bluuebunny/crossref_metadata_2025 huggingface dataset:
Quenching the Quantum Tunneling of Magnetization in Heterometallic Octanuclear {TMIII4DyIII4} (TM=Co and Cr) Single‐Molecule Magnets by Modification of the Bridging Ligands and Enhancing the Magnetic Exchange Coupling
Authors: Vignesh Kuduva R. , Langley Stuart K. , Murray Keith S. , Rajaraman Gopalan
Published: November 2016

We report the synthesis, structural characterisation, magnetic properties and provide an ab initio analysis of the magnetic behaviour of two new heterometallic octanuclear coordination complexes containing CoIII and DyIII ions. Single‐crystal X‐ray diffraction studies revealed molecular formulae of [CoIII4DyIII4(μ‐OH)4(μ3‐OMe)4{O2CC(CH3)3}4(tea)4 (H2O)4]⋅4 H2O (1) and [CoIII4DyIII4(μ‐F)4(μ3‐OH)4(o‐tol)8(mdea)4]⋅ 3 H2O⋅EtOH⋅MeOH (2; tea3−=triply deprotonated triethanolamine; mdea2−=doubly deprotonated N‐methyldiethanolamine; o‐tol=o‐toluate), and both complexes display an identical metallic core topology. Furthermore, the theoretical, magnetic and SMM properties of the isostructural complex, [CrIII4DyIII4(μ‐F4)(μ3‐OMe)1.25(μ3‐OH)2.75(O2CPh)8(mdea)4] (3), are discussed and compared with a structurally similar complex, [CrIII4DyIII4(μ3‐OH)4(μ‐N3)4(mdea)4(O2CC(CH3)3)4] (4). DC and AC magnetic susceptibility data revealed single‐molecule magnet (SMM) behaviour for 1–4. Each complex displays dynamic behaviour, highlighting the effect of ligand and transition metal ion replacement on SMM properties. Complexes 2, 3 and 4 exhibited slow magnetic relaxation with barrier heights (Ueff) of 39.0, 55.0 and 10.4 cm−1 respectively. Complex 1, conversely, did not exhibit slow relaxation of magnetisation above 2 K. To probe the variance in the observed Ueff values, calculations by using CASSCF, RASSI‐SO and POLY_ANISO routine were performed on these complexes to estimate the nature of the magnetic coupling and elucidate the mechanism of magnetic relaxation. Calculations gave values of JDy–Dy as −1.6, 1.6 and 2.8 cm−1 for complexes 1, 2 and 3, respectively, whereas the JDy–Cr interaction was estimated to be −1.8 cm−1 for complex 3. The developed mechanism for magnetic relaxation revealed that replacement of the hydroxide ion by fluoride quenched the quantum tunnelling of magnetisation (QTM) significantly, and led to improved SMM properties for complex 2 compared with 1. However, the tunnelling of magnetisation at low‐lying excited states was still operational for 2, which led to low‐temperature QTM relaxation. Replacement of the diamagnetic CoIII ions with paramagnetic CrIII led to CrIII⋅⋅⋅DyIII coupling, which resulted in quenching of QTM at low temperatures for complexes 3 and 4. The best example was found if both CrIII and fluoride were present, as seen for complex 3, for which both factors additively quenched QTM and led to the observation of highly coercive magnetic hysteresis loops above 2 K. Herein, we propose a synthetic strategy to quench the QTM effects in lanthanide‐based SMMs. Our strategy differs from existing methods, in which parameters such as magnetic coupling are difficult to control, and it is likely to have implications beyond the DyIII SMMs studied herein.
pH‐Gated Chloride Transport by a Triazine‐Based Tripodal Semicage
Authors: Roy Arundhati , Saha Debasis , Mandal Prashant Sahebrao , Mukherjee Arnab , Talukdar Pinaki
Published: November 2016

Triazine‐based preorganized tripodal receptors are reported as efficient transmembrane Cl− carriers. These receptors were designed based on triazine core and 3,7‐diazabicyclo[3.3.1]nonane arms to facilitate preorganized cavity formation. Each bicyclic arm was further functionalized to control protonation and lipophilicity, which are crucial for their efficient anion binding and effective transport through liposomal membranes. The benzyl‐substituted receptor was the most effective ion transporter followed by the pentafluorobenzyl‐substituted derivative. The nonsubstituted receptor was least active owing to its high polarity. Two active transporters were found to function as mobile carriers for Cl− via an antiport exchange mechanism. Molecular dynamic simulations with the most active receptor show a strong Cl− binding within the cavity by direct and water‐mediated H‐bonds with its N−H groups.
Scale‐up of Dry Hopping Trials: Importance of Scale for Aroma and Taste Perceptions
Authors: Schnaitter Martin , Kell Adrian , Kollmannsberger Hubert , Schüll Florian , Gastl Martina , Becker Thomas
Published: November 2016

In this study beers that were dry hopped in three different batch sizes were compared. The hop‐oil concentrations were measured and possible aroma‐active hop volatiles were identified in the hop pellets as well as in the beers. The analytical results were correlated with the tasting results from a trained tasting panel. Mass transfer rates were not comparable between the different scales, and significant differences could be detected by the tasters. The beers dry hopped on an industrial scale are not comparable in flavor and odor to those dry hopped on a laboratory scale.
Determination of Hg2+ in Tap Water Based on the Electrochemiluminescence of Ru(phen)32+ and Thymine at Bare and Graphene Oxide‐Modified Glassy Carbon Electrodes
Authors: Gao Yulong , Wang Tao , Liu Fengyu
Published: November 2016

