bluuebunny/crossref_metadata_2025 huggingface dataset:
Recent Developments in Enzymatic Synthesis of Modified Sialic Acid Derivatives
Authors: Yu Ching‐Ching , Withers Stephen G.
Published: May 2015

Sialic acid‐containing glycans play important roles in biology, but their synthesis by standard chemical approaches is challenging. Enzymatic assembly is generally a better approach. In the last two decades, a number of bacterial sialyltransferases (STs) and trans‐sialidases have been identified and a number of them found to exhibit broad substrate specificity. In this review, we will focus on the donor and acceptor substrate specificities of these enzymes along with the enzymatic routes employed to prepare sialosides bearing modifications at specific positions on the sialic acid carbon skeleton. Understanding the substrate tolerance of these enzymes will help researchers to choose the best biocatalyst for the assembly of specific sialosides, which can be valuable tools in the study of or inhibition of sialidases and STs and sialic acid‐binding proteins. In addition, the ability to study these processes using synthetic sialylated glycans will lead to a greater understanding of their biology and will lead to new therapeutic targets.

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Flexible Ion‐Conducting Composite Membranes for Lithium Batteries
Authors: Aetukuri Nagaphani B. , Kitajima Shintaro , Jung Edward , Thompson Leslie E. , Virwani Kumar , Reich Maria‐Louisa , Kunze Miriam , Schneider Meike , Schmidbauer Wolfgang , Wilcke Winfried W. , Bethune Donald S. , Scott J. Campbell , Miller Robert D. , Kim Ho‐Cheol
Published: May 2015

The use of metallic lithium anodes enables higher energy density and higher specific capacity Li‐based batteries. However, it is essential to suppress lithium dendrite growth during electrodeposition. Li‐ion‐conducting ceramics (LICC) can mechanically suppress dendritic growth but are too fragile and also have low Li‐ion conductivity. Here, a simple, versatile, and scalable procedure for fabricating flexible Li‐ion‐conducting composite membranes composed of a single layer of LICC particles firmly embedded in a polymer matrix with their top and bottom surfaces exposed to allow for ionic transport is described. The membranes are thin (<100 μm) and possess high Li‐ion conductance at thicknesses where LICC disks are mechanically unstable. It is demonstrated that these membranes suppress Li dendrite growth even when the shear modulus of the matrix is lower than that of lithium. It is anticipated that these membranes enable the use of metallic lithium anodes in conventional and solid‐state Li‐ion batteries as well as in future LiS and LiO2 batteries.
Common genetic variation and schizophrenia polygenic risk influence neurocognitive performance in young adulthood
Authors: Hatzimanolis Alex , Bhatnagar Pallav , Moes Anna , Wang Ruihua , Roussos Panos , Bitsios Panos , Stefanis Costas N. , Pulver Ann E. , Arking Dan E. , Smyrnis Nikolaos , Stefanis Nicholas C. , Avramopoulos Dimitrios
Published: May 2015

Neurocognitive abilities constitute complex traits with considerable heritability. Impaired neurocognition is typically observed in schizophrenia (SZ), whereas convergent evidence has shown shared genetic determinants between neurocognition and SZ. Here, we report a genome‐wide association study (GWAS) on neuropsychological and oculomotor traits, linked to SZ, in a general population sample of healthy young males (n = 1079). Follow‐up genotyping was performed in an identically phenotyped internal sample (n = 738) and an independent cohort of young males with comparable neuropsychological measures (n = 825). Heritability estimates were determined based on genome‐wide single‐nucleotide polymorphisms (SNPs) and potential regulatory effects on gene expression were assessed in human brain. Correlations with general cognitive ability and SZ risk polygenic scores were tested utilizing meta‐analysis GWAS results by the Cognitive Genomics Consortium (COGENT) and the Psychiatric Genomics Consortium (PGC‐SZ). The GWAS results implicated biologically relevant genetic loci encoding protein targets involved in synaptic neurotransmission, although no robust individual replication was detected and thus additional validation is required. Secondary permutation‐based analysis revealed an excess of strongly associated loci among GWAS top‐ranked signals for verbal working memory (WM) and antisaccade intra‐subject reaction time variability (empirical P < 0.001), suggesting multiple true‐positive single‐SNP associations. Substantial heritability was observed for WM performance. Further, sustained attention/vigilance and WM were suggestively correlated with both COGENT and PGC‐SZ derived polygenic scores. Overall, these results imply that common genetic variation explains some of the variability in neurocognitive functioning among young adults, particularly WM, and provide supportive evidence that increased SZ genetic risk predicts neurocognitive fluctuations in the general population. © 2015 The Authors American Journal of Medical Genetics Part B: Neuropsychiatric Genetics Published by Wiley Periodicals, Inc.
Hemorrhagic shock due to ruptured left and right gastric artery aneurysm
Authors: Nishimura Takeshi , Sakata Hiroyuki , Yamada Taihei , Osako Takaaki , Kohama Keisuke , Kako Yasukazu , Achiwa Sachiko , Furukawa Yoshitaka , Nakao Atsunori , Kotani Joji
Published: May 2015

Case

We report a case of hemorrhagic shock due to a ruptured gastric artery aneurysm successfully treated with transarterial embolization. A 72‐year‐old woman with cholangitis presented with hemoperitoneum following a ruptured aneurysm of the gastric artery.

Outcome

Emergent computed tomography and angiography were carried out and the patient was found to have spontaneous bleeding from both branches of the left and right gastric arteries. Transcatheter embolization was carried out at the distal branch of both gastric arteries with a coil. The patient recovered well with no recurrent bleeding.

