bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Sketching the Historical Development of Pyrimidones as the Inhibitors of the HIV Integrase
Authors: Patel Rahul V. , Keum Young‐Soo , Park Se Won
Published: July 2015

Review: 53 refs.
ChemInform Abstract: Spirooxindoles: Promising Scaffolds for Anticancer Agents
Authors: Yu Bin , Yu De‐Quan , Liu Hong‐Min
Published: July 2015

Review: 84 refs.
ChemInform Abstract: Recent Applications of 1,3‐Thiazole Core Structure in the Identification of New Lead Compounds and Drug Discovery
Authors: Ayati Adile , Emami Saeed , Asadipour Ali , Shafiee Abbas , Foroumadi Alireza
Published: July 2015

Review: 139 refs.
ChemInform Abstract: Recent Advanced in Bioactive Systems Containing Pyrazole Fused with a Five Membered Heterocycle
Authors: Raffa Demetrio , Maggio Benedetta , Raimondi Maria Valeria , Cascioferro Stella , Plescia Fabiana , Cancemi Gabriella , Daidone Giuseppe
Published: July 2015

Review: 60 refs.
ChemInform Abstract: Recent Advances in Bioactive Pyrazoles
Authors: Kuecuekguezel S. Gueniz , Senkardes Sevil
Published: July 2015

Review: 203 refs.
ChemInform Abstract: A Review on Anticancer Potential of Bioactive Heterocycle Quinoline
Authors: Afzal Obaid , Kumar Suresh , Haider Md Rafi , Ali Md Rahmat , Kumar Rajiv , Jaggi Manu , Bawa Sandhya
Published: July 2015

Review: 275 refs.
ChemInform Abstract: Manzamine Alkaloids as Antileishmanial Agents: A Review
Authors: Ashok Penta , Lathiya Hiren , Murugesan Sankaranarayanan
Published: July 2015

Review: 59 refs.
ChemInform Abstract: Recent Advances in the Use of Sodium Borohydride as a Solid State Hydrogen Store
Authors: Mao Jianfeng , Gregory Duncan H.
Published: July 2015

Review: 80 refs.
ChemInform Abstract: Catalytic Upgrading of Bio‐Oils by Esterification
Authors: Ciddor Lachlan , Bennett James A. , Hunns James A. , Wilson Karen , Lee Adam F.
Published: July 2015

Review: 162 refs.
ChemInform Abstract: Quantum‐Chemical Characterization of the Properties and Reactivities of Metal‐Organic Frameworks
Authors: Odoh Samuel O. , Cramer Christopher J. , Truhlar Donald G. , Gagliardi Laura
Published: July 2015

Review: 653 refs.
ChemInform Abstract: The Rapidly Changing Face of Electron Microscopy
Authors: Thomas John Meurig , Leary Rowan K. , Eggeman Alexander S. , Midgley Paul A.
Published: July 2015

Review: 68 refs.
Preparation and Intramolecular CC Coupling Reaction for Bis‐benzimidazolium Salt
Authors: Liu Rui , Huo Ran , Bi Yue , Zhao Zhixiang , Liu Qingxiang
Published: July 2015

Bis‐benzimidazolium salt 1 was prepared via a series of reactions using 2,2′‐diphenol as starting material. Compound 2 was afforded through the intramolecular CC coupling reaction of 1 under the catalysis of Pd(OAc)2. The structure of 2 is characterized through X‐ray diffraction analyses, 1H NMR and 13C NMR. In 2, two boat‐like seven‐membered rings are contained, where the CC bond distance newly formed is 1.461(5) Å, and it is between regular CC single bond (1.54 Å) and CC double bond (1.34 Å). This shows that new CC bond has partial double‐bond character. In the crystal packing of 2, the 2D supramolecular layers are formed via CH···F hydrogen bond.
Separation of Amyl Alcohol Isomers in ZIF‐77
Authors: Bueno‐Perez Rocio , Gutiérrez‐Sevillano Juan J. , Dubbeldam David , Merkling Patrick J. , Calero Sofia
Published: July 2015

The separation of pentanol isomer mixtures is shown to be very efficient using the nanoporous adsorbent zeolitic imidazolate framework ZIF‐77. Through molecular simulations, we demonstrate that this material achieves a complete separation of linear from monobranched—and these from dibranched—isomers. Remarkably, the adsorption and diffusion behaviors follow the same decreasing trend, produced by the channel size of ZIF‐77 and the guest shape. This separation based on molecular branching applies to alkanes and alcohols and promises to encompass numerous other functional groups.
Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb3+ Complexes
Authors: Berardozzi Roberto , Di Bari Lorenzo
Published: July 2015

We used a very simplified electrostatic model based on charge and polarizability of atoms and groups on an organic ligand around a lanthanide ion to predict the near‐infrared electronic circular dichroism (NIR ECD) spectra of Yb3+ (a monoelectronic ion). We tuned our method by using two widely different complexes. The first was the heterobimetallic species CsYb(hfbc)4 [hfbc=(−)‐3‐heptafluorobutyrylcamphorate], in which the ligand is a diketonate and, as such, is endowed with a chromophore with strong UV absorption (π–π*). Its oxygen atoms define a square antiprism, which provides a symmetric coordination polyhedron. The second system was Yb DOTMA [DOTMA=(1R,4R,7R,10R)‐α,α′,α′′,α′′′‐tetramethyl‐1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid], a chiral Yb analogue of Gd DOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid), in which the ligand lacks relevant electronic transitions and provides a dissymmetric cage. The relative weights of dynamic (ligand polarization) and static contributions to Yb NIR ECD were evaluated, and the spectra appear to have been well predicted by theory through the introduction of a heuristic weight factor. To validate the approach and to confirm the value of the weight factor, we applied it to two other compounds, namely, Na3Yb(BINOLate)3 and Yb(BINOLAM)3 [BINOLate=2,2′‐dihydroxy‐1,1′‐binaphthyl; BINOLAM=3,3′‐bis(diethylaminomethyl)‐1‐1′‐bi‐2‐naphthol].
Electrocatalytic Activity of Tungsten Oxide Nanoclusters Grafted on Mesoporous Nitrogen‐Rich Carbon Material in the Dioxygen Reduction Reaction
Authors: Tiwari Aarti , Nagaiah Tharamani C. , Bordoloi Ankur
Published: July 2015

