bluuebunny/crossref_metadata_2025 huggingface dataset:
One‐Pot Facile Fabrication of Multiple Nickel Nanoparticles Confined in Microporous Silica Giving a Multiple‐Cores@Shell Structure as a Highly Efficient Catalyst for Methane Dry Reforming
Authors: Peng Honggen , Zhang Xianhua , Zhang Li , Rao Cheng , Lian Jie , Liu Wenming , Ying Jiawei , Zhang Guohua , Wang Zheng , Zhang Ning , Wang Xiang
Published: November 2016

Methane dry reforming (MDR) is a very important reaction, which can efficiently use two kinds of greenhouse gases (CO2 and CH4) to prepare synthesis gas or produce green hydrogen energy. What inhibits the industrialization of MDR is the sintering of active Ni nanoparticles and severe carbon deposition for Ni‐based catalysts. To resolve these problems, a novel structured catalyst with multiple ultra‐small Ni nanoparticles (4.3 nm) as the core and microporous silica as the shell was rationally fabricated by a facial one‐pot reverse micelle method and applied for MDR. The multiple‐cores@shell (M‐Ni@SiO2) catalyst displays superior carbon resistance and long‐term durability with the methane and carbon dioxide conversion close to thermodynamic equilibrium and a H2 to CO molar ratio near 1, whereas the commercial catalyst, Ni/Al2O3, and Ni directly supported on silica spheres (Ni/SiO2) show low stability and notable carbon deposition. The ultra‐small Ni particle size and confinement effect of the porous silica shell are believed to be the determining factors for the outstanding performance of the multiple‐cores@shell catalyst. The novel multiple‐cores@shell structure catalyst could be potentially used for industrial applications of MDR.
Deciphering the Platinized Surface Reactivity to Improve the Detection of Hydrogen Peroxide in Bioanalyses
Authors: Badets Vasilica , Pandard Justine , Sojic Neso , Arbault Stéphane
Published: November 2016

The reactivity of platinized electrode surface (Pt‐black) towards the oxidation of hydrogen peroxide is analyzed in the most common physiological buffer, namely phosphate buffer saline, used in the development of biosensors. It is shown here that the oxidation of hydrogen peroxide by Pt‐black involves first the adsorption of phosphate anions, which facilitates the oxidation of hydrogen peroxide at lower potentials when compared to classic polycrystalline platinum. This gives insight in the excellent analytical features of platinized electrodes for the detection of H2O2, even at nanomolar concentrations. The reactivity of platinized electrodes can be further improved by an oxygen plasma treatment. We demonstrate herein that such treatment creates an outermost layer of PtO2 oxides on the deposit, which improves the oxidation of hydrogen peroxide thermodynamically and kinetically, as well as of hydroquinone and superoxide radical anion.
Converting a Semiconducting Polymer from Ambipolar into n‐Type Dominant by Amine End‐Capping
Authors: Quinn Jesse , Patel Haritosh , Haider Fezza , Khan Daid A. , Li Yuning
Published: November 2016

A donor‐acceptor polymer of (3E,7E)‐3,7‐bis(2‐oxoindolin‐3‐ylidene)benzo[1,2‐b : 4,5‐b′]difuran‐2,6(3H,7H)‐dione (IBDF) and bithiophene (BT) exhibits typical ambipolar charge transport behaviour in organic thin film transistors. Using the electron rich triphenylamine as an end capping group, a notable suppression of hole transport is observed. This interesting phenomenon is accounted for by the hole trapping effect of the triphenylamine end‐capper. Thus, this study provides a novel and facile approach to tuning the charge carrier polarity of a polymer semiconductor from ambipolar to n‐type dominant.
Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study
Authors: Caturello Naidel A. M. S. , Csók Zsolt , Fernández Gustavo , Albuquerque Rodrigo Q.
Published: November 2016

The nature of intermolecular interactions governing supramolecular polymerizations is very important for controlling their cooperativity. In order to address this problem, supramolecular columns made of PtII and PdII complexes of oligo(phenylene ethynylene)‐based pyridine (OPE) and tetrazolylpyridine ligands (TEP) were investigated through the dispersion‐corrected PM6 method. Aromatic, CH–π, M–Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of PtII led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor for controlling cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger preformed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons.
Inverse Kinetic and Equilibrium Isotope Effects on Self‐Assembly and Supramolecular Chirality of Porphyrin J‐Aggregates
Authors: Zagami Roberto , Romeo Andrea , Castriciano Maria A. , Monsù Scolaro Luigi
Published: November 2016

When mixtures of D2O/DCl are used to foster the self‐assembly formation of TPPS4 porphyrin J‐aggregates in aqueous solutions, an inverse kinetic isotope effect of 0.4 and an inverse equilibrium isotope effect of 0.6 are clearly detected. Most importantly, the addition of at least 10 % D2O causes an inversion in the handedness of the final chiral J‐aggregates, thus evidencing an important role of deuterium in driving the enantiomeric excess in the scalemic mixture of such supramolecular assemblies.
Alkynylthioimidazolium Salts: Efficient Reagents for the Synthesis of Alkynyl Sulfides by Electrophilic Thioalkynylation
Authors: Peña Javier , Talavera Garazi , Waldecker Bernd , Alcarazo Manuel
Published: November 2016

The efficient synthesis of a series of alkynylthioimidazolium salts through reaction of organozinc compounds with dibromo(imidazolium)sulfuranes is reported. Addition of Grignard reagents to these new species provided a highly modular, clean, and scalable access to a broad variety of alkynyl sulfides in good‐to‐excellent yields. The utility of this protocol was showcased by the preparation of alkynyl sulfides, which are particularly difficult to obtain or simply unavailable through the existing methodologies. In addition, the synthetic method was extended to the preparation of alkynyl selenides.
Enantioselective Synthesis of Quaternary α‐Amino Acids Enabled by the Versatility of the Phenylselenonyl Group
Authors: Clemenceau Antonin , Wang Qian , Zhu Jieping
Published: November 2016

