bluuebunny/crossref_metadata_2025 huggingface dataset:
The dispersion relations of dispersive Alfvén waves in superthermal plasmas
Authors: Gaelzer Rudi , Ziebell Luiz F.
Published: November 2014

The effects of velocity distribution functions (VDFs) that exhibit a power law dependence on the high‐energy tail have been the subject of intense research by the space plasma community. Such functions, known assuperthermalorkappadistributions, have been found to provide a better fitting to the VDF measured by several spacecraft in the plasma environment of the solar wind. In the literature, the general treatment for waves excited by (bi‐)Maxwellian plasmas is well established. However, for kappa distributions, either isotropic or anisotropic, the wave characteristics have been studied mostly for the limiting cases of purely parallel or perpendicular propagation. Contributions for the general case of obliquely propagating waves have been scarcely reported so far. In this work we introduce a mathematical formalism that provides expressions for the dielectric tensor components and subsequent dispersion relations for oblique propagating dispersive Alfvén waves (DAWs) resulting from a kappa VDF. We employ an isotropic distribution, but the methods used here can be easily applied to more general anisotropic distributions, such as the bi‐kappa or product‐bi‐kappa. The effect of the kappa index and thermal corrections on the dispersion relations of DAW is discussed.
Widespread gas hydrate instability on the upper U.S. Beaufort margin
Authors: Phrampus Benjamin J. , Hornbach Matthew J. , Ruppel Carolyn D. , Hart Patrick E.
Published: November 2014

The most climate‐sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three‐dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5–7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.
Teleseismic traveltimes residuals across the Dead Sea basin
Authors: Hofstetter A. , Dorbath C.
Published: November 2014

New findings of the structure of the Dead Sea sedimentary basin and its eastern and western bordering regions are obtained by P and PKP wave relative traveltime residuals of 644 teleseisms, as recorded by the Dead Sea Integrated Research portable seismic network in the Dead Sea basin and its neighboring regions. The Lisan Peninsula is characterized by relatively small teleseismic traveltime residuals of about 0.14 s, in the latitude range of 31.22°–31.37° and at the longitude of 35.50°, slowly decreasing toward the west. The largest teleseismic traveltime residuals are in the southern Dead Sea basin, south of the Lisan Peninsula in the latitude range of 31.05°–31.15° and along longitude 35.45° and continuing southward toward the Amaziahu Fault, reaching values of 0.4–0.5 s. There is a small positive residual at the Amaziahu Fault and a small negative residual south of it probably marking the southern end of the Dead Sea basin. East and west of the Dead Sea basin the mean teleseismic traveltime residuals are negative with overall averages of −0.35 s and −0.45 s, respectively. Using the teleseismic residuals, we estimate the horizontal dimensions of the Lisan salt diapir to be 23 km × 13 km at its widest and a maximal thickness of about 7.2 km. The thickness of the Mount Sodom salt diapir is estimated as 6.2 km.
Relationship between coral distributions and physical variables in Amitori Bay, Iriomote Island, Japan
Authors: Shimokawa Shinya , Murakami Tomokazu , Ukai Akiyuki , Kohno Hiroyoshi , Mizutani Akira , Nakase Kouta
Published: November 2014

The relationship between coral distributions and physical variables was investigated in Amitori Bay, Iriomote Island, Japan. Field observations were conducted to obtain data on coral distributions, sea temperature, sea salinity, wind speed, and river flow rate. The observed data were then used in ocean and wave model numerical simulations and soil particle tracking analysis to obtain the spatial and temporal distributions of wave height and the numbers of soil particles. The main results of this study indicate that wave height and the number of soil particles have a significant correlation with coral distribution. Higher wave heights result in greater coverage of tabular coral and lower coverage of branching coral. A greater number of soil particles relates to lesser coverage of tabular coral. On the contrary, the number of soil particles is not correlated with branching coral coverage. The potential habitats for tabular corals largely depend on the species. Acropora hyacinthus is distributed in conditions with low numbers of soil particles, A. digitifera is distributed in conditions with low numbers of soil particles and high wave heights, and A. millepora is distributed in conditions with high numbers of soil particles and low wave heights. Averages of diversity index of the coral types at the mouth and inner parts of the bay are lower than average of the whole region, but average of diversity index at the intermediate part of the bay with the intermediate physical disturbances is higher than it, which seems to support the intermediate disturbance hypothesis.
Strong control of surface roughness variations on the simulated dry season regional atmospheric response to contemporary deforestation in Rondônia, Brazil
Authors: Khanna Jaya , Medvigy David
Published: November 2014

