bluuebunny/crossref_metadata_2025 huggingface dataset:
Neutrino Astrophysics
Authors: Haxton Wick C.
Published: September 2014

The article contains sections titled:

Introduction

Solar Neutrinos

The Standard Solar Model

SNOand Super‐Kamiokande

Neutrino Mass and Oscillations

Solar Neutrinos: Outlook

Atmospheric Neutrinos

The Neutrino Source

Atmospheric Neutrinos and Proton‐Decay Detectors

Outlook

Supernovae Neutrinos and Nucleosynthesis

The Explosion Mechanism and Neutrino Burst

Supernova Neutrino Physics

Neutrinos and Nucleosynthesis

Neutrinos in Big‐Bang Nucleosynthesis (BBN)

The Neutrino Process

The r‐Process

Neutrino Cooling and Red Giants

Red Giants and Helium Ignition

Neutrino Magnetic Moments

High‐Energy Astrophysical Neutrinos

Neutrino Production by Cosmic Rays

Point Sources and Neutrino Telescopes

Acknowledgments
Rhodium‐Catalyzed Direct Oxidative CH Acylation of 2‐Arylpyridines with Terminal Alkynes: A Synthesis of Pyrido[2,1‐a]isoindoles
Authors: Zhao Binlin , Yu Mengxuan , Liu Hui , Chen Yu , Yuan Yu , Xie Xuejian
Published: September 2014

A synthesis of pyrido[2,1‐a]isoindoles is reported by the rhodium‐catalyzed direct oxidative CH acylation of 2‐aryl pyridines with terminal alkynes. The desired products were obtained in moderate to excellent yields. This is an efficient and clean method to construct CC/CN bonds in one step. In addition, the effective rhodium(III) catalyst was isolated and characterized by X‐ray crystallography.

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Bioproduction of Chiral Epoxyalkanes using Styrene Monooxygenase from Rhodococcus sp. ST‐10 (RhSMO)
Authors: Toda Hiroshi , Imae Ryouta , Itoh Nobuya
Published: September 2014

We describe the enantioselective epoxidation of straight‐chain aliphatic alkenes using a biocatalytic system containing styrene monooxygenase from Rhodococcus sp. ST‐10 and alcohol dehydrogenase from Leifsonia sp. S749. The biocatalyzed enantiomeric epoxidation of 1‐hexene to (S)‐1,2‐epoxyhexane (>44.6 mM) using 2‐propanol as the hydrogen donor was achieved under optimized conditions. The biocatalyst had broad substrate specificity for various aliphatic alkenes, including terminal, internal, unfunctionalized, and di‐ and tri‐substituted alkenes. Here, we demonstrate that this biocatalytic system is suitable for the efficient production of enantioenriched (S)‐epoxyalkanes.

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Palladium‐Catalyzed Suzuki Carbonylative Reaction of α‐Halomethyl Oxime Ethers: A Regioselective Route to Unsymmetrical 1,3‐Oxyiminoketones
Authors: Noverges Bárbara , Medio‐Simón Mercedes , Asensio Gregorio
Published: September 2014

The three‐component reaction of α‐halomethyl oxime ethers, boronic acids and carbon monoxide at atmospheric pressure catalyzed by tetrakis(triphenylphosphine)palladium(0) gives efficiently unsymmetrical β‐alkoxyimino carbonyl compounds with total control of the regioselectivity, in high yield and atomic economy. Simple commercially available starting materials are used in this synthetic procedure. The three components assembly takes place preferentially versus the competing direct coupling or other possible side reactions. The mechanism of the transformation was investigated by NMR and intermediate palladium(II) complexes were detected.

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Reaction kinetics and mechanism of catalyzed hydrolysis of waste PET using solid acid catalyst in supercritical CO2
Authors: Li Xue‐Kun , Lu Hui , Guo Wen‐Ze , Cao Gui‐Ping , Liu Hong‐Lai , Shi Yun‐Hai
Published: September 2014

Hydrolysis of waste poly(ethylene terphthalate) (PET) using solid acid catalyst in SCCO2 is presented in this work for the first time. The mechanism of PET chains scission was proved to be a combination of chain end and random chain scission by Fourier transform ‐ infrared spectroscopy (FT‐IR) and titration analysis. A new reaction kinetics model of PET hydrolysis in SCCO2 was setup by introducing the Arrhenius equation into an ordinary reaction rate equation, the frequency factor and apparent activation energy were expressed in terms of temperature and CO2 pressure, respectively. With this reaction kinetics model, the effects of temperature, and pressure were investigated. An interesting mechanism was proposed to describe the reaction process that both water molecules and hydroniums were carried and penetrated into the amorphous regions of the swollen PET by SCCO2, subsequently hydrolysis reaction preferentially took place in the amorphous regions of both surface and bulk of PET matrix. © 2014 American Institute of Chemical Engineers AIChE J, 61: 200–214, 2015
Delineation of the 3p14.1p13 microdeletion associated with syndromic distal limb contractures
Authors: Thevenon Julien , Monnier Nicole , Callier Patrick , Dieterich Klaus , Francoise Michel , Montgomery Tara , Kjaergaard Susanne , Neas Katherine , Dixon Joanne , Dahm Thomas Lee , Huet Frédéric , Ragon Clémence , Mosca‐Boidron Anne‐Laure , Marle Nathalie , Duplomb Laurence , Aubriot‐Lorton Marie‐Hélène , Mugneret Francine , Vokes Steve A. , Tucker Haley W. , Lunardi Joël , Faivre Laurence , Jouk Pierre Simon , Thauvin‐Robinet Christel
Published: September 2014

