bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reactivity of 4‐phenylthiazoles in ruthenium catalyzed direct arylations
Authors: Daher Ahmad , Jacquemin Denis , Guerchais Véronique , Soulé Jean‐François , Doucet Henri 
Published: February 2019

The reactivity of the phenyl substituent of 4‐phenylthiazoles in Ru‐catalyzed direct arylation was studied. 4‐Phenylthiazole was found to be unreactive; whereas, the introduction of an aryl unit at C5‐position of 4‐phenylthiazole enhances its reactivity, allowing the selective mono‐arylation of the phenyl unit of 4‐phenylthiazoles in moderate to high yields using 5 mol% of [Ru(p‐cymene)Cl2]2 catalyst precursor associated to KOPiv as base. These results reveal that the conformation and electronic properties of 4‐phenylthiazoles are crucial to allow the formation of suitable intermediates in the course of the catalytic cycle. The reaction tolerated both electron‐rich and electron‐poor aryl bromides allowing the straightforward tuning of the electronic properties of the arylated 2‐methyl‐4‐phenyl‐5‐arylthiazoles.
A novel modeling and controlling approach for high‐order nonlinear systems
Authors: Chen Lei , Yan Yan , Sun Changyin 
Published: February 2019

AbstractThis paper proposes a completely data–driven control law for a class of high–order nonlinear systems based on their virtual characteristic models. With sampled–data techniques and estimation methods, a novel lower–order adaptive characteristic model is constructed to reduce the system complexities. Moreover, a corresponding sliding mode control law is designed, which can guarantee tracking errors of the resulting closed‐loop system converging into a predefined bound in finite time. The practical examples are provided to illuminate the effectiveness of the proposed approaches.
Availability and Utility of Peer Review and Emotional Support for Paediatricians Involved in Safeguarding in the UK
Authors: Richardson Michelle , Josty Tamsin 
Published: February 2019

Key Practitioner Messages

This survey suggests that peer review is widely available to responding UK paediatricians, and is considered very useful for maintaining skills, knowledge and confidence.
Peer review is less effective at meeting clinicians' emotional support needs, with many relying instead on discussions with colleagues, family and friends, raising confidentiality concerns.
The majority of survey respondents would value access to some form of additional skilled support such as formal debriefing or psychologist‐ or counsellor‐mediated input.
Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides
Authors: Sicignano Marina , Schettini Rosaria , Sica Luisa , Pierri Giovanni , De Riccardis Francesco , Izzo Irene , Maity Bholanath , Minenkov Yury , Cavallo Luigi , Della Sala Giorgio 
Published: February 2019

AbstractThe first highly enantioselective arylogous Michael reaction (AMR) of 3‐unsubstituted phthalides has been described. This phase‐transfer methodology, which uses catalytic amounts of KOH/18‐crown‐6 catalyst in mesitylene in the presence of N,O‐bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3‐monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3‐unsubstituted derivatives and diverse α,β‐unsaturated carbonyl compounds. The reaction also applies to unactivated 3‐alkyl phthalides to afford 3,3‐dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.
Identification of an Overlooked Halogen‐Bond Synthon and Its Application in Designing Fluorescent Materials
Authors: Cheng Lu , Zhu Bingqing , Ma Xiaoyu , Zhang Zaiyong , Wang Jian‐rong , Zhang Qi , Mei Xuefeng 
Published: February 2019

AbstractResearch on new supramolecular synthons facilitates the progress of materials design. Herein, the ability of sp2 carbonyl oxygen atoms to act as halogen‐bond acceptors was established through cocrystallization. Four sets of carbonyl compounds, including aldehydes, ketones, esters, and amides, were selected as halogen‐bond acceptors. In the absence of strong hydrogen bonds, 14 out of 16 combinations of halogen‐bond donors and acceptors could form cocrystals, whereby the supramolecular synthon C=O⋅⋅⋅X acts as the main interaction. Further, the geometric parameters of the C=O⋅⋅⋅X interaction were statistically revealed on the basis of the crystallographic database. The bifurcated interaction mode that has been observed in other halogen‐bond synthons rarely occurs in the case of C=O⋅⋅⋅X. The robustness of C=O⋅⋅⋅X makes its application in crystal engineering possible and opens up new opportunities in designing multicomponent fluorescent materials, as indicated by multicolor emission of cocrystals D through C=O⋅⋅⋅X interactions.
Yttrium‐Mediated Ring‐Opening Copolymerization of Oppositely Configurated 4‐Alkoxymethylene‐β‐Propiolactones: Effective Access to Highly Alternated Isotactic Functional PHAs
Authors: Ligny Romain , Guillaume Sophie M. , Carpentier Jean‐François 
Published: February 2019

