bluuebunny/crossref_metadata_2025_split huggingface dataset:
Parameterization of mixing by secondary circulation in estuaries
Authors: Basdurak N. B. , Huguenard K. D. , Valle‐Levinson A. , Li M. , Chant R. J. 
Published: June 2017

AbstractEddy viscosity parameterizations that depend on a gradient Richardson number Ri have been most pertinent to the open ocean. Parameterizations applicable to stratified coastal regions typically require implementation of a numerical model. Two novel parameterizations of the vertical eddy viscosity, based on Ri, are proposed here for coastal waters. One turbulence closure considers temporal changes in stratification and bottom stress and is coined the “regular fit.” The alternative approach, named the “lateral fit,” incorporates variability of lateral flows that are prevalent in estuaries. The two turbulence parameterization schemes are tested using data from a Self‐Contained Autonomous Microstructure Profiler (SCAMP) and an Acoustic Doppler Current Profiler (ADCP) collected in the James River Estuary. The “regular fit” compares favorably to SCAMP‐derived vertical eddy viscosity values but only at relatively small values of gradient Ri. On the other hand, the “lateral fit” succeeds at describing the lateral variability of eddy viscosity over a wide range of Ri. The modifications proposed to Ri‐dependent eddy viscosity parameterizations allow applicability to stratified coastal regions, particularly in wide estuaries, without requiring implementation of a numerical model.
Smoothing‐based compressed state Kalman filter for joint state‐parameter estimation: Applications in reservoir characterization and CO2 storage monitoring
Authors: Li Y. J. , Kokkinaki Amalia , Darve Eric F. , Kitanidis Peter K. 
Published: June 2017

AbstractThe operation of most engineered hydrogeological systems relies on simulating physical processes using numerical models with uncertain parameters and initial conditions. Predictions by such uncertain models can be greatly improved by Kalman‐filter techniques that sequentially assimilate monitoring data. Each assimilation constitutes a nonlinear optimization, which is solved by linearizing an objective function about the model prediction and applying a linear correction to this prediction. However, if model parameters and initial conditions are uncertain, the optimization problem becomes strongly nonlinear and a linear correction may yield unphysical results. In this paper, we investigate the utility of one‐step ahead smoothing, a variant of the traditional filtering process, to eliminate nonphysical results and reduce estimation artifacts caused by nonlinearities. We present the smoothing‐based compressed state Kalman filter (sCSKF), an algorithm that combines one step ahead smoothing, in which current observations are used to correct the state and parameters one step back in time, with a nonensemble covariance compression scheme, that reduces the computational cost by efficiently exploring the high‐dimensional state and parameter space. Numerical experiments show that when model parameters are uncertain and the states exhibit hyperbolic behavior with sharp fronts, as in CO2 storage applications, one‐step ahead smoothing reduces overshooting errors and, by design, gives physically consistent state and parameter estimates. We compared sCSKF with commonly used data assimilation methods and showed that for the same computational cost, combining one step ahead smoothing and nonensemble compression is advantageous for real‐time characterization and monitoring of large‐scale hydrogeological systems with sharp moving fronts.
Impact of spatially correlated pore‐scale heterogeneity on drying porous media
Authors: Borgman Oshri , Fantinel Paolo , Lühder Wieland , Goehring Lucas , Holtzman Ran 
Published: June 2017

AbstractWe study the effect of spatially‐correlated heterogeneity on isothermal drying of porous media. We combine a minimal pore‐scale model with microfluidic experiments with the same pore geometry. Our simulated drying behavior compares favorably with experiments, considering the large sensitivity of the emergent behavior to the uncertainty associated with even small manufacturing errors. We show that increasing the correlation length in particle sizes promotes preferential drying of clusters of large pores, prolonging liquid connectivity and surface wetness and thus higher drying rates for longer periods. Our findings improve our quantitative understanding of how pore‐scale heterogeneity impacts drying, which plays a role in a wide range of processes ranging from fuel cells to curing of paints and cements to global budgets of energy, water and solutes in soils.
Future sea level change from Antarctica's Lambert‐Amery glacial system
Authors: Pittard M. L. , Galton‐Fenzi B. K. , Watson C. S. , Roberts J. L. 
Published: June 2017

