bluuebunny/crossref_metadata_2025_split huggingface dataset:
A platform for probabilistic Multimodel and Multiproduct Streamflow Forecasting
Authors: Roy Tirthankar , Serrat‐Capdevila Aleix , Gupta Hoshin , Valdes Juan 
Published: December 2016

AbstractWe develop and test a probabilistic real‐time streamflow‐forecasting platform, Multimodel and Multiproduct Streamflow Forecasting (MMSF), that uses information provided by a suite of hydrologic models and satellite precipitation products (SPPs). The SPPs are bias‐corrected before being used as inputs to the hydrologic models, and model calibration is carried out independently for each of the model‐product combinations (MPCs). Forecasts generated from the calibrated models are further bias‐corrected to compensate for the deficiencies within the models, and then probabilistically merged using a variety of model averaging techniques. Use of bias‐corrected SPPs in streamflow forecasting applications can overcome several issues associated with sparsely gauged basins and enable robust forecasting capabilities. Bias correction of streamflow significantly improves the forecasts in terms of accuracy and precision for all different cases considered. Results show that the merging of individual forecasts from different MPCs provides additional improvements. All the merging techniques applied in this study produce similar results, however, the Inverse Weighted Averaging (IVA) proves to be slightly superior in most cases. We demonstrate the implementation of the MMSF platform for real‐time streamflow monitoring and forecasting in the Mara River basin of Africa (Kenya & Tanzania) in order to provide improved monitoring and forecasting tools to inform water management decisions.
Phase exposure‐dependent exchange
Authors: Ginn T. R. , Schreyer L. G. , Zamani K. 
Published: December 2016

AbstractSolutes and suspended material often experience delays during exchange between phases one of which may be moving. Consequently transport often exhibits combined effects of advection/dispersion, and delays associated with exchange between phases. Such processes are ubiquitous and include transport in porous/fractured media, watersheds, rivers, forest canopies, urban infrastructure systems, and networks. Upscaling approaches often treat the transport and delay mechanisms together, yielding macroscopic “anomalous transport” models. When interaction with the immobile phase is responsible for the delays, it is not the transport that is anomalous, but the lack of it, due to delays. We model such exchanges with a simple generalization of first‐order kinetics completely independent of transport. Specifically, we introduce a remobilization rate coefficient that depends on the time in immobile phase. Memory‐function formulations of exchange (with or without transport) can be cast in this framework, and can represent practically all time‐nonlocal mass balance models including multirate mass transfer and its equivalent counterparts in the continuous time random walk and time‐fractional advection dispersion formalisms, as well as equilibrium exchange. Our model can address delayed single‐/multievent remobilizations as in delay‐differential equations and periodic remobilizations that may be useful in sediment transport modeling. It is also possible to link delay mechanisms with transport if so desired, or to superpose an additional source of nonlocality through the transport operator. This approach allows for mechanistic characterization of the mass transfer process with measurable parameters, and the full set of processes representable by these generalized kinetics is a new open question.
Chiral Induction in Intramolecular Rhodium‐Catalyzed [2+2+2] Cycloadditions of Optically Active Allene–ene/yne–allene Substrates
Authors: Haraburda Ewelina , Fernández Martí , Gifreu Anna , Garcia Jordi , Parella Teodor , Pla‐Quintana Anna , Roglans Anna 
Published: December 2016

AbstractAllene‐yne‐allene and allene‐ene‐allene N‐tosyl‐linked substrates with two chiral centres in the α‐position of the allene moiety were satisfactorily prepared starting both from racemic and chiral propargylic alcohols. The Wilkinson's complex‐catalyzed [2+2+2] cycloaddition reaction of these substrates was evaluated. In the case of enantiomerically pure bisallenes, high stereoselectivity was observed, giving a diastereomerically pure cycloadduct. The chirality of starting bisallene substrates can be completely transferred to the cycloadducts, representing an atom‐economical and enantiospecific process for the construction of fused polycycles. However, when reacting an oxygen‐linked allene‐ene‐allene substrate, the stereoselectivity decreased and two diastereoisomers were formed. A detailed characterization study of the resulting cycloadducts allowed us to identify the enantioisomer generated in the cycloaddition.magnified image
Efficient Synthesis of Anthraquinones from Diaryl Carboxylic Acids via Palladium(II)‐Catalyzed and Visible Light‐Mediated Transformations
Authors: Kim Kiho , Min Minsik , Hong Sungwoo 
Published: December 2016