The atmospheric effects of Amazon deforestation have frequently been studied in the context of small scales (≈1 km) and very large scales (hundreds of kilometers). However, analysis of intermediate‐scale deforestation (tens of kilometers) has received less attention, despite the fact that it better represents the contemporary landscape in some parts of the Amazon. In this study, the dynamic and thermodynamic effects of contemporary intermediate‐scale deforestation in Rondônia, Brazil are investigated through variable resolution Global Circulation Model (GCM) simulations carried out with the Ocean‐Land‐Atmosphere Model. In particular, the atmospheric response to surface roughness changes brought about by deforestation is emphasized. This study shows that reductions in surface roughness associated with intermediate‐scale deforestation give rise to a mesoscale circulation. This circulation is capable of convective triggering, but it also weakens the turbulent exchange of energy between land and atmosphere. Furthermore, this mesoscale circulation has distinct impacts on the hydroclimates of the western and eastern halves of Rondônia, increasing shallow cloudiness in the former while suppressing it in the latter. These results show that the atmospheric response to contemporary intermediate‐scale deforestation in Rondônia is likely to be more influenced by differences in surface roughness between forest and forest clearings than by the differences in the surface energy partitioning.
An Expeditious and Metal‐Free Synthetic Route towards Quinolones, Naphthyridones and Benzonaphthyridones
Authors: Victor Napoleon John , Muraleedharan Kannoth Manheri
Published: November 2014

An efficient, two‐step synthetic strategy has been developed to access the quinolone, naphthyridone and benzonaphthyridone classes of chemotherapeutic agents from Baylis–Hillman adducts. The method involves tandem aza‐Michael addition, SNAr cyclisation followed by oxidation of the resulting 4‐hydroxy‐1,2,3,4‐tetrahydroquinoline or 4‐hydroxy‐1,2,3,4‐tetrahydro‐1,8‐naphthyridine derivative using IBX, and works well with substrates having a wide variety of substitution pattern.

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Transition Metal‐Free Direct Trifluoromethylation of 2,3‐Dihydropyridin‐4(1H)‐ones at Room Temperature
Authors: Yu Yi‐Yun , Ranade Adwait R. , Georg Gunda I.
Published: November 2014

A transition metal‐free, regioselective C‐5 trifluoromethylation of 2,3‐dihydropyridin‐4(1H)‐ones (cyclic enaminones) with trimethyl(trifluoromethyl)silane (TMSCF3) was developed that proceeds under mild conditions at room temperature. This direct transformation was successful with both electron‐rich and electron‐deficient cyclic enaminones. This method bypasses substrate prefunctionalization and transition metal catalysis, and allows the convenient and direct access to a variety of medicinally important 3‐trifluoromethylpiperidine derivatives. This chemistry also represents a rare example of a direct trifluoromethylation of an internal olefinic CH bond. A radical mechanism is proposed for this reaction.

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Molecular Basis for the Enantio‐ and Diastereoselectivity of Burkholderia cepacia Lipase toward γ‐Butyrolactone Primary Alcohols
Authors: Eum Heesung , Kazlauskas Romas J. , Ha Hyun‐Joon
Published: November 2014

Burkholderia cepacia lipase (BCL) shows high enantioselectivity toward chiral primary alcohols, but this enantioselectivity is often unpredictable, especially for substrates that contain an oxygen at the stereocenter. For example, BCL resolves β‐substituted‐γ‐acetyloxymethyl‐γ‐butyrolactones (acetates of a chiral primary alcohol) by hydrolysis of the acetate, but the enantioselectivity varies with the nature and orientation of the β‐alkyl substituent. BCL favors the (R)‐primary alcohol when the β‐alkyl substituent is hydrogen (E=30) or trans methyl (E=38), but the (S)‐primary alcohol when it is cis methyl (E=145). To rationalize this unusual selectivity, we used a combination of experiments to show the importance of polar interactions and modeling to reveal differences in orientations of the enantiomers. Removal of either the lactone carbonyl in the substrate or the polar side chains in the enzyme by using a related enzyme without these side chains decreased the enantioselectivity at least four‐fold. Modeling revealed that the slow enantiomers do not bind by exchanging the location of two substituents relative to the fast enantiomer. Instead, three substituents remain in the same region, but the fourth substituent, hydrogen, inverts to a new location, like an umbrella in a strong wind. In this orientation the favored stereoisomers have similar shapes, thus accounting for the unusual stereoselectivity. The ratio of catalytically productive orientations for the fast vs. slow enantiomers in a molecular dynamic simulation correlated (R2=0.82) with the degree of enantioselectivity including the case where the enantioselectivity reversed. Weighting this ratio by the ratio of H‐bonds in the polar interaction to account for different binding strengths improved the correlation with the measured enantioselectivity to R2=0.97. The modeling identifies key interactions responsible for high enantioselectivity in this class of substrates.

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A Palladium‐Catalyzed Carbonylative–Deacetylative Sequence to 1,3‐Keto Amides
Authors: Nielsen Dennis U. , Korsager Signe , Lindhardt Anders T. , Skrydstrup Troels
Published: November 2014

An efficient three‐component reaction involving carbon monoxide with a range of aryl bromides and N‐substituted acetoacetamides is reported for the synthesis of β‐keto amides. This transformation is promoted by Pd‐catalysis followed by an acid‐mediated deacetylation upon work‐up, enabling a large number of β‐keto amides to be isolated. Finally, d2‐13C‐dyclonine could be synthesized in three steps utilizing the developed catalytic system as the key step.