Conclusions

 Although rare, visceral artery rupture should be considered in the differential diagnosis of unexplained hemorrhagic shock with abrupt onset of hemoperitoneum. Computed tomography and angiography are useful tools for obtaining prompt and accurate localization of the bleeding points.
The Mechanism of Ligand‐Induced Activation or Inhibition of μ‐ and κ‐Opioid Receptors
Authors: Yuan Shuguang , Palczewski Krzysztof , Peng Qian , Kolinski Michal , Vogel Horst , Filipek Slawomir
Published: May 2015

G‐protein‐coupled receptors (GPCRs) are important targets for treating severe diseases. However why certain molecules act as activators whereas others, with similar structures, block GPCR activation, is poorly understood since the same molecule can activate one receptor subtype while blocking another closely related receptor. To shed light on these central questions, we used all‐atom, long‐time‐scale molecular dynamics simulations on the κ‐opioid and μ‐opioid receptors (κOR and μOR). We found that water molecules penetrating into the receptor interior mediate the activating versus blocking effects of a particular ligand–receptor interaction. Both the size and the flexibility of the bound ligand regulated water influx into the receptor. The solvent‐accessible inner surface area was found to be a parameter that can help predict the function of the bound ligand.
Mussel‐Inspired Protein Nanoparticles Containing Iron(III)–DOPA Complexes for pH‐Responsive Drug Delivery
Authors: Kim Bum Jin , Cheong Hogyun , Hwang Byeong Hee , Cha Hyung Joon
Published: May 2015

A novel bioinspired strategy for protein nanoparticle (NP) synthesis to achieve pH‐responsive drug release exploits the pH‐dependent changes in the coordination stoichiometry of iron(III)–3,4‐dihydroxyphenylalanine (DOPA) complexes, which play a major cross‐linking role in mussel byssal threads. Doxorubicin‐loaded polymeric NPs that are based on FeIII–DOPA complexation were thus synthesized with a DOPA‐modified recombinant mussel adhesive protein through a co‐electrospraying process. The release of doxorubicin was found to be predominantly governed by a change in the structure of the FeIII–DOPA complexes induced by an acidic pH value. It was also demonstrated that the fabricated NPs exhibited effective cytotoxicity towards cancer cells through efficient cellular uptake and cytosolic release. Therefore, it is anticipated that FeIII–DOPA complexation can be successfully utilized as a new design principle for pH‐responsive NPs for diverse controlled drug‐delivery applications.
A Nonaromatic Thiophene‐Fused Heptalene and Its Aromatic Dianion
Authors: Oshima Hiroya , Fukazawa Aiko , Sasamori Takahiro , Yamaguchi Shigehiro
Published: May 2015

Heptalene, a nonaromatic, bicyclic 12 π‐electron system with a twisted structure, is of great interest with regard to its potential Hückel aromaticity in the two‐electron oxidized or reduced forms. The synthesis of thiophene‐fused heptalene 5 from the reductive transannular cyclization of bisdehydro[12]annulene 4, and its solid‐state structure, which was confirmed by X‐ray crystallographic analysis, is presented. Chemical reduction of 5 readily generated the corresponding dianion, which was successfully isolated as [(K[2.2.2]cryptand)+]252−. The X‐ray crystallographic analysis of the dianion revealed a shallower saddle structure for the heptalene moiety and a lesser degree of bond alternation relative to 5. 1H NMR spectroscopy exposed the effect of a diamagnetic ring current on dianion 52−, which was corroborated by nucleus‐independent chemical shift (NICS) calculations. These results demonstrate that the heptalene dianion, containing 14 π‐electrons, does indeed exhibit pronounced degrees of Hückel aromaticity.
Cobalt(III)‐katalysierte C‐H‐Aminocarbonylierung von Arenen und Alkenen mit Isocyanaten und Acylaziden
Authors: Li Jie , Ackermann Lutz
Published: May 2015

Nützliche C‐H‐Aminocarbonylierungen von nichtaktivierten (Hetero)Arenen und Alkenen mit hoher Toleranz für funktionelle Gruppen konnten mit einem Cobalt(III)‐Katalysator realisiert werden. Die C‐H‐Funktionalisierungen zeigten exzellente Chemo‐, Regio‐ und Diastereoselektivitäten und ermöglichten eine stufenökonomische Umsetzung von Isocyanaten oder Acylaziden.
Verursacht Dynamik das komplexe Infrarotspektrum von NO an Kupfer(II)‐Zentren in Zeolithen?
Authors: Göltl Florian , Sautet Philippe , Hermans Ive
Published: May 2015

Kupfer‐ausgetauschte SSZ‐13‐Zeolithe sind sehr effiziente Materialien für die selektive katalytische Reduktion von NOx mit Ammoniak (deNOx‐SCR). Die Charakterisierung der Verteilung der Kupfer‐Zentren in solchen Materialien ist von größter Bedeutung, um deren Aktivität zu verstehen. In dieser Studie haben wir Infrarotspektren von NO adsorbiert an Kupfer‐Zentren mittels Ab‐initio‐Molekulardynamiksimulationen modelliert. Für die meisten Zentren haben wir komplexe Infrarotspektren mit mehreren Peaks gefunden, die durch thermische Bewegung der Kationen und der Adsorbate verursacht werden. Wir konstruierten ein Spektrum eines spezifischen Katalysators bei endlicher Temperatur, welches exzellent mit Literaturdaten übereinstimmt. Die Resultate ermöglichen eine Zuordnung der aktiven und inaktiven Zentren für die deNOx‐SCR. Unseres Wissens ist dies die erste Arbeit, die über solch komplexe Spektren für einzelne adsorbierte Moleküle an einzelnen aktiven Zentren in heterogenen Katalysatoren berichtet. Wir gehen davon aus, dass ähnliche Effekte auch in einer Vielzahl anderer Systeme mit beweglichen aktiven Zentren zu finden sind.
A Simple, High‐Yield Synthesis of DNA Duplexes Containing a Covalent, Thermally Cleavable Interstrand Cross‐Link at a Defined Location
Authors: Gamboa Varela Jacqueline , Gates Kent S.
Published: May 2015