AbstractFuture global mean sea level (GMSL) change is dependent on the complex response of the Antarctic ice sheet to ongoing changes and feedbacks in the climate system. The Lambert‐Amery glacial system has been observed to be stable over the recent period yet is potentially at risk of rapid grounding line retreat and ice discharge given that a significant volume of its ice is grounded below sea level, making its future contribution to GMSL uncertain. Using a regional ice sheet model of the Lambert‐Amery system, we find that under a range of future warming and extreme scenarios, the simulated grounding line remains stable and does not trigger rapid mass loss from grounding line retreat. This allows for increased future accumulation to exceed the mass loss from ice dynamical changes. We suggest that the Lambert‐Amery glacial system will remain stable or gain ice mass and mitigate a portion of potential future sea level rise over the next 500 years, with a range of +3.6 to −117.5 mm GMSL equivalent.
Shallow marine response to global climate change during the Paleocene‐Eocene Thermal Maximum, Salisbury Embayment, USA
Authors: Self‐Trail Jean M. , Robinson Marci M. , Bralower Timothy J. , Sessa Jocelyn A. , Hajek Elizabeth A. , Kump Lee R. , Trampush Sheila M. , Willard Debra A. , Edwards Lucy E. , Powars David S. , Wandless Gregory A. 
Published: June 2017

AbstractThe Paleocene‐Eocene Thermal Maximum (PETM) was an interval of extreme warmth that caused disruption of marine and terrestrial ecosystems on a global scale. Here we examine the sediments, flora, and fauna from an expanded section at Mattawoman Creek‐Billingsley Road (MCBR) in Maryland and explore the impact of warming at a nearshore shallow marine (30–100 m water depth) site in the Salisbury Embayment. Observations indicate that at the onset of the PETM, the site abruptly shifted from an open marine to prodelta setting with increased terrestrial and fresh water input. Changes in microfossil biota suggest stratification of the water column and low‐oxygen bottom water conditions in the earliest Eocene. Formation of authigenic carbonate through microbial diagenesis produced an unusually large bulk carbon isotope shift, while the magnitude of the corresponding signal from benthic foraminifera is similar to that at other marine sites. This proves that the landward increase in the magnitude of the carbon isotope excursion measured in bulk sediment is not due to a near instantaneous release of 12C‐enriched CO2. We conclude that the MCBR site records nearshore marine response to global climate change that can be used as an analog for modern coastal response to global warming.
2017 American College of Rheumatology/American Association of Hip and Knee Surgeons Guideline for the Perioperative Management of Antirheumatic Medication in Patients With Rheumatic Diseases Undergoing Elective Total Hip or Total Knee Arthroplasty
Authors: Goodman Susan M. , Springer Bryan , Guyatt Gordon , Abdel Matthew P. , Dasa Vinod , George Michael , Gewurz‐Singer Ora , Giles Jon T. , Johnson Beverly , Lee Steve , Mandl Lisa A. , Mont Michael A. , Sculco Peter , Sporer Scott , Stryker Louis , Turgunbaev Marat , Brause Barry , Chen Antonia F. , Gililland Jeremy , Goodman Mark , Hurley‐Rosenblatt Arlene , Kirou Kyriakos , Losina Elena , MacKenzie Ronald , Michaud Kaleb , Mikuls Ted , Russell Linda , Sah Alexander , Miller Amy S. , Singh Jasvinder A. , Yates Adolph 
Published: June 2017

