bluuebunny/crossref_metadata_2025 huggingface dataset:
Probabilistic Inferences Under Emotional Stress: How Arousal Affects Decision Processes
Authors: Wichary Szymon , Mata Rui , Rieskamp Jörg
Published: August 2015

Many models of decision making neglect emotional states that could affect individuals' cognitive processes. The present work explores the effect of emotional stress on people's cognitive processes when making probabilistic inferences. Two contrasting hypotheses are tested against one another: the uncertainty‐reduction and attention‐narrowing hypotheses of how emotional stress affects decision making. In the experimental study, emotional stress was induced through the use of highly aversive pictures immediately before each decision. Emotional state was assessed by both subjective (state anxiety, arousal, and pleasantness ratings) and objective (skin conductance) measures. The results show that emotional stress impacts decision making; in particular, emotionally aroused participants seem to have focused on the most important information and selected simpler decision strategies relative to participants in a control condition. The results are in line with the attention‐narrowing hypothesis and suggest that emotional stress can impact decision making through limited predecisional information search and the selection of simpler decision strategies. Copyright © 2015 John Wiley & Sons, Ltd.
Morphological and functional characterization of human induced pluripotent stem cell‐derived neurons (iCell Neurons) in defined culture systems
Authors: Berry Bonnie J. , Akanda Nesar , Smith Alec S.T. , Long Christopher J. , Schnepper Mark T. , Guo Xiufang , Hickman James J.
Published: August 2015

Pre‐clinical testing of drug candidates in animal models is expensive, time‐consuming, and often fails to predict drug effects in humans. Industry and academia alike are working to build human‐based in vitro test beds and advanced high throughput screening systems to improve the translation of preclinical results to human drug trials. Human neurons derived from induced pluripotent stems cells (hiPSCs) are readily available for use within these test‐beds and high throughput screens, but there remains a need to robustly evaluate cellular behavior prior to their incorporation in such systems. This study reports on the characterization of one source of commercially available hiPSC‐derived neurons, iCell® Neurons, for their long‐term viability and functional performance to assess their suitability for integration within advanced in vitro platforms. The purity, morphology, survival, identity, and functional maturation of the cells utilizing different culture substrates and medium combinations were evaluated over 28 days in vitro (DIV). Patch‐clamp electrophysiological data demonstrated increased capacity for repetitive firing of action potentials across all culture conditions. Significant differences in cellular maturity, morphology, and functional performance were observed in the different conditions, highlighting the importance of evaluating different surface types and growth medium compositions for application in specific in vitro protocols. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:1613–1622, 2015
A novel colorimetric assay of β‐D‐glucans in basidiomycete strains by alcian blue dye in a 96‐well microtiter plate
Authors: C. Semedo Magda , Karmali Amin , Fonseca Luís
Published: August 2015

Basidiomycete strains synthesize several types of β‐d‐glucans, which play a major role in the medicinal properties of mushrooms. Therefore, the specific quantification of these β‐d‐glucans in mushroom strains is of great biochemical importance. Because published assay methods for these β‐d‐glucans present some disadvantages, a novel colorimetric assay method for β‐d‐glucan with alcian blue dye was developed. The complex formation was detected by following the decrease in absorbance in the range of 620 nm and by hypsochromic shift from 620 to 606 nm (∼14 nm) in UV‐Vis spectrophotometer. Analysis of variance was used for optimization of the slope of the calibration curve by using the assay mixture containing 0.017% (w/v) alcian blue in 2% (v/v) acetic acid at pH 3.0. The high‐throughput colorimetric assay method on microtiter plates was used for quantification of β‐d‐glucans in the range of 0–0.8 μg, with a slope of 44.15 × 10−2 and a limit of detection of 0.017 μg/well. Recovery experiments were carried out by using a sample of Hericium erinaceus, which exhibited a recovery of 95.8% for β‐1,3‐d‐glucan. The present assay method exhibited a 10‐fold higher sensitivity and a 59‐fold lower limit of detection compared with the published method with congo red. β‐d‐glucans of several mushrooms strains were isolated from fruiting bodies and mycelia, and they were quantified by this assay method. This assay method is fast, specific, simple, and it can be used to quantify β‐d‐glucans from other biological sources. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:1526–1535, 2015
Human Acid β‐Glucosidase Inhibition by Carbohydrate Derived Iminosugars: Towards New Pharmacological Chaperones for Gaucher Disease
Authors: Parmeggiani Camilla , Catarzi Serena , Matassini Camilla , D'Adamio Giampiero , Morrone Amelia , Goti Andrea , Paoli Paolo , Cardona Francesca
Published: August 2015

A collection of carbohydrate‐derived iminosugars belonging to three structurally diversified sub‐classes (polyhydroxylated pyrrolidines, piperidines, and pyrrolizidines) was evaluated for inhibition of human acid β‐glucosidase (glucocerebrosidase, GCase), the deficient enzyme in Gaucher disease. The synthesis of several new pyrrolidine analogues substituted at the nitrogen or α‐carbon atom with alkyl chains of different lengths suggested an interpretation of the inhibition data and led to the discovery of two new GCase inhibitors at sub‐micromolar concentration. In the piperidine iminosugar series, two N‐alkylated derivatives were found to rescue the residual GCase activity in N370S/RecNcil mutated human fibroblasts (among which one up to 1.5‐fold). This study provides the starting point for the identification of new compounds in the treatment of Gaucher disease.
Scaffold‐Hopping of Multicationic Amphiphiles Yields Three New Classes of Antimicrobials
Authors: Mitchell Myles A. , Iannetta Anthony A. , Jennings Megan C. , Fletcher Madison H. , Wuest William M. , Minbiole Kevin P. C.
Published: August 2015