Interstrand DNA–DNA cross‐links are highly toxic to cells because these lesions block the extraction of information from the genetic material. The pathways by which cells repair cross‐links are important, but not well understood. The preparation of chemically well‐defined cross‐linked DNA substrates represents a significant challenge in the study of cross‐link repair. Here a simple method is reported that employs “post‐synthetic” modifications of commercially available 2′‐deoxyoligonucleotides to install a single cross‐link in high yield at a specified location within a DNA duplex. The cross‐linking process exploits the formation of a hydrazone between a non‐natural N4‐amino‐2′‐deoxycytidine nucleobase and the aldehyde residue of an abasic site in duplex DNA. The resulting cross‐link is stable under physiological conditions, but can be readily dissociated and re‐formed through heating–cooling cycles.
Copper‐Catalyzed Intermolecular Asymmetric Propargylic Dearomatization of Indoles
Authors: Shao Wen , Li He , Liu Chuan , Liu Chen‐Jiang , You Shu‐Li
Published: May 2015

The first copper‐catalyzed intermolecular dearomatization of indoles by an asymmetric propargylic substitution reaction was developed. This method provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee.
Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite
Authors: Rasmussen Dominik B. , Christensen Jakob M. , Temel Burcin , Studt Felix , Moses Poul Georg , Rossmeisl Jan , Riisager Anders , Jensen Anker D.
Published: May 2015

Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated acetic acid (CH2DCOOD), when D2O is introduced in the feed during the carbonylation reaction.
Highly Stereoselective Synthesis of Natural‐Product‐Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence
Authors: Echemendía Radell , de La Torre Alexander F. , Monteiro Julia L. , Pila Michel , Corrêa Arlene G. , Westermann Bernhard , Rivera Daniel G. , Paixão Márcio W.
Published: May 2015

In an endeavor to provide an efficient route to natural product hybrids, described herein is an efficient, highly stereoselective, one‐pot process comprising an organocatalytic conjugate addition of 1,3‐dicarbonyls to α,β‐unsaturated aldehydes followed by an intramolecular isocyanide‐based multicomponent reaction. This approach enables the rapid assembly of complex natural product hybrids including up to four different molecular fragments, such as hydroquinolinone, chromene, piperidine, peptide, lipid, and glycoside moieties. The strategy combines the stereocontrol of organocatalysis with the diversity‐generating character of multicomponent reactions, thus leading to structurally unique peptidomimetics integrating heterocyclic, lipidic, and sugar moieties.
Cobalt(III)‐Catalyzed Aryl and Alkenyl CH Aminocarbonylation with Isocyanates and Acyl Azides
Authors: Li Jie , Ackermann Lutz
Published: May 2015

Expedient CH aminocarbonylations of unactivated (hetero)arenes and alkenes were accomplished with a cobalt(III) catalyst that shows high functional group tolerance. The CH functionalization occurred with excellent chemo‐, site‐, and diastereoselectivity and enabled step‐economical reactions with isocyanates or acyl azides.
Can Dynamics Be Responsible for the Complex Multipeak Infrared Spectra of NO Adsorbed to Copper(II) Sites in Zeolites?
Authors: Göltl Florian , Sautet Philippe , Hermans Ive
Published: May 2015

Copper‐exchanged SSZ‐13 is a very efficient material in the selective catalytic reduction of NOx using ammonia (deNOx‐SCR) and characterizing the underlying distribution of copper sites in the material is of prime importance to understand its activity. The IR spectrum of NO adsorbed to divalent copper sites are modeled using ab initio molecular dynamics simulations. For most sites, complex multi‐peak spectra induced by the thermal motion of the cation as well as the adsorbate are found. A finite temperature spectrum for a specific catalyst was constructed, which shows excellent agreement with previously reported data. Additionally these findings allow active and inactive species in deNOx‐SCR to be identified. To the best of our knowledge, this is the first time such complex spectra for single molecules adsorbed to single active centers have been reported in heterogeneous catalysis, and we expect similar effects to be important in a large number of systems with mobile active centers.
Titanium Trisulfide Monolayer: Theoretical Prediction of a New Direct‐Gap Semiconductor with High and Anisotropic Carrier Mobility
Authors: Dai Jun , Zeng Xiao Cheng
Published: May 2015

A new two‐dimensional (2D) layered material, namely, titanium trisulfide (TiS3) monolayer, is predicted to possess novel electronic properties. Ab initio calculations show that the perfect TiS3 monolayer is a direct‐gap semiconductor with a bandgap of 1.02 eV, close to that of bulk silicon, and with high carrier mobility. More remarkably, the in‐plane electron mobility of the 2D TiS3 is highly anisotropic, amounting to about 10 000 cm2 V−1 s−1 in the b direction, which is higher than that of the MoS2 monolayer, whereas the hole mobility is about two orders of magnitude lower. Furthermore, TiS3 possesses lower cleavage energy than graphite, suggesting easy exfoliation for TiS3. Both dynamical and thermal stability of the TiS3 monolayer is examined by phonon‐spectrum calculation and Born–Oppenheimer molecular dynamics simulation. The desired electronic properties render the TiS3 monolayer a promising 2D atomic‐layer material for applications in future nanoelectronics.
Interfacial crystallization of low‐crystallinity elastomer incorporated by multi‐walled carbon nanotubes: Mechanical reinforcement, structural evolution and enhanced thermal stability
Authors: Wu Siduo , Huang Guangsu , Wu Jinrong , Li Hui
Published: May 2015