AbstractThe ring‐opening copolymerization (ROCOP) of functional 4‐alkoxymethylene‐β‐propiolactones (BPLORs) by yttrium‐bisphenolate complexes was investigated. The ROCOP of equimolar mixtures of BPLORs of opposite configurations, namely (R)‐BPLOR1/(S)‐BPLOR2 [R1, R2=OMe, OAllyl, OCH2Ph (=OBn), OSiMe2tBu (=OTBDMS)], by the syndioselective Y{ONOOcum}/iPrOH catalyst/initiator system affords P(HBOR1‐alt‐HBOR2) copolymers with high alternation degrees (altern.=89–94 %), as determined by comprehensive kinetic, 13C{1H} NMR spectroscopy, MALDI‐ToF MS and ESI MS/MS fragmentation studies. The ROCOP of the (R)‐BPLOMe/(S)‐BPLOTBDMS combination, featuring a large difference in the substituents’ bulkiness, constitutes the only observed exception to this trend (altern.=64 %). On the other hand, the isoselectivity of the Y{ONNOCl}/iPrOH catalyst/initiator system has been exploited to generate, in a one‐pot/one‐step procedure, original mixtures of isotactic poly(hydroxyalkanoate)s (PHAs). This system efficiently transforms equimolar mixtures of (R)‐BPLOAll/(S)‐BPLOMe into a 1:1 mixture of the corresponding isotactic iso‐(R)‐PHBOAll and iso‐(S)‐PHBOMe homopolymers; almost no copolymerization defects are observed. This new approach has been extended successfully to the ROCOP of equimolar mixtures of racemic monomers, rac‐BPLOAll/rac‐BPLOMe.
Pharmacokinetics, Food Effect, Ketoconazole Interaction, and Safety of JTK‐853, a Novel Nonnucleoside HCV Polymerase Inhibitor, After Ascending Single and Multiple Doses in Healthy Subjects
Authors: Tamaki Sekihiro , Shibata Tsutomu , Hunt Thomas , Gerhardt Barbara , Yamada Hiroyuki , Pai Sudhakar M. 
Published: February 2019

AbstractPharmacokinetics, safety, and tolerability of JTK‐853, a novel HCV polymerase inhibitor, were evaluated in single and multiple ascending dose (SAD, MAD) studies, with food‐ and ketoconazole‐related effects on exposure to JTK‐853 and its active (CYP3A4 mediated) metabolite M2. JTK‐853 was safe and well tolerated in both studies. In the SAD study, at doses >1600 mg (with standard breakfast [SBF]), JTK‐853 exposure did not increase further, was substantially higher (AUCinf increase: 3‐ to 8‐fold) with SBF (vs fasted), with a moderate increase in AUCinf (approximately 1.5‐fold [1600 mg]) with a high‐fat breakfast (vs SBF). In the SAD study (400–1600 mg, SBF), mean effective half‐life (t1/2(eff)) of JTK‐853 was 8.3 to 10.9 hours, and 20.3 to 27.3 hours in the MAD study (twice daily dosing, fed condition), with 2‐ to 3‐fold accumulation in exposure (AUCtau). At steady‐state, AUCtau increased dose proportionally, and was approximately 2‐fold higher with ketoconazole coadministration. Metabolite M2 (equipotent to JTK‐853 in vitro) did not contribute significantly to parent drug exposure and decreased with increase in dose, repeated dosing, and ketoconazole coadministration. Trial simulation‐based ratios (n = 1000/dose level) of trough JTK‐853 plasma concentrations to the in vitro EC90 for HCV genotype 1b were assessed for dose selection in a separate proof‐of‐concept study in patients. The studies enabled delineation of key drug attributes for further assessments in the target population.
Give or take? Consumers' ambivalent perspectives on the relationship between a firm's corporate social responsibility engagement and its responsible tax payments
Authors: Toder‐Alon Anat , Rosenstreich Eyal , Te'eni Harari Tali 
Published: February 2019