Quaternary ammonium compounds (QACs) are a vital class of antiseptics. Recent investigations into their construction are uncovering novel and potent multicationic variants. Based on a trisQAC precedent, we have implemented a scaffold‐hopping approach to develop alternative QAC architectures that display 1–3 long alkyl chains in specific projections from cyclic and branched core structures bearing 3–4 nitrogen atoms. The preparation of 30 QAC structures allowed for correlation of scaffold structure with antimicrobial activity. We identified QACs with limited conformational flexibility that have improved bioactivity against planktonic bacteria as compared to their linear counterparts. We also confirmed that resistance, as evidenced by an increased minimum inhibitory concentration (MIC) for methicillin‐resistant Staphylococcus aureus (MRSA) compared to methicillin‐susceptible Staphylococcus aureus (MSSA), can reduce efficacy up to 64‐fold for monocationic QACs. Differentiation of antimicrobial and anti‐biofilm activity, however, was not observed, suggesting that these compounds utilize a non‐specific mode of eradication.
Abnormal expression of DNA methyltransferases and genomic imprinting in cloned goat fibroblasts
Authors: Wan Yongjie , Deng Mingtian , Zhang Guomin , Ren Caifang , Zhang Hao , Zhang Yanli , Wang Lizhong , Wang Feng
Published: August 2015

Somatic cell nuclear transfer (SCNT) is a useful way to produce cloned animals. However, SCNT animals exhibit DNA methylation and genomic imprinting abnormalities. These abnormalities may be due to the faulty epigenetic reprogramming of donor cells. To investigate the consequence of SCNT on the genomic imprinting and global methylation in the donor cells, growth patterns and apoptosis of cloned goat fibroblast cells (CGFCs) at passage 7 were determined. Growth patterns in CGFCs were similar to the controls; however, the growth rate in log phase was lower and apoptosis in CGFCs were significantly higher (P < 0.01). In addition, quantitative expression analysis of three DNA methyltransferases (Dnmt) and two imprinted genes (H19, IGF2R) was conducted in CGFCs: Dnmt1 and Dnmt3b expression was significantly reduced (P < 0.01), and H19 expression was decreased sixfold (P < 0.01); however, the expression of Dnmt3a was unaltered and IGF2R expression was significantly increased (P < 0.05). Finally, we used bisulfite sequencing PCR to compare the DNA methylation patterns in differentially methylated regions (DMRs) of H19 and IGF2R. The DMRs of H19 (P < 0.01) and IGF2R (P < 0.01) were both highly methylated in CGFCs. These results indicate that the global genome might be hypomethylated. Moreover, there is an aberrant expression of imprinted genes and DMR methylation in CGFCs.
Diversity‐Oriented Synthesis through Rh‐Catalyzed Selective Transformations of a Novel Multirole Directing Group
Authors: Su Bo , Wei Jiang‐bo , Wu Wen‐lian , Shi Zhang‐jie
Published: August 2015

In the context of transition‐metal‐catalyzed CH functionalization, directing‐group strategy was developed for the improvement of chemical reactivity and selectivity. Recently, to avoid the inherent limitations of traditional mono‐role directing groups, a dual‐role oxidizing‐directing‐group strategy was developed, in which the directing group acts both as directing group and oxidant. Herein, we report a multirole directing group, which possesses multiple reactive sites, exhibits unique reactivity and selectivity, and leads to four different types of products from a single starting material through rhodium‐catalyzed CH activation/alkyne annulation reactions. The excellent product diversity and regio‐ and redox selectivity were well controlled by the tuning of solvents and oxidants.
Recent Advances in the Synthesis and Electrocatalytic Applications of Platinum‐Based Bimetallic Alloy Nanostructures
Authors: Lai Jianping , Luque Rafael , Xu Guobao
Published: August 2015

Pt‐based bimetallic alloy nanomaterials with a low Pt loading can exhibit promising catalytic properties with exciting electrochemical applications. An effective structure control of Pt‐based bimetallic alloy nanomaterials is critical to achieve enhanced catalytic properties. This review article focuses on recent advances in the controllable synthesis and electrocatalytic applications of Pt‐based bimetallic alloy nanostructures. Recent contributions on the controllable synthesis of a rich variety of Pt‐based bimetallic alloy nanostructures, for example, PtPd, PtCu, PtNi, PtCo, and PtFe, and hybrid nanostructures based on Pt‐based bimetallic alloy nanomaterials are summarized. Different Pt‐based bimetallic alloy nano‐electrocatalysts with enhanced activity and durability for different electrocatalytic reactions, such as the fuel cell reaction and the hydrogen evolution reaction, are outlined. Finally, an outlook on future trends and developments is provided.
Black Titania for Superior Photocatalytic Hydrogen Production and Photoelectrochemical Water Splitting
Authors: Zhu Guilian , Yin Hao , Yang Chongyin , Cui Houlei , Wang Zhou , Xu Jijian , Lin Tianquan , Huang Fuqiang
Published: August 2015

