bluuebunny/crossref_metadata_2025 huggingface dataset:
Morphological Control for High Performance, Solution‐Processed Planar Heterojunction Perovskite Solar Cells
Authors: Eperon Giles E. , Burlakov Victor M. , Docampo Pablo , Goriely Alain , Snaith Henry J.
Published: September 2013

Organometal trihalide perovskite based solar cells have exhibited the highest efficiencies to‐date when incorporated into mesostructured composites. However, thin solid films of a perovskite absorber should be capable of operating at the highest efficiency in a simple planar heterojunction configuration. Here, it is shown that film morphology is a critical issue in planar heterojunction CH3NH3PbI3‐xClx solar cells. The morphology is carefully controlled by varying processing conditions, and it is demonstrated that the highest photocurrents are attainable only with the highest perovskite surface coverages. With optimized solution based film formation, power conversion efficiencies of up to 11.4% are achieved, the first report of efficiencies above 10% in fully thin‐film solution processed perovskite solar cells with no mesoporous layer.
Efficiency Roll‐Off in Organic Light‐Emitting Diodes
Authors: Murawski Caroline , Leo Karl , Gather Malte C.
Published: September 2013

Organic light‐emitting diodes (OLEDs) have attracted much attention in research and industry thanks to their capability to emit light with high efficiency and to deliver high‐quality white light that provides good color rendering. OLEDs feature homogeneous large area emission and can be produced on flexible substrates. In terms of efficiency, OLEDs can compete with highly efficient conventional light sources but their efficiency typically decreases at high brightness levels, an effect known as efficiency roll‐off. In recent years, much effort has been undertaken to understand the underlying processes and to develop methods that improve the high‐brightness performance of OLEDs. In this review, we summarize the current knowledge and provide a detailed description of the relevant principles, both for phosphorescent and fluorescent emitter molecules. In particular, we focus on exciton‐quenching mechanisms, such as triplet–triplet annihilation, quenching by polarons, or field‐induced quenching, but also discuss mechanisms such as changes in charge carrier balance. We further review methods that may reduce the roll‐off and thus enable OLEDs to be used in high‐brightness applications.
Gold(I)‐Catalyzed Bis‐Alkynylation Reaction of Aromatic Aldehydes with Alkynylsilanes
Authors: Rubial Belén , Ballesteros Alfredo , González José M.
Published: September 2013

The first successful gold(I)‐catalyzed reaction of aryl aldehydes with trimethyl(arylethynyl)silanes to furnish bis‐alkynylated derivatives is reported. Key CC bond‐forming events involved in the catalytic cycle are analyzed.

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An Effective Dual Copper‐ and Sulfide‐Catalytic System for the Epoxidation of Aldehydes with Phenyldiazomethane
Authors: Pereira Ana , Martín Carmen , Maya Celia , Belderrain Tomás R. , Pérez Pedro J.
Published: September 2013

Epoxides have been obtained from aldehydes and phenyldiazomethane using catalytic amounts of both the copper homoscorpionate complexes TpxCuL (Tpx=homoscorpionate ligand; L=acetonitrile or tetrahydrofuran, THF) and dimethyl sulfide (SMe2) in high yields and diasteroselectivities, and with activities higher (TOF=46 h−1) than those already known with rhodium‐ or copper‐based catalysts. Among the copper(I) homoscorpionate complexes tested, TpBr3Cu(NCCH3) showed the highest catalytic activity under mild conditions. The catalytic activity is controlled by electronic effects induced by the Tpxligand as well as by the stability of the TpxCu(SR2) adducts. Indeed, in the case of TpMsas ligand, the TpMsCu(THT) (THT=tetrahydrothiophene) and TpMsCu(SMe2) species could be isolated as very stable crystalline solids, the molecular structure of the former being confirmed by single‐crystal X‐ray diffraction analysis. Thein situgeneration of PhCHN2from benzaldehyde tosylhydrazone sodium salt at 60 °C in methyltert‐butyl ether as solvent and TpMsCu(THF) as the catalyst also showed high catalytic activities, improving those already reported with copper‐based catalysts.

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Oxidation and adsorption of arsenic species by means of hybrid polymer containing manganese oxides
Authors: Ociński Daniel , Jacukowicz‐Sobala Irena , Kociołek‐Balawejder Elżbieta
Published: September 2013

The aim of this work was a comprehensive study of the oxidative and sorptive properties of a hybrid polymer containing manganese oxide toward As(III) and As(V). A poly(styrene‐divinylbenzene) copolymer containing oxidative functional groups (SO2NBrNa) was used as the supporting material for MnO2. The inorganic component was deposited as a result of the oxidation reaction of Mn(II) with oxidative groups of the host polymer. The surface of the polymer matrix was evenly covered with a thin layer of manganese oxide. The obtained product (R/S/Mn) exhibited high oxidative capacity over a wide pH range (2–12); however, under acidic and neutral conditions, the reaction ran significantly faster. The studied material shows some sorption properties but its sorption capacity is much lower than its oxidation capacity. The treatment, in a column regime, of the arsenic solution containing 1 mg As(III) dm−3 and coexisting ions in concentrations similar to those in natural waters, confirmed the excellent oxidation capacity of the obtained product. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39489.
Characterization and use of ultraviolet‐reactive low‐molecular‐weight polyhydroxybutyrate to prepare biodegradable acrylates
Authors: Hong Shinn‐Gwo , Hsu Heng‐Wei , Ye Min‐Tzung
Published: September 2013