AbstractIrradiation of 9‐ester‐substituted anthracenes with visible light results in the formation of endoperoxides in the absence of a photocatalyst, which further undergo base‐assisted fragmentation to afford anthraquinones. The excited state species of anthracene generated by energy transfer, interacts with 3O2 to afford 1O2 by energy transfer and undergoes cycloaddition with 1O2. By employing palladium(II)‐catalyzed and visible light‐mediated transformations, we have developed an efficient synthetic protocol for accessing diverse anthraquinones from readily available diaryl carboxylic acids. The optimal result was obtained with palladium(II) acetate, Ac‐Ile‐OH, benzoquinone and potassium carbonate in tert‐amyl alcohol under O2 at 90 °C with irradiation from a 30 W fluorescent light bulb.magnified image
Direct ortho‐Trifluoroethylation of Aromatic Ureas by Palladium Catalyzed C‐H activation: A Missing Piece of Aromatic Substitutions
Authors: Kovács Szabolcs , Tóth Balázs L. , Borsik Gábor , Bihari Tamás , May Nóra V. , Stirling András , Novák Zoltán 
Published: December 2016

AbstractDevelopment of direct late‐stage installation of alkyl groups into aromatic systems is an important and challenging task of current organic chemistry. In spite of the existing functionalization methods in organic chemistry for the substitution reactions on aromatic systems, the direct alkylation of aromatic ureas is unknown. Herein, as a first example we report a novel palladium catalyzed fluoroalkylation process by C−H activation for the access of ortho trifluoroethylated aromatic ureas. The application of novel, highly active trifluoroethyl(mesityl)iodonium salt enables the efficient introduction of the trifluoroethyl group at 25 °C in 3 hours in high yields (up to 95%) with good functional group tolerance. DFT calculations have revealed a rate determining oxidative alkyl‐group transfer preceded by an unexpected C−H activation route on the Pd center during the catalytic cycle, where the deprotonation is assisted by an external triflate anion.magnified image
Telesimulation: An Innovative Tool for Health Professions Education
Authors: McCoy Christopher Eric , Sayegh Julie , Alrabah Rola , Yarris Lalena M. 
Published: December 2016

AbstractTelesimulation is a new and innovative concept and process that has been used to provide education, training, and assessment in health‐related fields such as medicine. This new area of simulation, and its terminology, has its origins within the past decade. The face validity and ability to provide the benefits of simulation education to learners at off‐site locations has allowed the wide and rapid adoption of telesimulation in the field of medical education. Telesimulation has been implemented in areas such as pediatric resuscitation, surgery, emergency medicine, ultrasound‐guided regional anesthesia in anesthesiology, nursing, and neurosurgery. However, its rapid expansion and current use has outgrown its recent description less than a decade ago. To date, there is no unifying definition of telesimulation that encompasses all the areas where it has been used while simultaneously allowing for growth and expansion in this field of study. This article has two main objectives. The first objective is to provide a comprehensive and unifying definition of telesimulation that encompasses all the areas where it has been used while allowing for growth and expansion in the field of study. The secondary objective is to describe the utility of telesimulation for emergency medicine educators in the context of the current evidence to serve as a background and framework that educators may use when considering creating educational programs that incorporate telecommunication and simulation resources. This article is complementary to the large group presentation where this new comprehensive and unifying definition was introduced to the simulation community at the International Meeting on Simulation in Healthcare in January 2016.
Ein stabiles neutrales Radikal in der Koordinationssphäre des Aluminiums
Authors: Li Bin , Kundu Subrata , Stückl A. Claudia , Zhu Hongping , Keil Helena , Herbst‐Irmer Regine , Stalke Dietmar , Schwederski Brigitte , Kaim Wolfgang , Andrada Diego M. , Frenking Gernot , Roesky Herbert W. 
Published: December 2016

