bluuebunny/crossref_metadata_2025 huggingface dataset:
Sexual reproduction in the Caribbean coral genusIsophyllia(Scleractinia: Mussidae)
Authors: Soto Derek , Weil Ernesto
Published: November 2016

The sexual pattern, reproductive mode, and timing of reproduction ofIsophyllia sinuosaandIsophyllia rigida, two Caribbean Mussids, were assessed by histological analysis of specimens collected monthly during 2000–2001. Both species are simultaneous hermaphroditic brooders characterized by a single annual gametogenetic cycle. Spermatocytes and oocytes of different stages were found to develop within the same mesentery indicating sequential maturation for extended planulation. Oogenesis took place during May through April inI. sinuosaand from August through June inI. rigida. Oocytes began development 7–8 months prior to spermaries but both sexes matured simultaneously. Zooxanthellate planulae were observed inI. sinuosaduring April and inI. rigidafrom June through September. Higher polyp and mesenterial fecundity were found inI. rigidacompared toI. sinuosa. Larger oocyte sizes were found inI. sinuosathan inI. rigida, however larger planula sizes were found inI. rigida. Hermaphroditism is the exclusive sexual pattern within the Mussidae while brooding has been documented within the related generaMussa,ScolymiaandMycetophyllia. This study represents the first description of the sexual characteristics ofI. rigidaand provides an updated description ofI. sinuosa.
Comparative analysis of the complete chloroplast genome sequences in psammophyticHaloxylonspecies (Amaranthaceae)
Authors: Dong Wenpan , Xu Chao , Li Delu , Jin Xiaobai , Li Ruili , Lu Qi , Suo Zhili
Published: November 2016

TheHaloxylongenus belongs to the Amaranthaceae (formerly Chenopodiaceae) family. The small trees or shrubs in this genus are referred to as the King of psammophytic plants, and perform important functions in environmental protection, including wind control and sand fixation in deserts. To better understand these beneficial plants, we sequenced the chloroplast (cp) genomes ofHaloxylon ammodendron(HA) andHaloxylon persicum(HP) and conducted comparative genomic analyses on these and two other representative Amaranthaceae species. Similar to other higher plants, we found that theHaloxyloncp genome is a quadripartite, double-stranded, circular DNA molecule of 151,570 bp in HA and 151,586 bp in HP. It contains a pair of inverted repeats (24,171 bp in HA and 24,177 bp in HP) that separate the genome into a large single copy region of 84,214 bp in HA and 84,217 bp in HP, and a small single copy region of 19,014 bp in HA and 19,015 bp in HP. EachHaloxyloncp genome contains 112 genes, including 78 coding, 30 tRNA, and four ribosomal RNA genes. We detected 59 different simple sequence repeat loci, including 44 mono-nucleotide, three di-nucleotide, one tri-nucleotide, and 11 tetra-nucleotide repeats. Comparative analysis revealed only 67 mutations between the two species, including 44 substitutions, 23 insertions/deletions, and two micro-inversions. The two inversions, with lengths of 14 and 3 bp, occur in thepetA-psbJ intergenic region andrpl16 intron, respectively, and are predicted to form hairpin structures with repeat sequences of 27 and 19 bp, respectively, at the two ends. The ratio of transitions to transversions was 0.76. These results are valuable for future studies onHaloxylongenetic diversity and will enhance our understanding of the phylogenetic evolution of Amaranthaceae.
Identifying Clinical Factors Associated With Low Disease Activity and Remission of Rheumatoid Arthritis During Pregnancy
Authors: Ince‐Askan Hilal , Hazes Johanna M. W. , Dolhain Radboud J. E. M.
Published: November 2016

Objective

To identify a combination of clinical factors associated with low disease activity and remission in the third trimester during pregnancy in women with rheumatoid arthritis (RA).

Methods

This study is embedded in the Pregnancy‐Induced Amelioration of Rheumatoid Arthritis study, a prospective cohort study. There were data available on 190 pregnancies from first trimester until delivery. Multivariate regression analyses were performed on the disease activity (Disease Activity Score in 28 joints [DAS28] using the C‐reactive protein [CRP] level) in the third trimester. Independent covariates were the DAS28‐CRP‐3 in first trimester, prednisone and sulfasalazine use in the first trimester, parity, methotrexate use in the past, autoantibody status, the presence of erosions, and RA disease duration.

Results

In multivariate regression models, the DAS28‐CRP‐3, use of prednisone in the first trimester, and the presence of autoantibodies were negatively associated with low disease activity (DAS28‐CRP‐3 <3.2) in the third trimester (P < 0.05), and the DAS28‐CRP‐3 and presence of autoantibodies were also associated with remission (DAS28‐CRP‐3 <2.6) (P < 0.001). Subgroup analysis revealed that the associations of prednisone use and presence of autoantibodies were only present in patients with moderate‐to‐high disease activity (DAS28‐CRP‐3 ≥3.2) in the first trimester.

Conclusion

RA patients who have a low DAS28‐CRP‐3 in the first trimester (irrespective of autoantibody status or prednisone use) are likely to have low disease activity or remission in the third trimester. Also, women with higher disease activity who are not taking prednisone and who express no autoantibodies still have a fair chance of low disease activity in the last trimester.
1,3‐Diamine‐Derived Bifunctional Organocatalyst Prepared from Camphor
Authors: Ričko Sebastijan , Svete Jurij , Štefane Bogdan , Perdih Andrej , Golobič Amalija , Meden Anže , Grošelj Uroš
Published: November 2016

Chiral 1,2‐diamines are privileged structural motifs in organocatalysis, whereas efficient 1,3‐diamine‐derived organocatalysts are very rare. Herein we report a highly efficient camphor‐1,3‐diamine‐derived squaramide organocatalyst. Its catalytic activity in Michael additions of 1,3‐dicarbonyl nucleophiles to trans‐β‐nitrostyrene derivatives provides excellent enantioselectivities (up to >99% ee).

