bluuebunny/crossref_metadata_2025 huggingface dataset:
The role of aerosol absorption in driving clear‐sky solar dimming over East Asia
Authors: Persad Geeta G. , Ming Yi , Ramaswamy V.
Published: August 2014

Surface‐based observations indicate a significant decreasing trend in clear‐sky downward surface solar radiation (SSR) over East Asia since the 1960s. This “dimming” is thought to be driven by the region's long‐term increase in aerosol emissions, but little work has been done to quantify the underlying physical mechanisms or the contribution from aerosol absorption within the atmospheric column. Given the distinct climate impacts that absorption‐driven dimming may produce, this constitutes an important, but thus far rather neglected, line of inquiry. We examine experiments conducted in the Geophysical Fluid Dynamics Laboratory's atmospheric general circulation models, AM2.1 and AM3, in order to analyze the model‐simulated East Asian clear‐sky SSR trends. We also use the models' stand‐alone radiation module to examine the contribution from various aerosol characteristics in the two models (such as burden, mixing state, hygroscopicity, and seasonal distribution) to the trends. Both models produce trends in clear‐sky SSR that are comparable to that observed but via disparate mechanisms. Despite their different aerosol characteristics, the models produce nearly identical increases in aerosol absorption since the 1960s, constituting as much as half of the modeled clear‐sky dimming. This is due to a compensation between the differences in aerosol column burden and mixing state assumed in the two models, i.e., plausible clear‐sky SSR simulations can be achieved via drastically different aerosol parameterizations. Our novel results indicate that trends in aerosol absorption drive a large portion of East Asian clear‐sky solar dimming in the models presented here and for the time periods analyzed and that mechanistic analysis of the factors involved in aerosol absorption is an important diagnostic in evaluating modeled clear‐sky solar dimming trends.
WWBs, ENSO predictability, the spring barrier and extreme events
Authors: Lopez Hosmay , Kirtman Ben P.
Published: August 2014

This study examines how semi‐stochastic Westerly Wind Bursts (WWBs) affect El Niño Southern Oscillation (ENSO) predictability. An ensemble ENSO prediction experiment is presented in which the Community Climate System Model version 3 (CCSM3) and CCSM3 with a state‐dependent WWB parameterization are used as both “truth” and as predictor systems. Inclusion of WWBs has little effect on ENSO predictability if the “truth” lacks WWBs. If the “truth” includes WWBs, the limit of ENSO predictability is larger for a forecast system that captures the correct statistics of WWBs. Predictability drops considerably if a forecast system that lacks WWB events is used to predict a “truth” that includes WWBs. At longer lead times, predictability is more dependent on the dynamical properties of the truth; that is, the importance of capturing the WWB statistics becomes less important and the statistics (e.g., signal‐to‐noise ratio) of the truth determine the limit of predictability. At short leads, ENSO predictability depends on the prediction system and the “truth.” ENSO prediction skill is model and phase dependent. Predictability of extreme warm events remains a challenge as the number of ensemble members required to capture these events is on the order of 100 members. Finally, we examine real ENSO predictions with and without the WWB parameterization. It is found that including WWBs in the prediction system significantly increases ENSO prediction skill compared with a prediction system that lacks WWBs. Also, it is found that the so‐called forecast spring prediction barrier is, at least partially, caused by the lack of WWB representation in the forecast system.
West African monsoon demise: Climatology, interannual variations, and relationship to seasonal rainfall
Authors: Zhang Gang , Cook Kerry H.
Published: August 2014

The climatology and interannual variations of the West African monsoon demise are investigated using the Tropical Rainfall Measuring Mission and the Global Precipitation Climatology Project precipitation data sets along with the ERA‐Interim reanalysis. During monsoon demise, the rainfall maximum progresses southward from the Sahel to the Gulf of Guinea. The West African monsoon demise is smooth, with no evidence of a meridional jump of the rainfall maximum as occurs during monsoon onset. The climatological monsoon demise date, defined by using a 2 mm d−1 rainfall threshold for the Sahel, is 20 October. The demise date varies up to 25 days during the period 1979–2012, between 5 and 30 October. An early (late) demise is associated with an anomalously strong (weak) North Atlantic subtropical high, which extends over the Mediterranean and the Sahara throughout the demise period. The monsoon season total rainfall is found to be significantly correlated with the demise date. In a composite of early (late) demise cases, northerly (southerly) moisture flux anomalies, which enhance (reduce) moisture divergence, are associated with an anomalously strong (weak) North Atlantic subtropical high. In addition, the early (late) demise of the West African monsoon is accompanied by cold (warm) sea surface temperature anomalies in the subtropical North Atlantic.
Aquarius: Status and recent results
Authors: Le Vine D. M. , Dinnat E. P. , Lagerloef G. S. E. , de Matthaeis P. , Abraham S. , Utku C. , Kao H.
Published: August 2014

Aquarius is a combination active/passive instrument at L band designed to map sea surface salinity globally from space. The radiometer (passive) is the primary instrument for retrieving salinity, and the scatterometer (active) provides information to correct for a major source of error, sea surface roughness (waves). In addition, the radiometer includes a number of special features designed to meet the goal for this challenging measurement, including measurement of the third Stokes parameter to help with the correction for Faraday rotation and rapid sampling to help with the mitigation of radio frequency interference. Aquarius was launched on 10 June 2011 aboard the Aquarius/SAC‐D observatory and has been working well. The salinity retrieval continues to improve, and the special features suggest the potential for new applications of remote sensing from space at L band.
High Throughput, Polymeric Aqueous Two‐Phase Printing of Tumor Spheroids
Authors: Atefi Ehsan , Lemmo Stephanie , Fyffe Darcy , Luker Gary D. , Tavana Hossein
Published: August 2014