ObjectiveThis collaboration between the American College of Rheumatology and the American Association of Hip and Knee Surgeons developed an evidence‐based guideline for the perioperative management of antirheumatic drug therapy for adults with rheumatoid arthritis (RA), spondyloarthritis (SpA) including ankylosing spondylitis and psoriatic arthritis, juvenile idiopathic arthritis (JIA), or systemic lupus erythematosus (SLE) undergoing elective total hip (THA) or total knee arthroplasty (TKA).MethodsA panel of rheumatologists, orthopedic surgeons specializing in hip and knee arthroplasty, and methodologists was convened to construct the key clinical questions to be answered in the guideline. A multi‐step systematic literature review was then conducted, from which evidence was synthesized for continuing versus withholding antirheumatic drug therapy and for optimal glucocorticoid management in the perioperative period. A Patient Panel was convened to determine patient values and preferences, and the Grading of Recommendations Assessment, Development and Evaluation methodology was used to rate the quality of evidence and the strength of recommendations, using a group consensus process through a convened Voting Panel of rheumatologists and orthopedic surgeons. The strength of the recommendation reflects the degree of certainty that benefits outweigh harms of the intervention, or vice versa, considering the quality of available evidence and the variability in patient values and preferences.ResultsThe guideline addresses the perioperative use of antirheumatic drug therapy including traditional disease‐modifying antirheumatic drugs, biologic agents, tofacitinib, and glucocorticoids in adults with RA, SpA, JIA, or SLE who are undergoing elective THA or TKA. It provides recommendations regarding when to continue, when to withhold, and when to restart these medications, and the optimal perioperative dosing of glucocorticoids. The guideline includes 7 recommendations, all of which are conditional and based on low‐ or moderate‐quality evidence.ConclusionThis guideline should help decision‐making by clinicians and patients regarding perioperative antirheumatic medication management at the time of elective THA or TKA. These conditional recommendations reflect the paucity of high‐quality direct randomized controlled trial data.
Diethyloxalate as “CO” Source for Palladium‐Catalyzed Ethoxycarbonylation of Bromo‐ and Chloroarene Derivatives
Authors: Monrose Amandine , Salembier Helori , Bousquet Till , Pellegrini Sylvain , Pélinski Lydie 
Published: June 2017

AbstractPalladium(II)‐catalyzed ethoxycarbonylation of aryl bromides with diethyloxalate oxalate is described. Functionalized aromatic esters can be efficiently synthesized with only 0.65 mol % PdCl2(PPh3)2 catalyst under microwave irradiation and without additional ligand. This method illustrates an inexpensive and operationally simple method for the preparation of aromatic esters.magnified image
Offenzellige Schwämme mit niedrigen Dichten als Funktionsmaterialien
Authors: Jiang Shaohua , Agarwal Seema , Greiner Andreas 
Published: June 2017

AbstractMakroporöse Schwämme sind eine Chance und Herausforderung für die Chemie und Materialwissenschaften. Die Herausforderung liegt in der Herstellung der Schwämme, die bestimmte Eigenschaftskombinationen aufweisen und zu neuen Anwendungen führen. Kennzeichnend für derartige Schwämme sind geringes Gewicht, Atmungsaktivität, spezielle Benetzungseigenschaften, großer Massentransfer, mechanische Stabilität und große Porenvolumina. Bottom‐up‐ und Top‐down‐Methoden zur Herstellung von Schwämmen aus Kohlenstoff und Polymeren sowie ausgewählte Eigenschaften und mögliche Anwendungen werden in diesem Aufsatz diskutiert.
Bildung von α‐Ketoradikalen aus Vinylbromiden und molekularem Sauerstoff mit sichtbarem Licht: Synthese von Indenonen und Dihydroindeno[1,2‐c]chromenen
Authors: Pagire Santosh K. , Kreitmeier Peter , Reiser Oliver 
Published: June 2017

