bluuebunny/crossref_metadata_2025_split huggingface dataset:
Plant transpiration and groundwater dynamics in water‐limited climates: Impacts of hydraulic redistribution
Authors: Luo Xiangyu , Liang Xu , Lin Jeen‐Shang 
Published: May 2016

AbstractThe role of groundwater in sustaining plant transpiration constitutes an important but not well‐understood aspect of the interactions between groundwater, vegetation, the land surface, and the atmosphere. The effect of the hydraulic redistribution (HR) process by plant roots on the interplay between plant transpiration and groundwater dynamics under water‐limited climates is investigated by using the Variable Infiltration Capacity Plus (VIC+) land surface model. Numerical experiments, with or without explicitly considering HR, are conducted on soil columns over a range of groundwater table depths (GWTDs) under different vegetative land covers, soil types, and precipitation conditions. When HR is not included, this study obtains transpiration–GWTD relationships consistent with those from watershed studies that do not include HR. When HR is included, the transpiration–GWTD relationships are modified. The modification introduced by HR is manifested in the soil moisture of the root zone. The mechanism of HR is explained by detailing the roles of the hydraulically redistributed water, the upward diffusion of soil water, and the daytime root uptake. We have found that HR is particularly important in water‐limited climates under which plants have high transpiration demand. At the beginning stage of a dry period, HR modulates the severe impacts that climate has on plant transpiration. Only after a prolonged dry period, impacts of HR are lessened when the groundwater table drops below the depth of water uptake by roots and are diminished when plant transpiration is decoupled from groundwater dynamics.
Pore water chemistry reveals gradients in mineral transformation across a model basaltic hillslope
Authors: Pohlmann Michael , Dontsova Katerina , Root Robert , Ruiz Joaquin , Troch Peter , Chorover Jon 
Published: May 2016

AbstractThe extent of weathering incongruency during soil formation from rock controls local carbon and nutrient cycling in ecosystems, as well as the evolution of hydrologic flow paths. Prior studies of basalt weathering, including those that have quantified the dynamics of well‐mixed, bench‐scale laboratory reactors or characterized the structure and integrated response of field systems, indicate a strong influence of system scale on weathering rate and trajectory. For example, integrated catchment response tends to produce lower weathering rates than do well mixed reactors, but the mechanisms underlying these disparities remain unclear. Here we present pore water geochemistry and physical sensor data gathered during two controlled rainfall‐runoff events on a large‐scale convergent model hillslope mantled with 1 m uniform depth of granular basaltic porous media. The dense sampler and sensor array (1488 samplers and sensors embedded in 330 m3 of basalt) showed that rainfall‐induced dissolution of basaltic glass produced supersaturation of pore waters with respect to multiple secondary solids including allophane, gibbsite, ferrihydrite, birnessite and calcite. The spatial distribution of saturation state was heterogeneous, suggesting an accumulation of solutes leading to precipitation of secondary solids along hydrologic flow paths. Rapid dissolution of primary silicates was widespread throughout the entire hillslope, irrespective of up‐gradient flowpath length. However, coherent spatial variations in solution chemistry and saturation indices were observed in depth profiles and between distinct topographic regions of the hillslope. Colloids (110–2000 nm) enriched in iron (Fe), aluminum (Al), and phosphorus (P) were mobile in soil pore waters.
Heat advection processes leading to El Niño events as depicted by an ensemble of ocean assimilation products
Authors: Ballester Joan , Bordoni Simona , Petrova Desislava , Rodó Xavier 
Published: May 2016

AbstractThe oscillatory nature of El Niño‐Southern Oscillation results from an intricate superposition of near‐equilibrium balances and out‐of‐phase disequilibrium processes between the ocean and the atmosphere. The main objective of the present work is to perform an exhaustive spatiotemporal analysis of the upper ocean heat budget in an ensemble of state‐of‐the‐art ocean assimilation products. We put specific emphasis on the ocean heat advection mechanisms, and their representation in individual ensemble members and in the different stages of the ENSO oscillation leading to EN events. Our analyses consistently show that the initial subsurface warming in the western equatorial Pacific is advected to the central Pacific by the equatorial undercurrent, which, together with the equatorward advection associated with anomalies in both the meridional temperature gradient and circulation at the level of the thermocline, explains the heat buildup in the central Pacific during the recharge phase. We also find that the recharge phase is characterized by an increase of meridional tilting of the thermocline, as well as a southward upper‐ocean cross‐equatorial mass transport resulting from Ekman‐induced anomalous vertical motion in the off‐equatorial regions. Although differences between data sets are generally small, and anomalies tend to have the same sign, the differences in the magnitude of the meridional term are seen to be key for explaining the different propagation speed of the subsurface warming tendency along the thermocline. The only exception is GECCO, which does not produce the patterns of meridional surface Ekman divergence (subsurface Sverdrup convergence) in the western and central equatorial Pacific.
Trends in Functional Disability and Determinants of Clinically Meaningful Change Over Time in Hispanic Patients With Rheumatoid Arthritis in the US
Authors: Karpouzas George A. , Draper Taylor , Moran Rosalinda , Hernandez Elizabeth , Nicassio Perry , Weisman Michael H. , Ormseth Sarah 
Published: May 2016

