bluuebunny/crossref_metadata_2025 huggingface dataset:
Major fraction of black carbon is flushed from the melting New Hampshire snowpack nearly as quickly as soluble impurities
Authors: Lazarcik James , Dibb Jack E. , Adolph Alden C. , Amante Jacqueline M. , Wake Cameron P. , Scheuer Eric , Mineau Madeleine M. , Albert Mary R.
Published: December 2016

Seasonal snowpacks accumulate impurities derived from atmospheric aerosols and trace gases throughout the winter and release them during snowmelt. Previous field and laboratory studies have shown that a snowpack can lose up to 80% of the soluble ion burden in the first 20% of the melt, an event commonly known as an ionic pulse. Other studies have concluded that particulate impurities (e.g., black carbon (BC)) concentrate in surface layers during melt which can have important implications for snowpack albedo. However, model and field studies have indicated that meltwater scavenging efficiency of BC in melting snowpacks is still an area of uncertainty. To quantify BC melt dynamics and the release of soluble impurities, we collected and analyzed near‐daily chemical profiles in the snowpack at three sites during two winters in New Hampshire, United States of America. We observe an ionic pulse and a pulse of BC from the snowpack at the onset of melt; up to 62% of BC leaves within the first 24% of the melt. Surface concentrations of BC are higher than seasonal medians at the end of the winter season, but surface enhancements do not appear to be closely linked to decreases in snow‐water equivalence caused by melting.
Land surface temperature over global deserts: Means, variability, and trends
Authors: Zhou Chunlüe , Wang Kaicun
Published: December 2016

Land surface air temperature (LSAT) has been a widely used metric to study climate change. Weather observations of LSAT are the fundamental data for climate change studies and provide key evidence of global warming. However, there are very few meteorological observations over deserts due to their uninhabitable environment. This study fills this gap and provides independent evidence using satellite‐derived land surface temperatures (LSTs), benefiting from their global coverage. The frequency of clear sky from MODerate Resolution Imaging Spectroradiometer (MODIS) LST data over global deserts was found to be greater than 94% for the 2002–2015 period. Our results show that MODIS LST has a bias of 1.36°C compared to ground‐based observations collected at 31 U.S. Climate Reference Network (USCRN) stations, with a standard deviation of 1.83°C. After bias correction, MODIS LST was used to evaluate existing reanalyses, including ERA‐Interim, Japanese 55‐year Reanalysis (JRA‐55), Modern‐Era Retrospective Analysis for Research and Applications (MERRA), MERRA‐land, National Centers for Environmental Prediction (NCEP)‐R1, and NCEP‐R2. The reanalyses accurately reproduce the seasonal cycle and interannual variability of the LSTs, but their multiyear means and trends of LSTs exhibit large uncertainties. The multiyear averaged LST over global deserts is 23.5°C from MODIS and varies from 20.8°C to 24.5°C in different reanalyses. The MODIS LST over global deserts increased by 0.25°C/decade from 2002 to 2015, whereas the reanalyses estimated a trend varying from −0.14 to 0.10°C/decade. The underestimation of the LST trend by the reanalyses occurs for approximately 70% of the global deserts, likely due to the imperfect performance of the reanalyses in reproducing natural climate variability.
The substorm cycle as reproduced by global MHD models
Authors: Gordeev E. , Sergeev V. , Tsyganenko N. , Kuznetsova M. , Rastäetter L. , Raeder J. , Tóth G. , Lyon J. , Merkin V. , Wiltberger M.
Published: December 2016

Recently, Gordeev et al. (2015) suggested a method to test global MHD models against statistical empirical data. They showed that four community‐available global MHD models supported by the Community Coordinated Modeling Center (CCMC) produce a reasonable agreement with reality for those key parameters (the magnetospheric size, magnetic field, and pressure) that are directly related to the large‐scale equilibria in the outer magnetosphere. Based on the same set of simulation runs, here we investigate how the models reproduce the global loading‐unloading cycle. We found that in terms of global magnetic flux transport, three examined CCMC models display systematically different response to idealized 2 h north then 2 h south interplanetary magnetic field (IMF) Bz variation. The LFM model shows a depressed return convection and high loading rate during the growth phase as well as enhanced return convection and high unloading rate during the expansion phase, with the amount of loaded/unloaded magnetotail flux and the growth phase duration being the closest to their observed empirical values during isolated substorms. Two other models exhibit drastically different behavior. In the BATS‐R‐US model the plasma sheet convection shows a smooth transition to the steady convection regime after the IMF southward turning. In the Open GGCM a weak plasma sheet convection has comparable intensities during both the growth phase and the following slow unloading phase. We also demonstrate potential technical problem in the publicly available simulations which is related to postprocessing interpolation and could affect the accuracy of magnetic field tracing and of other related procedures.
MoS2‐Based Nanocomposites for Electrochemical Energy Storage
Authors: Wang Tianyi , Chen Shuangqiang , Pang Huan , Xue Huaiguo , Yu Yan
Published: December 2016

Typical layered transition‐metal chalcogenide materials, in particular layered molybdenum disulfide (MoS2) nanocomposites, have attracted increasing attention in recent years due to their excellent chemical and physical properties in various research fieldsHere, a general overview of synthetic MoS2 based nanocomposites via different preparation approaches and their applications in energy storage devices (Li‐ion battery, Na‐ion battery, and supercapacitor) is presented. The relationship between morphologies and the electrochemical performances of MoS2‐based nanocomposites in the three typical and promising rechargeable systems is also discussed. Finally, perspectives on major challenges and opportunities faced by MoS2‐based materials to address the practical problems of MoS2‐based materials are presented.
A Novel Class of Multiferroic Material, Bi4Ti3O12·nBiFeO3 with Localized Magnetic Ordering Evaluated from Their Single Crystals
Authors: Zhao Hongyang , Cai Kang , Cheng Zhenxiang , Jia Tingting , Kimura Hideo , Ma Zhibin , Fu Qiuming , Huang Zhideng , Matsumoto Takao , Tohei Tetsuya , Shibata Naoya , Ikuhara Yuichi
Published: December 2016

