bluuebunny/crossref_metadata_2025 huggingface dataset:
Dome growth at Mount Cleveland, Aleutian Arc, quantified by time series TerraSAR‐X imagery
Authors: Wang Teng , Poland Michael P. , Lu Zhong
Published: December 2015

Synthetic aperture radar imagery is widely used to study surface deformation induced by volcanic activity; however, it is rarely applied to quantify the evolution of lava domes, which is important for understanding hazards and magmatic system characteristics. We studied dome formation associated with eruptive activity at Mount Cleveland, Aleutian Volcanic Arc, in 2011–2012 using TerraSAR‐X imagery. Interferometry and offset tracking show no consistent deformation and only motion of the crater rim, suggesting that ascending magma may pass through a preexisting conduit system without causing appreciable surface deformation. Amplitude imagery has proven useful for quantifying rates of vertical and areal growth of the lava dome within the crater from formation to removal by explosive activity to rebirth. We expect that this approach can be applied at other volcanoes that host growing lava domes and where hazards are highly dependent on dome geometry and growth rates.
Hail potential in Europe based on a regional climate model hindcast
Authors: Mohr S. , Kunz M. , Geyer B.
Published: December 2015

Due to the local‐scale nature of hail and a lack of appropriate observation systems, comprehensive, reliable, and consistent information about hail frequency and intensity in Europe is not available. To overcome this constraint, we developed a logistic hail model that quantifies the potential of the atmosphere to form hailstorms. The model is based on a combination of appropriate hail‐relevant meteorological parameters. This paper presents the application of an adjusted version of the logistic model with the objective being to estimate the hail potential across Europe based on dynamically downscaled National Centers for Environmental Prediction/National Center for Atmospheric Research1 reanalysis over a long‐term period of 60 years (1951–2010). The model output, in terms of the potential hail index (PHI), identified several hot spots that are well known from other observational studies. Time series of the PHI over the 60 year period show a high correlation at different sites across Europe and high annual and multiannual variability, but no overall trend.
SAR arcs we have seen: Evidence for variability in stable auroral red arcs
Authors: Mendillo Michael , Baumgardner Jeffrey , Wroten Joei
Published: December 2015

Since 1987, an all‐sky airglow imaging system has operated from a site at the Millstone Hill/Haystack Observatory in Westford, MA. During the ~2.5 solar cycles from 1987 to 2014, many studies using all‐sky images, in conjunction with incoherent scatter radar and satellite data, described subauroral, ionospheric disturbances observed during individual geomagnetic storms. The most prominent storm time optical feature from a subauroral site is a stable auroral red (SAR) arc. The standard use of a SAR arc's position is to locate the ionospheric footprint of the narrow plasmapause‐ring current interaction region where heat conduction from the inner magnetosphere excites emission within the F layer trough. When mapped from an emission altitude of 400 km to the geomagnetic equatorial plane, SAR arcs from Millstone Hill give the location of the plasmapause at radial distances between 2 to 4.5 Earth radii. A total of 314 SAR arcs have been observed during the 27 years of imaging at Millstone Hill. We find no single morphology for all SAR arcs, but rather patterns that occasionally depart from stability in space and time. We have classified these into five categories: longevity, multiplicity, zonal structure, latitudinal inhomogeneity, and tilt with respect to geomagnetic coordinates. In each case, the implications for the inner magnetosphere sources that drive SAR arcs are explored. While individual SAR arc variability characteristics have been noted in previous studies, here we describe for the first time all five types from the same site—an aspect not yet addressed in either magnetosphere or ionosphere modeling studies.
Inkjet‐Printed Flexible Gold Electrode Arrays for Bioelectronic Interfaces
Authors: Khan Yasser , Pavinatto Felippe J. , Lin Monica C. , Liao Amy , Swisher Sarah L. , Mann Kaylee , Subramanian Vivek , Maharbiz Michel M. , Arias Ana C.
Published: December 2015

Bioelectronic interfaces require electrodes that are mechanically flexible and chemically inert. Flexibility allows pristine electrode contact to skin and tissue, and chemical inertness prevents electrodes from reacting with biological fluids and living tissues. Therefore, flexible gold electrodes are ideal for bioimpedance and biopotential measurements such as bioimpedance tomography, electrocardiography (ECG), electroencephalography (EEG), and electromyography (EMG). However, a manufacturing process to fabricate gold electrode arrays on plastic substrates is still elusive. In this work, a fabrication and low‐temperature sintering (≈200 °C) technique is demonstrated to fabricate gold electrodes. At low‐temperature sintering conditions, lines of different widths demonstrate different sintering speeds. Therefore, the sintering condition is targeted toward the widest feature in the design layout. Manufactured electrodes show minimum feature size of 62 μm and conductivity values of 5 × 10 6 S m−1. Utilizing the versatility of printing and plastic electronic processes, electrode arrays consisting of 31 electrodes with electrode‐to‐electrode spacing ranging from 2 to 7 mm are fabricated and used for impedance mapping of conformal surfaces at 15 kHz. Overall, the fabrication process of an inkjet‐printed gold electrode array that is electrically reproducible, mechanically robust, and promising for bioimpedance and biopotential measurements is demonstrated.
Surface Rutilization of Anatase TiO2 Nanorods for Creation of Synergistically Bridging and Fencing Electron Highways
Authors: Chen Jiazang , Yang Hong Bin , Tao Hua Bing , Zhang Liping , Miao Jianwei , Wang Hsin‐Yi , Chen Junze , Zhang Hua , Liu Bin
Published: December 2015