This paper presents a new 3D culture microtechnology for high throughput production of tumor spheroids and validates its utility for screening anti‐cancer drugs. Two immiscible polymeric aqueous solutions are used and a submicroliter drop of the “patterning” phase containing cells is microprinted into a bath of the “immersion” phase. Selecting proper formulations of biphasic systems using a panel of biocompatible polymers results in the formation of a round drop that confines cells to facilitate spontaneous formation of a spheroid without any external stimuli. Adapting this approach to robotic tools enables straightforward generation and maintenance of spheroids of well‐defined size in standard microwell plates and biochemical analysis of spheroids in situ, which is not possible with existing techniques for spheroid culture. To enable high throughput screening, a phase diagram is established to identify minimum cell densities within specific volumes of the patterning drop to result in a single spheroid. Spheroids show normal growth over long‐term incubation and dose‐dependent decrease in cellular viability when treated with drug compounds, but present significant resistance compared to monolayer cultures. The unprecedented ease of implementing this microtechnology and its robust performance will benefit high throughput studies of drug screening against cancer cells with physiologically relevant 3D tumor models.
Towards High‐Performance Nonaqueous Redox Flow Electrolyte Via Ionic Modification of Active Species
Authors: Wei Xiaoliang , Cosimbescu Lelia , Xu Wu , Hu Jian Zhi , Vijayakumar M. , Feng Ju , Hu Mary Y. , Deng Xuchu , Xiao Jie , Liu Jun , Sprenkle Vincent , Wang Wei
Published: August 2014

Nonaqueous redox flow batteries are emerging flow‐based energy storage technologies that have the potential for higher energy densities than their aqueous counterparts because of their wider voltage windows. However, their performance has lagged far behind their inherent capability due to one major limitation of low solubility of the redox species. Here, a molecular structure engineering strategy towards high performance nonaqueous electrolyte is reported with significantly increased solubility. Its performance outweighs that of the state‐of‐the‐art nonaqueous redox flow batteries. In particular, an ionic‐derivatized ferrocene compound is designed and synthesized that has more than 20 times increased solubility in the supporting electrolyte. The solvation chemistry of the modified ferrocene compound. Electrochemical cycling testing in a hybrid lithium–organic redox flow battery using the as‐synthesized ionic‐derivatized ferrocene as the catholyte active material demonstrates that the incorporation of the ionic‐charged pendant significantly improves the system energy density. When coupled with a lithium‐graphite hybrid anode, the hybrid flow battery exhibits a cell voltage of 3.49 V, energy density about 50 Wh L−1, and energy efficiency over 75%. These results reveal a generic design route towards high performance nonaqueous electrolyte by rational functionalization of the organic redox species with selective ligand.
Central 22q11.2 deletions
Authors: Rump Patrick , de Leeuw Nicole , van Essen Anthonie J. , Verschuuren‐Bemelmans Corien C. , Veenstra‐Knol Hermine E. , Swinkels Mariëlle E.M. , Oostdijk Wilma , Ruivenkamp Claudia , Reardon Willie , de Munnik Sonja , Ruiter Mariken , Frumkin Ayala , Lev Dorit , Evers Christina , Sikkema‐Raddatz Birgit , Dijkhuizen Trijnie , van Ravenswaaij‐Arts Conny M.
Published: August 2014

22q11.2 deletion syndrome is one of the most common microdeletion syndromes. Most patients have a deletion resulting from a recombination of low copy repeat blocks LCR22‐A and LCR22‐D. Loss of the TBX1 gene is considered the most important cause of the phenotype. A limited number of patients with smaller, overlapping deletions distal to the TBX1 locus have been described in the literature. In these patients, the CRKL gene is deleted. Haploinsufficiency of this gene has also been implicated in the pathogenesis of 22q11.2 deletion syndrome. To distinguish these deletions (comprising the LCR22‐B to LCR22‐D region) from the more distal 22q11.2 deletions (located beyond LCR22‐D), we propose the term “central 22q11.2 deletions”. In the present study we report on 27 new patients with such a deletion. Together with information on previously published cases, we review the clinical findings of 52 patients. The prevalence of congenital heart anomalies and the frequency of de novo deletions in patients with a central deletion are substantially lower than in patients with a common or distal 22q11.2 deletion. Renal and urinary tract malformations, developmental delays, cognitive impairments and behavioral problems seem to be equally frequent as in patients with a common deletion. None of the patients had a cleft palate. Patients with a deletion that also encompassed the MAPK1 gene, located just distal to LCR22‐D, have a different and more severe phenotype, characterized by a higher prevalence of congenital heart anomalies, growth restriction and microcephaly. Our results further elucidate genotype‐phenotype correlations in 22q11.2 deletion syndrome spectrum. © 2014 Wiley Periodicals, Inc.
Segmental uniparental isodisomy of chromosome 6 causing transient diabetes mellitus and merosin‐deficient congenital muscular dystrophy
Authors: Andrade Raissa Coelho , Nevado Julián , de Faria Domingues de Lima Maria Angélica , Saad Tânia , Moraes Lucia , Chimelli Leila , Lapunzina Pablo , Vargas Fernando Regla
Published: August 2014

