bluuebunny/crossref_metadata_2025_split huggingface dataset:
Genetic potential for changes in breeding systems: Predicted and observed trait changes during artificial selection for male and female allocation in a gynodioecious species
Authors: Campbell Diane R. , Sakai Ann K. , Weller Stephen G. , Culley Theresa M. , Dunbar‐Wallis Amy K. , Andres Allen M. , Wong Tiffany G. , Dang Tam , Au Bryan , Ku Mickey , Marcantonio Andrea R. , Ngo Paul J. , Nguyen Andrew A. , Tran My Hanh , Tran Quoc‐Phong 
Published: November 2022

AbstractPremiseEvolution of separate sexes from hermaphroditism often proceeds through gynodioecy, but genetic constraints on this process are poorly understood. Genetic (co‐)variances and between‐sex genetic correlations were used to predict evolutionary responses of multiple reproductive traits in a sexually dimorphic gynodioecious species, and predictions were compared with observed responses to artificial selection.MethodsSchiedea (Caryophyllaceae) is an endemic Hawaiian lineage with hermaphroditic, gynodioecious, subdioecious, and dioecious species. We measured genetic parameters of Schiedea salicaria and used them to predict evolutionary responses of 18 traits in hermaphrodites and females in response to artificial selection for increased male (stamen) biomass in hermaphrodites or increased female (carpel, capsule) biomass in females. Observed responses over two generations were compared with predictions in replicate lines of treatments and controls.ResultsIn only two generations, both stamen biomass in hermaphrodites and female biomass in females responded markedly to direct selection, supporting a key assumption of models for evolution of dioecy. Other biomass traits, pollen and ovule numbers, and inflorescence characters important in wind pollination evolved indirectly in response to selection on sex allocation. Responses generally followed predictions from multivariate selection models, with some responses unexpectedly large due to increased genetic correlations as selection proceeded.ConclusionsResults illustrate the power of artificial selection and utility of multivariate selection models incorporating sex differences. They further indicate that pollen and ovule numbers and inflorescence architecture could evolve in response to selection on biomass allocation to male versus female function, producing complex changes in plant phenotype as separate sexes evolve.
Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single‐Atom Catalysts throughp‐nJunction Rectification
Authors: Zhuang Zechao , Xia Lixue , Huang Jiazhao , Zhu Peng , Li Yong , Ye Chenliang , Xia Minggang , Yu Ruohan , Lang Zhiquan , Zhu Jiexin , Zheng Lirong , Wang Yu , Zhai Tianyou , Zhao Yan , Wei Shiqiang , Li Jun , Wang Dingsheng , Li Yadong 
Published: November 2022

AbstractFine‐tuning single‐atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploitp‐type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeNx) and rectify their local charge density by ann‐type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing ann‐type gallium monosulfide that features a low work function generates a space‐charged region across the junction interface, and causes distortion of the FeN4moiety and spin‐state transition in the FeIIcenter. This catalyst shows an over two‐fold higher specific oxygen‐reduction activity than that of pristine FePc. We further employ three othern‐type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN4and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.
Visible‐Light‐Switchable Tellurium‐Based Chalcogen Bonding: Photocontrolled Anion Binding and Anion Abstraction Catalysis
Authors: Duan Hong‐Ying , Han Shi‐Tao , Zhan Tian‐Guang , Liu Li‐Juan , Zhang Kang‐Da 
Published: November 2022

AbstractExploring new noncovalent bonding motifs with reversibly tunable binding affinity is of fundamental importance in manipulating the properties and functions of supramolecular self‐assembly systems and materials. Herein, for the first time, we demonstrate a unique visible‐light‐switchable telluro‐triazole/triazolium‐based chalcogen bonding (ChB) system in which the Te moieties are connected by azobenzene cores. The binding strengths between these azo‐derived ChB receptors and the halide anions (Cl−, Br−) could be reversibly regulated upon irradiation by visible light of different wavelengths. Thecis‐bidentate ChB receptors exhibit enhanced halide anion binding ability compared to thetrans‐monodentate receptors. In particular, the telluro‐triazolium‐based ChB receptor can achieve both high and significantly photoswitchable binding affinities for halide anions, which enable it to serve as an efficient photocontrolled organocatalyst for ChB‐assisted halide abstraction in a Friedel–Crafts alkylation benchmark reaction.
Multi‐Dimensional Structure and Dynamics Landscape of Proteins in Mammalian Cells Revealed by In‐Cell NMR
Authors: Kadavath Harindranath , Cecilia Prymaczok Natalia , Eichmann Cédric , Riek Roland , Gerez Juan Atilio 
Published: November 2022

