bluuebunny/crossref_metadata_2025 huggingface dataset:
A high‐order local time stepping finite volume solver for one‐dimensional blood flow simulations: application to the ADAN model
Authors: Müller Lucas O. , Blanco Pablo J. , Watanabe Sansuke M. , Feijóo Raúl A.
Published: December 2015

In recent years, the complexity of vessel networks for one‐dimensional blood flow models has significantly increased, because of enhanced anatomical detail or automatic peripheral vasculature generation, for example. This fact, along with the application of these models in uncertainty quantification and parameter estimation poses the need for extremely efficient numerical solvers. The aim of this work is to present a finite volume solver for one‐dimensional blood flow simulations in networks of elastic and viscoelastic vessels, featuring high‐order space‐time accuracy and local time stepping (LTS). The solver is built on (i) a high‐order finite volume type numerical scheme, (ii) a high‐order treatment of the numerical solution at internal vertexes of the network, often called junctions, and (iii) an accurate LTS strategy. The accuracy of the proposed methodology is verified by empirical convergence tests. Then, the resulting LTS scheme is applied to arterial networks of increasing complexity and spatial scale heterogeneity, with a number of one‐dimensional segments ranging from a few tens up to several thousands and vessel lengths ranging from less than a millimeter up to tens of centimeters, in order to evaluate its computational cost efficiency. The proposed methodology can be extended to any other hyperbolic system for which network applications are relevant. Copyright © 2016 John Wiley & Sons, Ltd.
Efficient bit‐parallel subcircuit extraction using CUDA
Authors: Hung Che‐Lun , Lin Chun‐Yuan , Ou Chia‐Shin , Tseng Yuan‐Hong , Hung Po‐Yen , Li Ship‐Peng , Fu Chun‐Ting
Published: December 2015

Wafer processing technology has been improving rapidly. Moore's law has been exceeded as the number of transistors in a dense integrated circuit, now increases threefold or more, approximately every year. The integrated circuit has gone from very large scale to giga large scale. The extraction of subcircuits has therefore become computation‐intensive. In this paper, we propose an efficient bit‐parallel subcircuit extraction algorithm using graphic processing units. We conducted experimental trials and demonstrated that the proposed algorithm can achieve high throughput, suggesting practical applications in the extraction of subcircuits. Copyright © 2015 John Wiley & Sons, Ltd.
Qespera: an adaptive framework for prediction of queue waiting times in supercomputer systems
Authors: Murali Prakash , Vadhiyar Sathish
Published: December 2015

Production parallel systems are space‐shared, and resource allocation on such systems is usually performed using a batch queue scheduler. Jobs submitted to the batch queue experience a variable delay before the requested resources are granted. Predicting this delay can assist users in planning experiment time‐frames and choosing sites with less turnaround times and can also help meta‐schedulers make scheduling decisions. In this paper, we present an integrated adaptive framework, Qespera, for prediction of queue waiting times on parallel systems. We propose a novel algorithm based on spatial clustering for predictions using history of job submissions and executions. The framework uses adaptive set of strategies for choosing either distributions or summary of features to represent the system state and to compare with history jobs, varying the weights associated with the features for each job prediction, and selecting a particular algorithm dynamically for performing the prediction depending on the characteristics of the target and history jobs. Our experiments with real workload traces from different production systems demonstrate up to 22% reduction in average absolute error and up to 56% reduction in percentage prediction error over existing techniques. We also report prediction errors of less than 1 h for a majority of the jobs. Copyright © 2015 John Wiley & Sons, Ltd.
Exploiting multi‐cores for efficient interchange of large messages in distributed systems
Authors: Zhao Dongfang , Qiao Kan , Zhou Zhou , Li Tonglin , Zhou Xiaobing , Raicu Ioan
Published: December 2015

Conventional data serialization tools assume that objects to be coded are usually small in size so a single CPU core can encode it in a timely manner. In the era of Big Data, however, object gets increasingly complex and larger, which makes data serialization become a new performance bottleneck. This paper describes an approach to parallelize data serialization by leveraging multiple cores. Parallelizing data serialization introduces new questions such as how to split the (sub)objects, how to allocate the available cores, and how to minimize its overhead in practice. In this paper we design a framework for parallelly serializing large objects and analyze the design tradeoffs under different scenarios. To validate the proposed approach, we implemented parallel protocol buffers—the parallel version of Google's Protocol Buffers, a widely‐used data serialization utility. Experimental results confirm the effectiveness of Parallel Protocol Buffers: multiple cores employed in data serialization achieve highly scalable performance and incur negligible overhead. Copyright © 2015 John Wiley & Sons, Ltd.
Co‐conformational Exchange Triggered by Molecular Recognition in a Di(acylamino)pyridine‐Based Molecular Shuttle Containing Two Pyridine Rings at the Macrocycle
Authors: Martinez‐Cuezva Alberto , Carro‐Guillen Fernando , Pastor Aurelia , Marin‐Luna Marta , Orenes Raul‐Angel , Alajarin Mateo , Berna Jose
Published: December 2015

We describe the incorporation of endo‐pyridine units into the tetralactam ring of di(acylamino)pyridine‐based rotaxanes. This macrocycle strongly associates with the linear interlocked component as confirmed by X‐ray diffraction studies of rotaxane 2 b. Dynamic NMR studies of 2 b in solution revealed a rotational energy barrier that was higher than that of the related rotaxane 2 a, which lacks of pyridine rings in the macrocycle. The macrocycle distribution of the molecular shuttle 4 b, containing two endo‐pyridine rings, shows that the major co‐conformer is that with the cyclic component sitting over the di(acylamino)pyridine station. DFT calculations also support the marked preference of the ring for occupying the heterocyclic binding site. The association of N‐hexylthymine with the di(acylamino)pyridine binding site of 4 b led to the formation of a rare ‘S’‐shaped co‐conformer in which the tetralactam ring interacts simultaneously with both stations of the thread.
Allostatic load as a complex clinical construct: A case‐based computational modeling approach
Authors: Galen Buckwalter J. , Castellani Brian , Mcewen Bruce , Karlamangla Arun S. , Rizzo Albert A. , John Bruce , O'donnell Kyle , Seeman Teresa
Published: December 2015

