bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reduced nitrogen rate sustains malt barley yield and quality in malt barley‐pea rotation
Authors: Sainju Upendra M. 
Published: October 2024

AbstractRotational benefit of pea (Pisum sativum L.) may reduce N fertilization rate and sustain malt barley (Hordeum vulgare L.) yield and quality in the malt barley‐pea rotation. This study examined the effect of cover crop [oat (Avena sativa L.) cover crop vs. none] and N fertilization rate (0, 40, 50, 60, 70, and 80 kg N ha−1) on malt barley growth, yield, and quality in the malt barley‐pea rotation from 2012 to 2019 in the northern Great Plains. Cover crop biomass yield and N accumulation were greater in 2016 than other years. Compared to fallow, malt barley plant density with cover crop was 9%–13% lower from 2013 to 2015, but 10% greater in 2017. Malt barley straw yield was 38% greater in 2017 and grain yield 15%–39% greater in 2017 and 2018, but grain plumpness was 5%–10% lower in 2014 and 2017 with than without cover crop. Increasing N fertilization rate linearly increased grain yield and N uptake, but reduced grain test weight and plumpness in most years. Straw N concentration and uptake and grain protein concentration varied by year. Because of the similar grain yield, protein concentration, plumpness, and test weight between 60 and 80 kg N ha−1, 60 kg N ha−1 can be recommended to sustain malt barley yield and quality in the malt barley‐pea rotation, regardless of cover crops. This helps to reduce N fertilization rate by 20 kg N ha−1 for malt barley in dryland cropping systems of the US northern Great Plains.
Synthesis of 2‐Pyrones by Base‐Induced [3+3] Annulation Reaction of Phenacyl Phosphonium Ylides with Cyclopropenones
Authors: Zhang Yuanyuan , Wang Xiaoyu , Wen Jiangwei , Li Qiuyun , Xue Wenyue , Liu Hancong , Yan Kelu 
Published: October 2024

AbstractThe base‐induced [3+3] annulation reaction of phenacyl phosphonium ylides with cyclopropenones has been proposed. Various polysubstituted 2‐pyrones are achieved in moderate to good yields through C−P bond cleavage and C−O/C−C coupling under simple and easy‐to‐operate conditions. The synthetic application and reaction mechanism have also been preliminarily explored to gain a deeper understanding of this strategy in practicality and reaction details. This protocol offers an alternative approach for the synthesis of useful 2‐pyrone derivatives.
Switching biologics in chronic rhinosinusitis with nasal polyps: A multicenter Canadian experience
Authors: Dorling Marisa , Sarafan Masih , Voizard Béatrice , Ammar Yousif Al , Hernaiz‐Leonardo Juan Carlos , Chalmers Kieran , MacInnis Patrick , Nugent James , Janjua Arif , Javer Amin , Sommer Doron , Lee John , Chan Yvonne , Thamboo Andrew 
Published: October 2024

AbstractBackgroundType 2 biologics have been used increasingly for the treatment of chronic rhinosinusitis with nasal polyps (CRSwNP). However, patterns of biologic switching are understudied, and established guidelines for sequential or simultaneous use do not yet exist.MethodsThis is a Canadian multicenter retrospective study of real‐world patient data. Patients were included if they had recurrent CRSwNP despite maximal medical and surgical management, and received at least one dose of a type 2 biologic. Patients who remained on their initial biologic comprised the continuous group. Patients with sequential or simultaneous use of more than one biologic comprised the switched group. We compared the characteristics of patients who continued and switched biologics.ResultsNote that 225 consecutive patients were included. Thirty‐six (16%) switched biologics at least once, and six (3%) switched twice. The most common switch was from mepolizumab to dupilumab, with poor control of CRSwNP symptoms being the leading cause for this switch. Lack of efficacy was the main reason for switching off mepolizumab and omalizumab, while adverse events were the leading cause for switching off dupilumab. Additionally, mepolizumab patients were more likely to switch biologics late in their treatment, while dupilumab patients rarely switched after 12 months of therapy (p‐value < 0.001).ConclusionsSwitching biologics for CRSwNP is frequent in Canadian rhinology practices, with 16% of patients switching at least once. The most common switch is from mepolizumab to dupilumab with inadequate CRSwNP control driving this switch. This study may help guide sequential or simultaneous use of biologics in CRSwNP patients.
RNA Binding Protein Dysfunction Links Smoldering/Slowly Expanding Lesions to Neurodegeneration in Multiple Sclerosis
Authors: Messmer Miranda L. , Salapa Hannah E. , Popescu Bogdan F. , Levin Michael C. 
Published: October 2024

