bluuebunny/crossref_metadata_2025_split huggingface dataset:
Na‐Rich Na3V2(PO4)3 Cathodes for Long Cycling Rechargeable Sodium Full Cells
Authors: Liu Yao , Wu Xiangyong , Moeez Abdul , Peng Zhi , Xia Yongyao , Zhao Dongyuan , Liu Jun , Li Wei 
Published: December 2022

AbstractNASICON‐type sodium vanadium phosphate (Na3V2(PO4)3, or NVP) cathode materials have great potential for fast charging and long cycling sodium‐ion batteries (SIBs) similar to lithium iron phosphate (LiFePO4, or LFP) cathode materials used in lithium‐ion batteries (LIBs). However, the cycle life and energy density in the full cell using NVP materials need to be significantly improved. This paper investigates the degradation mechanisms of NVP‐based SIBs and identifies the Na loss from the cathode to the anode solid electrolyte interphase (SEI) reactions as the main cause of capacity degradation. A new Na‐rich NVP cathode (e.g., Na4V2(PO4)3, or Na4VP) is developed to address the Na loss problem. Conventional NVP can be easily transformed into the Na4VP by a facile and fast chemical solution treatment (30 s). Na‐free‐anode Na4VP and hard carbon‐Na4VP full cells are assembled to evaluate the electrochemical properties of the Na‐rich NVP cathode. The Na4VP cathode provides excess Na to compensate for the Na loss, resulting much longer cycle life in the full cells (>400 cycles) and a high specific energy and power density. Good low‐temperature performance is also observed.
Jack pine of all trades: Deciphering intraspecific variability of a key adaptive trait at the rear edge of a widespread fire‐embracing North American conifer
Authors: Pelletier Emmanuelle , de Lafontaine Guillaume 
Published: December 2022

AbstractPremiseUnderstanding mechanisms fostering long‐term persistence of marginal populations should provide key insights about species resilience facing climate change. Cone serotiny is a key adaptive trait in Pinus banksiana (jack pine), which shows phenotypic variation according to the fire regime. Compared to range‐core populations within the fire‐prone boreal forest, low and variable serotiny in rear‐edge populations suggest local adaptation to uncommon and unpredictable wildfire regime. We assessed environmental/physiological factors that might modulate intraspecific variation in cone serotiny.MethodsWe experimentally subjected closed cones to incrementing temperatures, then tested seed germination to determine whether and how various ecological factors (cone age, branch height, tree size, tree age) are related to cone dehiscence and seed viability in jack pines from rear‐edge and range‐core populations in eastern Canada.ResultsCones from rear‐edge populations dehisce at a lower opening temperature, which increases with cone age. Cones from range‐core stands open at a more constant, yet higher temperature. Cones from rear‐edge stands take between 13 and 27 years to reach the level of serotiny achieved at the range core. At the rear edge, seed viability is steady (51%), whereas it decreases from 70% to 30% in 20 years at the range core.ConclusionsWe inferred the mechanisms of a bet‐hedging strategy in rear‐edge populations, which ensures steady recruitment during fire‐free intervals and successful postfire regeneration. This capacity to cope with infrequent and unpredictable fire regime should increase the resilience of jack pine populations as global changes alter fire dynamics of the boreal forest.
Pollen‐feeding behavior of diverse insects on Geranium delavayi, a flower with large, accessible pollen grains
Authors: Hao Kai , Xu Qi , Huang Shuang‐Quan 
Published: December 2022