AbstractGoverning function, half‐life and subcellular localization, the 3D structure and dynamics of proteins are in nature constantly changing in a tightly regulated manner to fulfill the physiological and adaptive requirements of the cells. To find evidence for this hypothesis, we applied in‐cell NMR to three folded model proteins and propose that the splitting of cross peaks constitutes an atomic fingerprint of distinct structural states that arise from multiple target binding co‐existing inside mammalian cells. These structural states change upon protein loss of function or subcellular localisation into distinct cell compartments. In addition to peak splitting, we observed NMR signal intensity attenuations indicative of transient interactions with other molecules and dynamics on the microsecond to millisecond time scale.
Azaarenes: 13 Rings in a Row by Cyclopentannulation
Authors: Maier Steffen , Hippchen Nikolai , Jester Fabian , Dodds Marcus , Weber Michel , Skarjan Leon , Rominger Frank , Freudenberg Jan , Bunz Uwe H. F. 
Published: November 2022

AbstractCyclopentannulation was explored as a strategy to access large, stable azaarenes. Buchwald–Hartwig coupling of previously reported di‐ and tetrabrominated cyclopentannulatedN,N′‐dihydrotetraazapentacenes furnished stable azaarenes with up to 13 six‐membered rings in a row and a length of 3.1 nm. Their optoelectronic and semi‐conducting properties as well as their aromaticity were investigated.
Polyetheretherketone/Nano‐Ag‐TiO2 composite with mechanical properties and antibacterial activity
Authors: Ru Xiaona , Chu Minghui , Jiang Jiazhen , Yin Tong , Li Jiamin , Gao Shijun 
Published: November 2022

AbstractPolyetheretherketone (PEEK) is of interest because of its excellent biocompatibility. However, the lack of antimicrobial activity of PEEK limits its use in clinical applications. Silver‐loaded nano titanium dioxide (Nano‐Ag‐TiO2)/PEEK composites with different mass fractions (1, 2, 3, and 4 wt%) were prepared by hot compression molding to achieve better mechanical and antimicrobial properties. The results of scanning electron microscopy (SEM) and energy dispersive spectrum (EDS) showed that Nano‐Ag‐TiO2 successfully modified PEEK. The contact angle of Nano‐Ag‐TiO2/PEEK increased compared to PEEK (p < 0.01). The flexural strength, compressive strength, and Vickers hardness of Nano‐Ag‐TiO2/PEEK composites first increased and then decreased. When the Nano‐Ag‐TiO2 content is 3 wt%, the flexural strength of Nano‐Ag‐TiO2/PEEK composite reaches its maximum, which is 171.19 MPa; the compressive strength reaches the maximum, which is 24.7% higher than that of pure PEEK specimens; the Vickers hardness of Nano‐Ag‐TiO2/PEEK composite reaches its maximum, which is 19.84% higher than that of pure PEEK specimens. The in vitro antibacterial evaluation reveals that all Nano‐Ag‐TiO2/PEEK samples exhibited good resistance and anti‐adhesive properties against Staphylococcus aureus (S. aureus). This finding suggests that the 3 wt% Nano‐Ag‐TiO2/PEEK composite has better mechanical properties and antimicrobial ability, which is promising for dental applications.
The Effects of Daily Prednisone and Tocilizumab on Hemoglobin A1c During the Treatment of Giant Cell Arteritis
Authors: Patel Naomi J. , Tozzo Veronica , Higgins John M. , Stone John H. 
Published: November 2022

