bluuebunny/crossref_metadata_2025 huggingface dataset:
Near‐inertial kinetic energy budget of the mixed layer and shear evolution in the transition layer in the Arabian Sea during the monsoons
Authors: Majumder Sudip , Tandon Amit , Rudnick Daniel L. , Thomas Farrar J.
Published: September 2015

We present the horizontal kinetic energy (KE) balance of near‐inertial currents in the mixed layer and explain shear evolution in the transition layer using observations from a mooring at 15.26° N in the Arabian Sea during the southwest monsoon. The highly sheared and stratified transition layer at the mixed‐layer base varies between 5 m and 35 m and correlates negatively with the wind stress. Results from the mixed layer near‐inertial KE (NIKE) balance suggest that wind energy at times can energize the transition layer and at other times is fully utilized within the mixed layer. A simple two layer model is utilized to study the shear evolution in the transition layer and shown to match well with observations. The shear production in this model arises from alignment of wind stress and shear. Although the winds are unidirectional during the monsoon, the shear in the transition layer is predominantly near‐inertial. The near‐inertial shear bursts in the observations show the same phasing and magnitude at near‐inertial frequencies as the wind‐shear alignment term.
Evidence for a new geomagnetic jerk in 2014
Authors: Torta J. Miquel , Pavón‐Carrasco F. Javier , Marsal Santiago , Finlay Christopher C.
Published: September 2015

The production of quasi‐definitive data at Ebre observatory has enabled us to detect a new geomagnetic jerk in early 2014. This has been confirmed by analyzing data at several observatories in the European‐African and Western Pacific‐Australian sectors in the classical fashion of looking for the characteristic V shape of the geomagnetic secular variation trend. A global model produced with the latest available satellite and observatory data supports these findings, giving a global perspective on both the jerk and a related secular acceleration pulse at the core‐mantle boundary. We conclude that the jerk was most visible in the Atlantic and European sectors.
Shelf response to intense offshore wind
Authors: Grifoll Manel , Aretxabaleta Alfredo L. , Espino Manuel
Published: September 2015

Cross and along‐shelf winds drive cross‐shelf transport that promotes the exchange of tracers and nutrients to the open sea. The shelf response to cross‐shelf winds is studied in the north shelf of the Ebro Delta (Mediterranean Sea), where those winds are prevalent and intense. Offshore winds in the region exhibit strong intensities (wind stress larger than 0.8 Pa) during winter and fall. The monthly average flow observed in a 1 year current meter record at 43.5 m was polarized following the isobaths with the along‐shelf variability being larger than the cross‐shelf. Prevalent southwestward along‐shelf flow was induced by the three‐dimensional regional response to cross‐shelf winds and the coastal constraint. Seaward near‐surface velocities occurred predominantly during offshore wind events. During intense wind periods, the surface cross‐shelf water transport exceeded the net along‐shelf transport. During typically stratified seasons, the intense cross‐shelf winds resulted in a well‐defined two‐layer flow and were more effective at driving offshore transport than during unstratified conditions. While transfer coefficients between wind and currents were generally around 1%, higher cross‐shelf transfer coefficients were observed in the near‐inertial band. The regional extent of the resulting surface cold water during energetic cross‐shelf winds events was concentrated around the region of the wind jet. Cross‐shelf transport due to along‐shelf winds was only effective during northeast wind events. During along‐shelf wind conditions, the transport was estimated to be between 10 and 50% of the theoretical Ekman transport.
Source regions and reflection of infragravity waves offshore of the U.S.s Pacific Northwest
Authors: Neale Jennifer , Harmon Nicholas , Srokosz Meric
Published: September 2015

Infragravity waves are oceanic surface gravity waves but with wavelengths (tens of km) and periods (>30 s) much longer than wind waves and swell. Mostly studied in shallow water, knowledge of infragravity waves in deep water has remained limited. Recent interest in deep water infragravity waves has been motivated by the error they may contribute to future high‐resolution satellite radar altimetry measurements of sea level. Here deep water infragravity waves offshore of the Pacific Northwest of the U.S. were studied using differential pressure gauges which were deployed as part of the Cascadia Initiative array from September 2012 to May 2013. Cross correlation of the records revealed direction of infragravity wave propagation across the array, from which source regions were inferred. The dominant source was found to be the coastline to the east, associated with large wind waves and swell incident on the eastern side of the basin. The source shifted southward during northern‐hemisphere summer, and on several days in the record infragravity waves arrived from the western side of the Pacific. Asymmetry of cross‐correlation functions for five of these westerly arrivals was used to calculate the ratio of seaward to shoreward propagating energy, and hence estimate the strength of infragravity wave reflection at periods of 100–200 s. Reflection of these remote arrivals from the west appeared to be strong, with a lower bound estimate of r = 0.49 ± 0.29 (reflection coefficient ± standard error) and an upper bound estimate of r = 0.74 ± 0.06. These results suggest that reflection at ocean boundaries may be an important consideration for infragravity waves in the deep ocean.
Association of Body Mass Index With Incidence and Progression of Knee Effusion on Magnetic Resonance Imaging and on Knee Examination
Authors: Hung Amy , Sayre Eric C. , Guermazi Ali , Esdaile John M. , Kopec Jacek A. , Thorne Anona , Singer Joel , Wong Hubert , Nicolaou Savvas , Cibere Jolanda
Published: September 2015

Objective

To determine the association of body mass index (BMI) with incidence and progression of knee effusion on magnetic resonance imaging (MRI) and physical examination (PE) in a longitudinal cohort with knee pain.