AbstractPremiseWhy have pollen grains evolved to be exceptionally large in some species? Pollen‐feeding hypothesis suggests that if the proportion of pollen amounts for feeding is reduced in a flower, the low allocation to pollen number would allow pollen grains to be larger.MethodsTo examine whether species with large pollen grains experience low pollen consumption, the behavior of insects feeding on nectar and pollen was observed and pollen transfer efficiency was estimated for four visitor types in Geranium delavayi. To see whether bees actively collected pollen, the numbers of grains in pollen baskets and on the body were compared. Both nutritional value (total protein and lipid) and chemical defense (phenolic metabolites) in pollen against pollen feeders were measured.ResultsBumblebees and honeybees foraged for nectar, rarely groomed pollen into corbiculae, and had >5× higher pollen transfer efficiency than smaller solitary bees and flies, which were pollen eaters that removed more pollen but deposited less. Pollen grains were characterized by low protein and high lipid content with a low protein‐lipid ratio, an unfavorable combination for bumblebees. Three secondary metabolites were significantly higher in pollen grains (7.77 mg/g) than in petals (1.08 mg/g) or in nectar (0.44 mg/g), suggesting stronger chemical defense in pollen.ConclusionsOur results indicated that large bees took nectar but little of the nutritionally poor and highly toxic pollen. These data support one prediction of the pollen‐feeding hypothesis, that species with few and large pollen grains would also have low pollen‐consumption rates.
Climate warming causes photobiont degradation and carbon starvation in a boreal climate sentinel lichen
Authors: Meyer Abigail R. , Valentin Maria , Liulevicius Laima , McDonald Tami R. , Nelsen Matthew P. , Pengra Jean , Smith Robert J. , Stanton Daniel 
Published: December 2022

AbstractPremiseThe long‐term potential for acclimation by lichens to changing climates is poorly known, despite their prominent roles in forested ecosystems. Although often considered “extremophiles,” lichens may not readily acclimate to novel climates well beyond historical norms. In a previous study (Smith et al., 2018), Evernia mesomorpha transplants in a whole‐ecosystem climate change experiment showed drastic mass loss after 1 yr of warming and drying; however, the causes of this mass loss were not addressed.MethodsWe examined the causes of this warming‐induced mass loss by measuring physiological, functional, and reproductive attributes of lichen transplants.ResultsSevere loss of mass and physiological function occurred above +2°C of experimental warming. Loss of algal symbionts (“bleaching”) and turnover in algal community compositions increased with temperature and were the clearest impacts of experimental warming. Enhanced CO2 had no significant physiological or symbiont composition effects. The functional loss of algal photobionts led to significant loss of mass and specific thallus mass (STM), which in turn reduced water‐holding capacity (WHC). Although algal genotypes remained detectable in thalli exposed to higher stress, within‐thallus photobiont communities shifted in composition toward greater diversity.ConclusionsThe strong negative impacts of warming and/or lower humidity on Evernia mesomorpha were driven by a loss of photobiont activity. Analogous to the effects of climate change on corals, the balance of symbiont carbon metabolism in lichens is central to their resilience to changing conditions.
Bone health in RASopathies
Authors: Stevenson David A. , Viscogliosi Germana , Leoni Chiara 
Published: December 2022

AbstractThe RASopathies are a group of disorders due to pathogenic variants in genes involved in the Ras/MAPK pathway, many of which have overlapping clinical features (e.g., neurofibromatosis type 1, Costello syndrome, cardiofaciocutaneous syndrome and Noonan syndrome) including musculoskeletal manifestations. Osteopenia and osteoporosis are reported in many of the RASopathies suggesting a shared pathogenesis. Even though osteopenia and osteoporosis are often detected and fractures have been reported, the clinical impact of bone mineralization defects on the skeleton of the various syndromes is poorly understood. Further knowledge of the role of the Ras/MAPK pathway on the bone cellular function, and more detailed musculoskeletal phenotyping will be critical in helping to develop therapies to improve bone health in the RASopathies.
Mosaic RASopathies: A review of disorders caused by somatic pathogenic variants in the genes of the RAS/MAPK pathway
Authors: Carli Diana , Resta Nicoletta , Ferrero Giovanni Battista , Ruggieri Martino , Mussa Alessandro 
Published: December 2022

AbstractMosaic RASopathies are a heterogeneous group of diseases characterized by the presence at birth or early onset of congenital anomalies, cutaneous and vascular anomalies, segmental overgrowth, and increased cancer risk. They are caused by somatic pathogenic variants of the genes belonging the RAt Sarcoma Mitogen‐activated protein kinase (RAS/MAPK) pathway causing its hyperactivation. Here, we review the clinical and molecular characteristics of this heterogeneous group of diseases, including the possibilities of molecular diagnosis and new therapeutic perspectives.
Concurrent hearing and vision impairment and 8‐year memory decline in community‐dwelling older adults
Authors: Huang Alison R. , Rebok George W. , Swenor Bonnielin K. , Reed Nicholas , Griswold Michael , Zhu Xiaoqian , Deal Jennifer A. 
Published: December 2022

