bluuebunny/crossref_metadata_2025 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

The 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

The 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

The 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

Objective

To identify determinants of clinically meaningful change in functional disability in low‐income Hispanic patients with established rheumatoid arthritis (RA) in the US.

Methods

We 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.

Results

At 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.

Conclusion

Results 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

Objective

To 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.

Methods

We 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.

Results

During 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.

Conclusion

The 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

Objective

Little 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.

Methods

Data 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.

Results

Between 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).

Conclusion

In 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

Objective

To highlight the opportunities and challenges of developing and implementing performance outcome measures in rheumatology for accountability purposes.

Methods

We 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.

Results

Our 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.

Conclusion

Performance 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

Objective

To 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.

Methods

A 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).

Results

A 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.

Conclusion

Precision 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.
Surface Structural Transition Induced by Gradient Polyanion‐Doping in Li‐Rich Layered Oxides: Implications for Enhanced Electrochemical Performance
Authors: Zhao Ying , Liu Jiatu , Wang Shuangbao , Ji Ran , Xia Qingbing , Ding Zhengping , Wei Weifeng , Liu Yong , Wang Peng , Ivey Douglas G.
Published: May 2016

Lithium‐rich layered oxides (LLOs) exhibit great potential as high‐capacity cathode materials for lithium‐ion batteries, but usually suffer from capacity/voltage fade during electrochemical cycling. Herein, a gradient polyanion‐doping strategy is developed to initiate surface structural transition to form a spinel‐like surface nanolayer and a polyanion‐doped layered core material in LLOs simultaneously. This strategy integrates the advantages of both bulk doping and surface modification as the oxygen close‐packed structure of LLOs is stabilized by polyanion doping, and the LLO cathodes are protected from steady corrosion induced by electrolytes. A LLO material modified with 5 at% phosphate (5%P@LLO) shows a high reversible discharge capacity of ≈300 mAh g−1 at 0.1 C, excellent cycling stability with a capacity retention of 95% after 100 cycles, and enhanced electrode kinetics. This gradient doping strategy can be further extended to other polyanion‐doped LLO materials, such as borate and silicate polyanions.
Plasmonic Airy Beam Generation by Both Phase and Amplitude Modulation with Metasurfaces
Authors: Li Zhi , Cheng Hua , Liu Zhaocheng , Chen Shuqi , Tian Jianguo
Published: May 2016

The Airy beam represent the only possible nondiffracting wave packets in 1D planar systems with curved trajectory, which has attracted considerable research interest due to its nondiffracting, self‐healing properties, and unique self‐bending behavior in the absence of any external potential. Because of the complexity of the Airy function and generation structure, an Airy beam with both phase and amplitude modulation is hard to realize. Here, a simplified metasurface composed of orthogonal nanorods is proposed, which can generate plasmonic Airy beams with both phase and amplitude modulation. By changing the configuration of the nanorods, the phase and amplitude can be simultaneously modulated. The bending degree of the generated Airy beam can be easily controlled by changing the number of nanorods. The proposed controllable Airy beam with both phase and amplitude modulation overcomes certain limitations of the customary Airy beam and can aid in the development of more accurate applications of the Airy beam in microfields.
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

So 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.

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Metal‐Organic Framework‐Based Nanomaterials for Electrocatalysis
Authors: Mahmood Asif , Guo Wenhan , Tabassum Hassina , Zou Ruqiang
Published: May 2016

Metal‐organic frameworks (MOFs) with high surface area and tunable chemical structures have attracted tremendous attention. Recently, there has been increasing interest in deriving advanced materials from MOFs for electrochemical energy storage and conversion. This progress report highlights recent breakthroughs in electrocatalysis by using MOF‐based novel catalysts, such as in oxygen reduction and evolution, hydrogen evolution and carbon dioxide reduction. The advantages of preparing electrocatalysts from MOFs are introduced and discussed. Then, the development of MOF derived electrocatalysis‐active products, such as heteroatom‐doped carbon, metal oxide (MO), metal sulfide (MS), metal carbide (MC), metal phosphide (MP) and their hybrids with carbon, are summarized. The detailed functions of these materials in representative electrocatalysis systems are also reviewed. The demonstrated examples will provide understanding in preparing highly active and stable electrocatalysts. The progress report concludes with the future applications of MOF‐based materials in the field of electrocatalysis.
Development of formation and growth models of CO2hydrate film
Authors: Abe Yutaka , Ma Xiao , Yanai Takehiko , Yamane Kenji
Published: May 2016