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Organocatalytic Morita–Baylis–Hillman/Michael/Acetalization Cascade: Procedure‐Controlled Diastereodivergence in the Asymmetric Synthesis of Fully Substituted Tetrahydropyrans
Authors: Han Bo , Xie Xin , Huang Wei , Li Xiang , Yang Lei , Peng Cheng
Published: November 2014

Modulating the diastereoselectivity of stereochemically complex molecules in asymmetric synthesis remains a challenge, especially when the reaction cycle produces no net change in the catalysts, ligands, substrates or additives. Here we accomplish a controlled diastereodivergence in the asymmetric synthesis of fully functionalized tetrahydropyrans by adjusting the sequence of an organocatalytic cascade reaction. We also show that this one‐pot operation provides two synthetically important architectures with excellent stereocontrol. To the best of our knowledge, this is the first published kinetic resolution of MBH alcohols in an organocascade.

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Scale‐up of agitated drying: Effect of shear stress and hydrostatic pressure on active pharmaceutical ingredient powder properties
Authors: Remy Brenda , Kightlinger Weston , Saurer Eric M. , Domagalski Nathan , Glasser Benjamin J.
Published: November 2014

Scale‐up of agitated drying processes to minimize particle size changes in active pharmaceutical ingredients (API) can be challenging. Particle agglomeration or attrition problems due to agitated drying are often discovered on the initial scale‐up from the lab to the plant. Traditional laboratory drying equipment has not successfully reproduced the degree of agglomeration or attrition observed at scale. This discrepancy may be attributed to the ability of particulate solids, such as crystalline API's to transfer stresses from the normal direction into the shearing direction. As batch size increases during scale‐up, the compressive and shearing forces experienced by the API increase. To overcome this limitation, a modified laboratory setup was constructed which reproduces the range of hydrostatic pressures observed during scale‐up. This work highlights the use of the modified setup to characterize the propensity for particle attrition to occur at different stages of the drying process by measuring impeller torque. Torque measurements of the API powder at different hydrostatic pressures revealed a behavior consistent with Coulomb's law of friction. The torque data obtained from these measurements were used to determine the bulk friction coefficient for API powder beds at different liquid content. Additionally, the amount of work done by the impeller blades was correlated to the degree of particle attrition observed. A workflow for assessing risk of API attrition at scale is described. © 2014 American Institute of Chemical Engineers AIChE J, 61: 407–418, 2015
Catalytic combustion kinetics of isopropanol over novel porous microfibrous‐structured ZSM‐5 coating/PSSF catalyst
Authors: Chen Huanhao , Yan Ying , Shao Yan , Zhang Huiping , Chen Huanhao
Published: November 2014

Porous thin‐sheet cobalt–copper–manganese mixed oxides modified microfibrous‐structured ZSM‐5 coating/PSSF catalysts were developed by the papermaking/sintering process, secondary growth process, and incipient wetness impregnating method. Paper‐like sintered stainless steel fibers (PSSF) support with sinter‐locked three‐dimensional networks was built by the papermaking/sintering process, and ZSM‐5 coatings were fabricated on the surface of stainless steel fibers by the secondary growth process. Catalytic combustion performances of isopropanol at different concentrations over the microfibrous‐structured Co–Cu–Mn (1:1:1)/ZSM‐5 coating/PSSF catalysts were measured to obtain kinetics data. The catalytic combustion kinetics was investigated using power–rate law model and Mars–Van Krevelen model. It was found that the Mars–Van Krevelen model provided fairly good fits to the kinetic data. The catalytic combustion reaction occurred by interaction between isopropanol molecule and oxygen‐rich centers of modified microfibrous‐structured ZSM‐5 coating/PSSF catalyst. The reaction activation energies for the reduction and oxidation steps are 60.3 and 57.19 kJ/mol, respectively. © 2014 American Institute of Chemical Engineers AIChE J, 61: 620–630, 2015
Minimal residual disease as biomarker for optimal biologic dosing of ARA‐C in patients with acute myeloid leukemia
Authors: Maurillo Luca , Buccisano Francesco , Piciocchi Alfonso , Del Principe Maria Ilaria , Sarlo Chiara , Di Veroli Ambra , Panetta Paola , Irno‐Consalvo Maria , Nasso Daniela , Ditto Concetta , Refrigeri Marco , De Angelis Gottardo , Cerretti Raffaella , Arcese William , Sconocchia Giuseppe , Lo‐Coco Francesco , Amadori Sergio , Venditti Adriano
Published: November 2014

We assessed by flow cytometry minimal residual disease (MRD) in patients with acute myeloid leukemia (AML) given standard‐dose (SDAC) and high‐dose ARA‐C (HDAC) regimens. Of 163 patients enrolled, 130 (median age, 45 years; range, 18–59 years) qualified for analysis, all achieving complete remission after treatment with SDAC (n = 78) or HDAC (n = 52) plus etoposide and daunorubicin. Consolidation consisted of intermediate‐dose ARA‐C and daunorubicin. MRD negativity was significantly more frequent in the SDAC vs. HDAC arm after both induction (37% vs. 15%, P = 0.007) and consolidation (44% vs. 18%, P = 0.002). Respective median residual leukemic cell counts with SDAC and HDAC use were 1.5 × 10−3 and 4 × 10−3 (P = 0.033) after induction and 5.7 × 10−4 and 2.9 × 10−3 (P = 0.008) after consolidation. Based on ARA‐C schedule and post‐consolidation MRD status, the four patient groups (SDAC‐MRD−, HDAC‐MRD−, SDAC‐MRD+, and HDAC‐MRD+) displayed 5‐year overall survival rates of 60%, 33%, 24%, and 42% (P = 0.007), respectively, with 24%, 35%, 74%, and 48% (P < 0.0001) respective cumulative incidence of relapse estimates. MRD may serve as a biomarker for optimal biologic dosing of ARA‐C, and SDAC regimen appears to yield more frequent MRD negativity. Am. J. Hematol. 90:125–131, 2015. © 2014 Wiley Periodicals, Inc.
Diamant‐Nanodrähte: Herstellung, Struktur, Eigenschaften und Anwendungen
Authors: Yu Yuan , Wu Liangzhuan , Zhi Jinfang
Published: November 2014