To utilize visible‐light solar energy to meet environmental and energy crises, black TiO2 as a photocatalyst is an excellent solution to clean polluted air and water and to produce H2. Herein, black TiO2 with a crystalline core–amorphous shell structure reduced easily by CaH2 at 400 °C is demonstrated to harvest over 80 % solar absorption, whereas white TiO2 harvests only 7 %, and possesses superior photocatalytic performances in the degradation of organics and H2 production. Its water decontamination is 2.4 times faster and its H2 production was 1.7 times higher than that of pristine TiO2. Photoelectrochemical measurements reveal that the reduced samples exhibit greatly improved carrier densities, charge separation, and photocurrent (a 4.5‐fold increase) compared with the original TiO2. Consequently, this facile and versatile method could provide a promising and cost‐effective approach to improve the visible‐light absorption and performance of TiO2 in photocatalysis.
Hierarchically Structured MnO2‐Co/C Nanocomposites: Highly Efficient and Magnetically Recyclable Catalysts for the Aerobic Oxidation of Alcohols
Authors: Zhi Jian , Mitchell Sharon , Pérez‐Ramírez Javier , Reiser Oliver
Published: August 2015

Porous MnO2 microspheres distributed around magnetic carbon‐coated cobalt nanoparticles were developed. The performance of these nanoparticles rivals that of Pd‐based catalysts for the selective oxidation of alcohols. Excellent recyclability was conveniently achieved by magnetic decantation and is demonstrated in ten consecutive cycles with no apparent material or performance losses.
Enhanced Visible‐Light Photoelectrocatalytic Activity of {001}TiO2 Electrodes Assisted with Carbon Quantum Dots
Authors: Zhang Ya‐nan , Tian Hongyi , Zhao Guohua
Published: August 2015

Aiming at further developing the application of highly reactive {001}TiO2 in photoelectrocatalytic oxidation, which is only limited by its response in UV light, carbon quantum dots (CQDs) are introduced to provide the excitation sources for {001}TiO2 through upconversion from visible to UV light. The CQDs/{001}TiO2 photoelectrode is prepared by loading the CQDs on truncated square pyramid‐shaped TiO2 spheres exposed to high‐activity {001} facets, using a simple impregnation–drying method. The results indicate that the CQDs/{001}TiO2 possess enhanced photoelectrocatalytic ability with an increased photocurrent of 12 mA cm−2 and photocurrent decay time of 1.75 s. Compared with pure {001}TiO2, the surface photochemical reaction resistance of CQDs/{001}TiO2 decreases, whereas the number of photogenerated carriers increase greatly. This visible‐light photoelectrocatalytic activity results from the synergistic effect of CQDs and the {001} facet of anatase TiO2.
Electrospinning Synthesis of Porous CoWO4 Nanofibers as an Ultrasensitive, Nonenzymatic, Hydrogen‐Peroxide‐Sensing Interface with Enhanced Electrocatalysis
Authors: Liao Sheng‐Hui , Lu Shi‐Yu , Bao Shu‐Juan , Yu Ya‐Nan , Yu Ling
Published: August 2015

In this work, porous WO3, Co3O4, and CoWO4 nanofibers (NFs) were fabricated by using an electrospinning technique followed by high‐temperature calcination. The different NFs were used to modify biosensor electrodes and detect H2O2 without the help of an enzyme. The electrochemical results indicated that the CoWO4 NF‐based sensor presented a remarkable electrocatalytic activity towards H2O2 oxidation, including lower redox potential, lower detection limit, fast response, as well as the widest linear range among our designed biosensors of this type. Furthermore, we found that the ideal test potential of a nonenzymatic biosensor is closely dependent on the composition of the detected electrode surface, and the test potential has a great effect on the detection linear range of nanomaterial‐based biosensors. The results of this work provide a new way to explore excellent nanomaterials for modifying nonenzymatic biosensor electrodes.
Highly Stable PEMFC Electrodes Based on Electrospun Antimony‐Doped SnO2
Authors: Cavaliere Sara , Jiménez‐Morales Ignacio , Ercolano Giorgio , Savych Iuliia , Jones Deborah , Rozière Jacques
Published: August 2015

High durability and activity for the oxygen reduction reaction were demonstrated for oxide‐supported platinum catalysts. The supports were antimony‐doped SnO2 (ATO) fibres‐in‐tubes obtained by electrospinning and subsequent calcination. The doping with antimony instead of the already‐reported niobium, allowed the preparation of tin oxide with electrical conductivity that was similar to carbon, which also had an increased electrocatalyst loading. Platinum nanoparticles supported on electrospun ATO demonstrated higher electrochemical stability and comparable mass activity to commercial Pt/C during ex situ potential cycling. The in situ fuel cell tests also revealed improved corrosion resistance with no noticeable degradation of the oxide‐based membrane electrode assembly (MEA), but a slightly lower performance compared to the MEA with carbon‐supported catalysts.
Mechanism of Thioether Oxidation over Di‐ and Tetrameric Ti Centres: Kinetic and DFT Studies Based on Model Ti‐Containing Polyoxometalates
Authors: Skobelev Igor Y. , Zalomaeva Olga V. , Kholdeeva Oxana A. , Poblet Josep M. , Carbó Jorge J.
Published: August 2015