A novel Cinchona alkaloid‐catalyzed enantioselective conjugate addition of α‐alkyl substituted α‐nitroacetates to phenyl vinyl selenone was developed. The resulting enantio‐enriched α,α‐dialkyl substituted α‐nitroacetates were subsequently converted to various cyclic and acyclic quaternary α‐amino acids, taking advantage of the rich functionalities of the resulting Michael adducts. Novel protocols allowing chemoselective reduction of phenyl selenone to phenyl selenide and reduction of alkyl phenyl selenones to alkanes are also reported.
Enantioselective effects of metalaxyl on soil enzyme activity
Authors: Yue Heng , Fang Song , Zhang Yizhi , Ning Yang , Yu Weisong , Kong Fanyu , Qiu Jun
Published: November 2016

The enantioselective effects of the chiral pesticide metalaxyl on soil enzyme activity were investigated. Incubation experiments were conducted to investigate the effects of metalaxyl enantiomers at different concentrations on the activities of urease, invertase, and catalase as well as the type of activity change (activation vs. inhibition) at different times during incubation. The results indicated that the effects of metalaxyl on the activity of soil enzymes were not only related to the concentration of the enantiomers and soil incubation time, but also to the chiral configuration, suggesting the effects were enantioselective. A pattern of inhibition‐recovery‐slight stimulation was observed in urease activity of the soil samples treated with metalaxyl enantiomers, but the effects of (–) ‐R‐metalaxyl were stronger than those of (+)‐S‐metalaxyl at the same concentration. Invertase activity in soil samples treated with metalaxyl enantiomers initially sharply decreased before finally returning to the normal level, and the effects of (+)‐S‐metalaxyl were stronger than those of (–) ‐R‐metalaxyl at the same concentration. Metalaxyl enantiomers influenced catalase activity in a pattern of slight stimulation‐inhibition‐recovery, and the effects of (–) ‐R‐metalaxyl were stronger than those of (+)‐S‐metalaxyl at the same concentration.
Die Ausdampfung von Aromastoffen
Authors: Scheuren Hans , Dillenburger Michael
Published: November 2016

Das 500 jährige Reinheitsgebot verbietet die Zugabe und Fällung von Aromastoffen mit Mitteln außerhalb der definierten Zutaten. Von großer Bedeutung sind verfahrenstechnische Methoden wie die Würzekochung, die den Gehalt von Aromastoffen prägen. Die thermodynamischen und verfahrenstechnischen Grundlagen am Beispiel der zentralen Geschmackskomponente Dimethylsulfid (DMS) werden beschrieben und die Berechenbarkeit des Prozesses hin zu einem definierten Gehalt aufgezeigt. So ist es möglich, den Energiebedarf auf ein Optimum zu reduzieren und ein konstantes Geschmacksprofil trotz natürlich schwankender Eingangsgrößen zu erreichen.
Utility of the 2‐Nitrobenzenesulfonamide Group as a Chemical Linker for Enhanced Extracellular Stability and Cytosolic Cleavage in siRNA‐Conjugated Polymer Systems
Authors: Huang Chih Hao , Takemoto Hiroyasu , Nomoto Takahiro , Tomoda Keishiro , Matsui Makoto , Nishiyama Nobuhiro
Published: November 2016

Herein we report the 2‐nitrobenzenesulfonamide group as a new chemical linker that responds to the difference in redox potential across the cellular membrane, toward the construction of siRNA–polymer conjugates. PEG‐conjugated to siRNA via the 2‐nitrobenzenesulfonamide group (PEG–sul–siRNA) exhibited highly selective siRNA release under intracellular conditions due to the exclusive presence of the GSH/GST combination in the cell. In addition, siRNA release from PEG–sul–siRNA under extracellular reductive conditions was dramatically suppressed relative to PEG–siRNA conjugates containing a conventional redox‐sensitive disulfide linkage (PEG–disulfide–siRNA), indicating the enhanced extracellular stability of the 2‐nitrobenzenesulfonamide group. The enhanced gene‐silencing effect of PEG–sul–siRNA for cultured cells relative to PEG–siRNA, containing a non‐cleavable carboxylic amide linkage (PEG–car–siRNA), confirmed the intracellular release of siRNA via the PEG–sul–siRNA system. These results suggest that the 2‐nitrobenzenesulfonamide group could be a suitable chemical linker alternative to the conventional disulfide group.
Young Investigator Challenge: A novel, simple method for cell block preparation, implementation, and use over 2 years
Authors: Lindsey Kathryn G. , Houser Patricia M. , Shotsberger‐Gray Wanda , Chajewski Olga S. , Yang Jack
Published: November 2016

BACKGROUND

The cell block is an essential adjunct to conventional cytopreparatory techniques. The need for molecular analysis and immunostains will increase the need for successful cell block preparation. Even with this need, to the authors' knowledge very little has changed regarding the way in which cell blocks are produced.

METHODS

The authors developed A Formalin‐Fixed, paraffin Embedded Cytology cell block Technique (AFFECT) that uses a cytospin centrifuge and funnel to deposit a cell pellet into a well on a piece of open‐cell, absorbent foam. The foam and the pellet are then sent through normal processing. Herein, the authors present the implementation of this method and some of their experience with its performance over the course of 2 years.

