bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ruthenium(II) Complex‐Based G‐quadruplex DNA Selective Luminescent ‘Light‐up’ Probe for RNase H Activity Detection
Authors: Sheet Sanjoy Kumar , Rabha Monosh , Sen Bhaskar , Patra Sumit Kumar , Aguan Kripamoy , Khatua Snehadrinarayan 
Published: July 2021

AbstractA bis‐heteroleptic ruthenium(II) complex, 1[PF6]2 of benzothiazole amide substituted 2,2′‐bipyridine ligand (bmbbipy) has been synthesized for the selective detection of G‐quadruplex (GQ) DNA and luminescence‐assay‐based RNase H activity monitoring. Compound 1[PF6]2 exhibited aggregation‐caused quenching (ACQ) in water. Aggregate formation was supported by DLS, UV‐vis, and 1H NMR spectroscopy results, and the morphology of aggregated particles was witnessed by SEM and TEM. 1[PF6]2 acted as an efficient GQ DNA‐selective luminescent light‐up probe over single‐stranded and double‐stranded DNA. The competency of 1[PF6]2 for selective GQ structure detection was established by PL and CD spectroscopy. For 1[PF6]2, the PL light‐up is exclusively due to the rigidification of the benzothiazole amide side arm in the presence of GQ‐DNA. The interaction between the probe and GQ‐DNA was analyzed by molecular docking analysis. The GQ structure detection capability of 1[PF6]2 was further applied in the luminescent ‘off‐on’ RNase H activity detection. The assay utilized an RNA:DNA hybrid, obtained from 22AG2‐RNA and 22AG2‐DNA sequences. RNase H solely hydrolyzed the RNA of the RNA:DNA duplex and released G‐rich 22AG2‐DNA, which was detected via the PL enhancement of 1[PF6]2. The selectivity of RNase H activity detection over various other restriction enzymes was also demonstrated.
Identification and genetic characterization of extra soft kernel texture in soft kernel durum wheat (Triticum turgidum ssp. durum)
Authors: Ibba Maria Itria , Kumar Neeraj , Morris Craig F. 
Published: July 2021

AbstractBackground and objectivesKernel texture (grain hardness) is a key determinant of wheat quality and utilization. Among soft wheats, softer kernels possess some advantages in processing and end‐product quality. Here, an extra soft kernel phenotype was identified and characterized in soft kernel durum wheat.FindingsA RIL population was developed by crossing “Soft Strongfield” with Kamut Khorasan wheat. Progeny kernels were selected for chalky appearance in the F2, F3, and F4. Kernel texture phenotypes measured by the SKCS in the F5, F6, and F7 were all less than 20 and ranged down to −12.6. Among F5:7 full‐sib RILs, there was indication of a single segregating genetic locus that was associated with a difference of about 7 SKCS hardness index (HI) units. Single marker–trait association and composite interval mapping both identified significant QTLs on chromosomes 4B and 1B with phenotypic effects of about 5 and 4 HI, respectively.ConclusionsQTL detected in the present study may be used to reduce kernel texture in soft durum to below zero, creating “extra soft” durum. These QTLs should also be available to be used in hard kernel durum to reduce kernel texture and may be transferrable to hexaploid wheat.Significance and noveltyThe creation of soft kernel durum wheat expanded the processing, end‐product quality, and utilization of durum wheat. A further reduction in kernel softness may expand further durum wheat's importance as a global food.
Oxidative Coupling of Coumarins by Blue‐LED‐Driven in situ Activation of Horseradish Peroxidase in a Two‐Liquid‐Phase System
Authors: Zippilli Claudio , Bizzarri Bruno Mattia , Gabellone Sofia , Botta Lorenzo , Saladino Raffaele 
Published: July 2021