The characterizations of prepared low‐molecular‐weight polyhydroxybutyrate (LMWPHB) and the properties of LMWPHB photopolymerized with hydrophilic and hydrophobic acrylic monomers were studied with1H‐NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy, Instron tensile testing, and biodegradation tests. The results of1H‐NMR and FTIR spectroscopy confirmed that the prepared LMWPHB had transformed unsaturated ends that were photoreactive under UV light. The tensile strengths of the LMWPHB/acrylates decreased with increasing content of the added biodegradable LMWPHB because of the relatively long chains and large equivalent molar weights of LMWPHB. However, the flexibility of LMWPHB/acrylates changed differently with the type of acrylic monomer used. The LMWPHB/hydrophilic acrylate had a much more rapid biodegradation rate than the LMWPHB/hydrophobic acrylate because of the fast penetration of microorganisms. We demonstrated that the prepared LMWPHB could be used to control the biodegradation properties of acrylates and then could potentially be applied in biomedical fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2014,131, 39501.
Morphology, rheology, crystallization behavior, and mechanical properties of poly(lactic acid)/poly(butylene succinate)/dicumyl peroxide reactive blends
Authors: Ji Deyun , Liu Zhengying , Lan Xiaorong , Wu Feng , Xie Banghu , Yang Mingbo
Published: September 2013

The reactive blends were prepared by the blending of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) in the presence of dicumyl peroxide (DCP) as a radical initiator in the melt state. The gel fractions, morphologies, crystallization behaviors, and rheological and mechanical properties of the reactive blends were investigated. Some crosslinked/branched structures were formed according to the rheological measurement and gel fraction results, and the crosslinked/branched structures played the role of nucleation site for the reactive blends. The PLA–PBS copolymers of the reactive blends acted as a compatibilizer for the PLA and PBS phases and, hence, improved the compatibility between the two components. Moreover, it was found that the reactive blends showed the most excellent mechanical properties as the DCP contents were 0.2 and 0.3 phr. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39580.
Preparation and characterization of composite gels and films containing gelatin and hydroxypropyl methylcellulose phthalate
Authors: Bang S. H. , Son J. R. , Lee S. Y. , Park H. J.
Published: September 2013

Composite gels and films were prepared by the blending of hydrated gelatin as a base material and hydroxypropyl methylcellulose phthalate (HPMCP) at various mass ratios. A composite technology was applied to obtain improved mechanical, physicochemical, and antimicrobial properties of the gelatin used as a base material. We investigated the effects of different experimental conditions on the rheological and mechanical properties and antimicrobial activities of the composite gels, films, and solutions. The rheological values (storage modulus, loss modulus, and complex viscosity) of the composite solutions and gels increased with added HPMCP. Aerobic microorganisms, yeasts, and molds were not detected throughout the testing period in the gelatin–HPMCP composite solution. In contrast, many microorganisms were detected in the gelatin‐only samples beginning with day 3 of storage. The composite films exhibited relatively good mechanical and physical properties compared with the gelatin‐only film. The composite film containing HPMCP at a mass ratio greater than 1:4 did not dissolve in gastric juice (pH 1.2) for at least 2 h, but all other samples, including the gelatin‐only film dissolved in enteric juice (pH 6.8). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39597.
Preparation and functional evaluation of chitosan‐EGCG conjugates
Authors: Lei Fei , Wang Xiaoya , Liang Chunxuan , Yuan Fang , Gao Yanxiang
Published: September 2013

Chitosan, as a novel food additive, is proposed to conjugate with EGCG using a free radical grafting procedure. Chitosan is activated by hydroxyl free radicals produced by the redox reaction of hydrogen peroxide and ascorbic acid and subsequently react with EGCG. Chitosan‐EGCG conjugate has demonstrated by UV, FTIR, and 1H‐NMR spectroscopy and exhibits a dramatical increase in DPPH free radical scavenging activity. In addition, the LC (low‐molecular‐weight chitosan)‐EGCG conjugate is used to prepare O/W emulsion and then monitor the average droplet size, polydispersity index, zeta‐potential and transmission changes during centrifuge process, results show that the conjugate exhibited excellent emulsifying activity and superior emulsifying stability as compared with chitosan. Therefore, LC‐EGCG conjugate could be used as an efficient natural food antioxidant and emulsifier. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39732.
Batch and column adsorption of perfluorooctane sulfonate on anion exchange resins and granular activated carbon
Authors: Chularueangaksorn Pattarawan , Tanaka Shuhei , Fujii Shigeo , Kunacheva Chinagarn
Published: September 2013

Perfluorooctane sulfonate (PFOS) has been detected widely in the natural water matrix and is persistent, bioaccumulative, and toxic. To prevent the adverse effects of PFOS contamination on human health and the environment, effective removal techniques are needed. Adsorption is considered an effective technique for PFOS removal. In this study, five anion exchange resins and granular activated carbon (GAC) were examined to evaluate their performance for the removal of PFOS in both batch and column experiments. Experimental adsorption data for all of the adsorbents exhibited a high correlation with the Freundlich isotherm (R2 = 0.95 – 0.98). Most of the anion exchange resins demonstrated a higher adsorption capacity than the GAC. PFA300 had the highest adsorption capacity (455 mg/g). Continuous adsorption of PFOS was performed in column experiments using the same adsorbents that had been used in the batch experiments. The experimental breakthrough curves were set at C/C0 = 0.1. PFA300 showed the longest operation time before reaching the breakthrough point. The Yoon and Nelson model was used to predict the half‐saturation time of the anion exchange resins. Moreover, the anion exchange resins exhibited high recovery of PFOS by an organic solvent. Continuous PFOS adsorption on a column can be achieved using anion exchange resins for water/wastewater treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39782.
Primary Ammonium Monocarboxylate Synthon in Designing Supramolecular Gels: A New Series of Chiral Low‐Molecular‐Weight Gelators Derived from Simple Organic Salts that are Capable of Generating and Stabilizing Gold Nanoparticles
Authors: Das Uttam Kumar , Banerjee Subhabrata , Dastidar Parthasarathi
Published: September 2013