Novel multiferroic materials have attracted increasing attention in recent years. Aurivillius bismuth‐layer structured Bi4Ti3O12·nBiFeO3 (BTFO: n = 1–3, 5) compounds with potential multiferroic properties are such a compound. However, the data on these BTFOs are ambigious, inconsistent, and incomplete. Therefore BTFOs were grown into single crystals for a systematic evaluation. Their crystal structures and microstructures show that intergrowth of layer structure occurs easily in this class of material. Their ferroelectric measurements show strong anisotropy and dielectric peaks at high temperature, accompanied by an abnormal loss that corresponds to their polar phase transition. At room temperature, ferroelectric hysteresis loops were successfully measured; the loops show a strong dependence in their polarization and coercive field on different values of n and anisotropy. Magnetic measurement shows that all the single crystals display magnetic transitions at high temperatures and weak ferromagnetism at room temperature. Electron spin resonance (ESR) results show the coexistence of ferromagnetic and paramagnetic signal components in all the compounds. Scanning probe microscope measurements show magnetic domains switched together with electric domains by use of an electric field. Therefore we conclude that overall spin disorder with localized order is the character of this class of material, with observed magnetoelectric (ME) coupling. This work could also point the way to novel multiferroic materials in locally magnetic ordered systems.
Low‐Frequency CH Stretch Vibrations of Free Alkoxide Ions
Authors: Oomens Jos , Berden Giel , Morton Thomas Hellman
Published: December 2016

CH stretches in hydrocarbon cations often shift to lower frequencies relative to neutral molecules, because they do not have sufficient electrons to give every bond an electron pair. A parallel effect in negatively charged species has not been previously observed. Here we show that CH bond weakening occurs in alkoxide anions as a consequence of hyperconjugation. The reasoning differs somewhat from the case of positively charged ions, but the net effect is the same: to lower CH stretching frequencies by hundreds of wavenumbers.
Carboxylation of Terminal Alkynes with Carbon Dioxide Catalyzed by an In Situ Ag2O/N‐Heterocyclic Carbene Precursor System
Authors: Yuan Ye , Chen Cheng , Zeng Cheng , Mousavi Bibimaryam , Chaemchuen Somboon , Verpoort Francis
Published: December 2016

A carboxylation of terminal alkynes with carbon dioxide (CO2) at ambient conditions was developed in situ using a series of N‐heterocyclic carbene (NHC) precursors and Ag2O. The unique structure of NHCs largely increases the solubility of active Ag species and meanwhile activates CO2 by forming the NHC–CO2 adduct. This novel catalytic system demonstrated quite low Ag loading, very high activities, wide substrate generality and excellent tolerance for a variety of functionalities. In addition, avoiding cumbersome synthesis procedures, processing, and reserving of the photosensitive Ag complex, this system could be stored and operated as straightforward as the inorganic Ag salt catalysts.
Explicit Water Molecules Play a Key Role in the Mechanism of Rhodium‐Substituted Human Carbonic Anhydrase
Authors: Piazzetta Paolo , Marino Tiziana , Russo Nino , Salahub Dennis R.
Published: December 2016

The efficient conversion of carbon dioxide into useful products is a prime challenge to modern chemistry. An alternative route to address this challenge based on a rhodium‐substituted human carbonic anhydrase is described that can be considered the first cofactor‐independent reductase. This artificial enzyme is able to convert CO2 into formic acid, with potential applications in renewable energy. Our quantum mechanical investigation (QM/QM′ method), which considers the entire catalytic pocket (390 atoms), provides evidence that the catalytic process is governed by an energetically favored σ‐bond‐metathesis mechanism and the rate‐limiting step is the release of formic acid (11.7 kcal mol−1). Water molecules are found to play an active role during the chemical process by contributing to reduce dramatically the energy of the rate‐limiting step and favoring an efficient regeneration of the catalyst.
Methods for the Trace Oxygen Removal from Methane‐Rich Gas Streams
Authors: Peppel Tim , Seeburg Dominik , Fulda Gerhard , Kraus Markus , Trommler Ulf , Roland Ulf , Wohlrab Sebastian
Published: December 2016

Oxygen removal to very low residual contents in methane‐rich gas streams and carbon dioxide as co‐component (simulated biogas) was achieved via three different methods at various temperatures, namely, by reduction with hydrogen admixtures on Pt/γ‐Al2O3catalysts, by oxygen absorption affinity of YBaCo4O7+δ, and by the catalytic reaction with methane on both the materials, respectively. The three methods have characteristic advantages and disadvantages which are discussed in the context of existing methods for gas treatments focused on oxygen removal. Finally, the advantage of dielectric radio‐frequency heating on the powdered functional materials is suggested as alternative to conventional routes.
Anchoring Nitrogen‐Doped TiO2 Nanocrystals on Nitrogen‐Doped 3D Graphene Frameworks for Enhanced Lithium Storage
Authors: Liu Xiao‐Wu , Yang Zhen‐Zhong , Pan Fu‐Sen , Gu Lin , Yu Yan
Published: December 2016