This study aims to develop models to estimate the CO2hydrate film formation and growth for different temperature and flow velocity conditions. First, the CO2hydrate film thickness at the initial stage of its formation is experimentally measured under different temperature and flow velocity conditions using laser interferometry. Based on the results, the CO2hydrate film thickness was found to decrease with increasing temperature and flow velocity. Next, the CO2hydrate film formation model and growth model are developed, and the models are verified using the present experimental data. Finally, the long term growth of CO2hydrate film thickness is estimated by the proposed growth model of CO2hydrate film thickness. © 2016 American Institute of Chemical EngineersAIChE J, 62: 4078–4089, 2016
Early‐stage evaluation of biorefinery processing pathways using process network flux analysis
Authors: Ulonska Kirsten , Skiborowski Mirko , Mitsos Alexander , Viell Jörn
Published: May 2016

With growing interest in the biomass value chain, a multitude of reactions are proposed in literature for the conversion of biomass into a variety of biofuels. In the early design stage, data for a detailed design is scarce rendering an in‐depth analysis of all possibilities challenging. In this contribution, the screening methodology process network flux analysis (PNFA) is introduced assessing systematically the cost and energy performance of processing pathways. Based on the limited data available, a ranking of biorefinery pathways and a detection of bottlenecks is achieved by considering the reaction performance as well as the feasibility and energy demand of various separation strategies using thermodynamic sound shortcut models. PNFA is applied to a network of six gasoline biofuels from lignocellulosic biomass. While 2‐butanol is ruled out due to a lack in yield and selectivity, iso‐butanol and 2‐butanone are identified as economically promising fuels beyond ethanol.
: Process Systems Engineering. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3096–3108, 2016
Investigation of inhibitors efficacy in wax deposition mitigation using a laboratory scale flow loop
Authors: Chi Yuandao , Daraboina Nagu , Sarica Cem
Published: May 2016

Statistically reliable wax inhibition experimental data was obtained by utilizing the newly built laboratory scale flow loop. The comb‐shaped inhibitors are found more effective in decreasing the thickness compared to the linear inhibitor under the same conditions. Moreover, this becomes more predominant as the chain length of inhibitors increases. Interestingly, even though all the inhibitors decreased the deposit thickness, the wax content increased significantly. Besides, the longer chain length (PI‐B) of the inhibitor results in a higher wax content. Since the combination of growth and aging influenced by the presence of inhibitor significantly, paraffin inhibition efficiency (PIE) based on the wax mass was proposed to quantitatively assess the inhibitors. Based on the PIE, PI‐B, and PI‐C have more inhibition efficiency than PI‐A. Therefore, when selecting wax inhibitor, one should be aware about the strength of the deposit gel in addition to the reduction of the deposit mass. © 2016 American Institute of Chemical EngineersAIChE J, 62: 4131–4139, 2016
Rhodium‐Catalyzed Cycloisomerization of 2‐Alkynyl‐N′‐arylidenebenzohydrazides through exo‐Carboamination
Authors: Matsuda Takanori , Matsuda Yoshiya
Published: May 2016