AbstractA blue‐LED‐driven two‐liquid‐phase system has been set up for the in situ activation of horseradish peroxidase avoiding the use of hydrogen peroxide and drawbacks related to enzyme denaturation and undesired radical side‐reactions. The photobiocatalytic system was applied for the oxidative coupling of natural and synthetic coumarins to bicoumarins, allowing to obtain homodimers in only one step, avoiding the use of tedious protecting groups. Two natural C‐2 symmetric bicoumarins derived from the coupling of scopoletin were synthesized for the first time. UV‐visible spectrophotometry analysis confirmed the radical‐free and blue‐LED‐driven in situ oxidation of the green solvent 2‐methyltetrahydrofuran to the corresponding hydroperoxide, which in turn oxidizes the ferric heme of horseradish peroxidase to ferryl intermediate, triggering the oxidative coupling reaction.
Selbstheilende Polymere – auch rezyklierbar
Authors: Marinow Anja , Rupp Harald , Binder Wolfgang H. 
Published: July 2021

ZusammenfassungWährend noch vor wenigen Jahren selbstheilende Materialien eher als Konzept denn als brauchbare Alternative zu bestehenden Materialien angesehen wurden, hat sich dies inzwischen geändert. Besonders wenn es um eher geringe Materialmengen in Produkten geht (Beschichtungen, Elektrolyte, elektronische Bauteile) ist der Einsatz von Selbstheilung durchaus zielführend und auch wirtschaftlich ansprechend. Auch bei Massenanwendungen wie im Automobilbereich werden solche Konzepte bereits umgesetzt. Insgesamt ist aber immer eine grundlegende technologische Anpassung von Prozessen und auch Materialien nötig, wenn man neue Wege geht. Es ist erkennbar, dass die Industrie – sicher auch im Spannungsfeld von Umweltaspekten – bereit ist, diesen Weg zu gehen und selbstheilende, neue Materialien und Polymere breitflächig einzusetzen.
Combined molecular and histologic end points inform cancer risk estimates for thyroid nodules classified as atypia of undetermined significance
Authors: Onken Allison M. , VanderLaan Paul A. , Hennessey James V. , Hartzband Pamela , Nishino Michiya 
Published: July 2021

BackgroundThyroid nodules classified as atypia of uncertain significance (AUS) on fine‐needle aspiration cytology are heterogeneous. Prior studies reported a higher risk of noninvasive follicular thyroid neoplasm with papillary‐like nuclear features (NIFTP)/cancer among AUS nodules that had cytologic (AUS‐C) versus architectural (AUS‐A) atypia; however, such studies were generally confined to resected cohorts, introducing bias into risk calculations. The authors hypothesized that combined histologic and molecular end points would permit clinically meaningful calculations of NIFTP/malignancy risk among AUS nodules.MethodsThe study consisted of 279 thyroid nodules classified as AUS on initial fine‐needle aspiration and tested by the Afirma Gene Expression Classifier (GEC) between June 2013 and October 2017. Results of GEC testing and histopathologic diagnoses were stratified by AUS classifiers. The AUS‐A category was further subclassified as 1) hypocellular microfollicular or 2) cellular with mixed but predominantly microfollicular architecture. NIFTP/cancer risk was calculated for each subgroup, with the inclusion of unresected nodules that had benign GEC results as low‐risk end points comparable to histologically benign nodules.ResultsWhen only histologic end points were considered, there was no difference in NIFTP/cancer risk (25% vs 23%; P = .82). By using molecular and histologic end points, AUS cases with cytologic atypia trended toward higher NIFTP/cancer risk than AUS‐A cases (14% vs 6%; P = .06). Furthermore, AUS‐A cases showed a trend toward lower NIFTP/cancer risk for hypocellular microfollicular aspirates (3%) compared with cellular samples that had mixed/predominantly microfollicular architecture (13%; P = .18).ConclusionsThe inclusion of unresected benign GEC nodules in risk‐of‐malignancy calculations provides more accurate results, which may be helpful for informing patient management as well as quality improvement in the cytopathology laboratory.
Rational Development of a Metal‐Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation
Authors: Mahaut Damien , Chardon Aurélien , Mineur Loïc , Berionni Guillaume , Champagne Benoît 
Published: July 2021