Segmental uniparental isodisomy (iUPD) is a rare genetic event that may cause aberrant expression of imprinted genes, and reduction to homozygosity of a recessive mutation. Transient neonatal diabetes mellitus (TNDM) is typically caused by imprinting aberrations in chromosome 6q24 TNDM differentially‐methylated region (DMR). Approximately, 15.12 Mb upstream in 6q22‐q23 is located LAMA2, the gene responsible of merosin‐deficient congenital muscular dystrophy type 1A (MDC1A). We investigated a patient diagnosed both with TNDM and MDC1A, born from a twin dichorionic discordant pregnancy. Parents are first‐degree cousins. Methylation sensitive‐PCR of the imprinted 6q24 TNDM CpG island showed only the non‐methylated (paternal) allele. Microsatellite markers and SNP array profiling disclosed normal biparental inheritance at 6p and a segmental paternal iUPD, between 6q22.33 and 6q27. Sequencing of LAMA2 exons showed a homozygous frameshift mutation, c.7490_7493dupAAGA, which predicts p.Asp2498GlufsX4, in exon 54. Her father, but not her mother, was a carrier of the mutation. While segmental paternal iUPD6 causing TNDM was reported twice, there are no previous reports of MDC1A caused by this event. This is a child with two genetic disorders, yet neither is caused by the parental consanguinity, which reinforces the importance of considering different etiological mechanisms in the genetic clinic. © 2014 Wiley Periodicals, Inc.
Oxygen Reduction Reaction in a Droplet on Graphite: Direct Evidence that the Edge Is More Active than the Basal Plane
Authors: Shen Anli , Zou Yuqin , Wang Qiang , Dryfe Robert A. W. , Huang Xiaobing , Dou Shuo , Dai Liming , Wang Shuangyin
Published: August 2014

Carbon‐based metal‐free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium have been extensively investigated with the aim of replacing the commercially available, but precious platinum‐based catalysts. For the proper design of carbon‐based metal‐free electrocatalysts for the ORR, it would be interesting to identify the active sites of the electrocatalyst. The ORR was now studied with an air‐saturated electrolyte solution droplet (diameter ca. 15 μm), which was deposited at a specified position either on the edge or on the basal plane of highly oriented pyrolytic graphite. Electrochemical measurements suggest that the edge carbon atoms are more active than the basal‐plane ones for the ORR. This provides a direct way to identify the active sites of carbon materials for the ORR. Ball‐milled graphite and carbon nanotubes with more exposed edges were also prepared and showed significantly enhanced ORR activity. DFT calculations elucidated the mechanism by which the charged edge carbon atoms result in the higher ORR activity.
Rhodium(III)‐Catalyzed CC and CO Coupling of Quinoline N‐Oxides with Alkynes: Combination of CH Activation with O‐Atom Transfer
Authors: Zhang Xueyun , Qi Zisong , Li Xingwei
Published: August 2014

[Cp*RhIII]‐catalyzed CH activation of arenes assisted by an oxidizing NO or NN directing group has allowed the construction of a number of hetercycles. In contrast, a polar NO bond is well‐known to undergo O‐atom transfer (OAT) to alkynes. Despite the liability of NO bonds in both CH activation and OAT, these two important areas evolved separately. In this report, [Cp*RhIII] catalysts integrate both areas in an efficient redox‐neutral coupling of quinoline N‐oxides with alkynes to afford α‐(8‐quinolyl)acetophenones. In this process the NO bond acts as both a directing group for CH activation and as an O‐atom donor.
Regulation of Structure and Function of Sarcomeric Actin Filaments in Striated Muscle of the Nematode Caenorhabditis elegans
Authors: Ono Shoichiro
Published: August 2014

The nematode Caenorhabditis elegans has been used as a valuable system to study structure and function of striated muscle. The body wall muscle of C. elegans is obliquely striated muscle with highly organized sarcomeric assembly of actin, myosin, and other accessory proteins. Genetic and molecular biological studies in C. elegans have identified a number of genes encoding structural and regulatory components for the muscle contractile apparatuses, and many of them have counterparts in mammalian cardiac and skeletal muscles or striated muscles in other invertebrates. Applicability of genetics, cell biology, and biochemistry has made C. elegans an excellent system to study mechanisms of muscle contractility and assembly and maintenance of myofibrils. This review focuses on the regulatory mechanisms of structure and function of actin filaments in the C. elegans body wall muscle. Sarcomeric actin filaments in C. elegans muscle are associated with the troponin–tropomyosin system that regulates the actin–myosin interaction. Proteins that bind to the side and ends of actin filaments support ordered assembly of thin filaments. Furthermore, regulators of actin dynamics play important roles in initial assembly, growth, and maintenance of sarcomeres. The knowledge acquired in C. elegans can serve as bases to understand the basic mechanisms of muscle structure and function. Anat Rec, 297:1548–1559, 2014. © 2014 Wiley Periodicals, Inc.
Probing Muscle Ankyrin‐Repeat Protein (MARP) Structure and Function
Authors: Lun Alexander Shiang , Chen Ju , Lange Stephan
Published: August 2014