ObjectiveDespite the advances in treatments for multiple sclerosis (MS), unremitting neurodegeneration continues to drive disability and disease progression. Smoldering/slowly expanding lesions (SELs) and dysfunction of the RNA binding protein (RBP) heterogeneous nuclear ribonucleoprotein A1 (hnRNP A1) are pathologic hallmarks of MS cortex and intricately tied to disability and neurodegeneration, respectively. We hypothesized that neuronal hnRNP A1 dysfunction contributes to neurodegeneration and is exacerbated by smoldering/SELs in progressive MS.MethodsNeuronal hnRNP A1 pathology (nucleocytoplasmic mislocalization of hnRNP A1) was examined in healthy control and MS brains using immunohistochemistry. MS cases were stratified by severity of hnRNP A1 pathology to examine the link between RBP dysfunction, demyelination, and neurodegeneration.ResultsWe found that smoldering/SELs were only present within a subset of MS tissues characterized by elevated neuronal hnRNP A1 pathology (MS‐A1high) in adjacent cortical gray matter. In contrast to healthy controls and MS with low hnRNP A1 pathology (MS‐A1low), MS‐A1high showed elevated markers of neurodegeneration, including neuronal loss and injury, brain atrophy, axonal loss, and axon degeneration. Additionally, we discovered a subpopulation of morphologically intact neurons lacking expression of NeuN, a neuron‐specific RBP, in cortical projection neurons in MS‐A1high cases.InterpretationhnRNP A1 dysfunction contributes to neurodegeneration and may be exacerbated by smoldering/SELs in progressive MS. The discovery of NeuN‐negative neurons suggests that some cortical neurons may only be injured and not lost. By characterizing RBP pathology in MS cortex, this study has important implications for understanding the pathogenic mechanisms driving neurodegeneration, the substrate of disability and disease progression. ANN NEUROL 2025;97:313–328
Imidazolate‐Stabilized Cu(III): Dioxygen to Oxides at Type 3 Copper Sites
Authors: Large Tao A. G. , Keown William , Gary J. Brannon , Chiang Linus , Stack T. Daniel P. 
Published: October 2024

AbstractImidazole ligation of metals through histidine is extensive among metalloproteins, yet the role of the imidazolate conjugate base is often neglected, despite its potential accessibility when bonded to an oxidized metal center. Using synthetic models of oxygenated tyrosinase enzymes ligated exclusively by monodentate imidazoles, we find that deprotonation of the μ2‐η2:η2‐peroxidodicopper(II) species triggers redox isomerization to an imidazolate‐ligated bis(μ2‐oxido)dicopper(III) species. Formal two‐electron oxidation to Cu(III) remains biologically unprecedented, yet is effected readily by addition of base. Spectrophotometric titrations by UV/Visible/near‐IR and copper K‐edge X‐ray absorption spectroscopies are interpreted most simply as two cooperative, 2H+ transformations in which the peroxide O−O is cleaved in the first step. Elaboration from simple imidazoles to a protected histidine extends this isomerization into an amino acid environment. The role of phenolate as a base suggests this four‐electron reduction of O2 is energetically viable in a biological context and requires only two copper centers, which act as two‐electron shuttles when imidazole deprotonation assists. This existential precedent of viable imidazolate intermediates invites speculation into an alternative mechanism for phenol hydroxylation not previously considered at Type 3 copper sites such as tyrosinases. Structural biological evidence suggests imidazolate ligation of copper may be more widespread than generally understood.
Nanoparticle Transport in Proximal Tubules with Rhabdomyolysis‐Induced Necrosis
Authors: Huang Yingyu , Zheng Jie , Yu Mengxiao 
Published: October 2024