AbstractOrtho‐alkinylierte α‐Bromcinnamate können in einer Photokaskadenreaktion mit sichtbarem Licht und molekularem Sauerstoff zu Indenonen oder Dihydroindeno[1,2‐c]chromenen umgesetzt werden. Der einstufige Prozess verläuft über photochemische Schlüsselreaktionen wie die einleitende Aktivierung der Vinylbromide durch Energietransfer zu den entsprechenden α‐Ketoradikalen durch Reaktion mit molekularem Sauerstoff, gefolgt von der α‐Oxidation einer Areneinheit unter 6π‐Elektrocyclisierung. Die anschließende Hydroxylierung über eine Elektronenübertragung durch denselben Photokatalysator führt zu Dihydroinden[1,2‐c]chromenen.
Coupling of Magnetic and Elastic Domains in the Organic–Inorganic Layered Perovskite‐Like (C6H5C2H4NH3)2FeIICl4Crystal
Authors: Nakayama Yuki , Nishihara Sadafumi , Inoue Katsuya , Suzuki Takashi , Kurmoo Mohamedally 
Published: June 2017

AbstractMultiferroic materials coupling ferroelasticity and ferromagnetism show strong magnetoelastic effects as magnetization is induced by mechanical stress or alternately strain induced by applying a magnetic field. These effects were reported for inorganic multiferroics such as LaCoxSr1−xO3. (C6H5C2H4NH3)2FeIICl4is the first example of an organic–inorganic perovskite to exhibit such effects below the canted antiferromagnetism atTC=98 K and ferroelasticity atTC=433 K. This is shown by switching the magnetic hysteresis on and off by uniaxial pressure through the strong coupling of the magnetic and elastic domains. The spin‐canting direction was controlled by mechanical stress in the heating and cooling cycles. This unique observation gives additional impetus in the search for coupled hysteretic effect in organic–inorganic multiferroics.
Carbon Dioxide Electroreduction into Syngas Boosted by a Partially Delocalized Charge in Molybdenum Sulfide Selenide Alloy Monolayers
Authors: Xu Jiaqi , Li Xiaodong , Liu Wei , Sun Yongfu , Ju Zhengyu , Yao Tao , Wang Chengming , Ju Huanxin , Zhu Junfa , Wei Shiqiang , Xie Yi 
Published: June 2017

AbstractStructural parameters of ternary transition‐metal dichalcogenide (TMD) alloy usually obey Vegard law well, while interestingly it often exhibits boosted electrocatalytic performances relative to its two pristine binary TMDs. To unveil the underlying reasons, we propose an ideal model of ternary TMDs alloy monolayer. As a prototype, MoSeS alloy monolayers are successfully synthesized, in which X‐ray absorption fine structure spectroscopy manifests their shortened Mo−S and lengthened Mo−Se bonds, helping to tailor the d‐band electronic structure of Mo atoms. Density functional theory calculations illustrate an increased density of states near their conduction band edge, which ensures faster electron transfer confirmed by their lower work function and smaller charge‐transfer resistance. Energy calculations show the off‐center charge around Mo atoms not only benefits for stabilizing COOH* intermediate confirmed by its most negative formation energy, but also facilitates the rate‐limiting CO desorption step verified by CO temperature programmed desorption and electro‐stripping tests. As a result, MoSeS alloy monolayers attain the highest 45.2 % Faradaic efficiency for CO production, much larger than that of MoS2 monolayers (16.6 %) and MoSe2 monolayers (30.5 %) at −1.15 V vs. RHE. This work discloses how the partially delocalized charge in ternary TMDs alloys accelerates electrocatalytic performances at atomic level, opening new horizons for manipulating CO2 electroreduction properties.
Heterogeneous Sodium‐Manganese Oxide Catalyzed Aerobic Oxidative Cleavage of 1,2‐Diols
Authors: Escande Vincent , Lam Chun Ho , Coish Philip , Anastas Paul T. 
Published: June 2017