An advanced architecture design of nitrogen‐doped TiO2 anchored on nitrogen‐doped 3D graphene framework composites (denoted as N‐TiO2/N‐3D GFs) have been fabricated by a facile template process and further NH3 treatment. The 3D graphene framework allows the electrolyte to penetrate into the inverse opal structure, and possesses high electronic conductivity. The close contact between the N‐TiO2 and the graphene suppresses the growth and aggregation of TiO2 nanoparticles during heating process, leading to decreased Li+ diffusion length. The N‐doping in both TiO2 and the graphene matrix could improve the electronic conductivity on the TiO2 particle surface and between adjacent particles. As expected, when used as an anode for Li‐ion batteries (LIBs), the N‐TiO2/N‐3D GFs composite delivers an excellent reversible capacity of 165 mA h g−1 after 200 cycles at 100 mA g−1 and an outstanding rate capability of 114 mA h g−1 after 1000 cycles at 1 Ag−1. With rational design, this strategy could be extended to other electrode materials that may hold great promise for the development of high energy storage systems.
Reduction of [Cp*Sb]4with Subvalent Main‐Group Metal Reductants: Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge‐Missing Sb4Units
Authors: Ganesamoorthy Chelladurai , Krüger Julia , Wölper Christoph , Nizovtsev Anton S. , Schulz Stephan
Published: December 2016

[Cp*Sb]4(Cp*=C5Me5) reacts with [L1Mg]2and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2‐Sb4)] (L1=iPr2NC[N(2,6‐iPr2C6H3)]2,1) and [(L2Ga)2(μ,η2:2‐Sb4)] (L2=HC[C(Me)N(2,6‐iPr2C6H3)]2,2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4are the crucial steps in both reactions. The formation of1occurred by elimination of the Cp* anion and formation of Cp*MgL1, while2was formed by reductive elimination of Cp*2and oxidative addition of L2Ga to the Sb4unit.1and2were characterized by heteronuclear NMR spectroscopy and single‐crystal X‐ray diffraction, and their bonding situation was studied by quantum chemical calculations.
Bichromophoric Compounds with Orthogonally and Parallelly Arranged Chromophores Separated by Rigid Spacers
Authors: Meineke Dirk N. H. , Bossi Mariano L. , Ta Haisen , Belov Vladimir N. , Hell Stefan W.
Published: December 2016

Electronic energy transfer (EET) between chromophores is of fundamental importance for many biological processes and optoelectronic devices. However, common models fall short in fully describing the process, especially in bichromophoric model systems with a donor and acceptor connected by a rigid linker providing perpendicular geometries. Herein, we report a novel strategy for preparing bichromophores containing adamantane or 2‐(2‐adamantylidene)adamantane as rigid spacers, providing a fixed distance between chromophores, and their parallel or perpendicular arrangement without chromophore rotation. New fluorophores were developed and linked via spiroatoms. Bichromophores with identical (blue‐blue) or different (blue‐red) chromophores were synthesized, either in orthogonal or parallel geometry. These were characterized by absorption/fluorescence spectroscopy, time‐resolved fluorescence anisotropy, and fluorescence antibunching measurements. Based on the Förster point‐dipole approximation, EET efficiencies were estimated by using geometrical parameters from (time‐dependent) density functional calculations. For bichromophores with parallel geometry, the predicted EET efficiencies were near unity and fit the measurements. In spite of estimated values around 0.4 and 0.5, 100 % efficiency was observed also for bichromophores with orthogonal geometry. The new rigid scaffolds presented here open new possibilities for the synthesis of bichormophores with well‐defined parallel or perpendicular geometry.
Trimetallic Au‐Cu‐K/AC for acetylene hydrochlorination
Authors: Wang Lei , Shen Benxian , Zhao Jigang , Bi Xiaotao
Published: December 2016

The metal chloride of KCl was chosen to modify Au‐Cu/AC to decrease the noble metal of gold and enhance the catalytic performance. Then a mercury‐free catalyst of Au‐Cu‐K/AC was prepared by the impregnation method. The catalytic performances of mercury‐free catalyst for acetylene hydrochlorination were conducted for 1600 h in a fixed bed reactor by a single‐tube pilot unit. The fresh and used catalysts were also characterized in comparison. The results showed that the acetylene conversion on mercury‐free catalyst decreased slowly from 98 % to 89 %, and the vinyl chloride monomer (VCM) selectivity was kept at 99.7 % under reaction conditions of temperature 165 °C, gas hourly space velocity (GHSV) 40 h−1, and feed volume ratio of HCl to C2H2 of 1.05 during 1600 h on stream. The results showed that the additives of K with Cu can make the active species of gold dispersed well and retard the aggregation of particles. The reason for the slow decline of acetylene conversion for Au‐Cu‐K/AC catalyst was the whisker carbon deposition, shown in a faint yellow colour over the catalyst surface, which consisted of short‐chain hydrocarbon molecules. Further study for accelerated deactivation of sole metal in the catalyst gives the clues that the non‐noble metal of Cu in Au‐Cu‐K/AC catalyst plays a key role to form the deposition.
Potential effect of chemical and thermal treatment on the Kinetics, equilibrium, and thermodynamic studies for atrazine biosorption by the Moringa oleifera pods
Authors: Coldebella Priscila Ferri , Fagundes‐Klen Márcia Regina , Nishi Letícia , Valverde Karina Cardoso , Cavalcanti Eliane Bezerra , Andreo dos Santos Onélia Aparecida , Bergamasco Rosângela
Published: December 2016