AbstractBackgroundHearing and vision impairments are risk factors for cognitive decline; less is known about dual sensory impairment. This study quantifies the association between dual sensory impairment and 8‐year change in memory among older adults.MethodsData (N = 5552) were from the National Health and Aging Trends Study. Memory (immediate/delayed word recall, subjective memory) was measured annually (2011 to 2019). Hearing and vision impairments were measured by self‐report. Association between dual sensory impairment and 8‐year change in memory was assessed using multivariate linear mixed effect models and generalized logistic mixed models.ResultsRate of memory decline was most accelerated among participants with dual sensory impairment. For example, 8‐year decline in delayed word recall was −1.03 (95% confidene interval: ‐1.29, ‐0.77) for dual sensory impairment versus ‐0.79 (‐0.92, ‐0.67) for single and −0.56 (‐0.63, ‐0.48) for no impairment.ConclusionOlder adults with dual sensory impairment may be at particularly higher risk for cognitive decline.
Amorphous Mo‐doped NiS0.5Se0.5 Nanosheets@Crystalline NiS0.5Se0.5 Nanorods for High Current‐density Electrocatalytic Water Splitting in Neutral Media
Authors: Wang Yang , Li Xiaopeng , Huang Zhong , Wang Haozhi , Chen Zelin , Zhang Jinfeng , Zheng Xuerong , Deng Yida , Hu Wenbin 
Published: December 2022

AbstractIt is vitally important to develop highly active, robust and low‐cost transition metal‐based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo‐doped NiS0.5Se0.5 nanosheets@crystalline NiS0.5Se0.5 nanorods (Am−Mo−NiS0.5Se0.5) was synthesized using a facil one‐step strategy. In phosphate buffer saline solution, the Am−Mo−NiS0.5Se0.5 shows tiny overpotentials of 48 and 209 mV for hydrogen evolution reaction (HER), 238 and 514 mV for oxygen evolution reaction (OER) at 10 and 1000 mA cm−2, respectively. Moreover, Am−Mo−NiS0.5Se0.5 delivers excellent stability for at least 300 h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect‐rich amorphous structure of Am−Mo−NiS0.5Se0.5 owns higher electron state density and strengthened the binding energy of H2O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step.
Potent De Novo Macrocyclic Peptides That Inhibit O‐GlcNAc Transferase through an Allosteric Mechanism
Authors: Alteen Matthew G. , Peacock Hayden , Meek Richard W. , Busmann Jil A. , Zhu Sha , Davies Gideon J. , Suga Hiroaki , Vocadlo David J. 
Published: December 2022

AbstractGlycosyltransferases are a superfamily of enzymes that are notoriously difficult to inhibit. Here we apply an mRNA display technology integrated with genetic code reprogramming, referred to as the RaPID (random non‐standard peptides integrated discovery) system, to identify macrocyclic peptides with high binding affinities for O‐GlcNAc transferase (OGT). These macrocycles inhibit OGT activity through an allosteric mechanism that is driven by their binding to the tetratricopeptide repeats of OGT. Saturation mutagenesis in a maturation screen using 39 amino acids, including 22 non‐canonical residues, led to an improved unnatural macrocycle that is ≈40 times more potent than the parent compound (Kiapp=1.5 nM). Subsequent derivatization delivered a biotinylated derivative that enabled one‐step affinity purification of OGT from complex samples. The high potency and novel mechanism of action of these OGT ligands should enable new approaches to elucidate the specificity and regulation of OGT.
Tough and Conductive Nacre‐inspired MXene/Epoxy Layered Bulk Nanocomposites
Authors: Wang Huagao , Lu Rongjian , Yan Jia , Peng Jingsong , Tomsia Antoni P. , Liang Rui , Sun Guoxing , Liu Mingjie , Jiang Lei , Cheng Qunfeng 
Published: December 2022

