bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineering Ruthenium Species on Metal–organic Frameworks for Water Electrolysis at Industrial Current Densities
Authors: Li Dequan , Chen Mingpeng , Liu Di , Shen Congcong , Sun Huachuan , Zhang Yuxiao , He Tianwei , Lu Qingjie , Li Bo , Zhou Tong , Wang BoXue , Wu Yuewen , Na Guohao , Chen Yun , Zhao Jianhong , Zhang Yumin , Zhang Jin , Liu Feng , Cui Hao , Liu Qingju 
Published: December 2024

AbstractDeveloping highly active and stable electrocatalysts for hydrogen production at industrial current densities is pivotal to give an impetus to carbon neutrality. Recently, metal–organic frameworks (MOFs) with large surface area and adjustable structures have become a class of promising alternative electrocatalysts, while their low conductivity and poor stability limit their widespread applications. Here, a modified strategy is proposed to stabilize and modulate Ruthenium (Ru) species including Ru single atoms (Ru SAs) and Ru nanoparticles (Ru NPs) on MOFs for enhanced hydrogen evolution reaction (HER). Benefiting from the strong interaction between Ru and MOFs, the synthesized NiFeRuSA+NP‐DOBDC (DOBDC: 2,5‐dioxido‐1,4‐benzenedicarboxylate) exhibits an extraordinary HER performance with overpotentials of 25 and 271 mV at 10 and 1000 mA cm−2, respectively. Meanwhile, it enables robust HER at a high current density of 1 A cm−2 over 300 h. Remarkably, the assembled anion exchange membrane (AEM) electrolyzer realizes a low voltage for alkaline water electrolysis. In situ analyses demonstrate that NiFeRuSA+NP‐DOBDC enables optimized H2O adsorption and dissociation, and theoretical calculations indicate that Ru SAs and NPs accelerate the Volmer‐Heyrovsky pathway, synergistically promoted the HER performance. This work presents a competitive strategy to integrate supported metal species on the MOFs platform to efficiently drive industrial water electrolysis.
Photonic Generation for Frequency 12‐Tupling Millimeter‐Wave Signal Based on Three Parallel Polarization Modulators
Authors: Yan Xueyao , Wang Dongfei 
Published: December 2024

AbstractIn the work, a new photonic generation method for frequency 12‐tupling millimeter‐wave (mm‐wave) signals is proposed. In the proposed scheme, only three parallel polarization modulators are used to generate the wanted optical sidebands. Then by properly controlling the modulation index and electrical phase shifters, the undesired optical sidebands can be canceled. The theoretical and simulation results of the optical sideband suppression ratio (OSSR) and radio frequency spurious suppression ratio (RFSSR) are 58.36dB, 57.30dB, and 52.39dB, 52.06dB, respectively. The simulation values are almost consistent with the theoretical analysis results, which proves that the proposed scheme is feasible. However, there may be errors in the parameters of those components that can affect the quality of the obtained signal. Thus, the impact of errors caused by these parameters on OSSR and RFSSR is analyzed and an acceptable range of error is listed.
Near‐Infrared Light‐Triggered Cascade Nanosystems for Spatiotemporally Controlled Gene‐Silencing and Gas Synergistic Cancer Therapy
Authors: Cheng Yaru , Feng Youming , Zhao Jian , Li Lele , Dong Haifeng 
Published: December 2024

AbstractDespite the tremendous potential of DNAzymes in gene therapy, achieving gene regulation with spatiotemporal precision and satisfactory efficacy remains a key challenge. Herein, we developed a near‐infrared light (NIR)‐triggered cascade effect system that enables precise spatiotemporal gene silencing and gas‐synergistic cancer therapy. This nanoplatform was constructed using an enzyme‐activatable DNAzyme, a nitric oxide (NO) precursor, and upconversion nanoparticles (UCNPs). The UCNPs act as light converters, facilitating the precursor to produce NO under NIR light irradiation, while the generated NO not only participates directly in gas therapy but also induces the upregulation of cytoplasmic APE1 level, resulting in enhanced DNAzyme activation and spatially controlled gene silencing. By leveraging this mechanism, cascade effects mediated gas‐gene synergistic therapy is achieved through the combination of NIR light‐controlled NO release and APE1‐activatable gene therapy. We demonstrated that this nanoplatform enables enhanced anti‐tumor effects both in vitro and in vivo. This strategy represents a critical step forward in the quest for highly targeted and efficient cancer treatments.
Four‐allele combinations for high oleic, low linolenic soybeans
Authors: Hudson Karen , Carrero‐Colón Militza 
Published: December 2024