Methods

A population‐based cohort was assessed at baseline and 3 years (n = 163). BMI was categorized as normal (<25), overweight (25–29.9), and obese (≥30). Knee effusion was graded as 0–3 (absent/mild/moderate/severe) on MRI and 0–1 (absent/present) on PE. Progression of MRI effusion (MRIeff) was an increase of ≥1 grade in those with grade 1 or 2 at baseline. Incident MRIeff and PE effusion (PEeff) were any effusion at followup (>0) in those with grade 0 at baseline. A second type of incident MRIeff was effusion grade ≥2 at followup in those with grade <2 at baseline. Exponential regression analysis was used, adjusted for age, sex, and radiographic severity.

Results

Incident MRIeff ≥1, incident MRIeff ≥2, incident PEeff, and progression of MRIeff were seen in 14 of 73 (19%), 18 of 140 (13%), 26 of 127 (20%), and 18 of 86 (21%), respectively. There was a borderline statistical association of obesity with progression of MRIeff (hazard ratio [HR] 3.3 [95% confidence interval (95% CI) 1.0–11.2]) and with incident MRIeff ≥2 (HR 3.4 [95% CI 1.0–11.5]). BMI was not associated with incident MRIeff ≥1 (HR overweight 1.1 [95% CI 0.3–3.6], obese 1.0 [95% CI 0.2–5.0]). Overweight was associated with incident PEeff (HR 4.5 [95% CI 1.4–14.2]), while obesity was not statistically significant (HR 3.1 [95% CI 0.9–11.1]).

Conclusion

Obesity was a risk factor for incident and progressive knee effusion in this population‐based cohort. These findings highlight an important link between obesity and inflammation in knee osteoarthritis.
Solid‐State Approach for Fabrication of Photostable, Oxygen‐Doped Carbon Nanotubes
Authors: Ma Xuedan , Baldwin Jon K. S. , Hartmann Nicolai F. , Doorn Stephen K. , Htoon Han
Published: September 2015

A novel procedure for effective fabrication of photostable oxygen‐doped single‐walled carbon nanotubes (SWCNTs) in solid‐state matrices has been developed. SWCNTs drop‐cast on various types of substrates are coated with oxide dielectric thin films by electron‐beam evaporation. Single tube photoluminescence spectroscopy studies performed at room and cryogenic temperatures reveal that such thin film‐coated tubes exhibit characteristic spectral features of oxygen‐doped SWCNTs, indicating the oxide thin film coating process leads to oxygen doping of the tubes. It is also found that the doping efficiency can be effectively controlled by the thin film deposition time and by the types of surfactants wrapping the SWCNTs. Moreover, aside from being the doping agent, the oxide thin film also serves as a passivation layer protecting the SWCNTs from the external environment. Comparing the thin film coated SWCNTs with oxygen‐doped tubes prepared via ozonolysis, the former exhibit significantly higher photostability and photoluminescence on‐time. Therefore, this one‐step deposition/oxygen‐doping procedure provides a possible route toward scalable, versatile incorporation of highly photostable oxygen‐doped SWCNTs in novel optical and optoelectronic devices.
Supramolecular Chemistry in Molten Sulfur: Preorganization Effects Leading to Marked Enhancement of Carbon Nitride Photoelectrochemistry
Authors: Xu Jingsan , Cao Shaowen , Brenner Thomas , Yang Xiaofei , Yu Jiaguo , Antonietti Markus , Shalom Menny
Published: September 2015

Here, a new method for enhancing the photoelectrochemical properties of carbon nitride thin films by in situ supramolecular‐driven preorganization of phenyl‐contained monomers in molten sulfur is reported. A detailed analysis of the chemical and photophysical properties suggests that the molten sulfur can texture the growth and induce more effective integration of phenyl groups into the carbon nitride electrodes, resulting in extended light absorption alongside with improved conductivity and better charge transfer. Furthermore, photophysical measurements indicate the formation of sub‐bands in the optical bandgap which is beneficial for exciton splitting. Moreover, the new bands can mediate hole transfer to the electrolyte, thus improving the photooxidation activity. The utilization of high temperature solvent as the polymerization medium opens new opportunities for the significant improvement of carbon nitride films toward an efficient photoactive material for various applications.
Potassium tert‐Butoxide‐Mediated Amine Acyl Exchange Reaction of N,N‐Disubstituted Formamides with Aromatic Carbonyl Derivatives via Sequential CN Bond Cleavage/Formation: an Approach to Aromatic Amides
Authors: Zhang Ming‐Zhong , Guo Qing‐Hu , Sheng Wen‐Bing , Guo Can‐Cheng
Published: September 2015

A novel potassium tert‐butoxide‐mediated amine acyl exchange of N,N‐disubstituted formamides with aromatic carbonyl derivatives in a sequential CN bond cleavage/formation process leading to aromatic amides is described. This methodology tolerates a wide range of aromatic carbonyl compounds, including aromatic aldehydes, acyl chlorides, unactivated esters, and acid anhydrides. The usage of inexpensive and readily available reagents, broad substrate scope, and the simple, mild (50 °C) and transition metal‐free conditions make this protocol very practical. In addition, a plausible reaction mechanism is proposed on the basis of experimental observations.