Nanodrähte aus sp3‐C‐C‐gebundenem Diamant sind Halbleiter mit einer breiten Bandlücke und einer Kombination ausgezeichneter Eigenschaften wie einer negativen Elektronenaffinität, chemischer Inertheit, einem hohen Elastizitätsmodul, höchster Härte und höchster thermischer Leitfähigkeit bei Raumtemperatur. Über die Herstellung von 1D‐Diamant‐Nanodrähten können die zentralen Eigenschaften von Diamant durch Erhöhen des Verhältnisses von Oberfläche zu Volumen gesteuert und verbessert werden. Der theoretische Vergleich mit Kohlenstoff‐Nanoröhrchen zeigt, dass Diamant‐Nanodrähte energetisch und mechanisch existenzfähige Strukturen sind – die reproduzierbare Synthese kristalliner Diamant‐Nanodrähte bleibt aber schwierig. Wir geben eine aktuelle und umfassende Übersicht über Diamant‐Nanodrähte, in der wir ihre Synthese, Strukturen, Eigenschaften und Anwendungen diskutieren.
Early Main Group Metal Catalysis: How Important is the Metal?
Authors: Penafiel Johanne , Maron Laurent , Harder Sjoerd
Published: November 2014

Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal–alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca2+. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph2N−][Me4N+] and [Ph3C−][Me4N+]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of ArNCO and RNCNR (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated CC bonds in H2CCHCH2CPh2CH2NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.
Peptide‐Induced Hierarchical Long‐Range Order and Photocatalytic Activity of Porphyrin Assemblies
Authors: Liu Kai , Xing Ruirui , Chen Chengjun , Shen Guizhi , Yan Linyin , Zou Qianli , Ma Guanghui , Möhwald Helmuth , Yan Xuehai
Published: November 2014

Long‐range structural order and alignment over different scales are of key importance for the regulation of structure and functionality in biology. However, it remains a great challenge to engineer and assemble such complex functional synthetic systems with order over different length scales from simple biologically relevant molecules, such as peptides and porphyrins. Herein we describe the successful introduction of hierarchical long‐range order in dipeptide‐adjusted porphyrin self‐assembly by a thermodynamically driven self‐orienting assembly pathway associated with multiple weak interactions. The long‐range order and alignment of fiber bundles induced new properties, including anisotropic birefringence, a large Stokes shift, amplified chirality, and excellent photostability as well as sustainable photocatalytic activity. We also demonstrate that the aligned fiber bundles are able to induce the epitaxially oriented growth of Pt nanowires in a photocatalytic reaction.
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β‐O‐4 Linkages in Lignin
Authors: Lancefield Christopher S. , Ojo O. Stephen , Tran Fanny , Westwood Nicholas J.
Published: November 2014

Functionalized phenolic monomers have been generated and isolated from an organosolv lignin through a two‐step depolymerization process. Chemoselective catalytic oxidation of β‐O‐4 linkages promoted by the DDQ/tBuONO/O2 system was achieved in model compounds, including polymeric models and in real lignin. The oxidized β‐O‐4 linkages were then cleaved on reaction with zinc. Compared to many existing methods, this protocol, which can be achieved in one pot, is highly selective, giving rise to a simple mixture of products that can be readily purified to give pure compounds. The functionality present in these products makes them potentially valuable building blocks.
ZnO‐Functionalized Upconverting Nanotheranostic Agent: Multi‐Modality Imaging‐Guided Chemotherapy with On‐Demand Drug Release Triggered by pH
Authors: Wang Yinghui , Song Shuyan , Liu Jianhua , Liu Dapeng , Zhang Hongjie
Published: November 2014

Limited therapeutic efficiency and severe side effects in patients are two major issues existing in current chemotherapy of cancers in clinic. To design a proper theranostic platform seems thus quite needed to target cancer cells accurately by bioimaging and simultaneously release drugs on demand without premature leakage. A novel ZnO‐functionalized upconverting nanotheranostic platform has been fabricated for clear multi‐modality bioimaging (upconversion luminescence (UCL), computed tomography (CT), and magnetic resonance imaging (MRI)) and specific pH‐triggered on‐demand drug release. In our theranostic platform multi‐modality imaging provides much more detailed and exact information for cancer diagnosis than single‐modality imaging. In addition, ZnO can play the role of a “gatekeeper” to efficiently block the drug in the mesopores of the as‐prepared agents until it is dissolved in the acidic environment around tumors to realize sustained release of the drug. More importantly, the biodegradable ZnO, which is non‐toxic against normal tissues, endows the as‐prepared agents with high therapeutic effectiveness but very low side effects. These findings are of great interests and will inspire us much to develop novel effective imaging‐guided on‐demand chemotherapies in cancer treatment.
Understanding external plasticization of melt extruded PHBV–wheat straw fibers biodegradable composites for food packaging
Authors: Martino Lucrezia , Berthet Marie‐Alix , Angellier‐Coussy Hélène , Gontard Nathalie
Published: November 2014