The primary ammonium monocarboxylate (PAM) synthon has been exploited to generate a new series of PAM salts from the free amine of L‐phenylalanine‐3‐pyridyl amide, (S)‐2‐amino‐3‐phenyl‐N‐(pyridine‐3‐yl)propanamine (designated as “B”), and various substituted benzoic acids (designated as “A(R)”; R=4‐Me, 4‐Cl, 4‐Br, 4‐NO2, 3‐Me, 3‐Cl, 3‐Br, 3‐NO2, 2‐Me, 2‐Cl, 2‐Br, 2‐NO2). The 4‐ and 3‐substituted benzoate salts showed moderate‐to‐excellent gelation ability with a number of polar and apolar solvents. The gels were characterized by DSC, rheology, SEM and TEM, FTIR spectroscopy, etc. Structure–property studies based on single‐crystal powder X‐ray diffraction (PXRD) and FTIR data provided insights into the role of the PAM synthon in the formation of the gel networks. Interestingly, some of the gels were capable of forming and stabilizing gold nanoparticles at room temperature without the use of any exogenous reducing agents.
High‐Temperature Sulfur Removal from Biomass‐Derived Synthesis Gas over Bifunctional Molybdenum Catalysts
Authors: König Christian F. J. , Schuh Patrick , Schildhauer Tilman J. , Nachtegaal Maarten
Published: September 2013

The removal of sulfur species from the biomass‐derived producer gas after gasification is required to protect downstream catalysts. Finding suitable materials for high‐temperature desulfurization is one of the main challenges for the improvement in the efficiency of catalytic biomass conversion. The biomass‐derived producer gas usually contains not only H2S but also organic sulfur species such as thiophene (C4H4S), which cannot be removed by most sorbent materials. Herein, we explored Al2O3‐supported molybdenum catalysts as bifunctional materials for the removal of H2S and catalytic conversion of C4H4S at high temperatures. By using X‐ray absorption spectroscopy under reaction conditions, we show that H2S is removed through the sulfidation of MoO3. C4H4S is catalytically converted over MoO2 to MoS2 and hydrocarbon species. The subsequent oxidation of MoS2 to MoO3 and SO2 regenerates the material and allows the sequestration of sulfur from the gas stream. Furthermore, the negative effect of steam on sulfur removal is shown to be caused by competitive adsorption with sulfur species. These findings show the possibility of the high‐temperature desulfurization of biomass‐derived gas for catalytic conversion, for instance, to synthetic natural gas.
Inverse problems in 1D hemodynamics on systemic networks: A sequential approach
Authors: Lombardi D.
Published: September 2013

In this work, a sequential approach based on the unscented Kalman filter is applied to solve inverse problems in 1D hemodynamics, on a systemic network. For instance, the arterial stiffness is estimated by exploiting cross‐sectional area and mean speed observations in several locations of the arteries. The results are compared with those ones obtained by estimating the pulse wave velocity and the Moens–Korteweg formula. In the last section, a perspective concerning the identification of the terminal models parameters and peripheral circulation (modeled by a Windkessel circuit) is presented. Copyright © 2013 John Wiley & Sons, Ltd.
Bioavailability and Safety of the Factor Xa Inhibitor Edoxaban and the Effects of Quinidine in Healthy Subjects
Authors: Matsushima Nobuko , Lee Frank , Sato Toshiyuki , Weiss Daniel , Mendell Jeanne
Published: September 2013

Background

Edoxaban is an oral, once‐daily, direct factor Xa inhibitor under investigation for stroke prevention in patients with atrial fibrillation and for treatment and secondary prevention of venous thromboembolism. This study evaluated edoxaban absolute bioavailability and effects of the P‐glycoprotein inhibitor quinidine on edoxaban pharmacokinetics after intravenous edoxaban administration.

Methods

Healthy volunteers received three treatments in a randomized sequence: single oral 60‐mg edoxaban dose, single intravenous 30‐mg edoxaban dose, and concomitant single intravenous 30‐mg edoxaban dose with quinidine 300 mg every 8 hours for 4 days. The primary objective was to determine absolute bioavailability of edoxaban. Secondary objectives included pharmacokinetics and pharmacodynamics of edoxaban after oral or intravenous administration, quinidine effect on intravenous edoxaban pharmacokinetics, and safety.

Results

Thirty‐six subjects were randomized; five discontinued (three for adverse events [AEs]). Edoxaban oral absolute bioavailability was 61.8%. With concomitant quinidine, total edoxaban exposure increased ∼35% and total clearance decreased ∼25%. Coagulation parameters increased after edoxaban administration in most subjects, but returned to baseline within 24 hours postdose. No deaths, serious AEs, or bleeding‐related AEs occurred.