The electrochemiluminescence (ECL) of the Ru(phen)32+/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg2+ in tap water. The ECL intensity of Ru(phen)32+ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)32+/T system rapidly decreased with the addition of Hg2+ because of the formation of a T‐Hg2+‐T complex. A linear response (R2=0.9914) was obtained over a Hg2+ concentration range of 1.0×10−9 mol/L to 1.0×10−5 mol/L with a detection limit of 3.4×10−10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10−12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg2+ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg2+.
Gaussian process emulators for spatial individual‐level models of infectious disease
Authors: Pokharel Gyanendra , Deardon Rob
Published: November 2016

Statistical inference for spatial models of infectious disease spread is often very computationally expensive. These models are generally fitted in a Bayesian Markov chain Monte Carlo (MCMC) framework, which requires multiple iterations of the computationally cumbersome likelihood function. We here propose a method of inference based on so‐called emulation techniques. Once again the method is set in a Bayesian MCMC context, but avoids calculation of the computationally expensive likelihood function by replacing it with a Gaussian process approximation of the likelihood function built from simulated data. We show that such a method can be used to infer the model parameters and underlying characteristics of the spatial disease system, and this can be done in a computationally efficient manner. The Canadian Journal of Statistics 44: 480–501; 2016 © 2016 Statistical Society of Canada
Sorption of Pb, Cu, Cd, and Zn by Municipal Solid Waste Composts: Metal Retention and Desorption Mechanisms
Authors: Silvetti Margherita , Demurtas Daniela , Garau Giovanni , Deiana Salvatore , Castaldi Paola
Published: November 2016

In this study, the ability of two municipal solid waste composts to adsorb Pb, Cu, Cd, and Zn ions (Me(II)) from aqueous solutions was investigated. Sorption experiments, carried out at pH 4.5 to simulate acidic Me(II)‐polluted environments, showed for both composts higher affinity for Pb (∼0.45 mmol g−1) and Cu (∼0.31 mmol g−1) compared to Cd (∼0.25 mmol g−1) and Zn (∼0.10 mmol g−1). The sorption isotherms data fitted the Freundlich model better than the Langmuir in both composts, suggesting the presence of heterogeneous Me(II) adsorption sites. The humic acids (HA) extracted from composts contributed to 16, 23, 17, and 20% in the sorption of Pb, Cu, Cd, and Zn, respectively, while the compost water‐soluble‐fractions hardly affected the sorption/precipitation of the Me(II) (<5%). The Fourier transform infrared (FT‐IR) spectra of the different Me(II)–HA systems also indicated that the carboxylate groups of HA mainly interacted with Pb(II) and Cu(II) by forming monodentate and bidentate complexes, respectively. The sequential extraction data showed that a significant amount of Cd and Zn was retained by composts through electrostatic interactions (>65% of the respective total amounts sorbed) while most of Cu and Pb (40 and 54%) was strongly complexed and/or precipitated. The treatment of the Me(II)‐composts with citric and malic acids favored the release of >78 and 48% of Zn, 65 and 30% of Cu, and 40 and 30% of Cd, sorbed by both composts, respectively. This release was lower for Pb (<20%) as the cation more strongly retained by the organic or inorganic components of composts.
GABAergic innervation of the ciliary ganglion in macaque monkeys – A light and electron microscopic study
Authors: Barnerssoi Miriam , May Paul J. , Horn Anja K. E.
Published: November 2016

The vertebrate ciliary ganglion (CG) is a relay station in the parasympathetic pathway activating the iris sphincter and ciliary muscle to mediate pupillary constriction and lens accommodation, respectively. While the postganglionic motoneurons in the CG are cholinergic, as are their inputs, there is evidence from avian studies that GABA may also be involved. Here, we used light and electron microscopic methods to examine the GABAergic innervation of the CG in Macaca fascicularis monkeys. Immunohistochemistry for the gamma aminobutyric acid synthesizing enzyme glutamic acid decarboxylase (GAD) and choline acetyltransferase (ChAT) revealed that all CG neurons are contacted by ChAT‐positive terminals. A subpopulation of 17.5% of CG neurons was associated with terminal boutons expressing GAD‐immunoreactivity in addition. Double‐labeling for GAD and synaptophysin confirmed that these were synaptic terminals. Electron microscopic analysis in conjunction with GABA‐immunogold staining showed that (1) GAD‐positive terminals mainly target dendrites and spines in the perisomatic neuropil of CG neurons; (2) GABA is restricted to a specific terminal type, which displays intermediate features lying between classically excitatory and inhibitory endings; and (3) if a CG neuron is contacted by GABA‐positive terminals, virtually all perisomatic terminals supplying it show GABA immunoreactivity. The source of this GABAergic input and whether GABA contributes to a specific CG function remains to be investigated. Nevertheless, our data indicate that the innervation of the ciliary ganglion is more complex than previously thought, and that GABA may play a neuromodulatory role in the control of lens or pupil function. J. Comp. Neurol. 525:1517–1531, 2017. © 2016 Wiley Periodicals, Inc.
Suppression of Aluminum Current Collector Dissolution by Protective Ceramic Coatings for Better High‐Voltage Battery Performance
Authors: Heckmann Andreas , Krott Manuel , Streipert Benjamin , Uhlenbruck Sven , Winter Martin , Placke Tobias
Published: November 2016