In a photoelectrochemical cell, the most concerned issue in the nanostructured TiO2 electrode is the charge transport, which consists of the internal movement of electrons in TiO2 nanostructures and the intergrain charge transfer. Here, inspired by electrochemical studies on different polymorphs of TiO2, it is proposed to bridge the adjacent building blocks and fence the electron transport highways in TiO2 electrodes by surface rutilization of anatase nanorods. The ultrathin rutilized layer completely coated on the anatase surface has a slightly higher conduction band edge than that of anatase. The obtained surface rutilized anatase nanorods can not only improve the intergrain charge transfer while maintaining fast electron transport within anatase but also minimize the internal energy consumption and protect the electrons in TiO2 electrodes from recombination, which are beneficial to the charge collection and can significantly improve the photovoltaic performance of photoelectrochemical cells.
Microdeletions of the 7q32.2 imprinted region are associated with Silver–Russell syndrome features
Authors: Carrera Ignacio Arroyo , de Zaldívar María Solo , Martín Rebeca , Begemann Matthias , Soellner Lukas , Eggermann Thomas
Published: December 2015

The association of maternal uniparental disomy of human chromosome 7 (upd(7) mat) and the growth retardation disorder Silver–Russell syndrome (SRS) is well established, but the causative gene or region is currently unknown. However, several observations indicate that molecular alterations of the genomically imprinted MEST region in 7q32.2 are associated with growth retardation and a phenotype reminiscent to SRS. We now report on a second patient with a similar phenotype and a de novo 7q32.2 microdeletion including MEST affecting the paternal allele. This confirms the central role of imprinted genes in 7q32.2 in the etiology of a growth retardation phenotype associated with SRS features. © 2015 Wiley Periodicals, Inc.
Erzeugung von Festkörperlumineszenz durch Koordination der Lewis‐Säure B(C6F5)3 an nicht‐emittierende Aldehyde
Authors: Hansmann Max M. , López‐Andarias Alicia , Rettenmeier Eva , Egler‐Lucas Carolina , Rominger Frank , Hashmi A. Stephen K. , Romero‐Nieto Carlos
Published: December 2015

Die einfache Koordination der Lewis‐Säure B(C6F5)3 an klassische, nicht‐emittierende Aldehyde führt zu Festkörperphotolumineszenz. Das Variieren der elektronischen Eigenschaften der Carbonylverbindungen ermöglicht eine Wellenlängenmodulation der Festkörperemission, durch die das gesamte sichtbare Spektrum mit Quantenausbeuten bis zu 0.64 abgedeckt werden kann. Steady‐State‐Spektroskopie in Kombination mit Einkristall‐Röntgenstrukturanalyse und DFT‐Rechnungen bestätigt die intermolekularen Wechselwirkungen zwischen den Lewis‐Addukten als Ursache für die beobachtete Lumineszenz. Änderungen dieser intermolekularen Wechselwirkungen induzieren darüber hinaus bemerkenswerte Festkörperphänomene wie Piezochromie. Die Vielseitigkeit und Einfachheit unserer Methode erleichtert die zukünftige Entwicklung festkörperemittierender Materialien.
Amavadin and Homologues as Mediators of Water Oxidation
Authors: Domarus Magdalena , Kuznetsov Maxim L. , Marçalo Joaquim , Pombeiro Armando J. L. , da Silva José Armando L.
Published: December 2015

The vanadium(IV) N‐hydroxyiminodicarboxylate complexes [V(HIDPA)2]2− and [V(HIDA)2]2−, close models of the amavadin (a natural product from Amanita fungi lacking the V=O group but exhibiting a rare NO‐bound oxyiminate moiety), are shown to be the first recognized complexes of the early transition metals (up to periodic Group 7) that mediate the oxidation of water. The reactions were analyzed by visible spectrophotometry, mass spectrometry, and measurement of evolved dioxygen using Ce4+ as sacrificial oxidant. A mechanism proposed on the basis of DFT calculations involves the reversible oxidation to the mononuclear VV‐{ON˙<} center, where the redox active oxyimino group plays a key role and metal oxidation state variation is only one unit. The more similar model of the metallobiomolecule, [V(HIDPA)2]2−, displays a lower oxidation rate than [V(HIDA)2]2− but does not undergo appreciable degradation, in contrast to the latter.
Entropy‐Driven Selectivity for Chain Scission: Where Macromolecules Cleave
Authors: Pahnke Kai , Brandt Josef , Gryn'ova Ganna , Lin Ching Y. , Altintas Ozcan , Schmidt Friedrich G. , Lederer Albena , Coote Michelle L. , Barner‐Kowollik Christopher
Published: December 2015

We show that, all other conditions being equal, bond cleavage in the middle of molecules is entropically much more favored than bond cleavage at the end. Multiple experimental and theoretical approaches have been used to study the selectivity for bond cleavage or dissociation in the middle versus the end of both covalent and supramolecular adducts and the extensive implications for other fields of chemistry including, e.g., chain transfer, polymer degradation, and control agent addition are discussed. The observed effects, which are a consequence of the underlying entropic factors, were predicted on the basis of simple theoretical models and demonstrated via high‐temperature (HT) NMR spectroscopy of self‐assembled supramolecular diblock systems as well as temperature‐dependent size‐exclusion chromatography (TD SEC) of covalently bonded Diels–Alder step‐growth polymers.
Probing Force with Mechanobase‐Induced Chemiluminescence
Authors: Clough Jess M. , Balan Abidin , van Daal Tom L. J. , Sijbesma Rint P.
Published: December 2015