Conclusions

Absolute bioavailability of edoxaban in healthy volunteers was established (61.8%). Edoxaban, administered orally or intravenously, appeared to be safe and well tolerated.
Comparison of drug concentrations between whole blood and oral fluid
Authors: Langel Kaarina , Gjerde Hallvard , Favretto Donata , Lillsunde Pirjo , Øiestad Elisabeth Leere , Ferrara Santo Davide , Verstraete Alain G.
Published: September 2013

The relationship of drug concentrations between oral fluid and whole blood was evaluated by studying the linear correlation of concentrations and calculating the oral fluid to blood concentration ratios (OF/B) for different substances. Paired oral fluid and whole blood samples were collected from volunteers and persons suspected of drug use in four European countries. Oral fluid samples were collected with the Saliva∙Sampler™ device. All samples were analyzed for drugs of abuse and psychoactive medicines with validated gas and liquid chromatography‐mass spectrometric methods. The median OF/B ratios were, for amphetamines 19–22, for opioids 1.8–11, for cocaine and metabolites 1.7–17, for tetrahydrocannabinol (THC) 14, for benzodiazepines 0.035–0.33, and for other psychoactive medicines 0.24–3.7. Most of the these results were close to theoretical values based on the physicochemical properties of the drugs and to values presented earlier, but there was a lot of inter‐individual variation in the OF/B ratios. For all substances, except for lorazepam (R2 = 0.031) and THC (R2 = 0.030), a correlation between the oral fluid and whole blood concentrations was observed. Due to large variation seen here, drug findings in oral fluid should not be used to estimate the corresponding concentrations in whole blood (or vice versa). However, detection of drugs in oral fluid is a sign of recent drug use and oral fluid can be used for qualitative detection of several drugs, e.g. in epidemiological prevalence studies. By optimizing the sampling and the analytical cut‐offs, the potential of oral fluid as a confirmation matrix could be enhanced. Copyright © 2013 John Wiley & Sons, Ltd.
Unexpected genetic differentiation between recently recolonized populations of a long‐lived and highly vagile marine mammal
Authors: Bonin Carolina A. , Goebel Michael E. , Forcada Jaume , Burton Ronald S. , Hoffman Joseph I.
Published: September 2013

Many species have been heavily exploited by man leading to local extirpations, yet few studies have attempted to unravel subsequent recolonization histories. This has led to a significant gap in our knowledge of the long‐term effects of exploitation on the amount and structure of contemporary genetic variation, with important implications for conservation. The Antarctic fur seal provides an interesting case in point, having been virtually exterminated in the nineteenth century but subsequently staged a dramatic recovery to recolonize much of its original range. Consequently, we evaluated the hypothesis that South Georgia (SG), where a few million seals currently breed, was the main source of immigrants to other locations including Livingston Island (LI), by genotyping 366 individuals from these two populations at 17 microsatellite loci and sequencing a 263 bp fragment of the mitochondrial hypervariable region 1. Contrary to expectations, we found highly significant genetic differences at both types of marker, with 51% of LI individuals carrying haplotypes that were not observed in 246 animals from SG. Moreover, the youngest of three sequentially founded colonies at LI showed greater similarity to SG at mitochondrial DNA than microsatellites, implying temporal and sex‐specific variation in recolonization. Our findings emphasize the importance of relict populations and provide insights into the mechanisms by which severely depleted populations can recover while maintaining surprisingly high levels of genetic diversity.
The role of synoptic eddies in the tropospheric response to stratospheric variability
Authors: Domeisen Daniela I. V. , Sun Lantao , Chen Gang
Published: September 2013

The tropospheric response to sudden stratospheric warmings (SSWs) is analyzed in an idealized model setup regarding the respective roles of planetary‐scale and synoptic‐scale waves. The control model run includes a full interactive wave spectrum, while a second run includes interactive planetary‐scale waves but only the time‐mean synoptic‐scale wave forcing from the control run. In both runs, the tropospheric response is characterized by the negative phase of the respective tropospheric annular mode. But given their different latitudinal structure, the control run shows the expected response, i.e., an equatorward shift of the tropospheric jet, whereas the response in the absence of interactive synoptic eddies is characterized by a poleward jet shift. This opposite jet shift is associated with a different planetary wave variability that couples with the zonal flow between the stratosphere and the surface. These results indicate that the synoptic eddy feedback is necessary for the observed tropospheric response to SSWs.
Pharmacogenetic polymorphisms and response to escitalopram and venlafaxine over 8 weeks in major depression
Authors: Ng Chee , Sarris Jerome , Singh Ajeet , Bousman Chad , Byron Keith , Peh Lai Huat , Smith Deidre Joy , Tan Chay Hoon , Schweitzer Isaac
Published: September 2013

Objective

The objective of this study is to investigate the influence of the 5‐HTTLPR (serotonin transporter‐linked promoter region), cytochrome P450 2C19, and cytochrome P450 2D6 polymorphisms on escitalopram (ESC) and venlafaxine (VEN) responses in major depressive disorder.

Method

A prospective multi‐site study of 106 patients (Caucasian and Han Chinese ethnicities) with major depressive disorder treated with either ESC or VEN was conducted. The 17‐item Hamilton Depression scale (HDRS), Clinical Global Impression Scale, and an adverse events scale (UKU) were assessed over 8 weeks, blind to genotype.

Results

At the 8‐week end point, a significant HDRS reduction for both ESC and VEN occurred (p < 0.0001). The 5‐HTTLPR l/l genotype was associated with significantly greater score reductions on the HDRS compared with s/s carriers (p = 0.016) among Caucasian subjects receiving ESC (n = 47). Response rates were significantly higher for l/l (92%) compared with l/s (61%) and s/s (46%) variants (p = 0.042). For every l allele a participant carried, there was a 3.33 (95% confidence interval 1.25, 8.84; p = 0.02) times greater odds of ESC response. No significant associations between any of the genotypes and adverse effects were found.

