bluuebunny/crossref_metadata_2025 huggingface dataset:
Interseismic strain accumulation across the central North Anatolian Fault from iteratively unwrapped InSAR measurements
Authors: Hussain Ekbal , Hooper Andrew , Wright Tim J. , Walters Richard J. , Bekaert David P. S.
Published: December 2016

The North Anatolian Fault (NAF) is a major tectonic feature in the Middle East and is the most active fault in Turkey. The central portion of the NAF is a region of Global Navigation Satellite Systems (GNSS) scarcity. Previous studies of interseismic deformation have focused on the aseismic creep near the town of Ismetpasa using radar data acquired in a single line‐of‐sight direction, requiring several modeling assumptions. We have measured interseismic deformation across the NAF using both ascending and descending data from the Envisat satellite mission acquired between 2003 and 2010. Rather than rejecting incorrectly unwrapped areas in the interferograms, we develop a new iterative unwrapping procedure for small baseline interferometric synthetic aperture radar (InSAR) processing that expands the spatial coverage. Our method corrects unwrapping errors iteratively and increases the robustness of the unwrapping procedure. We remove long wavelength trends from the InSAR data using GNSS observations and deconvolve the InSAR velocities into fault‐parallel motion. Profiles of fault‐parallel velocity reveal a systematic eastward decrease in fault slip rate from 30 mm/yr (25–34, 95% confidence interval (CI)) to 21 mm/yr (14–27, 95% CI) over a distance of ∼200 km. Direct offset measurements across the fault reveal fault creep along a ∼130 km section of the central NAF, with an average creep rate of 8 ± 2 mm/yr and a maximum creep rate of 14 ± 2 mm/yr located ∼30 km east of Ismetpasa. As fault creep is releasing only 30–40% of the long‐term strain in the shallow crust, the fault is still capable of producing large, damaging earthquakes in this region.
High‐speed video observation of stepwise propagation of a natural upward positive leader
Authors: Wang Zhichao , Qie Xiushu , Jiang Rubin , Wang Caixia , Lu Gaopeng , Sun Zhuling , Liu Mingyuan , Pu Yunjiao
Published: December 2016

Using a high‐speed video camera operated at 150,000 frames per second, we have documented the upward propagation of an initial positive leader from a 325 m meteorological tower in Beijing. The stepwise development of the upward positive leader was clearly revealed during its self‐sustained propagation toward the cloud base, providing the first optical evidence for the stepping processes of a positive leader. The leader developed with definitive intermittent pauses and re‐establishment with abrupt jump of the leader top. Obvious brush‐like corona zone emitting outward from the leader top was identified in the frame of stepping, and the luminosity waves propagated downward along the already formed channel from the leader top immediately following the stepping, indicating that a current wave was generated at the leader top and subsequently traveled down the channel. The channel luminosity decreased during the leader pause stage, with the corona zone dimmed correspondingly. The positive leader experienced an average interstep interval of 61.7 µs (ranging between 30 µs and 120 µs) and an average 2‐D speed of 8.1 × 104 m/s. The transient speed of the step jump was estimated to be larger than 7.3 × 105 m/s with an average step length of 4.9 m. The need of sufficient positive charge accumulation at the leader top could be the main cause for the stepping characteristics.
Luminosity progression in dart‐stepped leader step formation
Authors: Wang D. , Takagi N. , Uman M. A. , Jordan D. M.
Published: December 2016

Using a high‐speed optical imaging system, we have observed the step formation bright pulse discharges occurring at the tip of dart‐stepped leaders of rocket triggered lightning with a time resolution of 0.1 µs and a spatial resolution of about 1.4 m. Each of the step formation pulse discharges appeared to initiate at a location immediately below the bottom of its previous pulse discharge and to propagate in bidirectional (upward and downward) waves with a speed on the order of 107 m/s. The downward waves of the pulse discharges tended to slow down significantly after they propagated a distance of about 2 m. Based on the results observed in this study and those published in literatures, we propose a conceptual view of leader step formation.
Spatial patterns of erosion in a bedrock gorge
Authors: Beer Alexander. R. , Turowski Jens M. , Kirchner James W.
Published: December 2016

Understanding the physical processes driving bedrock channel formation is essential for interpreting and predicting the evolution of mountain landscapes. Here we analyze bedrock erosion patterns measured at unprecedented spatial resolution (mm) over 2 years in a natural bedrock gorge. These spatial patterns show that local bedrock erosion rates depend on position in the channel cross section, height above the streambed, and orientation relative to the main streamflow and sediment path. These observations are consistent with the expected spatial distribution of impacting particles (the tools effect) and shielding by sediment on the bed (the cover effect). Vertical incision by bedrock abrasion averaged 1.5 mm/a, lateral abrasion averaged 0.4 mm/a, and downstream directed abrasion of flow obstacles averaged 2.6 mm/a. However, a single plucking event locally exceeded these rates by orders of magnitude (∼100 mm/a), and accounted for one third of the eroded volume in the studied gorge section over the 2 year study period. Hence, if plucking is spatially more frequent than we observed in this study period, it may contribute substantially to long‐term erosion rates, even in the relatively massive bedrock at our study site. Our observations demonstrate the importance of bedrock channel morphology and the spatial distribution of moving and static sediment in determining local erosion rates.
A novel cytochrome P450, CYP3201B1, is involved in (R)‐mandelonitrile biosynthesis in a cyanogenic millipede
Authors: Yamaguchi Takuya , Kuwahara Yasumasa , Asano Yasuhisa
Published: December 2016

