bluuebunny/crossref_metadata_2025_split huggingface dataset:
The association between patterns of physical activity and sedentary time with frailty in relation to cardiovascular disease
Authors: Kehler Dustin Scott , Clara Ian , Hiebert Brett , Stammers Andrew Nicholas , Hay Jacqueline , Schultz Annette , Arora Rakesh Christopher , Tangri Navdeep , Duhamel Todd Ashley 
Published: March 2019

AbstractObjectiveThe associations of moderate‐vigorous physical activity (MVPA) bouts and patterns of sedentary time (ST) with frailty according to cardiovascular disease (CVD) status are unknown.MethodsAccelerometry in adults ≥50 years old from the 2003‐2004 and 2005‐2006 National Health and Nutrition Examination Survey were used. Bouted and sporadic MVPA in ≥10‐minute or <1‐minute bouts were assessed based on meeting a percentage of physical activity guidelines of 150 minutes/wk, respectively. ST patterns included: prolonged ST lasting ≥30 minutes, and the frequency, intensity, and duration of breaks from ST. A 46‐item frailty index defined frailty. Multivariable linear regression was used.ResultsThere were 827 and 1490 CVD‐free and CVD participants, respectively. Meeting a higher percentage of the physical activity guidelines through bouted MVPA was associated with lower frailty in CVD‐only participants (P < 0.05 for CVD interaction). Sporadic MVPA was associated with lower frailty levels in both groups. Prolonged ST was associated with worse frailty in CVD (P > 0.05 for CVD interaction). Frequency of ST breaks was not associated with frailty. Average ST break intensity was protective in both groups. The duration of breaks in ST was associated with lower frailty in CVD participants only (P > 0.05 for CVD interaction).ConclusionInsufficient MVPA and prolonged ST are detrimental despite CVD status.
Height growth velocity during infancy and childhood in achondroplasia
Authors: del Pino Mariana , Fano Virginia , Adamo Paula 
Published: March 2019

There is a lack of knowledge about longitudinal growth during childhood in achondroplasia. We report patterns of linear growth and height growth velocity references. The sample consisted of 84 children, 41 girls and 43 boys. Growth data was collected from birth until mid‐childhood. The median (interquartile range) number of measurements per child was 13.5 (12, 15). Individual growth curves were estimated by fitting the Reed 1st model to each individual's height for age data. Height growth velocities references for age centiles were calculated by LMS method.Mean (SD) birth length was 46.14 cm (2.17) and 45.53 cm (2.16), for boys and girls respectively. Individual growth curves were analyzed. Shifts in growth channels were seen: out of 84 infants, 41 (48.8%) changed more than 1 SDS between birth to 5 years old. The numbers of infants shifting upward were similar (20/84) to the infants shifting downward (21/84). Height growth velocity curves show that after a period of fast decreasing growth velocity since birth, with a mean of 15.5 cm/year and 9.5 cm/year at 6 month and 1 year old, the growth velocity is stable in late preschool years, with a mean of 4.3 cm/year. Shifts in growth channels were seen between birth and 5 years old. Professionals who follow up them must consider this phenomenon during infancy. ACH children experienced a period of fast decreasing growth during infancy and the growth curve was similar in shape and lesser in magnitude than the general population.
Accelerated and Noise‐Resistant Protocol of Dissipation‐Based Knill–Laflamme–Milburn State Generation with Lyapunov Control
Authors: Wang Yu , Hu Chang‐Sheng , Shi Zhi‐Cheng , Huang Bi‐Hua , Song Jie , Xia Yan 
Published: March 2019