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What is the leanest stream to sustain a nonadiabatic loop reactor: Analysis and methane combustion experiments
Authors: Madai Aharon Y. , Nekhamkina Olga , Sheintuch Moshe
Published: November 2016

While previous studies experimentally demonstrated that loop reactor (LR) can be sustained with a lean feed (using ethylene combustion) and have analyzed the single‐reaction adiabatic case, this work analyzes the effects of heat loss and of reactor size to determine the leanest stream (expressed in terms of adiabatic temperature rise ΔTlim) that will sustain the operation. For an adiabatic infinitely long reactor ΔTlim→0 while for a finite reactor ΔTlim scales as (1 + Pe/4)−1 where Pe = Luρcpf/k, and heat loss increases this limit by (β/Pe)1/2. Thus, a good design of a LR will aim to decrease conductivity (k) and radial heat‐transfer coefficient (β) while increasing throughput (u) and reactor length. This article is also the first experimental demonstration of auto‐thermal operation in a LR for catalytic abatement of low‐concentration of methane, showing the leanest stream to be of 8000 ppm vs. 33,000 ppm in a once‐through reactor. Experimental combustion results of methane and of ethylene are compared with model predictions. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2030–2042, 2017
Empowerment Praxis: Community Organizing to Redress Systemic Health Disparities
Authors: Douglas Jason A. , Grills Cheryl T. , Villanueva Sandra , Subica Andrew M.
Published: November 2016

Social and environmental determinants of childhood obesity present a public health dilemma, particularly in low‐income communities of color. Case studies of two community‐based organizations participating in the Robert Wood Johnson Foundation's Communities Creating Healthy Environments (CCHE) childhood obesity initiative demonstrate multilevel, culturally situated community organizing strategies to address the root causes of this public health disparity. Informed by a 3‐lens prescription—Social Justice, Culture‐Place, and Organizational Capacity—contained in the CCHE Change Model and Evaluation Frame, we present examples of individual, organizational, and community empowerment to redress systemic inequities that manifest in poor health outcomes for people of color. These case studies offer compelling evidence that public health disparities in these communities may effectively be abated through strategies that employ bottom‐up, community‐level approaches for (a) identifying proximal and distal determinants of public health disparities, and (b) empowering communities to directly redress these inequities. Guided by this ecological framework, application of the CCHE evaluation approach demonstrated the necessity to document the granularity of community organizing for community health, adding to the community psychology literature on empowering processes and outcomes.
An Energetic Triazolo‐1,2,4‐Triazine and its N‐Oxide
Authors: Piercey Davin G. , Chavez David E. , Scott Brian L. , Imler Greg H. , Parrish Damon A.
Published: November 2016

The reaction of 3‐amino‐5‐nitro‐1,2,4‐triazole with nitrous acid produces the corresponding diazonium salt. When the diazonium salt is treated with nitroacetonitrile, a subsequent condensation and cyclization reaction occurres to produced 4‐amino‐3,7‐dinitrotriazolo‐[5,1‐c][1,2,4] triazine (DPX‐26). X‐ray crystallographic analysis shows that the DPX‐26 has a density of 1.86 g cm−3, while it is calculated to have a heat of formation of 398.3 kJ mol−1. DPX‐26 is predicted to approach the explosive performance of RDX but displays significantly better safety properties. Oxidation of DPX‐26 using hypofluorous acid produces 4‐amino‐3,7‐dinitrotriazolo‐[5,1‐c][1,2,4] triazine 4‐oxide (DPX‐27), which is also predicted to be a high‐performance material with enhanced safety properties.
A Square‐Planar Complex of Platinum(0)
Authors: Takeuchi Katsuhiko , Taguchi Hiro‐omi , Tanigawa Ippei , Tsujimoto Shota , Matsuo Tsukasa , Tanaka Hiromasa , Yoshizawa Kazunari , Ozawa Fumiyuki
Published: November 2016

The Pt0 complex [Pt(PPh3)(Eind2‐BPEP)] with a pyridine‐based PNP‐pincer‐type phosphaalkene ligand (Eind2‐BPEP) has a highly planar geometry around Pt with ∑(Pt)=358.6°. This coordination geometry is very uncommon for formal d10 complexes, and the Pd and Ni homologues with the same ligands adopt distorted tetrahedral geometries. DFT calculations reveal that both the Pt and Pd complexes are M0 species with nearly ten valence electrons on the metals whereas their atomic orbital occupancies are evidently different from one another. The Pt complex has a higher occupancy of the atomic 6s orbital because of strong s–d hybridization due to relativistic effects, thereby adopting a highly planar geometry reflecting the shape and orientation of the partially unoccupied
orbital.
Magneto‐Plasmonic Janus Vesicles for Magnetic Field‐Enhanced Photoacoustic and Magnetic Resonance Imaging of Tumors
Authors: Liu Yijing , Yang Xiangyu , Huang Zhiqi , Huang Peng , Zhang Yang , Deng Lin , Wang Zhantong , Zhou Zijian , Liu Yi , Kalish Heather , Khachab Niveen M. , Chen Xiaoyuan , Nie Zhihong
Published: November 2016