AbstractThe activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1‐aza‐9‐boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion‐interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1‐aza‐9‐boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side‐attack, and space proximity between the B and N atoms.
Collaborative governance: The role of university centers, institutes, and programs
Authors: Kern Michael A. , Smutko L. Steven 
Published: July 2021

AbstractFor almost four decades, universities have played a significant role in developing the field of collaborative governance in the United States, including the establishment of centers that contribute to teaching and training, research and scholarship, and practice. In this article, we describe the evolution of university‐based collaborative governance in the United States, summarize results and key findings from a survey of centers, identify a typology of centers, describe how these centers have adapted to fit the states and regions where they operate, present two centers as examples, and make observations about the future of collaborative governance at universities.
Low‐Temperature Methanol‐Water Reforming Over Alcohol Dehydrogenase and Immobilized Ruthenium Complex
Authors: Shen Yangbin , Wang Luqi , Xu Ziwen , Ning Fandi , Zhan Yulu , Bai Chuang , Zhou Xiaochun 
Published: July 2021

AbstractHydrogen is one of the most promising sustainable energy carriers for its high gravimetric energy density and abundance. Nowadays, hydrogen production and storage are the main constraints for its commercialization. As a current research focus, hydrogen production from methanol‐water reforming, especially at low temperature, is particularly important. In this study, a novel reaction path for low‐temperature methanol reforming through synergistic catalysis was developed. Alcohol dehydrogenase (ADH) and coenzyme I (nicotinamide adenine dinucleotide, NAD+) were employed for methanol catalytic dehydrogenation at low temperature, which could generate formaldehyde and reductive coenzyme I (NADH). Covalent triazine framework‐immobilized ruthenium complex (Ru‐CTF) was prepared afterwards. On one hand, the catalyst exhibited high activity for the formaldehyde–water shift reaction to generate hydrogen and carbon dioxide. On the other hand, the NADH dehydrogenation was also catalyzed by the Ru‐CTF, producing NAD+ and hydrogen. Additionally, the catalyst also showed high biocompatibility with ADH. Through the synergistic effect of the above two main processes, methanol could be converted into hydrogen and carbon dioxide stably at low temperature for more than 96 h. The hydrogen production rate was dependent on the pH of the reaction solution as well as the ADH dosage. A hydrogen production rate of 157 mmol h−1 mol−1Ru was achieved at the optimum pH (8.1). Additionally, the hydrogen production rate increased linearly with the ADH dosage, reaching 578 mmol h−1 mol−1Ru when the ADH dosage was 180 U at 35 °C. This research could not only help overcome the difficulties for methanol reforming near room temperature but also give new inspiration for designing new reaction pathways for methanol reforming.
The advent of ab initio simulations of dense plasmas
Authors: Clérouin Jean , Recoules Vanina , Soubiran Francois 
Published: July 2021

AbstractWe present the story of full three‐dimensional ab initio simulation techniques of dense plasmas based on the Kohn–Sham realization of the density functional theory, starting from early attempts using the Car–Parrinello method to the most recent approaches based on density matrix. We recall the decisive role played by two experiments, one on the Nova laser and the other at a much smaller scale, with pulsed electrical discharges. We emphasize that the essential roles of the Physics of Non‐Ideal Plasmas (PNP) and Strongly Coupled Coulomb Systems (SCCS) conference series were most results, and simulation tools were presented and discussed under the benevolent presence of Vladimir Fortov.
Grazing alters species relative abundance by affecting plant functional traits in a Tibetan subalpine meadow
Authors: He Qifang , Jiang Kai , Hou Weicheng , Zhao Yang , Sun Xinhang , Wang Lu , Zou Yike , Zhu Zhenhao , Zhang Hui 
Published: July 2021