The 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.
Whole exome sequencing in patients with white matter abnormalities
Authors: Vanderver Adeline , Simons Cas , Helman Guy , Crawford Joanna , Wolf Nicole I. , Bernard Geneviève , Pizzino Amy , Schmidt Johanna L. , Takanohashi Asako , Miller David , Khouzam Amirah , Rajan Vani , Ramos Erica , Chowdhury Shimul , Hambuch Tina , Ru Kelin , Baillie Gregory J. , Grimmond Sean M. , Caldovic Ljubica , Devaney Joseph , Bloom Miriam , Evans Sarah H. , Murphy Jennifer L. P. , McNeill Nathan , Fogel Brent L. ,   the Leukodystrophy Study Group, Schiffmann Raphael , van der Knaap Marjo S. , Taft Ryan J.
Published: May 2016

Here we report whole exome sequencing (WES) on a cohort of 71 patients with persistently unresolved white matter abnormalities with a suspected diagnosis of leukodystrophy or genetic leukoencephalopathy. WES analyses were performed on trio, or greater, family groups. Diagnostic pathogenic variants were identified in 35% (25 of 71) of patients. Potentially pathogenic variants were identified in clinically relevant genes in a further 7% (5 of 71) of cases, giving a total yield of clinical diagnoses in 42% of individuals. These findings provide evidence that WES can substantially decrease the number of unresolved white matter cases. Ann Neurol 2016;79:1031–1037
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

Nanorattles, 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

An 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

The 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

We 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

Woodward'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

The 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

Artificial 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

Thermal 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.
Palladium‐Catalyzed Directed para C−H Functionalization of Phenols
Authors: Patra Tuhin , Bag Sukdev , Kancherla Rajesh , Mondal Anirban , Dey Aniruddha , Pimparkar Sandeep , Agasti Soumitra , Modak Atanu , Maiti Debabrata
Published: May 2016

Various practical methods for the selective C−H functionalization of the ortho and recently also of the meta position of an arene have already been developed. Following our recent development of the directing‐group‐assisted para C−H functionalization of toluene derivatives, we herein report the first remote para C−H functionalization of phenol derivatives by using a recyclable silicon‐containing biphenyl‐based template. The effectiveness of this strategy was illustrated with different synthetic elaborations and by the synthesis of various phenol‐based natural products.
The Multiple Facets of Iodine(III) Compounds in an Unprecedented Catalytic Auto‐amination for Chiral Amine Synthesis
Authors: Buendia Julien , Grelier Gwendal , Darses Benjamin , Jarvis Amanda G. , Taran Frédéric , Dauban Philippe
Published: May 2016

Iodine(III) reagents are used in catalytic one‐pot reactions, first as both oxidants and substrates, then as cross‐coupling partners, to afford chiral polyfunctionalized amines. The strategy relies on an initial catalytic auto C(sp3)−H amination of the iodine(III) oxidant, which delivers an amine‐derived iodine(I) product that is subsequently used in palladium‐catalyzed cross‐couplings to afford a variety of useful building blocks with high yields and excellent stereoselectivities. This study demonstrates the concept of self‐amination of the hypervalent iodine reagents, which increases the value of the aryl moiety.
Synthesis and characterization of thermotropic liquid crystalline polyarylate with ether ether ketone segments in the main chain
Authors: Zeng Luxian , Li Ruosong , Chen Peng , Xu Jianjun , Liu Pengqing
Published: May 2016

A series of thermotropic liquid crystalline poly(ether ether ketone) arylates (PEEKARs) were synthesized by combining the synthetic oligomeric poly(ether ether ketone) with terminal acetoxyls (PEEK‐A) and oligomeric Polyester with terminal carboxyl (PES‐C). The structures of the synthesized monomers and oligomerics were characterized by Fourier transform infrared spectroscopy and 1H Nuclear magnetic resonance spectroscopy, which indicated that the products were successfully synthesized as designed, and three kinds of PEEKARs with different legend of polyester segments were synthesized. The morphologies and properties of PEEKARs were measured by differential scanning calorimetry, wide‐angle X‐ray diffraction, thermal gravimetric analysis and polarized optional microscopy. The results show that PEEKAR with the minimum polyester segments has the best crystallization properties, but the flowability of which is rather poor and the liquid crystal character is unobvious; meanwhile, PEEKAR with more polyester segments can form a thermotropic liquid crystal intermediate state, and PEEKAR with maximum polyester segments has a somewhat humble crystallization property; as the content of polyester segments increases, the crystal form of PEEKARs changes and the char yields at 600 °C is reduced. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43800.
Open‐cell polypropylene/polyolefin elastomer blend foams fabricated for reusable oil‐sorption materials
Authors: Wang Shusheng , Wang Kun , Pang Yongyan , Li Yang , Wu Fei , Wang Sui , Zheng Wenge
Published: May 2016