RESULTS

Although a comparison of the methods indicated good correlation for the production of a cell block between AFFECT and the agarose method, the AFFECT blocks demonstrated markedly improved cellular morphology. Over the first 6 months of use, AFFECT produced a successful cell block in 74% of cases overall, and in 65% of cases with a cell pellet measuring ≤0.1 mL. The year preceding the implementation of AFFECT and its first year of use were compared for endoscopic and bronchoscopic ultrasound‐guided fine‐needle aspiration specimens, and demonstrated an improved success rate.

CONCLUSIONS

The authors developed a novel method of cell block preparation that demonstrates improved histology and has increased the success rate of cell block production compared with the agarose method. Cancer Cytopathol 2016;124:885–892. © 2016 American Cancer Society.
Structural Diversity of Three Pyrazoyl–Carboxyl Bifunctional Ligand‐Based Metal–Organic Frameworks: Luminescence and Magnetic Properties
Authors: Li Gao‐Peng , Yang Hong‐Yun , Li Yong‐Zhi , Hou Lei , Liu Bin , Wang Yao‐Yu
Published: November 2016

Three metal–organic frameworks (MOFs), [Cd(Hpzbpdc)(H2O)]⋅H2O (1), [Mn2(Hpzbpdc)2(dmf)2] (2), and [H2N(CH3)2]0.5[Eu(Hpzbpdc)1.5(HCOO)0.5(dmf)0.5]⋅DMF⋅0.5 H2O (3) (H3pzbpdc=4′‐(2 H‐pyrazol‐3‐yl)biphenyl‐3,5‐dicarboxylic acid), have been solvothermally synthesized from one pyrazoyl–carboxyl bifunctional ligand and characterized by single‐crystal structures. The H3pzbpdc ligand in 1–3 displays various coordination modes through the pyrazoyl and carboxyl groups. Both 1 and 3 contain dinuclear cluster building units and reveal a four‐connected gismondine (gis) zeolite 3D framework and a 2D grid layer structure, respectively. Compound 1 shows blue luminescence, compound 3 reveals red luminescence that arises from efficient energy transfer from the organic ligand to the europium(III) ion, and compound 2 reveals an uncommon (3,8)‐connected tfz‐d; UO3 net with a rare Mn4(COO)6 cluster and shows antiferromagnetic interactions between the manganese(II) ions.
Potential Psychiatric Uses for MDMA
Authors: Yazar‐Klosinski BB , Mithoefer MC
Published: November 2016

Phase II trials of 3,4‐methylenedioxymethamphetamine (MDMA)‐assisted psychotherapy have demonstrated initial safety and efficacy for treatment of posttraumatic stress disorder (PTSD), with potential for expansion to depression and anxiety disorders. In these trials, single doses of MDMA are administered in a model of medication‐assisted psychotherapy, differing from trials involving daily drug administration without psychotherapy. This model presents an opportunity to utilize accelerated regulatory pathways, such as the US Food and Drug Administration (FDA) Breakthrough Therapy Designation, to most effectively and expeditiously test such novel approaches.
Photochemical Treatment of Powder Coatings and VOC‐Free Coatings with NIR Lasers Exhibiting Line‐Shaped Focus: Physical and Chemical Solidification
Authors: Schmitz Christian , Strehmel Bernd
Published: November 2016

NIR‐sensitized (NIR=near‐infrared) radical photopolymerization can be employed to chemically cure VOC‐free coatings; that is, either a powder coating or liquid monomer coating system with no significant components of volatile organic compounds (VOC). A NIR laser with line‐shaped focus was applied to cure the coatings. This system operated in multi‐wavelength mode where preferentially the emission wavelengths λ=808 nm and 980 nm of the laser system could be employed to solidify and crosslink the starting components as a transparent film; that is, chemical drying by photonic events. Cyanines absorbing at λ=980 nm and 808 nm functioned as heat generators to melt the powder and as sensitizers (Sens) to generate initiating radicals in combination with a radical initiator (RI). The radical initiator was either the iodonium salt RI‐1 ([(t‐C4H9‐Ph)2I+][(CF3SO2)2N−]) or triazine A (RI‐2). Photoinduced electron transfer between the excited states of Sens and RI was found to control the efficiency of initiating radicals. Line‐shape‐focused laser experiments demonstrated that both liquid VOC‐free coatings and solid powder coatings can be cured. Curing of solid powder coatings occurs with a curing rate of 3.6 m min−1, opening the possibility to introduce NIR laser curing as a new technology in coating sciences. Finally, rheological measurements and differential scanning calorimetry (DSC) were applied to characterize the flow properties of the molten powder and the glass transition temperatures of the crosslinked materials, respectively. The molten powder coating behaved like a liquid up to 160 °C as concluded from the complex shear modulus (G*), while the phase shift (∂) documents crosslinking above this temperature.
Immune monitoring in renal transplantation: The search for biomarkers
Authors: Danger Richard , Sawitzki Birgit , Brouard Sophie
Published: November 2016

It is now widely accepted that in order to improve long‐term graft function and survival, a more personalized immunosuppressive treatment of transplant patients according to the individual anti‐donor immune response status is needed. This applies to the identification of potentially “high‐risk” patients likely to develop acute rejection episodes or display an accelerated decline of graft function, patients who might need immunosuppression intensification, and operationally tolerant patients suitable for immunosuppression minimization or weaning off. Such a patient stratification would benefit from biomarkers, which enable categorization into low and high risk or, ideally, identification of operational tolerant patients. Here, we report on recent developments regarding identification and performance analysis of noninvasive biomarkers such as mRNA and miRNA expression profiles, chemokines, or changes in immune cell subsets in either blood or urine of renal transplant patients. We will also discuss which future steps are needed to accelerate their clinical implementation.
A novel Foxn1eGFP/+ mouse model identifies Bmp4‐induced maintenance of Foxn1 expression and thymic epithelial progenitor populations
Authors: Barsanti Marco , Lim Joanna M. C. , Hun Michael L. , Lister Natalie , Wong Kahlia , Hammett Maree V. , Lepletier Ailin , Boyd Richard L. , Giudice Antonietta , Chidgey Ann P.
Published: November 2016