AbstractDomestic livestock grazing has caused dramatic changes in plant community composition across the globe. However, the response of plant species abundance in communities subject to grazing has not often been investigated through a functional lens, especially for belowground traits. Grazing directly impacts aboveground plant tissues, but the relationships between above‐ and belowground traits, and their influence on species abundance are also not well known. We collected plant trait and species relative abundance data in the grazed and nongrazed meadow plant communities in a species‐rich subalpine ecosystem of the Qinghai–Tibet Plateau. We measured three aboveground traits (leaf photosynthesis rate, specific leaf area, and maximum height) and five belowground traits (root average diameter, root biomass, specific root length, root tissue density, and specific root area). We tested for shifts in the relationship between species relative abundance and among all measured traits under grazing compared with the nongrazed meadow. We also compared the power of above‐ and belowground traits to predict species relative abundance. We observed a significant shift from a resource conservation strategy to a resource acquisition strategy. Moreover, this resource conservation versus resource acquisition trade‐off can also determine species relative abundance in the grazed and nongrazed plant communities. Specifically, abundant species in the nongrazed meadow had aboveground and belowground traits that are associated with high resource conservation, whereas aboveground and belowground traits that are correlated with high resource acquisition determined species relative abundance in the grazed meadow. However, belowground traits were found to explain more variances in species relative abundance than aboveground traits in the nongrazed meadow, while aboveground and belowground traits had comparable predictive power in the grazed meadow. We show that species relative abundance in both the grazed and the nongrazed meadows can be predicted by both aboveground traits and belowground traits associated with a resource acquisition versus conservation trade‐off. More importantly, we show that belowground traits have higher predictive power of species relative abundance than aboveground traits in the nongrazed meadow, whereas in the grazed meadows, above‐ and belowground traits had comparable high predictive power.
Disparate movement behavior and feeding ecology in sympatric ecotypes of Atlantic cod
Authors: Kristensen Martin Lykke , Olsen Esben Moland , Moland Even , Knutsen Halvor , Grønkjær Peter , Koed Anders , Källo Kristi , Aarestrup Kim 
Published: July 2021

AbstractCoexistence of ecotypes, genetically divergent population units, is a widespread phenomenon, potentially affecting ecosystem functioning and local food web stability. In coastal Skagerrak, Atlantic cod (Gadus morhua) occur as two such coexisting ecotypes. We applied a combination of acoustic telemetry, genotyping, and stable isotope analysis to 72 individuals to investigate movement ecology and food niche of putative local “Fjord” and putative oceanic “North Sea” ecotypes—thus named based on previous molecular studies. Genotyping and individual origin assignment suggested 41 individuals were Fjord and 31 were North Sea ecotypes. Both ecotypes were found throughout the fjord. Seven percent of Fjord ecotype individuals left the study system during the study while 42% of North Sea individuals left, potentially homing to natal spawning grounds. Home range sizes were similar for the two ecotypes but highly variable among individuals. Fjord ecotype cod had significantly higher δ13C and δ15N stable isotope values than North Sea ecotype cod, suggesting they exploited different food niches. The results suggest coexisting ecotypes may possess innate differences in feeding and movement ecologies and may thus fill different functional roles in marine ecosystems. This highlights the importance of conserving interconnected populations to ensure stable ecosystem functioning and food web structures.
Top predator introduction changes the effects of spatial isolation on freshwater community structure
Authors: Pelinson Rodolfo Mei , Leibold Mathew A. , Schiesari Luis 
Published: July 2021