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Effect of Organic–Inorganic Hybrid Nanoparticles (POSS–PEG(n = 4)) on Thermal, Mechanical, and Electrical Properties of PEO‐Based Solid Polymer Electrolytes
Authors: Polu Anji Reddy , Rhee Hee‐Woo
Published: September 2015

Adding organic–inorganic hybrid nanoparticles is a potential way to enhance room temperature ionic conductivity and mechanical strength of solid polymer electrolytes (SPEs). In this work, a new nanocomposite solid polymer electrolyte (NSPE) based on poly(ethylene oxide)–lithium bis(trifluoromethane sulfonyl) imide (PEO12–LiTFSI) incorporating polyhedral oligomeric silsesquioxane–poly(ethylene glycol) (POSS–PEG(n = 4)) hybrid nanoparticles has been prepared and reported the effect of POSS–PEG(n = 4) hybrid nanoparticles on thermal, mechanical, and electrical properties of (PEO12–LiTFSI) SPE. Results from X‐ray diffraction and differential scanning calorimetry studies indicated that the conductivity increase was due to the decrease in crystallinity upon the addition of lithium salt and POSS–PEG hybrid nanoparticles into the SPE system. The mechanical properties of PEO12–LiTFSI SPE tended to increase with the addition of POSS–PEG(n = 4) nanoparticles up to 10 wt% and decreased afterwards. The NSPEs having solid state show quite high ionic conductivity (1.45 × 10−4 S/cm at 30°C), which is about 7.44 times of magnitude larger than that of the matrix polymer (PEO12–LiTFSI) electrolyte (1.95 × 10−5 S/cm at 30°C).
Optimal flowsheet configuration of a polymerization process with embedded molecular weight distributions
Authors: Zhang Chen , Shao Zhijiang , Chen Xi , Gu Xueping , Feng Lianfang , Biegler Lorenz T.
Published: September 2015

We consider the optimal reactor network synthesis of a polymerization process with detailed molecular weight distributions (MWDs). Based on an industrial high‐density polyethylene (HDPE) slurry process model including an embedded MWD, a fully connected process superstructure of continuous stirred tank reactors (CSTRs) is established through the introduction of splitters. Using this generalized superstructure as a basis, two nonlinear programming (NLP) problem formulations, which simultaneously maximize the monomer conversion and minimize the deviation between the calculated and target MWDs, are developed by applying multiobjective optimization (MO) methods. Different optimal flowsheet configurations are generated by systematically manipulating a set of continuous decision variables. Several case studies that consider different specifications on MWD are conducted to illustrate the effectiveness and efficiency of the proposed synthesis approach. Numerical results show that the optimal flowsheet configurations overcome the limitations of conventional reactor network structures and help to increase reactor productivity at the desired product quality. © 2015 American Institute of Chemical Engineers AIChE J, 62: 131–145, 2016
A novel framework for integrating data mining with control loop performance assessment
Authors: Das Laya , Srinivasan Babji , Rengaswamy Raghunathan
Published: September 2015

Data driven control loop performance assessment techniques assume that the data being analyzed correspond to single plant‐controller configuration. However, in an industrial setting where processes are affected due to the presence of feedstock variability and drifts, the plant‐controller configuration changes with time. Also, user‐defined benchmarking of control loops (common in industrial plants) requires that the data corresponding to optimal operation of the controller be known. However, such information might not be available beforehand in which case it is necessary to extract the same from routine plant operating data. A technique that addresses these fundamental requirements for ensuring reliable performance assessment is proposed. The proposed technique performs a recursive binary segmentation of the data and makes use of the fact that changes in controller settings translate to variations in plant output for identifying regions corresponding to single plant‐controller configurations. The statistical properties of the data in each such window are then compared with the theoretically expected behavior to extract the data corresponding to optimal configuration. This approach has been applied on: (1) raw plant output, (2) Hurst exponent, and (3) minimum variance index of the process data. Simulation examples demonstrate the applicability of proposed approach in industrial settings. A comparison of the three routes is provided with regard to the amount of data needed and the efficacy achieved. Key results are emphasized and a framework for applying this technique is described. This tool is of significance to industries interested in an automated analysis of large scale control loop data for multiple process variables that is otherwise left unutilized. © 2015 American Institute of Chemical Engineers AIChE J, 62: 146–165, 2016
Breakup dynamics for high‐viscosity droplet formation in a flow‐focusing device: Symmetrical and asymmetrical ruptures
Authors: Du Wei , Fu Taotao , Zhu Chunying , Ma Youguang , Li Huai Z.
Published: September 2015

The breakup mechanism of high‐viscosity thread for droplet formation in a flow‐focusing device is investigated using a high‐speed digital camera. Aqueous solution of 89.5%‐glycerol is used as the dispersed phase, while silicone oil as the continuous phase. The breakup process of the dispersed thread presents two categories: symmetrical rupture and asymmetrical rupture. Furthermore, the rupture behavior could be divided into two stages: the squeezing stage controlled by the squeezing pressure and the pinch‐off stage controlled by viscous stresses of both phases and surface tension. Specifically, it suggests that the differences in the shape of the liquid–liquid interface and the dynamics in the two breakup processes are caused by the disparity of the strain field at the point of detachment. Moreover, the thinning rate and the dynamics of the dispersed thread change with the viscosity of the continuous phase, but are less dependent of the flow rate of the continuous phase. © 2015 American Institute of Chemical Engineers AIChE J, 62: 325–337, 2016
Konformationsanalyse, thermische Umlagerung und EI‐MS‐Fragmentierungsmechanismus von (1(10)E,4E,6S,7R)‐Germacradien‐6‐ol durch 13C‐Markierungsexperimente
Authors: Rabe Patrick , Barra Lena , Rinkel Jan , Riclea Ramona , Citron Christian A. , Klapschinski Tim A. , Janusko Aron , Dickschat Jeroen S.
Published: September 2015