Allostatic load (AL) is a complex clinical construct, providing a unique window into the cumulative impact of stress. However, due to its inherent complexity, AL presents two major measurement challenges to conventional statistical modeling (the field's dominant methodology): it is comprised of a complex causal network of bioallostatic systems, represented by an even larger set of dynamic biomarkers; and, it is situated within a web of antecedent socioecological systems, linking AL to differences in health outcomes and disparities. To address these challenges, we employed case‐based computational modeling (CBM), which allowed us to make four advances: (1) we developed a multisystem, 7‐factor (20 biomarker) model of AL's network of allostatic systems; (2) used it to create a catalog of nine different clinical AL profiles (causal pathways); (3) linked each clinical profile to a typology of 23 health outcomes; and (4) explored our results (post hoc) as a function of gender, a key socioecological factor. In terms of highlights, (a) the Healthy clinical profile had few health risks; (b) the pro‐inflammatory profile linked to high blood pressure and diabetes; (c) Low Stress Hormones linked to heart disease, TIA/Stroke, diabetes, and circulation problems; and (d) high stress hormones linked to heart disease and high blood pressure. Post hoc analyses also found that males were overrepresented on the High Blood Pressure (61.2%), Metabolic Syndrome (63.2%), High Stress Hormones (66.4%), and High Blood Sugar (57.1%); while females were overrepresented on the Healthy (81.9%), Low Stress Hormones (66.3%), and Low Stress Antagonists (stress buffers) (95.4%) profiles. © 2015 Wiley Periodicals, Inc. Complexity 21: 291–306, 2016
Physician response to implementation of genotype‐tailored antiplatelet therapy
Authors: Peterson JF , Field JR , Unertl KM , Schildcrout JS , Johnson DC , Shi Y , Danciu I , Cleator JH , Pulley JM , McPherson JA , Denny JC , Laposata M , Roden DM , Johnson KB
Published: December 2015

Physician responses to genomic information are vital to the success of precision medicine initiatives. We prospectively studied a pharmacogenomics implementation program for the propensity of clinicians to select antiplatelet therapy based on CYP2C19 loss‐of‐function variants in stented patients. Among 2,676 patients, 514 (19.2%) were found to have a CYP2C19 variant affecting clopidogrel metabolism. For the majority (93.6%) of the cohort, cardiologists received active and direct notification of CYP2C19 status. Over 12 months, 57.6% of poor metabolizers and 33.2% of intermediate metabolizers received alternatives to clopidogrel. CYP2C19 variant status was the most influential factor impacting the prescribing decision (hazard ratio [HR] in poor metabolizers 8.1, 95% confidence interval [CI] [5.4, 12.2] and HR 5.0, 95% CI [4.0, 6.3] in intermediate metabolizers), followed by patient age and type of stent implanted. We conclude that cardiologists tailored antiplatelet therapy for a minority of patients with a CYP2C19 variant and considered both genomic and nongenomic risks in their clinical decision‐making.
A High Voltage Olivine Cathode for Application in Lithium‐Ion Batteries
Authors: Di Lecce Daniele , Brescia Rosaria , Scarpellini Alice , Prato Mirko , Hassoun Jusef
Published: December 2015

A new olivine composition (i.e., LiFe0.25Mn0.5Co0.25PO4) is proposed as electrode material with increased energy density for application in lithium‐ion batteries. The new formulation increases the working voltage and induces different electrochemical behavior with respect to bare olivine materials based on Fe. The study provides deep insight into the features of the Fe3+/Fe2+, Mn3+/Mn2+, and Co3+/Co2+ redox couples within the olivine lattice in terms of electrochemical activity, Li+ transport properties, and Li‐cell behavior. The electrochemical characterization clearly reveals the voltage signatures corresponding to the various metals; however, the Mn3+/Mn2+ process has higher intrinsic polarization with respect to Fe3+/Fe2+ and Co3+/Co2+. This issue is efficiently mitigated by carbon coating the material, resulting in enhanced electrochemical performances.
Fc‐fragment removal allows the EPO‐Fc fusion protein to be detected in blood samples by IEF‐PAGE
Authors: Postnikov Pavel , Krotov Grigory , Mesonzhnik Natalia , Efimova Yulia , Rodchenkov Grigory
Published: December 2015

EPO‐Fc proteins have been under investigation as a potential drug for treating anaemia and have shown larger half‐life values than other erythropoiesis‐stimulating agents (ESAs). Sodium dodecyl sulfate/sodium N‐lauroylsarcosinate polyacrylamide gel electrophoresis (SDS/SAR‐PAGE) methods and subsequent immunoblotting are used for routine anti‐doping analysis. This paper reports that EPO‐Fc fusion proteins can be detected in serum samples by isoelectric focusing‐polyacrylamide gel electrophoresis (IEF‐PAGE) in carrier ampholyte‐based gels with a pH 2–6 gradient after removing the Fc part via site‐specific IdeS protease cleavage. The IdeS‐digested EPO‐Fc protein yields three fragments: two Fc fragments and one dimeric EPO‐hinge fragment. After IEF‐PAGE was followed by double Western blotting with chemiluminescent detection, the dimeric EPO‐hinge fragment showed a unique isoelectric pattern, which differed from those of any other currently known analogue of EPO. We observed that the removal of the Fc fragment from EPO‐Fc reduced the apparent molecular weight of entire fusion protein and increased its electrophoretic mobility. As a result, the band for the EPO‐hinge fragment was located in a region between the rEPO and NESP standards, at which lower amounts of serum proteins are present. Simple and selective protocols for determining the EPO‐Fc protein in human serum were developed to extend the methodological anti‐doping arsenal. This protocol has been characterized. The limit of detection (LOD) of the IEF‐PAGE method was 20 pg, and that of SDS/SAR‐PAGE was 15 pg. Copyright © 2015 John Wiley & Sons, Ltd.
Towards catchment classification in data‐scarce regions
Authors: Auerbach Daniel A. , Buchanan Brian P. , Alexiades Alexander V. , Anderson Elizabeth P. , Encalada Andrea C. , Larson Erin I. , McManamay Ryan A. , Poe Gregory L. , Walter M.Todd , Flecker Alexander S.
Published: December 2015