Magneto‐plasmonic Janus vesicles (JVs) integrated with gold nanoparticles (AuNPs) and magnetic NPs (MNPs) were prepared asymmetrically in the membrane for in vivo cancer imaging. The hybrid JVs were produced by coassembling a mixture of hydrophobic MNPs, free amphiphilic block copolymers (BCPs), and AuNPs tethered with amphiphilic BCPs. Depending on the size and content of NPs, the JVs acquired spherical or hemispherical shapes. Among them, hemispherical JVs containing 50 nm AuNPs and 15 nm MNPs showed a strong absorption in the near‐infrared (NIR) window and enhanced the transverse relaxation (T2) contrast effect, as a result of the ordering and dense packing of AuNPs and MNPs in the membrane. The magneto‐plasmonic JVs were used as drug delivery vehicles, from which the release of a payload can be triggered by NIR light and the release rate can be modulated by a magnetic field. Moreover, the JVs were applied as imaging agents for in vivo bimodal photoacoustic (PA) and magnetic resonance (MR) imaging of tumors by intravenous injection. With an external magnetic field, the accumulation of the JVs in tumors was significantly increased, leading to a signal enhancement of approximately 2–3 times in the PA and MR imaging, compared with control groups without a magnetic field.
Electron Cryo‐microscopy as a Tool for Structure‐Based Drug Development
Authors: Merino Felipe , Raunser Stefan
Published: November 2016

For decades, X‐ray crystallography and NMR have been the most important techniques for studying the atomic structure of macromolecules. However, as a result of size, instability, low yield, and other factors, many macromolecules are difficult to crystallize or unsuitable for NMR studies. Electron cryo‐microscopy (cryo‐EM) does not depend on crystals and has therefore been the method of choice for many macromolecular complexes that cannot be crystallized, but atomic resolution has mostly been beyond its reach. A new generation of detectors that are capable of sensing directly the incident electrons has recently revolutionized the field, with structures of macromolecules now routinely being solved to near‐atomic resolution. In this review, we summarize some of the most recent examples of high‐resolution cryo‐EM structures. We put particular emphasis on proteins with pharmacological relevance that have traditionally been inaccessible to crystallography. Furthermore, we discuss examples where interactions with small molecules have been fully characterized at atomic resolution. Finally, we stress the current limits of cryo‐EM, and methodological issues related to its usage as a tool for drug development.
Magnetically water‐dispersible and recoverable rhodium organometallic catalyst derived from Wilkinson's catalyst for promoting organic reactions
Authors: Nejat Razieh , Mahjoub Alireza
Published: November 2016

A novel magnetic rhodium catalyst was prepared through immobilizing Wilkinson's catalyst on the surface of silica‐coated iron oxide nanoparticles. After (thio)diphenylphosphine (─S&─PPh2) was modified on the surface of the silica‐coated iron oxide nanoparticles, tris(triphenylphosphine)rhodium(I) chloride was employed to synthesize the Rh(Cl)(PPh3)2(Ph2P&─S&─) complex, affording a rhodium loading of 0.16 mmol g−1. The Rh(I) organometallic magnetic nanoparticles form a novel class of heterogeneous catalyst which is particularly suitable for the practice of organic synthesis. The prepared system exhibits high catalytic efficiency in Suzuki–Miyaura and Miyaura–Michael reactions in ethanol–water solution. High yield, low reaction times, use of green solvents and non‐toxicity of the catalyst are the main merits of this protocol. Also, magnetic separation is an environmentally friendly alternative for the recovery of the catalyst, since it minimizes energy and catalyst loss by preventing mass loss and oxidation. The produced catalyst was characterized using a variety of techniques.
Enhanced emission from Alq3 in amphiphilic block copolymers PEG‐b‐PVK‐co‐Alq3 synthesized via RAFT polymerization
Authors: Fang Fei , Kong Fan , Zhang Xueqin , Lin Mengqi , Zhang Yichi , Ding Shounian
Published: November 2016

A series of amphiphilic poly(N‐vinyl carbazole) (PVK) block copolymers containing tris(8‐hydroxyquinoline) aluminum (Alq3) have been synthesized via reversible addition‐fragmentation chain transfer (RAFT) radical polymerization with trithiocarbonate terminated polyethylene glycol (PEG) as a RAFT agent. The chemical structures of the block copolymers have been identified by 1H nuclear magnetic resonance and Fourier transform infrared spectrometer. The analysis of gel permeation chromatography indicates that the polydispersity indices of the block copolymers are lower than 1.30. The results of thermogravimetric analysis show that the decomposition temperatures of the copolymers are higher than 330  °C. The optical properties of the copolymers have been investigated and the obviously enhanced emission from Alq3 has been found due to resonance energy transfer from PVK to Alq3. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44573.
Esterification of Kraft lignin as a method to improve structural and mechanical properties of lignin‐polyethylene blends
Authors: Dehne Laura , Vila Carlos , Saake Bodo , Schwarz Katrin U.
Published: November 2016

Lignin is a promising candidate for blends with thermoplastic polymers. Still, this endeavour is a challenge due to poor compatibility between both components. In this article, the effect of lignin esterification on the improvement of the compatibility between hardwood Kraft lignin and high‐density polyethylene (PE‐HD) is investigated. For this purpose, lignin was esterified with acetic, propionic, and butyric anhydride; its amount in the blends varied from 10 to 40%. Light microscopic images of blends show a reduction in particle size and a more homogeneous distribution with increasing length of the ester carbon chains (C2 to C4). Modification of lignin enhances the moduli and strength characteristics of the blends. Butyrated lignin performs best, as tensile strength of blends can be retained near that of pure PE‐HD with up to 40% lignin content. An additional investigation of unmodified lignin with reduced particle size confirms that modification is the decisive factor to enhance blend properties; a sole reduction of particle size is insufficient. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44582.
Biobased isosorbide methacrylate monomer as an alternative to bisphenol A glycerolate dimethacrylate for dental restorative applications
Authors: Berlanga Duarte María Lydia , Reyna Medina Luis Alberto , Reyes Patricia Torres , González Pérez Sergio Emmanuel , Herrera González Ana María
Published: November 2016