Eine uncharakterisierte Terpenzyklase aus Streptomyces pratensis wurde als (+)‐(1(10)E,4E,6S,7R)‐Germacradien‐6‐ol‐Synthase identifiziert, deren Produkt als zwei ineinander konvertierbare Konformere existiert, wodurch komplexe NMR‐Spektren resultieren. Für eine komplette Zuordnung der NMR‐Daten wurden alle fünfzehn Isotopomere des (13C1)FPP sowie (13C15)FPP synthetisiert und enzymatisch umgesetzt und die Produkte durch diverse NMR‐Methoden einschließlich 13C,13C‐COSY analysiert. Die (13C)FPP‐Isotopomere wurden weiterhin für die Untersuchung der thermischen Umlagerung und des EI‐Fragmentierungsmechanismus des Enzymprodukts verwendet.
Electrical and photoelectrical behaviour of heterojunctions based on novel oligomeric metal complexes
Authors: Atlan Metin , Ocak Yusuf Selim , Pasa Salih , Temel Hamdi , Tombak Ahmet , Kilicoğlu Tahsin , Akkilic Kemal , Aydemir Murat
Published: September 2015

Naringenin‐based Schiff base ligands with 4‐aminobenzoic hydrazide were obtained as a unilateral form (L1). The ligand was oligomerized by oxidative polycondensation reaction with NaOCl as an oxidant in an aqueous alkaline medium at 90 °C to form a functional oligomer (L2), and its transition metal complexes such as those with Cu(II), Ni(II) and Zn(II) were prepared. The monomer and the oligomeric compounds were characterized using various techniques. Optical and electrical properties of the complexes were also investigated. All compounds showed indirect band gaps and they can be accepted as being in the semiconductor class. Organic–inorganic hybrid devices were obtained using n‐Si inorganic semiconductor and the complexes. The characteristic parameters of the devices were determined using current–voltage (I–V) and capacitance–voltage measurements in the dark. Photoelectrical properties of the devices were investigated using I–V measurements under a solar simulator with an AM1.5 global filter. Copyright © 2015 John Wiley & Sons, Ltd.
High glass transition temperature bismaleimide‐triazine resins based on soluble amorphous bismaleimide monomer
Authors: Ren Zhidong , Cheng Yuanrong , Kong Lingqiang , Qi Tianke , Xiao Fei
Published: September 2015

A novel bismaleimide (DOPO‐BMI) with unsymmetrical chemical structure and DOPO pendant group has been prepared. The particular molecular structure makes DOPO‐BMI show an intrinsic amorphous state with a Tg about 135°C and excellent solubility in most organic solvents, which is beneficial to the processability of bismaleimide composite materials. A series of bismaleimide‐triazine (BT) resins have been prepared based on DOPO‐BMI and 2,2‐bis(4‐cyanatophenyl)propane at various weight ratios. The prepared BT resins show outstanding solubility in organic solvent and low viscosity about 10–671 mPa s at 180°C. The cured BT resins exhibit high glass transition temperature (Tg) over 316°C. As the weight ratio of DOPO‐BMI increases to 80% (BT80), the Tg can rise to 369°C (tan δ). The cured BT resins also show good thermal stability with the 5% weight loss temperature over 400°C under both nitrogen and air atmosphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42882.
Viscoelastic properties of poly(ε‐caprolactone)/clay nanocomposites in solid and in melt state
Authors: Nikolic Marija S. , Mitric Miodrag , Dapcevic Aleksandra , Djonlagic Jasna
Published: September 2015

Viscoelastic properties in solid and in melt state of poly(ε‐caprolactone), PCL, nanocomposites with organomodified clays (Cloisite30B and Cloisite15A) are thoroughly investigated. Although WAXD is insensitive to the difference in the nanocomposites structure, the melt rheology reveals pronounced differences between the two series. Melt yield stress values, obtained from fittings by the Carreau–Yasuda model, are used as a measure of partial exfoliation of the clay. Temperature dependence of the shift factors, used for time–temperature superposition of the modulus curves, yields similar values of the flow activation energies for all the samples. Temperature dependences of the dynamic modulus and loss factor of solid nanocomposites were correlated to the structural differences deduced from the melt rheology. The increase in the storage modulus is compared to the theoretical predictions from the Halpin–Tsai model. The effective aspect ratio obtained from this comparison agrees reasonably with the value estimated from the melt rheology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42896.
Thermalizing a telescope in Antarctica – analysis of ASTEP observations
Authors: Guillot T. , Abe L. , Agabi A. , Rivet J.‐P. , Daban J.‐B. , Mékarnia D. , Aristidi E. , Schmider F.‐X. , Crouzet N. , Gonçalves I. , Gouvret C. , Ottogalli S. , Faradji H. , Blanc P.‐E. , Bondoux E. , Valbousquet F.
Published: September 2015

The installation and operation of a telescope in Antarctica represent particular challenges, in particular the requirement to operate at extremely cold temperatures, to cope with rapid temperature fluctuations and to prevent frosting. Heating of electronic subsystems is a necessity, but solutions must be found to avoid the turbulence induced by temperature fluctuations on the optical paths. ASTEP 400 is a 40cm Newton telescope installed at the Concordia station, Dome C since 2010 for photometric observations of fields of stars and their exoplanets. While the telescope is designed to spread star light on several pixels to maximize photometric stability, we show that it is nonetheless sensitive to the extreme variations of the seeing at the ground level (between about 0′′.1 and 5′′) and to temperature fluctuations between –30°C and –80 °C. We analyze both day‐time and night‐time observations and obtain the magnitude of the seeing caused by the mirrors, dome and camera. The most important effect arises from the heating of the primary mirror which gives rise to a mirror seeing of 0′′.23 K–1. We propose solutions to mitigate these effects. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Stellar science from a blue wavelength range
Authors: Hansen C. J. , Ludwig H.‐G. , Seifert W. , Koch A. , Xu W. , Caffau E. , Christlieb N. , Korn A. J. , Lind K. , Sbordone L. , Ruchti G. , Feltzing S. , de Jong R. S. , Barden S. , Schnurr O.
Published: September 2015