AbstractThe aerobic oxidative cleavage of 1,2‐diols using a heterogeneous catalyst only based on earth‐abundant metals manganese and sodium is reported for the first time. This reusable catalyst cleaves a variety of substrates into aldehydes or ketones with high selectivity. The reaction requires small catalytic loadings and is performed under mild conditions using ambient pressure O2 or air as the oxidant while producing water as the only by‐product. Mechanistic investigations reveal a monodentate, two‐electron oxidative fragmentation process involving a MnIV species. The eco‐friendly, innocuous catalyst is compatible with a wide range of functional groups and conditions, making it highly competitive with classical reagents, such as periodic acid or lead tetraacetate, as a preferred method for activated 1,2‐diols.
Low‐Density Open Cellular Sponges as Functional Materials
Authors: Jiang Shaohua , Agarwal Seema , Greiner Andreas 
Published: June 2017

AbstractLow‐density macroporous sponges with densities less than 100 mg cm−3 are both a challenge and an opportunity for advanced chemistry and material science. The challenge lies in the precise preparation of the sponges with property combinations that lead to novel applications. Bottom‐up and top‐down chemical and engineering methods for the preparation of sponges are a major focus of this Review, with an emphasis on carbon and polymer materials. The light weight, sustainability, breathability, special wetting characteristics, large mass transfer, mechanical stability, and large pore volume are typical characteristics of sponges made of advanced materials and could lead to novel applications. Some selected sponge properties and potential applications are discussed.
Metal‐Free, Room‐Temperature Oxygen‐Atom Transfer in the N2O/CO Redox Couple as Catalyzed by [Si2Ox].+ (x=2–5)
Authors: Sun Xiaoyan , Zhou Shaodong , Yue Lei , Schlangen Maria , Schwarz Helmut 
Published: June 2017

AbstractThe thermal reduction of N2O by CO mediated by the metal‐free cluster cations [Si2Ox].+ (x=2–5) has been examined in the gas phase using Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry in conjunction with quantum chemical calculations. Three successive oxidation/reduction steps occur starting from [Si2O2].+ and N2O to form eventually [Si2O5].+; the latter as well as the intermediate oxide cluster ions react sequentially with CO molecules to regenerate [Si2O2].+. Thus, full catalytic cycles occur at ambient conditions in the gas phase. Mechanistic aspects of these sequential redox processes have been addressed to reveal the electronic origins of these unparalleled reactions.
Practical Alkoxythiocarbonyl Auxiliaries for Iridium(I)‐Catalyzed C−H Alkylation of Azacycles
Authors: Tran Anh T. , Yu Jin‐Quan 
Published: June 2017

AbstractThe development of new and practical 3‐pentoxythiocarbonyl auxiliaries for IrI‐catalyzed C−H alkylation of azacycles is described. This method allows for the α‐C−H alkylation of a variety of substituted pyrrolidines, piperidines, and tetrahydroisoquinolines through alkylation with alkenes. While the practicality of these simple carbamate‐type auxiliaries is underscored by the ease of installation and removal, the method's utility is demonstrated in its ability to functionalize biologically relevant l‐proline and l‐trans‐hydroxyproline, delivering unique 2,5‐dialkylated amino acid analogues that are not accessible by other C−H functionalization methods.
Palladium‐Catalyzed Enantioselective Narasaka–Heck Reaction/Direct C−H Alkylation of Arenes: Iminoarylation of Alkenes
Authors: Bao Xu , Wang Qian , Zhu Jieping 
Published: June 2017

AbstractA palladium‐catalyzed reaction of γ,δ‐unsaturated oxime esters with oxadiazoles afforded dihydropyrroles in good to excellent yields through an intramolecular iminopalladation/intermolecular direct heteroarene C−H alkylation cascade. This unprecedented iminoarylation of alkenes was subsequently realized in an enantioselective manner in the presence of a chiral bidentate phosphine ligand (Synphos).
Efficacy, Safety, Pharmacokinetics, and Pharmacodynamics of Filgotinib, a Selective JAK‐1 Inhibitor, After Short‐Term Treatment of Rheumatoid Arthritis: Results of Two Randomized Phase IIa Trials
Authors: Vanhoutte Frédéric , Mazur Minodora , Voloshyn Oleksandr , Stanislavchuk Mykola , Van der Aa Annegret , Namour Florence , Galien René , Meuleners Luc , van 't Klooster Gerben 
Published: June 2017