The effectiveness of chemical and thermal pretreatments on Moringa oleifera pods for the atrazine removal from water was investigated. The untreated pods (MOPun), the chemically treated pods (MOPC), and the chemically treated pods followed by the thermally treated pods (MOPT) were physico‐chemically and morphologically characterized by elemental, pHZPC, N2 physisorption, FTIR, and SEM analysis. The effect of modified pods was significant in increasing surface porosity, favouring the surface chemistry, and improving the atrazine biosorption capacity. Kinetics data were best explained by pseudo‐second order model for all biosorbents. The equilibrium data for biosorption were analyzed by using Langmuir, Freundlich, Sips, and Polanyi‐Manes (PMM) isotherm models to define the best correlation for atrazine biosorption capacity. Among the four isotherm models, both Sips and PMM were the models best fitted with the equilibrium isotherm for atrazine. The maximum atrazine adsorption capacities were 0.629, 1.580, and 7.47 mg · g−1 for MOPun, MOPC, and MOPT respectively with a maximum removal percentage of 65 %, 82 %, and 99 %. The thermodynamic studies showed that atrazine biosorption is favourable. The biosorption experiments demonstrated that Moringa oleifera pods have great potential for removing atrazine and other organic contaminants from water.
Butachlor‐Induced Alterations in Ultrastructure, Antioxidant, and Stress‐Responsive Gene Regulations in Rice Cultivars
Authors: Islam Faisal , Ali Skhawat , Farooq Muhammad A. , Wang Jian , Gill Rafaqat A. , Zhu Jinwen , Ali Basharat , Zhou Weijun
Published: December 2016

Butachlor is an extensively applied herbicide in paddy fields. However, concerns have been raised about its potential adverse effects on the biochemical and physiological processes of non‐target plants. In the present investigation, butachlor‐induced toxic effects in two rice cultivars, Zhejing 88 (ZJ 88) and Xiushui 134 (XS 134), treated with different butachlor treatments were evaluated. A significant decrease in growth rate, pigment concentration, and chlorophyll fluorescence and alternations in chloroplast structures were observed in both rice cultivars at higher treatment levels. The malfunctioning of antioxidant enzymes, the higher uptake of butachlor, and the downregulation of the putative fatty acid elongase gene suggested severe oxidative damage, which was also indicated by enhanced reactive oxygen species (ROS) formation (H2O2,), lipid peroxidation, and electrolyte leakage and reduced total soluble protein levels in cultivar ZJ 88 than in cultivar XS 134. However, higher proline accumulation and pyrroline‐5‐carboxylate synthase and GABA‐transaminase transcript levels in ZJ 88 suggested their ameliorative role under butachlor‐induced oxidative stress in the sensitive cultivar. In contrast, the stimulated activation of antioxidant enzymes, glutathione, soluble sugars, and phenolics played a vital role in protection against butachlor stress in cultivar XS 134. Thus, butachlor‐induced oxidative stress tolerance in the resistant cultivar (XS 134) is related to the enhanced activation of different isoforms of antioxidant enzymes and a reduced uptake of butachlor compared to the sensitive cultivar (ZJ 88). The present work provides valuable insights into butachlor‐induced toxicity in rice plants.
Biodegradation of Isoprenoids, Steranes, Terpanes, and Phenanthrenes During In Situ Bioremediation of Petroleum‐Contaminated Groundwater
Authors: Beškoski Vladimir P. , Miletić Srdjan , Ilić Mila , Gojgić‐Cvijović Gordana , Papić Petar , Marić Nenad , Šolević‐Knudsen Tatjana , Jovančićević Branimir S. , Nakano Takeshi , Vrvić Miroslav M.
Published: December 2016

The objective of this study was to stimulate microbial biodegradation of petroleum pollution in groundwater and to analyze changes in the abundance and distribution of organic compounds detectable in petroleum. Bioremediation was conducted in a closed bipolar system, by bioaugmentation with consortia of hydrocarbon degrading microorganisms (HD) and biostimulation with nutrients. Comprehensive two‐dimensional gas chromatography–mass spectrometry (GC × GC–MS) was used to visualize all fractions simultaneously. During the study, the content of total petroleum hydrocarbon (TPH) in groundwater decreased by 92.7% of the initial level, and the average rate of biodegradation was 0.1 mg/L per day. Increased numbers of HD were observed and the dominant genera were Pseudomonas, Rhodococcus, Achromobacter, Bacillus, and Micromonospora. In the first 30 days of bioremediation, there was no significant biodegradation of n‐alkanes and petroleum biomarkers – isoprenoids such as pristane and phytane, and polycyclic‐saturated hydrocarbons such as terpanes and steranes. However, after 60 days of bioremediation, more than 95% of n‐alkanes, terpanes and steranes were biodegraded. Phenanthrene and its methyl‐, dimethyl‐, and trimethyl‐isomers were biodegraded and reduced by more than 99% of their initial levels. However, their decomposition had clearly commenced after just 30 days. This is a somewhat surprising result since it follows that the phenanthrenes were more susceptible to biodegradation than the n‐alkanes and isoprenoids. Depending on the microbial community used for bioaugmentation, biodegradation of phenanthrene can precede biodegradation of saturated hydrocarbons.
Enhanced Activity of Immobilized Horseradish Peroxidase by Carbon Nanospheres for Phenols Removal
Authors: Lu Yong‐Ming , Yang Qiao‐Yue , Wang Li‐Ming , Zhang Ming‐Zhu , Guo Wen‐Qiang , Cai Zheng‐Nan , Wang Dan‐Dan , Yang Wei‐Wei , Chen Yan
Published: December 2016