AbstractA protocol to generate steady Knill–Laflamme–Milburn (KLM) states of two Rydberg atoms with dissipation and Lyapunov control is proposed. Herein, combining with the quantum Zeno dynamics and the Rydberg antiblockade, a unique and steady solution of the master equation of the system is obtained, which satisfies the definition of KLM states. Furthermore, to polish the convergence rate, well‐designed additional coherent control (ACC) fields with Lyapunov control are added into the traditional dissipation process. Numerical simulation reveals that the steady target state generation is prominently accelerated and the protocol is robust against the stochastic noise errors caused by laser fields. It is hoped that the work may provide an alternative protocol to polish the generation of entanglement.
Selektive Synthese von Iridium(III)‐Metalla[2]catenanen durch Präorganisation der Komponenten über π‐π‐Wechselwirkungen
Authors: Shan Wei‐Long , Lin Yue‐Jian , Hahn F. Ekkehardt , Jin Guo‐Xin 
Published: March 2019

AbstractEine Reihe von molekularen Metalla[2]catenanen mit Cp*Ir‐Eckbausteinen wurde in einer templatfreien Selbstorganisation aus zweikernigen Iridiumakzeptoren und 1,5‐Bis[2‐(4‐pyridyl)ethinyl]anthracen‐Donoren erhalten. Die Metalla[2]catenane bilden sich beim Einsatz ausgewählter Brückenliganden, die Sandwich‐artige π‐π‐Wechselwirkungen ausbilden. Im Festkörper können die [2]Catenane zwei unterschiedliche Konfigurationen annehmen, die durch Halogenatome an den zweikernigen Brückenliganden bestimmt werden. Veränderungen des Lösungsmittels, der Konzentration sowie die Zugabe von Gastmolekülen erlauben die kontrollierte Umwandlung von Metalla[2]catenanen in molekulare Metalla‐Rechtecke.
Intermolekulare radikalische C(sp3)‐H‐Aminierung unter Iod‐Katalyse
Authors: Bosnidou Alexandra E. , Muñiz Kilian 
Published: March 2019

AbstractDie direkte Aminierung von aliphatischen C‐H‐Bindungen stellt eine der attraktivsten Umwandlungen in der organischen Chemie dar. Wir berichten hier über ein einzigartiges Katalysatorsystem, das die bislang schwierige intermolekulare C(sp3)‐H‐Aminierung möglich macht. Diese praktische Synthesestrategie eröffnet den Zugang zu aminierten Bausteinen und fördert die innovative mehrfache C‐H‐Aminierung innerhalb eines neuen Zugangs zu aminierten Heterocyclen. Der synthetische Nutzen wird anhand der Synthesen von vier relevanten Pharmazeutika demonstriert.
Intermolekulare, verzweigt‐selektive und redoxneutrale Cp*IrIII‐katalysierte allylische C‐H‐Amidierung
Authors: Knecht Tobias , Mondal Shobhan , Ye Jian‐Heng , Das Mowpriya , Glorius Frank 
Published: March 2019

AbstractWir berichten über die redoxneutrale, intermolekulare und verzweigt‐selektive Amidierung von allylischen C‐H‐Bindungen durch Cp*IrIII‐Katalyse. Eine Vielzahl leicht verfügbarer Carbonsäuren wurde in die entsprechenden Dioxazolone umgewandelt und effizient mit terminalen und internen Olefinen in hohen Ausbeuten und Selektivitäten gekuppelt. Mechanistische Untersuchungen stützen die Bildung eines nukleophilen IrIII‐Allyl‐Intermediats und nicht die direkte Insertion einer Ir‐Nitrenoidspezies in die allylische C‐H‐Bindung.
Dissecting FOXP2 Oligomerization and DNA Binding
Authors: Häußermann Katharina , Young Gavin , Kukura Philipp , Dietz Hendrik 
Published: March 2019

AbstractProtein–protein and protein–substrate interactions are critical to function and often depend on factors that are difficult to disentangle. Herein, a combined biochemical and biophysical approach, based on electrically switchable DNA biochips and single‐molecule mass analysis, was used to characterize the DNA binding and protein oligomerization of the transcription factor, forkhead box protein P2 (FOXP2). FOXP2 contains domains commonly involved in nucleic‐acid binding and protein oligomerization, such as a C2H2‐zinc finger (ZF), and a leucine zipper (LZ), whose roles in FOXP2 remain largely unknown. We found that the LZ mediates FOXP2 dimerization via coiled‐coil formation but also contributes to DNA binding. The ZF contributes to protein dimerization when the LZ coiled‐coil is intact, but it is not involved in DNA binding. The forkhead domain (FHD) is the key driver of DNA binding. Our data contributes to understanding the mechanisms behind the transcriptional activity of FOXP2.
Esters as Radical Acceptors: β‐NHC‐Borylalkenyl Radicals Induce Lactonization by C−C Bond Formation/Cleavage on Esters
Authors: Shimoi Masaki , Maeda Katsuhiro , Geib Steven J. , Curran Dennis P. , Taniguchi Tsuyoshi 
Published: March 2019