AbstractSoybean oil accounts for approximately 29% of global oil consumption. The polyunsaturated linoleic and linolenic acids comprise more than 60% of commodity soybean oil, while oleic acid makes up 20%. To make a healthier soybean oil with improved stability for food uses, genetic approaches in soybean composition breeding target reducing levels of linoleic and linolenic acids while simultaneously increasing the oleic acid fraction. Quadruple mutants were constructed to evaluate the combinations of fatty acid desaturase2 (fad2) and fatty acid desaturase3 (fad3) mutant alleles to achieve a high oleic, low linolenic soybean oil profile. Over three growing seasons we observed that all four combinations resulted in oleic acid levels from 75% to 82%, and linolenic acid levels from 1.9% to 2.7%. No significant differences in seed total protein or oil levels were observed in the quadruple mutants, suggesting that these combinations will be useful for breeding soybean with improved oil profiles.
An Eco‐Friendly and Sensitive Microwave‐Aided Spectrofluorophotometric Characterization of Mirabegron‐Loaded Nanocarriers by Amalgamation of Design of Experiments and White Analytical Chemistry
Authors: Prajapati Pintu , Patel Krishna , Shah Pranav , Surana Vilas , Haque Anzarul , Kalam Mohd Abul , Shah Shailesh 
Published: December 2024

ABSTRACTMirabegron, a drug for treatment of overactive bladder, has low water solubility and bioavailability. Researchers used quality by design to develop and characterize second‐generation lipid nanocarriers for mirabegron, aiming to provide spatially and temporally sustained drug release. Numerous analytical methodologies for assessing mirabegron in pharmaceutical and biological fluids use chemical solvents in the mobile phase, potentially impacting aquatic ecosystems and the environment. The issue was addressed with a microwave‐assisted spectrofluorimetric technique, environmentally benign solvents, and a fluorescent probe known as 4‐chloro‐7‐nitrobenzofuran. Researchers used screening design and response‐surface methodology to minimize organic waste. The suggested technique satisfied ICH Q2 (R2) and M10 validation standards. This approach described the in vivo pharmacokinetics and in vitro drug release of mirabegron‐loaded lipid nano‐carriers. We anticipated the chemical reaction pathways that derivatized mirabegron with 4‐chloro‐7‐nitrobenzofuran by the analysis of mass spectra. We assessed the proposed method's environmental effect and sustainability compared to current methods using the RGB model, an analytical greenness calculator, and green analytical process index software. The proposed mirabegron estimate method was user‐friendly for analysts, cost‐effective, sensitive, robust, and environmentally sustainable, adhering to sustainable analytical practices and reducing ecological consequences.
The Impact of Hyperbaric Oxygen Therapy on Functional and Structural Plasticity in Rats With Spinal Cord Injury
Authors: Yang Xinyi , Wu Zhongyue , Lai Huimin , Chen Lingling , Cao Dairong , Liu Fang 
Published: December 2024

ABSTRACTIntroductionSpinal cord injury (SCI) can result in sensory and locomotor function loss below the injured segment. Hyperbaric oxygen therapy (HBOT) has been proven to alleviate SCI. This study aims to establish a reproducible rat model of SCI and investigate the impact of HBOT on alterations in brain neuronal activity and neuromotor function in this experimental rat SCI model using resting‐state functional magnetic resonance imaging (rs‐fMRI).MethodsThis is a prospective randomized controlled animal trial. A total number of 27 female SD rats were randomly divided into three groups: sham (n = 9), SCI (n = 9), and HBO (n = 9). rs‐fMRI was utilized to assess regional homogeneity (ReHo) values and functional connectivity (FC) strength over the whole brain with the motor cortex as seeds. Correlation between neuroimaging characteristics and behavioral assessment was calculated. We examined Nissl body, NeuN, and caspase‐3 expression in relevant brain regions.ResultsFollowing SCI, reduced ReHo values were observed in the left primary somatosensory cortex, left striatum, right agranular insular cortex, and partial cortex in the limbic system, which was reversed after HBOT. HBOT could increase FC strength between the motor cortex and other brain regions, including the left secondary motor cortex, right basal forebrain region, bilateral primary somatosensory cortex, bilateral thalamus, and another partial cortex in the limbic system. BBB scale scores showed that HBOT promoted motor function recovery in SCI rats. The ReHo and FC values in all positive clusters were positively correlated with BBB scores. By histopathological analysis, our study found that HBOT could reduce apoptotic proteins, increase the number of neurons, and protect neuronal function in brain regions with significant ReHo and FC alteration in SCI rats.ConclusionThis study reveals that HBOT facilitates functional and structural plasticity in the brain, contributing to the recovery of motor function in rats with SCI.
Urgent Coronary Angiography Following Cardiac Surgery: Insights from a High‐Volume Cardiac Surgery Center
Authors: Toselli M. , Cimaglia P. , Cereda A. , Fabbri G. , Latta F. , Giovannini D. , Galli M. , Calvi S. , Nerla R. , Castriota F. 
Published: December 2024