The oxidation of thioethers by the green oxidant aqueous H2O2 catalysed by the tetratitanium‐substituted Polyoxometalate (POM) (Bu4N)8[{γ‐SiTi2W10O36(OH)2}2(μ‐O)2], as a model catalyst comprising tetrameric titanium centres, was investigated by kinetic modelling and DFT calculations. Several mechanisms of sulfoxidation were evaluated by using methyl phenyl sulfide (PhSMe) as a model substrate in the experiments and dimethyl sulfide in the calculations. The first mechanism assumes that the active hydroperoxo species forms directly through interaction of the Ti2(μ‐OH)2 group in [{γ‐SiTi2W10O36(OH)2}2(μ‐O)2]8− (1 D) with H2O2. The second mechanism includes hydrolysis of Ti‐O‐Ti bonds linking two γ‐Keggin units in structure 1 D to produce the monomer [(γ‐SiW10Ti2O38H2)(OH)2]4− (1 M), followed by the formation of an active hydroperoxo species upon interaction of the Ti hydroxo group with H2O2. Both kinetic modelling and DFT calculations support the mechanism through the monomeric species that involves the hydrolysis step. According to the DFT studies the activation of H2O2 by compound 1 M is preferred by 6.5 kcal mol−1 with respect to anion 1 D due to the more flexible Ti environment of the terminal Ti hydroxo group in 1 M. The calculations also indicate that for the „monomeric“ mechanism two pathways are operative: the mono‐ and the multinuclear pathway. In the mononuclear mechanism, the active group is the terminal TiOH group, whereas in the multinuclear path the active group is the bridging Ti2(μ‐OH) moiety. Moreover, unlike previous studies, the sulfoxidation is preferred through a β‐oxygen atom transfer from the Ti hydroperoxo group because the α‐oxygen atom transfer leads to an unfavourable seven‐fold coordinated Ti environment in the transition state. Finally, we have generalised these results to other Ti‐containing POMs: the Ti‐monosubstituted α‐Keggin ion [α‐PTi(OH)W11O39]4− and the dititanium‐substituted sandwich‐type ion [Ti2(OH)2As2W19O67]8−.
Rearrangement Reactions of Tritylcarbenes: Surprising Ring Expansion and Computational Investigation
Authors: Banert Klaus , Hagedorn Manfred , Pester Tom , Siebert Nicole , Staude Cornelius , Tchernook Ivan , Rathmann Katharina , Hollóczki Oldamur , Friedrich Joachim
Published: August 2015

As a rule, acetylides and sulfonyl azides do not undergo electrophilic azide transfer because 1,2,3‐triazoles are usually formed. We show now that treatment of tritylethyne with butyllithium followed by exposure to 2,4,6‐triisopropylbenzenesulfonyl azide leads to products that are easily explained through the generation of short‐lived tritylethynyl azide and its secondary product cyanotritylcarbene. Furthermore, it is demonstrated that tritylcarbenes generally do not produce triphenylethenes exclusively, as was stated in the literature. Instead, these carbenes always yielded also (diphenylmethylidene)cycloheptatrienes (heptafulvenes) as side products. This result is supported by static DFT, coupled cluster, and ab initio molecular dynamics calculations. From these investigations, the fused bicyclobutane intermediate was found to be essential for heptafulvene formation. Although the bicyclobutane is also capable of rearranging to the triphenylethene product, only the heptafulvene pathway is reasonable from the energetics. The ethene is formed straight from cyanotritylcarbene.
An Efficient p–n Heterojunction Photocatalyst Constructed from a Coordination Polymer Nanoplate and a Partically Reduced Graphene Oxide for Visible‐Light Hydrogen Production
Authors: Xu Xinxin , Lu Tingting , Liu Xiaoxia , Wang Xiuli
Published: August 2015

A new p–n heterojunction photocatalyst has been synthesized successfully through chemical‐bond‐mediated combination of coordination polymer nanoplates (CPNPs) and partially reduced graphene oxide (PRGO) with a simple colloidal blending process. Photocatalytic H2 production by the p–n heterojunction photocatalyst PRGO/CPNP was investigated under visible‐light irradiation, which illustrates that PRGO/CPNP exhibits a much higher photocatalytic H2 production rate than neat the CPNPs. The improvement of this photocatalytic property can be attributed to the inner electrical field formed in the p–n heterojunction, which impedes recombination of photogenerated electrons and holes. In PRGO/CPNP, the existence of the p–n heterojunction has been confirmed by electrochemical methods clearly. For PRGO/CPNP, the reductive degree of the PRGO has a great influence on the H2 production rate and an ideal condition to get a PRGO/CPNP photocatalyst with higher performance has been obtained.
Bamboo‐Like Nitrogen‐Doped Carbon Nanotubes with Co Nanoparticles Encapsulated at the Tips: Uniform and Large‐Scale Synthesis and High‐Performance Electrocatalysts for Oxygen Reduction
Authors: Cao Tai , Wang Dingsheng , Zhang Jiatao , Cao Chuanbao , Li Yadong
Published: August 2015

In recent years, various non‐precious metal electrocatalysts for the oxygen reduction reaction (ORR) have been extensively investigated. The development of an efficient and simple method to synthesize non‐precious metal catalysts with ORR activity superior to that of Pt is extremely significant for large‐scale applications of fuel cells. Here, we develop a facile, low‐cost, and large‐scale synthesis method for uniform nitrogen‐doped (N‐doped) bamboo‐like CNTs (NBCNT) with Co nanoparticles encapsulated at the tips by annealing a mixture of cobalt acetate and melamine. The uniform NBCNT shows better ORR catalytic activity and higher stability in alkaline solutions as compared with commercial Pt/C and comparable catalytic activity to Pt/C in acidic media. NBCNTs exhibit outstanding ORR catalytic activity due to high defect density, uniform bamboo‐like structure, and the synergistic effect between the Co nanoparticles and protective graphitic layers. This facile method to synthesize catalysts, which is amenable to the large‐scale commercialization of fuel cells, will open a new avenue for the development of low‐cost and high‐performance ORR catalysts to replace Pt‐based catalysts for applications in energy conversion.
Fluorogenic Strain‐Promoted Alkyne–Diazo Cycloadditions
Authors: Friscourt Frédéric , Fahrni Christoph J. , Boons Geert‐Jan
Published: August 2015

