bluuebunny/crossref_metadata_2025_split huggingface dataset:
Contrasting the Mechanism of H2Activation by Monomeric and Potassium‐Stabilized Dimeric AlIComplexes: Do Potassium Atoms Exert any Cooperative Effect?
Authors: Villegas‐Escobar Nery , Toro‐Labbé Alejandro , Schaefer Henry F. 
Published: October 2021

AbstractAluminyl anions are low‐valent, anionic, and carbenoid aluminum species commonly found stabilized with potassium cations from the reaction of Al‐halogen precursors and alkali compounds. These systems are very reactive toward the activation ofσ‐bonds and in reactions with electrophiles. Various research groups have detected that the potassium atoms play a stabilization role via electrostatic and cationinteractions with nearby (aromatic)‐carbocyclic rings from both the ligand and from the reaction with unsaturated substrates. Since stabilizing K⋯H bonds are witnessed in the activation of this class of molecules, we aim to unveil the role of these metals in the activation of the smaller and less polarizable H2molecule, together with a comprehensive characterization of the reaction mechanism. In this work, the activation of H2utilizing a NON‐xanthene‐Al dimer, [K{Al(NON)}]2(D) and monomeric, [Al(NON)]−(M) complexes are studied using density functional theory and high‐level coupled‐cluster theory to reveal the potential role of K+atoms during the activation of this gas. Furthermore, we aim to reveal whetherDis more reactive thanM(or vice versa), or if complicity between the two monomer units exits within theDcomplex toward the activation of H2. The results suggest that activation energies using the dimeric and monomeric complexes were found to be very close (around 33 kcal mol−1). However, a partition of activation energies unveiled that the nature of the energy barriers for the monomeric and dimeric complexes are inherently different. The former is dominated by a more substantial distortion of the reactants (and increased interaction energies between them). Interestingly, during the oxidative addition, the distortion of the Al complex is minimal, while H2distorts the most, usually over 0.77. Overall, it is found here that electrostatic and induction energies between the complexes and H2are the main stabilizing components up to the respective transition states. The results suggest that the K+atoms act as stabilizers of the dimeric structure, and their cooperative role on the reaction mechanism may be negligible, acting as mere spectators in the activation of H2. Cooperation between the two monomers inDis lacking, and therefore the subsequent activation of H2is wholly disengaged.
Palladium‐Catalyzed Carbonylative Four‐Component Synthesis of β‐Perfluoroalkyl Amides
Authors: Zhang Youcan , Geng Hui‐Qing , Wu Xiao‐Feng 
Published: October 2021

AbstractTransition‐metal‐catalyzed multicomponent carbonylation is one of the most efficient strategies to construct carbonyl‐containing compounds. Herein, a palladium‐catalyzed four‐component perfluoroalkylation/aminocarbonylation of unactivated alkenes with perfluoroalkyl halides, and amines was developed. A wide range of substrates, including anilines, alkylamines, sulfonamides, and hydrazines are all suitable reaction partners for this catalyst system, resulting in various β‐perfluoroalkyl amides with good functional‐group tolerance and excellent chemoselectivity. Furthermore, not only alkyl olefins, but also aliphatic alkynes, and even alkyl allenes can all be employed. Notably, several medical and bioactive related molecules are compatible here as well.
The relationship between job standardization and abusive supervision
Authors: Mao Hsiao‐Yen , Hsieh An‐Tien , Mao Chueh‐Wei 
Published: October 2021

AbstractJob standardization is widely used to ensure uniform, efficient, and effective production and resultant organizational performance. However, phenomena suggests that employees with high job standardization seem to have a negative relationship with their supervisors. Using job demands–resources theory as an underlying explanation, this study proposes that job standardization enhances a negative supervisor–subordinate relationship characterized by abusive supervision. Three‐wave panel and two‐source survey data were collected from 255 employees and their supervisors. Empirical results indicated job standardization enhanced abusive supervision partially through the decreased appraisal respect of subordinates for supervisors and that of supervisors for subordinates. The results indicate a dilemma in employing the job design of standardization: on the one hand, it facilitates managerial effectiveness; on the other hand, it can decrease that effectiveness by deteriorating the supervisor–subordinate relationship. This study extends and shifts the understanding of the consequences of job standardization from the employee perspective to the managerial perspective.
Selective Monovalent Galectin‐8 Ligands Based on 3‐Lactoylgalactoside
Authors: Girardi Benedetta , Manna Martina , Van Klaveren Sjors , Tomašič Tihomir , Jakopin Žiga , Leffler Hakon , Nilsson Ulf J. , Ricklin Daniel , Mravljak Janez , Schwardt Oliver , Anderluh Marko 
Published: October 2021