Mechanophores capable of releasing N‐heterocyclic carbene (NHC), a strong base, are combined with triggerable chemiluminescent substrates to give a novel system for mechanically induced chemiluminescence. The mechanophores are palladium bis‐NHC complexes, centrally incorporated in poly(tetrahydrofuran) (pTHF). Chemiluminescence is induced from two substrates, adamantyl phenol dioxetane (APD) and a coumaranone derivative, upon sonication of dilute solutions of the polymer complex and either APD or the coumaranone. Control experiments with a low molecular weight Pd complex showed no significant activation and the molecular weight dependence of the coumaranone emission supports the mechanical origin of the activation. The development of this system is a first step towards mechanoluminescence at lower force thresholds and catalytic mechanoluminescence.
Tailor‐Made Ruthenium‐Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams
Authors: Meuresch Markus , Westhues Stefan , Leitner Walter , Klankermayer Jürgen
Published: December 2015

The development of a tailored tridentate ligand enabled the synthesis of a molecular ruthenium‐triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity.
Iron‐Catalyzed Intramolecular C(sp2)−H Amination
Authors: Alt Isabel T. , Plietker Bernd
Published: December 2015

The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the direct intramolecular C−H amination of α‐azidobiaryls and (azidoaryl)alkenes into the corresponding carbazoles and indoles, respectively, under mild conditions and with low catalyst loadings. These features and the broad functional‐group tolerance render this method a particularly attractive alternative to established noble‐metal‐based procedures.
Flame‐retardant and thermal degradation mechanism of low‐density polyethylene modified with aluminum hypophosphite and microencapsulated red phosphorus
Authors: Wang De Kang , He Hui , Yu Peng
Published: December 2015

Aluminum hypophosphite (AHP), a novel flame retardant, was used to improve the flame retardancy of low‐density polyethylene (LDPE) with microencapsulated red phosphorus (MRP). The synergistic effect between MRP and AHP was investigated by the limiting oxygen index (LOI), vertical burning test (UL‐94), and thermogravimetric analysis. When the contents of MRP and AHP were 10 and 30 phr, the LOI of LDPE/10MRP/30AHP composite was 25.5%, and it passed the UL‐94 V‐0 rating (the number before “MRP” and “AHP” is the loading of MRP and AHP, In LDPE/10MRP/30AHP, the content of the LDPE, MRP and AHP is 100phr, 10phr and 30phr, where phr refers to parts per hundreds of resin). The results of cone calorimetry testing show that the heat release rate of the composites was significantly reduced, and the strength of the char layer improved when the loading of AHP increased. The thermal stability of the LDPE/10MRP/30AHP composite was enhanced. The structure of the char was investigated by Fourier transform infrared spectrometry and scanning electron microscopy/energy‐dispersive spectrometry. The results indicate that AHP promoted the formation of stable char. This research provided a good way to prepare flame‐retardant materials with a halogen‐free flame retardant and contributed to environmental protection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43225.
Rapid fabrication of poly(ε‐caprolactone) nanofibers using needleless alternating current electrospinning
Authors: Lawson Caitlin , Stanishevsky Andrei , Sivan Manikandan , Pokorny Pavel , Lukáš David
Published: December 2015

Poly(ε‐caprolactone) (PCL) biopolymer nanofibers and micro‐fibers have been fabricated for the first time at the rates up to 14.0 g per hour using a needleless and collectorless alternating current electrospinning technique. By combining the ac‐voltage, “green” low toxicity glacial acetic acid (AA) as the solvent and sodium acetate (NaAc) as an additive, beadless PCL fibers with diameters tunable from 150 nm to 2000 nm, varying surface morphology and degree of self‐bundling are obtained. In this new approach, the addition of NaAc plays a crucial role in improving the spinnability of PCL solution and fiber morphology. NaAc reveals the concentration‐dependent effect on charge transfer and rheological properties of the PCL/AA precursor, which results in broader ranges of spinnable PCL concentrations and ac‐voltages suitable for rapid manufacturing of PCL‐based fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43232.
Diluent selection forNylon 11 andNylon 12 thermally induced phase separation systems
Authors: Funk Caleb V. , Koreltz Michael S. , Billovits Gerald F.
Published: December 2015

Nylon 11 and Nylon 12 are commercially important polymers due to their unique combination of mechanical strength, chemical resistance, and processability. Products have been prepared from these polymers via thermally induced phase separation (TIPS) for many years. Nevertheless, known diluents for Nylon 11 and 12 pose specific processing problems, and it would be desirable to find a diluent that allows low processing temperatures, has a high flash point, is inexpensive, and exhibits low toxicity. This work investigated a variety of alternative diluents not previously documented in the literature. A fundamental study was also performed to determine which factors are important in selecting a diluent for preparing Nylon liquid–liquid TIPS membranes. The information gathered in this study, including phase diagrams for all feasible systems investigated, will be important in shaping future formulation work for Nylon use in microporous membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43237.
Syndiotactic polypropylene nanofibers obtained from solution electrospinning process at ambient temperature
Authors: Maeda Tomoki , Takaesu Keita , Hotta Atsushi
Published: December 2015

Fabrication of semicrystalline syndiotactic polypropylene (sPP) nanofibers by solution electrospinning was studied. It was found that sPP nanofibers with an average diameter of 230 nm were successfully fabricated via solution electrospinning with methylcyclohexane as solvent at room temperature (25°C). The obtained diameter was significantly thinner than the minimum diameter of 350 nm of PP fibers that were reported previously. It was also found that increasing viscosity of the sPP solution, which was customarily a useful way of fabricating noncrystalline thin fibers, was found ineffectual in producing thinner semicrystalline sPP fibers in our experiments. In fact, a careful selection of solvent by considering the evaporation rate and the specific viscosity could effectively lead to the fabrication of thinner sPP fibers by imposing proper elongation and preventing the sPP solution from gelation. The results could be applied to other semicrystalline polyolefins with similar gelation characteristics analogous to sPP to produce thinner nanofibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43238.
Mechanical and thermal properties of modified kaolin clay/unsaturated polyester nanocomposites
Authors: George Manoj , Kochimoolayil George Elias , Jayadas Narakathra Haridas
Published: December 2015