Specialized arthropods and more than 2500 plant species biosynthesize hydroxynitriles and release hydrogen cyanide as a defensive mechanism. The millipede Chamberlinius hualienensis accumulates (R)‐mandelonitrile as a cyanide precursor. Although biosynthesis of hydroxynitriles in cyanogenic plants and in an insect are extensively studied, (R)‐mandelonitrile biosynthesis in cyanogenic millipedes has remained unclear. In this study, we identified the biosynthetic precursors of (R)‐mandelonitrile and an enzyme involved in (R)‐mandelonitrile biosynthesis. Using deuterium‐labelled compounds, we revealed that (E/Z)‐phenylacetaldoxime and phenylacetonitrile are the biosynthetic precursors of (R)‐mandelonitrile in the millipede as well as other cyanogenic organisms. To identify the enzymes involved in (R)‐mandelonitrile biosynthesis, 50 cDNAs encoding cytochrome P450s were cloned and coexpressed with yeast cytochrome P450 reductase in yeast, as cytochrome P450s are involved in the biosynthesis of hydroxynitriles in other cyanogenic organisms. Among the 50 cytochrome P450s from the millipede, CYP3201B1 produced (R)‐mandelonitrile from phenylacetonitrile but not from (E/Z)‐phenylacetaldoxime, whereas plant and insect cytochrome P450s catalysed the dehydration of aldoximes and hydroxylation of nitriles. CYP3201B1 is not phylogenetically related to cytochrome P450s from other cyanogenic organisms, indicating that hydroxynitrile biosynthetic cytochrome P450s have independently evolved in distant species. Our study will shed light on the evolution of cyanogenesis among plants, insects and millipedes.

Database

Nucleotide sequence data are available in the DDBJ/EMBL/GenBank databases under the accession numbers LC125356–LC125405.
A Protein‐Nanocellulose Paper for Sensing Copper Ions at the Nano‐ to Micromolar Level
Authors: Weishaupt Ramon , Siqueira Gilberto , Schubert Mark , Kämpf Michael M. , Zimmermann Tanja , Maniura‐Weber Katharina , Faccio Greta
Published: December 2016

Tracing heavy metals is a crucial issue in both environmental and medical samples. In this work, a sensing biomolecule, the cyanobacterial C‐phycocyanin (CPC), is integrated into a nanocellulose matrix, and with this, a biosensor for copper ions is developed. The assembly of CPC‐functionalized nanocellulose into a red‐fluorescent, copper‐sensitive hybrid film “CySense”, enhances protein stability and facilitates the reuse and the regeneration of the sensor for several cycles over 7 days. CySense is suitable for the analysis of complex medical samples such as human serum filtrate. The reported biosensor reliably detects copper ion contents with a lower detection limit of 200 × 10−9mand an IC50 of 4.9 × 10−6mas changes in fluorescence emission intensity that can be measured with a fluorimeter or a microarray laser scanner.
High Voltage, Transition Metal Complex Enables Efficient Electrochemical Energy Storage in a Li‐Ion Battery Full Cell
Authors: Zheng Qi , Niu Zhihui , Ye Jing , Zhang Shun , Zhang Luwei , Li Lixing , Zhao Yu , Zhang Xiaohong
Published: December 2016

Efficient energy storage systems impact profoundly the renewable energy future. The performance of current electrical energy storage technologies falls well short of requirements for using electrical energy efficiently in transportation, commercial, and residential applications. This paper explores the possibility by using transition‐metal‐based complexes as active materials in a Li‐ion battery full cell that synergizes the concept of both lithium‐ion batteries and redox flow batteries. A cathode made from transition metal complex, [Fe(bpy)3](BF4)2, exhibits high discharge voltage approaching 4 V (vs Li/Li+). When coupled with a Li4Ti5O12 anode, the Li‐ion full battery exhibits a cell voltage exceeding 2.2 V and decent cycling efficiencies with Coulombic efficiency and energy/voltage efficiencies above 99% and 92%/93%, respectively. Such a Li‐ion battery full cell offers distinct features such as low cost and flexibility in molecular structure design. The result reveals a generic design route toward iron‐based complexes as cathode materials with good electrochemical performances.
An Inkjet‐Printed, Ultralow Voltage, Flexible Organic Field Effect Transistor
Authors: Conti Silvia , Lai Stefano , Cosseddu Piero , Bonfiglio Annalisa
Published: December 2016

A very simple procedure for fabricating inkjet‐printed organic field effect transistors (OFETs) is reported. A reliable process for the deposition of a thin and uniform polymeric dielectric film of poly(4‐vinylphenol) (PVP) is established as a key factor for obtaining high performance devices operating at low voltages. To this aim, ink formulations, printing parameters, and cross‐linking processes are investigated. Morphological characterization of the fabricated films by means of contact profilometry and atomic force micro­scopy is provided, as well as capacitive measurements proving ideal dielectric properties. OFET structures based on PVP gate dielectric are reported: in particular, inkjet‐printed devices operated at voltages below 1 V with remarkable transistor performances such as high charge carrier mobility and low subthreshold swing are presented.
Advanced Materials for Printed Wearable Electrochemical Devices: A Review
Authors: Kim Jayoung , Kumar Rajan , Bandodkar Amay J. , Wang Joseph
Published: December 2016