From stellar spectra, a variety of physical properties of stars can be derived. In particular, the chemical composition of stellar atmospheres can be inferred from absorption line analyses. These provide key information on large scales, such as the formation of our Galaxy, down to the small‐scale nucleosynthesis processes that take place in stars and supernovae. By extending the observed wavelength range toward bluer wavelengths, we optimize such studies to also include critical absorption lines in metal‐poor stars, and allow for studies of heavy elements (Z ≥ 38) whose formation processes remain poorly constrained. In this context, spectrographs optimized for observing blue wavelength ranges are essential, since many absorption lines at redder wavelengths are too weak to be detected in metal‐poor stars. This means that some elements cannot be studied in the visual‐redder regions, and important scientific tracers and science cases are lost. The present era of large public surveys will target millions of stars. It is therefore important that the next generation of spectrographs are designed such that they cover a wide wavelength range and can observe a large number of stars simultaneously. Only then, we can gain the full information from stellar spectra, from both metal‐poor to metal‐rich ones, that will allow us to understand the aforementioned formation scenarios in greater detail. Here we describe the requirements driving the design of the forthcoming survey instrument 4MOST, a multi‐object spectrograph commissioned for the ESO VISTA 4 m‐telescope. While 4MOST is also intended for studies of active galactic nuclei, baryonic acoustic oscillations, weak lensing, cosmological constants, supernovae and other transients, we focus here on high‐density, wide‐area survey of stars and the science that can be achieved with high‐resolution stellar spectroscopy. Scientific and technical requirements that governed the design are described along with a thorough line blending analysis. For the high‐resolution spectrograph, we find that a sampling of ≥2.5 (pixels per resolving element), spectral resolution of 18000 or higher, and a wavelength range covering 393–436 nm, is the most well‐balanced solution for the instrument. A spectrograph with these characteristics will enable accurate abundance analysis (±0.1 dex) in the blue and allow us to confront the outlined scientific questions. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
On the angular distribution of IceCube high‐energy events
Authors: de la Fuente Marcos R. , de la Fuente Marcos C.
Published: September 2015

The detection of high‐energy astro‐physical neutrinos of extraterrestrial origin by the IceCube neutrino observatory in Antarctica has opened a unique window to the cosmos that may help to probe both the distant Universe and our cosmic backyard. The arrival directions of these high‐energy events have been interpreted as uniformly distributed on the celestial sphere. Here, we revisit the topic of the putative isotropic angular distribution of these events applying Monte Carlo techniques to investigate a possible anisotropy. A modest evidence for anisotropy is found. An excess of events appears projected towards a section of the Local Void, where the density of galaxies with radial velocities below 3000 km s–1 is rather low, suggesting that this particular group of somewhat clustered sources are located either very close to the Milky Way or perhaps beyond 40 Mpc. The results of further analyses of the subsample of southern hemisphere events favour an origin at cosmological distances with the arrival directions of the events organized in a fractal‐like structure. Although a small fraction of closer sources is possible, remote hierarchical structures appear to be the main source of these very energetic neutrinos. Some of the events may have their origin at the IBEX ribbon. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Green synthesis of fluorescence carbon nanoparticles from yum and application in sensitive and selective detection of ATP
Authors: Zhan Zixuan , Cai Jiao , Wang Qi , Su Yingying , Zhang Lichun , Lv Yi
Published: September 2015

Fluorescent carbon nanoparticles (CPs), a fascinating class of recently discovered nanocarbons, have been widely known as some of the most promising sensing probes in biological or chemical analysis. In this study, we demonstrate a green synthetic methodology for generating water‐soluble CPs with a quantum yield of approximately 24% via a simple heating process using yum mucilage as a carbon source. The prepared carbon nanoparticles with an ~10 nm size possessed excellent fluorescence properties, and the fluorescence of the CPs was strongly quenched by Fe3+, and recovered by adenosine triphosphate (ATP), thus, an ‘off’ and ‘on’ system can be easily established. This ‘CPs‐Fe3+‐ATP’ strategy was sensitive and selective at detecting ATP with the linear range of 0.5 µmol L−1 to 50 µmol L−1 and with a detection limit of 0.48 µmol L−1. Copyright © 2015 John Wiley & Sons, Ltd.
Study on the interaction of β‐carotene and astaxanthin with trypsin and pepsin by spectroscopic techniques
Authors: Li Xiangrong , Li Peihong
Published: September 2015

β‐Carotene and astaxanthin are two carotenoids with powerful antioxidant properties, but the binding mechanisms of β‐carotene/astaxanthin to proteases remain unclear. In this study, the interaction of these two carotenoids with trypsin and pepsin was investigated using steady‐state and time‐resolved fluorescence measurements, synchronous fluorescence spectroscopy, UV–vis absorption spectroscopy and circular dichroism (CD) spectroscopy. The experimental results indicated that the quenching mechanisms of trypsin/pepsin by the two carotenoids are static processes. The binding constants of trypsin and pepsin with these two carotenoids are in the following order: astaxanthin–trypsin > astaxanthin–pepsin > β‐carotene–trypsin > β‐carotene–pepsin, respectively. Thermodynamic investigations revealed that the interaction between the two carotenoids and trypsin/pepsin is synergistically driven by enthalpy and entropy, and hydrophobic forces and electrostatic attraction have a significant role in the reactions. In addition, as shown by synchronous fluorescence spectroscopy, UV–vis absorption spectroscopy and CD, the two carotenoids may induce conformational and microenvironmental changes in trypsin/pepsin. The study provides an accurate and full basic data for clarifying the binding mechanisms of the two carotenoids with trypsin/pepsin and is helpful in understanding their effect on protein function and their biological activity in vivo. Copyright © 2015 John Wiley & Sons, Ltd.
Cell‐free protein synthesis enables high yielding synthesis of an active multicopper oxidase
Authors: Li Jian , Lawton Thomas J. , Kostecki Jan S. , Nisthal Alex , Fang Jia , Mayo Stephen L. , Rosenzweig Amy C. , Jewett Michael C.
Published: September 2015