Batteries based on cathode materials that operate at high cathode potentials, such as LiNi0.5Mn1.5O4 (LNMO), in lithium‐ion batteries or graphitic carbons in dual‐ion batteries suffer from anodic dissolution of the aluminum (Al) current collector in organic solvent‐based electrolytes based on imide salts, such as lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). In this work, we developed a protective surface modification for the Al current collector by applying ceramic coatings of chromium nitride (CrxN) and studied the anodic Al dissolution behavior. By magnetron sputter deposition, two different coating types, which differ in their composition according to the CrN and Cr2N phases, were prepared and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and their electronic conductivity. Furthermore, the anodic dissolution behavior was studied by cyclic voltammetry and chronocoulometry measurements in two different electrolyte mixtures, that is, LiTFSI in ethyl methyl sulfone and LiTFSI in ethylene carbonate/dimethyl carbonate 1:1 (by weight). These measurements showed a remarkably reduced current density or cumulative charge during the charge process, indicating an improved anodic stability of the protected Al current collector. The coating surfaces after electrochemical treatment were characterized by means of SEM and XPS, and the presence or lack of pit formation, as well as electrolyte degradation products could be well correlated to the electrochemical results.
Zika Virus: Quantification, Propagation, Detection, and Storage
Authors: Agbulos Darrell S. , Barelli Larissa , Giordano Bryan V. , Hunter Fiona F.
Published: November 2016

Zika virus (ZIKV), belonging to the family Flaviviridae, genus Flavivirus, is an arthropod‐borne virus that was first discovered from the Zika forest in Uganda in 1947. Recent outbreaks in South America have linked ZIKV to cases of microcephaly and Guillain‐Barré syndrome in humans. With the increased interest in ZIKV, protocols must be established to facilitate proper research. Here we describe the laboratory techniques required to quantify, propagate, and store ZIVK. We also review the proper safety protocol for the handling of ZIKV, which is classified as a Biosafety Level 2 pathogen by the United States Centers for Disease Control and Prevention. © 2016 by John Wiley & Sons, Inc.
Variants in Pharmacokinetic Transporters and Glycemic Response to Metformin: A Metgen Meta‐Analysis
Authors: Dujic T , Zhou K , Yee SW , van Leeuwen N , de Keyser CE , Javorský M , Goswami S , Zaharenko L , Hougaard Christensen MM , Out M , Tavendale R , Kubo M , Hedderson MM , van der Heijden AA , Klimčáková L , Pirags V , Kooy A , Brøsen K , Klovins J , Semiz S , Tkáč I , Stricker BH , Palmer CNA , 't Hart LM , Giacomini KM , Pearson ER
Published: November 2016

Therapeutic response to metformin, a first‐line drug for type 2 diabetes (T2D), is highly variable, in part likely due to genetic factors. To date, metformin pharmacogenetic studies have mainly focused on the impact of variants in metformin transporter genes, with inconsistent results. To clarify the significance of these variants in glycemic response to metformin in T2D, we performed a large‐scale meta‐analysis across the cohorts of the Metformin Genetics Consortium (MetGen). Nine candidate polymorphisms in five transporter genes (organic cation transporter [OCT]1, OCT2, multidrug and toxin extrusion transporter [MATE]1, MATE2‐K, and OCTN1) were analyzed in up to 7,968 individuals. None of the variants showed a significant effect on metformin response in the primary analysis, or in the exploratory secondary analyses, when patients were stratified according to possible confounding genotypes or prescribed a daily dose of metformin. Our results suggest that candidate transporter gene variants have little contribution to variability in glycemic response to metformin in T2D.
Synthesis of TiC Nanoparticles Anchored on Hollow Carbon Nanospheres for Enhanced Polysulfide Adsorption in Li–S Batteries
Authors: Cao Bokai , Chen Yong , Li De , Yin Lihong , Mo Yan
Published: November 2016

A novel spatial confinement strategy based on a carbon/TiO2/carbon sandwich structure is proposed to synthesize TiC nanoparticles anchored on hollow carbon nanospheres (TiC@C) through a carbothermal reduction reaction. During the synthesis process, two carbon layers not only serve as reductant to convert TiO2 into TiC nanoparticles, but also create a spatial confinement to suppress the aggregation of TiO2, resulting in the formation of well‐dispersed TiC nanoparticles. This unique TiC@C structure shows an outstanding long‐term cycling stability at high rates owing to the strong physical and chemical adsorption of lithium polysulfides (i.e., a high capacity of 732.6 mA h g−1 at 1600 mA g−1) and it retains a capacity of 443.2 mA h g−1 after 1000 cycles, corresponding to a decay rate of only 0.0395 % per cycle. Therefore, this unique TiC@C composite could be considered as an important candidate for the cathode material in Li–S batteries.
Nitrogen‐Doped Carbon Vesicles with Dual Iron‐Based Sites for Efficient Oxygen Reduction
Authors: Li Qianru , Wan Gang , Zhao Han , Pan Linyu , Wang Ning , Zhao Wanpeng , Zhou Xiaoxia , Cui Xiangzhi , Chen Hangrong
Published: November 2016