AbstractSubstituted propargyl acetates are converted into 4‐boryl‐2(5H)‐furanones upon thermolysis in the presence of an N‐heterocyclic carbene borane (NHC‐borane) and di‐tert‐butyl peroxide. The acetyl methyl group is lost during the reaction as methane. Evidence suggests that the reaction proceeds by a sequence of radical events including: 1) addition of an NHC‐boryl radical to the triple bond; 2) cyclization of the resultant β‐borylalkenyl radical to the ester carbonyl group; 3) β‐scission of the so‐formed alkoxy radical to provide the 4‐boryl‐2(5H)‐furanone and a methyl radical; and 4) hydrogen abstraction from the NHC‐borane to return the initial NHC‐boryl radical and methane.
Bimetallic Cooperative Cleavage of Dinitrogen to Nitride and Tandem Frustrated Lewis Pair Hydrogenation to Ammonia
Authors: Doyle Laurence R. , Wooles Ashley J. , Liddle Stephen T. 
Published: March 2019

AbstractAlthough reductive cleavage of dinitrogen (N2) to nitride (N3−) and hydrogenation with dihydrogen (H2) to yield ammonia (NH3) is accomplished in heterogeneous Haber–Bosch industrial processes on a vast scale, sequentially coupling these elementary reactions together with a single metal complex remains a major challenge for homogeneous molecular complexes. Herein, we report that the reaction of a chloro titanium triamidoamine complex with magnesium effects complete reductive cleavage of N2 to give a dinitride dititanium dimagnesium ditriamidoamine complex. Tandem H2 splitting by a phosphine–borane frustrated Lewis pair (FLP) shuttles H atoms to the N3−, evolving NH3. Isotope labelling experiments confirmed N2 and H2 fixation. Though not yet catalytic, these results give unprecedented insight into coupling N2 and H2 cleavage and N−H bond formation steps together, highlight the importance of heterobimetallic cooperativity in N2 activation, and establish FLPs in NH3 synthesis.
Boran‐Addukte von Stickstoffwasserstoffsäure und Organischen Aziden: Intermediate bei der Bildung von Aminoboranen
Authors: Bläsing Kevin , Bresien Jonas , Labbow René , Michalik Dirk , Schulz Axel , Thomas Max , Villinger Alexander 
Published: March 2019

AbstractDie Reaktion von HN3 mit der starken Lewis‐Säure B(C6F5)3 führte zur Bildung des sehr labilen Addukts HN3−B(C6F5)3, das oberhalb von −20 °C unter Freisetzung von molekularem Stickstoff und gleichzeitiger Migration einer C6F5‐Gruppe von Bor zu Stickstoff zu einem Aminoboran, H(C6F5)NB(C6F5)2, zerfällt. Die intermediäre Bildung von Azid‐Boran‐Addukten mit B(C6F5)3 und deren Staudinger‐ähnliche Zersetzung mit C6F5‐Gruppenmigration wurde ebenfalls für eine Reihe verschiedener organischer Azide R−N3 (R=Me3Si=TMS, Ph, 3,5‐(CF3)2C6H3=Btp) nachgewiesen. In Übereinstimmung mit dem Experiment ergaben Berechnungen, dass die hochlabilen Azidaddukte relativ kleine Barrieren für die Freisetzung von Stickstoff für alle organischen Substituenten außer R=Me3Si (Schmelzpunkt 120 °C, TZers.=189 °C) aufweisen. Die Hydrolyse der Aminoborane lieferte C6F5‐substituierte Amine, HN(R)(C6F5), in guter Ausbeute.
Synthesis of Eight‐Membered Lactams through Formal [6+2] Cyclization of Siloxy Alkynes and Vinylazetidines
Authors: Wu An , Feng Qiang , Sung Herman H. Y. , Williams Ian D. , Sun Jianwei 
Published: March 2019