In this study, a new biobased isosorbide urethane methacrylic monomer [isosorbide‐derived urethane dimethacrylate (Is‐UDMA)] was evaluated as a replacement for currently used bisphenol A glycerolate dimethacrylate (Bis‐GMA) based dental restorative materials. Dental composites were prepared at different Is‐UDMA and Bis‐GMA concentrations. For these composites, the photocuring kinetics, volumetric shrinkage, viscoelastic properties, water sorption, and solubility were evaluated. The photocuring kinetics, followed by real‐time IR spectroscopy, showed higher double‐bond conversion (DC) values for the formulations containing the Is‐UDMA monomer; the highest DC (82%) was achieved by the formulation prepared with only the Is‐UDMA monomer. The volumetric shrinkage was reduced to 23.7% as compared with the dental resin formulated with Bis‐GMA. The viscoelastic properties of the formulations containing both Is‐UDMA and Bis‐GMA monomers in a 50:50 composition were superior to the rest of the tested formulations, including those prepared with pure polymers. This behavior was explained in terms of a compromise between crosslinking and rigidity (or flexibility) of the resulting polymer network. A preliminary test on microleakage in a dental enamel demonstrated that the new Is‐UDMA monomer is a potential replacement for the Bis‐GMA monomer in dental restorative materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44591.
A constructive approach to the quadrics of revolution using 3D dynamic geometry systems with algebraic capabilities
Authors: Roanes‐Lozano Eugenio
Published: November 2016

Conics and quadrics are classic topics at Engineering Schools. Conics are usually introduced from constructive properties and their equations and classification are presented later. Meanwhile, quadrics are introduced directly from their equations. The availability of 3D dynamic geometry systems allows introducing the quadrics of revolution (degenerate and non‐degenerate) in a constructive way too. How the approach can be used to obtain the equations of one parameter families of quadrics will be also shown. © 2016 Wiley Periodicals, Inc. Comput Appl Eng Educ 25:26–38, 2017; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21775
Effective reuse and sharing of best teaching practices
Authors: Al‐Rasheed Amal , Berri Jawad
Published: November 2016

The widespread use of computer technologies in education has reshaped the roles of instructors, who are encouraged to innovate interactive forms of technology‐supported instruction that promote participation and collaboration. This in turn engenders new experiences of teaching that need to be gathered and capitalized as teaching assets to be shared among communities of instructors. Among these experiences, best teaching practices (BTPs) are instructional practices accumulated in teaching that have been proven to work well, give good results, and can therefore be recommended as a model. Identifying and sharing best practices means duplicating successes which help instructors learn from each other and deliver better quality teaching. This paper presents a knowledge management framework for acquiring, coding, sharing, and reusing BTPs. To encourage instructors’ participation, the framework is based on peer scoring of BTPs, which stimulates contribution and interaction. The framework has been implemented as a knowledge portal that allows instructors to create, store, search, and share BTPs and to receive feedback and comments from other users, providing many useful functionalities and services to users as individuals and communities. The paper presents also a real‐life case study, lessons learned from using the system within a community of instructors, and a system evaluation of the effectiveness of reusing BTPs using the reuse effort and impact metrics. © 2016 Wiley Periodicals, Inc. Comput Appl Eng Educ 25:163–178, 2017; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21776
Surface‐Atom Dependence of ZnO‐Supported Ag@Pd Core@Shell Nanocatalysts in CO2 Hydrogenation to CH3OH
Authors: Li Xinliang , Zeng Ziyan , Hu Bing , Qian Lihua , Hong Xinlin
Published: November 2016

Carbon dioxide is the primary greenhouse gas and its emission has caused serious problems with respect to climate change. Unremitting efforts are being made to recycle of CO2 through its hydrogenation to liquid fuels such as CH3OH. Pd–ZnO based nanoarchitectures are one type of ideal catalysts for CO2 hydrogenation. However, owing to the lack of palladium reserves, enhancing the catalytic efficiency and selectivity of the palladium nanostructures so that low loadings can be used remains a scientific challenge. Three types of ZnO‐supported Ag@Pd core@shell, AgPd alloy, and pure Pd nanocatalysts were controllably and successfully synthesized. Benefiting from the electron‐rich Pd shell and the formation of the PdZn phase in the Ag@Pd–ZnO core@shell structure, we achieved a catalytic efficiency per gram of palladium that is 3.32 times higher than the Pd–ZnO nanostructure. In particular, electron transfer at the interfaces and the adsorption of the intermediate species significantly enhance catalytic selectivity of the Ag@Pd–ZnO core@shell structure. This work proposes a novel strategy to enhance the methanol yield during CO2 hydrogenation by the sophisticated tailoring of the surface composition in noble‐metal catalysts.
Prediction of H2S Solubility in Liquid Electrolytes by Multilayer Perceptron and Radial Basis Function Neural Networks
Authors: Barati‐Harooni Ali , Nasery Saeid , Tatar Afshin , Najafi‐Marghmaleki Adel , Isafiade Adeniyi Jide , Bahadori Alireza
Published: November 2016

Industrial natural gas treating plants commonly employ amine‐based treatments for hydrogen sulfide elimination from crude oil and gas. Some deficiencies boost the motivation to find an appropriate alternative. Due to their advantageous properties, liquid electrolytes are considered as possible substitutes for classical alkanolamine solvents in such processes. The solubility of gases in ionic solutions at different temperatures and pressures is a crucial factor in the examination of ionic liquids as a potential alternative. Two intelligent methods, namely, simple multilayer perceptron (MLP) and radial basis function neural networks, are proposed to accurately predict the solubility of H2S in various ionic liquids. The predicted values agree well with the experimental data. A comparison to other intelligent models, which were recently suggested, reveals the superiority of the proposed simple MLP model.
High‐Throughput Electrochemical Screening Assay for Free and Immobilized Oxidases: Electrochemiluminescence and Intermittent Pulse Amperometry
Authors: Aymard Chloé , Bonaventura Celia , Henkens Robert , Mousty Christine , Hecquet Laurence , Charmantray Franck , Blum Loïc J. , Doumèche Bastien
Published: November 2016