Fluorogenic reactions, in which non‐ or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl‐DIBO) can undergo fast strain‐promoted cycloaddition reactions under catalyst‐free conditions with azides, nitrones, nitrile oxides, as well as mono‐ and disubstituted diazo‐derivatives. Although the reaction with nitrile oxides, nitrones, and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H‐pyrazole derivatives that exhibited an approximately 160‐fold fluorescence enhancement over Fl‐DIBO combined with a greater than 10 000‐fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H‐pyrazoles, which are formed by reaction with disubstituted diazo‐derivatives, is likely due to the presence of energetically low‐lying (n,π*) states. The fluorogenic probe Fl‐DIBO was successfully employed for the labeling of diazo‐tagged proteins without detectable background signal. Diazo‐derivatives are emerging as attractive reporters for the labeling of biomolecules, and the studies presented herein demonstrate that Fl‐DIBO can be employed for visualizing such biomolecules without the need for probe washout.
Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions
Authors: Camps Pelayo , Gómez Tània , Otermin Ane , Font‐Bardia Mercè , Estarellas Carolina , Luque Francisco Javier
Published: August 2015

Two domino Diels–Alder adducts were obtained from 3,7‐bis(cyclopenta‐2,4‐dien‐1‐ylidene)‐cis‐bicyclo[3.3.0]octane and dimethyl acetylenedicarboxylate or N‐methylmaleimide under microwave irradiation. From the first adduct, a C20H24 diene with C2v symmetry was obtained by Zn/AcOH reduction, hydrolysis, oxidative decarboxylation, and selective hydrogenation. Photochemical [2+2] cycloaddition of this diene gave a thermally unstable cyclobutane derivative, which reverts to the diene. However, both the diene and the cyclobutane derivatives could be identified by X‐ray diffraction analysis upon irradiation of the diene crystal. New six‐membered rings are formed upon the transannular addition of bromine or iodine to the diene. The N‐type selectivity of the addition was examined by theoretical calculations, which revealed the distinct susceptibility of the doubly bonded carbon atoms to the bromine attack.
An N‐Acetyl Cysteine Ruthenium Tricarbonyl Conjugate Enables Simultaneous Release of CO and Ablation of Reactive Oxygen Species
Authors: Seixas João D. , Chaves‐Ferreira Miguel , Montes‐Grajales Diana , Gonçalves Ana M. , Marques Ana R. , Saraiva Lígia M. , Olivero‐Verbel Jesus , Romão Carlos C. , Bernardes Gonçalo J. L.
Published: August 2015

We have designed and synthesised a [Ru(CO)3Cl2(NAC)] pro‐drug that features an N‐acetyl cysteine (NAC) ligand. This NAC carbon monoxide releasing molecule (CORM) conjugate is able to simultaneously release biologically active CO and to ablate the concurrent formation of reactive oxygen species (ROS). Complexes of the general formulae [Ru(CO)3(L)3]2+, including [Ru(CO)3Cl(glycinate)] (CORM‐3), have been shown to produce ROS through a water–gas shift reaction, which contributes significantly, for example, to their antibacterial activity. In contrast, NAC‐CORM conjugates do not produce ROS or possess antibacterial activity. In addition, we demonstrate the synergistic effect of CO and NAC both for the inhibition of nitric oxide (formation) and in the expression of tumour‐necrosis factor (TNF)‐α. This work highlights the advantages of combining a CO‐releasing scaffold with the anti‐oxidant and anti‐inflammatory drug NAC in a unique pro‐drug.
Photolithographic Encoding of Metal Complexes
Authors: Lang Christiane , Bestgen Sebastian , Welle Alexander , Müller Rouven , Roesky Peter W. , Barner‐Kowollik Christopher
Published: August 2015

A platform technology for the creation of spatially resolved surfaces encoded with a monolayer consisting of different metal complexes was developed. The concept entails the light‐triggered activation of a self‐ assembled monolayer (SAM) of UV‐labile anchors, that is, phenacylsulfides, and the subsequent cycloaddition of selected diene‐functionalized metal complexes at defined areas on the surface. The synthesis and characterization of the metal complexes for the UV‐light assisted anchoring on the surface and a detailed study of a short‐chain oligomer model system in solution confirm the high efficiency of the photoreaction. The hybrid materials obtained by this concept can potentially be utilized for the design of highly valuable catalytic or (opto‐)electronic devices.
Divergent Gold(I)‐Catalyzed Skeletal Rearrangements of 1,7‐Enynes
Authors: Meiß Rebecca , Kumar Kamal , Waldmann Herbert
Published: August 2015

The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n‐enynes (n=5–7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6‐enynes, readily accessible homologous 1,7‐enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all‐carbon 1,7‐enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7‐enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro‐anthracenes through a novel dehydrogenative Diels–Alder reaction.
Membrane‐Active Small Molecules: Designs Inspired by Antimicrobial Peptides
Authors: Ghosh Chandradhish , Haldar Jayanta
Published: August 2015