AbstractA new approach for the efficient synthesis of eight‐membered lactams through formal [6+2] cyclization of siloxy alkynes and vinylazetidines has been developed. Evidence from a chirality transfer experiment suggests that the reaction proceeds via a [3,3]‐sigmatropic rearrangement from a ketene intermediate. This insight led to the development of alternative conditions and use of acyl chlorides as ketene precursors for the [6+2] reaction with vinylazetidines.
Exploding Chemical Gardens: A Phase‐Change Clock Reaction
Authors: Ding Yang , Gutiérrez‐Ariza Carlos M. , Ignacio Sainz‐Díaz C. , Cartwright Julyan H. E. , Cardoso Silvana S. S. 
Published: March 2019

AbstractChemical gardens and clock reactions are two of the best‐known demonstration reactions in chemistry. Until now these have been separate categories. We have discovered that a chemical garden confined to two dimensions is a clock reaction involving a phase change, so that after a reproducible and controllable induction period it explodes.
Protection‐Group‐Free Synthesis of Sequence‐Defined Macromolecules via Precision λ‐Orthogonal Photochemistry
Authors: Konrad Waldemar , Fengler Christian , Putwa Sarrah , Barner‐Kowollik Christopher 
Published: March 2019

AbstractAn advanced light‐induced avenue to monodisperse sequence‐defined linear macromolecules via a unique photochemical protocol is presented that does not require any protection‐group chemistry. Starting from a symmetrical core unit, precision macromolecules with molecular weights up to 6257.10 g mol−1 are obtained via a two‐monomer system: a monomer unit carrying a pyrene functionalized visible light responsive tetrazole and a photo‐caged UV responsive diene, enabling an iterative approach for chain growth; and a monomer unit equipped with a carboxylic acid and a fumarate. Both light‐induced chain growth reactions are carried out in a λ‐orthogonal fashion, exciting the respective photosensitive group selectively and thus avoiding protecting chemistry. Characterization of each sequence‐defined chain (size‐exclusion chromatography (SEC), high‐resolution electrospray ionization mass spectrometry (ESI‐MS), and NMR spectroscopy), confirms the precision nature of the macromolecules.
Synthesis and characterization of eco‐friendly siloxane‐semifluorinated polyurethane coatings for underwater application
Authors: Yesudass Sebastin Anthony , Mohanty Smita , Nayak Sanjay K. 
Published: March 2019

ABSTRACTSiloxane‐semifluorinated polyurethane coatings were prepared for robust underwater application. Initially, acrylic polyol (FS‐GPTACP)‐containing fluoroalkoxysilane (1H,1H,2H,2H‐Perfluorooctyltrimethoxysilane) pendant group was synthesized by the free‐radical polymerization method. Different weight percentages of polydimethylsiloxane (0, 10, and 20 wt %) were added to the polyol to tune the mechanical and the surface energy of the coating. Subsequently, this polyol mixture was cured with 4, 4′‐methylenebis(cyclohexyl isocyanate) (H12MDI) to prepare a series of siloxane‐semifluorinated polyurethane–urea hybrid coatings (APUS 0%, APUS 10%, and APUS 20%). The synthesized coating showed low surface energy, hydrophobicity with exceptional water, and alkali resistance. Moreover, the coating displayed excellent mechanical properties with low pseudobarnacle adhesion strength. The coatings also showed nontoxicity against gram‐positive and gram‐negative bacterial strains. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47720.
Meeting the 24‐hr movement guidelines: An update on US youth with autism spectrum disorder from the 2016 National Survey of Children's Health
Authors: Healy Seán , Aigner Carrie J. , Haegele Justin A. , Patterson Freda 
Published: March 2019