ABSTRACTBackgroundPost‐operative myocardial infarction is a possible complication following cardiac surgery. Data on the incidence, predictors and prognosis of urgent coronary angiography (UCA) after cardiac surgery are scarce.Aims (Objectives)This study aims to report in hospital and 1‐year follow‐up outcomes of a recent large cohort of patients undergoing UCA after cardiac surgery.MethodsThis study provides a retrospective analysis of an high volume cardiac center (Maria Cecilia Hospital, Italy), from 2016 to 2021 regarding patients treated with coronary artery bypass grafting (CABG), valve, or aortic root surgery, focusing on those who required UCA within the same hospitalization.ResultsOut of 6505 cardiac surgeries, 119 patients (1.83%) underwent UCA, with a median age of 69 years. The study found that UCA was more frequent post‐CABG (2.62%) than non‐CABG interventions (1.35%, p < 0.001). A graft failure was detected in 31.1% of the cases, while a native vessel complication in 36.1%. The leading reasons for UCA included ST/T abnormalities, ventricular arrhythmias, and hemodynamic instability, with 92% of UCAs performed within a week post‐surgery. The in‐hospital mortality rate was 32%, with no significant difference between CABG and non‐CABG patients. Predictive factors for in‐hospital mortality included Euroscore II, hemodynamic instability and late UCA. One‐year follow‐up showed a low mortality rate (2.5%) among discharged patients.ConclusionUCA resulted to have a pivotal role in detecting coronary complications after cardiac surgery, guiding subsequent treatment decisions. Despite the high in‐hospital mortality rate, survival showed an overall low mortality at the 1‐year mark.
Active Site Engineering of a Glycerol Dehydrogenase Improves its Oxidative Activity and Scope Toward Glycerol Derivatives
Authors: Grajales‐Hernández Daniel A. , Roca Maite , Moliner Vicent , López‐Gallego Fernando 
Published: December 2024

AbstractRegioselective oxidation of glyceryl alkyl ethers is of utmost importance for the fabrication of substituted hydroxy ketones and enantiopure 1,2‐diols as green solvents and pharmaceutical building blocks, respectively. An engineered glycerol dehydrogenase from Bacillus stearothermophilus was described to perform the regioselective oxidation of alkyl glycerol ethers, identifying position 252 as key for accepting larger substrates than glycerol. In this work, we further engineer that position through partial saturation mutagenesis to broaden the substrate scope toward other glycerol derivatives, improving enzyme kinetics and minimizing product inhibition. In particular, the BsGlyDH−L252S variant becomes the most efficient biocatalyst for the deracemization of alkyl glyceryl ethers in a two‐step, one‐pot immobilized system. The discovery and use of these alternative mutants of GlyDH opens the road to more applications and increases the enzymatic toolbox for the modifications of glyceryl ethers.
Development of a Synthetic Platform for Ent‐Pimaranes Reveals their Potential as Novel Non‐Redox Active Ferroptosis Inhibitors
Authors: Plangger Immanuel , Mühlsteiger Alex , Berger Julia , Feilner Julian , Wurst Klaus , Koeberle Andreas , Koeberle Solveigh C. , Magauer Thomas 
Published: December 2024