A nitrogen‐doped vesicle‐like porous carbon with well‐integrated dual iron‐based catalytic sites was developed through direct pyrolysis of inexpensive and abundant precursors. Benefiting from the mesoporous structures with synchronous construction of Fe–Nx and Fe/Fe3C@NC sites, the optimized catalyst exhibited outstanding performance for the oxygen reduction reaction (ORR) in alkaline media, even superior to the commercial Pt/C catalyst. Detailed characterizations revealed that Fe/Fe3C@NC sites can make major catalytic contributions in basic media, whereas the Fe–Nx sites were found to play an indispensable role for ORR in acidic media.
Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline‐Based, Proton‐Responsive Ligand
Authors: Wang Lin , Onishi Naoya , Murata Kazuhisa , Hirose Takuji , Muckerman James T. , Fujita Etsuko , Himeda Yuichiro
Published: November 2016

A series of new imidazoline‐based iridium complexes has been developed for hydrogenation of CO2 and dehydrogenation of formic acid. One of the proton‐responsive complexes bearing two −OH groups at ortho and para positions on a coordinating pyridine ring (3 b) can catalyze efficiently the chemical fixation of CO2 and release H2 under mild conditions in aqueous media without using organic additives/solvents. Notably, hydrogenation of CO2 can be efficiently carried out under CO2 and H2 at atmospheric pressure in basic water by 3 b, achieving a turnover frequency of 106 h−1 and a turnover number of 7280 at 25 °C, which are higher than ever reported. Moreover, highly efficient CO‐free hydrogen production from formic acid in aqueous solution employing the same catalyst under mild conditions has been achieved, thus providing a promising potential H2‐storage system in water.
Area‐oriented comparison of lightweight block ciphers implemented in hardware for the activation mechanism in the anti‐counterfeiting schemes
Authors: Marchand Cédric , Bossuet Lilian , Gaj Kris
Published: November 2016

Over the past 10 years, the multitude of highly constrained applications such as radio‐frequency identification and sensor networks has led to a new trend in the development of cryptographic primitives. Many algorithms categorized as lightweight cryptographic algorithms have been developed specifically for these new applications. Comparing them is very important but also very challenging because every application has its own constraints. This fact leads to a different choice of design strategies, and the best algorithm for one application is not necessarily the best for all applications. Moreover, the definition of what is lightweight is not always the same because lightweight covers a reduction in power and energy consumption just as well as a reduction in area for hardware. This article proposes and compares lightweight hardware implementations of four recent block ciphers (Klein, Led, Lilliput, and Ktantan). This work is included in a large project that aims to protect the hardware against cloning and counterfeiting. The main constraint in this field is the area required by the protection scheme. As a result, we chose to target only the smallest possible area for each selected algorithm. Consequently, two strategies are presented: full width and serial hardware implementations. All results were generated and verified for Xilinx Spartan‐6 and Spartan‐3 field‐programmable gate arrays and also for application‐specific integrated circuit. Additionally, all the design files are available online. Copyright © 2016 John Wiley & Sons, Ltd.
Balancing competition for resources with multiple pest regulation in diversified agroecosystems: a process‐based approach to reconcile diversification and productivity
Authors: Poeydebat Charlotte , Carval Dominique , de Lapeyre de Bellaire Luc , Tixier Philippe
Published: November 2016

Agroecosystem plant diversification can enhance pest biological regulation and is a promising alternative to pesticide application. However, the costs of competition for resources between plants may exceed the benefits gained by pest regulation. To disentangle the interactions between pest regulation and competition, we developed a generic process‐based approach that accounts for the effects of an associated plant and leaf and root pests on biomass production. We considered three crop–plant associations that differ in competition profiles, and we simulated biomass production under wide ranges of both pest regulation rates and resources’ availability. We analyzed outputs to quantify the pest regulation service level that would be required to attain monoculture yield and other production goals. Results showed that pest regulation requirements were highly dependent on the profile of resource interception of the associated plant and on resources’ availability. Pest regulation and the magnitude of competition between plants interacted in determining the balance between nitrogen and radiation uptake by the crop. Our findings suggest that productivity of diversified agroecosystems relative to monoculture should be optimized by assembling plants whose characteristics balance crops’ resource acquisition. The theoretical insights from our study draw generic rules for vegetation assemblage to optimize trade‐offs between pest regulation and production. Our findings and approach may have implications in understanding, theorizing and implementing agroecosystem diversification. By its generic and adaptable structure, our approach should be useful for studying the effects of diversification in many agroecosystems.
Application of different thermal analysis techniques to characterize oxidized olive oils
Authors: Vecchio Ciprioti Stefano , Paciulli Maria , Chiavaro Emma
Published: November 2016

The deep changes caused by oxidation on virgin olive oil (VOO), which is a high‐quality product, not subjected to ameliorative refining, make this phenomenon one of the most studied. Among the techniques used to study oxidation in olive oil, thermal analysis (TA) provides useful information about the thermal behavior of the samples as affected by oxidation. Thermogravimetry (TG), measuring the changes in the sample mass, can monitor the kinetics of oil mass loss in decomposition processes or oxidation and has been found particularly useful, especially when operating simultaneously with Differential Thermal Analysis (DTA) or Differential Scanning Calorimetry (DSC). The DSC thermal curves of olive oil, both on cooling and heating, has been found to be largely influenced by the oxidative status of the samples and different statistical approaches have been successfully proposed to correlate the thermal parameters with the conventional chemical indicators of oxidation. DSC can be also used to study the kinetics of phase transition phenomena as affected by oxidation. This review provides an exhaustive survey about the application of the thermoanalytical techniques on this topic proposing them as as a fast and green alternative to conventional chemical methods.