Distal limb contractures (DLC) represent a heterogeneous clinical and genetic condition. Overall, 20–25% of the DLC are caused by mutations in genes encoding the muscle contractile apparatus. Large interstitial deletions of the 3p have already been diagnosed by standard chromosomal analysis, but not associated with a specific phenotype. We report on four patients with syndromic DLC presenting with a de novo 3p14.1p13 microdeletion. The clinical features associated multiple contractures, feeding problems, developmental delay, and intellectual disability. Facial dysmorphism was constant with low‐set posteriorly rotated ears and blepharophimosis. Review of previously reported cases with a precise mapping of the deletions, documented a 250 kb smallest region of overlap (SRO) necessary for DLC. This region contained one gene, EIF4E3, the first three exons of the FOXP1 gene, and an intronic enhancer of FOXP1 named hs1149. Sanger sequencing and locus quantification of hs1149, EIF4E3, and FOXP1 in a cohort of 11 French patients affected by DLC appeared normal. In conclusion, we delineate a new microdeletion syndrome involving the 3p14.1p13 locus and associated with DLC and severe developmental delay. © 2014 Wiley Periodicals, Inc.
Handing the pen to the patient: Reflective writing for children and families affected by genetic conditions
Authors: Murali Chaya , Fernbach Susan D. , Potocki Lorraine
Published: September 2014

Genetic diagnoses impact the Quality of Life (QoL) of patients and their families. While some patients and families report a positive impact on QoL, others are affected negatively by a genetic diagnosis. No matter the impact, it is clear that social support is needed for this population. Genetic healthcare providers should be aware of the need for psychosocial support and be equipped to provide or direct patients and families to the appropriate resources. Reflective writing offers a unique opportunity for families and health care providers to engage in self‐reflection and expression, activities which have the potential to enhance QoL in a positive manner. The therapeutic potential of writing has been studied in many populations, from caregivers of elderly individuals with dementia, to cancer survivors, to survivors of traumatic experiences. Some of these interventions have shown promise for improving participants' QoL. However, reflective writing has never been studied in patients and families affected by genetic conditions. We propose that reflective writing therapy is a feasible, reproducible, and enjoyable approach to providing psychosocial support for our patients. Get it Write is a reflective writing workshop pilot project for those who have a personal or family history of a genetic diagnosis. Our hypothesis is that reflective writing will help engender acceptance and alleviate feelings of isolation. Get it Write does not focus on the stressful factors in the participants' lives, rather it serves to facilitate interactions with peers facing the same struggles, and with medical students in a non‐medical context. © 2014 Wiley Periodicals, Inc.
Possible preventive effect of high doses of folic acid for isolated hypospadias: A national population‐based case–control study
Authors: Mavrogenis Stelios , Urban Róbert , Czeizel Andrew E. , Ács Nándor
Published: September 2014

Hypospadias is a common structural birth defect (congenital abnormality) of the male genital organ. The objective of this study was to test the hypothesis regarding the possible preventive effect of folic acid for isolated hypospadias (IH). Folic acid use was compared in 3,038 cases with IH and 24,814 male controls without any defects in the national population‐based Hungarian Case–Control Surveillance of Congenital Abnormalities, 1980–1996. In Hungary only one kind of folic acid tablet, containing 3 mg/tablet was available during the study period. Hungarian obstetricians recommended daily use of 1–3 tablets, that is, 3–9 mg of folic acid during pregnancy; the estimated daily dose was 5.7 or 5.6 mg in the mothers of cases with IH and controls, respectively. Of 3,038 mothers of cases 1,474 (48.5%) were supplemented with high doses of folic acid during pregnancy and 13,509/24,814 mothers of controls (54.9%) as reference were supplemented at this level as well (OR 95% CI: 0.79, 0.73–0.85). If only medically recorded folic acid use in the critical period of IH was evaluated, the preventive effect was more apparent (OR 95% CI: 0.36, 0.32–0.41). The intake of folic acid among mothers of infants with severe IH was lower than among mothers of infants with mild IH, suggesting a dose–response relationship. In conclusion, this study suggests that high doses of folic acid are associated with a reduced risk of IH. However, this analysis was based on observational data; therefore, confirmation in a well‐controlled study is needed. © 2014 Wiley Periodicals, Inc.
Efficient Copper Catalyzed CN Coupling Reaction in Water by Using 2‐Hydroxybenzohydrazides as Ligands
Authors: Yan Nan‐Nan , Wu Feng‐Tian , Zhang Jie , Wei Qian‐Bing , Liu Ping , Xie Jian‐Wei , Dai Bin
Published: September 2014

An efficient and environmentally friendly protocol has been developed for CuSO4‐catalyzed N‐arylation of nitrogen‐containing nucleophiles with aryl halides in water. The method uses 2‐hydroxybenzohydrazides as ligand, avoids the use of organic solvents, and tolerates functional groups well.
Zusammenrücken und Stapeln: von atmenden Poren zu dreidimensionaler ionischer Selbstorganisation unter elektrochemischer Kontrolle
Authors: Cui Kang , Mali Kunal S. , Ivasenko Oleksandr , Wu Dongqing , Feng Xinliang , Walter Michael , Müllen Klaus , De Feyter Steven , Mertens Stijn F. L.
Published: September 2014

Wir zeigen mithilfe der Rastertunnelmikroskopie den spontanen und reversiblen Übergang zwischen zwei‐ und dreidimensionaler Selbstorganisation eines supramolekularen Systems an der Grenzfläche zwischen Flüssigkeit und Metalloberfläche unter elektrochemischer Kontrolle. Durch Abstimmen des Grenzflächenpotentials können wir unsere Zielmoleküle selektiv zu einem Muster aus offenen Poren organisieren und diese mit Gastmolekülen füllen oder aber in einer Doppellage stapeln. Mithilfe eines einfachen elektrostatischen Modells können wir erklären, welche Ladungsdichte zur Bildung von Doppellagen und im Gegenzug welches Molekülgröße/Ladungs‐Verhältnis zum Design neuer Bausteine nötig ist. Unsere Befunde können zu einer neuen Klasse elektrochemisch kontrollierter dynamischer Wirt‐Gast‐Systeme, künstlicher Rezeptoren und “intelligenter” Materialien führen.
Recognition of Nucleic Acid Junctions Using Triptycene‐Based Molecules
Authors: Barros Stephanie A. , Chenoweth David M.
Published: September 2014

