
Authors: Ng Ted K. S. , Beck Todd , Desai Pankaja , Dhana Klodian , Wilson Robert S. , Evans Denis A. , Rajan Kumar B. 
Published: October 2024

AbstractINTRODUCTIONIt is unclear whether inflammation, that is, high interleukin‐6 (IL‐6) levels, and genetic risk, that is, apolipoprotein E (APOE) ε4 allele, have a compounding effect on cognitive decline (CD).METHODSWe analyzed a subset of participants from the longitudinal cohort study, Chicago Health and Aging Project, comprising 1120 biracial community‐dwelling older adults (60% Black and 62% women), and mean follow‐up = 6.4 years. We ran adjusted mixed‐effects models on2 longitudinal CD.RESULTSIn APOE ε4 carriers, higher serum IL‐6 was not associated with the rate of CD (β = –0.0091 [standard deviation (SD) = 0.0165, p = 0.5800]). Conversely, in non‐ε4 carriers, compared to the lower tertile, those with the upper tertile of serum IL‐6 levels experienced significantly accelerated CD (β = –0.0257 [SD = 0.0084, p = 0.0023]).DISCUSSIONEven without the largest genetic risk factor for late‐onset Alzheimer's disease/Alzheimer's disease and related dementias (AD/ADRD), elevated serum IL‐6 still accelerate the rate of CD in non‐APOE ε4 carriers. Hence, interventions ameliorating inflammation may prevent AD/ADRD.Highlights
Interleukin‐6 (IL‐6) and the apolipoprotein E (APOE) ε4 allele have been separately associated with an increased risk for cognitive decline, but their interaction remains unclear.
In ε4 carriers, IL‐6 was not associated with cognitive decline. However, even without the biggest genetic risk factor for Alzheimer's disease (AD), that is, APOE ε4, elevated serum IL‐6 still could confer accelerated rate of cognitive decline, with a detrimental effect half of that imposed by APOE ε4 alone.
We found no racial differences in these associations.
These findings contribute complementary evidence on non–APOE ε4‐dependent and non‐AD biological pathways through which cognitive decline can still be accelerated in non‐APOE ε4 carriers and highlight a specific subgroup of older adults who are at a higher risk of AD and thus may benefit from anti‐inflammatory interventions.