The improvement in thermal and mechanical properties of Nanocomposites prepared with unsaturated polyester (UP) as polymer matrix and various loadings of amino‐modified nano kaolinite clay as filler has been studied. Mechanical stirring and ultrasonication resulted in better dispersion of the clay. For curing polyester resin, cobalt naphthenate was used as accelerator and MEKP as initiator. Dynamic Mechanical Analysis (DMA) was carried out to find storage and loss modulus. Thermal stability was found through thermogravimetric analysis and the evaluation of structure and morphology of the nanocomposites were done through XRD, SEM, and TEM. Nanocomposite with 3 phr of amino modified clay has shown higher storage modulus and an improved thermal stability of UP/clay nanocomposites has been established. Tensile strength and toughness of the composite have been found to achieve maximum values at 1 phr of clay and the storage modulus has had an improvement of 38% compared to neat UPR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43245.
Quantitative measurement of physisorbed silane on a silica particle surface treated with silane coupling agents by thermogravimetric analysis
Authors: Yamazaki Ryota , Karyu Nozomi , Noda Masayo , Fujii Syuji , Nakamura Yoshinobu
Published: December 2015

We investigated a new method for estimating the amount of silanes physisorbed on a silica particle surface treated with silane coupling agents from a weight loss curve measured by thermogravimetric (TG) analysis. The silica particles were treated with 3‐glycidoxypropyl trimethoxysilane (GPTMS) or 3‐mercaptopropyl trimethoxysilane (MrPTMS) with both dry and wet treatment methods. In the TG curve for silica particles treated with GPTMS, the weight decreased in three steps: 100–170°C (first step), 170–250°C (second step), and 250–400°C (third step). The weight loss in the first step decreased with heating or acetone washing to remove the physisorbed molecules as the posttreatment. The three weight losses were found to be based on physisorbed monomeric silanes (first step), physisorbed polycondensed silanes (second step), and chemisorbed silanes (third step), respectively. The amount of physisorbed silanes on the silane‐treated layer could be estimated from the TG curve without solvent washing to remove the physisorbed molecules. The amounts obtained were almost equal to those measured from a comparison of the weight losses for the treated particles before and after acetone washing. A similar tendency was observed for MrPTMS‐treated silica. Thus, the amount of physisorbed silanes in silane‐coupling‐agent‐treated silica particles was successfully estimated from the TG measurements. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43256.
Design and Discovery of Some Novel Chalcones as Antioxidant and Anti‐Inflammatory Agents via Attenuating NF‐κB
Authors: Chu Jun , Guo Chun‐Liang
Published: December 2015

Concerning the role of antioxidant and anti‐inflammatory agents for hepatic fibrosis patients, the current study deals with the development of novel chalcone derivatives 5a–i via efficient synthetic methodology in a two‐step reaction involving Claisen–Schmidt condensation. The obtained target analogs were screened for in vitro antioxidant activity by various methods (H2O2, DPPH, ferrous reducing power, and nitric oxide), where they exhibit considerable radical scavenging activity. These compounds were also evaluated for inhibitory potency against NF‐κB activation induced by LPS for the determination of their anti‐inflammatory activity. The inhibition values indicate that the entire set of compounds efficiently inhibits the NF‐κB activation provoked by LPS. Among the series, compound 5i was identified as the most potent inhibitor of NF‐κB, with a relative NF‐κB activity of 1.12 ± 0.53. It also inhibits various inflammatory mediators, such as TNF‐α, IL‐1β, IL‐6, and PGE2.
Apoferritin‐templated biosynthesis of manganese nanoparticles and investigation of direct electron transfer of MnNPs–HsAFr at modified glassy carbon electrode
Authors: Rafipour Ronak , Kashanian Soheila , Hashemi Sadegh , Omidfar Kobra , Ezzati Nazhad Dolatabadi Jafar
Published: December 2015

Manganese nanoparticles (MnNPs) were created within horse spleen apoferritin (HsAFr) cavity nanotemplates. Transmission electron microscopy revealed the particle size to be 6 nm. Intrinsic fluorescence data showed that the mineralization acted as a quencher of the HsAFr fluorescence, and extrinsic fluorescence data revealed that the hydrophobic binding site at the surface of HsAFr was not changed. Finally, the MnNP‐HsAFr was immobilized onto multiwalled carbon nanotubes entrapped into chitosan (CS) matrices by through sequential 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide–N‐hydroxysuccinimide and glutaraldehyde coupling. The MnNPs–HsAFr immobilized on CNT‐CS/GC electrode was characterized by cyclic voltammetry. This charge transfer coefficient (α) and the exchange current (i0) of MnNPs–HsAFr immobilized on modified electrode in 0.1 M phosphate solution (pH 7.5) were found to be 0.57 and 0.48 μA, respectively.
New class of Johnson distributions and its associated regression model for rates and proportions
Authors: Lemonte Artur J. , Bazán Jorge L.
Published: December 2015