The modulation of nucleic acids by small molecules is an essential process across the kingdoms of life. Targeting nucleic acids with small molecules represents a significant challenge at the forefront of chemical biology. Nucleic acid junctions are ubiquitous structural motifs in nature and in designed materials. Herein, we describe a new class of structure‐specific nucleic acid junction stabilizers based on a triptycene scaffold. Triptycenes provide significant stabilization of DNA and RNA three‐way junctions, providing a new scaffold for the development of nucleic acid junction binders with enhanced recognition properties. Additionally, we report cytotoxicity and cell uptake data in two human ovarian carcinoma cell lines.
Gold(I)‐Catalyzed Highly Diastereo‐ and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6‐Enynes
Authors: Qian Deyun , Hu Haoxiang , Liu Feng , Tang Bin , Ye Weimin , Wang Yidong , Zhang Junliang
Published: September 2014

A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo[3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers with high enantioselectivity (up to e.r. 98:2). Control experiments suggest that the quinoline moiety of the β‐gold vinyloxyquinolinium intermediate in the reaction plays an important role in promoting good enantioselectivity through a transitional auxiliary effect in the transition state.
Squeezing, Then Stacking: From Breathing Pores to Three‐Dimensional Ionic Self‐Assembly under Electrochemical Control
Authors: Cui Kang , Mali Kunal S. , Ivasenko Oleksandr , Wu Dongqing , Feng Xinliang , Walter Michael , Müllen Klaus , De Feyter Steven , Mertens Stijn F. L.
Published: September 2014

We demonstrate the spontaneous and reversible transition between the two‐ and three‐dimensional self‐assembly of a supramolecular system at the solid–liquid interface under electrochemical conditions, using in situ scanning tunneling microscopy. By tuning the interfacial potential, we can selectively organize our target molecules in an open porous pattern, fill these pores to form an auto‐host–guest structure, or stack the building blocks in a stratified bilayer. Using a simple electrostatic model, we rationalize which charge density is required to enable bilayer formation, and conversely, which molecular size/charge ratio is necessary in the design of new building blocks. Our results may lead to a new class of electrochemically controlled dynamic host–guest systems, artificial receptors, and smart materials.
Highly Tin‐Selective Stille Coupling: Synthesis of a Polymer Containing a Stannole in the Main Chain
Authors: Linshoeft Julian , Baum Evan J. , Hussain Andreas , Gates Paul J. , Näther Christian , Staubitz Anne
Published: September 2014

The incorporation of heavier Group 14 element heteroles into semiconducting polymers leads to unusual optoelectronic properties. However, polymers containing stannoles have not been accessible to date. We report a synthetic route to a well‐defined, stannole‐containing polymer, the first example of this class of π‐conjugated polymers. This route was made possible by developing difunctionalized stannole monomers and highly tin‐selective Stille coupling reactions that leave the tin in the stannole untouched. Compared to poly(3‐n‐hexylthiophene), the resulting polymer displays a remarkable bathochromic shift in its absorption.
A Heterometallic FeII–DyIII Single‐Molecule Magnet with a Record Anisotropy Barrier
Authors: Liu Jun‐Liang , Wu Jie‐Yi , Chen Yan‐Cong , Mereacre Valeriu , Powell Annie K. , Ungur Liviu , Chibotaru Liviu F. , Chen Xiao‐Ming , Tong Ming‐Liang
Published: September 2014

A record anisotropy barrier (319 cm−1) for all d‐f complexes was observed for a unique FeII‐DyIII‐FeII single‐molecule magnet (SMM), which possesses two asymmetric and distorted FeII ions and one quasi‐D5h DyIII ion. The frozen magnetization of the DyIII ion leads to the decreased FeII relaxation rates evident in the Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks to the exchange doublets.
Substitution‐Inert Trinuclear Platinum Complexes Efficiently Condense/Aggregate Nucleic Acids and Inhibit Enzymatic Activity
Authors: Malina Jaroslav , Farrell Nicholas P. , Brabec Viktor
Published: September 2014

The trinuclear platinum complexes (TriplatinNC‐A [{Pt(NH3)3}2‐μ‐{trans‐Pt(NH3)2(NH2(CH2)6NH2)2}]6+, and TriplatinNC [{trans‐Pt(NH3)2(NH2(CH2)6NH3+)}2‐μ‐{trans‐Pt(NH3)2(NH2(CH2)6NH2)2}]8+) are biologically active agents that bind to DNA through noncovalent (hydrogen bonding, electrostatic) interactions. Herein, we show that TriplatinNC condenses DNA with a much higher potency than conventional DNA condensing agents. Both complexes induce aggregation of small transfer RNA molecules, and TriplatinNC in particular completely inhibits DNA transcription at lower concentrations than naturally occurring spermine. Topoisomerase I‐mediated relaxation of supercoiled DNA was inhibited by TriplatinNC‐A and TriplatinNC at concentrations which were 60 times and 250 times lower than that of spermine. The mechanisms for the biological activity of TriplatinNC‐A and TriplatinNC may be associated with their ability to condense/aggregate nucleic acids with consequent inhibitory effects on crucial enzymatic activities.
Potential role of nanofillers as compatibilizers in immiscible PLA/LDPE Blends
Authors: Vrsaljko Domagoj , Macut Dejan , Kovačević Vera
Published: September 2014