Nowadays it is still of great demand to find a feasible, inexpensive and green material for industrial enzyme immobilization for wastewater treatment. In this work, horseradish peroxidase (HRP) was successfully immobilized on glutaraldehyde activated carbon nanospheres. Compared with free HRP, the immobilized one showed better tolerance of temperature and pH. Meanwhile the storability and reusability were also greatly improved after immobilization. The immobilized HRP could be used for removal of several phenolic compounds from an aqueous solution and exhibited excellent removal efficiency, especially for chlorophenols, 4‐methoxyphenol, and bisphenol A. The immobilization could also make the enzyme more tolerant of ions and preserve its bioactivity. Moreover, by the introduction of support‐enzyme interaction a remarkably enhanced biodegradation was observed. The biodegradation of phenols with electron‐donor groups were found to be doubled after immobilization on active carbon nanospheres. These findings might be useful for further construction of immobilized enzymes for industrial applications, which exhibit excellent stability together with high activity.
Integrated Ultrafiltration Membrane Unit for Efficient Petroleum Refinery Effluent Treatment
Authors: Martini Sri , Ang Ha Ming , Znad Hussein
Published: December 2016

Petroleum refinery effluent (PRE) needs treatment before discharge. One treatment option is the filtration of PRE through membranes but membranes can be become fouled, reducing their efficiency. This study evaluates the improvement of polymeric ultra‐filtration (UF) membrane performance by integrating membrane filtration with a Fenton‐flocculation process to treat PRE prior to sending it through the membrane. The results show that the integrated‐UF membrane system increased the permeate flux by 50% compared to only using the membrane. Similarly, the integrated system increased the chemical oxygen demand, and the oil and grease removal efficiencies by 55 and 4.23%, respectively. The integrated system was further investigated under different conditions of transmembrane pressure (TMP) (1, 1.5, 2 bar) and cross flow velocity (CFV) (250, 300, 600 mL/min). Using Hermia's model, it was found that the cake formation model controlled fouling regardless of the applied TMP and CFV conditions. The extent of fouling was analyzed and characterised via Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy and energy dispersive spectrometry (SEM‐EDS). SEM‐EDS demonstrated different morphologies between fresh and fouled membrane, where irregularly distributed microparticles/oil droplets on the membrane surface and pores were dominant in the fouled membrane. The inclusion of the pre‐treatment stage is therefore, important for improving polymeric UF membrane performance for treating PRE.
Agro‐Industrial Effluent Phytoremediation with Lemna gibba and Hydrocotyle ranunculoides in Water Recirculating Mesocosms
Authors: Basílico Gabriel , Magdaleno Anahí , Paz Marta , Moretton Juan , Faggi Ana , de Cabo Laura
Published: December 2016

Treatment of agro‐industrial effluents can be carried out via phytoremediation with mono‐ or multi‐specific macrophyte crops. A 6 day phytoremediation assay was performed in mesocosms with continuous recirculation of wastewater from a poultry industry with the macrophytes Lemna gibba and/or Hydrocotyle ranunculoides. The plant effects over removal of nutrients (N, P and C), fecal contamination indicators (total coliforms and Escherichia coli) and the genotoxicity of wastewater by the Allium cepa test were evaluated. A decrease by about 97.6% of total coliforms and E. coli, without significant differences between treatments was observed. The highest removal rates of ammonium (77.9%), dissolved inorganic nitrogen (77.9%), soluble reactive phosphorus (47.6%), total phosphorus (60.6%), and particulate organic carbon (82.1%) were observed in mesocosms with L. gibba + H. ranunculoides, although there were no significant differences (p > 0.05) with respect to the monospecific culture of L. gibba. Lower rates of nutrients removal were observed in monospecific cultures of H. ranunculoides. Moreover, the use of both species meant a reduction of the genotoxicity of wastewater, with no chromosomal aberrations and micronuclei in meristematic root cells of A. cepa. The obtained results confirm the benefits of the joint use of H. ranunculoides and L. gibba for phytoremediation of wastewater from the poultry industry, being preferable to the use of monospecific crops.
Polyvinylpyrrolidone (PVP)‐Capped Pt Nanocubes with Superior Peroxidase‐Like Activity
Authors: Ye Haihang , Liu Yuzi , Chhabra Ashima , Lilla Emily , Xia Xiaohu
Published: December 2016

Peroxidase mimics composed of inorganic nanoparticles are expected to circumvent the inherent difficulties of natural peroxidases, and to provide enhanced performance in important applications such as diagnosis and imaging. Despite the reports of a variety of peroxidase mimics in the past decade, very limited progress has been made on improving their catalytic efficiency. The catalytic efficiencies of most previously reported mimics are only up to one order of magnitude higher than those of natural peroxidases. In this work, we demonstrate a highly efficient peroxidase—polyvinylpyrrolidone (PVP)‐capped Pt nanocubes of sub‐10 nm in size. These PVP‐capped Pt cubes are ≈200‐fold more active than the natural counterparts and exhibit a record‐high specific catalytic efficiency. In addition to the superior efficiency, the new mimic shows several other promising features, including excellent stabilities, well‐controlled uniformity in both size and shape, controllable sizes, and facile and scalable production.
Laser Alloying of Co Nanorods and Al Nanoparticles in a Liquid
Authors: Barmina Ekaterina V. , Sukhov Ilya A. , Viau Guillaume , Shafeev Georgy A.
Published: December 2016