Nanosized clusters of tungsten oxide grafted onto a mesoporous nitrogen‐rich carbon material (WOx/MNCx) have been synthesized and explored for their remarkable ability towards dioxygen reduction. The composite catalyst exhibits a lower overpotential and significant stability, which paves the way towards improvement of the nonprecious yet proficient electrocatalyst for the oxygen reduction reaction (ORR) occurring at the cathode in alkaline medium. The electrocatalytic activity of the synthesized catalyst towards the ORR have been examined by electrochemical techniques, such as cyclic voltammetry, rotating disk electrode and rotating ring disk electrode measurements, along with electrochemical quartz crystal microbalance studies in alkaline medium. The WOx/MNCx catalyst shows better electrocatalytic activity towards the ORR in alkaline medium and could be used for successful application in low‐temperature fuel cells.
Transesterification of Tributyrin and Dehydration of Fructose over a Carbon‐Based Solid Acid Prepared by Carbonization and Sulfonation of Glucose
Authors: Wang Chuanxu , Yuan Fulong , Liu Lijing , Niu Xiaoyu , Zhu Yujun
Published: July 2015

A series of carbon‐based sulfonated solid acid (CS) catalysts can be prepared through a facile method of direct simultaneous carbonization and sulfonation of d‐glucose with concentrated sulfuric acid without a hydrothermal process. Temperature is a key factor in obtaining CS catalysts with higher amounts of ‐SO3H acid sites. The transesterification of tributyrin with methanol and the dehydration of fructose to 5‐hydroxymenthylfurfural (5‐HMF) are investigated over the CS catalysts. The CS‐150 catalyst, which is the CS catalyst prepared at 150 °C, shows much higher catalytic activity to give a tributyrin conversion of 99.4 %. The yield of methyl butyrate is 97.2 % and a remarkably high yield of 5‐HMF (93 %) can be obtained efficiently; these yields result from the high acid density of ‐SO3H. Good linearity is displayed between the total acid density and yield of methyl butyrate/5‐HMF. The CS‐150 catalyst has high stability and good recyclability for the dehydration of fructose.
Biochemical Capacitance of Geobacter Sulfurreducens Biofilms
Authors: Bueno Paulo R. , Schrott Germán D. , Bonanni Pablo S. , Simison Silvia N. , Busalmen Juan P.
Published: July 2015

An electrical model able to decouple the electron pathway from microbial cell machinery impedance terms is introduced. In this context, capacitance characteristics of the biofilm are clearly resolved. In other words, the model allows separating, according to the advantage of frequency and spectroscopic response approach, the different terms controlling the performance of the microbial biofilm respiratory process and thus the directly related electricity production process. The model can be accurately fitted to voltammetry measurements obtained under steady‐state conditions and also to biofilm discharge amperometric measurements. The implications of biological aspects of the electrochemical or redox capacitance are discussed theoretically in the context of current knowledge with regard to structure and physiological activity of microbial Geobacter biofilms.
Hindered Glymes for Graphite‐Compatible Electrolytes
Authors: Shanmukaraj Devaraj , Grugeon Sylvie , Laruelle Stephane , Armand Michel
Published: July 2015

Organic carbonate mixtures are used almost exclusively as lithium battery electrolyte solvents. The linear compounds (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate) act mainly as thinner for the more viscous and high‐melting ethylene carbonate but are the least stable component and have low flash points; these are serious handicaps for lifetime and safety. Polyethers (glymes) are useful co‐solvents, but all formerly known representatives solvate Li+ strongly enough to co‐intercalate in the graphite negative electrode and exfoliate it. We have put forward a new electrolyte composition comprising a polyether to which a bulky tert‐butyl group is attached (“hindered glyme”), thus completely preventing co‐intercalation while maintaining good conductivity. This alkyl‐carbonate‐free electrolyte shows remarkable cycle efficiency of the graphite electrode, not only at room temperature, but also at 50 and 70 °C in the presence of lithium bis(fluorosulfonimide). The two‐ethylene‐bridge hindered glyme has a high boiling point and a flash point of 80 °C, a considerable advantage for safety.
Effect of Mesoporous Structured Cathode Materials on Charging Potentials and Rate Capability of Lithium–Oxygen Batteries
Authors: Park Jihee , Jeong Jooyoung , Lee Seonggyu , Jo Changshin , Lee Jinwoo
Published: July 2015