ObjectiveTo study the longitudinal effects of both glucocorticoids and tocilizumab, an interleukin‐6 receptor inhibitor, on hemoglobin A1c (HbA1c) levels during glucocorticoid tapering.MethodsWe analyzed patients with complete data from the Giant Cell Arteritis Clinical Research Study (GiACTA) to investigate the impact of both glycemic and nonglycemic factors on changes in HbA1c levels over the 52‐week trial. Giant cell arteritis (GCA) patients were randomized to receive either tocilizumab or placebo in addition to glucocorticoids. We used a multivariable mixed‐effects model to evaluate associations of HbA1c level with daily glucocorticoid dose, randomization to receive tocilizumab, and red blood cell count in patients with and those without diabetes mellitus at baseline, over 52 weeks.ResultsIn 209 patients, the median HbA1c level decreased by 0.50% (P < 0.01) in the group that received both tocilizumab and glucocorticoids (tocilizumab/glucocorticoid) and by 0.10% (P < 0.01) in the glucocorticoid‐only group. Randomization to tocilizumab/glucocorticoid was associated with lower HbA1c (β = −0.209% in those without diabetes, P < 0.01; β = −0.290% in those with diabetes, P = 0.23). These changes had a sizable impact on glucose tolerance classification: 42.5% of patients in the tocilizumab/glucocorticoid group improved from prediabetes status to normal, compared to only 12.5% of patients treated with glucocorticoids alone. Daily glucocorticoid dose was associated with HbA1c level in patients with baseline diabetes (β = 0.018%/mg, P < 0.01) and those without baseline diabetes (β = 0.005%/mg, P < 0.01).ConclusionTocilizumab treatment was associated with a substantial reduction in HbA1c level, independent of glucocorticoid exposure, which may be achieved through a combination of glycemic and nonglycemic effects.
Synthesis, Structures, and Complexation with Phenolic Guests of Acridone‐Incorporated Arylene–Ethynylene Macrocyclic Compounds
Authors: Komori Takashi , Tsurumaki Eiji , Toyota Shinji 
Published: November 2022

AbstractAcridone units were incorporated into the arylene–ethynylene structure as polar arene units. Cyclic trimers consisting of three acridone‐2,7‐diyl units and three 1,3‐phenylene units were synthesized by Sonogashira couplings via stepwise or direct route. X‐ray analysis revealed that the trimer had a nearly planar macrocyclic framework with a cavity surrounded by three carbonyl groups. In contrast, the corresponding tetramer had a nonplanar macrocyclic framework. 1H NMR measurements showed that the trimer formed a 1 : 1 complex as a macrocyclic host with dihydric phenol guests, and the association constants were determined to be ca. 1.0×103 L mol−1 for hydroquinone or resorcinol guests in CDCl3 at 298 K. The calculated structures of these complexes by the DFT method supported the presence of two sets of OH⋅⋅⋅O=C hydrogen bonds between the host and guest molecules. The spectroscopic data of the cyclic trimers and tetramers are compared with those of reference acridone compounds.
Randomized preclinical study of machine perfusion in vascularized composite allografts
Authors: Amin K R , Stone J P , Kerr J , Geraghty A , Joseph L , Montero-Fernandez A , Wong J K , Fildes J E 
Published: November 2022

Abstract

Background
Attempts to improve limb preservation for transplantation using ex vivo perfusion have yielded promising results. However, metabolic acidosis, aberrant perfusate biochemistry and significant perfusion-induced oedema are reported universally. Optimizing perfusion protocols is therefore essential for maintaining tissue health.

Methods
A randomized, two-stage open preclinical trial design was used to determine the optimal temperature and mean arterial pressure for machine perfusion. Conditions compared were: normothermic machine perfusion at 70 mmHg (NMP-70); subnormothermic perfusion (28°C) at 70 mmHg; subnormothermic (28°C) perfusion at 50 mmHg; and hypothermic perfusion (10°C) at 30 mmHg. Following this, a head-to-head experiment was undertaken comparing the optimal machine perfusion with static cold storage. Paired bilateral limbs (10 in total) were randomized to either 8 h of static cold storage, or 2 h of static cold storage and 6 h of optimal machine perfusion. Both groups of limbs were then reperfused on a circuit primed with matched blood from unrelated donors for 4 h without immunosuppression.

Results
NMP-70 resulted in less tissue injury and stable perfusion biochemistry. Assessing reperfusion outcomes, static cold storage resulted in acidosis with increased lactate and a worsening electrolyte profile, necessitating bolus infusions of bicarbonate to prevent graft loss. Conversely, NMP-70 was associated with haemodynamic and biochemical stability. Histologically, on reperfusion with allogeneic whole blood, limbs subjected to static cold storage exhibited multifocal ischaemic injury and increased inflammation, which was absent with NMP-70. Static cold storage also resulted in significant oedema compared with NMP-70.