AbstractRenal‐clearable engineered nanoparticles are being explored for their potential to deliver therapeutic agents for kidney disease treatment. A fundamental understanding of how these nanoparticles accumulate in diseased kidneys at the cellular level is essential to enhance their effectiveness and minimize side effects on adjacent healthy tissues. Herein, we report that the accumulation of glutathione‐coated, near‐infrared emitting gold nanoparticles (GS‐AuNPs) correlates strongly with the necrotic stages of injured proximal tubular cells. Using a rhabdomyolysis‐induced acute kidney injury (AKI) mouse model, we observed that GS‐AuNPs were significantly accumulated in the extracellular lumen of proximal tubular epithelial cells (PTECs) at advanced necrotic stage, where cellular debris and released intracellular contents impeded their clearance. In contrast, during early necrosis, GS‐AuNPs were still cleared through the unobstructed lumen. Additionally, intracellular uptake of GS‐AuNPs was significantly reduced across all necrotic stages. These findings underscore the need for new strategies to design nanoparticles that can effectively target and be taken up by the diseased tubular cells before extensive necrosis occurs; so that nanoparticle‐mediated drug delivery for kidney disease treatment can be achieved with desired efficacy and precision.
Deep Neural Network Enhanced Mesoscopic Thermodynamic Model for Unlocking the Electrode/Electrolyte Interface
Authors: Tao Haolan , Wang Sijie , Liu Honglai , Lian Cheng 
Published: October 2024

AbstractStructure and properties of the electrode/electrolyte interface significantly influence the electrochemical processes of energy storage and conversion, yet the challenge lies in accurate description of both molecular characteristics and external field effects. Here, we develop a mesoscopic thermodynamic model that calculates the thermodynamic properties of electrolytes based on chemical potential, and its efficiency is enhanced by a deep neural network. The deep neural network enhanced mesoscopic thermodynamic (DeepMT) model effectively bridges the gap between micro‐level characteristics of ions and macro‐level effects of external field, enabling precise presentation of ion density distributions over complex conditions. Our result indicates that the DeepMT model not only demonstrates a computational efficiency improvement of approximately four orders of magnitude over direct theoretical calculations, but also accurately predicts interface properties including ion adsorption, surface charge, and differential capacitance through the statistical analysis of density distributions.
Microfluidic Precision Manufacture of High Performance Liquid Chromatographic Microspheres
Authors: Sun Kaiyue , Zeng Juxing , Liu Ya , Zhou Zhuoheng , Chen Jikai , Chen Jiawei , Huang Xiangyu , Gao Fan , Wang Xin , Zhang Xin , Wang Xiaofei , Eeltink Sebastiaan , Zhang Bo 
Published: October 2024

AbstractA key bottleneck in developing chromatographic material is the chemically entangled control of morphology, pore structure, and material chemistry, which holds back precision material manufacture in order to pursue advanced separation performance. In this work, a precision manufacture strategy based on droplet microfluidics was developed, for production of highly efficient chromatographic microspheres with independent control over particle morphology, pore structure and material chemistry. The droplet‐synthesized microspheres display extremely narrow particle size distribution (CV<3 %), enabling a 100 % production yield due to complete elimination of sieving steps. More importantly, the size of the droplet‐synthesized microspheres is freely adjustable without the need for re‐optimizing chemical recipes or reaction conditions. The resulting materials exhibit excellent separation efficiencies, achieving a reduced plate height of hmin=1.67. This precision manufacture strategy also allows for flexible pore design and continuous pore size adjustment across three orders of magnitudes, providing a novel vehicle for resolution fine‐tuning targeting protein separation. Besides traditional silica, organic–inorganic hybrid silica, zirconia, and titania microspheres can also be precisely synthesized on the same platform, supporting various separation applications and operating conditions. Powered by precision manufacture, super‐throughput production, and versatile chemistry, the high‐performance droplet‐synthesized separation material will pave the way towards green and precision chromatographic industry.
Strengthen Water O−H Bond in Electrolytes for Enhanced Reversibility and Safety in Aqueous Aluminum Ion Batteries
Authors: Zhao Z. , Zhang Z. , Wang W. , Xu T. , Yu X. 
Published: October 2024

AbstractAqueous aluminum‐ion batteries present a promising prospect for large‐scale energy storage applications, owing to the abundance, inherent safety, and the high theoretical capacity of aluminum. However, their voltage output and energy density are significantly hindered by challenges such as complex hydrogen evolution and uncontrollable solvation reactions. In this work, we demonstrate that water decomposition is restrain by increasing the electron density of water protons and increasing the dissociation energy of H2O through robust dipole interactions with highly polar dimethylformamide (DMF) molecules. Moreover, the incorporation of dimethyl methylphosphonate (DMMP) flame retardant effectively addresses the flammability risk arising from a substantial presence of organic additives The in‐depth study with experimental and theoretical simulations reveals that the water‐poor solvation structure with reduced water activity is achieved, which can (i) effectively mitigate undesired solvated H2O‐mediated side reactions on the Al anode; (ii) boost the de‐solvation kinetics of Al3+ while preventing cathode structural distortion; (iii) reduce the flammability of hybrid electrolytes. As a proof of concept, the Al//AlxMnO2 full cell employing a hybrid electrolyte demonstrate enhanced stability (deliver 335 mAh g−1 while retaining 71 % capacity for 400 cycles) compared to those with pure electrolyte.
Electrolyte Reconfiguration by Cation/Anion Cross‐coordination for Highly Reversible and Facile Sodium Storage
Authors: Hou Xin , Wang Shuo , Wang Bo , Qiu Yanling , Jiang Mingqin , Tang Yongfu , Zheng Qiong , Li Xianfeng 
Published: October 2024