The field of printed wearable electronics has witnessed spectacular growth due to its promise to offer low‐cost, high‐performance devices for a broad range of applications. Among the sub‐fields of printed wearable electronics, printed wearable electrochemical systems are of special importance due to their widespread applications in healthcare, energy and security fields. These systems have opened up new avenues for body‐integrated electronics that were earlier impossible to achieve. These include wearable energy systems and sensors for a wide variety of applications. Much of the success of printed wearable electrochemical systems can be attributed to innovations in materials engineering that have led to novel inks comprising of new nanomaterials, polymers and composites. New generation of printed electrochemical devices include soft, stretchable and anatomically‐compliant devices that enable efficient bio‐integration and withstand high tensile stress associated with on‐body applications. Progress in materials science has also led to the development of self‐healing printed electrochemical systems for wearable applications. This review provides an overview of the key material requirements for ink formulations for realizing efficient wearable electrochemical systems such as batteries, supercapacitors, biofuel cells and sensors. Finally, major challenges impeding the field of wearable electrochemical systems are discussed along with future prospects of this exciting field.
Graphene/Fe3O4 Nanocomposites as Efficient Anodes to Boost the Lifetime and Current Output of Microbial Fuel Cells
Authors: Song Rong‐Bin , Zhao Cui‐e , Gai Pan‐Pan , Guo Dan , Jiang Li‐Ping , Zhang Qichun , Zhang Jian‐Rong , Zhu Jun‐Jie
Published: December 2016

The enhancement of microbial activity and electrocatalysis through the design of new anode materials is essential to develop microbial fuel cells (MFCs) with longer lifetimes and higher output. In this research, a novel anode material, graphene/Fe3O4 (G/Fe3O4) composite, has been designed for Shewanella‐inoculated MFCs. Because the Shewanella species could bind to Fe3O4 with high affinity and their growth could be supported by Fe3O4, the bacterial cells attached quickly onto the anode surface and their long‐term activity improved. As a result, MFCs with reduced startup time and improved stability were obtained. Additionally, the introduction of graphene not only provided a large surface area for bacterial attachment, but also offered high electrical conductivity to facilitate extracellular electron transfer (EET). The results showed that the current and power densities of a G/Fe3O4 anode were much higher than those of each individual component as an anode.
Improved control performance of the 3‐DoF aeroelastic wing section: a TP model based 2D parametric control performance optimization
Authors: Szollosi Alexandra , Baranyi Peter
Published: December 2016

Based on the most recent Tensor Product model transformation solutions, the paper presents an improved control performance for the most recent version of the three Degree of Freedom aeroelastic wing section model including Stribeck friction, according to signals pitch, plunge, trailing edge and control value, based on practical engineering criteria such as overshoot, undershoot, signal end values and settling time. This is achieved through proposing a novel two dimensional parametric convex hull manipulation based method for Tensor Product model transformation based Control Design Frameworks. The approach provides two TP model representations for the different requirements of the controller and observer of a given model, opening the possibility to utilize the TP model transformation's convex hull manipulation potential in control performance optimization for a separate optimization of the two TP model representations. Numerical simulation results are provided to illustrate the control performance improvements of the aeroelastic wing section model through the proposed 2D parametric convex hull manipulation based design method.
Puerarin offsets the anticoagulation effect of warfarin in rats by inducing rCyps, upregulating vitamin K epoxide reductase and inhibiting thrombomodulin
Authors: Ge Beikang , Zhang Zhen , Lam Teddy Taining , Zuo Zhong
Published: December 2016

Purpose

The current study was conducted to investigate the potential pharmacokinetic and pharmacodynamic interactions between warfarin and puerarin which is the most abundant component in Pueraria lobata (Gegen). In vivo and ex vivo rat models were used to reveal the underlying mechanisms of such interactions.

Methods

Apart from one control group, five groups of Sprague–Dawley rats were treated with warfarin, oral puerarin, oral puerarin with warfarin, intravenous puerarin, intravenous puerarin with warfarin. The treatment lasted for 5 consecutive days. Thereafter, the levels of warfarin, warfarin metabolites and puerarin in plasma of these rats were monitored and compared. The rCyps activity and expression in rat livers of different treatment groups were assessed. The prothrombin time was observed. The vitamin K epoxide reductase (VKOR) activity and expression in rat livers were evaluated. Thrombomodulin activity and expression in the rat lung and rat plasma were assessed. The soluble thrombomodulin (sTM) concentrations of different treatment groups were examined.

Results

Intravenously administered puerarin altered the pharmacokinetics of warfarin significantly by shortening t1/2, decreasing AUC0–96 h and increasing the clearance of warfarin. Further mechanistic studies suggested that both oral and intravenous administration of puerarin significantly induced the activities and expressions of rCyp2b1, rCyp2c6 and rCyp1a1. In addition, co‐administration of puerarin reduced the prothrombin time of rat plasma by enhancing VKOR and inhibiting thrombomodulin.