Infectious diseases continue to be one of the major contributors to human morbidity. The rapid rate at which pathogenic microorganisms have developed resistance against frontline antimicrobials has compelled scientists to look for new alternatives. Given their vast antimicrobial repertoire, substantial research effort has been dedicated toward the development of antimicrobial peptides (AMPs) as alternative drugs. However, inherent limitations of AMPs have driven substantial efforts worldwide to develop synthetic mimics of AMPs. This review focuses on the progress that has been made toward the development of small molecules that emulate the properties of AMPs, both in terms of design and biological activity. Herein we provide an extensive discussion of the structural features of various designs and we examine biological properties that have been exploited. Furthermore, we raise a number of questions for which the field has yet to provide solutions and discuss possible future research directions that remain either unexploited or underexploited.
Particle transport in the human respiratory tract: formulation of a nodal inverse distance weighted Eulerian–Lagrangian transport and implementation of the Wind–Kessel algorithm for an oral delivery
Authors: Kannan Ravishekar , Guo Peng , Przekwas Andrzej
Published: August 2015

This paper is the first in a series wherein efficient computational methods are developed and implemented to accurately quantify the transport, deposition, and clearance of the microsized particles (range of interest: 2 to 10 µm) in the human respiratory tract. In particular, this paper (part I) deals with (i) development of a detailed 3D computational finite volume mesh comprising of the NOPL (nasal, oral, pharyngeal and larynx), trachea and several airway generations; (ii) use of CFD Research Corporation's finite volume Computational Biology (CoBi) flow solver to obtain the flow physics for an oral inhalation simulation; (iii) implement a novel and accurate nodal inverse distance weighted Eulerian–Lagrangian formulation to accurately obtain the deposition, and (iv) development of Wind–Kessel boundary condition algorithm. This new Wind–Kessel boundary condition algorithm allows the ‘escaped’ particles to reenter the airway through the outlets, thereby to an extent accounting for the drawbacks of having a finite number of lung generations in the computational mesh. The deposition rates in the NOPL, trachea, the first and second bifurcation were computed, and they were in reasonable accord with the Typical Path Length model. The quantitatively validated results indicate that these developments will be useful for (i) obtaining depositions in diseased lungs (because of asthma and COPD), for which there are no empirical models, and (ii) obtaining the secondary clearance (mucociliary clearance) of the deposited particles. Copyright © 2015 John Wiley & Sons, Ltd.
Multiple‐Site SO2‐Capture Ionic Liquids with Nearly Uniform Site Performance
Authors: Tang Huarong , Lu Dongmei
Published: August 2015

We propose a series of azolium poly(azolyl)borate ionic liquids (ILs) for reversible SO2 capture. Density functional calculations demonstrate that the designed borate anions can strongly bond to SO2 at multiple sites with nearly uniform binding energies. Thus, as well as high overall uptakes, the ILs can achieve much higher effective uptakes (the uptake difference between absorption and desorption conditions) than existing SO2‐capture reagents. The larger size of the borate anions, the evenly distributed negative charge among the azolyl rings, and the blocking of the conjugation by the tetrahedral boron concertedly reduce absorbate–absorbate repulsion, which leads to a large disparity among binding sites in other multiple‐site SO2 sorbents.
Bournonite PbCuSbS3: Stereochemically Active Lone‐Pair Electrons that Induce Low Thermal Conductivity
Authors: Dong Yongkwan , Khabibullin Artem R. , Wei Kaya , Salvador James R. , Nolas George S. , Woods Lilia M.
Published: August 2015

An understanding of the structural features and bonding of a particular material, and the properties these features impart on its physical characteristics, is essential in the search for new systems that are of technological interest. For several relevant applications, the design or discovery of low thermal conductivity materials is of great importance. We report on the synthesis, crystal structure, thermal conductivity, and electronic‐structure calculations of one such material, PbCuSbS3. Our analysis is presented in terms of a comparative study with Sb2S3, from which PbCuSbS3 can be derived through cation substitution. The measured low thermal conductivity of PbCuSbS3 is explained by the distortive environment of the Pb and Sb atoms from the stereochemically active lone‐pair s2 electrons and their pronounced repulsive interaction. Our investigation suggests a general approach for the design of materials for phase‐change‐memory, thermal‐barrier, thermal‐rectification and thermoelectric applications, as well as other functions for which low thermal conductivity is purposefully sought.
Sonochemical Synthesis of Layered Copper Hydroxy Nitrate Nanosheets
Authors: Anandan Sambandam , Wu Jerry J. , Ashokkumar Muthupandian
Published: August 2015

Sonochemical reduction of copper nitrate, using 20 kHz ultrasound in aqueous solutions in the presence of urea, led to the formation of layered copper hydroxy nitrate nanosheets, as evidenced by scanning and transmission electron microscopy images. Fourier‐transform infrared, X‐ray diffraction, and X‐ray photoelectron spectroscopy analyses were used to characterize layered Cu2(OH)3NO3 nanosheets. The ultrasound‐assisted progressive hydrolysis of urea and in situ formation of Cu(0) through the sonochemical reduction process induced homogeneous nucleation and crystallization of layered Cu2(OH)3NO3 nanosheets.
Immobilization of a Molecular Ruthenium Catalyst on Hematite Nanorod Arrays for Water Oxidation with Stable Photocurrent
Authors: Fan Ke , Li Fusheng , Wang Lei , Daniel Quentin , Chen Hong , Gabrielsson Erik , Sun Junliang , Sun Licheng
Published: August 2015