ObjectiveTo identify determinants of clinically meaningful change in functional disability in low‐income Hispanic patients with established rheumatoid arthritis (RA) in the US.MethodsWe evaluated 156 low‐socioeconomic status, uninsured, largely immigrant Hispanic patients, collectively described as vulnerable patients, on 3 consecutive visits (baseline, 6, and 12 months followup) at a single center. Disability (Health Assessment Questionnaire [HAQ] disability index [DI]), pain (visual analog scale), and depression (Patient Health Questionnaire [PHQ‐9]) were assessed each time. Disease activity (Disease Activity Score in 28 joints [DAS28] using the erythrocyte sedimentation rate), serology results, radiographs, treatments, and irreversible articular damage were also recorded.ResultsAt baseline, 71% had significant disability (HAQ DI >1), and 34% were depressed. HAQ DI improved significantly over time (P = 0.032), and absence of depression (PHQ‐9 <10), lower pain, lack of erosions, and no biologic agent use at baseline all predicted the greatest improvement (P < 0.001). Baseline to 12‐month HAQ DI recovery exceeding the minimum clinically important difference (MCID) occurred in 42% of patients. Recovery was associated with concurrent improvements in DAS28, pain, and PHQ‐9 scores (albeit below their respective MCIDs), as well as with absence of erosions. Notably, isolated shifts in PHQ‐9 or pain scores over MCID were sufficient to yield clinically meaningful HAQ DI changes.ConclusionResults suggest that disease activity, depression, and pain are modifiable parameters with consistent, significant, independent, and additive contributions to HAQ DI changes across the disease trajectory in vulnerable Hispanic patients with RA. Their improvement over time, collectively or in isolation, may yield clinically measurable improvements in functional disability and reaffirms these parameters as actionable items in a patient‐centered treat‐to‐target approach.
Distribution and Drivers of Average Direct Cost of Osteoarthritis in Canada From 2003 to 2010
Authors: Sharif Behnam , Kopec Jacek A. , Wong Hubert , Anis Aslam H. 
Published: May 2016

ObjectiveTo estimate the distribution and drivers of the average direct cost of osteoarthritis (OA) in Canada using a population‐based health microsimulation model of OA from 2003 to 2010.MethodsWe used a previously published microsimulation model to estimate the distribution of average cost of OA across different cost components and OA stages. OA stages were defined according to the patient flow within the health care system. Cost components associated with pharmacologic and nonpharmacologic treatments, physician visits, and hospitalization were included. Scenario analysis was performed to evaluate average cost drivers from 2003 to 2010.ResultsDuring the study period, the OA population size grew from 2.9 to 3.6 million, while the average cost increased from $577 to $811 (Canadian) per patient per year. The highest increase in share of cost components was for total joint replacement (TJR) surgery (24% to 32%). The highest average cost was incurred by patients in stage 4 (during and after revision surgery), while around 80% of OA patients were in stage 1 (OA diagnosed but has not visited an orthopedic surgeon). Increase in the proportion of OA patients receiving TJR surgeries (34%) and price inflation (29%) were the most significant drivers of average cost.ConclusionThe average cost of OA has been increasing during the study period mostly due to an increase in the proportion of patients receiving TJR surgeries and price inflation. The distribution of average cost of OA across disease stages needs to be considered when designing policies targeting specific aspects of OA care.
Cervical Spinal Fracture and Other Diagnoses Associated With Mortality in Hospitalized Ankylosing Spondylitis Patients
Authors: Wysham Katherine D. , Murray Sara G. , Hills Nancy , Yelin Edward , Gensler Lianne S. 
Published: May 2016

