bluuebunny/crossref_metadata_2025 huggingface dataset:
Paramagnetic NMR of Phenolic Oxime Copper Complexes: A Joint Experimental and Density Functional Study
Authors: Bühl Michael , Ashbrook Sharon E. , Dawson Daniel M. , Doyle Rachel A. , Hrobárik Peter , Kaupp Martin , Smellie Iain A.
Published: September 2016

1H and 13C pNMR properties of bis(salicylaldoximato)copper(II) were studied in the solid state using magic‐angle‐spinning NMR spectroscopy and, for the isolated complex and selected oligomers, using density‐functional theory at the PBE0‐
//PBE0‐D3 level. Large paramagnetic shifts are observed, up to δ(1H)=272 ppm and δ(13C)=1006 ppm (at 298 K), which are rationalised through spin delocalisation from the metal onto the organic ligand and the resulting contact shifts arising from hyperfine coupling. The observed shift ranges are best reproduced computationally using exchange‐correlation functionals with a high fraction of exact exchange (such as PBE0‐
). Through a combination of experimental techniques and first‐principles computation, a near‐complete assignment of the observed signals is possible. Intermolecular effects on the pNMR shifts, modelled computationally in the dimers and trimers through effective decoupling between the local spins via A‐tensor and total spin rescaling in the pNMR expression, are indicated to be small. Addition of electron‐donating substituents and benzannelation of the organic ligand is predicted computationally to induce notable changes in the NMR signal pattern, which suggests that pNMR spectroscopy can be a sensitive probe for the spin distribution in paramagnetic phenolic oxime copper complexes.
One‐Step Synthesis of Hybrid Liquid–Crystal ZnO Nanoparticles: Existence of a Critical Temperature Associated with the Anisotropy of the Nanoparticles
Authors: Zheng Zhiqin , Butynska Rémy , Serrano Clara Valverde , Marty Jean‐Daniel , Mingotaud Christophe , Kahn Myrtil L.
Published: September 2016

Zinc oxide nanoparticles were obtained from the hydrolysis of an organometallic precursor in pure hexadecylamine. Interestingly, we demonstrate that the final (anisotropic or isotropic) shape of the nanoparticles is strongly correlated to the existence of a critical temperature. This suggests that the organization of the fatty amines is a paramount parameter in this synthesis. Moreover, the final hybrid ZnO materials systematically exhibit a liquid–crystal smectic phase, whereas no liquid–crystal phase was observed in the pristine reaction media. This simple process is, therefore, a direct and straightforward method to synthesize liquid–crystal hybrid materials.
Visible‐Light‐Induced Direct Oxidative C−H Amidation of Heteroarenes with Sulfonamides
Authors: Tong Kun , Liu Xiaodong , Zhang Yan , Yu Shouyun
Published: September 2016

A direct oxidative C−H amidation of heteroarenes with sulfonamides via nitrogen‐centered radicals has been achieved. Nitrogen‐centered radicals are directly generated from oxidative cleavage of N−H bonds under visible‐light photoredox catalysis. Sulfonamides, which are easily accessed, are used as tunable nitrogen sources and bleach (aqueous NaClO solution) is used as the oxidant. A variety of heteroarenes, including indoles, pyrroles and benzofurans, can undergo this amidation with high yields (up to 92 %). These reactions are highly regioselective, and all the products are isolated as single regioisomer.
Few‐Layer Nanosheets of n‐Type SnSe2
Authors: Saha Sujoy , Banik Ananya , Biswas Kanishka
Published: September 2016

Layered p‐block metal chalcogenides are renowned for thermoelectric energy conversion due to their low thermal conductivity caused by bonding asymmetry and anharmonicity. Recently, single crystalline layered SnSe has created sensation in thermoelectrics due to its ultralow thermal conductivity and high thermoelectric figure of merit. Tin diselenide (SnSe2), an additional layered compound belonging to the Sn‐Se phase diagram, possesses a CdI2‐type structure. However, synthesis of pure‐phase bulk SnSe2 by a conventional solid‐state route is still remains challenging. A simple solution‐based low‐temperature synthesis is presented of ultrathin (3–5 nm) few layers (4–6 layers) nanosheets of Cl‐doped SnSe2, which possess n‐type carrier concentration of 2×1018 cm−3 with carrier mobility of about 30 cm2 V−1 s−1 at room temperature. SnSe2 has a band gap of about 1.6 eV and semiconducting electronic transport in the 300–630 K range. An ultralow thermal conductivity of about 0.67 Wm−1 K−1 was achieved at room temperature in a hot‐pressed dense pellet of Cl‐doped SnSe2 nanosheets due to the anisotropic layered structure, which gives rise to effective phonon scattering.
Technical and US regulatory issues in triaging material for the molecular laboratory
Authors: Fischer Andrew H. , Hutchinson Lloyd M.
Published: September 2016

Cytology samples offer many advantages for molecular testing, but the devil is in the details. In addition, regulatory issues may end up being the most significant challenge for cytology.
In Situ Growth of Co3O4 Nanoparticles on Interconnected Nitrogen‐Doped Graphene Nanoribbons as Efficient Oxygen Reduction Reaction Catalyst
Authors: Lu Hengyi , Yan Jiajie , Zhang Youfang , Huang Yunpeng , Gao Wei , Fan Wei , Liu Tianxi
Published: September 2016