Multicopper oxidases (MCOs) are broadly distributed in all kingdoms of life and perform a variety of important oxidative reactions. These enzymes have potential biotechnological applications; however, the applications are impeded by low expression yields in traditional recombinant hosts, solubility issues, and poor copper cofactor assembly. As an alternative to traditional recombinant protein expression, we show the ability to use cell‐free protein synthesis (CFPS) to produce complex MCO proteins with high soluble titers. Specifically, we report the production of MCOs in an Escherichia coli‐based cell‐free transcription‐translation system. Total yields as high as 1.2 mg mL−1 were observed after a 20‐h batch reaction. More than 95% of the protein was soluble and activity was obtained by simple post‐CFPS addition of copper ions in the form of CuSO4. Scale‐up reactions were achieved from 15 to 100 µL without a decrease in productivity and solubility. CFPS titers were higher than in vivo expression titers and more soluble, avoiding the formation of inclusion bodies. Our work extends the utility of the cell‐free platform to the production of active proteins containing copper cofactors and demonstrates a simple method for producing MCOs.
Ethical Issues Raised by Epigenetic Testing for Alcohol, Tobacco, and Cannabis
Authors: Erwin Cheryl
Published: September 2015

Epigenetic testing is one of the most significant new technologies to provide insight into the behavioral and environmental factors that influence the development and reconfiguration of the human genetic code. This technology allows us to identify structural changes in the genome that occur due to exposure to a wide variety of substances including alcohol, tobacco, and cannabis. The information gained can be used to promote health but it also raises a variety of ethical, legal, and social issues. As society progresses in understanding the epigenetic mechanisms of substance use and addiction, there is an opportunity to use these use this knowledge to enable medical, behavioral, and environmental interventions to alleviate the burden of addiction. This article describes the ethical issues associated with use of epigenetic testing for alcohol, tobacco, and cannabis and the implications of this technology. A further review of the scientific basis for the relevance of epigenetics is found in the accompanying article by Philibert and Erwin in this issue. Copyright © 2015 John Wiley & Sons, Ltd.
ODAM inhibits RhoA‐dependent invasion in breast cancer
Authors: Lee Hye‐Kyung , Choung Han‐Wool , Yang Young‐Il , Yoon Hye‐Jung , Park In Ae , Park Joo‐Cheol
Published: September 2015

Odontogenic ameloblast‐associated protein (ODAM) contributes to cell adhesion. In human cancer, ODAM is down‐regulated, and the overexpression of ODAM results in a favourable prognosis; however, the molecular mechanisms underlying ODAM‐mediated inhibition of cancer invasion and metastasis remain unclear. Here, we identify a critical role for ODAM in inducing cancer cell adhesion. ODAM induced RhoA activity and the expression of downstream factors, including Rho‐associated kinase (ROCK). ODAM‐mediated RhoA signalling resulted in actin filament rearrangement by activating PTEN and inhibiting the phosphorylation of AKT. When ODAM is overexpressed in MCF7 breast cancer cells and AGS gastric cancer cells that activate RhoA at high levels, it decreases motility, increases adhesion and inhibits the metastasis of MCF7 cells. Conversely, depletion of ODAM in cancer cells inhibits Rho GTPase activation, resulting in increased cancer migration and invasion. These results suggest that ODAM expression in cells maintains their adhesion, resulting in the prevention of their metastasis via the regulation of RhoA signalling in breast cancer cells. Copyright © 2015 John Wiley & Sons, Ltd.

SIGNIFICANCE Breast cancer represents the first most frequent cancer, and the ratio of mortality is high in women. Of utmost importance for reducing risk by breast cancer are their anti‐invasion mechanisms, particularly in the non‐invasive cancer cells because metastasis is the principal cause of death among cancer patients. ODAM induced RhoA activity. ODAM‐mediated RhoA signalling resulted in actin filament rearrangement, increased cell adhesion and inhibited the migration/invasion of MCF7 cells. These results suggest that ODAM expression maintains their adhesion, resulting in the prevention of their metastasis via the regulation of RhoA signalling in breast cancer cells.
Methyl 3‐Hydroxymyristate, a Diffusible Signal Mediating phc Quorum Sensing in Ralstonia solanacearum
Authors: Kai Kenji , Ohnishi Hideyuki , Shimatani Mika , Ishikawa Shiho , Mori Yuka , Kiba Akinori , Ohnishi Kouhei , Tabuchi Mitsuaki , Hikichi Yasufumi
Published: September 2015