The fabrication of high‐performance oil sorbents is of great significance for oil spill cleanup. The main objective of this study was to prepare open‐cell polypropylene/polyolefin elastomer (PP/POE) blend foams for fabrication of reusable sorbents for oil sorption. Open‐cell PP/POE blend foams were prepared via continuous‐extrusion foaming using supercritical carbon dioxide as the blowing agent. The interconnected open‐cell structure was characterized by scanning electron microscopy. The hydrophobicity and lipophilicity of PP/POE open‐cell foams were revealed by tests of contact‐angle measurement, water and cyclohexane sorption on the foam surface, CCl4 and cyclohexane sorption in water, and oil/water separation. Further, the sorption tests indicated that PP/POE blend foams showed larger oil‐uptake capacities than pure PP foams. In addition, cyclic compression tests showed that PP/POE open‐cell foams had excellent ductility and significantly improved recoverability compared to pure PP foams. In cyclic sorption–desorption tests, the sorption kinetics was studied in terms of capacity and saturation time, showing that PP/POE foams kept larger sorption capacities for 10 cycles, with larger sorption rates and good reusability. Based on the high open‐cell content, the good hydrophobic and oleophilic properties, the high oil‐sorption capacity, the improved recoverability, the large sorption rate, and the good reusability in cyclic oil‐sorption performance, the PP/POE open‐cell foams have shown promise as potential oil sorbents in applications for oil spill cleanup. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43812.
A Comparative Analysis of the Peptide Repertoires of HLA–DR Molecules Differentially Associated With Rheumatoid Arthritis
Authors: Scholz Erika , Mestre‐Ferrer Anna , Daura Xavier , García‐Medel Noel , Carrascal Montserrat , James Eddie A. , Kwok William W. , Canals Francesc , Álvarez Iñaki
Published: May 2016

Objective

To evaluate similarity of the peptide repertoires bound to HLA–DR molecules that are differentially associated with rheumatoid arthritis (RA), and to define structural features of the shared peptides.

Methods

Peptide pools bound to HLA–DRB1*01:01, HLA–DRB1*04:01, and HLA–DRB1*10:01 (RA associated) and those bound to HLA–DRB1*15:01 (non–RA–associated) were purified and analyzed by liquid chromatography (LC) matrix‐assisted laser desorption ionization–time‐of‐flight mass spectrometry (MS) and LC–ion‐trap MS. Peptide pools from each allotype were compared in terms of size, protein origin, composition, and affinity (both theoretical and experimental with some peptides). Finally, 1 peptide sequenced from DR1, DR4, and DR10, but not from DR15, was modeled in complex with all 4 HLA–DRB1 molecules and HLA–DRB5*01:01.

Results

A total of 6,309 masses and 962 unique peptide sequences were compared. DR10 shared 29 peptides with DR1, 9 with DR4, and 1 with DR15; DR1 shared 6 peptides with DR4 and 9 with DR15; and DR4 and DR15 shared 4 peptides. The direct identification of peptide ligands indicated that DR1 and DR10 were the most similar molecules regarding the peptides that they could share. The peptides common to these molecules contained a high proportion of Leu at P4 and basic residues at P8 binding core positions.