Conclusion

Puerarin increased warfarin metabolism and offset warfarin anticoagulation by inducing rCyps, upregulating VKOR and inhibiting thrombomodulin in rats. The clinical impact of such potential interactions warrants further verification. Copyright © 2016 John Wiley & Sons, Ltd.
A novel method for blood‐typing using nitrocellulose
Authors: Afshari Parastoo , Abolfathi Nabiollah
Published: December 2016

Blood wicking in its steady‐state form, i.e. the uniform distribution of blood cells in plasma, is completely different from that in its coagulated form on a porous surface like paper. The hydrophilic property of the cellulose leads to a significant wicking of the blood cells on paper fibers after rinsing with isotonic solution. The difference in the wicking length of the blood cells in steady state and that in the coagulated form could be considered as a criterion to recognize the blood type in a paper‐based kit. However, owing to the molecular structure of the nitrocellulose, a better process occurs while separating the coagulated blood from the steady‐state form of cells. Therefore, it is possible to use the nitrocellulose for the blood‐typing kit which leads to a simpler way to diagnose a blood type. Two series of experiments were performed on nitrocellulose membrane. First, antibody solutions and blood samples were sequentially absorbed on nitrocellulose strips, allowed to interact, rinsed with an isotonic solution and distilled water, and image processing performed on a digital picture of the remaining blood cells. The efficiency of the agglutinated blood cell fixation was quantified by red color intensity. Then, it was demonstrated that there is no considerable difference in fixation of agglutinated blood cells with rinsing using isotonic and nonisotonic solutions. This fact can be a considerable advantage over paper since it can eliminate the probable mistake from using unisotonic solution for rinsing. Second, owing to the nonwicking property of the blood cells on the hydrophobic nitrocellulose fibers, we employed another diagnostic criterion and investigated nitrocellulose blood‐typing prototypes. The nitrocellulose blood‐typing kit provides more simple, sensitive and trustworthy assay for rapid blood typing in situations with no access to laboratory facilities.
Relative tissue distribution and excretion studies of gastrodin and parishin from powder and extract of Gastrodiae Rhizoma in rat by UHPLC‐ESI‐MS/MS
Authors: Jiang Zhengmeng , Zheng Xiuyan , Gong Xiaojian , Zhao Chao , Zhou Xin , Zhao Yang , Yan Yanfang
Published: December 2016

New research has indicated that Gastrodiae Rhizome (GR) has potential anti‐diabetic and anti‐asthmatic effects in mouse models. On the basis of our previous study of the relative bioavailability of gastrodin (GAS) and parishin (PA) from extract and powder of GR, we performed further research on the tissue distribution and excretion of the two analytes. A reliable bioanalytical method for the quantification of GAS and PA in rat tissues and excretion is required. Chromatographic separation was carried out on a gradient mobile phase of acetonitrile–water with 0.1% formic acid. Calibration curves (1/x2 weighted) offered satisfactory linearity (r2 > 0.9835) within 100–3000 ng mL−1 for GAS and (r2 > 0.9862) within 10–1000 ng mL−1 for PA. The relative standard deviations of the intra‐day and inter‐day precision were all <14.98%, whilst the relative errors of the intra‐day and inter‐day accuracy were all within ±14.71%. The matrix effect and recovery values were satisfactory in all of the biological matrices examination. The data of relative differences in tissue distribution and excretion of GAS and PA from powder and extract of GR indicated that higher bioavailabilities for GAS and PA were obtained when a dosage of 4 g kg−1 GR powder was used.
Association of vitamin D status and clinical and radiological outcomes in a treated MS population in Poland
Authors: Wawrzyniak Sławomir , Mikołajewska Emilia , Kuczko‐Piekarska Ewelina , Niezgodzińska‐Maciejek Anna , Goch Aleksander
Published: December 2016

Background

Vitamin D influences the immune system significantly. Previous studies have found that vitamin D deficiency in adolescence can play a significant role in increasing the risk of developing autoimmune diseases including multiple sclerosis. The aim of this study was to investigate the relationship between the vitamin D status in serum and clinical and radiological outcomes in a treated population in Poland.

Methods

Inclusion criteria met 83 adult patients aged 20–61 years with diagnosis of relapsing‐remitting multiple sclerosis, who underwent immunomodulatory treatment which lasted at least 12 months. Levels of serum 25‐hydroxyvitamin D were determined using radio‐immuno assay. Magnetic resonance imaging of the brain and cervical part of a spinal cord was performed each time after 12 months of the treatment. Patients were assessed neurologically after 12 months of treatment, the level of disability was also assessed using Extended Disability Status Scale.

Results

The largest group (63.8%) showed significant vitamin D deficiency (<20 ng/ml), 21.7% showed the suboptimal level of vitamin D (20–30 ng/ml). The normal level of 25(OH)D (>30 ng/ml) was observed in 14.5% of the patients. Statistically significant correlation was observed between the vitamin D status and frequency of relapses.

Conclusions

Our findings confirm that deficiency of vitamin D in patients with MS is correlated with clinical and radiological course of the disease.
Asymmetric Catalytic Aza‐Diels–Alder/Ring‐Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis
Authors: Li Yang , Barløse Casper , Jørgensen Julie , Carlsen Bjørn Dreiø , Jørgensen Karl Anker
Published: December 2016

Invited for the cover of this issue is the group of Karl Anker Jørgensen at Aarhus University. The image depicts the basic reaction concept of the asymmetric catalytic aza‐Diels–Alder/ring‐closing cascade by the operation mode of a zipper. The two molecules (red 2,4‐dienal; blue hydrazone) in this reaction are mosaicked into the two chains of the zipper. The chiral slider, the diarylprolinol‐silyl ether catalyst, zips together the two molecules by sliding the hand down the chains forming the bicyclic aza‐heterocyclic products in a highly stereoselective manner. Read the full text of the article at 10.1002/chem.201604310.
A prospective, multicenter cohort study to validate a simple performance status–based survival prediction system for oncologists
Authors: Yamada Takeshi , Morita Tatsuya , Maeda Isseki , Inoue Satoshi , Ikenaga Masayuki , Matsumoto Yoshihisa , Baba Mika , Sekine Ryuichi , Yamaguchi Takashi , Hirohashi Takeshi , Tajima Tsukasa , Tatara Ryohei , Watanabe Hiroaki , Otani Hiroyuki , Takigawa Chizuko , Matsuda Yoshinobu , Ono Shigeki , Ozawa Taketoshi , Yamamoto Ryo , Shishido Hideki , Yamamoto Naoki
Published: December 2016