This article describes the use of commercial silica (SiO2) and calcium carbonate (CaCO3) nanofillers as compatibilizers in immiscible polylactide/low‐density polyethylene (PLA/LDPE) blends. The general aim of the study was to investigate the possibilities of replacing standard commodity plastics such as LDPE based on non‐renewable mineral oil resources with the biodegradable renewable polymer PLA in compatibilized PLA/LDPE blends for use in the packaging industry. The calculations of the minimal interfacial energy and optimal wetting abilities indicated that SiO2 filler was a better potential compatibilizer than CaCO3 for a given PLA/LDPE blend. This was due to its preferential localization at the interface. The significantly improved morphology of the ternary PLA/LDPE/SiO2 blend was found to present an increased strength, toughness, and crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41414.
Effects of surface modification of carbon nanofibers on the mechanical properties of polyamide 1212 composites
Authors: Cai Ziqing , Meng Xiaoyu , Zhang Xiaocan , Cui Lishan , Zhou Qiong
Published: September 2014

In this study, the effects of carbon nanofiber (CNF) surface modification on mechanical properties of polyamide 1212 (PA1212)/CNFs composites were investigated. CNFs grafted with ethylenediamine (CNF‐g‐EDA), and CNFs grafted with polyethyleneimine (CNF‐g‐PEI) were prepared and characterized. The mechanical properties of the PA1212/CNFs composites were reinforced efficiently with addition of 0.3 wt % modified CNFs after drawing. The reinforcing effect of the drawn composites was investigated in terms of interfacial interaction, crystal orientation, crystallization properties and so on. After the surface modification of CNFs, the interfacial adhesion and dispersion of CNFs in PA1212 matrix were improved, especially for CNF‐g‐PEI. The improved interfacial adhesion and dispersion of CNFs in PA1212 matrix was beneficial to reinforcement of the composites. Compared with pure PA1212, improved degree of crystal orientation in the PA1212/CNF‐g‐PEI (CNF‐g‐EDA) composites was responsible for reinforcement of mechanical properties after drawing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41424.
Influence of compositions and polymerization processes on morphologies, molar mass distributions, and phase structures of n‐Butyl acrylate–methyl methacrylate copolymers
Authors: Erola Markus O. A. , Suvanto Sari , Pakkanen Tuula T.
Published: September 2014

The target of the research is to examine influence of a polymerization process and monomer ratio on structures and compositions of phases in an emulsion copolymerization of n‐butyl acrylate (BA) and methyl methacrylate (MMA). Emulsion copolymerizations are performed using three different BA/MMA weight ratios (60%/40%, 50%/50%, and 40%/60%) and two different processes, statistical batch and seeded emulsion polymerizations. Phase structures, monomer compositions, and morphological stabilities of copolymers are investigated by differential scanning calorimetry, 1H‐NMR, and scanning electron microscopy. Gel permeation chromatography is used to follow the changes in the molar mass distribution during syntheses. The gel content and backbiting level of end products are measured by extraction and 13C‐NMR, respectively. Copolymerizations give products with a bimodal molar mass distribution and three or two separate phases having different BA/MMA compositions. The morphological stability of particles decreases with the increasing BA fraction in the feed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41467.
Physical and mechanical properties of the fully interconnected chitosan ice‐templated scaffolds
Authors: Pourhaghgouy Masoud , Zamanian Ali
Published: September 2014

Porous chitosan scaffolds were prepared with a freeze‐casting technique with different concentrations, 1.5 and 3 wt %, and also different cooling rates, 1 and 4°C/min. The pore morphology, porosity, pore size, mechanical properties, and water absorption characteristics of the scaffolds were studied. Scanning electron microscopy images showed that the freeze‐cast scaffolds were fully interconnected because of the existence of pores on the chitosan walls in addition to many unidirectionally elongated pores. Increases in the chitosan concentration and freezing rate led to elevations in the thickness of the chitosan walls and reductions in the pores size, respectively. These two results led to the enhancement of the compressive strength from 34 to 110 kPa for the scaffolds that had 96–98% porosity. Also, augmentation of the chitosan concentration and decreases in the freezing rate led to the reduction of the number of pores on the chitosan walls. Furthermore, the volume of water absorption increased with a reduction in the chitosan concentration and cooling rate from 690 to 1020%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41476.
Polypropylene/silica micro‐ and nanocomposites modified with poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)
Authors: Pustak Anđela , Denac Matjaž , Leskovac Mirela , Švab Iztok , Musil Vojko , Šmit Ivan
Published: September 2014

The effects of different silica loadings and elastomeric content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with 5, 10, 15, and 20 vol % of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) SEBS added to total composite volume were investigated. Four silica fillers differing in size (nano‐ vs. micro‐) and in surface properties (untreated vs. treated) were chosen as fillers. Elastomer SEBS was added as impact modifier and compatibilizer at the same time. The morphology of ternary polymer composites revealed by light and scanning electron microscopies was compared with morphology predicted models based on interfacial properties. The results indicated that general morphology of composite systems was determined primarily by interfacial properties, whereas the spherulitic morphology of polypropylene matrix was a result of two competitive effects: nucleation effect of filler and solidification effect of elastomer. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough SEBS elastomer. Spherulitic morphology of polypropylene matrix might affect some mechanical properties additionally. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41486.
Design, Synthesis, and Biological Evaluation of Hydrazone Incorporated 1,2,4‐Triazines as Anticonvulsant Agents
Authors: Amir Mohammed , Ali Israr , Hassan Mohd. Zaheen , Mulakayala Naveen
Published: September 2014