Conclusion

The degree of overlap between peptide repertoires associated with different HLA–DR molecules is low. The repertoires associated with DR1 and DR10 have the highest similarity among the molecules analyzed (∼10% overlap). Among the peptides shared between DR1 and DR10, a high proportion contained Leu4 and basic residues at the P8 position of the binding core.
Brief Report: A Prospective Open‐Label Phase IIa Trial of Tocilizumab in the Treatment of Polymyalgia Rheumatica
Authors: Lally Lindsay , Forbess Lindsy , Hatzis Christopher , Spiera Robert
Published: May 2016

Objective

Interleukin‐6 (IL‐6) is a pivotal cytokine in the pathogenesis of polymyalgia rheumatica (PMR), yet the efficacy of IL‐6 blockade with tocilizumab (TCZ) for the treatment of PMR is unknown. The aim of this study was to assess the efficacy and safety of TCZ in newly diagnosed PMR.

Methods. In a single‐center open‐label study, patients with newly diagnosed PMR who had been treated with glucocorticoids (GCs) for <1 month were treated monthly with intravenous (IV) TCZ 8 mg/kg for 1 year, with a rapid tapering of GCs according to standardized protocol. The primary end point was the proportion of patients in relapse‐free remission without GC treatment at 6 months. Secondary outcome measures included duration of GC use and cumulative GC dose. Patients were followed up for 15 months.

Results

Ten patients were enrolled in the study. One patient withdrew after 2 months, leaving 9 patients in whom the primary end point was assessed. The primary end point of relapse‐free remission without GC treatment at 6 months was achieved by all 9 of these patients. All patients who received TCZ treatment were able to discontinue GCs within 4 months of study entry. The cumulative mean ± SD prednisone dose was 1,085 ± 301 mg and the total duration of GC exposure was 3.9 ± 0.9 months. Remission persisted without relapse, in all 9 patients, throughout the entire 15‐month study.

Conclusion

Our findings suggest that TCZ may be an effective, safe, and well‐tolerated treatment for newly diagnosed patients with PMR, with a robust steroid‐sparing effect.
Brief Report: Causes of Stillbirths in Women With Systemic Lupus Erythematosus
Authors: Vinet Évelyne , Genest Geneviève , Scott Susan , Pineau Christian A. , Clarke Ann E. , Platt Robert W. , Bernatsky Sasha
Published: May 2016

Objective

There are few precise or recent estimates of the risk or causes of stillbirths in women with systemic lupus erythematosus (SLE). Thus, we undertook the present study to examine causes of stillbirths in mothers with SLE versus those without SLE.

Methods

The Offspring of SLE Mothers Registry (OSLER) is a large population‐based cohort, identified through Quebec's health care databases (1989–2009), including all women who had ≥1 hospitalization for delivery after SLE diagnosis, and a randomly selected control group of women matched for age and year of delivery. We identified stillbirths and ascertained the cause of death as indicated on death certificates. Odds ratios (ORs) and 95% confidence intervals (95% CIs) were calculated, and multivariate logistic regression analysis was performed to estimate the risk of stillbirth in women with SLE versus controls.

Results

In our cohort, 509 women with SLE had 729 births, including 9 stillbirths, while 5,829 matched controls had 8,541 births, including 47 stillbirths. We observed more stillbirths in mothers with SLE than in controls (1.24% versus 0.55%, difference 0.69% [95% CI 0.03, 1.88]). Women with SLE had an increased risk of stillbirth compared to controls (adjusted OR 2.13 [95% CI 1.02, 4.45]). We also observed a trend toward more stillbirths due to placenta‐mediated pregnancy complications in mothers with SLE than in controls (44% [95% CI 14, 79] versus 15% [95% CI 6, 28]).