In this paper, we report interfacial crystallization in olefin block copolymer (OBC) with low crystallinity incorporated by multi‐walled carbon nanotubes (MWCNTs). A hybrid shish‐kebab (HSK) superstructure in nanocomposites is observed that MWCNTs act as central shish and OBC crystals grow perpendicular to the nanotubes axis. The mechanical properties of nanocomposites are significantly improved with incorporation of MWCNTs. The most ideal reinforcing and toughening effect is both observed in nanocomposites with MWCNTs content of 1 wt % that can increase tensile strength by 122% as well as elongation at break by 36%. Efficient load transfer are confirmed with in‐situ Raman spectra that G’ band of MWCNTs in OBC matrix exhibit a downshifting trend and symmetric broadening of line shape which reveals additional macroscale strain from axial extension of MWCNTs in nanocomposites, thus suggesting a certain load is carried by HSK superstructure. The structural evolution of OBC and nanocomposites are investigated by in‐situ wide‐angle X‐Ray Diffraction (WAXD). The Herman's orientation factor of nanocomposites with 2 wt % MWCNTs incorporation is lower than that of neat matrix at mall and intermediate strains, indicating a heterogeneous stress distribution and low compliance of HSK superstructure, which is consistent with in‐situ Raman results. Moreover, the nanocomposites presents significantly enhanced thermal stability. The onset decomposition temperature of nanocomposites with 3 wt % MWCNTs can be 60.2°C higher than that of neat OBC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42368.
Synthesis of Novel Triplets with a 1,3,5‐Trioxazatriquinane Skeleton and Their Pharmacologies for Opioid Receptors
Authors: Nagase Hiroshi , Kutsumura Noriki
Published: May 2015

We designed and synthesized novel triplet molecules with 1,3,5‐trioxazatriquinane skeletons. One class comprises double‐capped triplets with a morphinan skeleton; the other class comprises simple phenol derivatives with phenethylamine moieties. One compound with m‐phenolic hydroxyl group, called SYK‐146, is a highly selective, potent agonist for the κ receptor, with activity nearly equivalent to that of U‐50488H. The o‐phenolic isomer of SYK‐146, called SYK‐524, showed potent but non‐selective agonistic activity for the opioid receptors. We also added several simple phenol derivatives to a library of compounds that target opioid receptors, and they showed high hit rates for the receptor. This library might also be expected to show high hit rates for other receptors.
Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers
Authors: Zakaria Mohamed B. , Hu Ming , Pramanik Malay , Li Cuiling , Tang Jing , Aldalbahi Ali , Alshehri Saad M. , Malgras Victor , Yamauchi Yusuke
Published: May 2015

A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction.
Facile Synthesis of Prussian Blue Derivate‐Modified Mesoporous Material via Photoinitiated Thiol–Ene Click Reaction for Cesium Adsorption
Authors: Qian Jun , Ma Jiaqi , He Weiwei , Hua Daoben
Published: May 2015

A novel strategy to synthesize a functional mesoporous material for efficient removal of cesium is reported. Specifically, Prussian blue derivate‐modified SBA‐15 (SBA‐15@FC) was prepared by photoinitiated thiol–ene reaction between thiol‐modified SBA‐15 and pentacyano(4‐vinyl pyridine)ferrate complex. The effects of weight percentage of the Prussian blue derivate, pH, adsorbent dose, co‐existing ions, and initial concentration were evaluated on the adsorption of cesium ions. The adsorption kinetically follows a pseudo‐second‐order model and reaches equilibrium within 2 h with a high adsorption capacity of about 13.90 mg Cs g−1, which indicates that SBA‐15@FC is a promising adsorbent to effectively remove cesium from aqueous solutions.
The Influence of Dimensional Effects on the Composition and Properties of Polydicarbonfluoride
Authors: Makotchenko Victor G. , Pinakov Dmitry V. , Logvinenko Vladimir A.
Published: May 2015

The influence of dimensional effects on the compositions and properties of polydicarbonfluoride (C2F)n prepared from multilayered graphenes was investigated. Multilayered graphenes were produced by destructive thermal decomposition of intercalation compounds of “idealized” (C2F)n that were obtained by reaction of gaseous ClF3 with natural graphite at a room temperature. The precursors of multilayered graphenes have a common formula (C2F⋅xR)n where R is an organic or inorganic component. It was shown that polydicarbonfluoride prepared from multilayered graphene does not form stable intercalation compound with ClF3, in contrast to polydicarbonfluoride prepared from graphite, that forms its intercalation compound with ClF3 during fluorination of initial graphite in the ClF3 excess. Investigations of polydicarbonfluoride prepared from multilayered graphene showed that it cannot form intercalation compounds with different classes of organic and inorganic compounds as polydicarbonfluoride prepared from graphite can do. The absence of such intercalation activity for polydicarbonfluoride prepared from multilayered graphene can be explained by high exfoliation degree of multilayered graphene (3–4 nm) along the c‐axis that results in the presence of two‐dimensional (2D) structure properties in multilayered graphene. Dimensional effects transformed the chemical properties of polydicarbonfluoride prepared from multilayered graphene and lowered its decomposition temperature by 150 K in comparison with polydicarbonfluoride prepared from graphite.
An experimental and simulation study of performance and emission of ethanol fueled direct injection in high compression ignition engine
Authors: Murugasen Velliangiri , AnnurSrinivasan Krishnan
Published: May 2015