Assessing spatial variation in hydrologic processes can help to inform freshwater management and advance ecological understanding, yet many areas lack sufficient flow records on which to base classifications. Seeking to address this challenge, we apply concepts developed in data‐rich settings to public, global data in order to demonstrate a broadly replicable approach to characterizing hydrologic variation. The proposed approach groups the basins associated with reaches in a river network according to key environmental drivers of hydrologic conditions. This initial study examines Colorado (USA), where long‐term streamflow records permit comparison with previously distinguished flow regime types, and Ecuador, where data limitations preclude such analysis. The flow regime types assigned to gages in Colorado corresponded reasonably well to the classes distinguished from environmental features. The divisions in Ecuador reflected major known biophysical gradients while also providing a higher resolution supplement to an existing depiction of freshwater ecoregions. Although freshwater policy and management decisions occur amidst uncertainty and imperfect knowledge, this classification framework offers a rigorous and transferrable means to distinguish catchments in data‐scarce regions. The maps and attributes of the resulting ecohydrologic classes offer a departure point for additional study and data collection programmes such as the placement of stations in under‐monitored classes, and the divisions may serve as a preliminary template with which to structure conservation efforts such as environmental flow assessments. Copyright © 2015 John Wiley & Sons, Ltd.
Endothelial progenitor cells as markers of severity in hypertrophic cardiomyopathy
Authors: Kalyva Athanasia , Marketou Maria E. , Parthenakis Fragiskos I. , Pontikoglou Charalampos , Kontaraki Joanna E. , Maragkoudakis Spyros , Petousis Stylianos , Chlouverakis Gregory , Papadaki Helen A. , Vardas Panos E.
Published: December 2015

Aims

Endothelial progenitor cells (EPCs) are bone marrow‐derived cells that are mobilized into the circulation to migrate and differentiate into mature endothelial cells contributing to post‐natal physiological and pathological neovascularization. In this study, we evaluated circulating EPCs in patients with hypertrophic cardiomyopathy (HCM) and examined a potential association with clinical parameters of the disease.

Methods and results

We included 40 HCM patients and 23 healthy individuals. Using flow cytometry we measured EPCs in peripheral blood as two subpopulations of CD45–/CD34+/VEGFR2+ and CD45–/CD34+/CD133+ cells. Circulating CD45–/CD34+/VEGFR2+ cells were significantly increased in HCM patients in comparison with the controls (0.000238 ± 0.0003136 vs. 0.000057 ± 0.0001316, respectively, P = 0.002). However, there was no significant difference in the number of circulating CD45–/CD34+/CD133+ cells (0.003079 ± 0.0033288 vs. 0.002065 ± 0.0022173, respectively, P = 0.153). The CD45–/CD34+/VEGFR2+ subpopulation revealed a moderate correlation with LV mass index (r = 0.35, P = 0.026), while both EPC subpopulation levels showed strong positive correlations with th E/e' ratio (r = 0.423, P = 0.007 for CD45–/CD34+/VEGFR2+ and r = 0.572, P < 0.001 for CD45–/CD34+/CD133+).

Conclusion

HCM patients showed an increased mobilization of EPCs compared with healthy individuals that correlated with diastolic dysfunction. Our findings may open up new dimensions in the pathophysiology, prognostication, and treatment of HCM.
Loop diuretics, renal function and clinical outcome in patients with heart failure and reduced ejection fraction
Authors: Damman Kevin , Kjekshus John , Wikstrand John , Cleland John G.F. , Komajda Michel , Wedel Hans , Waagstein Finn , McMurray John J.V.
Published: December 2015

Aim

We aimed to study the relationships of loop diuretic dose with renal function and clinical outcomes in patients with chronic heart failure (HF).

Methods and results

Loop diuretic dose at baseline was recorded in patients included in the Controlled Rosuvastatin Multinational Trial in Heart Failure (CORONA). The relationship to change in estimated glomerular filtration rate (eGFR) over time and to the first occurrence of the composite outcome of cardiovascular (CV) death or hospitalization owing to HF was examined in propensity score matched cohorts. Of the 5011 patients, 2550, 745, and 449 were receiving >80 mg (high), 41–80 mg (medium) and ≤40 mg (low) of loop diuretics in furosemide equivalent daily dosages, respectively, which were used to assemble 229, 385, and 1045 pairs of propensity‐matched high, medium, and low dose cohorts. Compared with matched no loop diuretic groups, eGFR declined 0.3 ± 0.2, 0.3 ± 0.3 and 1.2 ± 0.5 mL/min/1.73 m2/year in the low‐, medium‐, and high‐dose groups, respectively. Compared with matched no loop diuretic groups, hazard ratios (HR) (95% confidence intervals) for outcome associated with low‐, medium‐ and high‐dose groups were 1.71 (1.41–2.06), 1.99 (1.50–2.64), and 2.94 (1.95–4.41), respectively. Higher loop diuretic dose was particularly associated with increased risk for hospitalization owing to HF: HR 4.80 (2.75–8.37), P < 0.001.