The objective of this work is to get further knowledge on the external plasticization mechanisms of melt extruded polyhydroxyl‐3‐butyrate‐co−3‐valerate (PHBV) when combined with wheat straw fibers (WSF). Different types of biodegradable substances, all authorized for food contact according to the European regulation, i.e., acetyltributyl citrate (ATBC), glycerol triacetate (GTA) and (PEG) at different molecular weights, were tested at different percentages (5, 10 and 20 wt %). Thermal and mechanical characterization of PHBV/plasticizer blends showed that a significant plasticizing effect was obtained using hydrophobic substances such as ATBC and GTA, with an increase of the elongation at break from 1.8% up to about 6% for an additive content of 10 wt %. However, the incorporation of WSF in plasticized PHBV led to a dramatic decrease in the elongation at break of composites, neutralizing the increase of this parameter by the addition of the plasticizers. The stress at break of plasticized films was also significantly decreased by the introduction of fibers. Such a loss of ductility was mainly explained by the occurrence of microscopic defects in the materials induced by the presence of fibers and to a poor adhesion at the fiber/matrix interface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41611.
Self‐assembled polypyrrole film by interfacial polymerization for supercapacitor applications
Authors: Yang Qinghao , Hou Zhenzhong , Huang Tianzhu
Published: November 2014

A facile interfacial synthesis strategy is proposed to synthesize self‐assembled polypyrrole (PPy) free‐standing films for electrochemical capacitors with the assistance of surfactants. The chemical structure of the obtained samples is characterized by Fourier transform infrared. The morphologies of the samples are studied by scanning electron microscope. The results show that the prepared PPy films own highly porous structures using Tween80 as a surfactant, while the synthesized PPy films have vesicular structures by adding Span80 as a surfactant. Furthermore, lowering polymerization temperature makes PPy films have smaller and more pores or vesicles. The PPy films prepared at 0°C with Tween80 as a surfactant possess a high specific capacitance of 261 F g−1 at 25 mV s−1 as well as retain 75% of the initial specific capacitance value after 1000 cycles. The good electrochemical properties can be attributed to the highly porous structural advantage of the PPy films caused by Tween80. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41615.
Preparation of a poly(phthalazine ether sulfone ketone) membrane with propanedioic acid as an additive and the prediction of its structure
Authors: Qin Peiyong , Liu Anni , Chen Cuixian
Published: November 2014

In this study, propanedioic acid was investigated as a potential additive in poly(phthalazine ether sulfone ketone) (PPESK)/N‐methyl‐2‐pyrrolidone solutions. Compared with poly(ethylene glycol) with a molecular weight of 1000 and Tween 80 as additives, different phenomena were observed: (1) both fingerlike and spongelike structures of asymmetric ultrafiltration membranes were induced by rapid gelation, and (2) a spongelike structure membrane with a high pure water flux was obtained under a high gelation rate. Moreover, the PPESK membrane formation process was recorded with a recently developed optical microscopy (OM)–charge‐coupled device (CCD) camera experimental system. The predicted membrane structure with an OM–CCD system gave good correspondence with the final membrane structure and performance, as detected by scanning electron microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41621.
Effect of Point Sampling Density in Quantifying Mouse Lung Emphysema
Authors: Limjunyawong Nathachit , Kearson Alexandra , Das Sandhya , Mitzner Wayne
Published: November 2014

In the official joint policy document of the American Thoracic Society and European Respiratory Society (Hsia et al., Am J Respir Crit Care Med 181:394‐418), the need for proper stereologic assessment of lungs was emphasized. In this document it was emphasized that for the quantitative analysis of lung histologic sections, one of the most robust and reliable methods is point and intercept counting (Knudsen et al., J Appl Physiol 108:412‐421). One of the practical aspects of this method is how many points or intercepts are needed. The answer to this question has been considered from a theoretical perspective, and it depends on the relative magnitudes of the methodological and biologic variabilities. Although it is generally accepted that in a normal lung, one needs only 100–200 points to sufficiently lower the methodological variability, given the increased variability often seen in experimental emphysematous lung injury, the requisite number of points of intercepts has not been evaluated. In this study, we examined this question by focusing on some of the relevant sampling levels in mice with extensive elastase‐induced emphysema. Using fixed samples of tissue blocks, we varied the number of sampling points or intercepts from about 25 to 1,000 in control and emphysematous lungs. Our results show that, at the sampling levels investigated, even with the increased heterogeneity in the lung tissue damage caused by elastase, the number of sampling points needed to detect changes is similar to what is needed for control mice. Anat Rec, 298:531–537, 2015. © 2014 Wiley Periodicals, Inc.
The Distinct Distributions of Immunocompetent Cells in Rat Dentin Pulp After Pulpotomy
Authors: Zhang Min , Kokabu Shoichiro , Nakatomi Chihiro , Sugiyama Goro , Matsuo Kou , Jimi Eijiro
Published: November 2014