AbstractDas neuartige neutrale Radikal (Me2‐cAAC)2AlCl2 (2) wird durch cyclische Alkylaminocarbene (cAACs) stabilisiert. Die Synthese erfolgte in Gegenwart eines weiteren Äquivalents Me2‐cAAC durch Reduktion des Addukts Me2‐cAAC:AlCl3 (1) mit KC8. Anhand der Kristallstruktur zeigt sich, dass die beiden Carbene, die an das Aluminiumatom gebunden sind, deutlich unterschiedliche Al‐C‐Bindungen aufweisen. Dies lässt sich vermutlich auf die intermolekularen Wechselwirkungen zurückführen. Quantenmechanische Rechnungen ergaben dagegen eine Gleichgewichtsstruktur mit identischen Al‐C‐Bindungslängen. Verbindung 2 weist einen Monoradikalcharakter auf, der durch eine ESR‐Messung bestätigt werden konnte. Die Bindungsanalyse deutet darauf hin, dass das ungepaarte Elektron hauptsächlich am Carbenkohlenstoffatom lokalisiert ist. Somit ist 2 ein Beispiel für ein ungewöhnliches neutrales Al‐Radikal.
Polymersome Popping by Light‐Induced Osmotic Shock under Temporal, Spatial, and Spectral Control
Authors: Peyret Ariane , Ibarboure Emmanuel , Tron Arnaud , Beauté Louis , Rust Ruben , Sandre Olivier , McClenaghan Nathan D. , Lecommandoux Sebastien 
Published: December 2016

AbstractThe light‐triggered, programmable rupture of cell‐sized vesicles is described, with particular emphasis on self‐assembled polymersome capsules. The mechanism involves a hypotonic osmotic imbalance created by the accumulation of photogenerated species inside the lumen, which cannot be compensated owing to the low water permeability of the membrane. This simple and versatile mechanism can be adapted to a wealth of hydrosoluble molecules, which are either able to generate reactive oxygen species or undergo photocleavage. Ultimately, in a multi‐compartmentalized and cell‐like system, the possibility to selectively burst polymersomes with high specificity and temporal precision and to consequently deliver small encapsulated vesicles (both polymersomes and liposomes) is demonstrated.
Stereospecific Palladium‐Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions
Authors: Wang Chao‐Yuan , Ralph Glenn , Derosa Joseph , Biscoe Mark R. 
Published: December 2016

AbstractWe report the development of a Pd‐catalyzed process for the cross coupling of unactivated primary, secondary, and tertiary alkylcarbastannatrane nucleophiles with acyl electrophiles. Reactions involving optically active alkylcarbastannatranes occur with exceptional stereofidelity and with net retention of absolute configuration. Because the stereochemistry of the resulting products is entirely reagent‐controlled, this process may be viewed as a general, alternative approach to the preparation of products typically accessed via asymmetric enolate methodologies. Additionally, we report a new method for the preparation of optically active alkylcarbastannatranes, which should facilitate their future use in stereospecific reactions.
Non‐Viral CRISPR/Cas Gene Editing In Vitro and In Vivo Enabled by Synthetic Nanoparticle Co‐Delivery of Cas9 mRNA and sgRNA
Authors: Miller Jason B. , Zhang Shuyuan , Kos Petra , Xiong Hu , Zhou Kejin , Perelman Sofya S. , Zhu Hao , Siegwart Daniel J. 
Published: December 2016

AbstractCRISPR/Cas is a revolutionary gene editing technology with wide‐ranging utility. The safe, non‐viral delivery of CRISPR/Cas components would greatly improve future therapeutic utility. We report the synthesis and development of zwitterionic amino lipids (ZALs) that are uniquely able to (co)deliver long RNAs including Cas9 mRNA and sgRNAs. ZAL nanoparticle (ZNP) delivery of low sgRNA doses (15 nm) reduces protein expression by >90 % in cells. In contrast to transient therapies (such as RNAi), we show that ZNP delivery of sgRNA enables permanent DNA editing with an indefinitely sustained 95 % decrease in protein expression. ZNP delivery of mRNA results in high protein expression at low doses in vitro (<600 pM) and in vivo (1 mg kg−1). Intravenous co‐delivery of Cas9 mRNA and sgLoxP induced expression of floxed tdTomato in the liver, kidneys, and lungs of engineered mice. ZNPs provide a chemical guide for rational design of long RNA carriers, and represent a promising step towards improving the safety and utility of gene editing.
Chemoselective Suzuki–Miyaura Cross‐Coupling via Kinetic Transmetallation
Authors: Fyfe James W. B. , Fazakerley Neal J. , Watson Allan J. B. 
Published: December 2016

AbstractChemoselective Suzuki–Miyaura cross‐coupling generally requires a designed deactivation of one nucleophile towards transmetallation. Here we show that boronic acids can be chemoselectively reacted in the presence of ostensibly equivalently reactive boronic acid pinacol (BPin) esters by kinetic discrimination during transmetallation. Simultaneous electrophile control allows sequential chemoselective cross‐couplings in a single operation in the absence of protecting groups.
Catalysis with Chalcogen Bonds
Authors: Benz Sebastian , López‐Andarias Javier , Mareda Jiri , Sakai Naomi , Matile Stefan 
Published: December 2016