This research article mainly focuses on the influence of split injection (split into three injections) technique that was used to improve the ethanol fuel combustion in high compression ignition (CI) mode, with and without zirconia surface coating. This experimental and simulation was used (95% ethanol +5% water) as a fuel in a four‐stroke single‐cylinder variable compression ratio (VCR) engine. The VCR engine was used with optimized compression ratio (28.8:1) and experimental conducted on various load conditions. Performance and exhaust emissions of nitrogen oxides (NOx), carbon monoxide (CO) and unburned hydrocarbon (UHC) emissions of diesel, ethanol fuel single and split injection mode with coating and without coating were compared. The brake thermal efficiency (BTE) of split injection with coating mode was better than single injection mode. The VCR engine operating with ethanol fuel split injection mode showed peak BTE of 29%, which is nearly operating range in the baseline diesel engine. Ethanol fuel was mixed with 3% castorene R40 (lubrication oil) oil by volume due to fully soluble in alcohol fuels. It is used both air and liquid cooled engines running on methanol and ethanol fuel. Ethanol fuel split injection simulation was reduction of NOx compared with single injection simulation mode of operation. In comparison of diesel mode operation with zirconia coating was 3.8% increased than without coating. Ethanol single injection with coating CO emissions various from 0.5 to 3.0 g/kW‐hr. Ethanol split injection with coating mode CO emission various from 0.29 to 2.4 g/kW‐hr. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd
The role of aspirations in young children's emotional and behavioural problems
Authors: Moulton Vanessa , Flouri Eirini , Joshi Heather , Sullivan Alice
Published: May 2015

Using data from a largeUKcohort (n = 11,656), we investigated the determinants of 7‐year‐old children's aspirations, and the role of these aspirations in emotional and behavioural problems, as reported by both parents and teachers. Aspirations were classified to reflect their occupational status, masculinity/femininity and intrinsic/extrinsic motivation. Children's aspirations had significant antecedents in social disadvantage, parental involvement in learning, parental values and cognitive ability. Children with low occupational aspirations had more emotional problems as reported by both parents and teachers, and more teacher‐reported peer problems. In the teacher report, masculine aspirations were also related to hyperactivity. Gender differences in the association between aspirations and emotional and behavioural problems were few and weak. Intrinsic aspirations were related to peer problems, especially in boys. The inverse relation between feminine aspirations and hyperactivity and peer problems was relatively stronger in girls, as was the association between low aspirations and emotional problems.
Asymmetric damage segregation at cell division via protein aggregate fusion and attachment to organelles
Authors: Coelho Miguel , Tolić Iva M.
Published: May 2015

The segregation of damaged components at cell division determines the survival and aging of cells. In cells that divide asymmetrically, such as Saccharomyces cerevisiae, aggregated proteins are retained by the mother cell. Yet, where and how aggregation occurs is not known. Recent work by Zhou and collaborators shows that the birth of protein aggregates, under specific stress conditions, requires active translation, and occurs mainly at the endoplasmic reticulum. Later, aggregates move to the mitochondrial surface through fis1‐dependent association. During replicative aging, aggregate association with the mother‐cell mitochondria contributes to the asymmetric segregation of aggregates, because mitochondria in the daughter cell do not carry aggregates. With increasing age of mother cells, aggregates lose their connection to the mitochondria, and segregation is less asymmetric. Relating these findings to other mechanisms of aggregate segregation in different organisms, we postulate that fusion between aggregates and their tethering to organelles such as the vacuole, nucleus, ER, or mitochondria are common principles that establish asymmetric segregation during stress resistance and aging.
Sensitive fluorimetric assays for α‐glucosidase activity and inhibitor screening based on β‐cyclodextrin‐coated quantum dots
Authors: Liu Si‐Yao , Wang Huan , He Tian , Qi Liang , Zhang Zhi‐Qi
Published: May 2015

A fluorescence method was established for a α‐glucosidase activity assay and inhibitor screening based on β‐cyclodextrin‐coated quantum dots. p‐Nitrophenol, the hydrolysis product of the α‐glucosidase reaction, could quench the fluorescence of β‐cyclodextrin‐coated quantum dots via an electron transfer process, leading to fluorescence turn‐off, whereas the fluorescence of the system turned on in the presence of α‐glucosidase inhibitors. Taking advantage of the excellent properties of quantum dots, this method provided a very simple, rapid and sensitive screening method for α‐glucosidase inhibitors. Two α‐glucosidase inhibitors, 2,4,6‐tribromophenol and acarbose, were used to evaluate the feasibility of this screening model, and IC50 values of 24 μM and 0.55 mM were obtained respectively, which were lower than those previously reported. The method may have potential application in screening α‐glucosidase inhibitors. Copyright © 2015 John Wiley & Sons, Ltd.
Taurine, a major amino acid of oyster, enhances linear bone growth in a mouse model of protein malnutrition
Authors: Moon Phil‐Dong , Kim Min‐Ho , Lim Hun‐Sun , Oh Hyun‐A , Nam Sun‐Young , Han Na‐Ra , Kim Myong‐Jo , Jeong Hyun‐Ja , Kim Hyung‐Min
Published: May 2015