Pulpotomy involves the removal of the coronal portion of pulp, including the diseased tissue, with the intent of maintaining the vitality of the remaining pulpal tissue via a therapeutic dressing. Once odontoblasts suffer injuries, the differentiation of mesenchymal cells is induced from the precursor cell population in the dental pulp, and these cells are recruited to the injured site to differentiate into odontoblasts. However, the involvement of immunocompetent cells during pulpal regeneration remains unclear. Thus, the purpose of this study was to investigate the properties of macrophages that infiltrated wound healing sites in rats between 1 and 28 days after pulpotomy (dap). During the inflammatory phase, ED1+ (CD68+) macrophages significantly increased throughout root pulp, especially apical to the demarcation zone, and this population persisted until 3 dap before decreasing gradually until 28 dap. OX6+ macrophages expressing class II MHC also increased in the apical pulp at 1 dap and declined thereafter. However, OX6+ cells appeared prior to dentin bridge formation at 3 dap and appeared again apical to the dentin bridge during the healing stage at 14 dap. The shift from ED1+ cells in the inflammation phase to OX6+ cells during dentin bridge formation might contribute to wound healing. Anat Rec, 298:741–749, 2015. © 2014 Wiley Periodicals, Inc.
Expedient Construction of the [5‐6‐7] Tricyclic Core of Calyciphylline A‐Type Alkaloids
Authors: Guo Jing‐Jing , Li Yun , Cheng Bin , Xu Tingting , Tao Cheng , Yang Xinkan , Zhang Denghong , Yan Guangqi , Zhai Hongbin
Published: November 2014

An efficient synthetic route toward the highly congested [5‐6‐7] tricyclic core of calyciphylline A‐type alkaloids has been developed. This approach features a highly efficient intramolecular Diels–Alder cycloaddition to establish the aza‐five‐membered C ring as well as the C1 all‐carbon quaternary center, and a subsequent cyclopropanation together with a ring‐expansion reaction of the resulted adduct to construct the seven‐membered D ring.
Population pharmacokinetics of etomidate in neonates and infants with congenital heart disease
Authors: Su Felice , El‐Komy Mohammed H. , Hammer Gregory B. , Frymoyer Adam , Cohane Carol A. , Drover David R.
Published: November 2014

Background

Etomidate is a rapid‐onset, short‐acting hypnotic medication administered for the induction of anesthesia. It is currently approved by the Food and Drug Administration for use in older children and adults. Pharmacokinetic data to help guide dosing in neonates and infants are lacking.

Objective

The aim of this study was to determine the pharmacokinetics of etomidate in neonates and infants with congenital heart disease undergoing cardiac surgery.

Methods

Four neonates and 16 infants, postnatal age 0.3–11.7 months, requiring open‐heart surgery received 0.3 mg/kg of etomidate administered as a single intravenous dose prior to surgery. Blood sampling for plasma etomidate concentration occurred immediately following etomidate administration until the initiation of cardiopulmonary bypass. A population pharmacokinetic approach using nonlinear mixed‐effects modeling was applied to characterize etomidate pharmacokinetics.

Results

The pharmacokinetics of etomidate was described by a two‐compartment model with first‐order elimination. An allometric weight‐based model was applied to scale results to a 70 kg adult. Covariates including age and cardiac physiology were not found significantly to impact etomidate pharmacokinetics. The study population was found to have a central and intercompartmental clearance of 0.624 l/min/70 kg and 0.44 l/min/70 kg, respectively; central and peripheral distribution volume of 9.47 l/70 kgand 22.8 l/70 kg, respectively. Inter‐individual variability was 94–142% for all parameters and the residual variability was 29%.

Conclusions

The clearance of etomidate is lower in neonates and infants with congenital heart disease compared with published values for older children without congenital heart disease. In addition, etomidate pharmacokinetics is highly variable in this pediatric cardiac population. Copyright © 2014 John Wiley & Sons, Ltd.
Association between maternal single nucleotide polymorphisms in genes regulating glucose metabolism and risk for neural tube defects in offspring
Authors: Fu Yunting , Wang Lin‐lin , Yi Deqing , Jin Lei , Liu Jufen , Zhang Yali , Ren Aiguo
Published: November 2014

Background

Maternal pregestational hyperglycemia, diabetes, and obesity are well‐established risk factors for neural tube defects (NTDs). As a common underlying mechanism, the imbalance of glucose homeostasis is directly related to the development of NTDs. Polymorphisms in genes regulating glucose metabolism in women may impact their chance of having an NTD‐affected pregnancy.

Methods

We conducted a two‐stage case‐control study to investigate the association between maternal genetic variants in genes regulating glucose metabolism and risk for NTDs. The cases were 547 women who gave birth to a child with an NTD (anencephaly, spina bifida, or encephalocele); the controls were 543 women who gave birth to a full‐term healthy infant. In the first stage, 12 single nucleotide polymorphisms were genotyped in 160 cases and 162 controls. In the second stage, five single nucleotide polymorphisms found in the first stage and potentially associated with NTD risk were genotyped for validation, in an additional 387 cases and 381 controls.