AbstractHerein, we introduce catalysts that operate with chalcogen bonds. Compared to conventional hydrogen bonds, chalcogen bonds are similar in strength but more directional and hydrophobic, thus ideal for precision catalysis in apolar solvents. For the transfer hydrogenation of quinolines and imines, rate enhancements well beyond a factor of 1000 are obtained with chalcogen bonds. Better activities with deeper σ holes and wider bite angles, chloride inhibition and correlation with computed anion binding energies are consistent with operational chalcogen bonds. Comparable to classics, such as 2,2′‐bipyrroles or 2,2′‐bipyridines, dithieno[3,2‐b;2′,3′‐d]thiophenes (DTTs), particularly their diimides, but also wide‐angle cyclopentadithiazole‐4‐ones are identified as privileged motifs to stabilize transition states in the focal point of the σ holes on their two co‐facial endocyclic sulfur atoms.
Expression of Epithelial and Mesenchymal Differentiation Markers in the Early Human Gonadal Development
Authors: Martinovic Vlatka , Vukusic Pusic Tanja , Restovic Ivana , Bocina Ivana , Filipovic Natalija , Saraga‐Babic Mirna , Vukojevic Katarina 
Published: December 2016

ABSTRACTExpressions of cytokeratin 8 (CK8), vimentin, nestin, and alpha‐smooth‐muscle‐actin (alpha‐SMA) were analyzed in the developing gonads of 12, 5–9 week old (W) human conceptuses by immunohistochemistry and immunofluorescence. During the investigated period, the number of CK8 positive cells increased from 56% to 92% in the gonadal surface epithelium, from 50% to 60% in the stroma, and from 23% to 42% in the medulla. In the early fetal period, the cell expression of CK8 increased in all gonadal parts, whereas primordial germ cells (PGC) remained negative. The expression of vimentin increased in the gonad stroma (gs) from 73% to 88%, and in the surface epithelium from 18% to 97% until ninth W. The medulla had the highest expression of vimentin in the seventh to eighth W (93%). Vimentin and CK8 colocalized in the somatic cells, while some PGCs showed vimentin expression only. Initially, nestin was positive in the gonad surface epithelium (8%) and stroma (52%), however during further development it decreased to 1% and 33%, respectively. In the early fetal period, the nestin positive cells decreased from 44% to 31% in the gonad medulla. Alpha‐SMA was positive only in the blood vessels and mesonephros. The described pattern of expression of intermediate filaments (IF) in developing human gonads suggests their role in the control of PGC apoptosis, early differentiation of gs cells and cell migration. Both epithelial and mesenchymal origins of follicular cells and possible epithelial‐to‐mesenchymal transition of somatic cells is proposed. Lastly, IF intensity expression varies depending on the cell type and developmental period analyzed. Anat Rec, 300:1315–1326, 2017. © 2017 Wiley Periodicals, Inc.
Competition and regulation in a new integrated transit system across jurisdictional borders
Authors: Du Haoming , Gao Ziyou , Ren Hualing 
Published: December 2016

SummaryIt is often argued lately that some regional transit systems should be integrated to improve the transit services across jurisdictional borders. One of the important issues concerning this integrated transit system is how to make proper use of the competition and regulation to improve its performance and to increase relevant benefits to the authorities, the operators and the passengers. This paper deals with this problem in a new integrated transit system across jurisdictional borders. An optimization model is used to investigate the competition of transit operators in oligopolistic competition transit market (OCTM). An optimization model with nonlinear complementarity constraints is proposed to guide the competition of transit operators using transit subsidy as the regulation means in system optimum transit system (SOTM). By analyzing and comparing the performances of the integrated transit system in two markets, numerical studies show that the competition mechanism should be made full use of and transit subsidy is an important regulation means that should be valued by the transit authorities in the integrated transit system. Copyright © 2016 John Wiley & Sons, Ltd.
Life cycle analysis of corn‐stover‐derived polymer‐grade l‐lactic acid and ethyl lactate: greenhouse gas emissions and fossil energy consumption
Authors: Adom Felix K. , Dunn Jennifer B. 
Published: December 2016