Conclusion

Compared to women from the general population, women with SLE have an increased risk of stillbirth. Stillbirths in women with SLE might be more often caused by placenta‐mediated pregnancy complications compared to stillbirths in mothers without SLE.
Reductive Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10
Authors: Brotsman Victor A. , Bogdanov Viktor P. , Rybalchenko Alexey V. , Galanicheva Evgenia P. , Belov Nikita M. , Markov Vitaliy Yu. , Lukonina Natalia S. , Ioffe Ilya N. , Troyanov Sergey I. , Kemnitz Erhard , Goryunkov Alexey A.
Published: May 2016

CF3‐derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends—hydrogen atoms. Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10 by means of reduction with Zn/Cu couple in the presence of water proceeds regioselectively, yielding only one major isomer of C70(CF3)8H2 and only two for C70(CF3)10H2, whose addition patterns are combined in the only abundant isomer of C70(CF3)10H4. The observed selectivity is governed by the electronic structure of trifluoromethylated substrates. Interestingly, we discovered that Clar's theory can be utilized to predict the regiochemistry of functionalization, and we look forward to testing it on forthcoming cases of derivatization of pre‐functionalized fullerene building blocks.
Atypical rapid audio‐visual temporal recalibration in autism spectrum disorders
Authors: Noel Jean‐Paul , De Niear Matthew A. , Stevenson Ryan , Alais David , Wallace Mark T.
Published: May 2016

Changes in sensory and multisensory function are increasingly recognized as a common phenotypic characteristic of Autism Spectrum Disorders (ASD). Furthermore, much recent evidence suggests that sensory disturbances likely play an important role in contributing to social communication weaknesses—one of the core diagnostic features of ASD. An established sensory disturbance observed in ASD is reduced audiovisual temporal acuity. In the current study, we substantially extend these explorations of multisensory temporal function within the framework that an inability to rapidly recalibrate to changes in audiovisual temporal relations may play an important and under‐recognized role in ASD. In the paradigm, we present ASD and typically developing (TD) children and adolescents with asynchronous audiovisual stimuli of varying levels of complexity and ask them to perform a simultaneity judgment (SJ). In the critical analysis, we test audiovisual temporal processing on trial t as a condition of trial t − 1. The results demonstrate that individuals with ASD fail to rapidly recalibrate to audiovisual asynchronies in an equivalent manner to their TD counterparts for simple and non‐linguistic stimuli (i.e., flashes and beeps, hand‐held tools), but exhibit comparable rapid recalibration for speech stimuli. These results are discussed in terms of prior work showing a speech‐specific deficit in audiovisual temporal function in ASD, and in light of current theories of autism focusing on sensory noise and stability of perceptual representations. Autism Res 2017, 10: 121–129. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Personal space regulation in childhood autism: Effects of social interaction and person's perspective
Authors: Candini Michela , Giuberti Virginia , Manattini Alessandra , Grittani Serenella , di Pellegrino Giuseppe , Frassinetti Francesca
Published: May 2016

Studies in children with Typical Development (TD) and with Autism Spectrum Disorder (ASD) revealed that autism affects the personal space regulation, influencing both its size (permeability) and its changes depending on social interaction (flexibility). Here, we investigate how the nature of social interaction (Cooperative vs. Uncooperative) and the person perspective influence permeability and flexibility of interpersonal distance. Moreover, we tested whether the deficit observed in ASD children, reflects the social impairment (SI) in daily interactions. The stop‐distance paradigm was used to measure the preferred distance between the participant and an unfamiliar adult (first‐person perspective, Experiment 1), and between two other people (third‐person perspective, Experiment 2). Interpersonal distance was measured before and after the interaction with a confederate. The Wing Subgroups Questionnaire was used to evaluate SI in everyday activities, and each ASD participant was accordingly assigned either to the lower (children with low social impairment [low‐SI ASD]), or to the higher SI group (children with high social impairment [high‐SI ASD]). We observed larger interpersonal distance (permeability) in both ASD groups compared to TD children. Moreover, depending on the nature of social interaction, a modulation of interpersonal distance (flexibility) was observed in TD children, both from the first‐ and third‐person perspective. Similar findings were found in low‐SI but not in high‐SI ASD children, in Experiment 1. Conversely, in Experiment 2, no change was observed in both ASD groups. These findings reveal that SI severity and a person's perspective may account for the deficit observed in autism when flexibility, but not permeability, of personal space is considered. Autism Res 2017, 10: 144–154. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.