Conclusion
Normothermic perfusion resulted in superior graft preservation and less reperfusion injury compared with the current static cold storage protocol.
Enabling Technologies in Carbohydrate Chemistry: Automated Glycan Assembly, Flow Chemistry and Data Science
Authors: Lin Mei‐Huei , Wolf Jakob B. , Sletten Eric T. , Cambié Dario , Danglad‐Flores José , Seeberger Peter H. 
Published: November 2022

AbstractThe synthesis of defined oligosaccharides is a complex task. Several enabling technologies have been introduced in the last two decades to facilitate synthetic access to these valuable biomolecules. In this concept, we describe the technological solutions that have advanced glycochemistry using automated glycan assembly, flow chemistry and data science as examples. We highlight how the synergies between these different technologies can further advance the field, with progress toward the realization of a self‐driving lab for glycan synthesis.
Coupling Value‐Added Anodic Reactions with Electrocatalytic CO2 Reduction
Authors: Xu Zikai , Peng Chen , Zheng Gengfeng 
Published: November 2022

AbstractElectrocatalytic CO2 reduction features a promising approach to realize carbon neutrality. However, its competitiveness is limited by the sluggish oxygen evolution reaction (OER) at anode, which consumes a large portion of energy. Coupling value‐added anodic reactions with CO2 electroreduction has been emerging as a promising strategy in recent years to enhance the full‐cell energy efficiency and produce valuable chemicals at both cathode and anode of the electrolyzer. This review briefly summarizes recent progresses on the electrocatalytic CO2 reduction, and the economic feasibility of different CO2 electrolysis systems is discussed. Then a comprehensive summary of recent advances in the coupled electrolysis of CO2 and potential value‐added anodic reactions is provided, with special focus on the specific cell designs. Finally, current challenges and future opportunities for the coupled electrolysis systems are proposed, which are targeted to facilitate progress in this field and push the CO2 electrolyzers to a more practical level.
Magnetically Induced CO2 Methanation In Continuous Flow Over Supported Nickel Catalysts with Improved Energy Efficiency
Authors: Ghosh Sourav , Ourlin Thibault , Fazzini Pier‐Francesco , Lacroix Lise‐Marie , Tricard Simon , Esvan Jerome , Cayez Simon , Chaudret Bruno 
Published: November 2022

AbstractA new selective and efficient catalytic system for magnetically induced catalytic CO2 methanation was developed, composed of an abundant iron‐based heating agent, namely a commercial iron wool, combined with supported Nickel nanoparticles (Ni NPs) as catalysts. The effect of metal oxide support was evaluated by preparing different 10 wt % Ni catalyst (TiO2, ZrO2, CeO2, and CeZrO2) via organometallic decomposition route. As‐prepared catalysts were thoroughly characterized using powder X‐ray diffraction, electron microscopy, elemental analysis, vibrating sample magnetometer, and X‐ray photoelectron spectroscopy techniques. High conversion and selectivity toward methane were observed at mid‐temperature range, hence improving energy efficiency of the process with respect to the previous results under magnetic heating conditions. To gain further insight into the catalytic system, the effects of the synthesis method and of 0.5 wt % Ru doping were evaluated. Finally, the dynamic nature of magnetically induced heating was demonstrated through fast stop‐and‐go experiments, proving the suitability of this technology for the storage of intermittent renewable energy through P2G process.
Catalytic Stereoselective Multicomponent Reactions for the Synthesis of Spiro Derivatives: Recent Progress
Authors: Patel Divyang M. , Patel Paras J. , Patel Hitendra M. 
Published: November 2022

AbstractSpiro derivatives are important scaffolding substances found in many natural products and pharmaceuticals. In the last decade, numerous new approaches based on multicomponent reactions have been explored for the selective and efficient development of new spiro derivatives using various organocatalytic and transition metal‐based catalytic systems. This Review discusses pioneering advances in the field of catalytic stereoselective multicomponent reactions for the preparation of various spiro derivatives. These include stereoselective Michael cascade cyclization reactions, cycloadditions, diastereoselective reactions, and miscellaneous reactions for the synthesis of spiro‐hetero/carbocycles. Advances in the last decade have made it possible to synthesize various spiro compounds with good to excellent stereoselectivity under appropriate reaction conditions. However, achieving high regioselectivity in several described multicomponent reactions remains a challenge. Organocatalysts and transition‐metal‐based catalysts play a crucial role in achieving this milestone. Proposed catalytic mechanisms and supporting evidence are highlighted in this Review. The progress described in catalytic stereoselective approaches for spiro derivatives is immense. However, it is expected that new stereoselective synthetic methods will soon be developed that can be widely used for the preparation of spiro‐heterocycles/carbocycles.
Cross‐Dehydrogenative Homocoupling of 2‐Aryl‐N‐heterocycles and Application to the Synthesis of Phenylpyridine Borane Dimers
Authors: Gao Longhui , Feuillastre Sophie , Clavier Gilles , Pieters Grégory 
Published: November 2022