Conclusion

Ethnicity may have differential effects on the 5‐HTTLPR genotype‐efficacy relationship. Results suggest that l/l allele for 5‐HTTLPR is associated with a robust treatment response to ESC in Caucasian subjects only. Copyright © 2013 John Wiley & Sons, Ltd.
Interaction of substorm injections with the subauroral geospace: 1. Multispacecraft observations of SAID
Authors: Mishin Evgeny V.
Published: September 2013

Subauroral ion drifts (SAID) are the prominent feature of the active subauroral geospace, just earthward of the electron plasma sheet (PS) boundary in the premidnight sector. We explore magnetically conjugate satellite observations of substorm SAID near the magnetic equator and in the topside ionosphere confirming and expanding on our previous results. The SAID channels reside between the hot electron (PS/auroral) boundary at the plasmapause and the drop in the hot ion flux inside the plasmasphere. The overall features are inconsistent with the paradigm of voltage and current generators. Rather, they are explained in terms of a short circuiting of substorm‒injected hot plasma jets over the plasmapause and formation of a turbulent plasmaspheric boundary layer. The short circuiting occurs when the cold plasma density exceeds a critical value of 5–10 cm−3. As the polarization field at the front of the hot plasma jet is shorted out, the hot electrons are arrested, while the hot ions yet move inward. This provides a natural explanation of the long‒known dispersionless auroral precipitation boundary. Enhanced plasma turbulence within the SAID channel provides anomalous circuit resistivity and magnetic diffusion, as with the well‒documented plasmoid‒magnetic barrier problem.
Space‐time interpolation of satellite winds in the tropics
Authors: Patoux Jérôme , Levy Gad
Published: September 2013

A space‐time interpolator for creating average geophysical fields from satellite measurements is presented and tested. It is designed for optimal spatiotemporal averaging of heterogeneous data. While it is illustrated with satellite surface wind measurements in the tropics, the methodology can be useful for interpolating, analyzing, and merging a wide variety of heterogeneous and satellite data in the atmosphere and ocean over the entire globe. The spatial and temporal ranges of the interpolator are determined by averaging satellite and in situ measurements over increasingly larger space and time windows and matching the corresponding variability at each scale. This matching provides a relationship between temporal and spatial ranges, but does not provide a unique pair of ranges as a solution to all averaging problems. The pair of ranges most appropriate for a given application can be determined by performing a spectral analysis of the interpolated fields and choosing the smallest values that remove any or most of the aliasing due to the uneven sampling by the satellite. The methodology is illustrated with the computation of average divergence fields over the equatorial Pacific Ocean from SeaWinds‐on‐QuikSCAT surface wind measurements, for which 72 h and 510 km are suggested as optimal interpolation windows. It is found that the wind variability is reduced over the cold tongue and enhanced over the Pacific warm pool, consistent with the notion that the unstably stratified boundary layer has generally more variable winds and more gustiness than the stably stratified boundary layer. It is suggested that the spectral analysis optimization can be used for any process where time‐space correspondence can be assumed.
Differential ubiquitin–proteasome and autophagy signaling following rotator cuff tears and suprascapular nerve injury
Authors: Joshi Sunil K. , Kim Hubert T. , Feeley Brian T. , Liu Xuhui
Published: September 2013

Previous studies have evaluated role of Akt/mTOR signaling in rotator cuff muscle atrophy and determined that there was differential in signaling following tendon transection (TT) and suprascapular nerve (SSN) denervation (DN), suggesting that atrophy following TT and DN was modulated by different protein degradation pathways. In this study, two muscle proteolytic systems that have been shown to be potent regulators of muscle atrophy in other injury models, the ubiquitin–proteasome pathway and autophagy, were evaluated following TT and DN. In addition to examining protein degradation, this study assessed protein synthesis rate following these two surgical models to understand how the balance between protein degradation and synthesis results in atrophy following rotator cuff injury. In contrast to the traditional theory that protein synthesis is decreased during muscle atrophy, this study suggests that protein synthesis is up‐regulated in rotator cuff muscle atrophy following both surgical models. While the ubiquitin–proteasome pathway was a major contributor to the atrophy seen following DN, autophagy was a major contributor following TT. The findings of this study suggest that protein degradation is the primary factor contributing to atrophy following rotator cuff injury. However, different proteolytic pathways are activated if SSN injury is involved. © 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 32:138–144, 2014.
Transforming growth factor‐β (TGF‐β) expression is increased in the subsynovial connective tissues of patients with idiopathic carpal tunnel syndrome
Authors: Chikenji Takako , Gingery Anne , Zhao Chunfeng , Passe Sandra M. , Ozasa Yasuhiro , Larson Dirk , An Kai‐Nan , Amadio Peter C.
Published: September 2013