Conclusions

The use of loop diuretics was associated with a slightly greater rate of decline in eGFR, which did not vary significantly by diuretic dose.Loop diuretic dose was associated with higher risks of (CV) mortality and predominantly hospitalization owing to HF, which appeared to be higher among those receiving higher daily doses.
Requirement of MyD88 signaling in keratinocytes for Langerhans cell migration and initiation of atopic dermatitis‐like symptoms in mice
Authors: Didovic Sonja , Opitz Friederike V. , Holzmann Bernhard , Förster Irmgard , Weighardt Heike
Published: December 2015

Atopic dermatitis (AD) is a chronic inflammatory disease controlled by the innate and adaptive immune system. To elucidate the impact of innate immune signaling in AD, we analyzed MyD88‐deficient mice in a murine model of AD‐like dermatitis by epicutaneous sensitization with ovalbumin (OVA). Global MyD88 deficiency led to reduced epidermal thickening and diminished accumulation of macrophages within the inflamed skin. In addition, we observed impaired emigration of Langerhans cells (LCs) out of the epidermis of MyD88‐deficient mice. These findings indicate that MyD88 deficiency affects various skin‐resident cell types in the AD model. Moreover, production of IFN‐g, IL‐17, and CCL17 was reduced in skin draining lymph node cells and OVA‐specific immunoglobulin levels were lower in MyD88‐deficient mice. We further investigated the role of MyD88 in keratinocytes, as keratinocytes contribute to AD pathology. Exclusive expression of MyD88 in epidermal keratinocytes partially restored LC emigration after AD induction and expression of CCL17 in skin draining lymph nodes (LNs), but did not promote epidermal thickening nor production of IL‐17. Altogether, these data demonstrate that MyD88 signaling in keratinocytes is able to restore LC migration in an otherwise MyD88‐deficient background, and significantly contributes to the development of AD‐like dermatitis.
Dynamic spatio‐temporal contribution of single β5t+ cortical epithelial precursors to the thymus medulla
Authors: Mayer Carlos E. , Žuklys Saulius , Zhanybekova Saule , Ohigashi Izumi , Teh Hong‐Ying , Sansom Stephen N. , Shikama‐Dorn Noriko , Hafen Katrin , Macaulay Iain C. , Deadman Mary E. , Ponting Chris P. , Takahama Yousuke , Holländer Georg A.
Published: December 2015

Intrathymic T‐cell development is critically dependent on cortical and medullary thymic epithelial cells (TECs). Both epithelial subsets originate during early thymus organogenesis from progenitor cells that express the thymoproteasome subunit β5t, a typical feature of cortical TECs. Using in vivo lineage fate mapping, we demonstrate in mice that β5t+ TEC progenitors give rise to the medullary TEC compartment early in life but significantly limit their contribution once the medulla has completely formed. Lineage‐tracing studies at single cell resolution demonstrate for young mice that the postnatal medulla is expanded from individual β5t+ cortical progenitors located at the cortico‐medullary junction. These results therefore not only define a developmental window during which the expansion of medulla is efficiently enabled by progenitors resident in the thymic cortex, but also reveal the spatio‐temporal dynamics that control the growth of the thymic medulla.
Preparation of Imidazol‐2‐ylidene Carbene Palladacycles with Bi‐ and Tridentate Schiff Bases – Analyses of the Spectroscopic, Molecular Structure, and DFT Calculation Data
Authors: Naya Leticia , Vázquez‐García Digna , Fernández Alberto , López‐Torres Margarita , Ojea Vicente , Marcos Ismael , Vila José M. , Fernández Jesús J.
Published: December 2015

The treatment of appropriate benzylideneimine palladacycles with potentially polydentate imidazol‐2‐ylidene silver carbene complexes produced new palladium organometallics with the N‐heterocyclic carbene (NHC) coordinated to the palladium center. The NHCs bearing two carbene moieties show a bridging coordination mode across the two metal atoms and may also display a simultaneous bridging/chelating behavior. DFT calculations were performed for the compounds for which the typical fluxional behavior of hemilabile carbenes was observed upon close inspection of the 1H NMR spectra. The crystal and molecular structure of 13 was determined by X‐ray crystallography and contrasted against the computational data for 14 to determine the most favorable disposition of the fluxional equilibrium of the latter.
Iridium(III) 2‐Phenylbenzimidazole Complexes: Synthesis, Structure, Optical Properties, and Applications in Dye‐Sensitized Solar Cells
Authors: Bezzubov Stanislav I. , Kiselev Yuri M. , Churakov Andrey V. , Kozyukhin Sergey A. , Sadovnikov Alexey A. , Grinberg Vitaly A. , Emets Viktor V. , Doljenko Vladimir D.
Published: December 2015

A series of bis‐cyclometalated iridium(III) complexes, [Ir(LH)2(H2dcbpy)][PF6] (1), [Ir(LMe)2(H2dcbpy)][PF6] (2), and [Ir(LPh)2(H2dcbpy)][PF6] (3), where LH = 1‐H‐2‐phenylbenzimidazole, LMe = 1‐methyl‐2‐phenylbenzimidazole, LPh = 1,2‐diphenylbenzimidazole, and H2dcbpy = 2,2′‐bipyridine‐4,4′‐dicarboxylic acid, has been synthesized and fully characterized by elemental analysis, 1H and 31P NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray analysis. The complexes show strong luminescence in the yellow–orange region in ethanol at room temperature (quantum yield is up to 22 %), and absorb light up to 550 nm with molar absorptivities of 1500–2000 M–1 cm–1. Complexes 1 and 2 possess very similar optical properties, whereas the introduction of the phenyl ring (complex 3) causes a hypsochromic shift (≈ 30 nm) of the luminescent maximum as well as resulting in an almost 50 % increase in the extinction coefficient at 490 nm compared with 1 and 2. A dye‐sensitized solar cell (DSSC) based on complex 3 exhibits a short‐circuit photocurrent of 2.8 mA cm–2, an open‐circuit photovoltage of 0.44 V, and a power conversion efficiency of 0.7 %.
Influence of Reinforcing Nonagglomerated Nanodiamond Particles on Metal Matrix Nanocomposite Structure Stability in the Course of Heat­ing
Authors: Popov Vladimir A. , Shelekhov Evgenij V. , Vershinina Ekaterina V.
Published: December 2015