Photoelectrochemical (PEC) cells for light‐driven water splitting are prepared using hematite nanorod arrays on conductive glass as the photoanode. These devices improve the photocurrent of the hematite‐based photoanode for water splitting, owing to fewer surface traps and decreased electron recombination resulting from the one‐dimensional structure. By employing a molecular ruthenium co‐catalyst, which contains a strong 2,6‐pyridine‐dicarboxylic acid anchoring group at the hematite photoanode, the photocurrent of the PEC cell is enhanced with high stability for over 10 000 s in a 1 m KOH solution. This approach can pave a route for combining one‐dimensional nanomaterials and molecular catalysts to split water with high efficiency and stability.
Rational Design of an Electron‐Reservoir PtII Complex for Efficient Photocatalytic Hydrogen Production from Water
Authors: Whang Dong Ryeol , Park Soo Young
Published: August 2015

Herein we report a PtII complex containing a 4,4′‐bis[4‐(triphenylsilyl)phenyl]‐2,2′‐bipyridine ligand as a molecular catalyst for water splitting. Systematic studies of the electrochemical and electronic properties of this catalyst, in comparison with two control complexes, reveal electron‐reservoir characteristics upon two‐electron reduction. A turnover number of 510 000 was recorded by employing this complex as a water reduction catalyst in combination with a state‐of‐the‐art photosensitizer and N,N‐dimethylaniline as a sacrificial electron donor, which represents a large improvement over the control complexes that do not contain the tetraphenylsilyl ligand substitution.
Does parental divorce moderate the heritability of body dissatisfaction? An extension of previous gene–environment interaction effects
Authors: O'Connor Shannon M. , Klump Kelly L. , VanHuysse Jessica L. , McGue Matt , Iacono William
Published: August 2015

Objective

Previous research suggests that parental divorce moderates genetic influences on body dissatisfaction. Specifically, the heritability of body dissatisfaction is higher in children of divorced versus intact families, suggesting possible gene–environment interaction effects. However, prior research is limited to a single, self‐reported measure of body dissatisfaction. The primary aim of this study was to examine whether these findings extend to a different dimension of body dissatisfaction: body image perceptions.

Method

Participants were 1,534 female twins from the Minnesota Twin Family Study, aged 16–20 years. The Body Rating Scale (BRS) was used to assess body image perceptions.

Results

Although BRS scores were heritable in twins from divorced and intact families, the heritability estimates in the divorced group were not significantly greater than estimates in the intact group. However, there were differences in nonshared environmental effects, where the magnitude of these environmental influences was larger in the divorced as compared with the intact families.

Discussion

Different dimensions of body dissatisfaction (i.e., negative self‐evaluation versus body image perceptions) may interact with environmental risk, such as parental divorce, in discrete ways. Future research should examine this possibility and explore differential gene–environment interactions using diverse measures. © 2015 Wiley Periodicals, Inc. (Int J Eat Disord 2016; 49:186–190).
Indices for assessing coral reef fish biodiversity: the need for a change in habits
Authors: Loiseau Nicolas , Gaertner Jean‐Claude
Published: August 2015

We present the first representative and quantified overview of the indices used worldwide for assessing the biodiversity of coral reef fishes. On this basis, we discuss the suitability and drawbacks of the indices most widely used in the assessment of coral fish biodiversity. An extensive and systematic survey of the literature focused on coral reef fish biodiversity was conducted from 1990 up to the present. We found that the multicomponent aspect of biodiversity, which is considered as a key feature of biodiversity for numerous terrestrial and marine ecosystems, has been poorly taken into account in coral reef fish studies. Species richness is still strongly dominant while other diversity components, such as functional diversity, are underestimated even when functional information is available. We also demonstrate that the reason for choosing particular indices is often unclear, mainly based on empirical rationales and/or the reproduction of widespread habits, but generally with no clear relevance with regard to the aims of the studies. As a result, the most widely used indices (species richness, Shannon, etc.) would appear to be poorly suited to meeting the main challenges facing the monitoring of coral reef fish biodiversity in the future. Our results clearly show that coral reef scientists should rather take advantage of the multicomponent aspect of biodiversity. To facilitate this approach, we propose general guidelines to serve as a basis for the selection of indices that provide complementary and relevant information for monitoring the response of coral reef fish biodiversity in the face of structuring factors (natural or anthropic). The aim of these guidelines was to achieve a better match between the properties of the selected indices and the context of each study (e.g. expected effect of the main structuring factors, nature of data available).
Does breeding population trajectory and age of nesting females influence disparate nestling sex ratios in two populations of Cooper's hawks?
Authors: Rosenfield Robert N. , Stout William E. , Giovanni Matthew D. , Levine Noah H. , Cava Jenna A. , Hardin Madeline G. , Haynes Taylor G.
Published: August 2015

Offspring sex ratios at the termination of parental care should theoretically be skewed toward the less expensive sex, which in most avian species would be females, the smaller gender. Among birds, however, raptors offer an unusual dynamic because they exhibit reversed size dimorphism with females being larger than males. And thus theory would predict a preponderance of male offspring. Results for raptors and birds in general have been varied although population‐level estimates of sex ratios in avian offspring are generally at unity. Adaptive adjustment of sex ratios in avian offspring is difficult to predict perhaps in part due to a lack of life‐history details and short‐term investigations that cannot account for precision or repeatability of sex ratios across time. We conducted a novel comparative study of sex ratios in nestling Cooper's hawks (Accipiter cooperii) in two study populations across breeding generations during 11 years in Wisconsin, 2001–2011. One breeding population recently colonized metropolitan Milwaukee and exhibited rapidly increasing population growth, while the ex‐Milwaukee breeding population was stable. Following life‐history trade‐off theory and our prediction regarding this socially monogamous species in which reversed sexual size dimorphism is extreme, first‐time breeding one‐year‐old, second‐year females in both study populations produced a preponderance of the smaller and cheaper sex, males, whereasASY(after‐second‐year), ≥2‐year‐old females in Milwaukee produced a nestling sex ratio near unity and predictably therefore a greater proportion of females compared toASYfemales in ex‐Milwaukee who produced a preponderance of males. Adjustment of sex ratios in both study populations occurred at conception. Life histories and selective pressures related to breeding population trajectory in two age cohorts of nesting female Cooper's hawk likely vary, and it is possible that these differences influenced the sex ratios we documented for two age cohorts of female Cooper's hawks in Wisconsin.
Soil permeability, aggregate stability and root growth: a pot experiment from a soil bioengineering perspective
Authors: Vergani C. , Graf F.
Published: August 2015