New hydrazone incorporated triazines were designed and synthesized using an appropriate synthetic route with regard to essential pharmacophores, and evaluated for their anticonvulsant activity through maximal electroshock seizure (MES) and subcutaneous pentylenetetrazole‐induced seizure (scPTZ) screenings. Among the tested compounds, 4‐[{2‐(5‐(3‐chlorobenzyl)‐3‐phenyl‐1,2,4‐triazine‐6‐yl)hydrazono}methyl]‐N,N‐dimethylaniline 6k (MES ED50 54.31, scPTZ ED50 92.01) and 4‐[{2‐(5‐(4‐chlorobenzyl)‐3‐phenyl‐1,2,4‐triazine‐6‐yl)hydrazono}methyl]‐N,N‐dimethylaniline 6r (MES ED50 46.05, scPTZ ED50 83.90) emerged as the most active anticonvulsant agents having GABAergic effects. Compounds 6k and 6r also showed lesser CNS depressant effect than the standard drug carbamazepine. To obtain further insights into the binding interactions of these molecules, molecular docking studies were carried out.
New CYP17 Hydroxylase Inhibitors: Synthesis, Biological Evaluation, QSAR, and Molecular Docking Study of New Pregnenolone Analogs
Authors: Al‐Masoudi Najim A. , Ali Dawood S. , Saeed Bahjat , Hartmann Rolf W. , Engel Matthias , Rashid Sajid , Saeed Aamer
Published: September 2014

A new series of pregnenonlone analogs were synthesized and evaluated for their inhibitory activity against cytochrome P450 (CYP17 hydroxylase enzyme). In general, the 5‐aryl‐1,3,4‐thiadiazol‐2‐yl)‐imino‐pregnenolone derivatives 11–15 were more active than the sulfonate 24–31 and the ester 37–41 analogs. Derivative 12 showed optimal activity in this series, with IC50 values of 2.5 µM compared with the standard abiraterone (IC50 = 0.07 µM). However, the analogs 11 and 25 showed a better selectivity profile (81.5 and 82.7% inhibition of hydroxylase, respectively), which may be a useful lead in CYP17 inhibition studies. Molecular docking studies demonstrated quite similar binding patterns of all new pregnenolone derivatives at the active site of CYP17 through hydrogen bonding and hydrophobic interaction.
Analyzing return asymmetry and quantiles through stochastic volatility models using asymmetric Laplace error via uniform scale mixtures
Authors: Wichitaksorn Nuttanan , Wang Joanna J. J. , Choy S. T. Boris , Gerlach Richard
Published: September 2014

This paper proposes a new approach to analyze stock return asymmetry and quantiles. We also present a new scale mixture of uniform (SMU) representation for the asymmetric Laplace distribution (ALD). The use of the SMU for a probability distribution is a data augmentation technique that simplifies the Gibbs sampler of the Bayesian Markov chain Monte Carlo algorithms. We consider a stochastic volatility (SV) model with an ALD error distribution. With the SMU representation, the full conditional distribution for some parameters is shown to have closed form. It is also known that the ALD can be used to obtain the coefficients of quantile regression models. This paper also considers a quantile SV model by fixing the skew parameter of the ALD at specific quantile level. Simulation study shows that the proposed methodology works well in both SV and quantile SV models using Bayesian approach. In the empirical study, we analyze index returns of the stock markets in Australia, Japan, Hong Kong, Thailand, and the UK and study the effect of S&P 500 on these returns. The results show the significant return asymmetry in some markets and the influence by S&P 500 in all markets at all quantile levels. Copyright © 2014 John Wiley & Sons, Ltd.
Motor Learning in Individuals With Autism Spectrum Disorder: Activation in Superior Parietal Lobule Related to Learning and Repetitive Behaviors
Authors: Travers Brittany G. , Kana Rajesh K. , Klinger Laura G. , Klein Christopher L. , Klinger Mark R.
Published: September 2014

Motor‐linked implicit learning is the learning of a sequence of movements without conscious awareness. Although motor symptoms are frequently reported in individuals with autism spectrum disorder (ASD), recent behavioral studies have suggested that motor‐linked implicit learning may be intact in ASD. The serial reaction time (SRT) task is one of the most common measures of motor‐linked implicit learning. The present study used a 3T functional magnetic resonance imaging scanner to examine the behavioral and neural correlates of real‐time motor sequence learning in adolescents and adults with ASD (n = 15) compared with age‐ and intelligence quotient‐matched individuals with typical development (n = 15) during an SRT task. Behavioral results suggested less robust motor sequence learning in individuals with ASD. Group differences in brain activation suggested that individuals with ASD, relative to individuals with typical development, showed decreased activation in the right superior parietal lobule (SPL) and right precuneus (Brodmann areas 5 and 7, and extending into the intraparietal sulcus) during learning. Activation in these areas (and in areas such as the right putamen and right supramarginal gyrus) was found to be significantly related to behavioral learning in this task. Additionally, individuals with ASD who had more severe repetitive behavior/restricted interest symptoms demonstrated greater decreased activation in these regions during motor learning. In conjunction, these results suggest that the SPL may play an important role in motor learning and repetitive behavior in individuals with ASD. Autism Res 2015, 8: 38–51. © 2014 International Society for Autism Research, Wiley Periodicals, Inc.
Assessing Theory of Mind Nonverbally in Those With Intellectual Disability and ASD: The Penny Hiding Game
Authors: San José Cáceres Antonia , Keren Noa , Booth Rhonda , Happé Francesca
Published: September 2014