Although forkhead‐box n1 (Foxn1) is a critical thymic epithelial cell regulator in thymus organogenesis, its association with epithelial differentiation and homeostasis in the postnatal and aged thymic microenvironment remains conflicting. Consequently, we have generated a Foxn1eGFP/+ knock‐in mouse model that allows for refined investigation of the aging thymic epithelium. This reporter line differs from those previously published in that concomitant expression of enhanced green fluorescent protein enables live cell sorting of Foxn1+ cell populations. Our heterozygotes did not exhibit haploinsufficiency, with Foxn1 expression resembling that of wild‐type mice. Comparative analysis between Foxn1 and enhanced green fluorescent protein at both the transcriptional and translational levels revealed co‐localization, with progressive down‐regulation observed predominantly in the aging cortical epithelium. Supplementation with bone morphogenetic protein (Bmp)‐4 enhanced Foxn1 expression and colony forming efficiency in both embryonic and adult progenitor 3D cultures. Strikingly, selective maintenance of immature cortical and medullary epithelial cells was observed which is consistent with the higher Bmp receptor 2 expression levels seen in these progenitor populations. This study demonstrates the significance of our mouse model in unraveling the role of this master regulator in thymus development, homeostasis and aging, providing a faithful reporter system for phenotypic and functional investigations.
HLA‐G promotes myeloid‐derived suppressor cell accumulation and suppressive activity during human pregnancy through engagement of the receptor ILT4
Authors: Köstlin Natascha , Ostermeir Anna‐Lena , Spring Bärbel , Schwarz Julian , Marmé Alexander , Walter Christina B. , Poets Christian F. , Gille Christian
Published: November 2016

Establishing and maintaining maternal‐fetal tolerance is essential for a successful pregnancy; failure of immunological adaptation to pregnancy leads to severe complications such as abortion or preterm delivery. Myeloid‐derived suppressor cells (MDSCs) are innate immune cells that suppress T‐cell responses, expand during pregnancy and thus may play a role in tolerance induction. Human leucocyte antigen G (HLA‐G) is a major histocompatibility complex (MHC) I molecule with immune‐modulatory properties, which is expressed during pregnancy. Here, we investigated the impact of HLA‐G on MDSCs accumulation and activation in pregnant women. We demonstrate that granulocytic MDSCs (GR‐MDSCs) express receptors for HLA‐G, namely immunoglobulin‐like transcript (ILT) 2 and 4, and that ILT4‐expression by GR‐MDSCs is regulated during pregnancy. Stimulation with soluble HLA‐G (sHLA‐G) increased suppressive activity of GR‐MDSCs, induced MDSCs from peripheral blood mononuclear cells (PBMCs) and led to phosphorylation of the signal transducer and activator of transcription 3 (STAT3) and induction of indoleamine‐2,3‐dioxygenase (IDO) in myeloid cells. Effects of sHLA‐G on MDSC accumulation were mediated through ILT4. These results suggest an interaction between MDSCs and HLA‐G in humans as a potential mechanism for maintaining maternal‐fetal tolerance. Modulating MDSC function during pregnancy via HLA‐G might provide new opportunities for a therapeutic manipulation of immunological pregnancy complications.
Synthesis and Characterization of the First Nickel(II)‐Centered Single‐Side Tris‐Functionalized Anderson‐Type Polyoxomolybdate
Authors: Gumerova Nadiia I. , Roller Alexander , Rompel Annette
Published: November 2016

The Ni‐centered Anderson‐type polyoxomolybdate [Ni(OH)3Mo6O18(OCH2)3CNH3]3– was prepared in a two‐step aqueous reaction by covalent postfunctionalization of [Ni(OH)6Mo6O18]4–, isolated as its sodium Tris–NH3 salt, and characterized by single‐crystal X‐ray diffraction, mass spectrometry, thermogravimetric analysis, and IR spectroscopy. The incorporation of a Tris–NH2 ligand into the framework of a heteropolymolybdate bearing a divalent heteroatom, which resulted in the single‐sided product, was shown for the first time.
Cell and Cell‐Free Mechanistic Studies on Two Gold(III) Complexes with Proven Antitumor Properties
Authors: Nardon Chiara , Boscutti Giulia , Gabbiani Chiara , Massai Lara , Pettenuzzo Nicolò , Fassina Ambrogio , Messori Luigi , Fregona Dolores
Published: November 2016

AuL10 ([AuIIICl2(dmdt)], dmdt = N,N‐dimethyldithiocarbamate) and AuL12 ([AuIIIBr2(esdt)], esdt = ethylsarcosine dithiocarbamate) are two extremely promising gold‐based anticancer compounds. Their mechanisms of action are still largely unknown although some specific hypotheses have been proposed. To shed light on their reactivity with probable biological targets, we report here on their interactions with serum albumin and calf‐thymus DNA, taken as model biomolecules. Quite unexpectedly, spectrophotometric investigations revealed substantially different patterns of interaction for these two gold complexes with the aforementioned biomolecules, probably arising from differences in redox chemistry. Afterwards, AuL12 was tested against A549 human non‐small‐cell lung carcinoma cells, evaluating its real‐time profile of cell‐growth inhibition by means of the xCELLigence Real‐Time Cell Analysis system. Measures of impedance by non‐invasive gold microelectrodes at the base of each well indicated that this gold complex inhibits cell proliferation after only 4 h of treatment, producing its cytotoxic effects probably at the membrane level.
Synthesis, Palladium(II) Complexes, and Catalytic Use of a Phosphanylferrocene Ligand Bearing a Guanidinium Pendant
Authors: Bárta Ondřej , Císařová Ivana , Štěpnička Petr
Published: November 2016