We show that the use of mechanical alloying makes it possible to produce metal matrix composites with uniformly distributed nonagglomerated nanodiamond (ND) reinforcing particles. An aluminium matrix has been used for this study. X‐ray analysis shows that a composite structure containing uniformly distributed nanoparticles of 4–6 nm can significantly slow down the process of recrystallization during heating, which becomes evident only when the material is heated above 350 °C. Higher volume fractions of diamond nanoparticles lead to higher starting recrystallization temperatures.
Hierarchical Meso‐Mesoporous and Macro‐Mesoporous Silica Templated by Mixtures of Polyoxyethylene ­Fluoroalkyl Ether and Triblock Copolymer
Authors: May‐Masnou Anna , Stébé Marie José , Blin Jean Luc
Published: December 2015

We report here the synthesis of different kinds of hierarchical porous silica materials by using mixtures of an amphiphilic block copolymer (Pluronic P123) and a nonionic fluorinated surfactant. In particular, we have taken advantage of the difference in polarities between the two compounds to design dual‐mesoporous materials through the cooperative templating mechanism (CTM). We have undertaken a complete study of this system by varying the composition of the mixed micelles and the synthesis conditions. We have shown that both the dual‐mesoporosity and the mesopore ordering are favored when materials are prepared with fluorine‐rich and P123‐rich micelles. However, when the P123‐rich micelles predominate, the mesostructure is less organized and the dual‐porosity depends on the P123 content. In addition, concentrated emulsions were formed by incorporating perfluorodecalin (PFD) in the surfactant mixture, and hierarchical macro‐mesoporous materials were prepared by combining the CTM and the emulsion templating mechanism.
Chiral Copper(II) Bis(oxazoline) Complexes Directly Coordinated to Amine‐Functionalized Phenylene/Biphenylene Periodic Mesoporous Organosilicas as Heterogeneous ­Catalysts
Authors: Carneiro Liliana , Silva Ana Rosa , Lourenço Mirtha A. O. , Mayoral Alvaro , Diaz Isabel , Ferreira Paula
Published: December 2015

Copper(II) complexes with commercial chiral bis(oxazoline)s were for the first time directly coordinated onto amine‐modified mesoporous phenylene and biphenylene silicas. All final materials maintained the 2D ordered mesoporous structure. The copper metal coordinates directly to the amine groups within the walls of the materials. The materials were tested as asymmetric heterogeneous catalysts in the kinetic resolution of hydrobenzoin. They were active, selective, and enantioselective in this reaction. The material containing the (S)‐(–)‐2,2′‐isopropylidene‐bis(4‐phenyl‐2‐oxazoline) (Me2PhBox) ligand, the best ligand in the homogeneous phase, presented the highest enantioselectivity of all the materials in the first cycle (73 %). The 2,2′‐methylenebis[(4S)‐4‐phenyl‐2‐oxazoline] (PhBox) ligand rendered the catalyst more stable, independent of the anion or organic moiety in the periodic mesoporous organosilica material; this catalyst was reused over five cycles without any significant loss of catalytic activity or enantioselectivity. This type of ligand plays an important role in the stability of the corresponding copper(II) complex upon immobilization and in the robustness of the heterogeneous catalyst upon reuse.
Scorpionate Hydrotris(indazolyl)borate Ligands as Tripodal Platforms for Surface‐Mounted Molecular Gears and Motors
Authors: Kammerer Claire , Rapenne Gwénaël
Published: December 2015

This microreview describes the use of scorpionate hydrotris(indazolyl)borate ligands to build structurally rigid bifunctional surface‐mounted molecular gears or motors. The article starts with the synthesis of 6‐functionalized indazoles and their corresponding scorpionate tris(indazolyl)borate tripodal ligands. Thioether groups allow the tripodal anchoring of such ligands on metallic surfaces, whereas ester functions enable anchoring on insulating surfaces. Finally, we present their coordination to ruthenium penta(aryl)cyclopentadienyl fragments for the preparation of prototypes of molecular gears and motors. The synthesis of the tetraferrocenylruthenium complex, a molecular motor that has been shown to exhibit controlled clockwise or anticlockwise unidirectional rotation, is also detailed.
Nickel‐Catalyzed Reductive Addition of Aryl/Benzyl Halides and Pseudohalides to Carbodiimides for the Synthesis of Amides
Authors: Panahi Farhad , Jamedi Fereshteh , Iranpoor Nasser
Published: December 2015

A Nickel‐catalyzed reductive process is described for the direct amidation of benzyl and aryl halides using carbodiimides as the amidating agent. Moreover, aryl and benzyl C–O electrophiles such as triflate, acetate, tosylate, trityl ether, and pivalate were converted into amides using this method. The in‐situ‐generated Ni0 acts as a catalyst for the reaction at room temperature for benzylic substrates, and 70 °C for aryl electrophiles. This new nickel‐catalyzed reductive coupling protocol provides a general and operationally simple method for the synthesis of diverse amides using carbodiimides. Amides bearing bulky substituents can be synthesized by this strategy in high yield, which demonstrates its effectiveness in amide synthesis.
Fluorescent Probes from Stable Aromatic Nitrile Oxides
Authors: Minuti Luigi Ferdinando , Memeo Misal Giuseppe , Crespi Stefano , Quadrelli Paolo
Published: December 2015

Stable aromatic nitrile oxides underwent a 1,3‐dipolar cycloaddition reaction with 1‐iodo‐4‐(prop‐2‐yn‐1‐yloxy)benzene to afford the expected isoxazoles in very good yields as single regioisomers. The formation of the 5‐substituted isoxazoles is in agreement with frontier orbital theory. The reductive cleavage of the N–O bond followed by complexation with BF3·Et2O afforded the corresponding boron complexes, which were further derivatized with a triple bond for click chemistry applications. The photochemical behavior and the fluorescence properties of the derivatives were investigated and discussed, taking theoretical calculations into consideration.
Two‐year Follow‐up of a Pragmatic Randomised Controlled Trial Examining the Effect of Adding a Carer's Skill Training Intervention in Inpatients with Anorexia Nervosa
Authors: Magill Nicholas , Rhind Charlotte , Hibbs Rebecca , Goddard Elizabeth , Macdonald Pamela , Arcelus Jon , Morgan John , Beecham Jennifer , Schmidt Ulrike , Landau Sabine , Treasure Janet
Published: December 2015

Background

Active family engagement improves outcomes from adolescent inpatient care, but the impact on adult anorexia nervosa is uncertain.