Analysis of a large number of samples by electrochemical methods for rapid optimization of amperometric biosensors or screening applications is still a challenge. To overcome this limitation, a system with 96 screen‐printed electrodes was developed to assay H2O2 produced by free and immobilized galactose oxidase as a model for oxidases. Detection was based on two electrochemical methods: intermittent pulse amperometry (IPA) and electrochemiluminescence (ECL). This 96‐well electrochemical device allowed rapid optimization of the parameters in half a day, regardless of the method used (i.e., IPA or ECL). We demonstrate that ECL is more sensitive for the detection of H2O2 (limit of detection of 1 μm for ECL vs. 10 μm for IPA) with lower interelectrode variability (1 vs. 19 %). Rapid determination of sensitivities, linear ranges, and limits of detection of galactose oxidase substrates (e.g., dihydroxyacetone and l‐erythrulose) by using free or immobilized enzyme was conducted in only 50 min by the mean of 5 different sets of 96 screen‐printed electrodes.
Direct Synthesis of Two Inorganic Catalysts on Carbon Fibres for the Electrocatalytic Oxidation of Water
Authors: Svengren Henrik , Jansson Kjell , Grins Jekabs , Wan Wei , Torapava Natallia , Johnsson Mats
Published: November 2016

Two electrodes for anodic water oxidation made by direct synthesis of inorganic catalysts onto conductive carbon fibre sheets are evaluated. As catalysts two Co‐ and Sb‐containing phases were tested, that is, Co3Sb4O6F6 and the new compound CoSbO4. The compounds express large differences in their morphology: CoSbO4 grows as thin needles whereas Co3Sb4O6F6 grows as larger facetted crystals. Despite the smaller surface area the latter compound shows a better catalytic performance. When the compound Co3Sb4O6F6 was used it gave a low increase of +0.028 mV h−1 at an overpotential of η=472 mV after 10 h and a stability of +0.48 mV h−1 at an overpotential of η=488 mV after 60 h. The leakages of Co and Sb were negligible and only <0.001 at % Co and approximately 0.02 at % Sb were detected in the electrolyte.
Light‐Induced Porphyrin‐Based Spectroscopic Ruler for Nanometer Distance Measurements
Authors: Di Valentin Marilena , Albertini Marco , Dal Farra Maria Giulia , Zurlo Enrico , Orian Laura , Polimeno Antonino , Gobbo Marina , Carbonera Donatella
Published: November 2016

We present a novel pulsed electron paramagnetic resonance (EPR) spectroscopic ruler to test the performance of a recently developed spin‐labeling method based on the photoexcited triplet state (S=1). Four‐pulse electron double resonance (PELDOR) experiments are carried out on a series of helical peptides, labeled at the N‐terminal end with the porphyrin moiety, which can be excited to the triplet state, and with the nitroxide at various sequence positions, spanning distances in the range 1.8–8 nm. The PELDOR traces provide accurate distance measurements for all the ruler series, showing deep envelope modulations at frequencies varying in a progressive way according to the increasing distance between the spin labels. The upper limit is evaluated and found to be around 8 nm. The PELDOR‐derived distances are in excellent agreement with theoretical predictions. We demonstrate that high sensitivity is acquired using the triplet state as a spin label by comparison with Cu(II)–porphyrin analogues. The new labeling approach has a high potential for measuring nanometer distances in more complex biological systems due to the properties of the porphyrin triplet state.
Luminescent Gold(III) Thiolates: Supramolecular Interactions Trigger and Control Switchable Photoemissions from Bimolecular Excited States
Authors: Currie Lucy , Fernandez‐Cestau Julio , Rocchigiani Luca , Bertrand Benoît , Lancaster Simon J. , Hughes David L. , Duckworth Helen , Jones Saul T. E. , Credgington Dan , Penfold Thomas J. , Bochmann Manfred
Published: November 2016

A new family of cyclometallated gold(III) thiolato complexes based on pyrazine‐centred pincer ligands has been prepared, (C^Npz^C)AuSR, where C^Npz^C=2,6‐bis(4‐ButC6H4)pyrazine dianion and R=Ph (1), C6H4tBu‐4 (2), 2‐pyridyl (3), 1‐naphthyl (1‐Np, 4), 2‐Np (5), quinolinyl (Quin, 6), 4‐methylcoumarinyl (Coum, 7) and 1‐adamantyl (8). The complexes were isolated as yellow to red solids in high yields using mild synthetic conditions. The single‐crystal X‐ray structures revealed that the colour of the deep‐red solids is associated with the formation of a particular type of short (3.2–3.3 Å) intermolecular pyrazine⋅⋅⋅pyrazine π‐interactions. In some cases, yellow and red crystal polymorphs were formed; only the latter were emissive at room temperature. Combined NMR and UV/Vis techniques showed that the supramolecular π‐stacking interactions persist in solution and give rise to intense deep‐red photoluminescence. Monomeric molecules show vibronically structured green emissions at low temperature, assigned to ligand‐based 3IL(C^N^C) triplet emissions. By contrast, the unstructured red emissions correlate mainly with a 3LLCT(SR→{(C^Npz^C)2}) charge transfer transition from the thiolate ligand to the π⋅⋅⋅π dimerized pyrazine. Unusually, the π‐interactions can be influenced by sample treatment in solution, such that the emissions can switch reversibly from red to green. To our knowledge this is the first report of aggregation‐enhanced emission in gold(III) chemistry.
Mechanism of the Copper/TEMPO‐Catalyzed Aerobic Oxidation of Alcohols
Authors: Iron Mark A. , Szpilman Alex M.
Published: November 2016