AbstractHard carbon (HC) materials are promising anodes for sodium‐ion batteries (SIBs) owing to low cost, high specific capacity and low working potential. However, the poor compatibility of the electrolyte with HC leads to low initial coulombic efficiency (ICE) and sluggish Na+ transport kinetics. Here, we propose an electrolyte reconfiguration strategy based on the hard and soft acid and base (HSAB) theory by introducing methyltriphenylphosphonium bromide (MTPPB). MTPPB can realize a spontaneous cross‐coordination solvation structure with NaPF6 by selective affinity, synchronously optimizing the interfacial chemistry and sodium storage process. The advantages of the chemical π–π bridging of MTPP+‐HC and interaction of MTPP+‐PF6− contribute to preferential and oriented reduction of PF6−, forming a low‐resistance supramolecular SEI. Additionally, Na+‐Br− coordination weakens the Na+‐solvent interactions, facilitating Na+ de‐solvation kinetics. Consequently, the HC||Na cell achieves a superior ICE of 96.6 %, desirable rate capability under 25 °C and invisible capacity decay after 500 cycles at 1 C under −20 °C. The Na4Fe3(PO4)2P2O7||HC pouch battery displays a high ICE of 90.3 % and a 15 % increment of energy density under 25 °C. This work provides a guidance through electrolyte reconfiguration engineering for designing practical HC‐based SIBs with high energy/power density and long‐life span in the extended operating‐temperature range.
Oxenoid Reactivity Enabled by Targeted Photoactivation of Periodate
Authors: Bossonnet Andre , Garner Ruth A. , O'Brien James , Trujillo Cristina , Trowbridge Aaron D. 
Published: October 2024

AbstractThe chemistry of low‐valent intermediates continues to inspire new modes of reactivity across synthetic chemistry. But while the generation and reactivity of both carbenes and nitrenes are well‐established, difficulties in accessing oxene, their oxygen‐based congener, has severely hampered its application in synthesis. Here, we report a conceptually novel approach towards oxenoid reactivity through the violet‐light photolysis of tetrabutylammonium periodate. Computational studies reveal an unexpected geometric change upon periodate photoexcitation that facilitates intersystem crossing and near‐barrierless dissociation of triplet periodate into oxene. Under these operationally simple conditions, we have demonstrated the epoxidation of a wide range of substituted olefins, revealing unprecedented functional group compatibility. By overcoming the historic challenges associated with employing oxene as an intermediate in organic chemistry, we believe that this platform will inspire the development of new reactive oxygen‐based methodologies across industry and academia.
Site‐Specific Quadruple‐Functionalised Antibodies
Authors: Journeaux Toby , Geeson Michael B. , Murray Thomas V. , Papworth Monika A. , Gothard Matt , Kettle Jason G. , Vasco Aldrin V. , Bernardes Gonçalo J. L. 
Published: October 2024

AbstractAntibody–drug conjugates (ADCs) are a growing class of chemotherapeutic agents that have yielded striking clinical successes. However, the efficacy of ADCs often suffers from issues associated with tumor heterogeneity and resistance. To overcome these problems, a new generation of ADCs comprising a single monoclonal antibody with multiple different payloads attached, termed multi‐payload ADCs, have been developed. Here we deploy multiple orthogonal site‐specific protein modification strategies to generate highly homogeneous multi‐functionalised antibody conjugates comprising up to four different functionalities installed at four unique sites on the antibody. This work, which includes the use of a site‐specific cyclopropenone (CPO)‐based reagent, represents the first example of a homogeneous multi‐payload ADC with a payload count greater than two, and thereby facilitates the development of the next generation of ADCs.
Multifunctional Nanocomposite Polymer‐integrated Ca‐doped CeO2 Electrolyte for Robust and High‐rate All‐solid‐state Sodium‐ion Batteries
Authors: Yang Pan , Wu Zhenzhen , Li Mingli , Zhang Cheng , Wang Yiqing , Zhu Yutong , Li Meng , Wang Yun , Li Dong‐sheng , Chen Hao , Zhang Shanqing 
Published: October 2024