Solid and nonconductive discharge products that form on the cathode of Li–O2 batteries are difficult to decompose efficiently into Li+ and O2 during charging, which induces a high overcharge potential, low energy efficiency, and poor cyclability. In this paper, we investigated the effects of the mesoporous structure on the morphology of the discharge products, the capacities of the cells, and the discharging/charging potentials. To isolate the effect of the mesostructures, mesoporous carbons, CMK‐3 and MSU‐F‐C, were used without the addition of other electrocatalysts. The discharge products were confined within the pores. Consequently, the charging potentials were decreased owing to small and amorphous lithium oxides. The large, 3 D interconnected pores of MSU‐F‐C lowered the charging potentials at a high current density and increased the rate capabilities relative to the parameters found for the small pores of CMK‐3. These results demonstrate that control of the porous structure is necessary to enhance the performance of Li–O2 batteries.
Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales
Authors: Ortiz Daniel , Jiménez Gordon Isabel , Baltaze Jean‐Pierre , Hernandez‐Alba Oscar , Legand Solène , Dauvois Vincent , Si Larbi Gregory , Schmidhammer Uli , Marignier Jean‐Louis , Martin Jean‐Frédéric , Belloni Jacqueline , Mostafavi Mehran , Le Caër Sophie
Published: July 2015

The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li‐ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li+, PF6−) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation‐matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g). The strong Lewis acid PF5 is also formed. This species then forms various R1R2R3P=O molecules, where R is mainly −F, −OH, and −OC2H5. Substitution reactions take place and oligomers are slowly formed. Similar results were obtained in the ageing of an electrochemical cell filled with the same model solution. This study demonstrates that radiolysis enables a description of the reactivity in LIBs from the picosecond timescale until a few days.
Synergistic Carbon Dioxide Capture and Conversion in Porous Materials
Authors: Zhang Yugen , Lim Diane S. W.
Published: July 2015

Global climate change and excessive CO2 emissions have caused widespread public concern in recent years. Tremendous efforts have been made towards CO2 capture and conversion. This has led to the development of numerous porous materials as CO2 capture sorbents. Concurrently, the conversion of CO2 into value‐added products by chemical methods has also been well‐documented recently. However, realizing the attractive prospect of direct, in situ chemical conversion of captured CO2 into other chemicals remains a challenge.
Freshwater wetlands: fertile grounds for the invasive Phragmites australis in a climate change context
Authors: Tougas‐Tellier Marie‐Andrée , Morin Jean , Hatin Daniel , Lavoie Claude
Published: July 2015

Climate change will likely affect flooding regimes, which have a large influence on the functioning of freshwater riparian wetlands. Low water levels predicted for several fluvial systems make wetlands especially vulnerable to the spread of invaders, such as the common reed (Phragmites australis), one of the most invasive species in North America. We developed a model to map the distribution of potential germination grounds of the common reed in freshwater wetlands of the St. Lawrence River (Québec, Canada) under current climate conditions and used this model to predict their future distribution under two climate change scenarios simulated for 2050. We gathered historical and recent (remote sensing) data on the distribution of common reed stands for model calibration and validation purposes, then determined the parameters controlling the species establishment by seed. A two‐dimensional model and the identified parameters were used to simulate the current (2010) and future (2050) distribution of germination grounds. Common reed stands are not widespread along the St. Lawrence River (212 ha), but our model suggests that current climate conditions are already conducive to considerable further expansion (>16,000 ha). Climate change may also exacerbate the expansion, particularly if river water levels drop, which will expose large bare areas propitious to seed germination. This phenomenon may be particularly important in one sector of the river, where existing common reed stands could increase their areas by a factor of 100, potentially creating the most extensive reedbed complex in North America. After colonizing salt and brackishwater marshes, the common reed could considerably expand into the freshwater marshes of North America which cover several million hectares. The effects of common reed expansion on biodiversity are difficult to predict, but likely to be highly deleterious given the competitiveness of the invader and the biological richness of freshwater wetlands.
Quantitative genetics of plumage color: lifetime effects of early nest environment on a colorful sexual signal
Authors: Hubbard Joanna K. , Jenkins Brittany R. , Safran Rebecca J.
Published: July 2015

Phenotypic differences among individuals are often linked to differential survival and mating success. Quantifying the relative influence of genetic and environmental variation on phenotype allows evolutionary biologists to make predictions about the potential for a given trait to respond to selection and various aspects of environmental variation. In particular, the environment individuals experience during early development can have lasting effects on phenotype later in life. Here, we used a natural full‐sib/half‐sib design as well as within‐individual longitudinal analyses to examine genetic and various environmental influences on plumage color. We find that variation in melanin‐based plumage color – a trait known to influence mating success in adult North American barn swallows (Hirundo rustica erythrogaster)–is influenced by both genetics and aspects of the developmental environment, including variation due to the maternal phenotype and the nest environment. Within individuals, nestling color is predictive of adult color. Accordingly, these early environmental influences are relevant to the sexually selected plumage color variation in adults. Early environmental conditions appear to have important lifelong implications for individual reproductive performance through sexual signal development in barn swallows. Our results indicate that feather color variation conveys information about developmental conditions and maternal care alleles to potential mates in North American barn swallows. Melanin‐based colors are used for sexual signaling in many organisms, and our study suggests that these signals may be more sensitive to environmental variation than previously thought.
Dioxygen Activation by an in situ Reduced CuII Hydrazone Complex
Authors: Radunsky Christian , Kösters Jutta , Letzel Matthias C. , Yogendra Sivathmeehan , Schwickert Christian , Manck Sinja , Sarkar Biprajit , Pöttgen Rainer , Weigand Jan J. , Neugebauer Johannes , Müller Jens
Published: July 2015