BACKGROUND

Survival prediction systems such as the Palliative Prognostic Index (PPI), which includes the Palliative Performance Scale (PPS), are used to estimate survival for terminally ill patients. Oncologists are, however, less familiar with the PPS in comparison with the Eastern Cooperative Oncology Group (ECOG) performance status (PS). This study was designed to validate a simple survival prediction system for oncologists, the Performance Status–Based Palliative Prognostic Index (PS‐PPI), which is a modified form of the PPI based on the ECOG PS.

METHODS

This multicenter, prospective cohort study enrolled all consecutive patients who were referred to 58 palliative care services in Japan. The primary responsible physicians rated the variables required to calculate the PS‐PPI and the PPI. Patient survival in these risk groups was compared, and the sensitivity and specificity of the PS‐PPI and the PPI were evaluated. Patients were subclassified as patients receiving care from in‐hospital palliative care teams, palliative care units, or home‐based palliative care services. Subsets of patients receiving chemotherapy were also analyzed.

RESULTS

This study included 2346 patients. Survival predictions based on the PPI and the PS‐PPI differed significantly among the 3 risk groups (P < .001). The PS‐PPI was more sensitive, whereas the PPI was more specific. All areas under the receiver operating characteristic curves of both indices were >0.78 for predicting survival at all times, from 3 weeks to 180 days.

CONCLUSIONS

In predicting the prognosis of patients with advanced cancer, the PS‐PPI was as accurate as the PPI. The PS‐PPI was useful for short‐ and long‐term survival prediction and for the prediction of survival for patients undergoing chemotherapy. Cancer 2017;123:1442–1452. © 2016 American Cancer Society.
Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach
Authors: Oregui‐Bengoechea Mikel , Gandarias Inaki , Arias Pedro L. , Barth Tanja
Published: December 2016

The role of formic acid together with the effect of the solvent type and their synergic interactions with a NiMo catalyst were studied for the conversion of lignin into bio‐oil in an alcohol/formic acid media. The replacement of formic acid with H2 or isopropanol decreased the oil yield to a considerable degree, increased the solid yield, and altered the nature of the bio‐oil. The differences induced by the presence of H2 were comparable to those observed in the isopropanol system, which suggests similar lignin conversion mechanisms for both systems. Additional semi‐batch experiments confirmed that formic acid does not act merely as an in situ hydrogen source or hydrogen donor molecule. Actually, is seems to react with lignin through a formylation–elimination–hydrogenolysis mechanism that leads to the depolymerization of the biopolymer. This reaction competes with formic acid decomposition, which gives mainly H2 and CO2, and forms a complex reaction system. To the best of our knowledge, this is the first time that the distinctive role/mechanism of formic acid has been observed in the conversion of real lignin feedstock. In addition, the solvent, especially ethanol, seems also to play a vital role in the stabilization of the depolymerized monomers and in the elimination/deformylation step.
Heterogeneously‐Catalyzed Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid with MnO2
Authors: Hayashi Eri , Komanoya Tasuku , Kamata Keigo , Hara Michikazu
Published: December 2016

A simple non‐precious‐metal catalyst system based on costeffective and ubiquitously available MnO2, NaHCO3, and molecular oxygen was used to convert 5‐hydroxymethylfurfural (HMF) to 2,5‐difurandicarboxylic acid (FDCA) as a bioplastics precursor in 91 % yield. The MnO2 catalyst could be recovered by simple filtration and reused several times. The present system was also applicable to the aerobic oxidation of other biomass‐derived substrates and the gram‐scale oxidation of HMF to FDCA, in which 2.36 g (86 % yield) of the analytically pure FDCA could be isolated.
Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study
Authors: Boyaval Amélie , Méreau Raphaël , Grignard Bruno , Detrembleur Christophe , Jerome Christine , Tassaing Thierry
Published: December 2016

The metal‐free coupling of a propargylic alcohol with CO2 catalysed by guanidine derivatives was investigated in detail through the combination of online kinetic studies by in situ attenuated‐total reflection IR (ATR–IR) spectroscopy and DFT calculations. Bicyclic guanidines, namely 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) and 7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) are effective catalysts for the conversion of 2‐methyl‐3‐butyn‐2‐ol to α‐methylene cyclic carbonate and oxoalkyl acyclic carbonate under mild reaction conditions. The lower selectivity of TBD in comparison with MTBD towards the formation of α‐methylene cyclic carbonate was elucidated from DFT calculations and is related to the bifunctional activity (base/H‐bond donor) of TBD decreasing the Gibbs free energy of the reaction path for the formation of the acyclic carbonate.
Mechanism of Water Oxidation Catalyzed by a Mononuclear Manganese Complex
Authors: Li Ying‐Ying , Ye Ke , Siegbahn Per E. M. , Liao Rong‐Zhen
Published: December 2016