A polar phosphanylferrocene donor equipped with a hydrophilic guanidinium pendant, Ph2PfcCH2NHC(NH)NH2·HCl (1·HCl; fc = ferrocene‐1,1′‐diyl), has been prepared from the corresponding amine hydrochloride, Ph2PfcCH2NH2·HCl (2·HCl), and studied as a ligand for PdII. The reactions of 1·HCl with [PdCl2(MeCN)2] in 1:1 and 1:2 Pd/ligand ratios led to an unexpected zwitterionic complex, [PdCl3(1H‐κP)] (3), and the expected bis(phosphane) complex, trans‐[PdCl2(1H‐κP)2]Cl2 (4), which were structurally characterized. The defined and air‐stable solvated complex 3·Me2CO and the in situ generated Pd(OAc)2/1·HCl system were found to be active catalysts for the Suzuki–Miyaura cross‐coupling of anionic triolborates with aryl bromides, giving the corresponding biphenyls. These reactions, which do not require the presence of an additional base, were advantageously performed in aqueous ethanol, and the coupling products were isolated in good to excellent yields.
Contribution to PNA–RNA Chimera Synthesis: One‐Pot Microwave‐Assisted Ugi Reaction to Obtain Dimeric Building Blocks
Authors: Ovadia Reuben , Mondielli Clémence , Vasseur Jean‐Jacques , Baraguey Carine , Alvarez Karine
Published: November 2016

We report a solution‐phase synthesis of dimeric PNA–RNA (PNA = peptide nucleic acid) building blocks by using a microwave‐assisted Ugi four‐component reaction. A mixture of a functionalized amine, a carboxymethyl nucleobase, paraformaldehyde, and N4,2′‐O,3′‐O‐tribenzoyl‐5′‐deoxy‐5′‐isocyanocytidine generates the dimeric chimeras in one step. The method is simple, and gives rapid access (5 min) to diversity, as exemplified by the products described here.
Screening of tyrosinase inhibitors by capillary electrophoresis with immobilized enzyme microreactor and molecular docking
Authors: Cheng Mengxia , Chen Zilin
Published: November 2016

A new method for screening tyrosinase inhibitors from traditional Chinese medicines (TCMs) was successfully developed by capillary electrophoresis with reliable online immobilized enzyme microreactor (IMER). In addition, molecular docking study has been used for supporting inhibition interaction between enzyme and inhibitors. The IMER of tyrosinase was constructed at the outlet of the capillary by using glutaraldehyde as cross‐linker. The parameters including enzyme reaction, separation of the substrate and product, and the performance of immobilized tyrosinase were investigated systematically. Because of using short‐end injection procedure, the product and substrate were effectively separated within 2 min. The immobilized tyrosinase could remain 80% active for 30 days at 4°C. The Michaelis–Menten constant of tyrosinase was determined as 1.78 mM. Kojic acid, a known tyrosinase inhibitor, was used as a model compound for the validation of the inhibitors screening method. The half‐maximal inhibitory concentration of kojic acid was 5.55 μM. The method was successfully applied for screening tyrosinase inhibitors from 15 compounds of TCM. Four compounds including quercetin, kaempferol, bavachinin, and bakuchiol were found having inhibitory potentials. The results obtained in this work were supported by molecular docking study.
Paper‐based solid‐phase microextraction for analysis of 8‐hydroxy‐2’‐deoxyguanosine in urine sample by CE‐LIF
Authors: Meng Xiangying , Liu Qinrui , Ding Yongsheng
Published: November 2016

An easy‐to‐do paper‐based solid‐phase microextraction (p‐SPME) was developed for determination of 8‐hydroxy‐2’‐deoxyguanosine (8‐OHdG) in urine sample by CE‐LIF. Small piece of filter paper was used as a solid phase to extract 8‐OHdG from urine sample. Its primary mechanism is based on the hydrogen‐bonding interaction between 8‐OHdG and cellulose molecules. The effects of the pH of the sample solution, extraction time, and temperature on the peak area of the analyte were investigated in order to obtain the optimal p‐SPME conditions. Comparing with the untreated sample, the p‐SPME can significantly reduce the interference to the separation of 8‐OHdG by CE‐LIF. Meanwhile, the p‐SPEM can provide more than three times concentrated effect. The developed method was evaluated according to an FDA guideline for biological analysis. The precisions (RSD%, n = 5) of the peak area and migration time of the analyte at three different concentrations were within 3.02–5.82% and 0.92–1.58%, respectively. The limit of identification of the method is about 5 nM according to the significant difference between two sets of the samples with and without spiking the standard (Student's t‐test, p < 0.05). Good linearity was obtained in the range of 10–1000 nM (R2>0.99) based on the standard addition. The recoveries at three different concentrations were within 99.8–103.5%. The results of the real sample analysis are consistent with those reported in our previous paper (Electrophoresis 2014, 35, 1873–1879).
Structural, Electrical, and Electrochemical Characteristics of LnBa0.5Sr0.5Co1.5Fe0.5O5+δ (Ln=Pr, Sm, Gd) as Cathode Materials in Intermediate‐Temperature Solid Oxide Fuel Cells
Authors: Jeong Donghwi , Jun Areum , Ju Young‐Wan , Hyodo Junji , Shin Jeeyoung , Ishihara Tatsumi , Lim Tak‐Hyoung , Kim Guntae
Published: November 2016