A CuII hydrazone complex has been synthesized that can be reduced in situ in boiling methanol to give the corresponding CuI complex. The latter complex readily activates dioxygen under ambient conditions, as was unambiguously shown by isotopic labeling studies. As a consequence of the dioxygen activation, the thienyl moiety appended to the hydrazone ligand is easily oxidized in β position (C–H → C–O), finally leading to a change in the coordination environment of the central metal ion. All relevant complexes have been structurally characterized by single‐crystal X‐ray diffraction analyses. The hydrazone ligand applied in this study does not mimic a biologically relevant coordination motif in copper‐containing oxygenases. Nonetheless, the reactivity of the CuI complex resembles that found in many oxygenases, indicating that hydrazone ligands may be well‐suited for the generation of novel bioinspired oxidation catalysts.
Towards Selective Light‐Activated RuII‐Based Prodrug Candidates
Authors: Mari Cristina , Pierroz Vanessa , Leonidova Anna , Ferrari Stefano , Gasser Gilles
Published: July 2015

Photoactivated chemotherapy (PACT) relies on the use of a drug and light to cause cell death. Unlike photodynamic therapy (PDT), its mechanism of action is independent of the presence of oxygen in tissues. This approach is therefore also effective for tumours characterized by hypoxic conditions. Herein we present the use of three novel RuII–polypyridyl complexes derivatized with a light‐sensitive cage and targeting peptides as selective PACT agents. Light irradiation allowed the selective release of the cytotoxic compounds from the molecular cages in living cells. Further selectivity was conferred on the system by a peptide carrier (i.e., bombesin), which targets receptors overexpressed on the membranes of HeLa cells. As expected, this peptide was found to provide an increased uptake of the systems in HeLa cells compared with normal MRC‐5 cells. As a result, for two of the compounds presented in this study, no cyto‐ or phototoxicity was observed in MRC‐5 cells, whereas in HeLa cells, upon light irradiation, IC50 values of 42.2 and 60.0 μM were obtained, which correspond to a two‐fold increase in toxicity.
Synthesis and Optical Properties of a Series of Green‐Light‐Emitting 2‐(4‐Phenylquinolin‐2‐yl)phenol–BF2 Complexes (Boroquinols)
Authors: Balijapalli Umamahesh , Iyer Sathiyanarayanan Kulathu
Published: July 2015

A series of 2‐(4‐phenylquinolin‐2‐yl)phenol derivatives were efficiently synthesized and complexed with boron trifluoride to give fluorescent organoboron complexes. All the synthesized compounds were characterized by 1H, 13C, 11B, 19F NMR, FTIR, and HRMS analyses, and single‐crystal structures of representative compounds were determined to examine the conformations of these compounds. The electronic properties of 2‐(4‐phenylquinolin‐2‐yl)phenol–BF2 complexes were studied by absorption and fluorescence spectroscopy and the complexes were found to be highly emissive in the solid state. The electrochemical properties of boroquinols were measured by using cyclic voltammetry (CV) in acetonitrile with 0.1 M tetrabutyl ammonium hexafluorophosphate as a supporting electrolyte and the LUMO values of boroquinols were calculated to range from –2.64 to –3.46 eV, with HOMO values of –5.32 to –6.10 eV.
Diastereoselective [4+2] Cycloaddition Reaction of 1‐Neomenthyl‐1,2‐diphosphole: Facile Synthesis of P‐Chiral Cage Phosphines
Authors: Zagidullin Almaz , Miluykov Vasili , Polyancev Fedor , Latypov Shamil , Sinyashin Oleg , Lönnecke Peter , Hey‐Hawkins Evamarie
Published: July 2015

3,4,5‐Triphenyl‐1‐(+)‐neomenthyl‐1,2‐diphosphole was obtained by alkylation of sodium 3,4,5‐triphenyl‐1,2‐diphosphacyclopentadienide with (–)‐menthyl tosylate. High delocalization within the planar heterocycle of the diphosphole is indicative of low aromaticity. Thus, the [4+2] cycloaddition reaction of this compound with maleic anhydride proceeded under mild conditions with high diastereoselectivity (up to 88 % de) and resulted in the corresponding enantiopure 1,7‐diphosphanorbornadiene as an individual enantiomer. The observed high diastereoselectivity may be explained by thermodynamic control of the reaction.
Synthesis, Characterization and Energetic Properties of 1,3,4‐Oxadiazoles
Authors: Wang Zuoquan , Zhang Hong , Killian Benjamin J. , Jabeen Farukh , Pillai Girinath G. , Berman Heather M. , Mathelier Michael , Sibble Ashani J. , Yeung Justin , Zhou Wenfeng , Steel Peter J. , Hall C. Dennis , Katritzky Alan R.
Published: July 2015

An efficient cyclization between nitro‐substituted benzoic acids and nitro‐substituted benzohydrazides affords 1,3,4‐oxadiazoles. Facile synthesis and a broad substrate scope produce a range of compounds, some of them with potential as high‐energy compounds. Heats of formation (ΔHf) and densities (ρ) were calculated, and heats of decomposition (ΔHd) and combustion (ΔHc) were determined experimentally. The densities of seven of the synthesized compounds were determined by gas pycnometry, and the respective values of detonation velocity (VD), detonation pressure (PD) and specific impulse (ISP) were calculated using the EXPLO5 program. An X‐ray structure of 2‐(2,4‐dinitrophenyl)‐5‐(3,5‐dinitrophenyl)‐1,3,4‐oxadiazole (4n) revealed the non‐planarity of the molecule and afforded a crystal density of 1.698 (at 120 K), close to the pycnometric value of 1.64 at room temperature.
Near‐Infrared Fluorescent 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene Probes for One‐ and Two‐Photon Fluorescence Bio­imaging
Authors: Kim Bosung , Yue Xiling , Sui Binglin , Zhang Xinfu , Xiao Yi , Bondar Mykhailo V. , Sawada Junko , Komatsu Masanobu , Belfield Kevin D.
Published: July 2015