Muscle ankyrin‐repeat proteins (MARPs) have been shown to serve diverse functions within cardiac and skeletal muscle cells. Apart from their interactions with sarcomeric proteins like titin or myopalladin that locate them along myofilaments, MARPs are able to shuttle to the nucleus where they act as modulators for a variety of transcription factors. The deregulation of MARPs in many cardiac and skeletal myopathies contributes to their use as biomarkers for these diseases. Many of their functions are attributed to their domain composition. MARPs consist of an N‐terminal coiled‐coil domain responsible for their dimerization. The C‐terminus contains a series of ankyrin repeats, whose best‐characterized function is to bind to the N2A region of the giant sarcomeric protein titin. Here we investigate the nature of their dimerization and their interaction with titin more closely. We demonstrate that the coiled‐coil domain in all MARPs enables their homo‐ and hetero‐dimerization in antiparallel fashion. Protein complementation experiments indicate further antiparallel binding of the ankyrin repeats to titin's N2A region. Binding of MARP to titin also affects its PKA mediated phosphorylation. We demonstrate further that MARPs themselves are phosphorylated by PKA and PKC, potentially altering their structure or function. These studies elucidate structural relationships within the stretch‐responsive MARP/titin complex in cross‐striated muscle cells, and may relate to disease relevant posttranslational modifications of MARPs and titin that alter muscle compliance. Anat Rec, 297:1615–1629, 2014. © 2014 Wiley Periodicals, Inc.
Understanding Cardiac Sarcomere Assembly With Zebrafish Genetics
Authors: Yang Jingchun , Shih Yu‐huan , Xu Xiaolei
Published: August 2014

Mutations in sarcomere genes have been found in many inheritable human diseases, including hypertrophic cardiomyopathy. Elucidating the molecular mechanisms of sarcomere assembly shall facilitate understanding of the pathogenesis of sarcomere‐based cardiac disease. Recently, biochemical and genomic studies have identified many new genes encoding proteins that localize to the sarcomere. However, their precise functions in sarcomere assembly and sarcomere‐based cardiac disease are unknown. Here, we review zebrafish as an emerging vertebrate model for these studies. We summarize the techniques offered by this animal model to manipulate genes of interest, annotate gene expression, and describe the resulting phenotypes. We survey the sarcomere genes that have been investigated in zebrafish and discuss the potential of applying this in vivo model for larger‐scale genetic studies. Anat Rec, 297:1681–1693, 2014. © 2014 Wiley Periodicals, Inc.
Tenascin‐C in Development and Disease of Blood Vessels
Authors: Imanaka‐Yoshida Kyoko , Yoshida Toshimichi , Miyagawa‐Tomita Sachiko
Published: August 2014

Tenascin‐C (TNC) is an extracellular glycoprotein categorized as a matricellular protein. It is highly expressed during embryonic development, wound healing, inflammation, and cancer invasion, and has a wide range of effects on cell response in tissue morphogenesis and remodeling including the cardiovascular system. In the heart, TNC is sparsely detected in normal adults but transiently expressed at restricted sites during embryonic development and in response to injury, playing an important role in myocardial remodeling. Although TNC in the vascular system appears more complex than in the heart, the expression of TNC in normal adult blood vessels is generally low. During embryonic development, vascular smooth muscle cells highly express TNC on maturation of the vascular wall, which is controlled in a way that depends on the embryonic site of cell origin. Strong expression of TNC is also linked with several pathological conditions such as cerebral vasospasm, intimal hyperplasia, pulmonary artery hypertension, and aortic aneurysm/ dissection. TNC synthesized by smooth muscle cells in response to developmental and environmental cues regulates cell responses such as proliferation, migration, differentiation, and survival in an autocrine/paracrine fashion and in a context‐dependent manner. Thus, TNC can be a key molecule in controlling cellular activity in adaptation during normal vascular development as well as tissue remodeling in pathological conditions. Anat Rec, 297:1747–1757, 2014. © 2014 Wiley Periodicals, Inc.
Mechanochromic Luminescence of Fluorenyl‐Substituted Ethylenes
Authors: Lv Yun , Liu Yang , Guo Dan , Ye Xin , Liu Guangfeng , Tao Xutang
Published: August 2014

It has been reported several times that some organic luminogens with aggregation‐induced emission (AIE) characteristics exhibit the abnormal phenomenon of crystallization‐induced blueshift fluorescence, which makes them suitable for utilization as luminescence color‐switching materials. Because of the attractive application potential and the numerous underlying structure–property relationships in such materials, we investigated a series of fluorenyl‐containing tetrasubstituted ethylenes for their novel optical properties and structural features. The dyes show morphology‐dependent luminescence. Their emission color can be switched between green and blue by means of mechanical grinding and solvent fuming. The transformation between crystalline and amorphous accounts for the luminescence changing. Through single‐crystal and X‐ray diffraction (XRD) analysis, the twisted molecular geometries and loose packing motifs in the crystalline samples are believed to be the intrinsic origin of the external‐stimuli‐induced structural transformation.
Proteasome Inhibitors with Photocontrolled Activity
Authors: Hansen Mickel J. , Velema Willem A. , de Bruin Gerjan , Overkleeft Herman S. , Szymanski Wiktor , Feringa Ben L.
Published: August 2014