Ralstonia solanacearum, a plant pathogenic bacterium causing “bacterial wilt” on crops, uses a quorum sensing (QS) system consisting of phc regulatory elements to control its virulence. Methyl 3‐hydroxypalmitate (3‐OH PAME) was previously identified as the QS signal in strain AW1. However, 3‐OH PAME has not been reportedly detected from any other strains, and this suggests that they produce another unknown QS signal. Here we identify (R)‐methyl 3‐hydroxymyristate [(R)‐3‐OH MAME] as a new QS signal that regulates the production of virulence factors and secondary metabolites. (R)‐3‐OH MAME was synthesized by the methyltransferase PhcB and sensed by the histidine kinase PhcS. The phylogenetic trees of these proteins from R. solanacearum strains were divided into two groups, according to their QS signal types—(R)‐3‐OH MAME or (R)‐3‐OH PAME. These results demonstrate that (R)‐3‐OH MAME is another crucial QS signal and highlight the unique evolution of QS systems in R. solanacearum.
Recyclable Poly‐Zn3(OAc)4–3,3′‐Bis(aminoimino)binaphthoxide Catalyst for Asymmetric Iodolactonization
Authors: Arai Takayoshi , Kojima Takahiro , Watanabe Ohji , Itoh Tsutomu , Kanoh Hirofumi
Published: September 2015

On the basis of the structure of the unimolecular Zn3(OAc)4–3,3′‐bis(aminoimino)binaphthoxide complex, a poly‐Zn3(OAc)4–3,3′‐bis(aminoimino)binaphthoxide (poly‐Zn) complex was prepared from 3,3′‐diformylbinaphthol, tetramine, and Zn(OAc)2. The first‐generation poly‐Zn catalyst (poly‐Zn1) was prepared from poly(aminoiminobinaphthol) and Zn(OAc)2. Although poly‐Zn1 showed high catalytic activity for iodolactonization, the catalyst could not be reused. The second‐generation poly‐Zn catalyst (poly‐Zn2) was prepared by the self‐organization of 3,3′‐diformylbinaphthol, tetramine, and Zn(OAc)2. This produced a stable and active poly‐Zn2 catalyst for asymmetric iodolactonization that was reused over five cycles.
Synthesis of α‐Chiral Butyrolactones by Highly Stereoselective Radical Transfer or Sequential Asymmetric Alkylations: Concise Preparation of Leupyrrin Moieties
Authors: Schrempp Michael , Thiede Sebastian , Herkommer Daniel , Gansäuer Andreas , Menche Dirk
Published: September 2015

Inspired by the bioactive natural metabolites leupyrrin A1 and B1, two novel stereoselective methods for the highly concise synthesis of densely substituted α‐chiral butyrolactones are reported. The first approach relies on an innovative three‐step TiIII‐catalyzed radical reaction that proceeds with excellent chemo‐, regio‐, and stereoselectivity. The alternative route utilizes sequential asymmetric alkylations and enables asymmetric synthesis of the authentic α‐tetrasubstituted butyrolactone motif of the leupyrrins in only four steps from commercially available substrates.
The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds
Authors: Chrostowska Anna , Darrigan Clovis , Dargelos Alain , Benidar Abdessamad , Guillemin Jean‐Claude
Published: September 2015

Cyanohydrins are usually formed by addition of hydrogen cyanide to aldehydes or ketones while the elimination of HCN from cyanohydrins is easily observed upon heating. The low thermal stability of these highly boiling compounds leads to difficult studies in the gas phase where partial or complete decomposition is usually observed. Consequently, the reported physicochemical properties of such compounds in the gas phase are still scarce. Keeping with this, four simple cyanohydrins, the glycolonitrile and methyl, vinyl and ethynyl derivatives, have been selected. These are possible candidates for the Interstellar Medium, where the corresponding aldehydes and HCN have been detected, and could have played an important role in prebiotic chemistry, as already proposed for some of them. Three well‐suited spectroscopic techniques, namely, UV photoelectron, infrared, and Raman spectroscopies, in tandem with quantum calculations, have been chosen for the structure analysis. Photoelectron spectroscopy, successfully performed with gaseous compounds, provides the first comparative study on cyanohydrins in the gas phase.
Investigation of the Storage Behavior of Shredded Lithium‐Ion Batteries from Electric Vehicles for Recycling Purposes
Authors: Grützke Martin , Krüger Steffen , Kraft Vadim , Vortmann Britta , Rothermel Sergej , Winter Martin , Nowak Sascha
Published: September 2015

Shredding of the cells is often the first step in lithium‐ion battery (LIB) recycling. Thus, LiNi1/3Mn1/3Co1/3O2 (NMC)/graphite lithium‐ion cells from a field‐tested electric vehicle were shredded and transferred to tinplate or plastic storage containers. The formation of hazardous compounds within, and being released from, these containers was monitored over 20 months. The tinplate cans underwent fast corrosion as a result of either residual charge in the active battery material, which could not fully be discharged because of contact loss to the current collector, or redox reactions between the tinplate surface and metal parts of the shredded material. The headspace compositions of the containers were investigated at room temperature and 150 °C using headspace–gas chromatography–mass spectrometry (HS–GC–MS). Samples of the waste material were also collected using microwave‐assisted extraction and the extracts were analyzed over a period of 20 months using ion chromatography–electrospray ionization–mass spectrometry (IC–ESI–MS). LiPF6 was identified as a conducting salt, whereas dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate were the main solvent components. Cyclohexylbenzene was also detected, which is an additive for overcharge protection. Diethyl carbonate, fluoride, difluorophosphate and several ionic and non‐ionic alkyl (fluoro)phosphates were also identified. Importantly, dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP) were quantified using HS–GC–MS through the use of an internal standard. DMFP, DEFP, and related compounds are known as chemical warfare agents, and the presence of these materials is of great interest. In the case of this study, these hazardous materials are present but in manageable low concentrations. Nonetheless, the presence of such compounds and their potential release during an accident that may occur during shredding or recycling of large amounts of LIB waste should be considered.
Syntheses and analytical characterizations of N‐alkyl‐arylcyclohexylamines
Authors: Wallach Jason , Colestock Tristan , Cicali Brian , Elliott Simon P. , Kavanagh Pierce V. , Adejare Adeboye , Dempster Nicola M. , Brandt Simon D.
Published: September 2015