Identifying the mechanism of a catalytic reaction is paramount for designing new and improved catalysts. Several alternative catalytic cycles for the copper/2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO)‐catalyzed aerobic oxidation of alcohols to the corresponding aldehydes or ketones were examined using DFT at the SMD(CH3CN)‐RIJCOSX‐DSD‐PBEB95/def2‐TZVP//DF‐PBED3BJ/def2‐SVP level of theory. A catalytic cycle in which TEMPO remains coordinated to copper throughout was identified as the most likely mechanism. There are three components to the catalytic cycle: 1) hydrogen transfer from the alkoxyl ligand to coordinated TEMPO, 2) oxygen activation with formation of a peroxo complex, and 3) alcohol activation with transfer of the OH proton to the peroxo ligand. The oxidation takes place via a six‐membered intramolecular hydrogen‐transfer transition state. Importantly, this is not the rate‐determining step, which instead involves oxygen activation and/or the initial alcohol activation.
Ferrocyanide‐Mediated Photoreduction of Ferricytochrome C Utilized to Selectively Probe Non‐native Conformations Induced by Binding to Cardiolipin‐Containing Liposomes
Authors: Malyshka Dmitry , Schweitzer‐Stenner Reinhard
Published: November 2016

Ferricytochrome c binding to cardiolipin‐containing liposomes produces a heterogeneous distribution of conformations comprising native‐like and non‐native misfolded proteins. We utilized the photoreduction of native ferricytochrome c in the presence of potassium ferrocyanide and resonance Raman spectroscopy to probe the population of native and misfolded cytochrome c on liposomes with 20 % tetraoleylcardiolipin (TOCL)/80 % dioleylphosphocholine (DOPC) and with 100 % TOCL as a function of TOCL concentration. Our data provided strong support for an earlier model, which predicts that the equilibrium between native and non‐native conformations is shifted to the latter with decreasing protein occupation of liposomes.
Focus on cannabinoids and synthetic cannabinoids
Authors: Le Boisselier R , Alexandre J , Lelong‐Boulouard V , Debruyne D
Published: November 2016

The recent emergence of a multitude of synthetic cannabinoids (SCs) has generated a wealth of new information, suggesting the usefulness of state‐of‐the‐art on lato sensu cannabinoids. By modulating a plurality of neurotransmission pathways, the endocannabinoid system is involved in many physiological processes that are increasingly explored. SCs desired and adverse effects are considered to be more intense than those observed with cannabis smoking, which is partly explained by the full agonist activity and higher affinity for cannabinoid receptors. Neurological and cardiovascular side effects observed after cannabinoid poisoning generally respond to conventional supportive care, but severe outcomes may occur in a minority of cases, mainly observed with SCs. The likelihood of severe abuse and addiction produced by SCs are of concern for the scientific community also interested in the potential therapeutic value of cannabinoids.
Catalytic Transfer Hydrogenation of Furfural to 2‐Methylfuran and 2‐Methyltetrahydrofuran over Bimetallic Copper–Palladium Catalysts
Authors: Chang Xin , Liu An‐Feng , Cai Bo , Luo Jin‐Yue , Pan Hui , Huang Yao‐Bing
Published: November 2016

The catalytic transfer hydrogenation of furfural to the fuel additives 2‐methylfuran (2‐MF) and 2‐methyltetrahydrofuran (2‐MTHF) was investigated over various bimetallic catalysts in the presence of the hydrogen donor 2‐propanol. Of all the as‐prepared catalysts, bimetallic Cu‐Pd catalysts showed the highest catalytic activities towards the formation of 2‐MF and 2‐MTHF with a total yield of up to 83.9 % yield at 220 °C in 4 h. By modifying the Pd ratios in the Cu‐Pd catalyst, 2‐MF or 2‐MTHF could be obtained selectively as the prevailing product. The other reaction conditions also had a great influence on the product distribution. Mechanistic studies by reaction monitoring and intermediate conversion revealed that the reaction proceeded mainly through the hydrogenation of furfural to furfuryl alcohol, which was followed by deoxygenation to 2‐MF in parallel to deoxygenation/ring hydrogenation to 2‐MTHF. Finally, the catalyst showed a high reactivity and stability in five catalyst recycling runs, which represents a significant step forward toward the catalytic transfer hydrogenation of furfural.
An altruism‐based trust‐dependent message forwarding protocol for opportunistic networks
Authors: Kumar Arun , Dhurandher Sanjay K. , Woungang Isaac , Obaidat Mohammad S. , Gupta Sahil , Rodrigues Joel J. P. C.
Published: November 2016

In opportunistic networks (OppNets), which are characterized by intermittent end‐to‐end connections, the messages are routed in a store‐carry‐and‐forward fashion using the locally inferred knowledge about the behavior of nodes. As such, most OppNets routing protocols use social metrics that are dependent on the nodes' past information. But the participation of nodes in the message forwarding process is not guaranteed without incentivizing them because most nodes are reluctant in sharing their private resources for public uses. In this paper, some socially derived psychological attributes of a node are introduced to ensure their trustworthy participation in the message forwarding process, leading to the design of an altruism‐dependent trust‐based data forwarding mechanism for OppNets (called ATDTN). In this protocol, each node is associated with a dynamically changing altruism value representing its trust in the network, which is used to determine its status with regard to its participation in message forwarding. Through trace‐driven simulations using the ONE simulator, it is shown that ATDTN outperforms IronMan and SimBet protocols for routing in OppNets (respectively, 18% and 48% improvement), in terms of delivery ratio, end‐to‐end delay, overhead count, and average number of hops, under varying buffer size and time‐to‐live.
Identification and analytical characterization of nine synthetic cathinone derivatives N‐ethylhexedrone, 4‐Cl‐pentedrone, 4‐Cl‐α‐EAPP, propylone, N‐ethylnorpentylone, 6‐MeO‐bk‐MDMA, α‐PiHP, 4‐Cl‐α‐PHP, and 4‐F‐α‐PHP
Authors: Liu Cuimei , Jia Wei , Li Tao , Hua Zhendong , Qian Zhenhua
Published: November 2016