Assessing the joint development of vegetation cover and soil properties is crucial to evaluate the efficiency of soil bioengineering techniques, especially during the most critical initial phase of vegetation colonization. We set up a laboratory experiment to quantify and disentangle the effect ofAlnus incanaroots on soil permeability and aggregate stability. Plants were grown in pots in a climate chamber for four different growing periods (1, 2, 4 and 8 months). Pots were filled with a soil coming from a moraine of a landslide area in Central Switzerland. After each growing period, surface permeability, soil volume permeability and soil aggregate stability were measured together with the development of the root systems. Our results show that alder roots significantly improve both surface and whole soil volume permeability already after 2 months of growth. Nevertheless, an increase in root length density does not necessarily correspond to an increase in permeability. We could set as a threshold a root length density of 0.1 cm/cm3until which an increase in root development corresponds to an increase in soil permeability, whereas after this threshold we observed a decrease in soil permeability. A significant increase in soil aggregate stability could be observed only with a root length density of 2 cm/cm3. No obvious correlation between soil permeability and aggregate stability could be found. Future work should validate these laboratory results with field data. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.
Chemical Aspects of the Generation, Trapping, and Decay of Atomic Hydrogen in AlF3 and CaF2
Authors: Stößer Reinhard , Ahrens Mike , Scholz Gudrun
Published: August 2015

Hydrogen atoms were generated in the matrices AlF3 and CaF2 at room temperature by ionizing radiation (γ and UV) and were investigated by electron paramagnetic resonance spectroscopy. To gain information on the nature of the hydrogen precursors and hydrogen traps within the solid matrices, studies regarding defined thermal and chemical influence, as well as mechanical impact on the fluoridic matrices before and after irradiation were the focus of this work. Impurities such as HO– and hydrocarbons were identified as potential precursors. The hydrogen traps were characterized by means of their spatial distribution within the different samples and by their energetic states (“trap‐depth”). In this respect, the rate constants, which were determined for different temperatures, turned out to be a valuable tool. Similarities and differences regarding the generation and stabilization of atomic hydrogen in AlF3 and CaF2 were worked out. Also, the influence of the type of ionizing radiation was elucidated. Whereas the comparison of AlF3 and CaF2 was dominated by similarities, significant differences were found for rather molecular siloxane cages R8Si8O12, especially regarding their reaction upon UV excitation and the possibility to resolve super‐hyperfine splittings.
Photoactivation of Butyric Acid from 6‐Aminobenzocoumarin Cages
Authors: Soares Ana M. S. , Hungerford Graham , Costa Susana P. G. , Gonçalves M. Sameiro T.
Published: August 2015

A new benzocoumarin bearing an amino group is proposed as a photocleavable protecting group for carboxylic acids. The novel heterocycle, 6‐amino‐4‐chloromethyl‐2‐oxo‐2H‐naphtho[1,2‐b]pyran was used in the preparation of ester conjugates of butyric acid, and of the corresponding mono‐ and dimethylated or ethylated derivatives. The photolability of the ester conjugates was studied by irradiation at selected wavelengths in methanol/HEPES buffer (80:20) solutions, and the release of butyric acid was followed with HPLC/UV and 1H NMR monitoring. Release of the carboxylic acid was faster for the monoalkylated derivatives (approximately within 20 min), at the longer wavelengths of irradiation (350 and 419 nm). The photophysics of the heterocyclic conjugates was also evaluated by both steady state and time‐resolved methods.
Modular Synthesis of Elongated Phosphonate Bipyridines
Authors: Braumüller Markus , Sorsche Dieter , Wunderlin Markus , Rau Sven
Published: August 2015

The synthesis and the photophysical properties of a series of bpy‐R2 derivatives L1–L3 (bpy = 2,2′‐bipyridine, R represents the substitution at the 4‐ and 4′‐positions of the bpy) are described. R includes phosphonic ester groups as precursors for potent phosphonate anchoring groups, which enable immobilization on transition metal oxide semiconductor surfaces for applications like dye‐sensitized solar cells (DSSCs) or dye‐sensitized photoelectrosynthesis cells (DSPECs). The ligands L1–L3 differ in the length of conjugated linker units between bpy core and anchoring groups. Phenylene and triazole moieties serve as building blocks for linker elongation. The resulting adjustability of the distance between semiconductor and chromophore represents a viable route to improve cell efficiency, as it will allow tuning of charge carrier recombination and dye aggregation. Furthermore the photophysical studies of the free ligands reveal a pronounced effect of the aryl substitution. The solid‐state structures of L1 and L2 are reported within this contribution, enabling the determination of distances between bipyridine nitrogen donor and anchoring group.