AbstractThe present study examines the mechanisms of the halo effect and the scepticism effect as alternative explanations for the association between a firm's corporate social responsibility (CSR) engagement and consumers' perceptions of its tax behaviour. The authors conduct two experimental studies to examine the impact of a company's CSR domain on consumers' perceptions of its tax practices (Study 1) and the impact of a company's CSR engagement and tax practices on consumers' evaluations of that company (Study 2). It was found that consumers' perceptions of a firm's tax practices critically depend on CSR domains. Specifically, when inferring tax perceptions from CSR engagement, consumers factor in their perceptions of the greater direct reputational benefits that firms derive from external CSR engagement (environmental and philanthropic CSR) compared with those they derive from internal CSR engagement (activities focused on intraorganisational stakeholders). Suggestions for managerial implications and future research are also discussed.
A few north Appalachian populations are the source of European black locust
Authors: Bouteiller Xavier Paul , Verdu Cindy Frédérique , Aikio Emmi , Bloese Paul , Dainou Kasso , Delcamp Adline , De Thier Olivier , Guichoux Erwan , Mengal Coralie , Monty Arnaud , Pucheu Marion , van Loo Marcela , Josée Porté Annabel , Lassois Ludivine , Mariette Stéphanie 
Published: February 2019

AbstractThe role of evolution in biological invasion studies is often overlooked. In order to evaluate the evolutionary mechanisms behind invasiveness, it is crucial to identify the source populations of the introduction. Studies in population genetics were carried out onRobinia pseudoacaciaL., a North American tree which is now one of the worst invasive tree species in Europe. We realized large‐scale sampling in both the invasive and native ranges: 63 populations were sampled and 818 individuals were genotyped using 113 SNPs. We identified clonal genotypes in each population and analyzed between and within range population structure, and then, we compared genetic diversity between ranges, enlarging the number of SNPs to mitigate the ascertainment bias. First, we demonstrated that European black locust was introduced from just a limited number of populations located in the Appalachian Mountains, which is in agreement with the historical documents briefly reviewed in this study. Within America, population structure reflected the effects of long‐term processes, whereas in Europe it was largely impacted by human activities. Second, we showed that there is a genetic bottleneck between the ranges with a decrease in allelic richness and total number of alleles in Europe. Lastly, we found more clonality within European populations. Black locust became invasive in Europe despite being introduced from a reduced part of its native distribution. Our results suggest that human activity, such as breeding programs in Europe and the seed trade throughout the introduced range, had a major role in promoting invasion; therefore, the introduction of the missing American genetic cluster to Europe should be avoided.
Prairie plant phenology driven more by temperature than moisture in climate manipulations across a latitudinal gradient in the Pacific Northwest, USA
Authors: Reed Paul B. , Pfeifer‐Meister Laurel E. , Roy Bitty A. , Johnson Bart R. , Bailes Graham T. , Nelson Aaron A. , Boulay Margaret C. , Hamman Sarah T. , Bridgham Scott D. 
Published: February 2019

AbstractPlant phenology will likely shift with climate change, but how temperature and/or moisture regimes will control phenological responses is not well understood. This is particularly true in Mediterranean climate ecosystems where the warmest temperatures and greatest moisture availability are seasonally asynchronous. We examined plant phenological responses at both the population and community levels to four climate treatments (control, warming, drought, and warming plus additional precipitation) embedded within three prairies across a 520 km latitudinal Mediterranean climate gradient within the Pacific Northwest, USA. At the population level, we monitored flowering and abundances in spring 2017 of eight range‐restricted focal species planted both within and north of their current ranges. At the community level, we used normalized difference vegetation index (NDVI) measured from fall 2016 to summer 2018 to estimate peak live biomass, senescence, seasonal patterns, and growing season length. We found that warming exerted a stronger control than our moisture manipulations on phenology at both the population and community levels. Warming advanced flowering regardless of whether a species was within or beyond its current range. Importantly, many of our focal species had low abundances, particularly in the south, suggesting that establishment, in addition to phenological shifts, may be a strong constraint on their future viability. At the community level, warming advanced the date of peak biomass regardless of site or year. The date of senescence advanced regardless of year for the southern and central sites but only in 2018 for the northern site. Growing season length contracted due to warming at the southern and central sites (~3 weeks) but was unaffected at the northern site. Our results emphasize that future temperature changes may exert strong influence on the timing of a variety of plant phenological events, especially those events that occur when temperature is most limiting, even in seasonally water‐limited Mediterranean ecosystems.
Phylofactorization: a graph partitioning algorithm to identify phylogenetic scales of ecological data
Authors: Washburne Alex D. , Silverman Justin D. , Morton James T. , Becker Daniel J. , Crowley Daniel , Mukherjee Sayan , David Lawrence A. , Plowright Raina K. 
Published: February 2019