A simple, low cost and nontoxic preparation method to obtain high performance oxygen reduction reaction (ORR) catalysts is of great significance in fuel cell fields. Herein, graphene nanoribbons (GNRs) with numerous graphitic edges are chosen as supporting material to hybridize with nitrogen atoms and cobalt oxide (Co3O4) through a simple one‐step hydrothermal reaction. With a high edge‐to‐plane ratio, the GNR sheets could increase the accessibility of N‐atom doping into the graphene edges to form active ORR sites, and be also interconnected with each other to form a conductive network, thus facilitating the fast electron transfer. The intimate contacts between Co3O4 nanoparticles and nitrogen‐doped GNRs (N‐GNRs) along with the porous structure impart the N‐GNR/Co3O4 hybrid with excellent ORR performance, which leads to a comparable onset‐potential to commercial Pt/C catalyst but larger current density, better long‐term stability and superior tolerance to crossover effects.
Collisions of FeO+ with H2 and He in a Cryogenic Ion Trap
Authors: Gerlich Dieter , Jašík Juraj , Andris Erik , Navrátil Rafael , Roithová Jana
Published: September 2016

The nominal temperature range of cryogenic radio‐frequency ion traps has recently been extended down to T=2.3 K. Whereas in situ He tagging of mass‐selected ions embedded in dense helium buffer gas is becoming common for recording IR spectra through photofragmentation of small and large ions, much less activity is devoted to the field of cold chemistry, which in this contribution means the two orders of magnitude extending from 300 to below 3 K. The importance of this temperature range for understanding the dynamics of bi‐ and termolecular reactions is illustrated with new results for the time‐honored reaction of FeO+ with H2 obtained with the cryogenic ion trap ISORI in Prague. The rate coefficient for forming Fe++H2O increases steeply with decreasing temperature. In addition more product channels open up, such as the stabilized reaction‐intermediate complexes H2FeO+ and Hen–FeO+ formed by ternary association with He. For the FeOH++H channel only a minor signal is observed. The rate coefficients provide deep insight into lifetimes, bottlenecks, and barriers impeding almost completely the exothermic, but spin‐forbidden, reaction at room temperature. For some of the He‐tagged ions, IR predissociation spectra are recorded. A breakthrough is obtaining the first spectrum of [(H2)FeO]+, synthesized and tagged in situ with He. These results pave the way to study the structures of reaction intermediates stabilized in the gas phase by means of collisions with helium.
Impact of exercise and a complex environment on hippocampal dendritic morphology,Bdnfgene expression, andDNAmethylation in male rat pups neonatally exposed to alcohol
Authors: Boschen K. E. , McKeown S. E. , Roth T. L. , Klintsova A. Y.
Published: September 2016

Alcohol exposurein uterocan result in Fetal Alcohol Spectrums Disorders (FASD). Measures of hippocampal neuroplasticity, including long‐term potentiation, synaptic and dendritic organization, and adult neurogenesis, are consistently disrupted in rodent models of FASD. The current study investigated whether third trimester‐equivalent binge‐like alcohol exposure (AE) [postnatal days (PD) 4–9] affects dendritic morphology of immature dentate gyrus granule cells, and brain‐derived neurotrophic factor (Bdnf) gene expression and DNA methylation in hippocampal tissue in adult male rats. To understand immediate impact of alcohol, DNA methylation was measured in the PD10 hippocampus. In addition, two behavioral interventions, wheel running (WR) and environmental complexity (EC), were utilized as rehabilitative therapies for alcohol‐induced deficits. AE significantly decreased dendritic complexity of the immature neurons, demonstrating the long‐lasting impact of neonatal alcohol exposure on dendritic morphology of immature neurons in the hippocampus. Both housing conditions robustly enhanced dendritic complexity in the AE animals. WhileBdnfexon I DNA methylation was lower in the AE and sham‐intubated animals compared with suckle controls on PD10, alterations toBdnfDNA methylation and gene expression levels were not present at PD72. In control animals, exercise, but not exercise followed by housing in EC, resulted in higher levels of hippocampalBdnfgene expression and lower DNA methylation. These studies demonstrate the long‐lasting negative impact of developmental alcohol exposure on hippocampal dendritic morphology and support the implementation of exercise and complex environments as therapeutic interventions for individuals with FASD. © 2016 Wiley Periodicals, Inc. Develop Neurobiol 77: 708–725, 2017
Interspecific variation in persistence of buried weed seeds follows trade‐offs among physiological, chemical, and physical seed defenses
Authors: Davis Adam S. , Fu Xianhui , Schutte Brian J. , Berhow Mark A. , Dalling James W.
Published: September 2016

Soil seedbanks drive infestations of annual weeds, yet weed management focuses largely on seedling mortality. As weed seedbanks increasingly become reservoirs of herbicide resistance, species‐specific seedbank management approaches will be essential to weed control. However, the development of seedbank management strategies can only develop from an understanding of how seed traits affect persistence.

We quantified interspecific trade‐offs among physiological, chemical, and physical traits of weed seeds and their persistence in the soil seedbank in a common garden study. Seeds of 11 annual weed species were buried in Savoy, IL, from 2007 through 2012. Seedling recruitment was measured weekly and seed viability measured annually. Seed physiological (dormancy), chemical (phenolic compound diversity and concentration; invertebrate toxicity), and physical traits (seed coat mass, thickness, and rupture resistance) were measured.

Seed half‐life in the soil (t0.5) showed strong interspecific variation (F10,30 = 15, p < .0001), ranging from 0.25 years (Bassia scoparia) to 2.22 years (Abutilon theophrasti). Modeling covariances among seed traits and seedbank persistence quantified support for two putative defense syndromes (physiological–chemical and physical–chemical) and highlighted the central role of seed dormancy in controlling seed persistence.