By starting from the Johnsondistribution pioneered by Johnson (), we propose a broad class of distributions with bounded support on the basis of the symmetric family of distributions. The new class of distributions provides a rich source of alternative distributions for analyzing univariate bounded data. A comprehensive account of the mathematical properties of the new family is provided. We briefly discuss estimation of the model parameters of the new class of distributions based on two estimation methods. Additionally, a new regression model is introduced by considering the distribution proposed in this article, which is useful for situations where the response is restricted to the standard unit interval and the regression structure involves regressors and unknown parameters. The regression model allows to model both location and dispersion effects. We define two residuals for the proposed regression model to assess departures from model assumptions as well as to detect outlying observations, and discuss some influence methods such as the local influence and generalized leverage. Finally, an application to real data is presented to show the usefulness of the new regression model.
Effect of age on survival in patients undergoing resection of hepatocellular carcinoma
Authors: Cucchetti A , Sposito C , Pinna A D , Citterio D , Ercolani G , Flores M , Cescon M , Mazzaferro V
Published: December 2015

Background

The benefit of surgical intervention for cancer should be estimated in relation to the life expectancy of the general population. The aim of this study was to provide a measure of relative survival after hepatectomy for hepatocellular carcinoma (HCC).

Methods

Consecutive patients with liver cirrhosis and HCC who underwent hepatectomy were divided into age quartiles for analysis. Short- and mid-term survival rates were used to estimate survival until death for all patients, in relation to age and other co-variables. Years of life lost (YLL) were estimated using a reference cohort, derived from the general population matched for sex, age and year of diagnosis.

Results

Some 919 patients were included in the study. The following age quartiles were identified: less than 60 years (229 patients), 60–66 years (230), 67–70 years (231) and over 70 years (229). Postoperative mortality rates were similar between age quartiles, as were survival rates up to 3 years (P = 0·404). A statistically significant reduction in 5–10-year survival rates was observed with ageing (P = 0·001). Relative survival calculation showed that the youngest age quartile (less than 60 years) experienced the longest entire postoperative lifespan (15·6 years) but also the greatest number of YLL (11·0 years). Patients aged over 70 years had the shortest entire postoperative lifespan (6·4 years) but also the smallest number of YLL (3·7 years).

Conclusion

Although survival after liver resection for HCC is shortest in elderly patients, relative survival estimates suggest that hepatectomy can be of benefit in these patients, with a small loss of the entire individual lifespan.
A quantitative determination of fluorochloridone in rat plasma by UPLC‐MS/MS method: application to a pharmacokinetic study
Authors: Liu Shihong , Shi Jingmin , Fan Junpei , Sun Jie , Zhang Suhui , Hu Yue , Wei Li , Wu Chunhua , Chang Xiuli , Tang Liming , Zhou Zhijun
Published: December 2015

A precise, high‐throughput and sensitive ultra‐performance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) method has been developed for the determination of fluorochloridone (FLC) in rat plasma. The extraction of analytes from plasma samples was carried out by protein precipitation procedure using acetonitrile prior to UPLC‐MS/MS analysis. Verapamil was proved as a proper internal standard (IS) among many candidates. The chromatographic separation based on UPLC was well optimized. Multiple reaction monitoring in positive electrospray ionization was used with the optimized MS transitions at: m/z 312.0 → 292.0 for FLC and m/z 456.4 → 165.2 for IS. This method was well validated with good linear response (r2 > 0.998) observed over the investigated range of 3–3000 ng/mL and with satisfactory stability. This method was also characterized with adequate intra‐ and inter‐day precision and accuracy (within 12%) in the quality control samples, and with high selectivity and less matrix effect observed. Total running time was only 1.5 min. This method has been successfully applied to a pilot FLC pharmacokinetic study after oral administration. Copyright © 2016 John Wiley & Sons, Ltd.
In vitro and in vivo metabolism studies of dimethazine
Authors: Geldof Lore , Tudela Eva , Lootens Leen , van Lysebeth Jasper , Meuleman Phillip , Leroux‐Roels Geert , van Eenoo Peter , Deventer Koen
Published: December 2015

The use of anabolic steroids is prohibited in sports. Effective control is done by monitoring their metabolites in urine samples collected from athletes. Ethical objections however restrict the use of designer steroids in human administration studies. To overcome these problems alternative in vitro and in vivo models were developed to identify metabolites and to assure a fast response by anti‐doping laboratories to evolutions on the steroid market. In this study human liver microsomes and an uPA+/+‐SCID chimeric mouse model were used to elucidate the metabolism of a steroid product called ‘Xtreme DMZ’. This product contains the designer steroid dimethazine (DMZ), which consists of two methasterone molecules linked by an azine group. In the performed stability study, degradation from dimethazine to methasterone was observed. By a combination of LC‐High Resolution Mass Spectrometry (HRMS) and GC‐MS(/MS) analysis methasterone and six other dimethazine metabolites (M1–M6), which are all methasterone metabolites, could be detected besides the parent compound in both models. The phase II metabolism of dimethazine was also investigated in the mouse urine samples. Only metabolites M1 and M2 were exclusively detected in the glucuro‐conjugated fraction; all other compounds were also found in the free fraction. For effective control of DMZ misuse in doping control samples, screening for methasterone and methasterone metabolites should be sufficient. Copyright © 2016 John Wiley & Sons, Ltd.
GeoTest—A system for the automatic evaluation of geometry‐based problems
Authors: Gergelitsová Šárka , Holan Tomáš
Published: December 2015