The rise in new psychoactive substances that are available as 'research chemicals’ (RCs) remains a significant forensic and legislative challenge. A number of arylcyclohexylamines have attracted attention as RCs and continue to be encountered, including 3‐MeO‐PCP, 3‐MeO‐PCE and 3‐MeO‐PCPr. These compounds are commonly perceived as ketamine‐like dissociative substances and are believed to act predominantly via antagonism of the N‐methyl‐D‐aspartate (NMDA) receptor. To aid in the identification of newly emerging substances of abuse, the current studies were performed. The syntheses of fifteen N‐alkyl‐arylcyclohexylamines are described. Analytical characterizations were performed via gas chromatography and high performance liquid chromatography coupled to multiple forms of mass spectrometry as well as nuclear magnetic resonance spectroscopy, ultraviolet diode array detection and infrared spectroscopy. The series consisted of the N‐alkyl derivatives (N‐methyl, N‐ethyl, N‐propyl) of phenyl‐substituted and isomeric 2‐, 3‐ and 4‐methoxy phenylcyclohexylamines, as well as the N‐alkyl derivatives obtained from 3‐methylphenyl and 2‐thienyl moieties. In addition to the presentation of a range of previously unreported data, it was also found that positional isomers of aryl methoxyl‐substituted arylcyclohexylamines were readily distinguishable under a variety of analytical conditions. Copyright © 2015 John Wiley & Sons, Ltd.
Relative Ease in Creating Detailed Orthographic Representations Contrasted with Severe Difficulties to Maintain Them in Long‐term Memory Among Dyslexic Children
Authors: Binamé Florence , Danzio Sophie , Poncelet Martine
Published: September 2015

Most research into orthographic learning abilities has been conducted in English with typically developing children using reading‐based tasks. In the present study, we examined the abilities of French‐speaking children with dyslexia to create novel orthographic representations for subsequent use in spelling and to maintain them in long‐term memory. Their performance was compared with that of chronological age (CA)‐matched and reading age (RA)‐matched control children. We used an experimental task designed to provide optimal learning conditions (i.e. 10 spelling practice trials) ensuring the short‐term acquisition of the spelling of the target orthographic word forms. After a 1‐week delay, the long‐term retention of the targets was assessed by a spelling post‐test. Analysis of the results revealed that, in the short term, children with dyslexia learned the novel orthographic word forms well, only differing from both CA and RA controls on the initial decoding of the targets and from CA controls on the first two practice trials. In contrast, a dramatic drop was observed in their long‐term retention relative to CA and RA controls. These results support the suggestion of the self‐teaching hypothesis (Share, 1995) that initial errors in the decoding and spelling of unfamiliar words may hinder the establishment of fully specified novel orthographic representations. Copyright © 2015 John Wiley & Sons, Ltd.
Migration of encephalitogenic CD8 T cells into the central nervous system is dependent on the α4β1‐integrin
Authors: Martin‐Blondel Guillaume , Pignolet Béatrice , Tietz Silvia , Yshii Lidia , Gebauer Christina , Perinat Therese , Van Weddingen Isabelle , Blatti Claudia , Engelhardt Britta , Liblau Roland
Published: September 2015

Although CD8 T cells are key players in neuroinflammation, little is known about their trafficking cues into the central nervous system (CNS). We used a murine model of CNS autoimmunity to define the molecules involved in cytotoxic CD8 T‐cell migration into the CNS. Using a panel of mAbs, we here show that the α4β1‐integrin is essential for CD8 T‐cell interaction with CNS endothelium. We also investigated which α4β1‐integrin ligands expressed by endothelial cells are implicated. The blockade of VCAM‐1 did not protect against autoimmune encephalomyelitis, and only partly decreased the CD8+ T‐cell infiltration into the CNS. In addition, inhibition of junctional adhesion molecule‐B expressed by CNS endothelial cells also decreases CD8 T‐cell infiltration. CD8 T cells may use additional and possibly unidentified adhesion molecules to gain access to the CNS.
Highly Selective and Sensitive Detection of Picric Acid Explosive by a Bisporphyrin Cleft: Synergistic Effects of Encapsulation, Efficient Electron Transfer, and Hydrogen Bonding
Authors: Mondal Pritam , Rath Sankar Prasad
Published: September 2015

A flexible diethylpyrrole‐bridged bisporphyrin (H4DEP) is employed to encapsulate highly explosive picric acid (PA) in its cleft, and information about the chemical environment in the interior of the host–guest assembly is obtained. The synthesis, X‐ray structure, and photophysical properties of the encapsulated host–guest complex (H4DEP·PA) are reported here. The host–guest assembly is also retained in solution with a binding constant (K) of (2.63 ± 0.2) × 105 M–1. Such an efficient complexation is due to the perfect match of the host–guest size, H bonding, and strong π–π interactions between the host and guest, which collectively make the binding of PA rapid and highly selective with a detection limit of 2.4 ppm. The host H4DEP can also discriminate the highly explosive PA from other nitroaromatic compounds. The extremely low HOMO–LUMO gap (HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) in the host–guest complex leads to an efficient and highly facile electron transfer from the host to the guest, which results in substantial quenching of the emission intensity of H4DEP. Such an efficient electron transfer is only possible if the donor and acceptor moieties are close to each other, as this lowers the reorganization energy. All of the experimental evidence is further substantiated by DFT calculations.