Oysters (Oys) contain various beneficial components, such as, antioxidants and amino acids. However, the effects of Oys or taurine (Tau), a major amino acid in Oys on bone growth have not been determined. In the present study, we evaluated the effects of Oys or Tau on linear bone growth in a mouse model of protein malnutrition. To make the protein malnutrition in a mouse, we used a low protein diet. Growth plate thickness was increased by Oys or Tau. Bone volume/tissue volume, trabecular thickness, trabecular number, connection density, and total porosity were also improved by Oys or Tau. Oys or Tau increased insulin‐like growth factor‐1 (IGF‐1) levels in serum, liver, and tibia‐growth plate. Phosphorylations of Janus kinase 2 (JAK2) and signal transducer and activator of transcription 5 (STAT5) were increased by Oys and by Tau. These findings show that Oys or Tau may increase growth plate thickness by elevating IGF‐1 levels and by promoting the phosphorylations of JAK2‐STAT5, and suggest that Oys or Tau are growth‐promoting substances of potential use in the food and pharmaceutical industries. © 2015 BioFactors, 41(3):190–197, 2015
The discovery of methionine sulfoxide reductase enzymes: An historical account and future perspectives
Authors: Achilli Cesare , Ciana Annarita , Minetti Giampaolo
Published: May 2015

l‐methionine (l‐Met) is the only sulphur‐containing proteinogenic amino acid together with cysteine. Its importance is highlighted by it being the initiator amino acid for protein synthesis in all known living organisms. l‐Met, free or inserted into proteins, is sensitive to oxidation of its sulfide moiety, with formation of l‐Met sulfoxide. The sulfoxide could not be inserted into proteins, and the oxidation of l‐Met in proteins often leads to the loss of biological activity of the affected molecule. Key discoveries revealed the existence, in rats, of a metabolic pathway for the reduction of free l‐Met sulfoxide and, later, in Escherichia coli, of the enzymatic reduction of l‐Met sulfoxide inserted in proteins. Upon oxidation, the sulphur atom becomes a new stereogenic center, and two stable diastereoisomers of l‐Met sulfoxide exist. A fundamental discovery revealed the existence of two unrelated families of enzymes, MsrA and MsrB, whose members display opposite stereospecificity of reduction for the two sulfoxides. The importance of Msrs is additionally emphasized by the discovery that one of the only 25 selenoproteins expressed in humans is a Msr. The milestones on the road that led to the discovery and characterization of this group of antioxidant enzymes are recounted in this review. © 2015 BioFactors, 41(3):135–152, 2015
Randomized clinical trial of mast cell inhibition in patients with a medium-sized abdominal aortic aneurysm
Authors: Sillesen H , Eldrup N , Hultgren R , Lindeman J , Bredahl K , Thompson M , Wanhainen A , Wingren U , Swedenborg J , Wanhainen A , Hultgren R , Janson I , Wingren U , Hellberg A , Larzon T , Drott C , Holst J , Sillesen H , Eldrup N , Jepsen J , Lindholdt J , Grønholdt M L , Thompson M , McCullum C
Published: May 2015

Background

Abdominal aortic aneurysm (AAA) is thought to develop as a result of inflammatory processes in the aortic wall. In particular, mast cells are believed to play a central role. The AORTA trial was undertaken to investigate whether the mast cell inhibitor, pemirolast, could retard the growth of medium-sized AAAs. In preclinical and clinical trials, pemirolast has been shown to inhibit antigen-induced allergic reactions.

Methods

Inclusion criteria for the trial were patients with an AAA of 39–49 mm in diameter on ultrasound imaging. Among exclusion criteria were previous aortic surgery, diabetes mellitus, and severe concomitant disease with a life expectancy of less than 2 years. Included patients were treated with 10, 25 or 40 mg pemirolast, or matching placebo for 52 weeks. The primary endpoint was change in aortic diameter as measured from leading edge adventitia at the anterior wall to leading edge adventitia at the posterior wall in systole. All ultrasound scans were read in a central imaging laboratory.

Results

Some 326 patients (mean age 70·8 years; 88·0 per cent men) were included in the trial. The overall mean growth rate was 2·42 mm during the 12-month study. There was no statistically significant difference in growth between patients receiving placebo and those in the three dose groups of pemirolast. Similarly, there were no differences in adverse events.

Conclusion

Treatment with pemirolast did not retard the growth of medium-sized AAAs. Registration number: NCT01354184 (https://www.clinicaltrials.gov).
LC‐ESI‐MS/MS analysis and pharmacokinetics of heterophyllin B, a cyclic octapeptide from Pseudostellaria heterophylla in rat plasma
Authors: Zhao Wai‐Ou , Pang Li , Dong Ning , Yang Shu
Published: May 2015

Heterophyllin B (HB) is a cyclic octapeptide isolated from Pseudostellaria heterophylla. HB is used as the quality control index for evaluating P. heterophylla in the Chinese Pharmacopoeia. A rapid and sensitive LC‐ESI‐MS/MS method was developed and validated for the analysis of HB in rat plasma. Sample preparation consisted of a solid‐phase extraction step for the removal of interference and preconcentration of the target analyte HB and the internal standard N‐acetylcysteine before chromatographic analysis by MS/MS detection. The separation of HB and N‐acetylcysteine was performed using a Hypersil GOLDTM C18 column and a mixture of methanol–water (60:40, v/v) containing 10 mmol/L ammonium formate and 0.1% formic acid as the mobile phase. The determination step was optimized in the selected reaction monitoring mode for the highly selective and sensitive quantitation of HB in rat plasma. Intra‐ and inter‐assay precision (as relative standard deviation) was ≤9.1%, and accuracy was between 92.6 and 102.7%. The validated method was successfully applied to quantify HB concentrations up to 7 h after tail intravenous injections of 2.08, 4.16 and 8.32 mg/kg HB in rats. The LC‐MS/MS method identified the relevant pharmacokinetic parameters of HB and its studied analog. Copyright © 2015 John Wiley & Sons, Ltd.
Determination of kynurenic acid in rat cerebrospinal fluid by HPLC with fluorescence detection
Authors: Bao Ye , Luchetti David , Schaeffer Eric , Cutrone Jingfang
Published: May 2015