Results

Combined analysis of data from the two stages showed an association between maternal AA genotype of GCKR rs780094 and increased risk for total NTDs [odds ratio, 1.73; 95% confidence interval, 1.16–2.59) and spina bifida subtype [odds ratio, 1.83; 95% confidence interval, 1.16–2.88). No association was found between the other four single nucleotide polymorphisms (LEPR rs1137100, HK1 rs748235, HHEX rs5015480, KCNQ1 rs2237892) and NTD risk.

Conclusion

The AA genotype in maternal GCKR rs780094 is associated with an increased risk for NTDs and spina bifida in the Chinese population. Birth Defects Research (Part A) 103:471–478, 2015. © 2014 Wiley Periodicals, Inc.
Mutational heterogeneity: A key ingredient of bet‐hedging and evolutionary divergence?
Authors: Ferenci Thomas , Maharjan Ram
Published: November 2014

Here, we propose that the heterogeneity of mutational types in populations underpins alternative pathways of evolutionary adaptation. Point mutations, deletions, insertions, transpositions and duplications cause different biological effects and provide distinct adaptive possibilities. Experimental evidence for this notion comes from the mutational origins of adaptive radiations in large, clonal bacterial populations. Independent sympatric lineages with different phenotypes arise from distinct genetic events including gene duplication, different insertion sequence movements and several independent point mutations. The breadth of the mutational spectrum in the ancestral population should be viewed as a form of bet‐hedging, reducing the risk of evolutionary dead ends and complementing the phenotypic and epigenetic heterogeneities that improve the survival capabilities of a population. Different mutational events arise from distinct cellular processes and are subject to separate environmental impacts, so the availability of any particular type of mutation may constrain or promote adaptive pathways in populations.
Google Glass, ultrasound and palpation: The anatomy teacher of the future?
Authors: Benninger Brion
Published: November 2014

Traditional palpation techniques are used less often in today's modern medical arena. Technological advances in imaging, for example, often supplant the need for such types of tactility. Herein, we discuss our recent experience using Google Glass in the teaching of anatomy to medical students, a method that melds traditional medical palpation with cutting edge technology. Based on our study, teachers of the new millennium might use Google Glass coupled with ultrasound and palpation in the teaching of human anatomy to medical students. Such a technology combines palpation, diagnosis, visualization, and learning of anatomy. Glass has provided a platform to position a live ultrasound image for us to view while examining the patient. This technology will allow the physicians of the future to embrace placing ones hand on the body while receiving both palpation and visual stimulation. Clin. Anat. 28:152–155, 2015. © 2014 Wiley Periodicals, Inc.
Simulation Studies on Growth and Death of Microorganisms Using the Oil‐Degrading Bacteria Petrotoga sp.
Authors: Daryasafar Amin , Azad Ehsan Ganji , Ghahfarokhi Ali Khorram , Mousavi Seyyedeh Fatemeh
Published: November 2014

Three models were developed to estimate the potential of the selected bacteria Petrotoga sp., a thermophilic anaerobic oil‐degrading microorganism. Fourteen data sets of these bacteria were simulated by a multilayer feed‐forward neural network and an adaptive neuro‐fuzzy interference system. Twelve data sets served for training and two for testing these models. A simplified numerical model was performed assuming two phases in the growth process of oil‐degrading microorganisms, the logarithmic growth phase and the death phase. Comparison between these models in predicting bacterial cell concentration for different data sets indicates little difference between the overall average relative errors of the three methods and that all can be applied for prediction. Effects of salinity concentration, amount of yeast extract, and temperature on bacterial cell concentration were simulated by numerical and neural network models.
Mathematical Modeling of Ocimum basilicum L. Supercritical CO2 Extraction
Authors: Zeković Zoran , Filip Snežana , Vidović Senka , Jokić Stela , Svilović Sandra
Published: November 2014

The effects of pressure and temperature on supercritical extraction of Ocimum basilicum L. in terms of extraction yield and aromatic compounds were investigated. Linalool, eugenol, and δ‐cadinene were indentified as three main compounds of the prepared extracts. The dominant compound in all investigated supercritical basil extracts was linalool. Within the experimental range the extraction parameters had a significant influence on the extraction yield. The obtained results for the sweet basil total extract, cadinene, and linalool best matched with the Gordillo et al. model, therefore, the solubility of total extract, linalool, and cadinene in supercritical CO2 at investigated temperatures is described as a function of pressure.
Relationship between Pyrite in the Precursor and the Pore Structure of High‐Surface Area Activated Carbon Preparations
Authors: Zhang Huaihao , Jiang Yuanyuan , Chen Kai , Hu Yongfeng , Wang Hui , Zhao Jing , Zhang Xiaoxing , Wang Chengyin
Published: November 2014

High‐surface area activated carbons (HAC) were prepared from analogous sulfur‐containing precursors by using KOH chemical activation. The relationship between pyrite (FeS2) in the precursor and the pore structure of the as‐prepared HAC was investigated comprehensively. The results suggest that FeS2 in the precursor reacts with KOH, producing K2SO4, K2S2O3, K2S, thioether (R‐S‐R'), and Fe3O4, which reduce the actual amount of KOH used to develop the porosity. As a result, the existence of the by‐product Fe3O4 further clarifies that FeS2 in the precursor can consume some amount of KOH, which leads to the decrease in the specific surface area and pore volume of HAC. Interestingly, part of the inorganic sulfur from FeS2 in the precursor can be transformed into organic sulfide R‐S‐R'.
Gold‐Nanoparticle‐Based Multifunctional Amyloid‐β Inhibitor against Alzheimer’s Disease
Authors: Gao Nan , Sun Hanjun , Dong Kai , Ren Jinsong , Qu Xiaogang
Published: November 2014