Non‐inflammatory fibrosis of the subsynovial connective tissue (SSCT) is a hallmark of carpal tunnel syndrome (CTS). The etiology of this finding and its relationship to the development of CTS remain poorly understood. Recent studies have found that transforming growth factor‐β (TGF‐β) plays a central role in fibrosis. The purpose of this study was to investigate the expression of TGF‐β and connective tissue growth factor (CTGF), a downstream mediator of TGF‐β, in the pathogenesis of CTS. We compared SSCT specimens from 26 idiopathic CTS patients with specimens from 10 human cadaver controls with no previous diagnosis of CTS. Immunohistochemistry was performed to determine levels TGF‐β1, CTGF, collagen 1(Col1) and collagen 3 (Col3) expression. TGF‐β1 (p < 0.01), CTGF (p < 0.01), and Col3 (p < 0.01) were increased in SSCT of CTS patients compared with control tissue. In addition, a strong positive correlation was found between TGF‐β1 and CTGF, (R2 = 0.80, p < 0.01) and a moderate positive correlation between Col3 and TGF‐β1 (R2 = 0.49, p < 0.01). These finding suggest that there is an increased expression of TGF‐β and CTGF, a TGF‐β regulated protein, and that this TGF‐β activation may be responsible for SSCT fibrosis in CTS patients. © 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 32:116–122, 2014.
Assessment of pain‐related behavior and pro‐inflammatory cytokine levels in the rat rotator cuff tear model
Authors: Yamazaki Hironori , Ochiai Nobuyasu , Kenmoku Tomonori , Ohtori Seiji , Sasho Takahisa , Miyagi Masayuki , Ishikawa Tetsuhiro , Kamoda Hiroto , Orita Sumihisa , Sasaki Yuu , Yamaguchi Takeshi , Kijima Takehiro , Takahashi Kazuhisa
Published: September 2013

The cause of pain following rotator cuff tear has not been fully elucidated. The purpose of this study was to evaluate behavior and inflammatory cytokines in a rat unstabilized rotator cuff defect (UCD) model. Forty‐five Sprague–Dawley rats were divided into three groups: sham; UCD; and stabilized rotator cuff defect (SCD). Gait analysis was examined using CatWalk. Tumor necrosis factor (TNF)‐α, interleukin(IL)‐1β, and IL‐6 were measured within the subacromial bursa and the glenohumeral joint synovium at 21 and 56 days after surgery using an enzyme‐linked immunosorbent assay (ELISA). Stride length, print area and contact intensity in the UCD group was significantly lower than in the sham group after surgery. Stride length, print area and contact intensity in the SCD group was significantly higher than in the UCD group. In contrast, TNF‐α, IL‐1β, and IL‐6 in the UCD group was significantly higher than in the sham group at days 21 and 56. However, TNF‐α, IL‐1β, and IL‐6 in the SCD group was significantly lower than in the UCD group at days 21 and 56. The present results suggest that SCD is effective not only in improving shoulder function but also in reducing inflammatory cytokines, which may serve as one source of pain due to rotator cuff tear. © 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 32:286–290, 2014.
Skeletal trauma generates systemic BMP2 activation that is temporally related to the mobilization of CD73+ cells
Authors: Marsell Richard , Steen Brandon , Bais Manish V. , Mortlock Douglas P. , Einhorn Thomas A. , Gerstenfeld Louis C.
Published: September 2013

The relationship between BMP2 expression and the recruitment of skeletogenic stem cells was assessed following bone marrow reaming. BMP2 expression was examined using transgenic mice in which β‐galactosidase had been inserted into the coding region of BMP2. Stem cell mobilization was analyzed by FACS analysis using CD73, a marker associated with bone marrow stromal stem cells. BMP2 expression was induced in endosteal lining cells, cortical osteocytes and periosteal cells in both the reamed and in contralateral bones. BMP2 mRNA expression in the reamed bone showed an early peak within the first 24 h of reaming followed by a later peak at 7 days, while contralateral bones only showed the 7 days peak of expression. FACS analysis sorting on CD73 positive cells showed a 50% increase of these cells at 3 and 14 days in the marrow of the injured bone and a single peak at 14 days of the marrow cell population of the contralateral bone. A ∼20% increase of CD73 positive cells was seen in the peripheral blood 2 days after reaming. These data showed that traumatic bone injury caused a systemic induction of BMP2 expression and that this increase is correlated with the mobilization of CD73 positive cells. © 2013 The Authors. Journal of Orthopaedic Research Published by Wiley Periodicals, Inc. on behalf of the Orthopaedic Research Society. J Orthop Res 32:17–23, 2014.
One‐Pot Synthesis of Multifunctional Polymers by Light‐Controlled Radical Polymerization and Enzymatic Catalysis with Candida antarctica Lipase B
Authors: Hrsic Emin , Keul Helmut , Möller Martin
Published: September 2013

The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.

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N‐acetyl‐L‐cysteine enhances fisetin‐induced cytotoxicity via induction of ROS‐independent apoptosis in human colonic cancer cells
Authors: Wu Ming‐Shun , Lien Gi‐Shih , Shen Shing‐Chuan , Yang Liang‐Yo , Chen Yen‐Chou
Published: September 2013

Oxidative stress or excessive antioxidant levels‐caused redox imbalance can alter apoptotic responses, and N‐acetyl‐L‐cysteine (NAC) was able to inhibit H2O2‐mediated cell death, but unable to prevent apoptosis induced by other chemicals such as etoposide. We now demonstrate that 10 and 20 mM NAC, non‐toxic concentrations, can enhance fisetin (FIS)‐mediated apoptosis in colon cancer cells COLO205. Compared to treatment with FIS alone, combination treatment with NAC increased the expression of cleaved caspase‐3 and PAPR protein, and produced greater density of DNA ladders. NAC reduced the mitochondrial membrane potential of FIS‐treated COLO205 cells with induction of caspase 9 protein cleavage. DNA ladders induced by FIS + NAC were diminished by adding the caspase 3 inhibitor, DEVD‐FMK, and the caspase 9 inhibitor, YVAD‐FMK. Combinatorial treatment COLO205 cells with NAC and FIS showed potent inhibition on ERK protein phosphorylation, compared with those from FIS or NAC‐treated groups by Western blotting using specific antibodies. Addition of the chemical ERK inhibitors, PD98059 and U0126, significantly inhibited ERK protein phosphorylation, accompanied by induced DNA ladder formation, cleavage of caspase 3 and PARP protein in COLO205 cells. Furthermore, NAC showed an enhancement on a FIS‐related chemical chrysin‐induced apoptosis of COLO205 cells, and NAC sensitization of colon cancer cells to FIS‐induced apoptosis was also identify in colonic cancer cells HCT‐116, HT‐29, and HCT‐15 cells. The evidence to support NAC sensitizing human colon cancer cells to FIS‐induced apoptosis was provided, and application of NAC and FIS as a strategy to treat colonic cancer deserved for further in vivo study. © 2013 Wiley Periodicals, Inc.
Using Graph Indices for the Analysis and Comparison of Chemical Datasets
Authors: Fourches Denis , Tropsha Alexander
Published: September 2013