Individuals with autism spectrum disorder (ASD) and low intellectual/language abilities are often omitted from experimental studies because of the challenges of testing these individuals. It is vital to develop appropriate and accessible tasks so that this significant part of the spectrum is not neglected. The theory of mind (ToM) has been extensively assessed in ASD, predominantly in relatively high‐functioning individuals with reasonable language skills. This study aims to assess the ToM abilities of a sample of 132 participants with intellectual disability (ID) with and without ASD, matched in verbal mental age (VMA) and chronological age, using a naturalistic and nonverbal deception task: the Penny Hiding Game (PHG). The relationship between performance on the PHG and everyday adaptation was also studied. The PHG proved accessible to most participants, suggesting its suitability for use with individuals with low cognitive skills, attentional problems, and limited language. The ASD + ID group showed significantly more PHG errors, and fewer tricks, than the ID group. PHG performance correlated with Vineland adaptation scores for both groups. VMA was a major predictor of passing the task in both groups, and participants with ASD + ID required, on average, 2 years higher VMA than those with ID only, to achieve the same level of PHG success. VMA moderated the association between PHG performance and real‐life social skills for the ASD + ID more than the ID group, suggesting that severely impaired individuals with ASD may rely on verbal ability to overcome their social difficulties, whereas individuals with ID alone may use more intuitive social understanding both in the PHG and everyday situations. Autism Res 2014, 7: 608–616. © 2014 International Society for Autism Research, Wiley Periodicals, Inc.
A designed buried salt bridge modulates heterodimerization of a membrane peptide
Authors: Shinde Sandip , Binder Jennifer K. , Goyal Bhupesh , Woodrum B. , De Munari Sonia , Levitus Marcia , Ghirlanda Giovanna
Published: September 2014

Specific helix–helix interactions underpin the correct assembly of multipass membrane proteins. Here, we show that a designed buried salt bridge mediates heterodimer formation of model transmembrane helical peptides in a pH‐dependent manner. The model peptides bear side chains functionalized with either a carboxylic acid or a primary amine within a hydrophobic segment. The association behavior was monitored by Förster resonance energy transfer, revealing that heterodimer formation is maximized at a pH close to neutrality (pH 6.5), at which each peptide is found in a charged state. In contrast, heterodimerization is disfavored at low and high values of pH, because either the carboxylic acid or the primary amine is present in its neutral state, thus preventing the formation of a salt bridge. These findings provide a blueprint for the design and modulation of protein–protein interactions in membrane proteins. © 2014 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 102: 437–443, 2014.
Solidification of floating organic drop liquid‐phase microextraction cell fishing with gas chromatography–mass spectrometry for screening bioactive components from Amomum villosum Lour
Authors: Xue Xue , Yang Depo , Wang Dongmei , Xu Xinjun , Zhu Longping , Zhao Zhimin
Published: September 2014

In this study, a novel solidification of floating organic drop liquid‐phase microextraction cell fishing with gas chromatography–mass spectrometry (SFOD‐LPME‐CF‐GC‐MS) method was established and used to screen, isolate and analyze bioactive components from Amomum villosum Lour. extract. Through comparision of its effect on the models of normal cell and inflammatory cells, anti‐inflammatory active components of essential oil from A. villosum Lour. were readily screened, and the components obtained are in agreement with related pharmacological articles. SFOD‐LPME‐CF‐GC‐MS was used to analyze the interaction of A. villosum Lour. extracts with normal and lipopolysaccharide‐stimulated RAW264.7 macrophage cells. The effect of A. villosum Lour. essential oil extracts in the LPS‐stimulated RAW264.7 model were also assessed in terms of cytotoxicity and nitric oxide production as an indication of bioactivity. Three potentially bioactive components were identified, demonstrating that SFOD‐LPME‐CF‐GC‐MS can be used successfully in the drug‐screening process. This approach avoids the requirement for protein precipitation, but more importantly, generates a high concentration ratio, allowing analysis of trace components in traditional Chinese medicines. SFOD‐LPME‐CF‐GC‐MS is a simple, fast, effective and reliable method for the screening and analysis of bioactive components, and it can be extended to screen other bioactive components from TCMs. Copyright © 2014 John Wiley & Sons, Ltd.
Immobilization of Proteins in their Physiological Active State at Functionalized Thiol Monolayers on ATR‐Germanium Crystals
Authors: Schartner Jonas , Gavriljuk Konstantin , Nabers Andreas , Weide Philipp , Muhler Martin , Gerwert Klaus , Kötting Carsten
Published: September 2014

Protein immobilization on solid surfaces has become a powerful tool for the investigation of protein function. Physiologically relevant molecular reaction mechanisms and interactions of proteins can be revealed with excellent signal‐to‐noise ratio by vibrational spectroscopy (ATR‐FTIR) on germanium crystals. Protein immobilization by thiol chemistry is well‐established on gold surfaces, for example, for surface plasmon resonance. Here, we combine features of both approaches: a germanium surface functionalized with different thiols to allow specific immobilization of various histidine‐tagged proteins with over 99 % specific binding. In addition to FTIR, the surfaces were characterized by XPS and fluorescence microscopy. Secondary‐structure analysis and stimulus‐induced difference spectroscopy confirmed protein activity at the atomic level, for example, physiological cation channel formation of Channelrhodopsin 2.
Nanoarchitectured Graphene‐Based Supercapacitors for Next‐Generation Energy‐Storage Applications
Authors: Salunkhe Rahul R. , Lee Ying‐Hui , Chang Kuo‐Hsin , Li Jing‐Mei , Simon Patrice , Tang Jing , Torad Nagy L. , Hu Chi‐Chang , Yamauchi Yusuke
Published: September 2014

Tremendous development in the field of portable electronics and hybrid electric vehicles has led to urgent and increasing demand in the field of high‐energy storage devices. In recent years, many research efforts have been made for the development of more efficient energy‐storage devices such as supercapacitors, batteries, and fuel cells. In particular, supercapacitors have great potential to meet the demands of both high energy density and power density in many advanced technologies. For the last half decade, graphene has attracted intense research interest for electrical double‐layer capacitor (EDLC) applications. The unique electronic, thermal, mechanical, and chemical characteristics of graphene, along with the intrinsic benefits of a carbon material, make it a promising candidate for supercapacitor applications. This Review focuses on recent research developments in graphene‐based supercapacitors, including doped graphene, activated graphene, graphene/metal oxide composites, graphene/polymer composites, and graphene‐based asymmetric supercapacitors. The challenges and prospects of graphene‐based supercapacitors are also discussed.
Selectfluor and NFSI exo‐Glycal Fluorination Strategies Applied to the Enhancement of the Binding Affinity of Galactofuranosyltransferase GlfT2 Inhibitors
Authors: Dumitrescu Lidia , Eppe Guillaume , Tikad Abdellatif , Pan Weidong , Bkassiny Sandy El , Gurcha Sudagar S. , Ardá Ana , Jiménez‐Barbero Jesús , Besra Gurdyal S. , Vincent Stéphane P.
Published: September 2014