AbstractGalectin‐8 has gained attention as a potential new pharmacological target for the treatment of various diseases, including cancer, inflammation, and disorders associated with bone mass reduction. To that end, new molecular probes are needed in order to better understand its role and its functions. Herein we aimed to improve the affinity and target selectivity of a recently published galectin‐8 ligand, 3‐O‐[1‐carboxyethyl]‐β‐d‐galactopyranoside, by introducing modifications at positions 1 and 3 of the galactose. Affinity data measured by fluorescence polarization show that the most potent compound reached a KD of 12 μM. Furthermore, reasonable selectivity versus other galectins was achieved, making the highlighted compound a promising lead for the development of new selective and potent ligands for galectin‐8 as molecular probes to examine the protein's role in cell‐based and in vivo studies.
Omission of sentinel node biopsy for breast cancer: Historical context and future perspectives on a modern controversy
Authors: Jatoi Ismail , Kunkler Ian H. 
Published: October 2021

For older patients with clinically lymph node‐negative breast cancer who have estrogen receptor‐positive tumors and are treated with tamoxifen, randomized trials comparing axillary lymph node dissection (ALND) versus no ALND show that the omission of ALND improves patient quality of life and has no adverse effects on mortality. These results have served to justify sentinel node biopsy (SNB) omission in selected older patients with breast cancer. More recently, clinical trials were launched to assess SNB omission in younger patients, with recurrence and survival as the primary outcomes of interest. Three important considerations serve as the basis for these ongoing trials. First, it is assumed that SNB omission will improve patient quality of life, although, to date, there is no level I evidence to support this assumption. Second, axillary surgery has never been shown to reduce breast cancer mortality, but it does reduce the risk of axillary recurrences, although adjuvant systemic therapy and radiotherapy also reduce these recurrence risks. Finally, nodal status is losing importance as a guide for adjuvant systemic therapy decision making because these decisions are now increasingly predicated on tumor biomarkers and gene profiling, but it is gaining importance for adjuvant radiotherapy decision making. Because quality‐of‐life considerations are the primary motivation for abandoning SNB, there is a need for randomized trials comparing SNB versus no SNB/no axillary surgery, with quality of life as the primary end point (level I evidence). Moreover, suitable alternatives to guide adjuvant radiotherapy decision making will require validation before SNB omission can be justified for patients of all ages who have clinically node‐negative breast cancer.Lay Summary

In this review article, the authors provide a brief historical overview of the role of axillary surgery in breast cancer management and discuss additional studies and ramifications that should be considered before abandoning the sentinel node biopsy (SNB) procedure.

Specifically, there is a need for level I evidence demonstrating that omission of the SNB procedure will improve patient quality of life and a need to validate suitable alternatives to SNB as a guide for adjuvant radiotherapy decision making.
Characterization and manipulation of Corticothalamic neurons in associative cortices using Syt6‐Cre transgenic mice
Authors: Vaasjo Lee O. , Han Xiao , Thurmon Abbigail N. , Tiemroth Alina S. , Berndt Hallie , Korn Madelyn , Figueroa Alexandra , Reyes Rosa , Feliciano‐Ramos Pedro A. , Galazo Maria J. 
Published: October 2021