Experimental results are presented on laser alloying of Co nanorods with Al spherical nanoparticles by laser exposure of their mixture in liquid ethanol. It is demonstrated that the initial morphology of the nanoparticles is modified upon laser exposure. The Co nanorods are transformed into Co nanospheres covered by a layer of Al. The evolution of the size distribution is studied as a function of the time of laser exposure. The average size of the nanoparticles has a maximum level with a corresponding optimal irradiation time. The results are discussed from the viewpoint of the interaction of molten nanoparticles inside a cavitation bubble filled with a liquid vapor.
“Practical” Electrospinning of Biopolymers in Ionic Liquids
Authors: Shamshina Julia L. , Zavgorodnya Oleksandra , Bonner Jonathan R. , Gurau Gabriela , Di Nardo Thomas , Rogers Robin D.
Published: December 2016

To address the need to scale up technologies for electrospinning of biopolymers from ionic liquids to practical volumes, a setup for the multi‐needle electrospinning of chitin using the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate, [C2mim]‐[OAc], was designed, built, and demonstrated. Materials with controllable and high surface area were prepared at the nanoscale using ionic‐liquid solutions of high‐molecular‐weight chitin extracted with the same ionic liquid directly from shrimp shells.
One‐Pot Preparation of Dimethyl Isosorbide from d‐Sorbitol via Dimethyl Carbonate Chemistry
Authors: Aricò F. , Aldoshin A. S. , Tundo P.
Published: December 2016

Direct synthesis of dimethyl isosorbide (DMI) from d‐sorbitol via dimethyl carbonate (DMC) chemistry is herein first reported. High yield of DMI was achieved using the nitrogen superbase 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90 to 200 °C. In this procedure, DMC features its full capacity acting in the different steps of the process as carboxymethylating, leaving‐group (cyclization), and methylating agent; DMC is also employed as the reaction media.
A Robust Molecular Catalyst Generated In Situ for Photo‐ and Electrochemical Water Oxidation
Authors: Younus Hussein A. , Ahmad Nazir , Chughtai Adeel H. , Vandichel Matthias , Busch Michael , Van Hecke Kristof , Yusubov Mekhman , Song Shaoxian , Verpoort Francis
Published: December 2016

Water splitting is the key step towards artificial photosystems for solar energy conversion and storage in the form of chemical bonding. The oxidation of water is the bottle‐neck of this process that hampers its practical utility; hence, efficient, robust, and easy to make catalytic systems based on cheap and earth‐abundant materials are of exceptional importance. Herein, an in situ generated cobalt catalyst, [CoII(TCA)2(H2O)2] (TCA=1‐mesityl‐1,2,3‐1H‐triazole‐4‐carboxylate), that efficiently conducts photochemical water oxidation under near‐neutral conditions is presented. The catalyst showed high stability under photolytic conditions for more than 3 h of photoirradiation. During electrochemical water oxidation, the catalytic system assembled a catalyst film, which proved not to be cobalt oxide/hydroxide as normally expected, but instead, and for the first time, generated a molecular cobalt complex that incorporated the organic ligand bound to cobalt ions. The catalyst film exhibited a low overpotential for electrocatalytic water oxidation (360 mV) and high oxygen evolution peak current densities of 9 and 2.7 mA cm−2 on glassy carbon and indium‐doped tin oxide electrodes, respectively, at only 1.49 and 1.39 V (versus a normal hydrogen electrode), respectively, under neutral conditions. This finding, exemplified on the in situ generated cobalt complex, might be applicable to other molecular systems and suggests that the formation of a catalytic film in electrochemical water oxidation experiments is not always an indication of catalyst decomposition and the formation of nanoparticles.
Effective Release of Lignin Fragments from Lignocellulose by Lewis Acid Metal Triflates in the Lignin‐First Approach
Authors: Huang Xiaoming , Zhu Jiadong , Korányi Tamás I. , Boot Michael D. , Hensen Emiel J. M.
Published: December 2016

Invited for this month′s cover is the group of Emiel Hensen at the Eindhoven University of Technology. The image shows how the lignin component can be effectively released from wood and converted into aromatics over a tandem Al‐triflate and Pd/C catalyst. The Communication itself is available at 10.1002/cssc.201601252.
Subacute right heart failure revealing three simultaneous causes of post‐embolic pulmonary hypertension in metastatic dissemination of breast cancer
Authors: Vincent Flavien , Lamblin Nicolas , Classe Marion , Schurtz Guillaume , Rauch Antoine , Fertin Marie , De Groote Pascal
Published: December 2016

A 72‐year‐old woman with history of breast cancer only treated surgically was referred to our department for pulmonary hypertension (PH) suspicion. Echocardiogram revealed elevated right ventricular systolic pressure. Computed tomography (CT) angiogram showed no pulmonary embolism (PE), but lung scan revealed two ventilation‐perfusion mismatch areas. Right cardiac catheterization established precapillary PH. Despite treatment with PH specific therapy (sildenafil, ambrisentan, and epoprostenol), her condition worsened rapidly with acute right heart failure (RHF). She died 22 days after admission. Post‐mortem microscopic examination showed a rare combination of PH etiologies consistent with metastasis of breast cancer in pulmonary vasculature including the rare pulmonary tumour thrombotic microangiopathy (PTTM).
Flavonoids biosynthesis in plants and its further analysis by capillary electrophoresis
Authors: Singh Baljinder , Kumar Ashwini , Malik Ashok Kumar
Published: December 2016

Flavonoids represent an important bioactive component in plants. Accumulation of flavonoids often occurs in plants subjected to abiotic stresses, including the adaptation of plants to the environment and in overcoming their stress conditions. This fact makes their analysis and determination an attractive field in food science since they can give interesting information on the quality and safety of foods. In this study, we discuss reports on plants flavonoids biosynthesis against abiotic stresses and advances in analytical capillary electrophoresis used for their identification and quantification in plants.
Slip‐driven electroosmotic transport through porous media
Authors: Gaikwad Harshad , Mondal Pranab Kumar
Published: December 2016