Aim

The aim of this study was to describe the 2‐year outcome following a pragmatic randomised controlled trial in which a skill training intervention (Experienced Caregivers Helping Others) for carers was added to inpatient care.

Method

Patient, caregiver and service outcomes were measured for 2 years following discharge from the index inpatient admission.

Results

There were small‐sized/moderate‐sized effects and consistent improvements in all outcomes from both patients and carers in the Experienced Caregivers Helping Others group over 2 years. The marked change in body mass index and carers' time caregiving following inpatient care was sustained. Approximately 20% of cases had further periods of inpatient care.

Conclusion

In this predominately adult anorexia nervosa sample, enabling carers to provide active support and management skills may improve the benefits in all symptom domains that gradually follow from a period of inpatient care. Copyright © 2015 John Wiley & Sons, Ltd and Eating Disorders Association.
Quality attributes of sweet potato flour as influenced by variety, pretreatment and drying method
Authors: Olatunde Ganiyat O. , Henshaw Folake O. , Idowu Michael A. , Tomlins Keith
Published: December 2015

The effect of pretreatment methods (soaking in water, potassium metabisulphite solution, and blanching) and drying methods (sun and oven) on some quality attributes of flour from ten varieties of sweet potato roots were investigated. The quality attributes determined were chemical composition and functional properties. Data obtained were subjected to descriptive statistics, multivariate analysis of variance, and Pearson's correlation. The range of values for properties of sweet potato flour were: moisture (8.06–12.86 ± 1.13%), starch (55.76–83.65 ± 6.82%), amylose (10.06–21.26 ± 3.92%), total sugar (22.39–125.46 ± 24.68 μg/mg), water absorption capacity (140–280 ± 26), water solubility (6.89–26.18 ± 3.80), swelling power (1.66–5.00 ± 0.50), peak viscosity (24.50–260.92 ± 52.61 RVU), trough (7.08–145.83 ± 34.48 RVU), breakdown viscosity (11.00–125.33 RVU), final viscosity (10.21–225.50 ± 60.55 RVU), setback viscosity (3.04–92.21 RVU), peak time (6.07–9.06 min) and pasting temperature (69.8–81.3°C). Variety had a significant (P < 0.001) effect on all the attributes of sweet potato flour. Pretreatment did not significantly (P > 0.05) affect moisture, fat and lightness (L*). Drying method did not significantly (P > 0.05) affect fiber and L*. The interactive effect of variety, pretreatment and drying method had a significant (P < 0.001) effect on all the attributes except fat and fiber. Total sugar correlated significantly (P < 0.01) with water solubility (r = 0.88) of the flour samples. Variety was a dominant factor influencing attributes of sweet potato flour and so should be targeted at specific end uses.
Risk‐Free Rates and Variance Futures Prices
Authors: Rompolis Leonidas S.
Published: December 2015

This paper investigates the relation between risk‐free rates and ex‐ante market volatility. It derives a theoretical model implying a negative linear relation between risk‐free rates and variance futures prices. The latter are employed as a direct market‐based ex‐ante estimate of risk‐neutral volatility. Empirical analysis, conducted using LIBOR and variance futures prices written on the S&P 500 index, indicates that the predictions of the model are supported by the data. The paper also provides evidence that, first, this negative relation varies smoothly over time following business cycles, and, second, the variance risk premium is a significant component of this documented relation. © 2015 Wiley Periodicals, Inc. Jrl Fut Mark 36:943–967, 2016
Geochemical features of the black shales from the Wuyu Basin, southern Tibet: implications for palaeoenvironment and palaeoclimate
Authors: Wang Zhongwei , Fu Xiugen , Feng Xinglei , Song Chunyan , Wang Dong , Chen Wenbin , Zeng Shengqiang
Published: December 2015

The Mangxiang Formation black shales are the most important hydrocarbon source rocks in the Wuyu Basin. Trace and rare earth element (REEs) of the black shales from the Wuyu Basin were studied in order to understand their depositional environments and palaeoclimate. Thirty one black shale samples from the Wuyu Basin were analysed by inductively coupled plasma–mass spectrometry and X‐ray fluorescence. The black shales are characterized by moderate SiO2 (52.55–58.73%) contents and medium K2O/Na2O (2.21–4.83) ratio values but relatively high MgO + Fe2O3 (5.8–6.91%) and Al2O3 (15.1–17.5%) contents. The Chemical Weathering Index of Alternation (CIA) ranges from 57 to 70, together with medium Th/U (2.66–4.97) ratio values, reflecting a weak to moderate degree of chemical weathering of the source area. The palaeoredox condition of black shale was slightly oxic (or dysoxic) during black shale deposition as evidenced by slightly Ce anomalies (0.92–0.99) and Mn enrichment (EF = 1.6). The moderate palaeosalinity values (9.32‰–17.75‰), together with medium B/Ga (3.90–5.57) ratio values, indicate a brackish water environment. The palaeoclimate index ∑(Fe + Mn + Cr + Ni + V + Co)/∑(Ca + Mg + Sr + Ba + K + Na) ranges from 0.28 to 0.50 and low Sr/Ba (0.15–1.22) ratio values, indicating a semiarid to semimoist climatic condition during the sedimentation of the black shale. The high ω(La)N/ω(Yb)N ratio values (1.02–1.09) indicate a fast sedimentary rate during black shale deposition. In this study, a preservation model of the Mangxiang Formation black shale was established. The model indicates that excellent preservation may be the major controlling factor for the accumulation of organic matter. Copyright © 2015 John Wiley & Sons, Ltd.
Disrupted subject‐specific gray matter network properties and cognitive dysfunction in type 1 diabetes patients with and without proliferative retinopathy
Authors: van Duinkerken Eelco , Ijzerman Richard G. , Klein Martin , Moll Annette C. , Snoek Frank J. , Scheltens Philip , Pouwels Petra J.W. , Barkhof Frederik , Diamant Michaela , Tijms Betty M.
Published: December 2015