This paper presents the design of a system for the assignment and evaluation of tasks in the area of geometry. The goal of this design is to help teachers specify and test/verify the initial level of knowledge and abilities required from students entering the relevant course. This design has been used for the implementation of GeoTest, a web based application using the GeoGebra dynamic geometry software. GeoTest has been in use by more than 100 teachers and 5,000 students at universities and secondary and elementary schools during the last 4 years. The feedback received from teachers confirms the usability of the application and its positive acceptance by teachers as well as students. © 2015 Wiley Periodicals, Inc. Comput Appl Eng Educ 24:297–304, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21712
Distal bile duct carcinomas and pancreatic ductal adenocarcinomas: postulating a common tumor entity
Authors: Schmuck Rosa B. , de Carvalho‐Fischer Cynthia V. , Neumann Christopher , Pratschke Johann , Bahra Marcus
Published: December 2015

The set definition of distal cholangiocarcinomas and adenocarcinomas of the pancreatic head is challenged by their close anatomical relation, similar growth pattern, and corresponding therapeutic outcome. They show a mutual development during embryologic organ formation and share phenotypic characteristics. This review will highlight the similarities with regard to the common origin of their primary organs, histopathological similarities, and modern clinical management. Thus, we propose to subsume those entities under a common superfamily.
Toluene Dioxygenase‐Catalysed Oxidation of Benzyl Azide to Benzonitrile: Mechanistic Insights for an Unprecedented Enzymatic Transformation
Authors: Vila María Agustina , Pazos Mariana , Iglesias César , Veiga Nicolás , Seoane Gustavo , Carrera Ignacio
Published: December 2015

Enzymatic dioxygenation of benzyl azide by toluene dioxygenase (TDO) produces significant amounts of the cis‐cyclohexadienediol derived from benzonitrile, along with the expected azido diols. We demonstrate that TDO catalyses the oxidation of benzyl azide to benzonitrile, which is further dioxygenated to produce the observed cis‐diol. A proposed mechanism for this transformation involves initial benzylic monooxygenation followed by a nitrene‐mediated rearrangement to form an oxime, which is further dehydrated to afford the nitrile. To the best of our knowledge, this is the first report of enzymatic oxidation of an alkyl azide to a nitrile. In addition, the described oxime‐dehydration activity has not been reported for Rieske dioxygenases.
Efficient Photocatalytic Oxygen Production over Nitrogen‐Doped Sr4Nb2O9 under Visible‐Light Irradiation
Authors: Wu Fangfang , Lv Meilin , Sun Xiaoqin , Xie Yinghao , Chen Hongmei , Ni Shuang , Liu Gang , Xu Xiaoxiang
Published: December 2015

Photocatalytic water splitting is an appealing process for solar energy conversions yet it is often limited by the slow oxidation of water to oxygen half‐reaction. Here we performed an investigation on N‐doped Sr4Nb2O9 as a water oxidation photocatalyst. Our results show that N doping is an effective approach to improve the visible‐light response of Sr4Nb2O9. Efficient photocatalytic oxygen production was observed after N doping, and the highest production rate of ∼27 μmol h−1 under visible‐light irradiation corresponds to an apparent quantum efficiency of ∼0.31 %. Clear anodic photocurrent can be generated under visible‐light illumination, and the flat‐band potential was determined to be ∼−1.25 V vs. Ag/AgCl at pH 7. Theoretical calculations reveal that N doping introduces additional valence bands and is responsible for the visible‐light response. Variations in light absorption and photo‐oxidation performance can be controlled by modifying these valence band positions using different nitridation temperatures.
Simple Continuous High‐Pressure Hydrogen Production and Separation System from Formic Acid under Mild Temperatures
Authors: Iguchi Masayuki , Himeda Yuichiro , Manaka Yuichi , Matsuoka Koichi , Kawanami Hajime
Published: December 2015

A simple and continuous high‐pressure (>120 MPa) hydrogen production system was developed by the selective decomposition of formic acid at 80 °C using an iridium complex as a catalyst, with a view to its application in future hydrogen fuel filling stations. The system is devoid of any compressing system. The described method can provide high‐pressure H2 with 85 % purity after applying an effective gas–liquid separation process to separate the generated gas obtained from the decomposition of formic acid (H2/CO2=1:1). The efficiency of the catalyst lies with its high turnover frequency (1800 h−1 at 40 MPa) to produce high‐pressure H2 with a good lifetime of >40 h. Interestingly, only very low levels carbon monoxide (less than 6 vol ppm) were detected in the generated gas, even at 120 MPa.
Low‐Temperature Preferential Oxidation of Carbon Monoxide on Pt3Ni Alloy Nanoparticle Catalyst with Engineered Surface
Authors: Hwang Sang Youp , Yurchekfrodl Eric , Zhang Changlin , Peng Zhenmeng
Published: December 2015

The front cover artwork for Issue 01/2016 is provided by the catalysis research group at the University of Akron (USA). The image shows an octahedral Pt3Ni alloy nanoparticle catalyst that benefits from unique surface geometry and electronic structure. This catalyst exhibits high activity and selectivity for the preferential oxidation of carbon monoxide in hydrogen. See the Communication itself at http://dx.doi.org/10.1002/cctc.201500783.
Reduction Process of Tetraplatin in the Presence of Deoxyguanosine Monophosphate (dGMP): A Computational DFT Study
Authors: Šebesta Filip , Burda Jaroslav V.
Published: December 2015