Two complementary methods for the synthesis of fluorinated exo‐glycals have been developed, for which previously no general reaction had been available. First, a Selectfluor‐mediated fluorination was optimized after detailed analysis of all the reaction parameters. A dramatic effect of molecular sieves on the course of the reaction was observed. The reaction was generalized with a set of biologically relevant furanosides and pyranosides. A second direct approach involving carbanionic chemistry and the use of N‐fluorobenzenesulfonimide (NFSI) was performed and this method gave better diastereoselectivities. Assignment of the Z/E configuration of all the fluorinated exo‐glycals was achieved based on the results of HOESY experiments. Furthermore, fluorinated exo‐glycal analogues of UDP‐galactofuranose were prepared and assayed against GlfT2, which is a key enzyme involved in the cell‐wall biosynthesis of major pathogens. The fluorinated exo‐glycals proved to be potent inhibitors as compared with a series of C‐glycosidic analogues of UDP‐Galf, thus demonstrating the double beneficial effect of the exocyclic enol ether functionality and the fluorine atom.
Palladium–N‐Heterocyclic Carbene (NHC)‐Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp3)H Activation: Scope and DFT Study
Authors: Katayev Dmitry , Larionov Evgeny , Nakanishi Masafumi , Besnard Céline , Kündig E. Peter
Published: September 2014

Invited for the cover of this issue is the group of E. Peter Kündig at the University of Geneva. The cover illustrates the regiodivergent reaction taken by two enantiomers when subjected to a chiral Pd(N‐heterocyclic carbene) catalyst. The combination of a divergent reaction with an enantioselective CH functionalization makes for fascinating chemistry. Read the full text of the article at 10.1002/chem.201403985.
Total Synthesis of the Anti‐inflammatory and Pro‐resolving Lipid Mediator MaR1n−3 DPA Utilizing an sp3–sp3 Negishi Cross‐Coupling Reaction
Authors: Tungen Jørn Eivind , Aursnes Marius , Dalli Jesmond , Arnardottir Hildur , Serhan Charles Nicholas , Hansen Trond Vidar
Published: September 2014

Invited for the cover of this issue are members of the groups of Professors Trond V. Hansen, University of Oslo and Charles N. Serhan, Brigham & Women’s Hospital, Harvard Institute of Medicine, Harvard Medical School. The image depicts the successful application of an sp3–sp3 Pd‐catalyzed Negishi cross‐coupling reaction using the PEPPSI™‐IPr catalyst. Read the full text of the article at 10.1002/chem.201404721.
ChemInform Abstract: Quaternary Arsenides ACdGeAs2 (A: K, Rb) Built of Ethane‐Like Ge2As6 Units.
Authors: Khatun Mansura , Stoyko Stanislav S. , Mar Arthur
Published: September 2014

KCdGeAs2 (I) and RbCdGeAs2 (II) are prepared by solid state reactions of stoichiometric mixtures of the elements (alumina crucible in evacuated silica tube, 650 °C (I) and 600 °C (II), 10 d).
ChemInform Abstract: Strontium Vanadium Oxide—Hydrides: “Square‐Planar” Two‐Electron Phases.
Authors: Denis Romero Fabio , Leach Alice , Moeller Johannes S. , Foronda Francesca , Blundell Stephen J. , Hayward Michael A.
Published: September 2014

SrVO2H, Sr2VO3H, and Sr3V2O5H2 are prepared by topochemical replacement of oxide ions in SrVO3, Sr2VO4, and Sr3V2O7, resp., by hydride ions using CaH2 (600—630 °C).
ChemInform Abstract: Synthesis and Electrochemical Performance of the Orthorhombic Li2Fe(SO4)2 Polymorph for Li‐Ion Batteries.
Authors: Lander Laura , Reynaud Marine , Rousse Gwenaelle , Sougrati Moulay T. , Laberty‐Robert Christel , Messinger Robert J. , Deschamps Michael , Tarascon Jean‐Marie
Published: September 2014

A new orthorhombic polymorph of Li2Fe(SO4)2 is prepared by high‐energy ball milling of stoichiometric amounts of FeSO4 and Li2SO4 which results in well crystallized samples without noticeable amounts of the precursors after 5—10 h.
ChemInform Abstract: Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2‐ Anion.
Authors: Bruns Joern , Kluener Thorsten , Wickleder Mathias S.
Published: September 2014

Direct oxidation of elemental Pt by oleum (65% SO3) in the presence of BaCO3 yields yellow single crystals of Ba[Pt(S2O7)3] (H2SO4)0.5 (H2S2O7)0.5 (sealed glass ampoule, 160 °C).
ChemInform Abstract: A Highly Efficient and Broadly Applicable Cationic Gold Catalyst.
Authors: Malhotra Deepika , Mashuta Mark S. , Hammond Gerald B. , Xu Bo
Published: September 2014

The title catalyst promotes intra‐ and intermolecular X—H (X=C, N, O) addition of alkynes and cycloisomerizations at low‐level loading and with high turnover numbers at room temperature or slightly elevated temperatures.
ChemInform Abstract: Merging Aerobic Oxidation and Enamine Catalysis in the Asymmetric α‐Amination of β‐Ketocarbonyls Using N‐Hydroxycarbamates as Nitrogen Sources.
Authors: Xu Changming , Zhang Long , Luo Sanzhong
Published: September 2014