A quantitative comparison between our results and other published work indicated that weed seed dormancy and seedbank persistence are linked across diverse environments and agroecosystems. Moreover, among seedbank‐forming early successional plant species, relative investment in chemical and physical seed defense varies with seedbank persistence.

Synthesis and applications. Strong covariance among weed seed traits and persistence in the soil seedbank indicates potential for seedbank management practices tailored to specific weed species. In particular, species with high t0.5 values tend to invest less in chemical defenses. This makes them highly vulnerable to physical harvest weed seed control strategies, with small amounts of damage resulting in their full decay.
Dynamics of non‐structural carbohydrates in terrestrial plants: a global synthesis
Authors: Martínez‐Vilalta Jordi , Sala Anna , Asensio Dolores , Galiano Lucía , Hoch Günter , Palacio Sara , Piper Frida I. , Lloret Francisco
Published: September 2016

Plants store large amounts of non‐structural carbohydrates (NSC). While multiple functions ofNSChave long been recognized, the interpretation ofNSCseasonal dynamics is often based on the idea that storedNSCis a reservoir of carbon that fluctuates depending on the balance between supply via photosynthesis and demand for growth and respiration (the source–sink dynamics concept). Consequently, relatively highNSCconcentrations in some plants have been interpreted to reflect excess supply relative to demand. An alternative view, however, is thatNSCaccumulation reflects the relatively highNSClevels required for plant survival; an important issue that remains highly controversial. Here, we assembled a new global database to examine broad patterns of seasonalNSCvariation across organs (leaves, stems, and belowground), plant functional types (coniferous, drought‐deciduous angiosperms, winter deciduous angiosperms, evergreen angiosperms, and herbaceous) and biomes (boreal, temperate, Mediterranean, and tropical). We compiled data from 121 studies, including seasonal measurements for 177 species under natural conditions. Our results showed that, on average,NSCaccount for ~10% of dry plant biomass and are highest in leaves and lowest in stems, whereas belowground organs show intermediate concentrations. TotalNSC, starch, and soluble sugars (SS) varied seasonally, with a strong depletion of starch during the growing season and a general increase during winter months, particularly in boreal and temperate biomes. Across functional types,NSCconcentrations were highest and most variable in herbaceous species and in conifer needles. Conifers showed the lowest stem and belowgroundNSCconcentrations. MinimumNSCvalues were relatively high (46% of seasonal maximums on average for totalNSC) and, in contrast to average values, were similar among biomes and functional types. Overall, although starch depletion was relatively common, seasonal depletion of totalNSCorSSwas rare. These results are consistent with a dual view ofNSCfunction: whereas starch acts mostly as a reservoir for future use, soluble sugars perform immediate functions (e.g., osmoregulation) and are kept above some critical threshold. If confirmed, this dual function ofNSCwill have important implications for the way we understand and model plant carbon allocation and survival under stress.
Intramolecular Cycloaddition in the (Diyne)iridium Complexes [Cp*Ir(CO)(η2‐ArC≡CC≡CAr)]: An Experimental and Computational Study
Authors: Li Yongjia , Leong Weng Kee
Published: September 2016

The diyne complex [Cp*Ir(CO)(η2‐ArC≡CC≡CAr)] reacts with two‐electron donor ligands to form the iridacyclobutenone [Cp*Ir(L){C(C≡CAr)=C(Ar)C=O}]. Kinetic measurements and computational studies support the proposal that the reaction pathway involves alkyne insertion followed by coordination of the two‐electron donor ligand.
Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW9O34]10– Leading to the Formation of a Ce6O4(OH)4 Core
Authors: Duval Sylvain , Trivelli Xavier , Roussel Pascal , Loiseau Thierry
Published: September 2016

The reaction of Na10[α‐SiW9O34] with 4f tetravalent cerium cations in aqueous solution in the presence of sodium acetate at different pH values leads to the stabilization of three cerium‐based polyanionic molecular clusters [Ce3(µ2‐OH)3(µ3‐O)(SiW9O34)2]13– (1), [Ce3(µ2‐O)3(SiW9O34)2]14– (2), and {[Ce6(µ3‐O)4(µ3‐OH)4]2(W8O32)(SiW9O34)4}32– (3). The condensation behavior of cerium in this kind of association with trivacant polyoxometalates (POMs) when a pH variation occurs is relatively unknown and needed to be explored. Compounds 1 and 2 consist of a trinuclear cerium cluster fragment stabilized by two POM moieties with a variation of the central cerium cluster from [Ce3(µ2‐OH)3(µ3‐O)] to [Ce3(µ2‐O)3]. Compound 3 appears much more condensed with two hexanuclear [Ce6(µ3‐O)4(µ3‐OH)4] groups that are stabilized by the SiW9O34 moieties and a W8O32 tungsten ring. This evolution in cluster size and composition reflects the pH variation applied during their synthesis. The molecules have been characterized by single‐crystal X‐ray diffraction, 183W and 29Si NMR spectroscopy, IR spectroscopy, thermogravimetric analysis (TGA), and SEM/energy‐dispersive X‐ray (EDX) microscopy. The three compounds obtained here exemplify the influence of pH on the condensation of tetravalent cations and open a new route toward the stabilization of polynuclear tetravalent clusters by nucleophilic O‐donating POM species.
Stereoselective Synthesis of Hydroxy Diamino Acid Derivatives and the Caprolactam Unit of Bengamide A through Organocatalytic α‐Hydroxylation and Reductive Amination of Aldehydes
Authors: Philip Anijamol T. , Raju Eerlapally , Ramapanicker Ramesh
Published: September 2016