Introduction

Type 1 diabetes mellitus (T1DM) patients, especially with concomitant microvascular disease, such as proliferative retinopathy, have an increased risk of cognitive deficits. Local cortical gray matter volume reductions only partially explain these cognitive dysfunctions, possibly because volume reductions do not take into account the complex connectivity structure of the brain. This study aimed to identify gray matter network alterations in relation to cognition in T1DM. Methods: We investigated if subject‐specific structural gray matter network properties, constructed from T1‐weighted MRI scans, were different between T1DM patients with (n = 51) and without (n = 53) proliferative retinopathy versus controls (n = 49), and were associated to cognitive decrements and fractional anisotropy, as measured by voxel‐based TBSS. Global normalized and local (45 bilateral anatomical regions) clustering coefficient and path length were assessed. These network properties measure how the organization of connections in a network differs from that of randomly connected networks. Results: Global gray matter network topology was more randomly organized in both T1DM patient groups versus controls, with the largest effects seen in patients with proliferative retinopathy. Lower local path length values were widely distributed throughout the brain. Lower local clustering was observed in the middle frontal, postcentral, and occipital areas. Complex network topology explained up to 20% of the variance of cognitive decrements, beyond other predictors. Exploratory analyses showed that lower fractional anisotropy was associated with a more random gray matter network organization. Conclusion: T1DM and proliferative retinopathy affect cortical network organization that may consequently contribute to clinically relevant changes in cognitive functioning in these patients. Hum Brain Mapp 37:1194–1208, 2016. © 2015 Wiley Periodicals, Inc.
Bilateral inferior alveolar nerve reconstruction with a vascularized sural nerve graft included in a free fibular osteocutaneous flap after segmental mandibulectomy
Authors: Tanaka Kentaro , Okazaki Mutsumi , Homma Tsutomu , Yano Tomoyuki , Mori Hiroki
Published: December 2015

Background

Segmental mandibulectomy with bilateral inferior alveolar nerve (IAN) resection results in complete sensory loss in the lower lip and chin. The purpose of this study was for us to report on a bilateral IAN reconstruction with a vascularized nerve graft after chemoradiotherapy during cancer ablation.

Methods

The mandible was reconstructed with a fibular osteocutaneous flap that included the sural nerve. The proximal ends of the right and left IAN were sutured to the proximal and distal ends of the sural nerve in an end‐to‐end manner. The 2 distal ends of the mental nerves were sutured to the sural nerve in an end‐to‐side manner. Sensations were measured using the Semmes–Weinstein monofilaments test.

Results

Sensory recovery was first noted after 5 months and the quantitative results of the Semmes–Weinstein test 45 months after surgery were 2.83 to 4.08.

Conclusion

One‐stage nerve reconstruction may be indicated for bilateral IAN resection. A vascularized nerve graft is effective especially in a perioperative radiotherapy case. © 2015 Wiley Periodicals, Inc. Head Neck 38: E111–E114, 2016
Predictors of stage at presentation and outcomes of head and neck cancers in a university hospital setting
Authors: Osazuwa–Peters Nosayaba , Christopher Kara M. , Hussaini Adnan S. , Behera Anit , Walker Ronald J. , Varvares Mark A.
Published: December 2015

Background

To increase early detection of head and neck cancers, it is important that disparities associated with access to care are addressed.

Methods

A total of 351 patients aged 20 to 91 years (58.72 ± 11.70 years) diagnosed with head and neck cancers at a university hospital from 1997 to 2010 were analyzed. Logistic regression assessed the association between clinical stage at presentation and predictors. Cox proportional hazards model assessed the effect of stage at presentation on survival.

Results

Being African American was associated with increased odds of late stage at presentation (adjusted odds ratio [OR] = 2.16; 95% confidence interval [CI] = 1.01–4.59), and those without health insurance were 10.97 times more likely to present at late stage (95% CI = 1.30–92.49). Unmarried patients were 1.6 times at an increased hazard of death (95% CI = 1.12–2.24).

Conclusion

Disparities, such as race and health insurance status, are important predictors of stage at presentation of patients with head and neck cancer. © 2015 Wiley Periodicals, Inc. Head Neck 38: E1826–E1832, 2016
Acetyl‐coenzyme A carboxylase alpha promotion of glucose‐mediated fatty acid synthesis enhances survival of hepatocellular carcinoma in mice and patients
Authors: Wang Ming‐Da , Wu Han , Fu Gong‐Bo , Zhang Hui‐Lu , Zhou Xu , Tang Liang , Dong Li‐Wei , Qin Chen‐Jie , Huang Shuai , Zhao Ling‐Hao , Zeng Min , Wu Meng‐Chao , Yan He‐Xin , Wang Hong‐Yang
Published: December 2015