In cheminformatics, compounds are represented as points in multidimensional space of chemical descriptors. When all pairs of points found within certain distance threshold in the original high dimensional chemistry space are connected by distance‐labeled edges, the resulting data structure can be defined as Dataset Graph (DG). We show that, similarly to the conventional description of organic molecules, many graph indices can be computed for DGs as well. We demonstrate that chemical datasets can be effectively characterized and compared by computing simple graph indices such as the average vertex degree or Randic connectivity index. This approach is used to characterize and quantify the similarity between different datasets or subsets of the same dataset (e.g., training, test, and external validation sets used in QSAR modeling). The freely available ADDAGRA program has been implemented to build and visualize DGs. The approach proposed and discussed in this report could be further explored and utilized for different cheminformatics applications such as dataset diversification by acquiring external compounds, dataset processing prior to QSAR modeling, or (dis)similarity modeling of multiple datasets studied in chemical genomics applications.
Validation of the problem gambling severity index using confirmatory factor analysis and rasch modelling
Authors: Miller Natalie V. , Currie Shawn R. , Hodgins David C. , Casey David
Published: September 2013

The Problem Gambling Severity Index (PGSI), a screening tool used to measure the severity of gambling problems in general population research, was subjected to confirmatory factor analysis and Rasch modelling to (a) confirm the one‐factor structure; (b) assess how well the items measure the continuum of problem gambling severity; (c) identify sources of differential item functioning among relevant subpopulations of gamblers. Analyses were conducted on a nationally representative sample of over 25,000 gamblers compiled by merging data from the Canadian Community Health Survey and Canadian Problem Gambling Index (CPGI) integrated datasets. Results provided support for a one‐factor model that was invariant across gender, age, income level, and gambler type. Rasch modelling revealed a well‐fitting, unidimensional model with no miss‐fitting items. The average severity assessed by the PGSI is consistent with moderately severe problem gambling. The PGSI is therefore weak in assessing low to moderate problem severity, a notable limitation of most brief gambling screens. Evidence of clinically significant differential item functioning was found with only one item, borrowing money to gamble, which behaved differently in gamblers who play electronic gaming machines or casino games compared to gamblers who avoid these games. Copyright © 2013 John Wiley & Sons, Ltd.
Mykotoxinkonjugate demaskieren
Authors: Maul Ronald , Brodehl Antje , Koch Matthias
Published: September 2013

Wenn in einem Lebensmittel keine Schimmelpilzgifte nachweisbar sind, muss das nicht bedeuten, dass keine enthalten sind. Prozesse der Lebensmittelverarbeitung, etwa das Mälzen in der Brauerei, führen dazu, dass Glucoside oder Sulfate der Toxine entstehen. Sie sind wenig charakterisiert und analytisch bisher kaum fassbar.
Evaluation of ubiquitinated proteins by proteomics reveals the role of the ubiquitin proteasome system in the regulation of Grp75 and Grp78 chaperone proteins during intestinal inflammation
Authors: Bertrand Julien , Tennoune Naouel , Marion‐Letellier Rachel , Goichon Alexis , Chan Philippe , Mbodji Khaly , Vaudry David , Déchelotte Pierre , Coëffier Moïse
Published: September 2013

The ubiquitin proteasome system (UPS) is the major pathway of intracellular protein degradation and may be involved in the pathophysiology of inflammatory bowel diseases or irritable bowel syndrome. UPS specifically degrades proteins tagged with an ubiquitin chain. We aimed to identify polyubiquitinated proteins during inflammatory response in intestinal epithelial HCT‐8 cells by a proteomic approach. HCT‐8 cells were incubated with interleukin 1β, tumor necrosis factor‐α, and interferon‐γ for 2 h. Total cellular protein extracts were separated by 2D gel electrophoresis and analyzed by an immunodetection using antiubiquitin antibody. Differential ubiquitinated proteins were then identified by LC‐ESI MS/MS. Seven proteins were differentially ubiquitinated between control and inflammatory conditions. Three of them were chaperones: Grp75 and Hsc70 were more ubiquitinated (p < 0.05) and Grp78 was less ubiquitinated (p < 0.05) under inflammatory conditions. The results for Grp75 and Grp78 were then confirmed in HCT‐8 cells and in 2‐4‐6‐trinitrobenzen sulfonic acid induced colitis in rats mimicking inflammatory bowel disease by immunoprecipitation. No difference was observed in irritable bowel syndrome like model. In conclusion, we showed that a proteomic approach is suitable to identify ubiquitinated proteins and that UPS‐regulated expression of Grp75 and Grp78 may be involved in inflammatory response. Further studies should lead to the identification of ubiquitin ligases responsible for Grp75 and Grp78 ubiquitination.
Expression pattern of human ATP‐binding cassette transporters in skin
Authors: Takenaka Saya , Itoh Tomoo , Fujiwara Ryoichi
Published: September 2013