Two new two‐photon absorbing near‐infrared (NIR) emitting 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives, DDC and SDC, were designed for one‐ and two‐photon fluorescence microscopy imaging. Linear and nonlinear photophysical properties, including UV/Vis absorption, fluorescence, excitation anisotropy, photostability, and two‐photon absorption cross sections, of the dyes were investigated to assess the potential of using the new probes as bioimaging agents. Cell viability and colocalization studies of DDC with Lysotracker Red, in COS 7 and HCT 116 cells demonstrated not only low toxicity but also selective targeting of lysosomes. SDC was encapsulated in silica‐based nanoparticles for in vitro and ex vivo fluorescence bioimaging. The nanoparticles were modified with an RGD peptide to target αVβ3 integrin. The nanoprobe exhibited good biocompatibility and highly selective uptake in αVβ3 integrin‐overexpressing cancers.
Electrodeposited Iron as a Biocompatible Material for Microneedle Fabrication
Authors: Miller Philip R. , Boehm Ryan D. , Skoog Shelby A. , Edwards Thayne L. , Rodriguez Mark , Brozik Susan , Brener Igal , Byrd Thomas , Baca Justin T. , Ashley Carlee , Narayan Roger J. , Polsky Ronen
Published: July 2015

Electroplated iron was investigated as a novel material for microneedle fabrication due to its recent success as a biocompatible metal in other medical device applications. Hollow polymer microneedles were made using a laser direct write process that involved two‐photon polymerization of a commercially available Class 2a biocompatible polymer and subsequent electroplating of this structure with iron. Electroplating bath and deposition conditions were shown to affect the mechanical properties of both iron plated microneedles and iron plated on planar polymer substrates. Conditions for depositing the iron coatings were investigated in terms of grain size, residual strain, and elemental composition for planar iron samples. Fracture strength and puncture mechanics into ex vivo porcine skin for iron coated hollow microneedles were examined. Biocompatibility testing was performed using the MTT assay against human epidermal keratinocytes with several concentrations of iron extract to investigate iron as a material used for transdermal applications. Iron coatings proved to significantly improve the strength of the hollow polymer microneedles and sustained structural integrity up to 7 insertions into porcine skin without bending. A commercially available device (Medtronic MiniMed Quick‐Serter®) was used for controlled application of microneedles into porcine skin and estimations of insertion forces for the device were made. Plating conditions were optimized such that an adherent, uniform, and high purity iron coating was deposited onto polymer substrates and polymer microneedles without delamination or fracturing of the microneedles upon ex vivo insertion into porcine skin.
Bismuth Nanoparticles Incorporated Centri‐voltammetry for Phenol Detection
Authors: Ören Tuğba , Tepeli Yudum , Anik Ülkü
Published: July 2015

A novel approach has been developed for phenol detection by combining centri‐voltammetry with bismuth nanoparticles that are used as carrier reagent. The interaction between bismuth and phenol and also the application of centrifugation provide the effective deposition of phenol onto the electrode surface. Direct voltammetric scan without applying any filtration or decantation prevents the analyte loss. As a result, very sensitive results were obtained with linear ranges of 2–75 μM and 100–500 μM and LOD values of 40 nM and 395 nM, respectively. Developed system was also applied for phenol detection in river sample and recovery value was calculated as 115 %.
Quantitation of Cu+‐catalyzed Decomposition of S‐Nitrosoglutathione Using Saville and Electrochemical Detection: a Pronounced Effect of Glutathione and Copper Concentrations
Authors: Ismail Abdulghani , Griveau Sophie , d'Orlyé Fanny , Varenne Anne , Bedioui Fethi
Published: July 2015

S‐nitrosothiols (RSNOs) are composed of nitric oxide (NO) bound to the sulfhydryl group of amino acids of peptides or proteins. There is a great interest for their quantitation in biological fluids as they have a crucial impact on physiological and pathophysiological events. Most analytical methodologies for quantitation of RSNOs are based on their decomposition followed by the detection of the released NO. In order to obtain the optimal sensitivity for each detection method, the total decomposition of RSNOs is highly desired. The decomposition of RSNOs can be obtained by using catalytically active metal ions, such as Cu+, obtained from CuSO4 in presence of a reducing agent such as glutathione (GSH) that is naturally present in biological environment. In this work, we have re‐investigated the decomposition of S‐nitrosoglutathione (GSNO) which is the most abundant in vivo low molecular weight RSNO, with a special emphasis on the effect of CuSO4, GSH, and GSNO concentrations and of their ratio. To this aim, GSNO decomposition optimization was performed by both indirect (Griess assay) and direct (real time electrochemical detection of NO at NO‐microsensor) quantitation methods. Our results show that the ratio between CuSO4, GSH and GSNO should be adjusted to tune the highest decomposition rate of GSNO and the most efficient electrochemical detection of released NO; also it shows the deleterious effect of very high GSH concentration on the detection of GSNO.
An efficient and accurate fully discrete finite element method for unsteady incompressible Oldroyd fluids with large time step
Authors: Guo Yingwen , He Yinnian
Published: July 2015