Solid tumors often suffer from suboptimal oxygen and nutrient supplies. This stress underlies the requirement for metabolic adaptation. Aberrantly activated de novo lipogenesis is critical for development and progression of human hepatocellular carcinoma (HCC). However, whether de novo lipogenesis influences biological behaviors of HCCs under conditions of metabolic stress are still poorly understood. Here, we show that HCCs display distinct levels of glucose‐derived de novo lipogenesis, which are positively correlated with their survival responses to glucose limitation. The enhanced lipogenesis in HCCs is characterized by an increased expression of rate‐limiting enzyme acetyl‐coenzyme A carboxylase alpha (ACCα). ACCα‐mediated fatty acid (FA) synthesis determines the intracellular lipid content that is required to maintain energy hemostasis and inhibit cell death by means of FA oxidation (FAO) during metabolic stress. In accord, overexpression of ACCα facilitates tumor growth. ACCα forms a complex with carnitine palmitoyltransferase 1A (CPT1A) and prevents its mitochondria distribution under nutrient‐sufficient conditions. During metabolic stress, phosphorylation of ACCα leads to dissociation of the complex and mitochondria localization of CPT1A, thus promoting FAO‐mediated cell survival. Therefore, ACCα could provide both the substrate and enzyme storage for FAO during glucose deficiency. Up‐regulation of ACCα is also significantly correlated with poorer overall survival and disease recurrence postsurgery. Multivariate Cox's regression analysis identified ACCα as an effective predictor of poor prognosis. Conclusion: These results present novel mechanistic insight into a pivotal role of ACCα in maintaining HCC survival under metabolic stress. It could be exploited as a novel diagnostic marker and therapeutic target. (Hepatology 2016;63:1272–1286)
Histidine‐rich glycoprotein promotes macrophage activation and inflammation in chronic liver disease
Authors: Bartneck Matthias , Fech Viktor , Ehling Josef , Govaere Olivier , Warzecha Klaudia Theresa , Hittatiya Kanishka , Vucur Mihael , Gautheron Jérémie , Luedde Tom , Trautwein Christian , Lammers Twan , Roskams Tania , Jahnen‐Dechent Willi , Tacke Frank
Published: December 2015

Pathogen‐ and injury‐related danger signals as well as cytokines released by immune cells influence the functional differentiation of macrophages in chronic inflammation. Recently, the liver‐derived plasma protein, histidine‐rich glycoprotein (HRG), was demonstrated, in mouse tumor models, to mediate the transition of alternatively activated (M2) to proinflammatory (M1) macrophages, which limit tumor growth and metastasis. We hypothesized that liver‐derived HRG is a critical endogenous modulator of hepatic macrophage functionality and investigated its implications for liver inflammation and fibrosis by comparing C57BL/6N wild‐type (WT) and Hrg−/−
mice. In homeostatic conditions, hepatic macrophages were overall reduced and preferentially polarized toward the anti‐inflammatory M2 subtype in Hrg−/−
mice. Upon chronic liver damage induced by CCl4 or methionine‐choline‐deficient (MCD) diet, liver injury and fibrosis were attenuated in Hrg−/−
, compared to WT, mice. Macrophage populations were reduced and skewed toward M2 polarization in injured livers of Hrg−/−
mice. Moreover, HRG‐deficient mice showed significantly enhanced hepatic vascularization by micro‐computed tomography and histology, corroborating proangiogenic activities of M2‐polarized liver macrophages. Purified HRG protein induced, but HRG‐deficient serum prevented, M1 macrophage differentiation in vitro. Accordingly, Hrg−/−
mice transplanted with Hrg+/+
bone marrow, but not Hrg−/−
‐transplanted Hrg+/+
mice, remained protected from experimental steatohepatitis. Consistent with these findings, patients with chronic hepatitis C and nonalcoholic steatohepatitis significantly up‐regulated hepatocytic HRG expression, which was associated with M1 polarization of adjacent macrophages. Conclusions: Liver‐derived HRG, similar to alarmins, appears to be an endogenous molecular factor promoting polarization of hepatic macrophages toward the M1 phenotype, thereby promoting chronic liver injury and fibrosis progression, but limiting angiogenesis. Therefore, controlling tissue levels of HRG or PGF might be a promising strategy in chronic inflammatory liver diseases. (Hepatology 2016;63:1310‐1324)
A functional variant in TP63 at 3q28 associated with bladder cancer risk by creating an miR‐140‐5p binding site
Authors: Wang Meilin , Du Mulong , Ma Lan , Chu Haiyan , Lv Qiang , Ye Dingwei , Guo Jianming , Gu Chengyuan , Xia Guowei , Zhu Yao , Ding Qiang , Yuan Lin , Fu Guangbo , Tong Na , Qin Chao , Yin Changjun , Xu Jianfeng , Zhang Zhengdong
Published: December 2015

The first genome‐wide association study (GWAS) for bladder cancer has identified a susceptibility locus at 3q28 in the European ancestry. However, the causal variant at 3q28 remains unknown. We conducted a three‐stage fine mapping study to identify potential causal variants in the region. A total of 41 single nucleotide polymorphisms (SNPs) across 120 kb at 3q28 were tested for association with bladder cancer risk among 3,094 bladder cancer cases and 3,738 controls. Resequencing and functional assays were further evaluated. The SNP rs35592567 in the 3′‐UTR of TP63 was consistently associated with bladder cancer risk in all three stages. In the combined analysis, the T allele of rs35592567 was significantly associated with a decreased risk for bladder cancer (OR = 0.82, 95% CI = 0.75–0.90, P = 9.797 × 10−6 in the additive model). Biochemical assays revealed that the T allele reduced the post‐transcriptional levels of TP63 mediated by interfering binding efficiency of miR‐140‐5p. In addition, overexpression of miR‐140‐5p inhibited bladder cancer cell proliferation and attenuated cell migration, invasion and G1 cell‐cycle arrest. Together, these results suggest that rs35592567 in TP63 may be a novel causal variant contributing to the susceptibility to bladder cancer, which provides additional insight into the pathogenesis of bladder carcinogenesis.