AbstractCorticothalamic interactions between associative cortices and higher order thalamic nuclei are involved in high‐cognitive functions such as decision‐making and working memory. Corticothalamic neurons (CTn) in the prefrontal cortex and other associative areas have been much less studied than their counterparts in the primary sensory areas. The availability of characterized transgenic tools to study CTn in associative areas will facilitate their study and contribute to overcome the scarcity of data about their properties, network dynamics, and contribution to cognitive functions.Here, we characterized the Syt6‐Cre (KI148Gsat/Mmud) transgenic mouse line, by tracking expression of a Cre‐mediated reporter. In this line, Cre‐reporter is strongly expressed in the prefrontal, motor, cingulate, and retrosplenial cortices, as well as in other brain areas including the cerebellum and the olfactory tubercle. Cortical expression starts embryonically and reaches the adult expression pattern by postnatal day 15. In the cortex, Cre‐reporter is expressed by layer 6‐CTn and by layer 5‐CTn to a lesser extent. We quantified Syt6‐Cre+ CTn axon varicosities to estimate the distribution and density of putative corticothalamic driver and modulator inputs to thalamic nuclei in the medial, midline, intralaminar, anterior, and motor groups. Also, we characterized the effect of optogenetic stimulation of Syt6‐Cre+ neurons in the activity of the prefrontal cortex. CTn stimulation in the prefrontal cortex induces an oscillatory activity in the local field potential that resembles the cortical downstates typically observed during slow‐wave sleep or quiet wake.
Mutation profile of acute myeloid leukaemia in a Chinese cohort by targeted next‐generation sequencing
Authors: Lit Benny Man Wai , Guo Belinda B. , Malherbe Jacques A. J. , Kwong Yok Lam , Erber Wendy N. 
Published: October 2021

AbstractBackgroundAcute myeloid leukaemia (AML) results from the clonal expansion of blast cells of myeloid origin driven by genomic defects. The advances in next‐generation sequencing (NGS) have allowed the identification of many mutated genes important in the pathogenesis of AML.AimsIn this study, we aimed to assess the mutation types and frequency in a Chinese cohort presenting with de novo AML cohort using a targeted NGS strategy.MethodsIn total, we studied samples from 87 adult patients with de novo AML who had no prior history of cytotoxic chemotherapy. Samples were evaluated using a 120‐gene targeted NGS panel to assess the mutation profile.ResultsOf the 87 AML patients, there were 60 (69%) with a normal karyotype. 89.7% of patients had variants, with an average of 1.9 mutations per patient (range: 0–5 mutations per patient). DNMT3A variants were the most common, being detected in 33 patients (37.9%). NPM1 (34.5%), IDH1/2 (24.1%) and FLT3‐ITD (20.7%) mutations was the next most common. Of the patients with DNMT3A mutations, 24.2% also had mutations NPM1 and FLT3‐ITD and 6.1% NPM1, FLT3‐ITD and IDH mutations.ConclusionBoth DNMT3A and NPM1 mutations were more common than in other Chinese and Western AML cohorts that have been studied. DNMT3A mutations tended to co‐occur with NPM1 and FLT3‐ITD mutations and were most commonly seen with a normal karyotype.
Informal preparation and years of experience: Key correlates of dyslexia knowledge among Massachusetts early elementary teachers
Authors: Mullikin Katelyn , Stransky Michelle , Tendulkar Shalini , Casey Mary , Kosinski Karen 
Published: October 2021

BackgroundDyslexia is a neurobiological condition affecting phonological processing and characterized by reading and phonological awareness difficulties. We assessed correlations between dyslexia knowledge and five independent variables among early elementary teachers in Massachusetts.MethodsWe designed a survey based on two published assessment tools and surveyed 92 early elementary teachers. Using univariate and multivariate linear regression models, we assessed the relationships among knowledge (dependent variable) and confidence, feelings of preparedness, years of teaching experience, informal education and professional development opportunities (independent variables).ResultsThe mean knowledge score was 68 ± 14%; teachers performed best on questions about perceptions of dyslexia, classroom management/teaching strategies and some dyslexia characteristics. Informal education and years of teaching experience were consistently positively associated with knowledge.Discussion and ConclusionsFormal training and professional development opportunities may need to focus more specifically on learning disabilities and dyslexia. Teachers should also have input on professional development needs. Our findings suggest a need for additional studies on strategies to improve educator knowledge of dyslexia and assess outcomes.
“No‐regrets” pathways for navigating climate change: planning for connectivity with land use, topography, and climate
Authors: Schloss Carrie A. , Cameron D. Richard , McRae Brad H. , Theobald David M. , Jones Aaron 
Published: October 2021