Layered perovskite oxides have received great attention as prospective cathode materials for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs) because of their high electrical conductivities and fast oxygen kinetics. Herein, we focus on the structural, electrical, and electrochemical properties of layered perovskites LnBa0.5Sr0.5Co1.5Fe0.5O5+δ (LnBSCF, Ln=Pr, Sm, and Gd) as a cathode material for IT‐SOFCs. Among the evaluated perovskites, PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) showed the highest electrical conductivity, the highest oxygen content, and the highest values of the oxygen bulk diffusion coefficient (D*) and surface exchange coefficient (k) measured by using isotope oxygen exchange. The composite cathode of PBSCF and gadolinium‐doped ceria is the most suitable cathode material for IT‐SOFCs among the materials investigated because of its excellent electrochemical properties and fast oxygen kinetics.
The effects of pharmaceuticals on a unionid mussel (Lampsilis siliquoidea): An examination of acute and chronic endpoints of toxicity across life stages
Authors: Gilroy Ève A.M. , Gillis Patricia L. , King Laura E. , Bendo Nicholas A. , Salerno Joseph , Giacomin Marina , de Solla Shane R.
Published: November 2016

The toxicity and bioconcentration of 3 pharmaceuticals (amitriptyline, iopamidol, and sertraline) were examined using multiple life stages (larval, juvenile, and adult) of the unionid mussel Lampsilis siliquoidea. The endpoints examined varied with life stage but included survival, behavior (algal clearance rate, filtering frequency), and oxidative stress. Iopamidol was not toxic at concentrations up to 101 mg/L. Sertraline was the most toxic chemical (50% lethal concentrations [LC50] and effect concentrations [EC50] = 0.02–0.04 mg/L), but exposure did not induce oxidative stress. Glochidia and juveniles were more sensitive than adult mussels. Algal clearance rate in juvenile mussels was the most sensitive endpoint assessed, similar to or lower than the LC50 values for glochidia. However, the compounds examined were not toxic at concentrations detected in the environment. The relative bioconcentration factors were sertraline > amitriptyline > iopamidol. These results suggest that glochidia toxicity could be a screening tool for rapidly assessing the toxicity of chemicals of concern to freshwater mussels. Environ Toxicol Chem 2017;36:1572–1583. © 2016 SETAC
Synthesis and Electrochemical Properties of BaFe1−xCuxO3−δ Perovskite Oxide for IT‐SOFC Cathode
Authors: Xie D. , Guo W. , Guo R. , Liu Z. , Sun D. , Meng L. , Zheng M. , Wang B.
Published: November 2016

A series of iron‐based perovskite oxides BaFe1−xCuxO3−δ (x = 0.10, 0.15, 0.20 and 0.25, abbreviated as BFC‐10, BFC‐15, BFC‐20 and BFC‐25, respectively) as cathode materials have been prepared via a combined EDTA‐citrate complexing sol‐gel method. The effects of Cu contents on the crystal structure, chemical stability, electrical conductivity, thermal expansion coefficient (TEC) and electrochemical properties of BFC‐x materials have been studied. All the BFC‐x samples exhibit the cubic phase with a space group Pm3m (221). The electrical conductivity decreases with increasing Cu content. The maximum electrical conductivity is 60.9 ± 0.9 S cm−1 for BFC‐20 at 600 °C. Substitution of Fe by Cu increases the thermal expansion coefficient. The average TEC increases from 20.6 × 10−6 K−1 for BFC‐10 to 23.7 × 10−6 K−1 for BFC‐25 at the temperature range of 30–850 °C. Among the samples, BFC‐20 shows the best electrochemical performance. The area specific resistance (ASR) of BFC‐20 on SDC electrolyte is 0.014 Ω cm2 at 800 °C. The single fuel cell with the configguration of BFC‐20/SDC/NiO‐SDC delivers the highest power density of 0.57 W cm−2 at 800 °C. The favorable electrochemical activities can be attributed to the cubic lattice structure and the high oxygen vacancy concentration caused by Cu doping.
Pricing the CBOE VIX Futures with the Heston–Nandi GARCH Model
Authors: Wang Tianyi , Shen Yiwen , Jiang Yueting , Huang Zhuo
Published: November 2016

We propose a closed‐form pricing formula for the Chicago Board Options Exchange Volatility Index (CBOE VIX) futures based on the classic discrete‐time Heston–Nandi GARCH model. The parameters are estimated using several sets of data, including the S&P 500 returns, the CBOE VIX, VIX futures prices and combinations of these data sources. Based on the resulting empirical pricing performances, we recommend the use of both VIX and VIX futures prices for a joint estimation of model parameters. Such estimation method can effectively capture the variations of the market VIX and the VIX futures prices simultaneously for both in‐sample and out‐of‐sample analysis. © 2016 Wiley Periodicals, Inc. Jrl Fut Mark 37:641–659, 2017
Equity Option Implied Probability of Default and Equity Recovery Rate
Authors: Chang Bo Young , Orosi Greg
Published: November 2016

There is a close link between prices of equity options and the default probability of a firm. We show that in the presence of positive expected equity recovery, standard methods that assume zero equity recovery at default misestimate the option‐implied default probability. We introduce a simple method to detect stocks with positive expected equity recovery by examining option prices and propose a method to extract the default probability from option prices that allows for positive equity recovery. We demonstrate possible applications of our methodology with examples that include financial institutions in the United States during the 2007–09 subprime crisis. © 2016 Wiley Periodicals, Inc. Jrl Fut Mark 37:599–613, 2017
Index Futures Trading Restrictions and Spot Market Quality: Evidence from the Recent Chinese Stock Market Crash
Authors: Han Qian , Liang Jufang
Published: November 2016