AbstractDue to the seamless interfaces between solid polymer electrolytes (SPEs) and electrode materials, SPEs‐based all‐solid‐state sodium‐ion batteries (ASSSIBs) are considered promising energy storage systems. However, the sluggish Na+ transport and uncontrollable Na dendrite propagation still hinder the practical application of SPEs‐based ASSSIBs. Herein, Ca‐doped CeO2 (Ca−CeO2) nanotube framework is synthesized and integrated with poly (ethylene oxide) methyl ether acrylate‐perfluoropolyether copolymer (PEOA‐PFPE), resulting in multifunctional solid nanocomposite electrolytes (namely SNEs, i.e., PEOA‐PFPE/Ca−CeO2). Our investigations demonstrate that the fluorous effect incurred by the fluorine‐containing PEOA‐PFPE and the oxygen vacancy effect induced by the Ca−CeO2 framework could synergistically promote the dissociation of sodium salt, ultimately enhancing the Na+ mobility in SNEs. Besides, the resultant SNEs construct rapid Na+ transport channels and homogenize the Na deposition in SNEs/Na interface, which effectively prevents the Na dendrite growth. Furthermore, the assembled carbon‐coated sodium vanadium phosphate (NVP@C)||PEOA‐PFPE/Ca−CeO2||Na coin cell delivers impressive rate capability of 97.9 mAh g−1 at 2 C and outstanding cycling stability with capacity retention of 84.3 % after 300 cycles at 1 C. This work illustrates that constructing multifunctional SNEs via incorporating functional inorganic frameworks into fluorine‐containing SPEs could be a promising strategy for the commercialization of robust and high‐performance ASSSIBs.
Facile Access to Phosphorus Ylide‐fused Heteroarenes Possessing Tunable Optoelectronic Properties and High Nonlinear Optical Performances
Authors: Zhang Kaihua , Wang Xiaofeng , Zhou Zhiruo , Guo Jing , Liu Hao , Zhai Yaxin , Yao Yifan , Yang Kun , Zeng Zebing 
Published: October 2024

AbstractWe report here a novel family of ylidic P‐heteroarenes (P1–P6), structurally featuring unique phosphonium cyclopentadienylide (P−Cp)‐fused π‐skeletons and synthetically prepared via an unexpected one‐pot [2+3]/[3+3] phospha‐annulation reaction. While the facile and modular synthesis allows the fine‐tuning of their optical absorptions and redox properties, single‐crystallographic and theoretical analysis of these P‐heteroarenes further reveal that the fusion of P−Cp moiety leads to substantial intramolecular charge‐separated features with high ylidic character values of up to 84 %. Benefitted from such dipolar structures, these P‐heteroarenes not only allows stepwise electrophilic substitution reaction for further structural π‐expansions, but also exhibit excellent nonlinear optical (NLO) responses and optical limiting (OL) performances comparable to or exceed those of C60. As a model compound, the persistent radical‐anion salt of P5a was also prepared through chemical reduction, thus offering valuable insights into the electronic structures of reduced P‐ylidic species. Our work not only established a highly efficient synthetic method toward new P‐heteroarenes, but also provide fundamental understanding of those fused‐ring ylidic P‐heterocycles with promising NLO/OL applications.
Carbon Nanotubes and Their Composites for Flexible Electrochemical Biosensors
Authors: Gazzato Luana , Frasconi Marco 
Published: October 2024

AbstractFlexible biosensors play a crucial role for healthcare management and disease diagnosis. Electrochemical biosensors have attracted significant attention for wearable sensing applications owing to their numerous advantages, including high sensitivity and selectivity, inherent miniaturization and rapid response times. Challenges lie in the development of highly conductive and flexible electrodes that can be integrated with biorecognition components to engineer selective biosensor interfaces. Carbon nanotubes (CNTs) hold significant promise as materials for wearable flexible sensor fabrication. This review highlights recent strategies for fabricating conductive and flexible electrodes, whether in the form of films or fibers, based on CNTs and their composites. Additionally, the review explores emerging biosensing applications, including flexible sensors for the direct electrochemical detection of biomarkers, sensors functionalized with enzymes, antibodies, or DNA, and sensors interfaced with cells to monitor transient biochemical signals.