AbstractAs both plant and animal species shift their ranges in response to a changing climate, maintaining connectivity between present habitat and suitable habitat in the future will become increasingly important to ensure lasting protection for biodiversity. Because the temporal period commensurate with planning for mid‐century change is multi‐generational for most species, connectivity designed to facilitate climate adaptation requires pathways with ‘stepping‐stones’ between current and future habitat. These areas should have habitats suitable not only for dispersal, but for all aspects of species lifecycles. We integrated present‐day land use, topographic diversity, and projections of shifting climate regimes into a single connectivity modeling approach to identify pathways for mid‐century shifts in species ranges. Using Omniscape we identified climate linkages, or areas important for climate change‐driven movement, as the areas with more current flow than would be expected in the absence of climate considerations. This approach identified connectivity potential between natural lands in the present climate and natural lands with future analogous climate following topo‐climatically diverse routes. We then translated the model output into a strategic framework to improve interpretation and to facilitate a more direct connection with conservation action. Across modified landscapes, pathways important to climate‐driven movement were highly coincident with the last remaining present‐day linkages, reinforcing their importance. Across unfragmented lands, the presence of climate‐adapted pathways helped inform the prioritization of conservation actions in areas where multiple connectivity options still exist. Many climate linkages follow major watercourses along elevational gradients, highlighting the importance of protecting or managing for these natural linear pathways that provide movement routes for climate adaptation. By integrating enduring landscape features with climate projections and present‐day land uses, our approach reveals “no‐regrets” pathways to plan for a connected landscape in an uncertain future.
Activity density at a continental scale: What drives invertebrate biomass moving across the soil surface?
Authors: Kaspari Michael , Weiser Michael D. , Marshall Katie E. , Miller Matthew , Siler Cameron , de Beurs Kirsten 
Published: October 2021

AbstractActivity density (AD), the rate that an individual taxon or its biomass moves through the environment, is used both to monitor communities and quantify the potential for ecosystem work. The Abundance Velocity Hypothesis posited that AD increases with aboveground net primary productivity (ANPP) and is a unimodal function of temperature. Here we show that, at continental extents, increasing ANPP may have nonlinear effects on AD: increasing abundance, but decreasing velocity as accumulating vegetation interferes with movement. We use 5 yr of data from the NEON invertebrate pitfall trap arrays including 43 locations and four habitat types for a total of 77 habitat–site combinations to evaluate continental drivers of invertebrate AD. ANPP and temperature accounted for one‐third to 92% of variation in AD. As predicted, AD was a unimodal function of temperature in forests and grasslands but increased linearly in open scrublands. ANPP yielded further nonlinear effects, generating unimodal AD curves in wetlands, and bimodal curves in forests. While all four habitats showed no AD trends over 5 yr of sampling, these nonlinearities suggest that trends in AD, often used to infer changes in insect abundance, will vary qualitatively across ecoregions.
n‐Butanol: An Ecologically and Economically Viable Extraction Solvent for Isolating Polar Products from Aqueous Solutions
Authors: Reetz Manfred T. , König Gerhard 
Published: October 2021

AbstractWater is the solvent of choice in terms of greenness and sustainability. However, it can be difficult to isolate very polar products from water. Here, we discuss the use of n‐butanol as a solvent to extract polar compounds from aqueous solution. n‐Butanol produces high yields and can also be sourced sustainably from biomass, which makes it attractive from a climate perspective. The reason for its high efficiency is that the wet n‐butanol phase is a nanomaterial that incorporates little pockets of water that can stabilize the polar solute. Thus, the environment remains very water‐like, and the presence of hydrophobic groups can tip the equilibrium towards the n‐butanol phase. We also discuss a simple estimate whether n‐butanol will be an efficient extraction solvent for the compound of interest based on common public databases. This should help to guide practicing organic chemists during the solvent selection process.
Asymmetric Synthesis of Pentasubstituted Cyclohexanes through Diphenylprolinol Silyl Ether Mediated Domino Michael/Michael Reaction
Authors: Odoh Amaechi Shedrack , Aidanpää Louise , Umekubo Nariyoshi , Matoba Hiroaki , Mori Naoki , Hayashi Yujiro 
Published: October 2021