Practical applications:

The evaluation of the oxidative status of olive oil requires the development of simple and fast analytical techniques. The most used analytical methods are based on the chemical evaluation of the presence of molecules markers of lipid oxidation, but thermal analysis may provide a fast and green tool in this field, as it does not require sample preparation and use of solvents. The application of thermal analysis for the assessment of the oxidative degradation of olive oil has today reached numerous evidences that attest its actual applicability, and they are all summarized in this review. By these studies it is possible to put in evidence its ability to give qualitative information about the oxidative status of olive oil, both in terms of fatty substance degradation and presence of oxidation molecules that could be very helpful in the field of quality assurance for this high‐quality vegetable oil.

Thermal analysis as a valuable tool to evaluate olive oil oxidation without sample preparation or use of solvents.
Synthesis of the 1,3,4‐Oxadiazole Core through Thermolysis of Geminal Diazides
Authors: Erhardt Hellmuth , Mohr Fabian , Kirsch Stefan F.
Published: November 2016

The thermolysis of geminal diazides derived from acylacetate compounds is an efficient tool for the rapid construction of the 1,3,4‐oxadiazole core. While a broad range of ethyl esters undergoes smooth transformation to the desired heterocycles that contain the ester moiety in moderate to high yields, the analogous tert‐butyl esters give rise to the oxadiazoles with acyl groups, presumably through a pathway of decarboxylation followed by a new acyl transfer.
Strategies for the Synthesis of Higher Acenes
Authors: Dorel Ruth , Echavarren Antonio M.
Published: November 2016

The outstanding performance of pentacene‐based molecules in molecular electronics, as well as the predicted enhanced semiconducting properties of extended acenes, have stimulated the development of new synthetic methods and functionalization strategies for the preparation of stable and soluble acenes larger than tetracene with the aim of obtaining improved functional materials.
Helix‐Rotaxane Hybrid Systems: Rotaxane‐Stabilized, Saccharide‐Induced Chiral Ethynylpyridine Helices by a Thermodynamic Process
Authors: Hirokane Shu , Takashima Shunsuke , Abe Hajime , Inouye Masahiko
Published: November 2016

The helical structures of m‐ethynylpyridine (2,6‐pyridyleneethynylene) oligomers have been stabilized by mechanical crosslinking. A heptameric oligomer, in which the two terminal pyridine rings bear two carbaldehyde groups, has been designed. When this heptamer was treated with octyl β‐d‐glucopyranoside, a circular dichroism (CD) band was induced at around 330 nm, which corresponds to the formation of a chiral ethynylpyridine helix. The CD band was enhanced by the addition of a diamine and a diammonium dumbbell as a result of the formation of a [3]rotaxane structure linked to the terminal pyridines of the helical structure. A decameric oligomer containing four diformylarene units showed stronger CD enhancement in similar experiments owing to two crosslinking events.
AgNP/Bi/Nafion‐modified Disposable Electrodes for Sensitive Zn(II), Cd(II), and Pb(II) Detection in Aerosol Samples
Authors: Mettakoonpitak Jaruwan , Mehaffy John , Volckens John , Henry Charles S.
Published: November 2016

A new method for modifying electrodes with Ag nanoparticles (AgNPs) using electrospray deposition for sensitive, selective detection of Zn(II), Cd(II), and Pb(II) in aerosol samples when combined with Bismuth and Nafion coating and square‐wave anodic stripping voltammetry (SWASV) is reported. Carbon stencil‐printed electrodes (CSPEs) fabricated on a polyethylene transparency (PET) sheet were produced for an inexpensive, simple to fabricate, disposable sensor that can be used with the microliter sample volumes for analysis. Sensor performance was improved by modifying the electrode surface with electrospray‐deposited AgNPs. The use of electrospray deposition resulted in more uniform particle dispersion across the electrode surface when compared to drop‐casting. Using AgNP‐modified electrodes combined with Bi and Nafion, experimental detection limits (LODs) of 5.0, 0.5, and 0.1 μg L−1 for Zn(II), Cd(II), and Pb(II), respectively, were achieved. The linear working ranges were 5.0–400.0 μg L−1, 0.5–400.0 μg L−1, and 0.1–500.0 μg L−1 for Zn(II), Cd(II), and Pb(II), respectively. Interference studies showed Cu(II) was the only metal that interfered with this assay but inference could be eliminated with the addition of ferricyanide directly to the sample solution. This electrochemical sensor was applied for the simultaneous determination of Zn(II), Cd(II), and Pb(II) within source particulate matter (PM) samples collected on filters using an aerosol test chamber.
Phospholipid bilayer affinities and solvation characteristics by electrokinetic chromatography with a nanodisc pseudostationary phase
Authors: Penny William M. , Steele Harmen B. , Ross J.B. Alexander , Palmer Christopher P.
Published: November 2016