The design and synthesis of biomimetic Mn complexes to catalyze oxygen evolution is a very appealing goal because water oxidation in nature employs a Mn complex. Recently, the mononuclear Mn complex [LMnII(H2O)2]2+ [1, L=Py2N(tBu)2, Py=pyridyl] was reported to catalyze water oxidation electrochemically at an applied potential of 1.23 V at pH 12.2 in aqueous solution. Density functional calculations were performed to elucidate the mechanism of water oxidation promoted by this catalyst. The calculations showed that 1 can lose two protons and one electron readily to produce [LMnIII(OH)2]+ (2), which then undergoes two sequential proton‐coupled electron‐transfer processes to afford [LMnVOO]+ (4). The O−O bond formation can occur through direct coupling of the two oxido ligands or through nucleophilic attack of water. These two mechanisms have similar barriers of approximately 17 kcal mol−1. The further oxidation of 4 to generate [LMnVIOO]2+ (5), which enables O−O bond formation, has a much higher barrier. In addition, ligand degradation by C−H activation has a similar barrier to that for the O−O bond formation, and this explains the relatively low turnover number of this catalyst.
Pro‐B cells propagated in stromal cell‐free cultures reconstitute functional B‐cell compartments in immunodeficient mice
Authors: von Muenchow Lilly , Tsapogas Panagiotis , Albertí‐Servera Llucia , Capoferri Giuseppina , Doelz Marianne , Rolink Hannie , Bosco Nabil , Ceredig Rhodri , Rolink Antonius G.
Published: December 2016

Up to now long‐term in vitro growth of pro‐B cells was thought to require stromal cells. However, here we show that fetal liver (FL) and bone marrow (BM) derived pro‐B cells can be propagated long‐term in stromal cell‐free cultures supplemented with IL‐7, stem cell factor and FLT3 ligand. Within a week, most cells expressed surface CD19, CD79A, λ5, and VpreB antigens and had rearranged immunoglobulin D‐J heavy chain genes. Both FL and BM pro‐B cells reconstituted the B‐cell compartments of immuno‐incompetent Rag2‐deficient mice, with FL pro‐B cells generating follicular, marginal zone (MZB) and B1a B cells, and BM pro‐B cells giving rise mainly to MZB cells. Reconstituted Rag2‐deficient mice generated significant levels of IgM and IgG antibodies to a type II T‐independent antigen; mice reconstituted with FL pro‐B cells generated surprisingly high IgG1 titers. Finally, we show for the first time that mice reconstituted with mixtures of pro‐B and pro‐T cells propagated in stromal cell‐free in vitro cultures mounted a T‐cell‐dependent antibody response. This novel stromal cell‐free culture system facilitates our understanding of B‐cell development and might be applied clinically.
Primary and secondary hemophagocytic lymphohistiocytosis have different patterns of T‐cell activation, differentiation and repertoire
Authors: Ammann Sandra , Lehmberg Kai , zur Stadt Udo , Janka Gritta , Rensing‐Ehl Anne , Klemann Christian , Heeg Maximilian , Bode Sebastian , Fuchs Ilka , Ehl Stephan ,   for the HLH study of the GPOH
Published: December 2016

Hemophagocytic lymphohistiocytosis (HLH) is a life‐threatening inflammatory syndrome characterized by hyperactivation of lymphocytes and histiocytes. T cells play a key role in HLH pathogenesis, but their differentiation pattern is not well characterized in patients with active HLH. We compared T‐cell activation patterns between patients with familial HLH (1°HLH), 2°HLH without apparent infectious trigger (2°HLH) and 2°HLH induced by a viral infection (2°V‐HLH). Polyclonal CD8+ T cells are highly activated in 1°HLH and 2°V‐HLH, but less in 2°HLH as assessed by HLA‐DR expression and marker combination with CD45RA, CCR7, CD127, PD‐1 and CD57. Absence of increased HLA‐DR expression on T cells excluded active 1° HLH with high sensitivity and specificity. A high proportion of polyclonal CD127−CD4+ T cells expressing HLA‐DR, CD57, and perforin is a signature of infants with 1°HLH, much less prominent in virus‐associated 2°HLH. The similar pattern and extent of CD8+ T‐cell activation compared to 2° V‐HLH is compatible with a viral trigger of 1°HLH. However, in most 1°HLH patients no triggering infection was documented and the unique activation of cytotoxic CD4+ T cells indicates that the overall T‐cell response in 1°HLH is different. This may reflect different pathways of pathogenesis of these two HLH variants.
Synthesis of Thiazolidine‐2‐thiones through a One‐Pot A3‐Coupling–Carbon Disulfide Incorporation Process
Authors: Nechaev Anton A. , Peshkov Anatoly A. , Van Hecke Kristof , Peshkov Vsevolod A. , Van der Eycken Erik V.
Published: December 2016

A copper‐catalyzed two‐step one‐pot procedure for the synthesis of thiazolidine‐2‐thiones has been developed. The process involves a three‐component coupling of an alkyne, an aldehyde, and an amine (A3‐coupling) followed by trapping the resulting propargylamine with carbon disulfide and subsequent cyclization.
Hybrid Perovskite Photovoltaic Devices: Properties, Architecture, and Fabrication Methods
Authors: Al‐Dainy Gailan A. , Bourdo Shawn E. , Saini Viney , Berry Brian C. , Biris Alexandru S.
Published: December 2016