Targeting amyloid‐β (Aβ)‐induced complex neurotoxicity has received considerable attention in the therapeutic and preventive treatment of Alzheimer’s disease (AD). The complex pathogenesis of AD suggests that it requires comprehensive treatment, and drugs with multiple functions against AD are more desirable. Herein, AuNPs@POMD‐pep (AuNPs: gold nanoparticles, POMD: polyoxometalate with Wells–Dawson structure, pep: peptide) were designed as a novel multifunctional Aβ inhibitor. AuNPs@POMD‐pep shows synergistic effects in inhibiting Aβ aggregation, dissociating Aβ fibrils and decreasing Aβ‐mediated peroxidase activity and Aβ‐induced cytotoxicity. By taking advantage of AuNPs as vehicles that can cross the blood–brain barrier (BBB), AuNPs@POMD‐pep can cross the BBB and thus overcome the drawbacks of small‐molecule anti‐AD drugs. Thus, this work provides new insights into the design and synthesis of inorganic nanoparticles as multifunctional therapeutic agents for treatment of AD.
Metal–Carbonyl Units for Vibrational and Luminescence Imaging: Towards Multimodality
Authors: Clède Sylvain , Policar Clotilde
Published: November 2014

Metal–carbonyl complexes are attractive structures for bio‐imaging. In addition to unique vibrational properties due to the CO moieties enabling IR and Raman cell imaging, the appropriate choice of ancillary ligands opens up the opportunity for luminescence detection. Through a classification by techniques, past and recent developments in the application of metal–carbonyl complexes for vibrational and luminescence bio‐imaging are reviewed. Finally, their potential as bimodal IR and luminescent probes is addressed.
Supramolecular Water Oxidation with Ru–bda‐Based Catalysts
Authors: Richmond Craig J. , Matheu Roc , Poater Albert , Falivene Laura , Benet‐Buchholz Jordi , Sala Xavier , Cavallo Luigi , Llobet Antoni
Published: November 2014

Extremely slow and extremely fast new water oxidation catalysts based on the Ru–bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s−1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π‐stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.
Chitosan‐Templated Synthesis of Few‐Layers Boron Nitride and its Unforeseen Activity as a Fenton Catalyst
Authors: Primo Ana , Navalón Sergio , Asiri Abdullah M. , García Hermenegildo
Published: November 2014

A novel procedure for the preparation of few‐layers boron nitride (BN), either as films or as suspended BN platelets, is presented, based on the pyrolysis of chitosan, which serves both as a matrix to embed ammonium borate and as a template for BN synthesis. The resulting BN samples are characterized by XRD, Raman and X‐ray photoelectron spectroscopy, and by TEM and AFM imaging. The samples exhibit deep UV emission, which is characteristic of high quality BN. This template synthesis and the easy exfoliation of BN platelets facilitate the use of BN as an extremely high‐efficiency Fenton catalyst for the generation of highly aggressive hydroxyl radicals in water.
Stereoselective Synthesis of α‐Linked 2‐Deoxy Glycosides Enabled by Visible‐Light‐Mediated Reductive Deiodination
Authors: Wang Hao , Tao Jinyi , Cai Xinpei , Chen Wei , Zhao Yueqi , Xu Yang , Yao Wang , Zeng Jing , Wan Qian
Published: November 2014

2‐Deoxy sugars and their derivatives occur abundantly in many pharmaceutically important natural products. However, the construction of specific 2‐deoxy‐glycosidic bonds remains as a challenge. Herein, we report an efficient way to prepare 2‐deoxy‐α‐glycosides by glycosylation of 2‐iodo‐glycosyl acetate and subsequent visible‐light‐mediated tin‐free reductive deiodination. We have successfully applied the postglycosylational‐deiodination strategy in the synthesis of more than 30 mono‐, di‐, tri‐, tetra‐ and pentadeoxysaccharides with excellent stereoselectivity and efficiency. This method has also been applied to the synthesis of a 2‐deoxy‐tetrasaccharide containing four α‐linkages.
Neue Trends in der homogenen Übergangsmetallkatalyse
Authors: Behr Arno , Vorholt Andreas J.
Published: November 2014

Dieser Beitrag gibt eine ausgewählte Übersicht über aktuelle Entwicklungen in der homogenen Übergangsmetallkatalyse. Im Vordergrund stehen hier vor allem technisch relevante Reaktionen, wie z. B. Hydroformylierung, Carbonylierung, Hydrierung, Oxidation, Aminierung, Metathese und resultierende Tandemreaktionen. Neben dem Einsatz klassischer petrochemischer Grundstoffe wird ebenfalls die Umsetzung nachwachsender Rohstoffe diskutiert. An ausgewählten Beispielen werden kontinuierlich durchgeführte Umsetzungen der Reaktionen in Miniplants gezeigt.