The purpose of this study was to examine how adherence to the physical activity (PA), screen‐time (ST), and sleep duration guidelines differ between youth with autism spectrum disorder (ASD) and youth with typical development (TD). A secondary objective was to assess how PA, ST, and sleep duration varied among youth with ASD by age and ASD severity. Utilizing the 2016 National Survey of Children's Health data, parental reports of time spent by youth in PA, ST, and sleep were used to determine adherence to the 24‐hr movement guidelines for 1008 youth with ASD and 34 489 youth with TD. Multivariate logistic regression analyses determined that children with ASD were less likely to meet the guidelines for PA, ST, and sleep duration, and adolescents with ASD were less likely to meet the guidelines for PA and ST than participants with TD. Furthermore, logistic regression analyses determined adolescents with severe ASD to be less likely to meet the sleep guideline compared to adolescents with mild ASD. Overall, youth with ASD were significantly less likely to adhere to all three guidelines. The findings highlight the breadth of health behaviors that require intervention to counteract the poorer health status among youth with ASD. Autism Res 2019, 12: 941–951. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.Lay SummaryNew health recommendations suggest children and adolescents should have at least 1 hr of physical activity, no more than 2 hr of screen‐time (e.g., television), and 9–11 hr of sleep (or 8–10 hr for children aged 14 or older) every day. This article looked at how children and adolescents with autism meet these new guidelines. The two main results were that: (a) children with autism were less likely to meet all three guidelines compared to children without autism, and (b) adolescents with autism were less likely to meet the guidelines for physical activity and screen‐time.
Hierarchically Designed CNF/S−Cu/CNF Nonwoven Electrode as Free‐Standing Cathode for Lithium−Sulfur Batteries
Authors: Bian Zihao , Xu Ying , Yuan Tao , Peng Chengxin , Pang Yuepeng , Yang Junhe , Zheng Shiyou 
Published: March 2019

AbstractA flexible lithium−sulfur (Li−S) battery cathode is prepared through uniformly depositing sulfur solution into an electrospun N‐rich and Cu‐decorated nonwoven carbon nanofiber (CNF) film to form sandwich structured CNF/S−Cu/CNF film electrodes. As a free‐standing cathode of Li−S battery, the unique structural CNF/S−Cu/CNF composite cathodes exhibit high capacity and rate capability as well as long cycling stability. The electrodes can deliver a reversible capacity of 1295 mAh g−1 at a current density of 0.1 A g−1, and maintain more than 530 mAh g−1 even at a high current rate of 1 A g−1 after 300 cycles along with a Coulombic efficiency close to 100 %. The exceptional performance of CNF/S−Cu/CNF as cathode in Li−S batteries is attributed to a synergistic contribution from the CNF layers, the decorated‐Cu nanoparticles and the doped N element in CNF, which can physically and chemically stabilize S and provide fast electronic conductivity. This facile strategy will pave the way to construct high‐performance flexible Li−S batteries.
Analysis of kombucha to teach biochemical concepts and techniques to undergraduate students
Authors: Applegate Kaitlin B. , Cheek Patrick R. , Inlow Jennifer K. 
Published: March 2019

AbstractLaboratory exercises for undergraduate biochemistry students are described in which changes in sugar content during fermentation of the trendy beverage kombucha are analyzed by three methods: thin layer chromatography, a 3,5‐dinitrosalicylic acid assay, and a standard commercial blood glucose meter. Each of the three analyses can be completed in a typical laboratory session lasting two to three hours. The exercises are designed to reinforce concepts typically covered in an undergraduate biochemistry course as well as to teach a variety of laboratory techniques. The exercises have been used with positive results in an upper level biochemistry laboratory course for junior/senior students majoring in chemistry or biology. © 2019 International Union of Biochemistry and Molecular Biology, 47(4):459–467, 2019.
Exploring environmental, social, and governance disclosure effects on the S&P 500 financial performance
Authors: Minutolo Marcel C. , Kristjanpoller Werner D. , Stakeley John 
Published: March 2019