As the need for green energy increases, particularly solar energy, perovskite‐based devices have become a promising alternative to more complex, costly semiconductor‐based photovoltaic devices. The major advantage of perovskite‐based devices is their relatively facile fabrication as a thin film at fairly low temperatures and their tunable optoelectronic properties. The chemical composition of perovskite structures, solvent and heat treatments used in processing, additives, and deposition methods produce films with different morphologies. Their ability to be used with other organic and inorganic subcells makes them a useful component for an efficient, cost‐effective approach to harvest solar energy. This review presents some of the latest approaches and considerations for the fabrication, architecture, and performance of perovskite‐based solar cells. Various perovskite device architectures are discussed, as well as the effects of environmental conditions on performance and degradation.
Analysis of community-level mesocosm data based on ecologically meaningful dissimilarity measures and data transformation
Authors: Tebby Cleo , Joachim Sandrine , Van den Brink Paul J. , Porcher Jean-Marc , Beaudouin Rémy
Published: December 2016

The principal response curve (PRC) method is a constrained ordination method developed specifically for the analysis of community data collected in mesocosm experiments, which provides easily understood summaries and graphical representations of community response to stress. It is a redundancy analysis method and is usually performed on log-transformed abundance data. The choice of a measure of dissimilarity between samples and the choice of the data transformation significantly affect the results of multivariate analysis. Dissimilarity measures that are more ecologically meaningful than the Euclidean distance can be incorporated into the PRC using distance-based redundancy analysis. The present study investigates the ordinations produced by a small selection of dissimilarity measures: the Euclidean distance using log-transformed and Hellinger-transformed data and the Bray-Curtis dissimilarity using raw and log-transformed data. It compares 2 data sets from experiments on the effect of the anti-inflammatory drug diclofenac and the insecticide chlorpyrifos on macroinvertebrate communities. The choice of dissimilarity measure can determine the outcome of a risk assessment. For the diclofenac data set, the PRCs were different depending on the dissimilarity measure: the community no-effect concentration was lowest for the Bray-Curtis on log-transformed data and Hellinger dissimilarity measures. For chlorpyrifos, however, the PRCs were similar for all dissimilarity measures. Environ Toxicol Chem 2017;36:1667–1679. © 2016 SETAC
Effect of natural organic matter on the photo-induced toxicity of titanium dioxide nanoparticles
Authors: Wormington Alexis M. , Coral Jason , Alloy Matthew M. , Delmarè Carmen L. , Mansfield Charles M. , Klaine Stephen J. , Bisesi Joseph H. , Roberts Aaron P.
Published: December 2016

Nano-titanium dioxide (TiO2) is the most widely used form of nanoparticles in commercial industry and comes in 2 main configurations: rutile and anatase. Rutile TiO2 is used in ultraviolet (UV) screening applications, whereas anatase TiO2 crystals have a surface defect that makes them photoreactive. There are numerous reports in the literature of photo-induced toxicity to aquatic organisms following coexposure to anatase nano-TiO2 and UV. All natural freshwater contains varying amounts of natural organic matter (NOM), which can drive UV attenuation and quench reactive oxygen species (ROS) in aquatic ecosystems. The present research examined how NOM alters the photo-induced toxicity of anatase nano-TiO2. Daphnia magna neonates were coexposed to NOM and photoexcited anatase nano-TiO2 for 48 h. Natural organic matter concentrations as low as 4 mg/L reduced anatase nano-TiO2 toxicity by nearly 100%. These concentrations of NOM attenuated UV by <10% in the exposure system. However, ROS production measured using a fluorescence assay was significantly reduced in a NOM concentration­–dependent manner. Taken together, these data suggest that NOM reduces anatase nano-TiO2 toxicity via an ROS quenching mechanism and not by attenuation of UV. Environ Toxicol Chem 2017;36:1661–1666. © 2016 SETAC
Life-cycle exposure of fathead minnows to environmentally relevant concentrations of the β-blocker drug propranolol
Authors: Parrott Joanne L. , Balakrishnan Vimal K.
Published: December 2016

Propranolol is a human pharmaceutical β-blocker that has been detected in municipal wastewater effluents at ng/L to low μg/L. To assess the potential of this compound to affect fish, fathead minnow (Pimephales promelas) were exposed for a life cycle in a flow-through system to nominal propranolol concentrations of 0.87 ng/L, 8.7 ng/L, 87 ng/L, 870 ng/L, and 8700 ng/L. Measured propranolol concentrations were below detection for the 2 lowest exposure concentrations, and were 76 ng/L, 580 ng/L, and 7800 ng/L for the 3 highest exposure concentrations. During the 162-d to 165-d exposure, no significant changes in weights or lengths were seen in fathead minnows, although the highest concentration of propranolol did cause a 15% decrease in survival of larval and juvenile stage fish compared with controls. At maturity, there were no significant changes in condition factor, liver-somatic index, or secondary sex characteristics in propranolol-exposed male or female fish. Female gonadosomatic index was significantly decreased in fish exposed to the highest concentrations of propranolol, probably because of increased egg-laying. Fathead minnows from all propranolol exposures produced more eggs than control fish, with fish exposed to 7800 ng/L propranolol producing 70% more eggs per female (p = 0.060), and having significantly increased clutch size (p = 0.008). Egg quality, % fertilization, % hatching, and % deformities in F1 fry were unaffected by propranolol exposure of fish. Propranolol exposure caused no effects in fathead minnows, except at the highest exposure concentration (7800 ng/L), where there were slight decreases in survival of juvenile minnows, and indications of increased reproduction. The present study is important because it is the first to assess the potential for effects in fish exposed to propranolol for a life cycle. Environ Toxicol Chem 2017;36:1644–1651. © 2016 SETAC
Microemulsions enhance the shelf‐life and processability of Smyrnium olusatrum L. essential oil
Authors: Cespi Marco , Quassinti Luana , Perinelli Diego Romano , Bramucci Massimo , Iannarelli Romilde , Papa Fabrizio , Ricciutelli Massimo , Bonacucina Giulia , Palmieri Giovanni Filippo , Maggi Filippo
Published: December 2016