AbstractA long‐standing quest in materials science has been the development of tough epoxy resin nanocomposites for use in numerous applications. Inspired by nacre, here we report tough and conductive MXene/epoxy layered bulk nanocomposites. The orientation of MXene lamellar scaffolds is enhanced by annealing treatment. The improved interfacial interactions between MXene lamellar scaffold and epoxy through surface chemical modification resulted in a synergistic effect. Tailoring the interlayer spacing of MXene nanosheets to a critical distance resulted in a fracture toughness about eight times higher than that of pure epoxy, surpassing other epoxy nanocomposites. Our nacre‐inspired MXene/epoxy layered bulk nanocomposites also show high electrical conductivity that provides self‐monitoring capability for structural integrity and exhibits an excellent electromagnetic interference shielding efficiency. Our proposed strategy provides an avenue for fabricating high‐performance epoxy nanocomposites.
Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering
Authors: Feng Xin , Bu Kejun , Liu Teng , Guo Songhao , Sun Zongdong , Fu Tonghuan , Xu Yongshan , Liu Kailang , Yang Sijie , Zhao Yinghe , Li Huiqiao , Lü Xujie , Zhai Tianyou 
Published: December 2022

AbstractThe unique intermolecular van der Waals force in emerging two‐dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α‐Sb2O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α‐Sb2O3 flake shows a sharp drop by 5 orders of magnitude in 0–3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.
Actinorhodin Biosynthesis Terminates with an Unprecedented Biaryl Coupling Reaction
Authors: Hashimoto Makoto , Watari Susumu , Taguchi Takaaki , Ishikawa Kazuki , Kumamoto Takuya , Okamoto Susumu , Ichinose Koji 
Published: December 2022

AbstractA plethora of dimeric natural products exist with diverse chemical structures and biological activities. A major strategy for dimerization is aryl coupling catalyzed by cytochrome P450 or laccase. Actinorhodin (ACT) from Streptomyces coelicolor A3(2) has a dimeric pyranonaphthoquinone structure connected by a C−C bond. In this study, we identified an NmrA‐family dimerizing enzyme, ActVA‐ORF4, and a cofactor‐independent oxidase, ActVA‐ORF3, both involved in the last step of ACT biosynthesis. ActVA‐ORF4 is a unique NAD(P)H‐dependent enzyme that catalyzes the intermolecular C−C bond formation using 8‐hydroxydihydrokalafungin (DHK‐OH) as the sole substrate. On the other hand, ActVA‐ORF3 was found to be a quinone‐forming enzyme that produces the coupling substrate, DHK‐OH and the final product, ACT. Consequently, the functional assignment of all essential enzymes in the biosynthesis of ACT, one of the best‐known model natural products, has been completed.
Comparison effect of thin microrod‐nanowhisker manganese oxide (MnO2) and spherical grain‐like cobalt oxide (Co3O4) as nanofiller for performance‐enhanced composite gel terpolymer electrolyte‐based dye‐sensitized solar cells
Authors: Razali Ridhwan , Goh Zhi Ling , Farhana Nur Khuzaimah , Kasi Ramesh , Subramaniam Ramesh 
Published: December 2022

AbstractGel polymer electrolyte (GPE) are better replacement of liquid electrolyte for dye‐sensitized solar cell (DSSC) but they have low efficiency due to insufficient segmental motion within the electrolyte. By incorporating transition metal oxide nanofiller, it can improve the performance of DSSC due to the existence of cross‐linking center that provides interaction with polymer side chain and redox mediator. Two different transition metal oxides (namely, manganese oxide, MnO2 and cobalt oxide, Co3O4) were synthesized using sonochemical method and incorporated as nanofiller. Poly (vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate) (P(VB‐co‐VA‐co‐VAc)) as a host terpolymer and sodium iodide (NaI) as a dopant salt were used to formulate the composite gel terpolymer electrolytes (CGPEs). The two different shapes of nanofiller have impacted the performance of CGPE proven by the structural analysis. It was found that both systems, the highest ionic conductivity achieved at 2.5 wt% of MnO2 and Co3O4 content with values of 6.40 and 5.2 mS cm−1, respectively. Surprisingly, the performance DSSC of Co3O4‐based CGPE was higher due to the strong Lewis's acidity of Co3O4, which absorb more iodide ions into the surface and facilitating the ions mobility. CGPE containing 2.5 wt% Co3O4 yield the highest efficiency, with value of 3.69%.
Effects of urea loading on soil biodegradation properties of melt‐processed polycaprolactone‐based composites for potential application in agriculture
Authors: Motloung Mpho Phillip , Mofokeng Tladi Gideon , Ray Suprakas Sinha 
Published: December 2022