A sensitive HPLC method using fluorescence detection was developed to determine kynurenic acid (KYNA) level in rat cerebrospinal fluid (CSF). The method development was accomplished by screening different columns, optimizing zinc acetate concentration and determining the optimal HPLC flow rate. This method allowed direct injection of the CSF samples onto an Xselect C18 column and KYNA levels were measured fluorometrically by forming a fluorescent complex with zinc acetate that was delivered post‐column. The limit of quantitation was 0.2 n m with 30 μL injection, corresponding to 6 fmol (signal‐to‐noise ratio = 10). The improved sensitivity enabled the measurement of KYNA in naive and drug‐treated rat CSF. Copyright © 2015 John Wiley & Sons, Ltd.
Oxygen availability effect on the performance of air‐breathing cathode microbial fuel cell
Authors: Mateo Sara , Rodrigo Manuel , Fonseca Luis Pina , Cañizares Pablo , Fernandez‐Morales Francisco Jesus
Published: May 2015

The effect of the oxygen availability over the performance of an air‐breathing microbial fuel cell (MFC) was studied by limiting the oxygen supply to the cathode. It was found that anodic reaction was the limiting stage in the performance of the MFC while oxygen was fully available at cathode. As the cathode was depleted of oxygen, the current density becomes limited by oxygen transport to the electrode surface. The exerted current density was maintained when oxygen mole fraction was higher than 10% due to the very good performance of the cathodic catalysts. However, the current density drastically falls when working at lower concentrations because of mass transfer limitations. In this sense it must be highlighted that the maximum exerted power, when oxygen mole fraction was higher than 10%, was almost three times higher than that obtained when oxygen mole fraction was 5%. Regarding to the wastewater treatment, a significant decrease in the COD removal was obtained when the MFC performance was reduced due to the limited availability of oxygen, which indicates the significant role of the electrogenic microorganisms in the COD removal in MFC. In addition, the low availability of oxygen at the cathode leads to a lower presence of oxygen at the anode, resulting in an increase in the coulombic efficiency. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:900–907, 2015
Create durable competitive advantage for coaches of women's teams
Authors: Wilson Mark
Published: May 2015

Summer camps are big business in the United States. In fact, more than 12,000 camps (day and overnight) operate annually and generate $15 billion in annual revenues, according to the American Camp Association, a leading camp accreditation organization.
Is it possible to respond with 100 percent compassion, 0 percent tolerance?
Authors: Nelson J. Dirk ,   in consultation with Elizabeth Briggs
Published: May 2015

According to Martha Stout in The Sociopath Next Door, workplace sociopaths — about 1 individual in 25 — do not have a conscience. They have no feelings of guilt or remorse. When the opportunity exists, a workplace sociopath will manipulate reality; hide evidence; stab others in the back; fabricate compelling lies; attempt to ruin the reputations of others; steamroll the weak; and bring down people who are smarter, more accomplished, classier or more admirable, all in the name of fun, adrenaline rush and vengeance.
Differentiation of C57/BL6 mice bone marrow mononuclear cells into early endothelial progenitors cells in different culture conditions
Authors: Carneiro Giane D. , Godoy Juliana A. P. , Werneck Claudio C. , Vicente Cristina P.
Published: May 2015

Endothelial progenitor cells (EPCs) can be isolated from bone marrow and characterized by the expression of cellular markers such as CD34, CD133, VEGFR2, CD31, and VE‐Cadherin, by the uptake of acetylated low‐density lipoprotein and by in vitro tube formation in tridimensional matrices. These cells are able to differentiate into mature endothelial cells and participate in the re‐endothelization of damaged vessels. In this work, we tested different cultured media that can promote the proliferation and differentiation of mononuclear cells (MNCs) into early EPCs, with defined concentrations of growth factors and serum in order to establish a composition that may ensure us the reproducibility of our cultures. MNCs from mice bone marrow were cultivated using selective culture media containing DMEM or M199 supplemented with 10% FBS, VEGF, bFGF, and IGF, for 3, 7, and 14 days. Differentiation into early EPCs was analyzed using immunohistochemistry, FACS and western blotting and by functional parameters as uptake of ac‐LDL, and formation of vessel‐like structures. The cells cultivated with medium DMEM‐M1 (DMEM plus VEGF, bFGF and IGF) expressed CD34, CD133, CD31, VEGFR2, and VE‐Cadherin at all culture time‐points with increased expression of these markers after 7 days. Only EPCs cultured for 30 days were able to form vessel‐like structure. The uptake of ac‐LDL was observed after 3, 7, 14, and 30 days, confirming the differentiation of mononuclear cells into early EPCs. DMEM‐M1 was able to sustain MNCs proliferation and differentiation, increasing the expression of the characteristic EPC markers, allowing the expansion of early EPCs in culture in a similar way to that observed in commercial available media.
Robust and Recyclable Nonprecious Bimetallic Nanoparticles on Carbon Nanotubes for the Hydrogenation and Hydrogenolysis of 5‐Hydroxymethylfurfural
Authors: Yu Lili , He Le , Chen Jin , Zheng Jianwei , Ye Linmin , Lin Haiqiang , Yuan Youzhu
Published: May 2015