AbstractMuch of the literature measuring the relationship between environmental, social, and governance (ESG) scores and firm performance treats the score as a measure of sustainability performance. In this study, we treat a firm's ESG score as a demonstration of strategic choice in the level of transparency that results in increased firm performance as measured by Tobin's Q and return on assets. Performance differences are a result of choice moderated by the size of the firm as measured by employees and sales. We analyze 467 firms in the S&P 500 from 2009 to 2015. Applying legitimacy and stakeholder theory, we find that there is significant difference between groups with respect to disclosure and performance. The results of quartile analysis by sales, capitalization, and Tobin's Q are relevant to understand the influence that the ESG score has on financial performance. ESG influences on Tobin's Q are greatest for large firms as measured by sales, as opposed to the ESG affects on Tobin's Q and return on asset for smallest firms as measured by market capitalization.
Gene Expression Inside Liposomes: From Early Studies to Current Protocols
Authors: Stano Pasquale 
Published: March 2019

AbstractSynthesizing proteins inside liposomes and other microcompartments is a well‐established practice. However, the origin of this research is not from the distant past, dating back to 1999–2004, when the first successful attempts were published. Protein synthesis inside artificial compartments is now under strong expansion in the context of synthetic biology (in bottom‐up approaches), and, in particular, it strongly contributes to the construction of artificial cell‐like systems. These systems, often called “synthetic cells”, can be used to model cellular processes, including membrane‐centered ones. They are very innovative models that complement traditional studies and promise future applications. This review does not discuss all current directions in synthetic cell research; in particular, it does not include all kinds of artificial compartments. Instead, it is uniquely dedicated to the analysis of historical and technical developments of protein synthesis inside liposomes, highlighting a selected list of open questions. One of the goals is to note the importance of mastering liposome technology together with cell‐free systems for the successful realization of this specific type of synthetic cell. With this aim, four currently employed protocols are compared and discussed, with a major emphasis on the droplet transfer method, which is attractive due to its simplicity and encapsulation efficiency.
Formation of the Charge‐Localized Dimer Radical Cation of 2‐Ethyl‐9,10‐dimethoxyanthracene in Solution Phase
Authors: Choi Jungkweon , Ahn Doo‐Sik , Fujitsuka Mamoru , Tojo Sachiko , Ihee Hyotcherl , Majima Tetsuro 
Published: March 2019

AbstractAlthough dimer radical ions of aromatic molecules in the liquid‐solution phase have been intensely studied, the understanding of charge‐localized dimers, in which the extra charge is localized in a single monomer unit instead of being shared between two monomer units, is still elusive. In this study, the formation of a charge‐localized dimer radical cation of 2‐ethyl‐9,10‐dimethoxyanthracene (DMA), (DMA)2.+ is investigated by transient absorption (TA) and time‐resolved resonance Raman (TR3) spectroscopic methods combined with a pulse radiolysis technique. Visible‐ and near‐IR TA signals in highly concentrated DMA solutions supported the formation of non‐covalent (DMA)2.+ by association of DMA and DMA.+. TR3 spectra obtained from 30 ns to 300 μs time delays showed that the major bands are quite similar to those of DMA except for small transient bands, even at 30 ns time delay, suggesting that the positive charge of non‐covalent (DMA)2.+ is localized in a single monomer unit. From DFT calculations for (DMA)2.+, our TR3 spectra showed the best agreement with the calculated Raman spectrum of charge‐localized edge‐to‐face T‐shaped (DMA)2.+, termed DT.+, although the charge‐delocalized asymmetric π‐stacked face‐to‐face (DMA)2.+, termed DF3.+, is the most stable structure of (DMA)2.+ according to the energetics from DFT calculations. The calculated potential energy curves for the association between DMA.+ and DMA showed that DT.+ is likely to be efficiently formed and contribute significantly to the TR3 spectra as a result of the permanent charge‐induced Coulombic interactions and a dynamic equilibrium between charge localized and delocalized structures.