AbstractThe problem of pattern and scale is a central challenge in ecology. In community ecology, an important scale is that at which we aggregate species to define our units of study, such as aggregation of “nitrogen fixing trees” to understand patterns in carbon sequestration. With the emergence of massive community ecological data sets, there is a need to objectively identify the scales for aggregating species to capture well‐defined patterns in community ecological data. The phylogeny is a scaffold for identifying scales of species‐aggregation associated with macroscopic patterns. Phylofactorization was developed to identify phylogenetic scales underlying patterns in relative abundance data, but many ecological data, such as presence‐absences and counts, are not relative abundances yet may still have phylogenetic scales capturing patterns of interest. Here, we broaden phylofactorization to a graph‐partitioning algorithm identifying phylogenetic scales in community ecological data. As a graph‐partitioning algorithm, phylofactorization connects many tools from data analysis to phylogenetically informed analyses of community ecological data. Two‐sample tests identify five phylogenetic factors of mammalian body mass which arose during the K‐Pg extinction event, consistent with other analyses of mammalian body mass evolution. Projection of data onto coordinates connecting the phylogeny and graph‐partitioning algorithm yield a phylogenetic principal components analysis which refines our understanding of the major sources of variation in the human gut microbiome. These same coordinates allow generalized additive modeling of microbes in Central Park soils, confirming that a large clade of Acidobacteria thrive in neutral soils. The graph‐partitioning algorithm extends to generalized linear and additive modeling of exponential family random variables by phylogenetically constrained reduced‐rank regression or stepwise factor contrasts. All of these tools can be implemented with the R package phylofactor.
Probing Magnetic Excitations in CoII Single‐Molecule Magnets by Inelastic Neutron Scattering
Authors: Stavretis Shelby E. , Cheng Yongqiang , Daemen Luke L. , Brown Craig M. , Moseley Duncan H. , Bill Eckhard , Atanasov Mihail , Ramirez‐Cuesta Anibal J. , Neese Frank , Xue Zi‐Ling 
Published: February 2019

AbstractInvited for the cover of this issue are groups of Zi‐Ling Xue from the University of Tennessee, Yongqiang Cheng, Luke Daemen, Timmy Ramirez‐Cuesta of Oak Ridge National Laboratory, Craig Brown of the NIST Center for Neutron Research and the University of Delaware, Eckhard Bill of Max Planck Institute for Chemical Energy Conversion, and Mihail Atanasov and Frank Neese of Max Planck Institute for Coal Research and Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences (MA). The cover image shows the use of inelastic neutron scattering (INS) to probe the Zeeman splitting of a single‐molecule magnet (SMM) inside a magnetic field.
Simple and Sensitive Determination of Sibutramine in Slimming Tea Beverages Using a Carbon Screen‐printed Electrode with Adsorptive Stripping Voltammetry
Authors: Lima Amanda B. , dos Santos Wallans T. P. , Compton Richard G. 
Published: February 2019

AbstractThe stimulant sibutramine is an anorexic agent found as an adulterant in natural products and multivitamins supplements used for weight‐loss. In this work, a carbon graphite screen‐printed electrode (SPE‐Gr) with adsorptive stripping pulse differential voltammetry (AdSDPV) is presented for the sensitive and simple detection of sibutramine in slimming tea beverages. The proposed electrochemical method shows a linear working range from 2.0 to 120 μM with a low LOD (0.3 μM) for sibutramine determination in slimming tea samples. The analytical performance of the SPE‐Gr with AdSDPV for sibutramine detection suggests its possible application as an easy, fast and low‐cost method to analyse adulterated tea samples with this stimulant at low levels (<0.1 %).
Developing a Coupled Statistical and Monte Carlo Approach for Geometric Modeling and Optimizing of Infiltrated Solid Oxide Fuel Cell Electrode
Authors: Tafazoli M. , Shakeri M. , Baniassadi M. , Babaei A. , Safdari M. 
Published: February 2019