Using a difference‐in‐difference approach, we find that restrictions placed on the CSI 300 and CSI 500 index futures trading during the recent Chinese stock market crisis deteriorated spot market quality, particularly the September trade restrictions. Our results can be explained by the sudden risk exposure faced by alpha‐strategy traders who stop trading spots after the index futures trading restrictions are introduced, thus worsening the spot market quality. © 2016 Wiley Periodicals, Inc. Jrl Fut Mark 37:411–428, 2017
Sparse multivariate factor analysis regression models and its applications to integrative genomics analysis
Authors: Zhou Yan , Wang Pei , Wang Xianlong , Zhu Ji , Song Peter X.‐K.
Published: November 2016

The multivariate regression model is a useful tool to explore complex associations between two kinds of molecular markers, which enables the understanding of the biological pathways underlying disease etiology. For a set of correlated response variables, accounting for such dependency can increase statistical power. Motivated by integrative genomic data analyses, we propose a new methodology—sparse multivariate factor analysis regression model (smFARM), in which correlations of response variables are assumed to follow a factor analysis model with latent factors. This proposed method not only allows us to address the challenge that the number of association parameters is larger than the sample size, but also to adjust for unobserved genetic and/or nongenetic factors that potentially conceal the underlying response‐predictor associations. The proposed smFARM is implemented by the EM algorithm and the blockwise coordinate descent algorithm. The proposed methodology is evaluated and compared to the existing methods through extensive simulation studies. Our results show that accounting for latent factors through the proposed smFARM can improve sensitivity of signal detection and accuracy of sparse association map estimation. We illustrate smFARM by two integrative genomics analysis examples, a breast cancer dataset, and an ovarian cancer dataset, to assess the relationship between DNA copy numbers and gene expression arrays to understand genetic regulatory patterns relevant to the disease. We identify two trans‐hub regions: one in cytoband 17q12 whose amplification influences the RNA expression levels of important breast cancer genes, and the other in cytoband 9q21.32‐33, which is associated with chemoresistance in ovarian cancer.
Health Effects of Economic Crises
Authors: Ruhm Christopher J.
Published: November 2016

This analysis summarizes prior research and uses national, US state and county‐level data from 1976 to 2013 to examine whether the mortality effects of economic crises differ in kind from those of the more typical fluctuations. The tentative conclusion is that economic crises affect mortality rates (and presumably other measures of health) in the same way as less severe downturns – leading to improvements in physical health. The effects of severe national recessions in the USA appear to have a beneficial effect on mortality that is roughly twice as strong as that predicted by the elevated unemployment rates alone, while the higher predicted rate of suicides during typical periods of economic weakness is approximately offset during severe recessions. No consistent pattern is obtained for more localized economic crises occurring at the state level – some estimates suggest larger protective mortality effects while others indicate offsetting deleterious consequences. Copyright © 2016 John Wiley & Sons, Ltd.
Careful in the Crisis? Determinants of Older People's Informal Care Receipt in Crisis‐Struck European Countries
Authors: Costa‐Font Joan , Karlsson Martin , Øien Henning
Published: November 2016

Macroeconomic downturns can have an important impact on the receipt of informal and formal long‐term care, because recessions increase the number of unemployed and affect net wealth. This paper investigates how the market for informal care changed during and after the Great Recession in Europe, with particular focus on the determinants of care receipt. We use data from the Survey of Health, Ageing and Retirement in Europe, which includes a rich set of variables covering waves before and after the Great Recession. We find evidence of an increase in the availability of informal care after the economic downturn when controlling for year and country fixed effects. This trend is mainly driven by changes in care provision of individuals not cohabiting with the care recipient. We also find evidence of several determinants of informal care receipt changing during the crisis – such as physical needs, personal wealth, and household structures. Copyright © 2016 John Wiley & Sons, Ltd.
Household Financial Distress and Initial Endowments: Evidence from the 2008 Financial Crisis
Authors: Olafsson Arna
Published: November 2016

This paper studies in utero exposure to the 2008 financial crisis. Exploiting the sudden and unexpected collapse of the Icelandic economy, I find that first‐trimester exposure to the crisis led to a sizable and significant reduction in birth weight, increased the probability of a low birth weight ( < 2500 g), and decreased the probability of a high birth weight ( > 4000 g). I also find evidence that the collapse reduced the sex ratio, indicating selection in utero due to maternal prenatal stress exposure. My results imply large welfare losses from financial distress that have hitherto been ignored – because children with worse health at birth can expect substantially lower lifetime earnings – and suggest that economic hardships may in general exacerbate income inequalities in the long run as low‐income households are typically more exposed to financial distress. Copyright © 2016 John Wiley & Sons, Ltd.
The postrhinal cortex is not necessary for landmark control in rat head direction cells
Authors: Peck James R. , Taube Jeffery S.
Published: November 2016