AbstractAn asymmetric domino Michael/Michael reaction of α,β‐unsaturated aldehydes 1 and α‐acetyl‐β‐substituted‐α,β‐unsaturated esters 2 catalyzed by diphenylprolinol silyl ether was developed. This is a formal carbo [4+2] cycloaddition reaction affording penta‐substituted cyclohexanes having the three continuous chiral centers with excellent diastereo‐ and enantioselectivity.
Ruthenium‐Catalyzed Sulfoalkenylation of Acetanilides and Dual‐Use of the Catalyst Directing Group
Authors: Sand Patrick , Schmidt Bernd 
Published: October 2021

AbstractIn contrast to vinylsulfonates and vinylsulfones, vinylsulfonamides are unreactive in Pd‐catalyzed oxidative Heck‐coupling reactions with acetanilides. This limitation has been resolved by using a C−H‐activation protocol based on Ru−Cu−Ag‐catalysis. Overall, the Ru−Cu−Ag‐catalyzed conditions turned out to be more reliable and showed better reproducibility than the Pd‐catalyzed C−H‐activation. The coupling products thus obtained are functionalized styrenyl sulfones and –sulfonamides which can be used as starting materials for the synthesis of sulfonyl pyrroles and sulfonyl pyrrolo[2,3‐c]quinolines.
Optical investigation on combustion and soot formation characteristics of isopropanol‐butanol‐ethanol (IBE)/diesel blends
Authors: Li Gang , Dai Jiayi , Li Yangyang , Lee Timothy H. 
Published: October 2021

AbstractIsopropanol‐butanol‐ethanol (IBE) is considered to be a promising alternative fuel for diesel to reduce soot emissions. However, currently researchers have not yet revealed its soot formation processes. In this regard, the forward illumination light extinction (FILE) technology was used to investigate the soot formation process of IBE/diesel blends. Diesel containing 50% of IBE in volume (IBE50), pure IBE (IBE100), and diesel were tested. The experimental results show that soot formation regions for the tested fuels are greatly affected by the ambient conditions. The lower the ambient temperature is, the smaller the soot formation region is. Besides, a low ambient temperature coupled with a small ambient oxygen concentration may further reduce soot formation regions of the tested fuels. Results also show that soot formation regions of IBE50 and IBE100 are obviously smaller than that of diesel. In most test conditions, the head of soot formation regions for IBE50 and IBE100 exhibits as a thin strip. Furthermore, soot formation duration and intensity of IBE50 and IBE100 are obviously small in comparison with diesel, especially at low ambient temperature. The results of this study indicate that when IBE is directly blended with diesel, it is able to reduce soot emissions.
Urban sustainability: Lessons from organisms and ecosystems
Authors: Edwards Peter 
Published: October 2021

AbstractThe services essential for urban life include provision of electricity and water, disposal of sewage and solid waste, and management of stormwater. In the past two centuries, the infrastructure providing these services has become increasingly large and centralized, which from a sustainability perspective is problematic. I argue that, to be sustainable, a city must be integrated like a living organism, while having the resilience properties of a mature ecosystem. For the provision of infrastructure, this means that today's massive, highly centralized facilities must give way to more distributed yet interconnected systems.
Clean Energy Goals Driving Utilities to Accelerate Pipeline Replacements and Leak Detection Technologies
Authors: Mangeney Estelle , Tiwari Ashish Mohan , Vangala Shreyas 
Published: October 2021

Maintaining pipeline safety is a primary function of natural gas utilities, referring to a publicly acceptable condition in which society is protected against leak incidents that can lead to explosions, fires, and death. Replacing pipelines is a difficult task, especially those in densely populated areas dominated by paved surfaces. Pipelines are often co‐located with other electric, telecommunications and water infrastructures in approved “rights of way.” Local regulations often restrict street closures and hours that crews can work on utility infrastructure. While the probability of a pipeline incident is low the consequences of an incident can be substantial. Gas leaks release methane in the atmosphere and it is important to note that methane breaks up in the atmosphere more quickly. Repairing gas leaks could also have an immediate effect toward meeting global emission‐reduction goals.