ObjectiveLittle data exist regarding mortality in ankylosing spondylitis (AS). We assessed diagnoses associated with in‐hospital mortality in AS using a population‐based inpatient data set.MethodsData were abstracted from the Healthcare Cost and Utilization Project Nationwide Inpatient Sample between 2007 and 2011. We identified AS admissions using International Classification of Diseases, Ninth Revision, Clinical Modification code 720.0. In‐hospital mortality was the primary outcome. Logistic regression was used to evaluate the association between top diagnoses and in‐hospital mortality. We performed a secondary analysis from the same years in all patients (with and without AS) with cervical spine (C‐spine) fracture to determine whether AS was an independent risk factor for mortality.ResultsBetween 2007 and 2011, we identified 12,484 admissions and 267 deaths in AS patients. C‐spine fracture with spinal cord injury and sepsis had the highest odds of death, with odds ratios (ORs) of 13.43 (95% confidence interval [95% CI] 8.00–22.55, P < 0.0001) and 7.63 (95% CI 5.62–10.36, P < 0.0001), respectively. In the same time period, there were 53,606 C‐spine fracture admissions, of which 408 were coded with AS. Among all C‐spine fracture hospitalizations, an AS diagnosis was associated with inpatient death (OR 1.61 [95% CI 1.16–2.22], P = 0.004).ConclusionIn AS patients admitted to the hospital, C‐spine fracture is a leading cause of in‐hospital mortality. Other diagnoses associated with mortality include sepsis, pneumonia, cardiovascular disease, and comorbid illnesses. Among all hospitalizations with C‐spine fracture, AS was associated with increased odds of death. C‐spine fracture–associated mortality warrants further study to elucidate risk factors in order to prevent such devastating fractures in AS patients.
American College of Rheumatology White Paper on Performance Outcome Measures in Rheumatology
Authors: Suter Lisa G. , Barber Claire E. , Herrin Jeph , Leong Amye , Losina Elena , Miller Amy , Newman Eric , Robbins Mark , Tory Heather , Yazdany Jinoos 
Published: May 2016

ObjectiveTo highlight the opportunities and challenges of developing and implementing performance outcome measures in rheumatology for accountability purposes.MethodsWe constructed a hypothetical performance outcome measure to demonstrate the benefits and challenges of designing quality measures that assess patient outcomes. We defined the data source, measure cohort, reporting period, period at risk, measure outcome, outcome attribution, risk adjustment, reliability and validity, and reporting approach. We discussed outcome measure challenges specific to rheumatology and to fields where patients have predominantly chronic, complex, ambulatory care–sensitive conditions.ResultsOur hypothetical outcome measure was a measure of rheumatoid arthritis disease activity intended for evaluating Accountable Care Organization performance. We summarized the components, benefits, challenges, and tradeoffs between feasibility and usability. We highlighted how different measure applications, such as for rapid cycle quality improvement efforts versus pay for performance programs, require different approaches to measure development and testing. We provided a summary table of key take‐home points for clinicians and policymakers.ConclusionPerformance outcome measures are coming to rheumatology, and the most effective and meaningful measures can only be created through the close collaboration of patients, providers, measure developers, and policymakers. This study provides an overview of key issues and is intended to stimulate a productive dialogue between patients, practitioners, insurers, and government agencies regarding optimal performance outcome measure development.
Patient‐Reported Outcomes Measurement Information System Tools for Collecting Patient‐Reported Outcomes in Children With Juvenile Arthritis
Authors: Brandon Timothy G. , Becker Brandon D. , Bevans Katherine B. , Weiss Pamela F. 
Published: May 2016