This paper proposes a second‐order accuracy in time fully discrete finite element method for the Oldroyd fluids of order one. This new approach is based on a finite element approximation for the space discretization, the Crank–Nicolson/Adams–Bashforth scheme for the time discretization and the trapezoid rule for the integral term discretization. It reduces the nonlinear equations to almost unconditionally stable and convergent systems of linear equations that can be solved efficiently and accurately. Here, the numerical simulations for L2, H1 error estimates of the velocity and L2 error estimates of the pressure at different values of viscoelastic viscosities α, different values of relaxation time λ1, different values of null viscosity coefficient μ0 are shown. In addition, two benchmark problems of Oldroyd fluids with different solvent viscosity μ and different relaxation time λ1 are simulated. All numerical results perfectly match with the theoretical analysis and show that the developed approach gives a high accuracy to simulate the Oldroyd fluids under a large time step. Furthermore, the difference and the connection between the Newton fluids and the viscoelastic Oldroyd fluids are displayed. Copyright © 2015 John Wiley & Sons, Ltd.
Impact of Macroeconomic Announcements on US Equity Prices: 2009–2013
Authors: Nadler Daniel , Schmidt Anatoly B.
Published: July 2015

Returns of several US equity exchange‐traded funds on the days of major macroeconomic announcements are examined for the period of January 2009 to July 2013. The ARMA+GARCH model with external linear regression terms that describe announcement events and their surprises is used. It is found that mean daily returns may be notably higher on the announcement days than those for the buy‐and‐hold strategy, though their difference may be not statistically significant. The ISM Manufacturing Reports, Non‐Farm Payrolls, International Trade Balance, Index of Leading Indicators, Housing Starts, and Jobless Claims turn out to be the most statistically significant factors in the model. Three trading strategies that realize daily returns on the various macroeconomic announcement days are compared with the buy‐and‐hold strategy. The choice of announcements with statistically significant regression coefficients yields higher mean daily returns and better Sharpe ratios but possibly lower compound returns. Transaction costs may significantly affect profitability of these trading strategies. Copyright © 2015 John Wiley & Sons, Ltd.
Fuel Pressure Distribution as a Criterion for the Bipolar Plate Geometry Optimization in PEM Fuel Cells, Modeling and Experiment
Authors: Antuñano M. A. Zamora , Encinas A. , García‐Gallegos J. H. , Moller A. Duarte , Jesús A. Marroquín de , Arriaga L. G. , Ramírez J. M. Olivares
Published: July 2015

In this study the pressure distribution homogeneity on the catalytic surface is found to provide a simple and reliable fuel flow parameter that can be used to optimize the bipolar plate geometry and the PEM fuel cell performance. Finite element commercial ANSYS software was used to determine the fuel velocity, pressure and mass distribution on eight different bipolar plate geometries. These geometries were also fabricated and characterized experimentally in order to establish a correlation between the power densities with the fuel flow parameters obtained from the simulations. The results show that a highly uniform pressure distribution of the fuel in the bipolar plate is necessary to obtain higher power densities. Inversely, non‐homogeneous pressure distributions lead to lower power densities. Additionally, the measured power density increases when the geometry dependent effective catalytic surface area increases. These results are interesting since they provide an optimization methodology for PEM fuel cells that simplifies and reduces computing requirements, experimentation and manufacturing time.
B cells expressing CD11b effectively inhibit CD4+ T‐cell responses and ameliorate experimental autoimmune hepatitis in mice
Authors: Liu Xiaoming , Jiang Xuechao , Liu Ronghua , Wang Luman , Qian Tingting , Zheng Yijie , Deng Yuting , Huang Enyu , Xu Fengkai , Wang Ji‐Yang , Chu Yiwei
Published: July 2015

Increasing evidence in recent years has suggested that B cells act as a crucial regulator in autoimmune diseases. However, little is known about their role in autoimmune hepatitis (AIH) and the underlying regulatory mechanisms. In this study, we show that B cells ameliorated experimental AIH (EAH) by suppressing CD4+ T‐cell responses and that CD11b expression on B cells was required for the regulatory function of B cells. In vitro studies reveal that the suppressive function of CD11b was mediated by the impairment of T‐cell antigen receptor (TCR) signaling transduction and the promotion of TCR down‐regulation. Moreover, we show that the increased CD11b expression on B cells was interleukin (IL)−10 dependent and that additional IL‐10 stimulation promoted CD11b expression on B cells, thereby enhancing B‐cell regulatory effects. Conclusion: These findings reveal a previously unrecognized role for CD11b in B‐cell regulatory function and its protective effect on EAH. (Hepatology 2015;62:1563–1575)
Retrospective study of the prevalence and progression of monoclonal gammopathy in HIV positive versus HIV negative patients
Authors: Jou Erin , Gligich Oleg , Chan Alvita C. Y. , Mohan Diwakar , Felsen Uriel R. , Ayyappan Sabarish , Billett Henny H. , Hui Edwin P. , Chan Anthony T. , Raghupathy Radha
Published: July 2015

The significance of HIV associated paraproteins and their risk of progression to hematological malignancies remains unclear. We compared the development of hematological malignancies among HIV+ (n = 266) and HIV− (n = 537) patients with monoclonal gammopathies. HIV+ and HIV− patients with a positive serum protein electrophoresis test (SPEP) were studied. HIV+ SPEP+ were more likely to have faint and oligoclonal paraproteins (F‐SPEP) and less likely to have discrete bands (D‐SPEP) compared to HIV− SPEP+. The incidence of hematological malignancies was significantly lower in the HIV+ compared to the HIV− (6.4% vs 15.4%, p < 0.0002). Upon subgroup analysis, the lower incidence of hematological malignancies was noted for HIV+ patients with F‐SPEP but not for those with D‐SPEP. Copyright © 2015 John Wiley & Sons, Ltd.
Farnesol and Candida albicans: Quorum Sensing or Not Quorum Sensing?
Authors: Krom Bastiaan P. , Levy Niva , Meijler Michael M. , Jabra‐Rizk Mary Ann
Published: July 2015