We investigate the slip‐driven transport of a Newtonian fluid through porous media under electrical double layer effect. We employ a semianalytical framework to obtain the underlying electrohydrodynamics for different configurations of porous media. We bring out an alteration in flow dynamics, stemming from interplay among the geometrical feature of the models and the interfacial slip as modulated by the electrical forcing. Further, we show the consequent effects of the underlying flow dynamics on the volumetric transport rate through different models. Also, we show the inception of reverse flow in the region close to the wall, resulting from the induced pressure gradient due to the convection of co‐ions in the opposite direction to flow and pinpoint its effect of the flow rate variation under the influence of interfacial slip. We believe that the inferences obtained from the present analysis may improve the design of bio‐MEMS (microelectromechanical systems) and microfluidic devices, which are used for in‐situ bioremediation.
Cyclic behavior and failure mechanism of self‐centering energy dissipation braces with pre‐pressed combination disc springs
Authors: Xu Long‐He , Fan Xiao‐Wei , Li Zhong‐Xian
Published: December 2016

A new type of bracing system composed of friction energy dissipation devices for energy dissipation, pre‐pressed combination disc springs for self‐centering and tube members as guiding elements is developed and experimentally studied in this paper. The mechanics of this system are explained, the equations governing its hysteretic responses are outlined and large‐scale validation tests of two braces with different types of disc springs are conducted under the condition of low cyclic reversed loading. The experimental results demonstrate that the proposed bracing system exhibits a stable and repeatable flag‐shaped hysteretic response with an excellent self‐centering capability and effective energy dissipation throughout the loading protocol. Furthermore, the maximum bearing force and stiffness are predicted well by the equations governing its mechanical behavior. Fatigue and destructive test results demonstrate that the proposed bracing system can maintain stable energy dissipation and self‐centering capabilities under large deformation cyclic loading even when the tube members exceed the elastic limit and that a larger bearing capacity is achieved by the system that has disc springs without a bearing surface. Copyright © 2016 John Wiley & Sons, Ltd.
Characterization of the Pro‐Inflammatory Cytokine IL‐1β on Butyrate Oxidation in Colorectal Cancer Cells
Authors: Johnstone Megan , Bennett Natalie , Standifer Cynthia , Smith Alexis , Han Anna , Bettaieb Ahmed , Whelan Jay , Donohoe Dallas R.
Published: December 2016

Cancer, in part, is driven, by alterations in cellular metabolism that promote cell survival and cell proliferation. Identifying factors that influence this shift in cellular metabolism in cancer cells is important. Interleukin‐1β (IL‐1β) is a pro‐inflammatory cytokine that has been reported to be elevated in colorectal cancer patients. While much is known toward the effect of dietary nutrients on regulating inflammation and the inflammatory response, which includes cytokines such as IL‐1β, far less is understood how cytokines impact nutrient fate to alter cancer cell metabolism. Butyrate, a nutrient derived from the fermentation of dietary fiber in the colon, is the preferential exogenous energetic substrate used by non‐cancerous colonocytes, but is used less efficiently by colorectal cancer cells. To test whether IL‐1β alters colonocyte energy metabolism, we measured butyrate oxidation in HCT116 colorectal cancer cells with and without IL‐1β. We hypothesize that IL‐1β will push cancerous colonocytes away from the utilization and oxidation of butyrate. In this study, we demonstrate that pretreatment of colorectal cancer cells with IL‐1β diminished butyrate oxidation and NADH levels. This effect was blocked with the interleukin receptor antagonist A (IL‐1RA). Moreover, IL‐1β suppressed basal mitochondrial respiration and lowered the mitochondrial spare capacity. By using inhibitors to block downstream targets of the interleukin‐1 receptor pathway, we show that p38 is required for the IL‐1β‐mediated decrease in butyrate oxidation. These data provide insight into the metabolic effects induced by IL‐1β in colorectal cancer, and identify relevant targets that may be exploited to block the effects of this cytokine. J. Cell. Biochem. 118: 1614–1621, 2017. © 2016 Wiley Periodicals, Inc.
Evidence for Pipecolate Oxidase in Mediating Protection Against Hydrogen Peroxide Stress
Authors: Natarajan Sathish Kumar , Muthukrishnan Ezhumalai , Khalimonchuk Oleh , Mott Justin L. , Becker Donald F.
Published: December 2016

Pipecolate, an intermediate of the lysine catabolic pathway, is oxidized to Δ1‐piperideine‐6‐carboxylate (P6C) by the flavoenzyme l‐pipecolate oxidase (PIPOX). P6C spontaneously hydrolyzes to generate α‐aminoadipate semialdehyde, which is then converted into α‐aminoadipate acid by α‐aminoadipatesemialdehyde dehydrogenase. l‐pipecolate was previously reported to protect mammalian cells against oxidative stress. Here, we examined whether PIPOX is involved in the mechanism of pipecolate stress protection. Knockdown of PIPOX by small interference RNA abolished pipecolate protection against hydrogen peroxide‐induced cell death in HEK293 cells suggesting a critical role for PIPOX. Subcellular fractionation analysis showed that PIPOX is localized in the mitochondria of HEK293 cells consistent with its role in lysine catabolism. Signaling pathways potentially involved in pipecolate protection were explored by treating cells with small molecule inhibitors. Inhibition of both mTORC1 and mTORC2 kinase complexes or inhibition of Akt kinase alone blocked pipecolate protection suggesting the involvement of these signaling pathways. Phosphorylation of the Akt downstream target, forkhead transcription factor O3 (FoxO3), was also significantly increased in cells treated with pipecolate, further implicating Akt in the protective mechanism and revealing FoxO3 inhibition as a potentially key step. The results presented here demonstrate that pipecolate metabolism can influence cell signaling during oxidative stress to promote cell survival and suggest that the mechanism of pipecolate protection parallels that of proline, which is also metabolized in the mitochondria. J. Cell. Biochem. 118: 1678–1688, 2017. © 2016 Wiley Periodicals, Inc.
Tomentosin Induces Telomere Shortening and Caspase‐Dependant Apoptosis in Cervical Cancer Cells
Authors: Merghoub Nawel , El Btaouri Hassan , Benbacer Laila , Gmouh Saïd , Trentesaux Chantal , Brassart Bertrand , Attaleb Mohammed , Madoulet Claudie , Wenner Thomas , Amzazi Saaid , Morjani Hamid , El Mzibri Mohamed
Published: December 2016