Proteasome inhibitors are widely used in cancer treatment as chemotherapeutic agents. However, their employment often results in severe side effects, due to their non‐specific cytotoxicity towards healthy tissue. This problem might be overcome by using a photopharmacological approach, that is, by attaining external, dynamic, spatiotemporal photocontrol over the activity of a cytotoxic agent, achieved by the introduction of a photoswitchable moiety into its molecular structure. Here we describe the design, synthesis, and activity of photoswitchable proteasome inhibitors. Substantial differences in proteasome inhibitory activity in cell extracts were observed before and after irradiation with light. The presented results show potential for the development of chemotherapeutic agents that can be switched on and off with light, constituting a new strategy for spatiotemporally modulating proteasomal activity.
Intriguing Manipulation of Metal‐Enhanced Fluorescence for the Detection of CuII and Cysteine
Authors: Ganguly Mainak , Pal Jaya , Mondal Chanchal , Pal Anjali , Pal Tarasankar
Published: August 2014

Commercially available salicylaldehyde, in alkaline medium, exhibits strong fluorescence after one hour of UV exposure in the presence of AgI. The phenolic group of salicylaldehyde is converted into the quinone form under alkaline conditions in the presence of AgNO3, resulting in aggregated Ag(0), which causes approximately 250 times fluorescence enhancement of the in situ produced quinone. Such high silver‐enhanced‐fluorescence (SEF) is selectively quenched by cysteine, arginine, histidine, methionine, and tryptophan. In contrast to the other amino acids, ageing brings selectivity of the cysteine‐induced quenching effect. Interestingly, CuII is found to be the only metal ion that exclusively regenerates the lost fluorescence. Thus, quenching and recovery of fluorescence (Turn Off/On) can be used for the selective and sensitive detection of cysteine as well as CuII ions in one pot. Alteration of the electric field density around the fluorophore (lightening rod effect) and scattering/absorption cross‐section have been proposed to account for the Off/On fluorescence.
Preparation of Dithienylphospholes by 1,1‐Carboboration
Authors: Möbus Juri , Galstyan Anzhela , Feldmann Andreas , Daniliuc Constantin G. , Fröhlich Roland , Strassert Cristian A. , Kehr Gerald , Erker Gerhard
Published: August 2014

In this study the scope of the 1,1‐carboboration reaction was extended to the preparation of mixed heterole‐based conjugated π‐systems. Two arylbis(alkynyl)phosphane starting materials 2 were synthesized bearing two thiophene isomers at the alkyne units and the bulky tipp‐substituent (tipp=2,4,6‐triisopropylphenyl) at the phosphorous atom. The bis(thienylethynyl)phosphanes 2 were converted into the corresponding 2,5‐thienyl‐substituted 3‐borylphospholes 4 in a double 1,1‐carboboration reaction sequence employing the strongly electrophilic B(C6F5)3 reagent under mild reaction conditions. Subsequent Suzuki–Miyaura type cross‐coupling yielded the corresponding 3‐phenylphospholes 7 in a one‐pot procedure from phosphanes 2 in high yields. Phospholes 7 were converted into the respective phosphole oxides 8. A photophysical characterization of derivatives 7 and 8 was carried out. The results presented here demonstrate the suitability of the 1,1‐carboboration reaction for the preparation of phosphole‐/thiophene‐based, light‐emitting systems.
Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds
Authors: Berger Olivier , Montchamp Jean‐Luc
Published: August 2014

The intermolecular radical functionalization of arenes with aryl and alkyl H‐phosphinate esters, as well as diphenylphosphine oxide and H‐phosphonate diesters, is described. The novel catalytic MnII/excess MnIV system is a convenient and inexpensive solution to directly convert Csp2H into CP bonds. The reaction can be employed to functionalize P‐stereogenic H‐phosphinates since it is stereospecific. With monosubstituted aromatics, the selectivity for para‐substitution increases in the order (RO)2P(O)H<R1P(O)(OR)H<Ph2P(O)H, a trend that may be explained by steric effects.
Comparison of different kinetic models for NOX storage on a lean NOX trap
Authors: Watling Timothy C. , Bolton Paul D. , Swallow Daniel
Published: August 2014

The kinetics of NOX storage on a lean NOX trap (LNT) were studied using NOX breakthrough curves measured with a laboratory reactor. A much wider range of temperatures (125–450°C) was used than in most studies to facilitate discrimination between potential models. The breakthrough curves were run until the LNT was saturated to (i) enable NO oxidation to NO2 to be studied in the absence of NOX storage, (ii) to enable the effective NOX capacity as a function of temperature to be determined, and (iii) to provide a more demanding test for potential models.

Breakthrough curves for 125 and 450°C were very similar, while curves at intermediate temperatures initially followed that for 125°C before breaking away from this curve at a point that became earlier with increasing temperature. Thus, the breakthrough curves have a temperature independent initial portion, followed by a temperature dependant portion. This was explained by there being two types of site: fast sites and slow sites. Fast sites are responsible for the initial part of the curve; both the rate of storage on these sites and the available capacity are independent of temperature. The rate of storage on slow sites, on the other hand, is temperature dependant, as is the available storage capacity. Slow sites are more abundant than fast sites. The performance of three NOX storage models for these sites was compared.