AbstractThis study proposes a novel geometric simulation methodology to estimate the performance of solid oxide fuel cells (SFOCs) electrodes using Monte‐Carlo approach coupled with a statistical algorithm to add infiltrated particles in the form of discrete voxels. Electrochemical performance of these infiltrated electrodes is then characterized by direct evaluation of triple phase boundary (TPB) density and active surface density of the particles. Study results, in agreement with experiment and analytical models, illustrate that there is an optimum point for particle loading, which is strongly depended on the backbone properties and particle aggregation behavior. Study also indicates that the reduction rate of the gas transport factor after adding particles strongly depends on the backbone porosity and the distribution of the particles. Further, it is shown that the average shape of aggregated particles alters the TPB density and gas transport behavior, but particle agglomeration always increases the surface density of particles. Finally, the geometric results are compared with electrochemical tests qualitatively and proposed theories in literature quantitatively. A case study is also performed to compare geometric properties of a realized model with a real reconstructed infiltrated electrode.
Intraoperative electron beam radiotherapy for locoregionally persistent or recurrent head and neck cancer
Authors: Wald Patrick , Grecula John , Walston Steve , Wei Lai , Bhatt Aashish , Martin Douglas , Bonomi Marcelo , Rocco James , Old Matthew , Teknos Theodoros , Blakaj Dukagjin 
Published: February 2019

AbstractBackgroundTo report our institutional experience with intraoperative radiotherapy for persistent or recurrent head and neck cancer.MethodsSixty‐one patients were treated with salvage surgery and intraoperative radiation therapy (IORT). Fifty‐eight patients (95%) had previously received external beam radiotherapy (EBRT) as a component of their definitive therapy. Forty‐four patients (72%) had squamous cell carcinoma (SCC). Surgical margins were positive in 28 patients (46%). IORT was prescribed to a median dose of 12.5 Gy (range, 10‐17.5). Twenty‐three patients (38%) received a course of postoperative EBRT (median 45 Gy). Clinical outcomes were retrospectively reviewed and univariate analysis was performed using log‐rank tests to correlate clinical outcomes with histology, surgical margin, and adjuvant therapy.ResultsMedian follow‐up among surviving patients was 15.9 months. Median progression‐free survival (PFS) and overall survival (OS) were 9.8 and 19.1 months, respectively. One‐ and 2‐year rates of locoregional control (LRC) were 59% and 35%, respectively. One‐ and 2‐year rates of PFS were 39% and 19%, respectively. One‐ and 2‐year rates of OS were 62% and 42%, respectively. Overall survival was better for non‐SCC histology (P = .03). For SCC patients, negative surgical margin showed a trend toward improved PFS (P = .09) and OS (P = .06). There was one grade‐5 toxicity due to carotid rupture.ConclusionsIORT has shown effective LRC and OS with an acceptably low rate of severe toxicity at our institution. OS was significantly better for non‐SCC histology. For SCC patients, there is a trend toward improved PFS and OS associated with negative surgical margins.
Hypopharyngeal cancer treatment: Does initial surgery confer survival benefit?
Authors: Tassler Andrew B. , Gooding William E. , Ferris Robert L. 
Published: February 2019

AbstractBackgroundOrgan preservation protocols have increasingly been applied for the treatment of head and neck cancers, including hypopharyngeal squamous cell carcinoma (HSCC). We sought to evaluate whether patients treated with primary surgery followed by adjuvant therapy had survival benefit over patients treated with initial nonsurgical modalities.MethodsWe retrospectively reviewed patients with new diagnosis of HSCC at the University of Pittsburgh (1994‐2014) treated with either primary total laryngectomy with pharyngectomy or organ preservation.ResultsOne hundred thirty‐seven patients were identified. Surgical cases were more likely to be of advanced T stage. Initial surgery was more likely to be performed in the earlier years of the cohort. After adjusting for this imbalance using a propensity score, primary surgery was associated with improved survival compared with nonoperative therapy (P = 0.02).ConclusionsDue to its survival advantage, primary surgery followed by adjuvant treatment should be considered as a viable treatment of HSCC.