ObjectiveTo evaluate the precision and construct validity of pediatric Patient‐Reported Outcomes Measurement Information System (PROMIS) instruments in a population of juvenile idiopathic arthritis (JIA) patients and parent proxies.MethodsA convenience sample of JIA patients and parents of JIA patients completed PROMIS instruments for 8 domains: anger, anxiety, depressive symptoms, fatigue, mobility, pain interference, peer relationships, and upper‐extremity function. Short form and computerized adaptive test (CAT) scores were derived from item bank responses. Raw scores were translated to standardized T scores with corresponding SEs. Discrimination between inactive versus active disease was evaluated as an indicator of each measure's construct validity. SEs were plotted to evaluate each instrument's relative precision. Patient‐parent concordance was assessed using intraclass correlations (ICCs).ResultsA total of 228 patients and 223 parents participated, providing 71–78 responses per domain. Patient‐ and parent‐reported anger, fatigue, mobility, and pain interference scores significantly differed between those with inactive and active disease. Anxiety, depressive symptoms, and peer relationships differed by disease activity levels for parent‐report only. Short forms and CATs provided comparable reliability to the full item banks across the full range of each outcome. Patient‐parent agreement ranged from ICC 0.3 to 0.8. CATs did not reduce the number of items for any domain compared to the short form.ConclusionPrecision and discriminatory abilities of PROMIS instruments depend on health domain and report type (self‐report versus parent proxy‐report) for children with JIA. Varying levels of patient‐parent concordance reinforces the importance of considering both perspectives in comprehensive health outcomes assessments.
Manganese‐Catalyzed ortho‐C−H Alkenylation of Aromatic N−H Imidates with Alkynes: Versatile Access to Mono‐Alkenylated Aromatic Nitriles
Authors: Yang Xiaoxu , Jin Xiqing , Wang Congyang 
Published: May 2016

AbstractSo far, the direct C−H alkenylation of aromatic nitriles with alkynes has not been achieved. Herein, we discribe the first manganese‐catalyzed C−H alkenylation of aromatic N−H imidates to access mono‐alkenylated aromatic nitriles. The reaction is accelerated by the presence of a catalytic amount of sodium pivalate. This protocol is also highlighted by the simple catalytic system, good compatibility of functional groups, and excellent mono‐/dialkenylation selectivity as well as E/Z stereoselectivity.magnified image
Rhodium‐Catalyzed Cycloisomerization of 2‐Alkynyl‐N′‐arylidenebenzohydrazides through exo‐Carboamination
Authors: Matsuda Takanori , Matsuda Yoshiya 
Published: May 2016

AbstractThe rhodium‐catalyzed cycloisomerization reaction of 2‐alkynyl‐N′‐arylidenebenzohydrazides is reported. The reaction provides 4‐alkenylphthalazin‐1(2 H)‐ones through an intramolecular exo‐carboamination.
Plasmonic Nanorattles as Next‐Generation Catalysts for Surface Plasmon Resonance‐Mediated Oxidations Promoted by Activated Oxygen
Authors: da Silva Anderson G. M. , Rodrigues Thenner S. , Correia Valquírio G. , Alves Tiago V. , Alves Rafael S. , Ando Rômulo A. , Ornellas Fernando R. , Wang Jiale , Andrade Leandro H. , Camargo Pedro H. C. 
Published: May 2016

AbstractNanorattles, comprised of a nanosphere inside a nanoshell, were employed as the next generation of plasmonic catalysts for oxidations promoted by activated O2. After investigating how the presence of a nanosphere inside a nanoshell affected the electric‐field enhancements in the nanorattle relative to a nanoshell and a nanosphere, the SPR‐mediated oxidation of p‐aminothiophenol (PATP) functionalized at their surface was investigated to benchmark how these different electric‐field intensities affected the performances of Au@AgAu nanorattles, AgAu nanoshells and Au nanoparticles having similar sizes. The high performance of the nanorattles enabled the visible‐light driven synthesis of azobenzene from aniline under ambient conditions. As the nanorattles allow the formation of electromagnetic hot spots without relying on the uncontrolled aggregation of nanostructures, it enables their application as catalysts in liquid phase under mild conditions using visible light as the main energy input.
Nickel‐Catalyzed Intramolecular C−O Bond Formation: Synthesis of Cyclic Enol Ethers
Authors: Han Seo‐Jung , Doi Ryohei , Stoltz Brian M. 
Published: May 2016

AbstractAn efficient and exceptionally mild intramolecular nickel‐catalyzed carbon–oxygen bond‐forming reaction between vinyl halides and primary, secondary, and tertiary alcohols has been achieved. Zinc powder was found to be an essential additive for obtaining high catalyst turnover and yields. This operationally simple method allows direct access to cyclic vinyl ethers in high yields in a single step.
Highly Efficient Perovskite Solar Cells Employing an Easily Attainable Bifluorenylidene‐Based Hole‐Transporting Material
Authors: Rakstys Kasparas , Saliba Michael , Gao Peng , Gratia Paul , Kamarauskas Egidijus , Paek Sanghyun , Jankauskas Vygintas , Nazeeruddin Mohammad Khaja 
Published: May 2016