The amount of NOX stored as a function of temperature was bell‐shaped. The models naturally predicted that storage was limited by kinetics at lower temperatures and nitrate stability at higher temperatures.
Detailed kinetic modelling of automotive exhaust NOx reduction over rhodium catalyst
Authors: Su Qingyun , Xie Liang , Li Yanbin , Qiao Xinqi
Published: August 2014

The reduction of NO with CO and H2 as the reductants was investigated on the rhodium‐based catalyst over a temperature range of 150–400 °C. Micro‐kinetic modelling method was utilized to compare the activities of CO and H2. Quasi‐elementary mechanisms of NO‐CO and NO‐H2 consisting of 11 and 25 steps, respectively, were proposed. The reaction steps and kinetic parameters were derived from literature and some parameters were optimized to fit the experimental data. Furthermore, to verify the validity range of the developed mechanism, the reaction intermediate N2O reduction by CO and by H2 over Rh were investigated. Over a wide range of reaction conditions, the detailed mechanism predicted experimental results quite well for both NO and N2O conversions with CO and/or H2 as reductant. The phenomenon that NO‐CO and NO‐H2 reactions commenced at similar temperature can be interpreted by the hindered H2 dissociative adsorption steps by extensive NO adsorption. Reaction profiles such as fractional coverages, reaction pathway and sensitivity analysis provided valuable insight into the reaction systems. N2O plays a crucial role in N2 formation for both NO‐CO and NO‐H2 reaction systems. The routes involving N2O formation and decomposition were identified as the dominant pathway in N2 formation at low temperatures.
Enhanced palm oil mill effluent treatment and biomethane production by co‐digestion of oil palm empty fruit bunches with Chlorella Sp
Authors: Ahmad Ashfaq , Shah Syed Muhammad Usman , Othman Mohd Fariduddin , Abdullah Mohd Azmuddin
Published: August 2014

Palm oil mill effluent (POME) has high chemical oxygen demand (COD) and biological oxygen demand (BOD) and minerals such as nitrogen and phosphorous which can cause severe pollution to the environment and water resources. In this study, aerobic and anaerobic co‐digestion of oil palm empty fruit bunches (OPEFB) with Chlorella sp. was developed for POME treatment and biomethane production. Higher removal efficiency (56–98 %) of COD, BOD, TOC, and TN after 3 and 7 days' treatment were achieved with microalgae than without microalgae. Using response surface methodology, the highest specific biogas production rate (0.128–0.129 m3/kg COD/day) and biomethane yield (5256.8–5295.8 mL/L POME/day) were achieved with Chlorella sp. at 2 mL/mL POME, and OPEFB at 0.12 g/mL POME. Without both microalgae and OPEFB, the methane yield was 1.4‐fold lower. The values for optimum conditions were predicted well by the model within 5 % error.
The theory of parallel channels manifolds (Ladder networks) revisited part 1: Discrete mesoscopic modelling
Authors: Midoux Noel , Tondeur Daniel
Published: August 2014

This article proposes a theoretical overview of the distribution of fluid flow through manifolds composed of parallel channels connected through T‐junctions to a distributor and to a collector channel, thus composing a ladder‐like network. Such networks are used in solar heaters, fuel cells, heat exchanger plates, and other engineering devices, one issue being to achieve a nearly uniform distribution. This first part focuses on the discrete mesoscopic momentum and energy balances governing the T‐junctions, with particular attention to the empirical, flow‐rate and geometry dependent, pressure change coefficients. By “mesoscopic”, it is meant that the control volume for the balance equations includes the junction zone and that the local flow‐field in that zone is not described. The existing results and correlations for these coefficients are reviewed, compared, and synthesized.

In keeping with the discrete character of the channel network, the overall network relations are compacted as a single non‐linear finite‐difference equation relating the flow‐rates in the different segments of the distributor. This formulation is suitable for convenient numerical resolution even when all the coefficients are allowed to vary with local conditions. The conditions for simplifications, such as assuming constancy of certain coefficients, are carefully investigated. A number of approximate analytical, semi‐explicit or explicit solutions are constructed. In particular, an original view of the structure of these solutions is proposed, relying on an invariance property which is demonstrated, and on the analogy with the classical McCabe‐Thiele construction in chemical engineering. These approximations are compared to exact numerical solutions.
The Relationship Between Revascularization Extent and the Long‐term Prognosis of Patients With Stable Angina Pectoris and Three‐Vessel Disease Treated by Percutaneous Coronary Intervention in the Era of Drug‐Eluting Stents
Authors: Li Quan , Yu Xianpeng , He Jiqiang , Gao Yuechun , Zhang Xiaoling , Wu Changyan , Luo Yawei , Zhang Yuchen , Ren Xuejun , Lv Shuzheng , Chen Fang
Published: August 2014

Background

The effects of revascularization extent (RE) on the long‐term prognosis of patients with stable angina pectoris and 3‐vessel disease who underwent percutaneous coronary intervention were unknown.

Hypothesis

The study was aimed at evaluating whether there was an effect of RE on patients presenting with stable angina pectoris and 3‐vessel disease.

Methods

RE, which was calculated by baseline SYNTAX (Synergy Between Percutaneous Coronary Intervention With Taxus and Cardiac Surgery) score minus residue SYNTAX score divided by baseline SYNTAX score, was initially used in our study. Five hundred fifty‐eight patients presenting with stable angina pectoris and 3‐vessel disease were assigned to and compared among tertiles according to RE and clinical outcomes. The primary end point was the major adverse cardiovascular event (MACE), a composite of cardiac death, nonfatal myocardial infarction (MI), and any repeat revascularization.