The reduction mechanism of [PtIV(dach)Cl4] (dach=diaminocyclohexyl) in the presence of dGMP was studied. The first step is substitution of a chloro ligand by dGMP, followed by nucleophilic attack of a phosphate or sugar oxygen atom to the C8‐position of guanine. Subsequent reduction forms the [PtII(dach)Cl2] complex. The whole process is completed by a hydrolysis. Two different pathways for the substitution reaction were examined: a direct associative and a Basolo–Pearson autocatalytic mechanism. All the explored structures were optimized at the B3LYP‐D3/6‐31G(d) level and by using the COSMO solvation model with Klamt's radii. Single‐point energetics was determined at the B3LYP‐GD3BJ/6‐311++G(2df,2pd)/PCM/scaled‐UAKS level. Activation barriers were used for an estimation of the rate constants and these were compared with experimental values. It was found that the rate‐determining step is the nucleophilic attack with a slightly faster performance in the 3′‐dGMP branch than in the case of 5′‐dGMP with activation barriers of 21.1 and 20.4 kcal mol−1(experimental: 23.8 and 23.2 kcal mol−1). The reduction reaction is connected with an electron flow from guanine. The product of the reduction reaction is a chelate structure, which dissociates within the last reaction step, that is, a hydrolysis reaction. The whole redox process (substitution, reduction, and hydrolysis) is exergonic by 34 and 28 kcal mol−1for 5′‐dGMP and 3′‐dGMP, respectively.
A Highly Energetic N‐Rich Metal–Organic Framework as a New High‐Energy‐Density Material
Authors: Zhang Huabin , Zhang Mingjian , Lin Ping , Malgras Victor , Tang Jing , Alshehri Saad M. , Yamauchi Yusuke , Du Shaowu , Zhang Jian
Published: December 2015

Metal–organic framework (MOF)‐based energetic material [Cu3(MA)2(N3)3] (1; MA=melamine) was synthesized and structurally characterized (47.55 % N). The structural analysis revealed the existence of unusual multiwalled tubular channels and interweaving of single and double helical units in 1. The standard molar enthalpy of formation was found to be 1788.73 kJ mol−1, which is the highest value among previously reported MOF‐based energetic materials. The calculated detonation properties showed that 1 can be used as a potential explosive. Sensitivity tests revealed that 1 is insensitive and thus can function as a high‐energy‐density material with a favorable level of safety.
A Modular Approach to Phosphoglycosyltransferase Inhibitors Inspired by Nucleoside Antibiotics
Authors: Walvoort Marthe T. C. , Lukose Vinita , Imperiali Barbara
Published: December 2015

Phosphoglycosyltransferases (PGTs) represent “gatekeeper” enzymes in complex glycan assembly pathways by catalyzing transfer of a phosphosugar from an activated nucleotide diphosphosugar to a membrane‐resident polyprenol phosphate. The unique structures of selected nucleoside antibiotics, such as tunicamycin and mureidomycin A, which are known to inhibit comparable biochemical transformations, are exploited as the foundation for the development of modular synthetic inhibitors of PGTs. Herein we present the design, synthesis, and biochemical evaluation of two readily manipulatable modular scaffolds as inhibitors of monotopic bacterial PGTs. Selected compounds show IC50 values down to the 40 μm range, thereby serving as lead compounds for future development of selective and effective inhibitors of diverse PGTs of biological and medicinal interest.
Sandmeyer‐Type Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero)Aromatic Amines Catalyzed by Copper
Authors: Matheis Christian , Wagner Victoria , Goossen Lukas J.
Published: December 2015

Invited for the cover of this issue is the group of Lukas J. Goossen at the Technische Universität Kaiserslautern (Germany). The image depicts the Me4NSCF3/Me4NSeCF3 reagent—in the form of an arrow—hitting the target benzenediazonium starting material at the center of the dartboard, helped on its way by a copper catalyst. Read the full text of the article at 10.1002/chem.201503524.
Was braucht man für eine Super‐Batterie?
Authors: Bieker Peter , Winter Martin
Published: December 2015

In einem zweigeteilten Aufsatz berichten wir über die Grundlagen und diversen Zellchemien von Hochenergieakkumulatoren. Hier, im ersten Teil, haben wir beschrieben, welche Voraussetzungen erfüllt sein müssen, um eine wiederaufladbare Batterie mit hohen Energieinhalten pro Gewicht, also eine “Superbatterie” zu realisieren. Dabei haben wir festgestellt, dass die Hochenergie‐Zukunftstechnologien Brennstoffzelle als auch Metall‐Luft‐Zelle schon zu Anfang der Batteriegeschichte entdeckt wurden, und dass eine Superbatterie mit Elektroden auf der Basis von Li‐Metall bzw. Li‐Einlagerungsmaterialien im Moment am vielversprechendsten erscheint. Im nächsten Teil werden wir diese Li‐Batterietechnologien im Detail beschreiben, aber auch Alternativsysteme vorstellen. Allen Batteriesystemen ist gemein, dass sie einem anderen energieliefernden Reaktionsmechanismus als eine thermische Verbrennung folgen. In Hinsicht auf elektromobile Anwendungen ist ein Vergleich der Energieanhalte von Batterie und Benzinverbrennungsmotor deshalb nur bedingt fair und zielführend.
Quality of life and mood predict posttraumatic stress disorder after hematopoietic stem cell transplantation
Authors: El‐Jawahri Areej R. , Vandusen Harry B. , Traeger Lara N. , Fishbein Joel N. , Keenan Tanya , Gallagher Emily R. , Greer Joseph A. , Pirl William F. , Jackson Vicki A. , Spitzer Thomas R. , Chen Yi‐Bin A. , Temel Jennifer S.
Published: December 2015

BACKGROUND

During hospitalization for hematopoietic stem cell transplantation (HCT), patients experience a steep deterioration in quality of life (QOL) and mood. To our knowledge, the impact of this deterioration on patients' QOL and posttraumatic stress disorder (PTSD) symptoms after HCT is unknown.