AbstractCo‐production of high‐value chemicals with biofuels could improve the economic viability of biorefineries while reducing biofuel life‐cycle greenhouse gas (GHG) emissions and fossil energy consumption (FEC). Polymer‐grade lactic acid (PGLA) is a high‐potential bioproduct currently produced from first‐generation feedstocks. Opportunity exists to enhance its environmental performance using cellulosic feedstocks. Moreover, ethyl lactate can be used as a functional replacement for high‐volume, energy‐intensive, and emissions‐intensive petroleum‐derived chemicals such as N‐methyl‐2‐pyrrolidone and ethyl acetate. Based on material and energy flows from Aspen Plus process models that we incorporated into the Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) model's bioproducts module, we developed life‐cycle GHG emissions and FEC estimates for ethyl lactate and PGLA produced from corn stover. We compared these results to those for fossil‐fuel‐derived counterparts, identified key LCA drivers, and explored the impact of end‐of‐life assumptions on LCA results. Irrespective of the end‐of‐life assumption, all the bioproducts demonstrated lower life‐cycle FEC (10–72%) and GHG emissions (23–90%) than fossil‐derived compounds for which they could serve as a functional replacement. Additionally, we reviewed the role of LCA in three major bioproduct sustainability certification schemes (the BioPreferred Program, the Roundtable on Sustainable Biomaterials, and International Sustainability and Carbon Certification Plus). None mandate an LCA of the bioproduct to assess whether, across the supply chain, these products offer environmental benefits as compared to conventional chemicals they could displace either directly or functionally. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Evaluation of drug efficacy of DPP‐4 inhibitors based on theoretical analysis with pharmacokinetics and pharmacodynamics
Authors: Takayanagi Risa , Uchida Takumi , Kimura Koji , Yamada Yasuhiko 
Published: December 2016

AbstractDipeptidyl peptidase‐4 (DPP‐4) inhibitors are used clinically as therapeutic agents for the treatment of diabetes. To determine the rate of DPP‐4 inhibition induced by these inhibitors, pharmacokinetic and pharmacodynamic parameters were used to theoretically examine the relationship between the rate of DPP‐4 inhibition and clinical efficacy following the administration of four different DPP‐4 inhibitors (sitagliptin, vildagliptin, alogliptin, linagliptin) by focusing on the increase in the level of glucagon‐like peptide‐1 (GLP‐1) induced by their administration. On the basis of the relationship shown, changes in clinical efficacy in association with dose change were examined in order to discuss clinical dosage from the standpoint of proper usage. The results indicate that a high rate of DPP‐4 inhibition is necessary for the onset of the effect of an administered the DPP‐4 inhibitor and that the average value for the DPP‐4 inhibition rate can be utilized as a common parameter of clinical efficacy. Furthermore, the efficacy profiles of the present DPP‐4 inhibitors could be demonstrated on the basis of an increase in the GLP‐1 level. It is considered that the present findings provide useful information for promoting the proper clinical use of DPP‐4 inhibitors. Copyright © 2016 John Wiley & Sons, Ltd.
LC–high‐resolution–MS/MS analysis of chemical compounds in rat plasma after oral administration of Nao‐Mai‐Tong and its individual herbs
Authors: Rong Yueying , Feng Suxiang , Wu Chunwei , Wang Shumei , Liang Shengwang , Liu Dongyun 
Published: December 2016

AbstractNao‐Mai‐Tong (NMT), a Chinese herbal formula, is used for treating ischemia cerebral apoplexy. To discover the components of NMT with potential in vivo bioactivity and investigate the differences between NMT and its single herb components, this study rigorously compared plasma samples collected from rats dosed with NMT and single‐herb extracts at different times through LC‐high resolution–MS/MS and data processing (Metworks). The plasma of the NMT group contained a total of 66 identified compounds (25 prototypes and 41 metabolites), including anthraquinones, triterpenoid saponins, isoflavones and phthalides. Additionally, glucuronidation, sulfation and cysteine conjugation were the major reactions through which the compounds in NMT were metabolized. The comparison of the groups revealed two metabolites that were only detected in the plasma from the NMT‐dosed group, whereas seven prototype ingredients (chrysophanol‐8‐O‐glucoside, ginsenoside Rf, Rg2, Rh1, F1, F2 and chikusetsusaponin IVa) and 12 metabolites (two novel triterpenoid saponins) were only discovered in the plasma samples from the single‐herb‐dosed groups. Moreover, the trends in the chemical compounds detected presented marked differences between NMT‐dosed rat plasma and plasma samples from the single‐herb‐dosed groups. The above data indicate that prescription compatibility affects the assimilation and elimination of ingredients and provides useful information for further pharmacokinetic studies.