Clinical and forensic toxicology laboratories are continuously confronted by analytical challenges when dealing with the new psychoactive substances (NPS) phenomenon. In this study, the analytical characterization of nine synthetic cathinones is described: 2‐(ethylamino)‐1‐phenylhexan‐1‐one (N‐ethylhexedrone 1), 1‐(4‐chlorophenyl)‐2‐(methylamino)pentan‐1‐one (4‐Cl‐pentedrone 2), 1‐(4‐chlorophenyl)‐2‐(ethylamino)pentan‐1‐one (4‐Cl‐α‐EAPP 3), 1‐(3,4‐methylenedioxyphenyl)‐2‐propylaminopropan‐1‐one (propylone 4), 1‐(3,4‐methylenedioxyphenyl)‐2‐ethylaminopentan‐1‐one (N‐ethylnorpentylone 5), 1‐(6‐methoxy‐3,4‐methylenedioxyphenyl)‐2‐methylaminopropan‐1‐one (6‐MeO‐bk‐MDMA 6), 4‐methyl‐1‐phenyl‐2‐(pyrrolidin‐1‐yl)pentan‐1‐one (α‐PiHP 7), 1‐(4‐chlorophenyl)‐2‐(pyrrolidin‐1‐yl)hexan‐1‐one (4‐Cl‐α‐PHP 8), and 1‐(4‐fluorophenyl)‐2‐(pyrrolidin‐1‐yl)hexan‐1‐one (4‐F‐α‐PHP 9). The identification was based on ultra‐high‐performance liquid chromatography‐quadrupole time‐of‐flight–mass spectrometry (UHPLC–QTOF‐MS), gas chromatography‐mass spectrometry (GC‐MS), and nuclear magnetic resonance (NMR) spectroscopy. The mass‐spectral fragmentations of these compounds following collision‐induced dissociation (CID) and electron ionization (EI) were studied to assist forensic laboratories in identifying these compounds or other substances with similar structure in their case work. To our knowledge, no analytical data about the compounds 1–4, 7, and 8 have appeared until now, making this the first report on these compounds. The GC‐MS data of 5, 6 and 9 has been reported, but this study added the LC‐MS, Fourier Transform Infrared (FTIR) and NMR data for additional characterization. Copyright © 2016 John Wiley & Sons, Ltd.
Increased complementarity in water‐limited environments in Scots pine and European beech mixtures under climate change
Authors: González de Andrés Ester , Seely Brad , Blanco Juan A. , Imbert J. Bosco , Lo Yueh‐Hsin , Castillo Federico J.
Published: November 2016

Management of mixedwoods is advocated as an effective adaptation strategy to increase ecosystem resiliency in the context of climate change. Although mixedwoods have been shown to have greater resource use efficiency relative to pure stands, considerable uncertainty remains with respect to the underlying ecological processes. We explored species interactions in Scots pine/European beech mixedwoods with the process‐based model FORECAST Climate. The model was calibrated for two contrasting forests in the southwestern Pyrenees (northern Spain): a wet Mediterranean site at 625 m.a.s.l. and a subalpine site at 1335 m.a.s.l. Predicted mixedwood yield was higher than that for beech stands but lower than pine stands. When simulating climate change, mixedwood yield was reduced at the Mediterranean site (−33%) but increased at the subalpine site (+11%). Interaction effects were enhanced as stands developed. Complementarity dominated the Mediterranean stand but neutral or net competition dominated the subalpine stand, which had higher stand density and water availability. Reduced water demand and consumption, increased canopy interception, and improved water‐use efficiency in mixtures compared to beech stands, suggest a release of beech intraspecific competition. Beech also facilitated pine growth through better litter quality, nonsymbiotic nitrogen fixation, and above‐ and belowground stratification, leading to higher foliar nitrogen content and deeper canopies in pines. In conclusion, mixtures may improve water availability and use efficiency for beech and light interception for pine, the main limiting factors for each species, respectively. Encouraging pine–beech mixtures could be an effective adaptation to climate change in drought‐prone sites in the Mediterranean region.
Selective Extraction of Americium(III) over Europium(III) Ions with Pyridylpyrazole Ligands: Structure–Property Relationships
Authors: Su Dongping , Liu Ying , Li Shimeng , Ding Songdong , Jin Yongdong , Wang Zhipeng , Hu Xiaoyang , Zhang Lirong
Published: November 2016

To clarify the structure–property relationships of pyridylpyrazole ligands and provide guidance for the design of new and more efficient ligands for the selective extraction of actinides over lanthanides, a series of alkyl‐substituted pyridylpyrazole ligands with different branched chains at different positions of the pyrazole ring were synthesized. Extraction experiments showed that the pyridylpyrazole ligands exhibited good selective extraction abilities for AmIII ions, and the steric effects of the branched chain had a significant impact on the distribution ratios of AmIII and EuIII ions as well as the separation factor. Moreover, both slope analyses and UV/Vis spectrometry titrations indicated the formation of a 1:1 complex of 2‐(1‐octyl‐1H‐pyrazol‐3‐yl)pyridine (C8‐PypzH) with EuIII ions. The stability constant (log K) for this complex obtained from the UV/Vis titration was 4.45 ± 0.04. Single crystals of the complexes of 3‐(2‐pyridyl)pyrazole (PypzH) with Eu(NO3)3 and Sm(NO3)3 were obtained; PypzH acts as a bidentate ligand in the crystal structures, and the N atom with a bound H atom did not participate in the coordination. In general, this study revealed some interesting findings on the effects of the alkyl‐chain structure and the special complexation between pyridylpyrazole ligands and LnIII ions.
Convenient Synthesis of 3‐Glycosylated Isocoumarins
Authors: Sudarshan Kasireddy , Aidhen Indrapal Singh
Published: November 2016