Phospholipid bilayer nanodiscs composed of 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphocholine and synthetic maleic acid–styrene copolymer belts have been introduced as a pseudostationary phase (PSP) in electrokinetic chromatography and demonstrated good performance. The nanodiscs provide a suitable migration range and high theoretical plate counts. Using this nanodisc pseudostationary phase, the affinity of the bilayer structure for probe solutes was determined and characterized. Good correlation is observed between retention factors and octanol water partition coefficients for particular categories of solutes, but the general correlation is weak primarily because the nanodiscs show stronger affinity than octanol for hydrogen bond donors. This suggests that a more appropriate application of this technology is to measure and characterize interactions between solutes and lipid bilayers directly. Linear solvation energy relationship analysis of the nanodisc–solute interactions in this study demonstrates that the nanodiscs provide a solvation environment with low cohesivity and weak hydrogen bond donating ability, and provide relatively strong hydrogen bond acceptor strength.
Does the host tree exert any influence on the aromatic composition of the black truffle (Tuber melanosporum)?
Authors: Culleré Laura , Ferreira Vicente , Marco Pedro , Venturini María E. , Blanco Domingo
Published: November 2016

This work examines whether the host tree influences the aroma of Tuber melanosporum truffles. Samples were gathered in the same place (Teruel, Spain) and on the same day from four host trees: hazel, Portuguese oak, kermes oak and holm oak. The truffles were subjected to sensory and chemical analysis. The sensory analysis comprised two stages. The first was based on a sorting task while the second consisted of a descriptive analysis of the samples selected from the first test. The chemical analysis examined the volatile compounds having the greatest influence on the aroma of Tuber melanosporum by means of headspace‐solid phase microextraction followed by analysis by gas chromatography mass spectrometry (HS‐SPME‐GC‐MS). The sensory tests demonstrated that truffles gathered from the Portuguese oak had a more intense aroma than the rest of the samples, and significantly more than the holm oak truffles. The same pattern occurred for the animal descriptor which was considerably more intense in Portuguese oak truffles and significantly higher than that of holm oak truffles. Chemically, these differences can be explained by the levels of isoamyl alcohol and 3‐ethyl‐5‐methylphenol which were significantly greater in the Portuguese oak than the holm oak samples. Copyright © 2016 John Wiley & Sons, Ltd.
The concept of generalized stresses for computational manufacturing and beyond
Authors: Mahnken Rolf , Cheng Chun , Düsing Martin , Ehlenbröker Ulrich , Leismann Thorben
Published: November 2016

Computational manufacturing aims at predicting the physical state of a part, structure or respectively its components resulting from a production process. Applicants of computational manufacturing expect reliable and predictive simulation results for various physical effects. Therefore, extended continuum models become increasingly important in modern field theories of materials. To this end, Gurtin and Forest propose the concept of generalized stresses, which shows a strong link between extended continuum mechanics in macroscopic modelling and phase field models in mesoscopic modelling. In this exposition, the concept of generalized stresses is exploited to three different scenarios of computational manufacturing: 1. Micromorphic elasticity considering rotational as well as deformable microstructural effects motivated for a cold box sand in a casting process. 2. Visco‐plasticity coupled to gradient phase transformation at large strains with applications to a cutting process and a hybrid forming process, each showing phase transformations and TRIP‐effects. 3. Multiphase field modelling coupled to Cahn‐Hilliard diffusion to simulate the complex lower bainite transformation in steel as a mesoscopic application of computational manufacturing. Each prototype model is illustrated by a representative finite‐element simulation. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Hydrogeochemical characteristics of deep saline aquifers in sedimentary basins in China and implications for CO2 geological storage with emphasis on total dissolved solids (TDS) and water type
Authors: Li Yiman , Pang Zhonghe
Published: November 2016

The hydrogeochemistry of deep saline aquifers in sedimentary basins, in particular total dissolved solids, is one of the key criteria for CO2 storage because CO2 solubility is greatly affected by it. A detailed investigation of total dissolved solids (TDS) and water type of formation water is presented in the paper to assess the suitability of sedimentary basins in China for CO2 sequestration. Deep saline aquifers are divided into three categories based on TDS and water type: fresh‐slightly saline water with TDS less than 10 g/L, semi saline–saline water with TDS ranging from 10 g/L to 50 g/L, and salty water with TDS higher than 50 g/L. The fresh, slightly saline water is dominated by water type of Cl·HCO3‐Na in sedimentary basins in East China. Semi saline‐saline and salty waters are of Cl‐Na type existing in the southeast and mid‐west. TDS limits are suggested for different regions of China to optimize the use of formation water. Solubility of CO2 in formation water with TDS of 1g/L∼260g/L is calculated. Results show it exhibits exponential correlation to water TDS and two sharp inflections are observed at 10 g/L and 50 g/L. For fresh‐slightly saline aquifer, TDS limit is defined as 3 g/L in East China while in West China, 5 g/L is suggested. For formation water with TDS of 10 g/L∼150 g/L, 10 g/L is proposed for the main sedimentary basins in China. For deep saline aquifers with TDS higher than 150 g/L, CO2 storage is not suggested to avoid conflicts with salts mineral resources exploration. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd.
Elevated FABP1 serum levels are associated with poorer survival in acetaminophen‐induced acute liver failure
Authors: Karvellas Constantine J. , Speiser Jaime L. , Tremblay Mélanie , Lee William M. , Rose Christopher F. ,   for the US Acute Liver Failure Study Group
Published: November 2016