Selective hydrogenation and hydrogenolysis of 5‐hydroxymethylfurfural were performed with carbon nanotube‐supported bimetallic NiFe (NiFe/CNT) catalysts. The combination of Ni and Fe in an appropriate atomic ratio of Ni/Fe (2.0) significantly increased the selectivity to 2,5‐furandimethanol or 2,5‐dimethylfuran depending on the reaction temperature. The selectivities to 2,5‐furandimethanol and 2,5‐dimethylfuran were as high as 96.1 % at 383 K and 91.3 % at 473 K, respectively. The characterization results confirmed that bimetallic particles with sizes less than 7 nm were formed on the catalyst. Several key molecules related to 5‐hydroxymethylfurfural transformation were used to investigate the product distribution and reaction pathway. The results indicated that the formation of NiFe alloy species is beneficial to the selective cleavage of the CO bond. Recycling experiments showed that the catalyst can be easily separated with a magnet and reused several times without significant loss of activity.
Effect of VOx Species and Support on Coke Formation and Catalyst Stability in Nonoxidative Propane Dehydrogenation
Authors: Sokolov Sergey , Bychkov Victor Yu. , Stoyanova Mariana , Rodemerck Uwe , Bentrup Ursula , Linke David , Tyulenin Yurij P. , Korchak Vladimir N. , Kondratenko Evgenii V.
Published: May 2015

VOx/SiO2–Al2O3 catalysts were prepared by grafting vanadyl acetylacetonate onto the supports with a SiO2 content between 0 and 100 wt. %. The degree of polymerization of VOx species and acidity both of pristine supports and the catalysts were evaluated. To determine their on‐stream stability and carbon deposition activity in nonoxidative propane dehydrogenation, continuous‐flow tests and in situ thermogravimetric measurements were performed. The rate constants of catalyst deactivation and carbon deposition were derived from kinetic evaluation of these experiments. Gathered experimental evidence pointed out that VOx species were significantly more active for coke formation than acid sites of the supports. The rate constant of carbon formation was found to increase with the degree of polymerization of VOx species, whereas no correlation between catalyst acidity and the rate constants of coking or deactivation could be drawn.
Charge Transfer and Photocatalytic Activity in CuO/TiO2 Nanoparticle Heterojunctions Synthesised through a Rapid, One‐Pot, Microwave Solvothermal Route
Authors: Moniz Savio J. A. , Tang Junwang
Published: May 2015

Rapid charge carrier recombination is a major limiting factor over efficiency in many semiconductor photocatalysts. To address this, copper(II) oxide/titanium dioxide (CuO/TiO2) heterojunctions were synthesised through a novel, rapid solvothermal microwave procedure using a low‐cost copper precursor and commercial P25 TiO2, taking as little as five minutes to synthesise well‐defined CuO nanoparticles onto the host TiO2, achieving an intimate contact. The resultant composites encompass pure CuO particles of approximately 6–7 nm diameter, confirmed by means of high resolution transmission electron microscopy and X‐ray photoelectron spectroscopy analysis. Photoelectrochemical water splitting was enhanced by nearly 2 times using the junction, whilst ≈1.6 times enhancement in the photocatalytic mineralisation of a model organic pollutant 2,4‐dichlorophenoxyacetic acid (2,4‐D) was observed. Furthermore, we studied the initial decomposition mechanism of 2,4‐D by means of GC‐MS analysis. The increase in catalytic activity, investigated by impedance analysis (Mott–Schottky plots) and photoluminescence spectra, is attributed to photoelectron transfer from the more negative conduction band (CB) of TiO2 to CuO, leaving the photohole on TiO2 to take part in oxidation reactions. This strategy allows for in situ charge separation which facilitates superior photocatalytic activity for both pollutant degradation and water splitting.
Hydrophobic Encapsulated Phosphonium Salts—Synthesis of Weakly Coordinating Cations and their Application in Wittig Reactions
Authors: Moritz Ralf , Wagner Manfred , Schollmeyer Dieter , Baumgarten Martin , Müllen Klaus
Published: May 2015

Large and rigid tetraarylphosphonium tetrafluoroborate salts have been synthesized representing weakly coordinating cations with diameters of several nanometers. Divergent dendritic growth by means of thermal Diels–Alder cycloaddition was employed for the construction of the hydrophobic polyphenylene framework up to the third generation. X‐ray crystal structure analysis of first‐generation phosphonium tetrafluoroborate supported the rigidity of the non‐collapsible shell around the phosphorus center and gave insight into solid‐state packing and cation–anion distances. Copper(I)‐catalyzed azide–alkyne ligation served as reliable method for the preparation of a first‐generation triazolylphenyl hybrid phosphonium cation under mild reaction conditions. Furthermore, from the synthesis of triarylbenzylphosphonium bromides, Wittig precursors with unprecedented bulky substituents in the α‐position were accessible. Employment of these precursors under Wittig conditions by treatment with base and subsequent reaction with aldehydes preferentially provided (Z)‐olefins with bulky polyphenylene substituents.
Folding Patterns in a Family of Oligoamide Foldamers
Authors: Kortelainen Minna , Suhonen Aku , Hamza Andrea , Pápai Imre , Nauha Elisa , Yliniemelä‐Sipari Sanna , Nissinen Maija , Pihko Petri M.
Published: May 2015

A series of small, unsymmetrical pyridine‐2,6‐dicarboxylamide oligoamide foldamers with varying lengths and substituents at the end groups were synthetized to study their conformational properties and folding patterns. The @‐type folding pattern resembled the oxyanion‐hole motifs of enzymes, but several alternative folding patterns could also be characterized. Computational studies revealed several alternative conformers of nearly equal stability. These folding patterns differed from each other in their intramolecular hydrogen‐bonding patterns and aryl–aryl interactions. In the solid state, the foldamers adopted either the globular @‐type fold or the more extended S‐type conformers, which were very similar to those foldamers obtained computationally. In some cases, the same foldamer molecule could even crystallize into two different folding patterns, thus confirming that the different folding patterns are very close in energy in spite of their completely different shapes. Finally, the best match for the observed NOE interactions in the liquid state was a conformation that matched the computationally characterized helix‐type fold.