The synthetic utility of proline‐catalyzed asymmetric α‐hydroxylation and subsequent reductive amination of aldehydes to afford chiral β‐amino alcohols is explored for the first time. Stereoselective synthesis of orthogonally protected 5‐hydroxylysine, 4‐hydroxyornithine and 2,4‐diamino‐3‐hydroxybutanoic acid was achieved. (2S,5S)‐5‐Hydroxylysine synthesized in this way was converted into the aminocaprolactam ring system of bengamide A.
Measuring Mechanical Properties during the Electrochemical Lithiation of Silicon
Authors: Epler Eike , Roddatis Vladimir V. , Volkert Cynthia A.
Published: September 2016

In situ nanoindentation is used to measure the modulus and hardness of amorphous LixSi during its formation by electrochemical lithiation of (111) silicon surfaces. Due to the large volume changes experienced during lithiation, accurate knowledge of an electrode′s mechanical properties is essential for predicting reliability and developing design guidelines for battery electrodes. We observe a clear decrease in modulus and hardness during lithiation. By accounting for the growing thickness of the amorphous layer, we obtain reliable in operando values for the modulus (45 GPa) and hardness (1 GPa) of the amorphous LixSi, which are in reasonable agreement with literature values obtained under less well‐defined electrochemical conditions. Furthermore, a small increase in modulus just prior to amorphization and the formation of amorphous islands at the early stages lend credence to the idea of the formation of precursor defects in the crystalline silicon prior to amorphization.
Zinc Oxide–Titania Heterojunction‐based Solid Nanospheres as Photoanodes for Electron‐Trapping in Dye‐Sensitized Solar Cells
Authors: Shejale Kiran P. , Laishram Devika , Gupta Ritu , Sharma Rakesh K.
Published: September 2016

Agile nanostructure architectures and smart combinations of semiconducting metal oxide materials are key features of high‐performing dye‐sensitized solar cells (DSSCs). Herein, we synthesize mesoporous solid nanospheres of ZnO–TiO2 with type‐II heterojunction and use these as an efficient photoanode material for excellent photoconversion. These polydisperse aggregates doped with 1 %, 5 %, and 10 % of ZnO exhibit improved solar cell performance with respect to pristine TiO2 under AM 1.5 G. The 1 % ZnO doped TiO2 nanosphere possess high specific surface area (84.23 m2 g−1) as a photoanode and shows high photoconversion efficiency of about 8.07 % with ca. 18 % improvement in the photocurrent density (Jsc) compare to TiO2 nanosphere. The improved solar cell performance (Δη=40 %) of ZnO decorated TiO2 nanospheres is ascribed to type‐II heterojunction of ZnO–TiO2, that reduces the electron recombination and synergistically enhances the electron mobility and charge collection capability.
Opportunity and challenge of seaweed bioethanol based on life cycle CO2 assessment
Authors: Jung Kyung A , Lim Seong‐Rin , Kim Yoori , Park Jong Moon
Published: September 2016

Seaweed bioethanol technology is being developed to mitigate climate change and to overcome economic and environmental drawbacks that terrestrial bioethanol has: biomass demand competition for food and energy, and land‐use change impacts. To investigate whether seaweed bioethanol is better than terrestrial bioethanol, we compare the global warming potentials (GWPs) of seaweed and terrestrial bioethanols from a life cycle perspective including land‐related GWP effects from carbon debt, soil carbon sequestration, and N2O emission. Our results demonstrated that seaweed bioethanol has lower GWP in the long term than terrestrial bioethanols from corn grain, corn stover, and switchgrass, primarily because seaweed cultivation does not consume fertilizers and incur carbon debt and N2O emission. It was noted that future R&D strategy for low‐carbon seaweed bioethanol needs to be directed to developing biomaterial‐based cultivation equipment and reusing existing equipment, as well as enhancing bioethanol conversion yield and biomass productivity. Due to the vast sea available for seaweed cultivation, seaweed bioethanol could significantly contribute to mitigating climate change. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 200–207, 2017
Geomorphic response of the Jingjiang Reach to the Three Gorges Project operation
Authors: Xia Junqiang , Deng Shanshan , Zhou Meirong , Lu Jinyou , Xu Quanxi
Published: September 2016

Upstream damming often causes significant downstream geomorphic adjustments. Remarkable channel changes have occurred in the Jingjiang Reach of the Middle Yangtze River, since the onset of the Three Gorges Project (TGP). Therefore, it is important to investigate the variations in different fluvial variables, for better understanding of the channel evolution characteristics as an example of the Jingjiang Reach. Recent geomorphic adjustments in the study reach have been investigated quantitatively, including variations in sediment rating curve, fluvial erosion intensity, channel deformation volume and bankfull channel geometry. These fluvial variables adjusted in varying degrees in response to the altered flow and sediment regime caused by the TGP operation. A focus of this study has been especially on variation in the bankfull channel geometry. Calculated bankfull dimensions at section‐ and reach‐scale indicate that: (i) there were significant bank‐erosion processes in local regions without bank‐protection engineering, with empirical relations being developed to reproduce the variation in bankfull widths at four typical sections; (ii) the variation in the reach‐scale channel geometry occurred mainly in the component of bankfull depth, owing to the construction of large‐scale bank‐revetment works, with the depth increasing from 13.7 m in 2002 to 15.0 m in 2014, and with an increase in the corresponding bankfull area of about 11%; and (iii) the reach‐scale bankfull channel dimensions responded to the previous 5‐year average fluvial erosion intensity during flood seasons at Zhicheng, with higher correlations for the depth and area being obtained when calibrated by the measurements in 2002–2012. Furthermore, these relations developed for the section‐ and reach‐scale bankfull channel geometry were also verified by the observed data in 2013–2014, with encouraging results being obtained. Copyright © 2016 John Wiley & Sons, Ltd.
Effects of carbon dioxide on juveniles of the freshwater mussel (Lampsilis siliquoidea [Unionidae])
Authors: Waller Diane L. , Bartsch Michelle R. , Fredricks Kim T. , Bartsch Lynn A. , Schleis Susan M. , Lee Sheldon H.
Published: September 2016