Tomentosin, a natural sesquiterpene lactone purified from of Inula viscosa L., was investigated for its anti‐proliferative, telomere shortening, and apoptotic effects on human cervical cancer HeLa and SiHa cell lines. Tomentosin was found to inhibit the growth of SiHa and HeLa cell lines in dose and time‐dependent manner (IC50 values of 7.10 ± 0.78 μM and 5.87 ± 0.36 μM, respectively after 96 h of treatment). As evidenced by TTAGGG telomere length assay, tomentosin target specifically the telomeric overhang lengthening. This was confirmed by the evaluation of the cytotoxic effects of tomentosin in the foetal fibroblast Wi38 and JW10 cells which were derived from Wi38 and express hTERT, the telomerase catalytic subunit. We found that JW10 cells are 4.7‐fold more sensitive to tomentosin which argues for telomere as its specific target. Furthermore, we found that tomentosin mediate this cytotoxic effect by inducing apoptosis and cell cycle arrest at G2/M phase. Morphological features of treated cells, as evidenced by Hoechst 33324 staining, revealed that the cytotoxic effect was due to induction of apoptosis. This was accompanied by pro‐caspase‐3 cleavage, an increase in caspase‐3 activity and a cleavage of poly (ADP‐ribose) polymerase (PARP). Moreover, tomentosin induced a decrease in mitochondrial membrane potential (ΔΨm) and an increase in reactive oxygen species (ROS), accompanied by a decrease in Bcl‐2 expression. This indicates that tomentosin‐induced apoptosis may involve a mitochondria‐mediated signaling pathway. This study provides the first evidence that tomentosin targets telomere machinery and induces apoptosis in cervical cancer cells. The molecular mechanism underlying tomentosin‐induced apoptosis may involve a mitochondria‐mediated signaling pathway. J. Cell. Biochem. 118: 1689–1698, 2017. © 2016 Wiley Periodicals, Inc.
Markov Mixed Effects Modeling Using Electronic Adherence Monitoring Records Identifies Influential Covariates to HIV Preexposure Prophylaxis
Authors: Madrasi Kumpal , Chaturvedula Ayyappa , Haberer Jessica E. , Sale Mark , Fossler Michael J. , Bangsberg David , Baeten Jared M. , Celum Connie , Hendrix Craig W.
Published: December 2016

Adherence is a major factor in the effectiveness of preexposure prophylaxis (PrEP) for HIV prevention. Modeling patterns of adherence helps to identify influential covariates of different types of adherence as well as to enable clinical trial simulation so that appropriate interventions can be developed. We developed a Markov mixed‐effects model to understand the covariates influencing adherence patterns to daily oral PrEP. Electronic adherence records (date and time of medication bottle cap opening) from the Partners PrEP ancillary adherence study with a total of 1147 subjects were used. This study included once‐daily dosing regimens of placebo, oral tenofovir disoproxil fumarate (TDF), and TDF in combination with emtricitabine (FTC), administered to HIV‐uninfected members of serodiscordant couples. One‐coin and first‐ to third‐order Markov models were fit to the data using NONMEM® 7.2. Model selection criteria included objective function value (OFV), Akaike information criterion (AIC), visual predictive checks, and posterior predictive checks. Covariates were included based on forward addition (α = 0.05) and backward elimination (α = 0.001). Markov models better described the data than 1‐coin models. A third‐order Markov model gave the lowest OFV and AIC, but the simpler first‐order model was used for covariate model building because no additional benefit on prediction of target measures was observed for higher‐order models. Female sex and older age had a positive impact on adherence, whereas Sundays, sexual abstinence, and sex with a partner other than the study partner had a negative impact on adherence. Our findings suggest adherence interventions should consider the role of these factors.
BEFORE ATTACHMENT THEORY: SEPARATION RESEARCH AT THE TAVISTOCK CLINIC, 1948–1956
Authors: POLAT BICAN
Published: December 2016

This article traces the formation of attachment theory to the pioneering research program of Bowlby and his colleagues at the Tavistock Clinic between 1948 and 1956. Through a discussion of the concepts and practices that informed Bowlby's program, I examine the efforts of his team to reconstruct psychoanalytic objects according to preventive objectives and operational criteria. I discuss how the exploratory techniques that Bowlby and his colleagues were developing during these years ultimately led to the establishment of a hybrid investigative framework, in which the prophylactic requirements of mental hygiene, the psychometric model of personality disturbances, the psychoanalytic theory of object relations, and a direct‐observational methodology were brought to bear on the problem of the psychological consequences of early separation experiences. I further claim that this shift in investigative practice was crucial for the succeeding theoretical developments that eventually gave rise to the statistically validated constructs of attachment theory.