Smyrnium olusatrum L. is a horticultural crop cultivated during the Roman age for culinary and curative uses. The essential oil extracted from this plant (AEO) is rich in bioactive constituents such as isofuranodiene and germacrone. Several previous studies revealed that AEO and its isolated components possess interesting therapeutic features, such as antiproliferative, neuritogenic, hepatoprotective and antioxidant properties. Nevertheless, AEO has stability problems because of the high concentration of its main components. This issue makes AEO very difficult to handle and use. Thus, AEO was formulated as microemulsions known for their thermodynamic stability and easiness of preparation. AEO was hydrodistilled from inflorescences of S. olusatrum and its composition determined by different chromatographic methods. The microemulsions were developed using a central composite design and their activity tested using the MTT assay. The present study demonstrated the possibility to formulate stable AEO microemulsions where the crystallization of isofuranodiene is avoided, and the AEO biological activity is maintained. Copyright © 2016 John Wiley & Sons, Ltd.
The miRNA landscape of colorectal polyps
Authors: Slattery Martha L. , Herrick Jennifer S. , Wolff Roger K. , Mullany Lila E. , Stevens John R. , Samowitz Wade
Published: December 2016

The genomic landscape of adenomas and polyps may help define disease pathways. Expression of miRNAs in adenomas and polyps may importantly contribute to these pathways. We evaluated miRNA expression in 293 polyp‐normal colorectal mucosa pairs. Polyps were classified as either adenomatous polyp (AD), hyperplastic polyp (HP), or sessile serrated polyp (SSP). We compared these miRNA expression profiles in polyps to miRNA expression in microsatellite unstable (MSI) and stable (MSS) tumors. A False Discovery Rate of 0.05 based on Benjamini and Hochberg was used to adjust for multiple comparisons. There were 70 miRNAs with differential expression by polyp type with a fold change <0.75 or >1.34 after adjusting for multiple comparisons. The major differences in miRNA expression were observed between AD and SSP and AD and HP, with few differences in expression noted for SSP and HP. AD polyps were more likely to be upregulated from normal colonic mucosa, while SSP and HP were more likely to be downregulated from normal colonic mucosa. MiRNA expression in the SSP and HP tumors almost uniformly go in opposite directions from the MSS tumor miRNA expression and was mixed with MSI tumors. We conclude that different types of polyps have unique miRNA expression profiles. © 2017 Wiley Periodicals, Inc.
Heating and Flow Analysis in Hot‐Rolled Stainless Strip Continuous Annealing Furnace Based on CFD Modeling
Authors: Su Fuyong
Published: December 2016

A three‐dimensional mathematical model was found for a continuous annealing furnace, the temperature field, and flow field of the furnace and the temperature of the stainless strip could be calculated by using this model. The simulation results were compared with measured data and the accuracy of the model was proved by the predicted temperature distribution. By using this model, the convective heat transfer coefficient and equivalent radiation heat transfer coefficient of the strip surface were also analyzed.
Effects of temperature on multiparametric evaluation of hindlimb ischemia with dynamic fluorescence imaging
Authors: Cai Wenjuan , Guang Huizhi , Cai Chuangjian , Luo Jianwen
Published: December 2016

Quantitative evaluation of hindlimb ischemia is essential for early diagnosis and therapy of peripheral arterial disease (PAD). Dynamic imaging using near‐infrared (NIR) fluorophore indocyanine green (ICG) is a noninvasive and effective tool to monitor multiple vascular parameters including perfusion rate (PR), perfusion vascular density (PVD) and hemodynamics. It has been previously demonstrated that temperature changes could lead to significant variations of blood flow rate and vascular perfusion. In this paper, multiparametric evaluation of hindlimb ischemia was performed at different temperatures. Five different parameters were extracted from dynamic fluorescence imaging, including PR, PVD, rising time (Trise), blood flow index (BFI) and mean fluorescence intensity (MFI). Temperatures varied from 15 °C to 40 °C were set on a mouse model of hindlimb ischemia. The aforementioned five parameters were obtained at each temperature. The results suggest that PVD, BFI and MFI could be effective indicators to distinguish ischemic tissues from normal tissues in mouse hindlimb at different temperatures. In contrast, PR is effective only when the temperature is higher than 25 °C, while Trise is effective only when the temperature is lower than 35 °C. The parameters of PVD, BFI and MFI could provide quantitative and comprehensive evaluation for PAD at different temperatures.

(A) Bright‐field image of the normal (left) and ischemic (right) hindlimbs. (B–D) Parametric images of perfusion vascular density, blood flow index and mean fluorescence intensity.

magnified image

(A) Bright‐field image of the normal (left) and ischemic (right) hindlimbs. (B–D) Parametric images of perfusion vascular density, blood flow index and mean fluorescence intensity.