Carbon dioxide (CO2) has shown promise as a tool to control movements of invasive Asian carp, but its effects on native freshwater biota have not been well studied. The authors evaluated lethal and sublethal responses of juvenile fatmucket (Lampsilis siliquoidea) mussels to CO2 at levels (43–269 mg/L, mean concentration) that bracket concentrations effective for deterring carp movement. The 28-d lethal concentration to 50% of the mussels was 87.0 mg/L (95% confidence interval [CI] 78.4–95.9) and at 16-d postexposure, 76.0 mg/L (95% CI 62.9–90.3). A proportional hazards regression model predicted that juveniles could not survive CO2 concentrations >160 mg/L for more than 2 wk or >100 mg/L CO2 for more than 30 d. Mean shell growth was significantly lower for mussels that survived CO2 treatments. Growth during the postexposure period did not differ among treatments, indicating recovery of the mussels. Also, CO2 caused shell pitting and erosion. Behavioral effects of CO2 included movement of mussels to the substrate surface and narcotization at the highest concentrations. Mussels in the 110 mg/L mean CO2 treatment had the most movements in the first 3 d of exposure. If CO2 is infused continuously as a fish deterrent, concentrations <76 mg/L are recommended to prevent juvenile mussel mortality and shell damage. Mussels may survive and recover from brief exposure to higher concentrations. Environ Toxicol Chem 2017;36:671–681. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.
Risk assessment from exposure to arsenic, antimony, and selenium in urban gardens (Madrid, Spain)
Authors: De Miguel Eduardo , Izquierdo Miguel , Gómez Amaia , Mingot Juan , Barrio-Parra Fernando
Published: September 2016

The authors discuss the geochemical behavior of arsenic (As), antimony (Sb), and selenium (Se) in urban gardens and the human health implications associated with urban agriculture. A total of 42 samples from 7 urban gardens in Madrid, Spain, were collected from the top 20 cm of soil. Concentrations of As, Sb, and Se and the main soil properties (i.e., total iron, pH, texture, calcium carbonate, and organic matter) were determined. A significant correlation was found between As and Sb and calcium carbonate, indicating the possibility of surface adsorption or ligand exchange with the carbonate group. Also, Sb seemed to form stable chelates with soil organic matter. On the other hand, Se showed a significant association with clay and iron content. The concentration of Sb in soil exceeded the recommended value for agricultural use in 70% of the urban gardens. A human health risk assessment resulted in acceptable levels of both noncarcinogenic and carcinogenic risks (although with elevated values of the latter), with As as the main risk driver and soil and food ingestion as the main exposure pathways. The numerical results of the risk assessment should be interpreted with caution given the considerable uncertainties in some exposure variables and the lack of quantitative values for the suspected carcinogenicity of Sb and Se. Environ Toxicol Chem 2017;36:544–550. © 2016 SETAC
Sucrose modifies growth and physiology in axenically grown Myriophyllum spicatum with potential effects on the response to pollutants
Authors: Nuttens Andréïna , Gross Elisabeth Maria
Published: September 2016

Sucrose as a carbon source in axenic tests affects plant growth and physiology. The high sucrose concentration in Organisation for Economic Co-operation and Development (OECD) guideline 238 for the submerged growing aquatic plant Myriophyllum spicatum might modify pollutant effects, thus impairing environmental risk assessment. In a factorial design experiment with axenic M. spicatum exposed to 3 sucrose concentrations (no, low, and high) with or without cadmium, growth, dry matter content, content in pigments or phenolic compounds, and elemental stoichiometry of carbon (C), nitrogen (N), and phosphorus (P) were measured. The results show that sucrose is crucial for growth but can be used at lower concentrations than currently considered. Sucrose-treated plants had higher dry matter content and C content but lower contents of chlorophyll and N. Cadmium affected the content in chlorophyll, phenolic compounds, and elemental stoichiometry. Interactive effects were observed on length growth, C and N content, and the C:N and N:P molar ratios. Remarkably, cadmium led to increased shoot length at low, but not at high, sucrose concentration. This contrasting effect might result from differences in osmotic potential caused by sucrose. Overall, the results suggest a strong effect of sucrose concentration on the growth and physiology of M. spicatum and modifications of the response to cadmium. Further studies should establish the lowest sucrose level needed to account for realistic environmental risk assessment based on the axenic OECD 238. Environ Toxicol Chem 2017;36:969–975. © 2016 SETAC.
General and histological indicators of health in wild fishes from a biological mercury hotspot in northeastern North America
Authors: Graves Stephanie D. , Kidd Karen A. , Houlahan Jeff E. , Munkittrick Kelly R.
Published: September 2016