AbstractWe present a comprehensive account on the evolution of a synthetic platform for a subfamily of ent‐pimaranes. For the most complex member, norflickinflimiod C, five distinct strategies relying on either cationic or radical polyene cyclizations to construct the requisite tricyclic carbon scaffold were explored. Insights from early and late stage oxidative and reductive dearomatization studies ultimately led to a mild, rhodium‐catalyzed arene hydrogenation for the final synthetic route. A Sharpless asymmetric dihydroxylation was found to be suitable to render the platform enantioselective and diversification of a late‐stage key intermediate culminated in the total synthesis of eight ent‐pimaranes in 11–16 steps. These compounds were found to inhibit the formation of pro‐inflammatory leukotrienes and other 5‐lipoxygenase products. Notably, three ent‐pimaranes exhibited low micromolar, non‐redox active ferroptosis inhibition with remarkable structural specificity.
Structures, Chiroptical Properties, and Unexpectedly Facile Helical Inversion of Highly Elongated Anthracene‐Fused Expanded Helicenes
Authors: Fukuda Hiroki , Kobayashi Moe , Tsurumaki Eiji , Yamashina Masahiro , Hasegawa Masashi , Wakamatsu Kan , Toyota Shinji 
Published: December 2024

AbstractHelical fused anthracenes were elongated by fusing additional aromatic units at both ends to yield novel expanded helicenes. Compounds [5]HA2N and [7]HA consisting of 19 and 21 benzene rings, respectively, were synthesized by fourfold cycloisomerization of the corresponding terminal alkyne precursors. The helical structures were confirmed by X‐ray crystallographic analysis, where the aromatic frameworks stacked effectively with the helical turn numbers exceeding two. The enantiomers of the two compounds were resolved by chiral HPLC. Whereas [5]HA2N readily underwent enantiomerization at room temperature at the barrier to enantiomerization of 91 kJ mol−1, the barrier was enhanced to 99 kJ mol−1 for the long analog [7]HA. The enantiomers of [7]HA exhibited strong responses in the circular dichroism (CD) and circularly polarized luminescence (CPL) spectra, as scaled by dissymmetry factors |gabs|=0.034 and |glum|=0.012. Theoretical calculations by the r2SCAN‐3c method suggested stepwise mechanisms for the enantiomerization via helical inversion with acceptable barrier heights. The unexpectedly flexible nature of the aromatic frameworks of [5]HA2N and [7]HA was discussed on the basis of the proposed mechanism.
Fault estimation for multi‐rate descriptor systems using bi‐directional long short‐term memory neural network
Authors: Gandhi Dhrumil , Srinivasarao Meka 
Published: December 2024

AbstractFault estimation in multi‐rate descriptor systems, which involve both differential and algebraic states, is particularly challenging due to the complexity introduced by multi‐rate measurements. This paper proposes a novel fault estimation approach that combines a differential‐algebraic equation based extended Kalman filter (DAE‐EKF) with a bi‐directional long short‐term memory (bi‐LSTM) neural network. The DAE‐EKF is used to generate multi‐rate residuals, which serve as inputs to neural networks to estimate faults. bi‐LSTM networks improve upon LSTMs by processing data in both forward and backward directions, using past and future information. This bidirectional approach enhances temporal dependency capture, making bi‐LSTMs ideal for accurate fault estimation. The efficacy of the proposed method is demonstrated using simulation studies on a two‐phase reactor‐condenser system with recycle and a reactive distillation system. The proposed approach has shown superior fault estimation capability for multi‐rate descriptor systems compared to DAE‐EKF with conventional feedforward neural networks and DAE‐EKF with LSTM.
Monitoring Surface Energy Flux Dynamics of Irrigated Maize Using a Large Aperture Scintillometer in a Semi‐Arid Region
Authors: Singh Pragya , Sehgal Vinay Kumar , Dhakar Rajkumar , Rani Alka , Das Deb Kumar , Mukherjee Joydeep , Patel Natoo Raghunathbhai , Jha Prakash Kumar , Singh Ram Narayan 
Published: December 2024