Results

The median follow‐up period was 56.9 months (interquartile range, 52.1–63.6). The incidence of MACE increased significantly as RE increased (13.3%, 31.4%, and 44.1%, log‐rank P < 0.001). The same tendency was observed in occurrences of target‐vessel failure (TVF) (a composite of cardiac death, MI, or target‐vessel revascularization) (8.8%, 20.3%, and 28.4%, log‐rank P < 0.001), repeat revascularization (11.8%, 26.2%, and 35.6%, log‐rank P < 0.001), and MI (1.1%, 2.9%, and 12.6%, log‐rank P < 0.001). Multivariate analysis confirmed the tendencies mentioned above.

Conclusions

For patients presenting with stable angina pectoris and 3‐vessel disease, the increasing extent of revascularization resulted in a less favorable prognosis.
Global Existence for Capillary Water Waves
Authors: Germain Pierre , Masmoudi Nader , Shatah Jalal
Published: August 2014

Consider the capillary water waves equations, set in the whole space with infinite depth, and consider small data (i.e., sufficiently close to zero velocity, and constant height of the water). We prove global existence and scattering. The proof combines in a novel way the energy method with a cascade of energy estimates, the space‐time resonance method and commuting vector fields. © 2015 Wiley Periodicals, Inc.
Transport Phenomena in Nanoporous Materials
Authors: Kärger Jörg
Published: August 2014

Diffusion, that is, the irregular movement of atoms and molecules, is a universal phenomenon of mass transfer occurring in all states of matter. It is of equal importance for fundamental research and technological applications. The present review deals with the challenges of the reliable observation of these phenomena in nanoporous materials. Starting with a survey of the different variants of diffusion measurement, it highlights the potentials of “microscopic” techniques, notably the pulsed field gradient (PFG) technique of NMR and the techniques of microimaging by interference microscopy (IFM) and IR microscopy (IRM). Considering ensembles of guest molecules, these techniques are able to directly record mass transfer phenomena over distances of typically micrometers. Their concerted application has given rise to the clarification of long‐standing discrepancies, notably between microscopic equilibrium and macroscopic non‐equilibrium measurements, and to a wealth of new information about molecular transport under confinement, hitherto often inaccessible and sometimes even unimaginable.
Methanol Steam Reforming Promoted by Molten Salt‐Modified Platinum on Alumina Catalysts
Authors: Kusche Matthias , Agel Friederike , Ní Bhriain Nollaig , Kaftan Andre , Laurin Mathias , Libuda Jörg , Wasserscheid Peter
Published: August 2014

We herein describe a straight forward procedure to increase the performance of platinum‐on‐alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature‐programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum‐on‐alumina catalyst at KOH loadings around 7.5 mass %.
Negative intergroup contact is more influential, but positive intergroup contact is more common: Assessing contact prominence and contact prevalence in five Central European countries
Authors: Graf Sylvie , Paolini Stefania , Rubin Mark
Published: August 2014

The present research tested the idea that the ecological impact of intergroup contact on outgroup attitudes can be fully understood only when relative frequency and relative influence of positive and negative contact are considered simultaneously. Participants from five European countries (Austria, the Czech Republic, Germany, Poland and Slovakia; N = 1276) freely described their contact experiences with people of neighboring nationalities and then reported on their outgroup attitudes. Contact descriptions were coded for positive versus negative valence and for person versus situation framing. Consistently across the five participant groups, positive intergroup contact was reported to occur three times more frequently than negative intergroup contact; however, positive contact was found to be only weakly related to outgroup attitudes. On the contrary, the less frequent negative (vs. positive) contact was comparatively more influential in shaping outgroup attitudes, especially when negativity was reported around the contact person, rather than the contact situation. This research's findings reconcile contrasting lines of past research on intergroup contact and suggest that the greater prevalence of positive contact may compensate for the greater prominence of negative contact, thus leading to modest net improvements in outgroup attitudes after intergroup contact. Copyright © 2014 John Wiley & Sons, Ltd.
RhoA/ROCK pathway mediates p38 MAPK activation and morphological changes downstream of P2Y12/13 receptors in spinal microglia in neuropathic pain
Authors: Tatsumi Emiko , Yamanaka Hiroki , Kobayashi Kimiko , Yagi Hideshi , Sakagami Masafumi , Noguchi Koichi
Published: August 2014

Recent studies have indicated an important role of ATP receptors in spinal microglia, such as P2Y12 or P2Y13, in the development of chronic pain. However, intracellular signaling cascade of these receptors have not been clearly elucidated. We found that intrathecal injection of 2‐(methylthio)adenosine 5′‐diphosphate (2Me‐SADP) induced mechanical hypersensitivity and p38 mitogen‐activated protein kinase (MAPK) phosphorylation in the spinal cord. Intrathecal administration of P2Y12/P2Y13 antagonists and Rho‐associated coiled‐coil‐containing protein kinase (ROCK) inhibitor H1152 suppressed not only p38 MAPK phosphorylation, but also mechanical hypersensitivity induced by 2Me‐SADP. In the rat peripheral nerve injury model, intrathecal administration of antagonists for the P2Y12/P2Y13 receptor suppressed activation of p38 MAPK in the spinal cord. In addition, subarachnoidal injection of H1152 also attenuated nerve injury‐induced spinal p38 MAPK phosphorylation and neuropathic pain behavior, suggesting an essential role of ROCK in nerve injury‐induced p38 MAPK activation. We also found that the antagonists of the P2Y12/P2Y13 receptor and H1152 had inhibitory effects on the morphological changes of microglia such as retraction of processes in both 2Me‐SADP and nerve injured rats. In contrast these treatments had no effect on the number of Iba1‐positive cells in the nerve injury model. Collectively, our results have demonstrated roles of ROCK in the spinal microglia that is involved in p38 MAPK activation and the morphological changes. Inhibition of ROCK signaling may offer a novel target for the development of a neuropathic pain treatment. GLIA 2015;63:216–228
Clinical evidence and bioinformatics characterization of potential hepatitis C virus resistance pathways for sofosbuvir
Authors: Donaldson Eric F. , Harrington Patrick R. , O'Rear Julian J. , Naeger Lisa K.
Published: August 2014