Kejimkujik National Park and National Historic Site, Nova Scotia, Canada, is considered a biological mercury (Hg) hotspot because the tissues of yellow perch (Perca flavescens) and common loons (Gavia immer) inhabiting the lakes frequently exceed so-called safe levels of Hg. In the present study, the relationships between Hg and overall health of males and females of 3 forage fish species (brown bullhead Ameirus nebulosus, banded killifish Fundulus diaphanus, and golden shiner Notemigonus crysoleucas; n = 6–18/sex/lake) in 6 lakes at the park were assessed using condition factor, liversomatic index (LSI), and macrophage aggregates (MAs; indicators of tissue damage). Mean muscle total Hg (THg) concentrations of brown bullhead, banded killifish, and golden shiner across lakes were 0.32 μg/g, 0.27 μg/g, and 0.34 μg/g, respectively. Condition was negatively related to muscle THg in golden shiner and banded killifish, LSI was not related to THg in any species, and all species showed evidence of increasing MA prevalence (counts and area) with increasing THg concentrations. The MAs were most prevalent in spleen tissues of golden shiner, with mean percentage cover ranging from 0.36% to 5.59% across lakes. In addition, the area of MAs appeared to be better predicted by THg concentration than was the number of MAs in the same tissue. These findings suggest that Hg is affecting the health of wild fishes in Kejimkujik National Park and National Historic Site and that other populations with similar or higher concentrations of this metal may also be at risk. Environ Toxicol Chem 2017;36:976–987. © 2016 SETAC
Postgraduate Outcomes in American Higher Education
Authors: Coughlin Mary Ann , Laguilles Jerold S. , Kelly Heather A. , Walters Allison M.
Published: September 2016

This chapter provides a big‐picture view of the postgraduate outcomes landscape. In an effort to promote understanding and to communicate the value of a higher education credential to various stakeholders, five national efforts are described, each of which provides a different perspective for defining, measuring, and collecting postgraduate outcomes.
Leading Gainful Employment Metric Reporting
Authors: Powers Kristina , MacPherson Derek
Published: September 2016

This chapter will address the importance of intercampus involvement in reporting of gainful employment student‐level data that will be used in the calculation of gainful employment metrics by the U.S. Department of Education. The authors will discuss why building relationships within the institution is critical for effective gainful employment reporting.
A Novel Method for the Synthesis of Newfangled Asymmetric Schiff Bases from α‐amino Acids under Ultrasonic Conditions and in Aqueous Medium
Authors: Şendil Kıvılcım , Tekin Turgay , Göksu Haydar , Oğuz Mehmet , Anıl Barış , Gültekin Mehmet Serdar
Published: September 2016

Chiral Schiff bases were obtained at high yields via a novel technique. Aryl aldehydes and chiral α‐amino acids were treated (1) in the presence of H3PO4 in ethanol at 80°C for 24 h, and (2) in the presence of K2CO3 under ultrasonic conditions in an aqueous ethanol medium within 5 min with yields reaching up to 96%. The results showed that the presented methodology under ultrasonic conditions was effective, practical, and eco‐friendly compared to that using an acidic medium. The corresponding asymmetric Schiff bases were synthesized for the first time, and were characterized by 1H and 13C nuclear magnetic resonance and infrared spectroscopy and high‐resolution mass spectrometry.
Magnitude of Species Diversity Effect on Aboveground Plant Biomass Increases Through Successional Time of Abandoned Farmlands on the Eastern Tibetan Plateau of China
Authors: Li Wenjin , Li Jinhua , Liu Shuangshuang , Zhang Rulan , Qi Wei , Zhang Renyi , Knops Johannes M. H. , Lu Junfeng
Published: September 2016

Recent empirical and theoretical studies have shown that magnitude and direction of biodiversity effects on ecosystem functioning can shifts over time. Here, we used species richness and plant abundance (total individual plant stem density) as proxies for species diversity and aboveground biomass for productivity. We used an analytical approach combining both chronosequence and 6 year of vegetation monitoring in a subalpine ecosystem as a model system to assess temporal species richness–abundance–aboveground biomass relationships at different successional stages and spatial scales. We observed that both species richness and plant aboveground biomass increased rapidly early in succession after land abandonment, then after 10 years of abandonment reached a steady state. We found that the relationship between species richness and plant abundance with aboveground biomass was strengthening over successional time. In all successional stages, species richness had stronger positive effects as compared with plant abundance on plant aboveground biomass. Species richness was linearly correlated with aboveground biomass, whereas plant abundance showed a humped‐back relationship with aboveground biomass across all successional stages. Our results showed an increase in the effect of plant diversity over time, and a combination of both plant species richness and abundance is correlated with plant productivity throughout successional time, knowledge that maybe important to managing ecological restoration and conservation. Copyright © 2016 John Wiley & Sons, Ltd.
Spatiotemporal Heterogeneity of Soil Available Nitrogen During Crop Growth Stages on Mollisol Slopes of Northeast China
Authors: Zhang Shaoliang , Huang Jing , Wang Yao , Shen Qingsong , Mu Linlin , Liu Zhihua
Published: September 2016