AbstractHerein, biodegradable composites of poly(ɛ‐caprolactone) (PCL)/hydroxyapatite (HAP)/urea, with potential application in agriculture, were developed. The concentration of HAP was fixed at 3 wt%, while urea concentration varied from 1 to 9 wt%. The effects of urea loading on the morphological, flow properties, and soil biodegradation of PCL/HAP composites were investigated. The morphological characterization showed well dispersion of HAP and urea particles in the PCL matrix. A decrease in viscosity of PCL was noticed upon the inclusion of urea at 1 wt%, indicating the plasticization effects of urea, whereas an increase in viscosity was observed with increasing the concentration. The morphological analysis after soil burial showed microbial adherence on the surface of the samples. In addition, the formation of cracks, holes, and uneven surfaces were noticed. The atomic force microscope analysis showed an increase in surface roughness due to surface degradation of the samples. On the other hand, two‐step degradation curves were noticed in the samples before soil degradation. In contrast, a single step degradation curve was observed after degradation, indicating the leaching of urea from the samples. Overall, PCL/HAP/urea composites with enhanced degradation rates were developed, and they can be applied in agriculture, where the materials can be buried after their end‐use.
Nanoporous membrane filter cascade for size‐selective analysis of nano‐ and microplastic particles
Authors: Miclea Paul‐Tiberiu , Richter Susanne , Hagendorf Christian 
Published: December 2022

AbstractAnalytical routes for sampling and analysis of microplastic particles in the range of several 10 µm to 1000 µm are well established in environmental research. However, the current scientific efforts are targeting human health impact with an enhanced focus on nanoparticle analysis in drinking water, the food chain, and its disposition in the human body. A major challenge lies in the availability of cascade filter setups spanning several orders of magnitude down to 10 nm dimensions in a single filtration workflow allowing fast and reliable routines for size‐selective nano‐ and microplastic (NMP) particle analysis. In this work, we present a novel cascade filter system containing filters made of microporous Si (pore size >10 µm) and nanoporous Al2O3 (pore size 100 nm), thus realizing the corresponding NMP size selectivity. Inorganic filter materials are chosen due to their beneficial properties as substrates for NMP particle analysis, which are nonpolymer materials with high planarity for micro‐spectroscopy investigations. In our first experiments, we demonstrate the successful NMP size separation on Si and Al2O3 filter substrates. For this purpose, we implement a well‐defined NMP test material composed of a mixture of polyethylene terephthalate microplastic reference material and monodisperse nanoscale polystyrene particles. The NMP test material is applied in a laboratory filtration workflow for samples in liquid solution. Both filter stages are subsequently investigated with optical microscopy, electron microscopy (scanning electron microscopy), Raman spectroscopy, and scanning force microscopy (atomic force microscopy) to demonstrate their applicability as combined NMP particle analytic substrates. Here, we characterize the fundamental NMP properties such as particle shape, size, and spectroscopic fingerprints—optical and chemical—both qualitatively and quantitatively. Finally, requirements and limitations for a standardized NMP filtration and analytic workflow will be discussed.
Synthesis, antimycobacterial, cytotoxicity, anti‐inflammatory, in silico studies and molecular dynamics of pyrazole‐embedded thiazolidin‐4‐one hybrids
Authors: Kamat Vinuta , Poojary Boja , Puthran Divyaraj , Das Vishwa B. , Kumar Banoth K. , Sankaranarayan Murugesan , Shetye Gauri , Ma Rui , Franzblau Scott G. , Nayak Suresh P. 
Published: December 2022

AbstractIn the present investigation, we devolved and synthesized a new series of pyrazole‐embedded thiazolidin‐4‐one derivatives (9a–p) with the goal to produce promising antitubercular leads. The in vitro antimycobacterial activity of the synthesized compounds was tested against replicating and nonreplicating Mtb H37Rv strains. With MIC ranging from 3.03 to 22.55 µg/ml, five compounds (9a, 9c, 9d, 9e, and 9f) emerged as promising antitubercular agents. The active molecules were nontoxic to normal Vero cells. All the synthesized compounds were evaluated for in vitro anti‐inflammatory studies. Compounds 9a, 9b, 9c, 9h, and 9i exhibited excellent anti‐inflammatory efficacy. Docking study was performed to understand the binding pattern of the significantly active compound 9a with 1P44.