ATP‐binding cassette (ABC) transporters transport a variety of substrates across cellular membranes coupled with hydrolysis of ATP. Currently 49 ABC transporters consisting of seven subfamilies, ABCA, ABCB, ABCC, ABCD, ABCE, ABCF, and ABCG, have been identified in humans and they are extensively expressed in various tissues. Skin can develop a number of drug‐induced toxicities' such as Stevens–Johnson syndrome and psoriasis. Concentration of drugs in the skin cells is associated with the development of adverse drug reactions. ABC transporters play important roles in absorption and disposition of drugs in the cells; however, the expression pattern of human ABC transporters in the skin has not been determined. In this study, the expression patterns of 48 human ABC transporters were determined in the human skin as well as in the liver and small intestine. Most of the ABCA, ABCB, ABCC, ABCD, ABCE, and ABCF family members were highly or moderately expressed in the skin, while ABCG family members were slightly expressed in the skin. Significant interindividual variability was also observed in the expression levels of those ATP transporters in the skin, except for ABCA5 and ABCF1, which were found to be expressed in all of the human skin samples tested in this study. In conclusion, this is the first study to identify the expression pattern of the whole human ABC family of transporters in the skin. The interindividual variability in the expression levels of ABC transporters in the human skin might be associated with drug‐induced skin diseases.
Influence of stoichiometry on the performance of MIM capacitors from plasma‐assisted ALD SrxTiyOz films
Authors: Aslam N. , Longo V. , Keuning W. , Roozeboom F. , Kessels W. M. M. , Waser R. , Hoffmann‐Eifert S.
Published: September 2013

Strontium titanate, SrxTiyOz (STO), thin films with various cation stoichiometries were deposited by plasma‐assisted atomic layer deposition (ALD) using cyclopentadienyl‐based metal precursors and oxygen plasma as counter‐reactant. [Sr]/([Sr] + [Ti]) compositions ranging from 0.46 to 0.57 were obtained by changing the (SrO)/(TiO2) ALD cycle ratios. As‐deposited 15–30 nm thick SrxTiyOz films prepared at 350 °C on Pt‐coated silicon substrates were amorphous. Post‐annealing at 600/650 °C for 10 min under N2 gas resulted in a crystallization into the perovskite phase. Stoichiometric STO and Sr‐rich STO films exhibited a certain degree of (111) texture while the Ti‐rich STO films showed a lower degree of crystallization. Crystallized layers exhibited a smaller band gap Eg than amorphous ones, while within the stoichiometry series the value of Eg increased with increasing Sr‐content. Within the stoichiometry series Pt/STO/Pt structures with Sr‐rich STO films showed the lowest leakage current densities. At 1.0 V values of about 2 × 10−8 and 5 × 10−6 A cm−2 were obtained for the as‐deposited and the annealed films, respectively. Highest capacitance density was obtained for 15 nm polycrystalline stoichiometric SrTiO3 films resulting in a capacitor equivalent thickness CET of about 0.7 nm. Pt/SrxTiyOz/Pt capacitors with the STO being in amorphous state exhibited a positive voltage nonlinearity factor α of about 400 ppm V−2, while the negative α‐values for crystallized films showed a systematic variation with the stoichiometry, the degree of crystallization and the thickness of the STO layer. This demonstrates that a broad performance range of MIM capacitors is accessible by controlling the stoichiometry and the degree of crystallization of plasma‐assisted ALD SrxTiyOz thin films.
Fragmentation pathways of 2‐substituted pyrrole derivatives using electrospray ionization ion trap and electrospray ionization quadrupole time‐of‐flight mass spectrometry
Authors: Liang Xianrui , Guo Zili , Yu Chuanming
Published: September 2013

RATIONALE

Pyrrole derivatives are of considerable importance and are present in a wide range of natural products and used extensively in drug discovery. Fragmentation pathway studies play an important role in the structural identification of pyrrole derivatives. As a part of our ongoing work on heterocycles, fragmentation pathways of 2‐substituted pyrrole derivatives were investigated by mass spectrometry (MS).

METHODS

Twelve pyrrole derivatives were synthesized and analyzed. Low‐resolution fragmentation ions of all the compounds were generated by ion trap mass spectrometry (ITMSn) with an electrospray ionization (ESI) source in positive mode. Hybrid quadrupole time‐of‐flight mass spectrometry (QTOFMS) was used to determine the elemental compositions of the resultant product ions.

RESULTS

The side‐chain substituents at the 2‐position influence the fragmentation pathways. Typical losses of H2O, aldehydes and pyrrole moieties from the [M + H]+ ion are observed for the compounds with side chains bearing aromatic groups at the 2‐position of the pyrrole. However, losses of H2O, alcohols and C3H6 are the main cleavage pathways for compounds 6 and 12 with nonphenyl‐substituted side chains at the 2‐position.

CONCLUSIONS

Typical fragmentation mechanisms of 2‐substituted pyrrole derivatives are proposed and elucidated based on the observations of ITMSn and QTOFMS spectra. The results showed that the fragmentation pathways were remarkably influenced by the side‐chain substituents at the 2‐position of pyrrole. This investigation should have value in the structural identification of this series of molecules or compounds with similar structures. Copyright © 2013 John Wiley & Sons, Ltd.