Quorum sensing (QS) molecules function within communities of single‐cell organisms to allow concerted behavior in response to changing conditions, and certain criteria have been established to determine whether a particular molecule is quorum sensing or not. Farnesol has been identified as a secreted molecule responsible for the inoculum size effect in Candida albicans and synthetic farnesol has been used as a QS molecule in different studies. However, farnesol also exhibits growth inhibitory effects, and so a critical evaluation of farnesol is warranted. Here we review the literature to determine whether or not farnesol can indeed be considered a QS molecule in C. albicans.
Intersex in fishes and amphibians: population implications, prevalence, mechanisms and molecular biomarkers
Authors: Abdel‐moneim Ahmed , Coulter David P. , Mahapatra Cecon T. , Sepúlveda Maria S.
Published: July 2015

Intersex is defined as the abnormal presence of both testicular and ovarian cells in gonads of gonochoristic animals. Its occurrence is widespread and reports on its presence in the gonads of vertebrates continues to increase. In this review, we use standardized terminology to summarize the current knowledge of intersex in gonochoristic fishes and amphibians. We describe the different indices that have been used to assess the severity of intersex and synthesize reports discussing the prevalence of intersex in relation to different types of pollutants. In addition, we evaluate the geographic distribution and chronology of the reported cases of intersex in fishes and amphibians, their pathological descriptions and severity and discuss species sensitivities. We also summarize molecular biomarkers that have been tested for early detection of intersex in wild populations and highlight additional biomarkers that target molecular pathways involved in gonadal development that require further investigation for use in the diagnosis of intersex. Finally, we discuss the needs for future research in this field. Copyright © 2015 John Wiley & Sons, Ltd.
IV and IP administration of rhodamine in visualization of WBC‐BBB interactions in cerebral vessels
Authors: Reichenbach Zachary Wilmer , Li Hongbo , Gaughan John P. , Elliott Melanie , Tuma Ronald
Published: July 2015

Epi‐illuminescence intravital fluorescence microscopy has been employed to study leukocyte‐endothelial interactions in a number of brain pathologies. Historically, dyes such as Rhodamine 6G have been injected intravenously. However, intravenous injections can predispose experimental animals to a multitude of complications and requires a high degree of technical skill. Here, we study the efficacy of injecting Rhodamine 6G into the peritoneum (IP) for the purpose of analyzing leukocyte‐endothelial interactions through a cranial window during real time intravital microscopy. After examining the number of rolling and adherent leukocytes through a cranial window, we found no advantage to the intravenous injection (IV). Additionally, we tested blood from both routes of injection by flow cytometry to gain a very precise picture of the two methods. The two routes of administration failed to show any difference in the ability to detect cells. The study supports the notion that IP Rhodamine 6G works as efficaciously as IV and should be considered a viable alternative in experimental design for investigations employing intravital microscopy. Facilitated intravital studies will allow for more exploration into cerebral pathologies and allow for more rapid translation from the laboratory to the patient with less chance of experimental error from failed IV access. Microsc. Res. Tech. 78:894–899, 2015. © 2015 Wiley Periodicals, Inc.
The composition of mobile matter in a floodplain topsoil: A comparative study with soil columns and field lysimeters
Authors: Fritzsche Andreas , Pagels Britt , Totsche Kai U.
Published: July 2015

Floodplain soils are characterized by frequent and extreme redox changes caused by inundation with river water or imbibition of groundwater. Depending on the duration and extent of inundation, biogeochemical processes run at sub‐/anoxic conditions, which may result in the mobilization and relocation of dissolved and particulate matter within the soil. In this study, we investigated the effect of inundation events on the composition of mobilized matter in the topsoil horizon of a floodplain soil. We conducted experiments with soil columns in the laboratory and gravitational lysimeters in the field to identify redox‐mediated (im)mobilization processes and to estimate their relevance under field conditions. The lysimeters were filled with topsoil monoliths and run under in situ conditions during a ≈ 2.5‐y period. The soil columns were run with the same soil material either under strictly anoxic or mixed oxic–anoxic conditions. Effluents from mixed oxic–anoxic soil were composed fundamentally different [comparably high: Mn, Al, nitrate, sulfate; comparably low: pH, organic C (OC); not detected: Fe, As] compared to effluents from strictly anoxic soil (comparably high: pH, Fe, Mn, OC, As; comparably low: Al; not detected: nitrate, sulfate). Matter, which was mobile under anoxic conditions (e.g., Fe, As, OC), was effectively immobilized as soon as the mobile phase passed anoxic–oxic boundaries within soil (exception: Mn). We assume that the solution in the soil monoliths always passed such anoxic–oxic boundaries during downwards migration independent of lysimeter flooding with river water. This is indicated by the similar composition of the lysimeter seepage water and the effluents from mixed oxic–anoxic soil columns. Both solutions contained “fingerprints” from anoxic (Mn) and oxic conditions (nitrate). Inundations with river water and the duration of these floods (1–22 d) did not affect the composition of the lysimeter seepage water. In conclusion, immediate changes in the composition of the solution, which enters either the subsoil or nearby receiving waters, cannot be expected from regular topsoil flooding.
Selective mass transport of azobenzene‐containing photosensitive films towards or away from the light intensity
Authors: Yadavalli Nataraja Sekhar , König Tobias , Santer Svetlana
Published: July 2015