METHODS

We conducted a prospective longitudinal study of patients hospitalized for HCT. They assessed QOL using the Functional Assessment of Cancer Therapy‐Bone Marrow Transplantation (FACT‐BMT) and depression and anxiety symptoms were assessed using the Patient Health Questionnaire‐9 (PHQ‐9) at the time of admission for HCT, during hospitalization, and 6 months after HCT. We also used the Hospital Anxiety and Depression Scale (HADS) to measure patients' anxiety and depression symptoms at baseline and during HCT hospitalization. The PTSD Checklist was used to assess for PTSD symptoms. Multivariable linear regression models were used to identify predictors of QOL and PTSD symptoms at 6 months.

RESULTS

We enrolled 90 of 93 consecutively eligible patients (97%) undergoing autologous and allogeneic HCT. Data at 6 months were available for 67 participants. At 6 months, 28.4% of participants met the criteria for PTSD and 43.3% had clinically significant depression. On multivariable regression analyses adjusting for significant covariates, changes in QOL and depression scores from week 2 of HCT hospitalization to baseline predicted worse QOL (changes in scores between week 2 and baseline [Δ] QOL: β, 0.94 [P<.0001] and Δ PHQ‐9: β, −2.59 [P = 0.001]) and PTSD symptoms (Δ QOL: β, −0.40 [P<.0001] and Δ PHQ‐9: β, 1.26 [P<.0001]) at 6 months after HCT.

CONCLUSIONS

Six months after HCT, a significant percentage of patients met the criteria for PTSD and depression. A decline in QOL and an increase in depressive symptoms during hospitalization for HCT were found to be the most important predictors of 6‐month QOL impairment and PTSD symptoms. Therefore, managing symptoms of depression and QOL deterioration during HCT hospitalization may be critical to improving QOL at 6 months and reducing the risk of PTSD. Cancer 2016;122:806–812. © 2015 American Cancer Society.
Inherited variation in OATP1B1 is associated with treatment outcome in acute myeloid leukemia
Authors: Drenberg CD , Paugh SW , Pounds SB , Shi L , Orwick SJ , Li L , Hu S , Gibson AA , Ribeiro RC , Rubnitz JE , Evans WE , Sparreboom A , Baker SD
Published: December 2015

Using broad interrogation of clinically relevant drug absorption, distribution, metabolism, and excretion (ADME) genes on the DMET platform, we identified a genetic variant inSLCO1B1(rs2291075; c.597C>T), encoding the transporter OATP1B1, associated with event‐free (P= 0.006, hazard ratio = 1.74) and overall survival (P= 0.012, hazard ratio = 1.85) in children withde novoacute myeloid leukemia (AML). Lack ofSLCO1B1expression in leukemic blasts suggested the association might be due to an inherited rather than a somatic effect. rs2291075 was in strong linkage with known functional variants rs2306283 (c.388A>G) and rs4149056 (c.521T>C). Functional studiesin vitrodetermined that four AML‐directed chemotherapeutics (cytarabine, daunorubicin, etoposide, and mitoxantrone) are substrates for OATP1B1 and the mouse ortholog Oatp1b2.In vivopharmacokinetic studies using Oatp1b2‐deficient mice further confirmed our results. Collectively, these findings demonstrate an important role for OATP1B1 in the systemic pharmacokinetics of multiple drugs used in the treatment of AML and suggest that inherited variability in host transporter function influences the effectiveness of therapy.
Improving therapeutic effectiveness and safety through big healthcare data
Authors: Schneeweiss S
Published: December 2015

Big healthcare data—electronically recorded longitudinal data generated during the provision and administration of healthcare for millions of patients—have become essential for understanding the effectiveness and safety of therapeutics. They are most effectively used in concert with experimental and laboratory research throughout the life cycle of a drug. Applications range from providing phenotype and health outcomes information in genome‐wide association studies to postmarketing studies that assure prescribers of the safety of approved drugs (Figure ).

The uses of big healthcare data and their analysis throughout the life cycle of prescription drugs.

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Synthesis conditions of europium tetrakis dibenzoylmethide triethylammonium crystals
Authors: Scheiner Margaret , Dickens Tarik J. , Okoli Okenwa
Published: December 2015

Europium tetrakis dibenzoylmethide triethylammonium crystals are highly triboluminescent, indicating possible use in structural health monitoring. This work investigates the effect of synthesis conditions on crystalline yield and morphology of this material. Less solvent yields more material, but may cause striations in crystal faces. No statistical effect on triboluminescent yield was recorded. Scanning electron microscopy shows crystal size varies from 30–400 μm based on synthesis conditions.
Copolymerization as a Strategy to Combine Epoxidized Linseed Oil and Furfuryl Alcohol: The Design of a Fully Bio‐Based Thermoset
Authors: Pin Jean‐Mathieu , Guigo Nathanaël , Vincent Luc , Sbirrazzuoli Nicolas , Mija Alice
Published: December 2015

Epoxidized linseed oil and furfuryl alcohol are bio‐sourced monomers known for their high‐potential applications in materials science. In this work, we propose the association of these monomers through copolymerization reactions with the target to design fully bio‐based thermosets. Herein, investigations on cationic polymerization reactivity have been explored using differential scanning calorimetry. The obtained structures have been confirmed by IR spectroscopy and 2 D NMR spectroscopy, which revealed the principal chain connections. In spite of the multiple capabilities of chemical connections, which include copolymerization and cross‐linking, the obtained networks are homogeneous as confirmed by dynamic mechanical analysis and SEM. Furthermore, the copolymer demonstrates a semiductile behavior if subjected to tensile measurements (tensile strain at break ≈40 %), which is a significant advance in terms of its applications as a furanic bio‐based thermoset material.