Spatiotemporal heterogeneity of soil available nitrogen (AN) (sum of NO3−–N and NH4+–N) is the essential basis for soil management and highly correlates to crop yield. Both geostatistical and traditional analyses were used to describe the spatiotemporal distribution of AN in the 0–20‐cm soil depth on typical Mollisol slopes (S1 and S2) in Northeast China. The concentration of NO3−–N dynamics at slope positions was typically opposite to NH4+–N. The peak values of AN typically moved from the summit of the slope to the bottom from spring to autumn and were mainly influenced by the content of NO3−–N (S1, 7·9–18·9 mg kg−1; S2, 1·2–103·6 mg kg−1), both of NO3−–N (S1, 3·9–8·3 mg kg−1; S2, 2·2–28·0 mg kg−1) and NH4+–N (S1, 21·4–30·5 mg kg−1; S2, 2·1–23·3 mg kg−1), and NH4+–N (S1, 10·5–28·9 mg kg−1; S2, 5·0–39·0 mg kg−1) in the seedling stage, vegetative growth stage, and reproductive growth stage, respectively. The spatial autocorrelation of AN was strong and was mainly influenced by structural factors during crop growth stages. This was mainly determined by soil erosion–deposition (SED) and soil temperature–moisture (STM) in the seedling stage; this was also mainly influenced by SED, STM, crop type, and crop growth in the vegetative growth stage and by early STM and early SED in the reproductive growth stage. Generally, the content of AN, NO3−–N, and NH4+–N on the whole slope was mainly determined by the early SED and local fertilizer application, while their spatiotemporal heterogeneity, especially the evenness, was mainly changed by SED, STM, crop growth, and crop types on the slope scale. In order to increase more crop yields, additional N fertilizer application on both the summit and the bottom during the vegetative growth stage and conservation tillage systems or additional soil amendments on the back slopes was necessary. Copyright © 2016 John Wiley & Sons, Ltd.
Room temperature operation of a deep etched buried heterostructure photonic crystal quantum cascade laser
Authors: Peretti Romain , Liverini Valeria , Süess Martin J. , Liang Yong , Vigneron Pierre‐ Baptiste , Wolf Johanna M. , Bonzon Christopher , Bismuto Alfredo , Metaferia Wondwosen , Balaji Manavaimaran , Lourdudoss Sebastian , Gini Emilio , Beck Mattias , Faist Jérome
Published: September 2016

High power single mode quantum cascade lasers with a narrow far field are important for several applications including surgery or military countermeasure. Existing technologies suffer from drawbacks such as operation temperature and scalability. In this paper we introduce a fabrication approach that potentially solves simultaneously these remaining limitations. We demonstrate and characterize deep etched, buried photonic crystal quantum cascade lasers emitting around a wavelength of 8.5 μm. The active region was dry etched before being regrown with semi‐insulating Fe:InP. This fabrication strategy results in a refractive index contrast of 10% allowing good photonic mode control, and simultaneously provides good thermal extraction during operation. Single mode emission with narrow far field pattern and peak powers up to 0.88 W at 263 K were recorded from the facet of the photonic crystal laser, and lasing operation was maintained up to room temperature. The lasing modes emitted from square photonic crystal mesas with a side length of 550μm, were identified as slow Bloch photonic crystal modes by means of three‐dimensional photonic simulations and measurements.

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Corrosion properties of model aluminium alloys for coating steel substrate
Authors: Stoulil J. , Domko B. , Šerák J.
Published: September 2016

This study focused on the corrosion and electrochemical behaviour of aluminium alloys (AlSi9Cu5, AlZn10Si8Mg1, AlZn4Mg1In, AlSi5Mg8 and AlSi5Mg8In) as potential galvanic coatings for steel. The properties of alloys were observed in solutions of artificial rain and seawater as well as in the atmosphere. Electrochemical properties were monitored using DC techniques (open‐circuit potential, zero‐resistance ammetry). The experiments showed promising corrosion and electrochemical behaviour characteristics for AlZn10Si8Mg1 and AlSi5Mg8In alloys, which had properties similar to those of zinc.
Atmospheric corrosion of copper exposed to different environments in the region of Valparaiso, Chile
Authors: Vera R. , Araya R. , Bagnara M. , Díaz‐Gómez A. , Ossandón S.
Published: September 2016

This article presents the results obtained for the atmospheric corrosion of copper after 3 years of exposure at different sites within the region of Valparaiso, Chile. Frames were installed with samples at seven sites located close to the coast and inland. They were accompanied by devices to measure atmospheric chloride and sulphur dioxide content and weather stations to obtain data on temperature, humidity, amount of rainfall and wind speed. The results show a correlation between corrosion rate and the environmental and meteorological conditions in the area, and with the morphology and electrochemical properties of the corrosion product formed on the copper surface. The sites gave corrosivity categories of C5, C4, C3 and C2. The behaviour of corrosion rate was modelled using power function models and neural networks. The main corrosion products were cuprite, posnjankite, covelite and atacamite.
Single nucleotide variants in metastasis‐related genes are associated with breast cancer risk, by lymph node involvement and estrogen receptor status, in women with European and African ancestry
Authors: Roberts Michelle R. , Sucheston‐Campbell Lara E. , Zirpoli Gary R. , Higgins Michael , Freudenheim Jo L. , Bandera Elisa V. , Ambrosone Christine B. , Yao Song
Published: September 2016