Acetaminophen (APAP)‐induced acute liver failure (ALF) is associated with significant mortality. Traditional prognostic scores lack sensitivity. Serum liver‐type fatty acid binding protein (FABP1) early (day 1) or late (day 3‐5) levels are associated with 21‐day mortality in the absence of liver transplant. Serum samples from 198 APAP‐ALF patients (nested case–control study with 99 survivors, 99 nonsurvivors) were analyzed by enzyme‐linked immunosorbent assay with clinical data from the US Acute Liver Failure Study Group registry (1998‐2014). APAP‐ALF survivors had significantly lower serum FABP1 levels early (238.6 versus 690.8 ng/mL, P < 0.0001) and late (148.4 versus 612.3 ng/mL, P < 0.0001) compared with nonsurvivors. FABP1 > 350 ng/mL was associated with significantly higher risk of death at early (P = 0.0004) and late (P < 0.0001) time points. Increased serum FABP1 early (log FABP1 odds ratio = 1.31, P = 0.027) and late (log FABP1 odds ratio = 1.50, P = 0.005) were associated with significantly increased 21‐day mortality after adjusting for significant covariates (Model for End‐Stage Liver Disease, vasopressor use). Areas under the receiver operating characteristic curve for early and late multivariable models were 0.778 and 0.907, respectively. The area under the receiver operating characteristic curve of the King's College criteria (early, 0.552 alone, 0.711 with FABP1; late, 0.604 alone, 0.797 with FABP1) and the Acute Liver Failure Study Group prognostic index (early, 0.686 alone, 0.766 with FABP1; late, 0.711 alone, 0.815 with FABP1) significantly improved with the addition of FABP1 (P < 0.002 for all). Conclusion: In patients with APAP‐ALF, FABP1 may have good potential to discriminate survivors from nonsurvivors and may improve models currently used in clinical practice; validation of FABP1 as a clinical prediction tool in APAP‐ALF warrants further investigation. (Hepatology 2017;65:938‐949)
The origin of fibrogenic myofibroblasts in fibrotic liver
Authors: Kisseleva Tatiana
Published: November 2016

Liver fibrosis results from chronic liver injury of different etiologies. It is characterized by dysregulation of physiological remodeling, activation of myofibroblasts, and formation of a fibrous scar. Myofibroblasts develop contractile functions and secrete the extracellular matrix proteins that form this fibrous scar. Myofibroblasts are not present in the normal liver but activate and proliferate in response to injury and inflammation. This review summarizes the understanding and controversies on the contribution of cell populations to the myofibroblasts in liver fibrosis. (Hepatology 2017;65:1039‐1043).
Ecotoxicological hazard and risk assessment of endocrine active substances
Authors: Leopold Annegaaike , Roberts Mike , Matthiessen Peter
Published: November 2016

This collection of papers provides state-of-the-art science on a complex topic that has been challenging for scientists and regulators for a long time. The papers emanated from the Society of Environmental Toxicology and Chemistry (SETAC) Pellston Workshop® Environmental Hazard and Risk Assessment Approaches for Endocrine-Active Substances (EHRA). Forty-eight international experts met in early February 2016 to discuss whether the environmental risks posed by endocrine-disrupting substances (EDS) can be reliably assessed. The primary conclusion of the workshop was that if data on environmental exposure, effects on sensitive species and life-stages, delayed effects, and effects at low concentrations are robust, initiating environmental risk assessment of EDS is scientifically sound and reliable. Integr Environ Assess Manag 2017;13:264–266. © 2016 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC)

Key Points

A SETAC Pellston Workshop “Environmental Hazard and Risk Assessment Approaches for Endocrine-Active Substances (EHRA)” was held in February 2016 to discuss whether the environmental risks posed by endocrine-disrupting substances (EDS) can be reliably assessed. The workshop and resulting papers address a clear need for objective advice, based on the current level of scientific understanding, to allow regulators and policy makers to make comprehensive, science-based decisions on the risk and hazard assessment of endocrine-disrupting substances.
Time‐dependent risk of depression, anxiety, and stress‐related disorders in patients with invasive and in situ breast cancer
Authors: Yang Haomin , Brand Judith S. , Fang Fang , Chiesa Flaminia , Johansson Anna L.V. , Hall Per , Czene Kamila
Published: November 2016

Despite concerns about the mental health of breast cancer patients, little is known regarding the temporal risk pattern and risk factors of common mental disorders among these patients. We estimated standardized incidence ratios (SIRs) of depression, anxiety and stress‐related disorders in a Swedish nationwide cohort of 40,849 women with invasive and 4,402 women with in situ breast cancer (2001–2010, median follow‐up = 4.5 years). The impact of patient, tumor and treatment characteristics was analyzed using flexible parametric survival models in a regional cohort of 7,940 invasive breast cancer patients (2001–2013, median follow‐up = 7.5 years). Women with invasive breast cancer showed increased rates of depression, anxiety and stress‐related disorders [overall SIR (95% CI) = 1.57 (1.46–1.69), 1.55 (1.43–1.68) and 1.77 (1.60‐1.95), respectively]. SIRs were highest shortly after diagnosis, but remained increased up to 5 years. Younger age at diagnosis, comorbidity, higher‐grade disease, lymph node involvement and chemotherapy were independently associated with the risk of depression and anxiety in invasive cancer patients, with chemotherapy and higher‐grade disease conferring short‐term risk only, while comorbidities were mainly associated with late‐onset events. No clinical risk factors were identified for stress‐related disorders except for a greater risk associated with younger age. Patients with in situ cancer only showed an increased incidence of stress‐related disorders during the first 6 months after diagnosis [SIR (95% CI) = 2.76 (1.31‐5.79)]. The time‐dependent risk profile of invasive cancer patients may guide health care professionals for timely and targeted psycho‐oncologic interventions.
Dietary trace element intake and liver cancer risk: Results from two population‐based cohorts in China
Authors: Ma Xiao , Yang Yang , Li Hong‐Lan , Zheng Wei , Gao Jing , Zhang Wei , Yang Gong , Shu Xiao‐Ou , Xiang Yong‐Bing
Published: November 2016