A new route for the synthesis of 3‐substituted and 8‐hydroxy‐3‐substituted isocoumarins was developed by modified Julia olefination for initial C–C bond formation between aldehydes and benzylic sulfones. Palladium‐catalyzed Meinwald rearrangement was used as a key step for the obtainment of ketone intermediates, which – upon base‐promoted intramolecular cyclization – afforded the desired isocoumarins. The developed method paves the way to hitherto unknown 3‐glycosylisocoumarins, in general, and 3‐glucosylisocoumarins, in particular, wherein the glucosyl moiety is attached to the pyrone ring of the isocoumarin framework.
Four‐Component Reaction for the Synthesis of Indolizines by Copper‐Catalyzed Aerobic Oxidative Dehydrogenative Aromatization
Authors: Xu Juanfang , Hu Huayou , Liu Yun , Wang Xiang , Kan Yuhe , Wang Chao
Published: November 2016

A one‐pot, four‐component reaction was developed for the synthesis of indolizines from pyridines, α‐halide carbonyl compounds, primary amines, and maleic anhydride. The key step in this reaction involved the copper‐catalyzed aerobic oxidative aromatization of a tetrahydrogen–indolizine intermediate. Oxygen gas was employed as a clean oxidant to facilitate the catalytic process. Notably, this transformation used readily available starting materials, exhibited broad substrate scope, was easy to handle, and required mild reaction conditions.
BSA‐templated Pb Nanocluster as a Biocompatible Signaling Probe for Electrochemical EGFR Immunosensing
Authors: Mousavi Mir F. , Mirsian Samaneh , Noori Abolhassan , Ilkhani Hoda , Sarparast Morteza , Moradi Nasrin , Bathaie S. Zahra , Mehrgardi Masoud A.
Published: November 2016

We report here a new electrochemical probe for the development of a sensitive, and selective sandwich‐type electrochemical immunosensor for the detection of epidermal growth factor receptor (EGFR). The probe is a newly synthesized bovine serum albumin (BSA)‐templated Pb nanocluster (PbNC@BSA). For fabrication of the immunosensor, we employed streptavidin‐coated magnetic beads (MB) as a platform for immobilization of the biotinylated primary antibody (Ab1), and utilized the PbNC@BSA conjugated to secondary antibody (Ab2) as a signaling probe. After sandwiching the target protein between Ab1 and Ab2, we dissolved PbNC@BSA into an acid, and recorded square wave anodic stripping voltammetric (SWASV) signal of the Pb ions as an analytical signal for quantification of the EGFR. The immunosensor responded linearly towards EGFR within the range of 0.4 ng/mL to 35 ng/mL, with a detection limit of 8 pg/mL. The immunosensor displayed good sensitivity, selectivity, stability, and reproducibility, and proved suitable for direct measurement of EGFR in human serum samples. Moreover, we used the as‐synthesized PbNC@BSA as a fluorescence label for in vitro cell viability analysis as well as bioimaging of cancerous HeLa and non‐cancerous HUVEC cells. PbNC@BSA exhibited low cytotoxicity and high biocompatibility in living cells, and was a suitable fluorescent probe for live cell imaging, with potential therapeutic applications.
Pressure reduction affects growth and morphology of Chlamydomonas reinhardtii
Authors: Wagner Ines , Posten Clemens
Published: November 2016

Cellular perception of pressure is a largely unknown field in microalgae research although it should be addressed for optimization of a photobioreactor design regarding typically occurring pressure cycles. Also for the purpose of using microalgae as basic modules for material cycles in controlled ecological life support systems, the absence of pressure in outer space or the low absolute pressures on other planets is an abiotic factor that needs to be considered for design of integrated microalgae‐based modules. The aim of this work is to study the effects of lowered pressure and pressure changes on photosynthesis as well as morphology. Two Chlamydomonas reinhardtii wild‐type strains were exposed to controlled pressure patterns during batch cultivations. Sudden pressure changes should test for existing threshold values for cell survival to mimic such events during space missions. Algae were grown inside a 2 L photobioreactor with an integrated vacuum pump ensuring constant pressures down to 700 mbar. Cultivation samples were analyzed for OD750, cell dry weight, and morphology via light microscope. Chlamydomonas reinhardtii CC‐1690 cells showed decreased growth rates, higher carbon dioxide uptake rates, and unchanged oxygen production rates at lower pressures. For sudden pressures changes in the range of 300 mbar no fatal threshold was determined. This study shows that pressure reduction affects growth, gas exchange rates, and morphology. Within the tested pressure range no fatal threshold value was reached.
Health Disparities by Income in Spain Before and After the Economic Crisis
Authors: Coveney Max , García‐Gómez Pilar , Van Doorslaer Eddy , Van Ourti Tom
Published: November 2016

Little is known about how health disparities by income change during times of economic crisis. We apply a decomposition method to unravel the contributions of income growth, income inequality and differential income mobility across socio‐demographic groups to changes in health disparities by income in Spain using longitudinal data from the Survey of Income and Living Conditions for the period 2004–2012. We find a modest rise in health inequality by income in Spain in the 5 years of economic growth prior to the start of the crisis in 2008, but a sharp fall after 2008. The drop mainly derives from the fact that loss of employment and earnings has disproportionately affected the incomes of the younger and healthier groups rather than the (mainly stable pension) incomes of the groups over 65 years. This suggests that unequal distribution of income protection by age may reduce health inequality in the short run after an economic recession. Copyright © 2016 John Wiley & Sons, Ltd.