ObjectiveJAK inhibitors have shown efficacy in rheumatoid arthritis (RA). We undertook this study to test our hypothesis that selective inhibition of JAK‐1 would combine good efficacy with a better safety profile compared with less selective JAK inhibitors.MethodsIn two 4‐week exploratory, double‐blind, placebo‐controlled phase IIa trials, 127 RA patients with an insufficient response to methotrexate (MTX) received filgotinib (GLPG0634, GS‐6034) oral capsules (100 mg twice daily or 30, 75, 150, 200, or 300 mg once daily) or placebo, added onto a stable regimen of MTX, to evaluate safety, efficacy, pharmacokinetics (PK), and pharmacodynamics (PD) of filgotinib. The primary efficacy end point was the number and percentage of patients in each treatment group meeting the American College of Rheumatology 20% improvement criteria (achieving an ACR20 response) at week 4.ResultsTreatment with filgotinib at 75–300 mg met the primary end point and showed early onset of efficacy. ACR20 response rates progressively increased to week 4, and the Disease Activity Score in 28 joints using the C‐reactive protein (CRP) level decreased. Marked and sustained improvements were observed in serum CRP level and other PD markers. The PK of filgotinib and its major metabolite was dose proportional over the 30–300 mg range. Early side effects seen with other less selective JAK inhibitors were not observed (e.g., there was no worsening of anemia [JAK‐2 inhibition related], no effects on liver transaminases, and no increase in low‐density lipoprotein or total cholesterol). A limited decrease in neutrophils without neutropenia was consistent with immunomodulatory effects through JAK‐1 inhibition. There were no infections. Overall, filgotinib was well tolerated. Events related to study drug were mild or moderate and transient during therapy, and the most common such event was nausea.ConclusionSelective inhibition of JAK‐1 with filgotinib shows initial efficacy in RA with an encouraging safety profile in these exploratory studies.
Determination of the serine palmitoyl transferase inhibitor myriocin by electrospray and Q‐trap mass spectrometry
Authors: Campisi Giuseppe Matteo , Signorelli Paola , Rizzo Jessica , Ghilardi Claudio , Antognetti Jacopo , Caretti Anna , Lazarević Jelena S. , Strettoi Enrica , Novelli Elena , Ghidoni Riccardo , Rubino Federico Maria , Paroni Rita 
Published: June 2017

AbstractMyriocin is a potent inhibitor of serine‐palmitoyl‐transferase, the first and rate‐determining enzyme in the sphingolipids biosynthetic pathway. This study developed, validated and applied a LC–MS/MS method to measure myriocin in minute specimens of animal tissue. The chemical analog 14‐OH–myriocin was used as the internal standard. The two molecules were extracted from the tissue homogenate by solid‐phase extraction, separated by gradient reversed‐phase liquid chromatography and measured by negative ion electrospray mass spectrometry in the triple quadrupole. Detection was accomplished by multiple reaction monitoring, employing the most representative transitions, 400@104 and 402@104 for myriocin and 14‐OH‐myriocin, respectively. The typical limit of detection and lower limit of quantitation of the optimized method were 0.9 pmol/mL (~0.016 pmol injected) and 2.3 pmol/mL, respectively, and the method was linear up to 250 pmol/mL range (r2 = 0.9996). The intra‐ and between‐day repeatability afforded a coefficient of variation ≤7.0%. Applications included quantification of myriocin in mouse lungs after 24 h from administration of ~4 nmol by intra‐tracheal delivery. Measured levels ranged from 4.11 (median; 2.3–7.4 IQR, n = 4) to 11.7 (median; 7.6–22.7 interquartile range (IQR), n = 6) pmol/lung depending on the different formulations used. Myriocin was also measured in retinas of mice treated by intravitreal injection and ranged from 0.045 (less than the limit of detection) to 0.35 pmol/retina.