ABSTRACTWater, a crucial input in agricultural production, is distributed based on geographical and topographical patterns. However, anthropogenic climate change has intensified water scarcity in semi‐arid regions. This research aims to precisely estimate crop evapotranspiration (ET) and examine the diurnal and seasonal patterns of surface energy fluxes in maize (Zea mays) crops cultivated in a semi‐arid region. The precision of our methodology is underscored by the use of a large‐aperture scintillometer (LAS), which measured surface energy fluxes at 5‐min intervals over two crop‐growing seasons. The results, a testament to the accuracy of the LAS, indicated that during the rainy (Kharif) season of 2015–2016, the seasonal sensible heat flux (H) and latent heat flux (LE) values were 185.91 and 242.14 mm, respectively. In the rainy (Kharif) season of 2017–2018, these values were 151.57 mm for H and 373.63 mm for LE. LE values ranged from 0.40 to 6.83 MJ m−2 day−1 throughout the growing season. The findings, which highlight the LAS's ability to accurately estimate surface energy fluxes, provide a deeper understanding of their interactions with microclimatic factors, such as weather, soil, and crop management. These insights, with their significant implications for ecophysiological studies and improving agricultural practices in semi‐arid regions, underscore the importance of our research.
As grain mineral densities have declined over time, have densities converged across wheat classes?—Insights from the US Pacific Northwest and worldwide benchmarks
Authors: Adams Curtis B. , Kongraksawech Teepakorn , Ross Andrew , Long Dan S. , Neely Clark , Marshall Juliet , Graebner Ryan , Reardon Catherine L. , Liang Xi 
Published: December 2024

AbstractStudies have generally shown that grain mineral density is lower in modern wheat (Triticum aestivum L.) compared to historic germplasm. The conclusion of a limited study from the US Pacific Northwest (PNW) was that grain mineral density of soft white wheat (SWW) had declined over time to meet already‐low mineral density of hard red wheat (HRW), though little else is known about this. Therefore, the primary objective of this study was to better understand grain mineral density (P, K, Mg, Ca, Mn, Fe, Zn, and Cu) of modern PNW wheats, with subobjectives to compare SWW and HRW wheat classes to each other and worldwide benchmarks, quantify effects of agronomic factors on grain minerals, and evaluate minerals in refined flour. Results indicated whole‐grain mineral density of PNW wheat was comparable to worldwide benchmark concentrations, with P and K most likely low, with no evidence of SWW and HRW class differences. Agronomically, there was significant variation in grain minerals among production sites and wheat varieties that could be utilized to generate mineral‐enriched grain to feed malnourished populations. In the process of refining flour from whole grain, the minerals most reduced were P, Mg, Mn, Fe, Zn, and Cu (60%–90%). Refined flour mineral concentrations were largely unassociated with flour yield or quality parameters, suggesting that efforts to enhance mineral density will not affect other flour traits. Overall, these results illustrate that the mineral density of modern SWW and HRW produced in the PNW are comparable to each other and to wheat globally. Considering reported historical changes, these results suggest a modern, worldwide convergence in mineral density across wheat classes.
Endogenous GABA levels decrease during grain maturation in wheat and do not play a role in the germination of immature grain
Authors: Himi Eiko 
Published: December 2024

AbstractIt has been known that gamma‐aminobutyric acid (GABA) is increased in germinating seeds such as those of wheat (Triticum aestivum L.). Techniques such as ninhydrin reaction method and high‐performance liquid chromatography are used to quantify GABA levels. However, these methods require multiple steps and make it difficult to analyze multiple samples simultaneously. In this study, an enzyme‐based assay for the rapid quantification of GABA levels in multiple wheat grain samples simultaneously was established. It was found that in developing grains, endogenous GABA levels were high but decreased with maturity. The maximum amount of GABA found in immature grains did not correlate with the degree of grain dormancy. However, the onset of decrease in GABA content was earlier in weak dormant lines compared to strong dormant lines. Endogenous GABA levels increased temporarily in strongly dormant grains upon imbibition, but quickly returned to their original levels, while they showed a sharp increase in intermediate dormant grains. Exogenous GABA promoted the germination of weakly dormant grains but was not sufficient to break dormancy in strongly dormant grains, suggesting that the maintenance of GABA levels may be related to the degree of grain dormancy.
The Norwegian legacy of resisting formal grading
Authors: Fjørtoft Henning , Tveit Sverre , Sandvik Lise Vikan 
Published: December 2024

AbstractNorway has a longstanding tradition of prohibiting formal grading in primary education. This paper traces a century of restrictive grading policies and their associated discourses. Using Bacchi's (2009) What's the Problem Represented to be framework, we present an analysis of the policy documents that have underpinned Norwegian assessment policies through major curriculum reforms from 1939 to 2020. Focusing on grades as discursive placeholders for broader educational issues, we identify three problems: (1) concerns for assessment quality, (2) determining the appropriate age for commencing grading and (3) balancing the need for high‐quality measurements with concerns for students' individual needs. We discuss the implications of the Norwegian system and the lessons learned for policy development and implementation in Norway and beyond.