Here, we report on two photosensitive amorphous polymers showing opposite behavior upon exposure to illumination. The first polymer (PAZO) consists of linear backbone to which azobenzene‐containing side chains are covalently attached, while in the second polymer (azo‐PEI), the azobenzene side chains are attached ionically to a polyelectrolyte backbone. When irradiated through a mask, the PAZO goes away from the intensity maxima, leaving behind topography trenches, while the direction of the mass transport of the azo‐PEI polymer points towards the intensity maxima. This kind of behavior has been reported only for certain liquid crystalline polymers that exhibit in‐phase reaction on illumination, that is, topography maxima coincides with the intensity maxima. Furthermore, flat nanocrystals placed on top of azo‐PEI film was found to be moved together with the mass transport of the underlying polymer film as visualized using in situ atomic force microscopy (AFM) measurements. It was also demonstrated that the two polymer films respond differently on irradiation with the polarization and intensity interference patterns (IPs). To record the kinetic of the surface relief grating formation within two polymers during irradiation with different IPs, we utilized a homemade setup combining the optical part for the generation of IP and AFM. A possible mechanism explaining different responses on the irradiation of amorphous polymers is discussed in the frame of a theoretical model proposed by Saphiannikova et al. (J. Phys. Chem. B 113, 5032–5045 (2009)).
Efficient Raman frequency conversion of high‐power fiber lasers in diamond
Authors: Williams Robert J. , Nold Johannes , Strecker Maximilian , Kitzler Ondrej , McKay Aaron , Schreiber Thomas , Mildren Richard P.
Published: July 2015

We report high‐power frequency conversion of a Yb‐doped fiber laser using a double‐pass pumped external‐cavity diamond Raman oscillator. Pumping with circular polarization is shown to be efficient while facilitating high‐power optical isolation between the pump and Raman laser. We achieved continuous‐wave average power of 154 W with a conversion efficiency of 50.5% limited by backward‐amplified light in the fiber laser. In order to prove further scalability, we achieved a maximum steady‐state Raman‐shifted output of 381 W with 61% conversion efficiency and excellent beam quality using 10 ms pump pulses, approximately a thousand times longer than the transient thermal time‐constant. No power saturation or degradation in beam quality is observed. The results challenge the present understanding of heat deposition in Raman crystals and foreshadow prospects for reduced thermal effects in diamond than originally anticipated. We also report the first experimental evidence for stimulated Brillouin scattering in diamond.

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Modulation bandwidth and energy efficiency of metallic cavity semiconductor nanolasers with inclusion of noise effects
Authors: Ding K. , Diaz J. O. , Bimberg D. , Ning C. Z.
Published: July 2015

Modulation bandwidth and energy efficiency of metallic cavity nanolasers are studied in both small signal and digital modulation formats. Special emphasis is placed on the effects of noise on data rate and energy efficiency. It is found that the data rate for nanolasers of small sizes is severely limited by noise‐induced bit‐error rate. The trade‐off between size‐reduction and noise effects leads to an optimal cavity size to achieve the highest data rate. The energy data‐rate ratio decreases in general with device size, but starts to increase in ultrasmall devices, due to increased threshold current and noise effects. However, relatively high modulation rate and energy efficiency can be achieved in metallic cavity nanolasers. Calculations show that a low energy consumption of 30 fJ/bit at a high data rate of 120 Gbit/s can be realized in nanolasers as small as V = 16 (λ/nr)3 (V is the laser cavity volume). Ultralow energy consumption per bit (<10 fJ/bit) does require smaller devices (V<2.1 (λ/nr)3), while the noise limits the data rate to below 50 Gbit/s. Such a balanced and holistic consideration between device size, data rate, noise effects, and energy efficiency offers new perspectives to nanolaser design strategy for future onchip integrated nanophotonics systems.

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Notch3‐specific inhibition using siRNA knockdown or GSI sensitizes paclitaxel‐resistant ovarian cancer cells
Authors: Kang Haeyoun , Jeong Ju‐Yeon , Song Ji‐Ye , Kim Tae Heon , Kim Gwangil , Huh Jin Hyung , Kwon Ah‐Young , Jung Sang Geun , An Hee Jung
Published: July 2015

Notch signaling plays an important role in ovarian cancer chemoresistance, which is responsible for recurrence. Gamma‐secretase inhibitor (GSI) is a broad‐spectrum Notch inhibitor, but it has serious side effects. The efficacy of Notch3‐specific inhibition in paclitaxel‐resistant ovarian cancers was assessed in this study, which has not yet been evaluated relative to GSI. To analyze the effect of Notch3‐specific inhibition on paclitaxel‐resistant ovarian cancers, we compared cell viability, apoptosis, cell migration, angiogenesis, cell cycle, and spheroid formation after treatment with either Notch3 siRNA or GSI in paclitaxel‐resistant SKpac cells and parental SKOV3 cells. Expression levels of survival, cell cycle, and apoptosis‐related proteins were measured and compared between groups. Notch3 was significantly overexpressed in chemoresistant cancer tissues and cell lines relative to chemosensitive group. In paclitaxel‐resistant cancer cells, Notch inhibition significantly reduced viability, migration, and angiogenesis and increased apoptosis, thereby boosting sensitivity to paclitaxel. Spheroid formation was also significantly reduced. Both Notch3 siRNA‐treated cells and GSI‐treated cells arrested in the G2/M phase of the cell cycle. Proteins of cell survival, cyclin D1 and cyclin D3 were reduced, whereas p21 and p27 were elevated. Both GSI and Notch3 siRNA treatment reduced expression of anti‐apoptotic proteins (BCL‐W, BCL2, and BCL‐XL) and increased expression of pro‐apoptotic proteins (Bad, Bak, Bim, Bid, and Bax). These results indicate that Notch3‐specific inhibition sensitizes paclitaxel‐resistant cancer cells to paclitaxel treatment, with an efficacy comparable to that of GSI. This approach would be likely to avoid the side effects of broad‐spectrum GSI treatment. © 2015 Wiley Periodicals, Inc.