Dietary factors have been hypothesized to affect the risk of liver cancer via various mechanisms, but the influence has been not well studied and the evidence is conflicting. We investigated associations of dietary trace element intake, assessed through a validated food frequency questionnaire, with risk of liver cancer in two prospective cohort studies of 132,765 women (1997–2013) and men (2002–2013) in Shanghai, China. The associations were first evaluated in cohort studies and further assessed in a case–control study nested within these cohorts adjusting for hepatitis B virus infection. For cohort analyses, Cox proportional hazard models were used to estimate hazard ratios and 95% confidence intervals. For nested case–control analyses, conditional logistic regression was used to calculate odds ratios and 95% confidence intervals. After a median follow‐up time of 15.2 years for the Shanghai Women's Health Study and 9.3 years for the Shanghai Men's Health Study, 192 women and 344 men developed liver cancer. Dietary intake of manganese was inversely associated with liver cancer risk (highest vs. lowest quintile, HR = 0.51, 95% CI: 0.35–0.73; ptrend = 0.001). Further adjustment for hepatitis B virus infection in the nested case–control study yielded a similar result (highest vs. lowest quintile, OR = 0.38, 95% CI: 0.21–0.69; ptrend < 0.001). No significant association was found between dietary intake of selenium, iron, zinc, copper and liver cancer risk. The results suggest that higher intake of manganese may be associated with a lower risk of liver cancer in China.
Lactation-Induced Changes in the Volume of Osteocyte Lacunar-Canalicular Space Alter Mechanical Properties in Cortical Bone Tissue
Authors: Kaya Serra , Basta-Pljakic Jelena , Seref-Ferlengez Zeynep , Majeska Robert J , Cardoso Luis , Bromage Timothy G , Zhang Qihong , Flach Carol R , Mendelsohn Richard , Yakar Shoshana , Fritton Susannah P , Schaffler Mitchell B
Published: November 2016

Osteocytes can remove and remodel small amounts of their surrounding bone matrix through osteocytic osteolysis, which results in increased volume occupied by lacunar and canalicular space (LCS). It is well established that cortical bone stiffness and strength are strongly and inversely correlated with vascular porosity, but whether changes in LCS volume caused by osteocytic osteolysis are large enough to affect bone mechanical properties is not known. In the current studies we tested the hypotheses that (1) lactation and postlactation recovery in mice alter the elastic modulus of bone tissue, and (2) such local changes in mechanical properties are related predominantly to alterations in lacunar and canalicular volume rather than bone matrix composition. Mechanical testing was performed using microindentation to measure modulus in regions containing solely osteocytes and no vascular porosity. Lactation caused a significant (∼13%) reduction in bone tissue-level elastic modulus (p < 0.001). After 1 week postweaning (recovery), bone modulus levels returned to control levels and did not change further after 4 weeks of recovery. LCS porosity tracked inversely with changes in cortical bone modulus. Lacunar and canalicular void space increased 7% and 15% with lactation, respectively (p < 0.05), then returned to control levels at 1 week after weaning. Neither bone mineralization (assessed by high-resolution backscattered scanning electron microscopy) nor mineral/matrix ratio or crystallinity (assessed by Raman microspectroscopy) changed with lactation. Thus, changes in bone mechanical properties induced by lactation and recovery appear to depend predominantly on changes in osteocyte LCS dimensions. Moreover, this study demonstrates that tissue-level cortical bone mechanical properties are rapidly and reversibly modulated by osteocytes in response to physiological challenge. These data point to a hitherto unappreciated role for osteocytes in modulating and maintaining local bone mechanical properties. © 2016 American Society for Bone and Mineral Research.
Synthesis and Structures of d10–d10M2(μ‐dppm)2 Complexes with Sensitive Metal–Metal Distances in Response to the Binding of Sigma Donors
Authors: Shiu Ler‐Chun , Liu Shih‐An , Wu Tian‐Shung , Shiu Kom‐Bei
Published: November 2016

Diphosphine‐bridged dicopper(I) acetate complexes [Cu2(μ‐dppm)2(μ‐OAc)]X (
2X; X− = , ) and [Cu2(μ‐dppm)2(μ‐OAc)(MeCN)]X (
4X) were prepared and the structures of 2(PF6
) and 4(PF6
) determined by X‐ray crystallography. The ground‐state geometries of [Cu2(μ‐dppm)2(μ‐OAc)]+ and [Cu2(μ‐dppm)2(μ‐OAc)(L)]+ (L = py, MeCN, THF, acetone, MeOH) were also obtained using density functional theory (DFT). The increased Cu–Cu distances found experimentally and theoretically by comparing the structures of cation [Cu2(μ‐dppm)2(μ‐OAc)]+ and its derivatives [Cu2(μ‐dppm)2(μ‐OAc)(L)]+ reflect the binding of various sigma donors (L). When using [Cu2(μ‐dppm)2(μ‐OAc)]+ as a structure sensor, the electron‐donating strength of a sigma donor can be quantitatively expressed as a DFT‐calculated Cu–Cu distance with the relative strength in the order py > MeCN > THF > acetone > MeOH, as determined.