AbstractA method for the synthesis of 2‐aryl‐N‐heterocyclic dimers via a cross‐dehydrogenative homocoupling (homo‐CDC) has been developed using commercially available Ruthenium on charcoal as catalyst and iron trichloride as oxidant. A large variety of heterocyclic scaffolds and functional groups are tolerated and a complete regioselectivity resulting from the activation of the less sterically hindered C−H bonds was observed for meta‐substituted substrates. Starting from several homocoupling products obtained, a series of pyridine‐borane complexes was synthesized and the impact of the dimerization on their photophysical properties was studied and rationalized using theoretical calculations.
Strength‐is‐Weakness: The (ir)relevant relation between resources and payoffs in coalition formation
Authors: Wissink Joeri , Cantiani Anabela , van de Ven Niels , Pronk Tila , Erle Thorsten M. , van Beest Ilja 
Published: November 2022

AbstractA key observation in coalition formation is that bargainers who control many resources are often excluded from coalitions by bargainers who control few resources, the Strength‐is‐Weakness effect. We argue that this effect is contingent on whether resources provide a legitimate claim to be included in a coalition. Across three incentivized coalition experiments (n = 2745; 915 triads), three participants (player A had four resources, player B had three resources, player C had two resources) negotiated about a payoff of 90 monetary units. Depending on condition, these resources were obtained randomly, earned, or earned and proportionally linked to the payoff. Results showed player As were less included when resources were obtained randomly and more often included in coalitions when resources were earned and/or proportionally linked to the payoff. This provides evidence that the Strength‐is‐Weakness is contingent on the legitimacy of the resources.
An approach for developing probabilistic models for temperature‐dependent properties of construction materials from fire tests and small data
Authors: Karaki Ghada , Naser Mohannad Z. 
Published: November 2022

AbstractProbabilistic approaches provide a more realistic look into assessing structures under fire conditions and overcome some limitations observed in the more traditional (deterministic) approaches. These approaches have also been introduced to the fire engineering domain, for example, fire probabilistic risk analysis and probabilistic structural fire engineering. In order to perform probabilistic‐based analysis, temperature‐dependent probabilistic models for material properties are needed. This paper presents a methodology to develop temperature‐dependent probabilistic models for the thermal and mechanical properties for commonly used construction materials, including normal‐strength, high‐strength, and high‐performance concrete and mild, high‐strength, and cold‐formed steels. The presented approach analyzes a comprehensive list of surveyed experimental data at different temperature groups, tests the goodness of fit for a number of distributions, and derives a continuous function to quantify temperature‐dependent parameters of the distribution. In addition, the newly derived models are also compared against those adopted by fire codes, and standards and others derived using machine learning. The newly developed models will complement existing efforts to facilitate probabilistic performance‐based structural fire engineering.
A cryptic EWSR1::DDIT3 fusion in myxoid liposarcoma: Potential pitfalls with FISH and cytogenetics
Authors: Ibstedt Sebastian , de Mattos Camila Bedeschi Rego , Köster Jan , Mertens Fredrik 
Published: November 2022

AbstractMyxoid liposarcoma (MLS) is molecularly characterized by fusions involving the DDIT3 gene in chromosome band 12q13; the fusion partner is FUS in band 16p11 in 90–95% of the cases and EWSR1 in band 22q12 in the remaining 5–10%. Hence, molecular studies, often fluorescence in situ hybridization (FISH) for DDIT3 rearrangement, are useful for establishing a correct diagnosis. Although all MLS tumors should have DDIT3 fusions, it is important to be aware of reasons for potential false‐negative results. We here present a case of MLS that was negative for FISH for DDIT3, that showed an unexpected t(11;22) at G‐banding, but that displayed a characteristic EWSR1::DDIT3 fusion at RNA‐sequencing. The results suggest that neoplasia‐associated fusions that, due to the transcriptional orientations of the two genes involved, cannot arise through only two double‐strand breaks are more likely to be associated with negative FISH‐findings and unexpected karyotypes.