AbstractThe 4,4′‐dimethoxydiphenylamine‐substituted 9,9′‐bifluorenylidene (KR216) hole transporting material has been synthesized using a straightforward two‐step procedure from commercially available and inexpensive starting reagents, mimicking the synthetically challenging 9,9′‐spirobifluorene moiety of the well‐studied spiro‐OMeTAD. A power conversion efficiency of 17.8 % has been reached employing a novel HTM in a perovskite solar cells.
UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase
Authors: Viglino Emilie , Shaffer Christopher J. , Tureček František 
Published: May 2016

AbstractWe report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas‐phase metal complexes. Oxidation of Tyr‐Ala‐Ala‐Ala‐Arg (YAAAR) produces Tyr‐O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala‐Ala‐Ala‐Tyr‐Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N‐terminal amino group in combination with hydrogen‐atom transfer from the Cα positions of the peptide backbone.
Activity‐Based Proteome Profiling Probes Based on Woodward's Reagent K with Distinct Target Selectivity
Authors: Qian Yong , Schürmann Marc , Janning Petra , Hedberg Christian , Waldmann Herbert 
Published: May 2016

AbstractWoodward's reagent K (WRK) is a reactive heterocyclic compound that has been employed in protein chemistry to covalently and unspecifically label proteins at nucleophilic amino acids, notably at histidine and cysteine. We have developed a panel of WRK‐derived activity‐based probes and show that surprisingly and unexpectedly, these probes are fairly selective for a few proteins in the human proteome. The WRK‐derived probes show unique reactivity towards the catalytic N‐terminal proline in the macrophage migration inhibitory factor (MIF) and can be used to label and, if equipped with a fluorophore, to image MIF activities in living cells.
Distance‐Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups
Authors: Hwang Jungwun , Li Ping , Smith Mark D. , Shimizu Ken D. 
Published: May 2016

AbstractThe stabilizing and destabilizing effects of alkyl groups on an aromatic stacking interaction were experimentally measured in solution. The size (Me, Et, iPr, and tBu) and position (meta and para) of the alkyl groups were varied in a molecular balance model system designed to measure the strength of an intramolecular aromatic interaction. Opposite stability trends were observed for alkyl substituents at different positions on the aromatic rings. At the closer meta‐position, smaller groups were stabilizing and larger groups were destabilizing. Conversely, at the farther para‐position, the larger alkyl groups were systematically more stabilizing with the bulky tBu group forming the strongest stabilizing interaction. X‐ray crystal structures showed that the stabilizing interactions of the small meta‐alkyl and large para‐alkyl groups were due to their similar distances and van der Waals contact areas with the edge of opposing aromatic ring.
Directional Regulation of Enzyme Pathways through the Control of Substrate Channeling on a DNA Origami Scaffold
Authors: Ke Guoliang , Liu Minghui , Jiang Shuoxing , Qi Xiaodong , Yang Yuhe Renee , Wootten Shaun , Zhang Fei , Zhu Zhi , Liu Yan , Yang Chaoyong James , Yan Hao 
Published: May 2016

AbstractArtificial multi‐enzyme systems with precise and dynamic control over the enzyme pathway activity are of great significance in bionanotechnology and synthetic biology. Herein, we exploit a spatially addressable DNA nanoplatform for the directional regulation of two enzyme pathways (G6pDH–MDH and G6pDH–LDH) through the control of NAD+ substrate channeling by specifically shifting NAD+ between the two enzyme pairs. We believe that this concept will be useful for the design of regulatory biological circuits for synthetic biology and biomedicine.
Spin‐Selective Thermal Activation of Methane by Closed‐Shell [TaO3]+
Authors: Zhou Shaodong , Li Jilai , Schlangen Maria , Schwarz Helmut 
Published: May 2016

AbstractThermal reactions of the closed‐shell metal‐oxide cluster [TaO3]+ with methane were investigated by using FTICR mass spectrometry complemented by high‐level quantum chemical calculations. While the generation of methanol and formaldehyde is somewhat expected, [TaO3]+ remarkably also has the ability to abstract two hydrogen atoms from methane with the elimination of CH2. Mechanistically, the generation of CH2O and CH3OH occurs on the singlet‐ground‐state surface, while for the liberation of 3CH2, a two‐state reactivity scenario prevails.