AbstractCurrent conceptual metacommunity models predict that the consequences of local selective pressures on community structure increase with spatial isolation when species favored by local conditions also have higher dispersal rates. This appears to be the case of freshwater insects in the presence of fish. The introduction of predatory fish can produce trophic cascades in freshwater habitats because fish tend to prey upon intermediate predatory taxa, such as predatory insects, indirectly benefiting herbivores and detritivores. Similarly, spatial isolation can limit dispersal and colonization rates of predatory insects more strongly than of herbivores and detritivores, thus generating similar cascading effects. Here we tested the hypothesis that the effect of introduced predatory fish on insect community structure increases with spatial isolation by conducting a field experiment in artificial ponds that manipulated the presence/absence of fish (the redbreast tilapia) at three different distances from a source wetland. Our results showed that fish have direct negative effects on the abundance of predatory insects but probably have variable net effects on the abundance of herbivores and detritivores because the direct negative effects of predation by fish may offset indirect positive ones. Spatial isolation also resulted in indirect positive effects on the abundance of herbivores and detritivores but this effect was stronger in the absence rather than in the presence of fish so that insect communities diverged more strongly between fish and fishless ponds at higher spatial isolation. We argue that an important additional mechanism, ignored in our initial hypothesis, was that as spatial isolation increases fish predation pressure upon herbivores and detritivores increases due to the relative scarcity of predatory insects, thus dampening the positive effect that spatial isolation confers to lower trophic levels. Our results highlight the importance of considering interspecific variation in dispersal and multiple trophic levels to better understand the processes generating community and metacommunity patterns.
Electrochemical Kinetic Modulators in Lithium–Sulfur Batteries: From Defect‐Rich Catalysts to Single Atomic Catalysts
Authors: Zhang Jing , You Caiyin , Lin Hongzhen , Wang Jian 
Published: July 2021

Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density (2600 W h kg−1) among next‐generation storage systems. However, the sluggish electrochemical kinetics of sulfur reduction reactions, sulfide oxidation reactions in the sulfur cathode, and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high‐rate conversions and uniform deposition to achieve high performances. Thanks to the “adsorption‐catalysis” synergetic effects, the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li2S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers, inhibiting polysulfide shuttling. Meanwhile, the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth. In this review, the various active catalysts in modulating lithium behaviors are summarized, especially for the defect‐rich catalysts and single atomic catalysts. The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted. Furthermore, the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected, shedding light on the future practical development.
Continuous Shape Measures Study of the Coordination Spheres of Actinide Complexes – Part 1: Low Coordination Numbers
Authors: Alvarez Santiago 
Published: July 2021

AbstractStructural analyses of a large set of molecular structures of actinide compounds allow us to establish trends for stereochemical preferences, common distortion paths, geometrical constraints imposed by different ligand topologies, and the existence of incipient bonds or of Van der Waals intramolecular interactions on purportedly vacant coordination sites. In this study the relative abundance of coordination numbers in actinide chemistry appears to be on average higher than that among the lanthanides. The detailed continuous shape measures study of normalized coordination polyhedra with coordination numbers between 1 and 6 presented here is based on more than 1,800 solid state and gas phase structural data sets.
Synthesis, Coordination and Electrochemistry of a Ferrocenyl‐Tagged Aminobisphosphane Ligand
Authors: Navrátil Michal , Císařová Ivana , Štěpnička Petr 
Published: July 2021

AbstractIntroducing a ferrocene moiety into a molecule results in the incorporation of a metal center and a redox active moiety. This contribution describes the synthesis of FcN(CH2PPh2)2 (1; Fc=ferrocenyl), a ferrocene analog of the widely studied bis‐phosphane pincer ligands, RN(CH2PPh2)2. Compound 1 was studied as a ligand in complexes of Group 10 and 11 metal ions. The following compounds were synthesized and characterized using a combination of spectroscopic methods and single‐crystal X‐ray diffraction analysis: the square planar complexes [MX2(1‐κ2P,P’)] (M/X=Ni/Cl, Pd/Cl, Pd/Br, Pd/I and Pt/Cl) and the tetrahedral complexes [M(1‐κ2P,P’)2]X (M/X=Cu/PF6, Ag/SbF6 and Au/SbF6). Furthermore, a pair of open and cyclic digold(I) complexes containing bis‐phosphane 1 as a P,P‐bridging ligand, viz. [(μ(P,P’)‐1)(AuCl)2] and [(μ(P,P’)‐1)2Au2][SbF6]2, were isolated. Ligand 1, the corresponding phosphane selenide 1‐Se and all complexes (except for the poorly soluble [(μ(P,P’)‐1)2Au2][SbF6] and unstable [Ag(1‐κ2P,P’)2][SbF6]) were further analyzed by cyclic voltammetry.