Single nucleotide polymorphisms (SNPs) in pathways influencing lymph node (LN) metastasis and estrogen receptor (ER) status in breast cancer may partially explain inter‐patient variability in prognosis. We examined 154 SNPs in 12 metastasis‐related genes for associations with breast cancer risk, stratified by LN and ER status, in European‐American (EA) and African‐American (AA) women. Two‐thousand six hundred and seventy‐one women enrolled in the Women's Circle of Health Study were genotyped. Pathway analyses were conducted using the adaptive rank truncated product (ARTP) method, with pARTP ≤ 0.10 as significant. Multi‐allelic risk scores were created for the ARTP‐significant gene(s). Single‐SNP and risk score associations were modeled using logistic regression, with false discovery rate (FDR) P‐value adjustment. Although single‐SNP associations were not significant at pFDR < 0.05, several genes were significant in the ARTP analyses. In AA women, significant ARTP gene‐level associations included CDH1 with LN+ (pARTP = 0.10; multi‐allelic OR = 1.13, 95%CI 1.07–1.19, pFDR = 0.0003) and SIPA1 with ER− breast cancer (pARTP = 0.10; multi‐allelic OR = 1.16, 95%CI 1.02–1.31, pFDR = 0.03). In EA women, MTA2 was associated with overall breast cancer risk (pARTP = 0.004), regardless of ER status, and with LN− disease (pARTP = 0.01). Also significant were SATB1 in ER− (pARTP = 0.03; multi‐allelic OR = 1.12, 95%CI 1.05–1.20, pFDR = 0.003) and KISS1 in LN− (pARTP = 0.10; multi‐allelic OR = 1.18, 95%CI 1.08–1.29, pFDR = 0.002) analyses. Among LN+ cases, significant ARTP associations were observed for SNAI1, CD82, NME1, and CTNNB1 (multi‐allelic OR = 1.09, 95%CI 1.04–1.14, pFDR = 0.001). Our findings suggest that variants in several metastasis genes may affect breast cancer risk by LN or ER status, although verification in larger studies is required. © 2016 Wiley Periodicals, Inc.
Diffusion MRI of the spinal cord: from structural studies to pathology
Authors: Cohen Yoram , Anaby Debbie , Morozov Darya
Published: September 2016

Diffusion MRI is extensively used to study brain microarchitecture and pathologies, and water diffusion appears highly anisotropic in the white matter (WM) of the spinal cord (SC). Despite these facts, the use of diffusion MRI to study the SC, which has increased in recent years, is much less common than that in the brain. In the present review, after a brief outline of early studies of diffusion MRI (DWI) and diffusion tensor MRI (DTI) of the SC, we provide a short survey on DTI and on diffusion MRI methods beyond the tensor that have been used to study SC microstructure and pathologies. After introducing the porous view of WM and describing the q‐space approach and q‐space diffusion MRI (QSI), we describe other methodologies that can be applied to study the SC. Selected applications of the use of DTI, QSI, and other more advanced diffusion MRI methods to study SC microstructure and pathologies are presented, with some emphasis on the use of less conventional diffusion methodologies. Because of length constraints, we concentrate on structural studies and on a few selected pathologies. Examples of the use of diffusion MRI to study dysmyelination, demyelination as in experimental autoimmune encephalomyelitis and multiple sclerosis, amyotrophic lateral sclerosis, and traumatic SC injury are presented. We conclude with a brief summary and a discussion of challenges and future directions for diffusion MRI of the SC. Copyright © 2016 John Wiley & Sons, Ltd.
Transmitting boundary conditions for 1D peridynamics
Authors: Wang Linjuan , Chen Yongshuai , Xu Jifeng , Wang Jianxiang
Published: September 2016

The peridynamic theory reformulates the equations of continuum mechanics in terms of integro‐differential equations instead of partial differential equations. It is not straightforward to apply the available artificial boundary conditions for continua to peridynamic modeling. We therefore develop peridynamic transmitting boundary conditions (PTBCs) for 1D wave propagation. Differently from the previous method where the matching boundary condition is constructed for only one boundary material point, the PTBCs are established by considering the interaction and exchange of information between a group of boundary material points and another group of inner material points. The motion of the boundary material points is recursively constructed in terms of their locations and is determined through matching the peridynamic dispersion relation. The effectiveness of the PTBCs is examined by reflection analyses, numerical tests, and numerical convergent conditions. Furthermore, two‐way interfacial conditions are proposed. The PTBCs are then applied to simulations of wave propagation in a bar with a defect, a composite bar with interfaces, and a domain with a seismic source. All the analyses and applications demonstrate that the PTBCs can effectively remove undesired numerical reflections at artificial boundaries. The methodology may be applied to modeling of wave propagation by other nonlocal theories. Copyright © 2016 John Wiley & Sons, Ltd.
Plasma‐catalytic reforming of biogas over supported Ni catalysts in a dielectric barrier discharge reactor: Effect of catalyst supports
Authors: Mei Danhua , Ashford Bryony , He Ya‐Ling , Tu Xin
Published: September 2016

In this study, plasma‐catalytic reforming of simulated biogas for the production of value‐added fuels and chemicals (e.g., H2) has been carried out in a coaxial dielectric barrier discharge (DBD) plasma reactor. The influence of four Ni catalysts (Ni/γ‐Al2O3, Ni/MgO, Ni/SiO2, and Ni/TiO2) on the plasma‐catalytic biogas reforming has been investigated in terms of the conversion of reactants, the yield and selectivity of target products, the carbon deposition on the catalysts, and the energy efficiency of the plasma‐catalytic process. The use of plasma combined with these Ni catalysts enhanced the performance of the biogas reforming. A maximum CO2 conversion of 26.2% and CH4 conversion of 44.1% were achieved when using the Ni/γ‐Al2O3 catalyst at a specific energy density (SED) of 72 kJ l−1. Compared to other Ni catalysts, placing the Ni/γ‐Al2O3 catalyst in the DBD produced more syngas and C3C4 hydrocarbons, but less C2H6. The lowest energy cost (EC) for biogas conversion and syngas production, as well as the highest energy efficiency and fuel production efficiency (FPE), were achieved when using the Ni/γ‐Al2O3 catalyst in the plasma process. The Ni/γ‐Al2O3 catalyst also showed the lowest surface carbon deposition of 3.8%, after catalysing the plasma biogas reforming process for 150 min at a SED of 60 kJ l−1. Compared to other Ni catalysts, the enhanced performance of the Ni/γ‐Al2O3 catalyst can be attributed to its higher specific surface area, higher reducibility and more, stronger basic sites on the catalyst surface.