The rodent postrhinal cortex (POR), homologous to primate areas TH/TF and the human 'parahippocampal place area', has been implicated in processing visual landmark and contextual information about the environment. Head direction (HD) cells are neurons that encode allocentric head direction, independent of the animal's location or behavior, and are influenced by manipulations of visual landmarks. The present study determined whether the POR plays a role in processing environmental information within the HD circuit. Experiment 1 tested the role of the POR in processing visual landmark cues in the HD system during manipulation of a visual cue. HD cells from POR lesioned animals had similar firing properties, shifted their preferred firing direction following rotation of a salient visual cue, and in darkness had preferred firing directions that drifted at the same rate as controls. Experiment 2 tested the PORs involvement in contextual fear conditioning, where the animal learns to associate a shock with both a tone and a context in which the shock was given. In agreement with previous studies, POR lesioned animals were able to learn the tone–shock pairing, but displayed less freezing relative to controls when reintroduced into the environment previously paired with a shock. Therefore, HD cells from POR lesioned animals, with demonstrated impairments in contextual fear conditioning, were able to use a visual landmark to control their preferred direction. Thus, despite its importance in processing visual landmark information in primates, the POR in rats does not appear to play a pivotal role in controlling visual landmark information in the HD system. © 2016 Wiley Periodicals, Inc.
Association between breast cancer genetic susceptibility variants and terminal duct lobular unit involution of the breast
Authors: Bodelon Clara , Oh Hannah , Chatterjee Nilanjan , Garcia‐Closas Montserrat , Palakal Maya , Sherman Mark E. , Pfeiffer Ruth M. , Geller Berta M. , Vacek Pamela M. , Weaver Donald L. , Chicoine Rachael E. , Papathomas Daphne , Xiang Jackie , Patel Deesha A. , Khodr Zeina G. , Linville Laura , Clare Susan E. , Visscher Daniel W. , Mies Carolyn , Hewitt Stephen M. , Brinton Louise A. , Storniolo Anna Maria , He Chunyan , Chanock Stephen J. , Gierach Gretchen L. , Figueroa Jonine D.
Published: November 2016

Terminal duct lobular units (TDLUs) are the predominant source of future breast cancers, and lack of TDLU involution (higher TDLU counts, higher acini count per TDLU and the product of the two) is a breast cancer risk factor. Numerous breast cancer susceptibility single nucleotide polymorphisms (SNPs) have been identified, but whether they are associated with TDLU involution is unknown. In a pooled analysis of 872 women from two studies, we investigated 62 established breast cancer SNPs and relationships with TDLU involution. Poisson regression models with robust variance were used to calculate adjusted per‐allele relative risks (with the non‐breast cancer risk allele as the referent) and 95% confidence intervals between TDLU measures and each SNP. All statistical tests were two‐sided; P < 0.05 was considered statistically significant. Overall, 36 SNPs (58.1%) were related to higher TDLU counts although this was not statistically significant (p = 0.25). Six of the 62 SNPs (9.7%) were nominally associated with at least one TDLU measure: rs616488 (PEX14), rs11242675 (FOXQ1) and rs6001930 (MKL1) were associated with higher TDLU count (p = 0.047, 0.045 and 0.031, respectively); rs1353747 (PDE4D) and rs6472903 (8q21.11) were associated with higher acini count per TDLU (p = 0.007 and 0.027, respectively); and rs1353747 (PDE4D) and rs204247 (RANBP9) were associated with the product of TDLU and acini counts (p = 0.024 and 0.017, respectively). Our findings suggest breast cancer SNPs may not strongly influence TDLU involution. Agnostic genome‐wide association studies of TDLU involution may provide new insights on its biologic underpinnings and breast cancer susceptibility.
Objectively-Verified Parental Non-Hip Major Osteoporotic Fractures and Offspring Osteoporotic Fracture Risk: A Population-Based Familial Linkage Study
Authors: Yang Shuman , Leslie William D , Walld Randy , Roos Leslie L , Morin Suzanne N , Majumdar Sumit R , Lix Lisa M
Published: November 2016

Parental hip fracture (HF) is associated with increased risk of offspring major osteoporotic fractures (MOFs; comprising hip, forearm, clinical spine or humerus fracture). Whether other sites of parental fracture should be used for fracture risk assessment is uncertain. The current study tested the association between objectively-verified parental non-hip MOF and offspring incident MOF. Using population-based administrative healthcare data for the province of Manitoba, Canada, we identified 255,512 offspring with linkage to at least one parent (238,054 mothers and 209,423 fathers). Parental non-hip MOF (1984–2014) and offspring MOF (1997–2014) were ascertained with validated case definitions. Time-dependent multivariable Cox proportional hazards regression models were used to estimate adjusted hazard ratios (HRs) and 95% confidence intervals (95% CIs). During a median of 12 years of offspring follow-up, we identified 7045 incident MOF among offspring (3.7% and 2.5% for offspring with and without a parental non-hip MOF, p < 0.001). Maternal non-hip MOF (HR 1.27; 95% CI, 1.19 to 1.35), paternal non-hip MOF (HR 1.33; 95% CI, 1.20 to 1.48), and any parental non-hip MOF (HR 1.28; 95% CI, 1.21 to 1.36) were significantly associated with offspring MOF after adjusting for covariates. The risk of MOF was even greater for offspring with both maternal and paternal non-hip MOF (adjusted HR 1.61; 95% CI, 1.27 to 2.02). All HRs were similar for male and female offspring (all pinteraction >0.1). Risks associated with parental HF only (adjusted HR 1.26; 95% CI, 1.13 to 1.40) and non-hip MOF only (adjusted HR 1.26; 95% CI, 1.18 to 1.34) were the same. The strength of association between any parental non-hip MOF and offspring MOF decreased with older parental age at non-hip MOF (ptrend = 0.028). In summary, parental non-hip MOF confers an increased risk for offspring MOF, but the strength of the relationship decreases with older parental age at fracture. © 2016 American Society for Bone and Mineral Research.

Abstract

The current study tested the effect of parental major osteoporotic fractures (MOF) on offspring MOF risk in 238,054 mothers, fathers 209,423 and 255,512 offspring using population-based administrative data linkage. There was an independent association between parental non-hip MOF and offspring MOF, but this relationship decreased with older parental age at the first fracture. Risks associated with parental hip and non-hip MOF were the same. We also demonstrated dose-response in terms of the number of parents with non-hip MOF, number of parental MOF, and presence of both parental hip and non-hip MOF in combination.