Sofosbuvir (Sovaldi, SOF) is a nucleotide analog prodrug that targets the hepatitis C virus (HCV) nonstructural protein 5B (NS5B) polymerase and inhibits viral replication. High sustained virological response rates are achieved when SOF is used in combination with ribavirin with or without pegylated interferon in subjects with chronic HCV infection. Potential mechanisms of HCV resistance to SOF and other nucleos(t)ide analog NS5B polymerase inhibitors are not well understood. SOF was the first U.S. Food and Drug Administration (FDA)‐approved antiviral drug for which genotypic resistance analyses were based almost entirely on next‐generation sequencing (NGS), an emerging technology that lacks a standard data analysis pipeline. The FDA Division of Antiviral Products developed an NGS analysis pipeline and performed independent analyses of NGS data from five SOF clinical trials. Additionally, structural bioinformatics approaches were used to characterize potential resistance‐associated substitutions. Using protocols we developed, independent analyses of the NGS data reproduced results that were comparable to those reported by Gilead Sciences, Inc. Low‐frequency, treatment‐emergent substitutions occurring at conserved NS5B amino acid positions in subjects who experienced virological failure were also noted and further evaluated. The NS5B substitutions, L159F (sometimes in combination with L320F or C316N) and V321A, emerged in 2.2%‐4.4% of subjects who failed SOF treatment across clinical trials. Moreover, baseline polymorphisms at position 316 were potentially associated with reduced response rates in HCV genotype 1b subjects. Analyses of these variants modeled in NS5B crystal structures indicated that all four substitutions could feasibly affect SOF anti‐HCV activity. Conclusion: SOF has a high barrier to resistance; however, low‐frequency NS5B substitutions associated with treatment failure were identified that may contribute to resistance of this important drug for chronic HCV infection. (Hepatology 2015;61:56–65)
Dynamic contrast enhanced MR imaging for rectal cancer response assessment after neo‐adjuvant chemoradiation
Authors: Intven Martijn , Reerink Onne , Philippens Marielle E.P.
Published: August 2014

Background

Patient selection for organ sparing treatment after good response to neo‐adjuvant chemoradiation (CRT) for locally advanced rectal cancer is challenging as no optimal restaging modality is available after CRT. In this study, we assessed the value of dynamic contrast enhanced magnetic resonance imaging (DCE‐MRI) for rectal cancer pathological response prediction.

Methods

In 51 patients with locally advanced rectal cancer, the tumor volume and volume transfer constant (Ktrans) were obtained at 3 Tesla before CRT and surgery. The predictive potential for pathological complete response (pCR) and good response (GR) was assessed. GR was defined as pCR and near‐pCR based on the tumor regression grade.

Results

The GR group consisted of 10 patients (19.6%) with six pCR (11.8%). Both the post‐CRT tumor volume and post‐CRT Ktrans values and the relative change in volume (ΔVolume) and Ktrans (ΔKtrans) were predictive for pathological response. ΔKtrans showed the best predictive potential with a positive predictive value (PPV) of 100% for GR using a cutoff value of 32% reduction in Ktrans. For pCR the best PPV was 80% with a multiparameter model containing ΔVolume and ΔKtrans.

Conclusion

DCE‐MRI has predictive potential for pathological response after CRT in rectal cancer with the relative ΔKtrans being the most predictive parameter.J. Magn. Reson. Imaging 2015;41:1646–1653. © 2014 Wiley Periodicals, Inc.
Pigment analysis of Portuguese portrait miniatures of 17th and 18th centuries by Raman Microscopy and SEM‐EDS
Authors: Veiga Alfredina , Mirão José , Candeias António J. , Simões Rodrigues Paulo , Martins Teixeira Dora , Muralha Vânia S. F. , Ginja Teixeira Jorge
Published: August 2014

Seventeen Portuguese miniature portraits on copper support from the Évora Museum collection (Portugal) were analyzed in situ and nondestructively by Raman microscopy (RM), SEM‐EDS, and stereomicroscopy. This work constitutes a great breakthrough in the study of miniature paintings from the 17th and 18th centuries, since the chemical information known about this unique kind of paintings are still scarce, and in particular, this exclusive collection was never been subjected to any physicochemical study. In this work, each portrait was examined in detail in order to characterize the pigments palette used by the miniaturists. The μ‐Raman analysis, in particular, guaranteed an exceptional visualization and good individual identification of small grains of pigments and other constituents of the pictorial layer. Using this technique, 19 compounds were identified, including bluish black covellite, a pigment rarely found in oil paintings. SEM‐EDS was used as an important complementary technique to confirm the chemical nature of some pigments and to identify shell gold (gold dust) in some portraits. Overall, the pigments identified in this large set of old paintings are broadly consistent with those mentioned in the painting treatises of that time or reported in other more modern bibliographic sources. Copyright © 2014 John Wiley & Sons, Ltd.