The title process includes the aerobic oxidation of N‐hydroxycarbamates to give nitrosocarbonyl intermediates which react with β‐keto compounds in the presence of an optically active amine catalyst.
ChemInform Abstract: A Facile Synthesis of β‐Amino Carbonyl Compounds Through an Aza‐Michael Addition Reaction under Solvent‐Free Conditions.
Authors: Huang Chao , Yin Yanqing , Guo Jiahui , Wang Jiong , Fan Baomin , Yang Lijuan
Published: September 2014

Primary and secondary aliphatic amines react at room temperature with oxanorbornene (I) to yield bicyclic adducts (III) whereas anilines produce significant amounts of (Z)‐β‐enamine esters (VI) as side products.
ChemInform Abstract: TsOH‐SiO2 as an Efficient and Eco‐Friendly Catalyst for Knoevenagel Condensation.
Authors: Siddiqui Zeba N. , Tarannum Saima
Published: September 2014

The catalyst is recyclable for six cycles.
ChemInform Abstract: Copper‐Mediated Trifluoromethylation of Aryl‐, Heteroaryl‐, and Vinyltrifluoroborates with Langlois′ Reagent.
Authors: Dubbaka Srinivas Reddy , Salla Manohar , Bolisetti Raghu , Nizalapur Shashidhar
Published: September 2014

The title compounds are obtained using less expensive and stable sodium trifluoromethanesulfinate as the CF3‐source.
ChemInform Abstract: Highly Efficient Direct Aerobic Oxidative Esterification of Cinnamyl Alcohol with Alkyl Alcohols Catalyzed by Gold Nanoparticles Incarcerated in a Nanoporous Polymer Matrix: A Tool for Investigating the Role of the Polymer Host.
Authors: Buonerba Antonio , Noschese Annarita , Grassi Alfonso
Published: September 2014

Direct aerobic oxidation and oxidative esterification of cinnamyl alcohol is achieved using gold nanoparticles supported in a semicrystalline multi‐block polystyrene‐co‐cis‐1,4‐polybutadiene matrix as the catalyst (all yields determined by GC‐analysis using anisole as an internal standard).
ChemInform Abstract: Facile Synthesis of Hybrid Core—Shell Nanospheres for the Asymmetric Transfer Hydrogenation of Aromatic Ketones.
Authors: Wei Juan , Zhang Xiaomin , Zhang Xiaoming , Zhao Yaopeng , Li Ruixiang , Yang Qihua
Published: September 2014

Aryl methyl ketones and α,β‐unsaturated ketones are reduced stereoselectively to secondary alcohols in the presence of Rh‐functionalized hybrid core—shell nanospheres.
ChemInform Abstract: Selective Transfer Hydrogenation and Hydrogenation of Ketones Using a Defined Monofunctional (P^N(Bn)^N(Bn)^P)—RuIIComplex.
Authors: Hsu Shih‐Fan , Plietker Bernd
Published: September 2014

The applied Ru‐complex represents one of the few highly active catalysts reported for transfer hydrogenation as well as hydrogenation of ketones.
ChemInform Abstract: DDQ‐Mediated Oxidation of sp3 C—H Bond for the Direct Synthesis of Vicinal Tricarbonyl Compounds.
Authors: Wang Zheng‐Lin , An Xing‐Lan , Ge Li‐Shi , Jin Jing‐Hai , Luo Xiaoyan , Deng Wei‐Ping
Published: September 2014

Purification of the aliphatic tricarbonyl compound obtained after conversion (V) fails, thus requiring further transformation to the quinoline (VII).
ChemInform Abstract: Ester‐Directed Selective Olefination of Acrylates by Rhodium Catalysis.
Authors: Feng Ruokun , Yu Wenlong , Wang Kai , Liu Zhanxiang , Zhang Yuhong
Published: September 2014

Various styrenes [(I) and (VIII)] react with acrylates [(II) and (V)] to give (Z,E)‐1,3‐dienes in high stereoselectivity.
ChemInform Abstract: One‐Pot Synthesis of 2‐Substituted Benzo[b]furans via Pd—Tetraphosphine Catalyzed Coupling of 2‐Halophenols with Alkynes.
Authors: Zhou Rong , Wang Wei , Jiang Zhi‐jie , Wang Kun , Zheng Xue‐li , Fu Hai‐yan , Chen Hua , Li Rui‐xiang
Published: September 2014

A highly efficient catalyst system [PdCl(allyl)2] and tetraphosphine ligand for the one‐pot synthesis of 2‐substituted benzo[b]furans from 2‐halophenols and alkynes is reported.
ChemInform Abstract: Highly Diastereo‐ and Enantioselective Michael Addition of 3‐Substituted Benzofuran‐2(3H)‐ones to 4‐Oxo‐enoates Catalyzed by Lanthanide(III) Complexes.
Authors: Wang Zhen , Yao Qian , Kang Tengfei , Feng Juhua , Liu Xiaohua , Lin Lili , Feng Xiaoming
Published: September 2014

For the first time optical benzofuran‐2(3H)‐ones (VIII) bearing thioatom‐substituted quaternary stereocenters could be constructed.
ChemInform Abstract: Solvent Free Selective Dehydrogenation of Indolic and Carbazolic Molecules with an Iridium Pincer Catalyst.
Authors: Brayton Daniel F. , Jensen Craig M.
Published: September 2014

Perhydro compounds obtained by high‐pressure hydrogenation with palladium on carbon undergo selective dehydrogenation of the heterocyclic ring using an iridium pincer catalyst IRC.
ChemInform Abstract: Nano‐Sized Polydopamine‐Based Biomimetic Catalyst for the Efficient Synthesis of Cyclic Carbonates.
Authors: Yang Zifeng , Sun Jian , Liu Xiaomin , Su Qian , Liu Ying , Li Qian , Zhang Suojiang
Published: September 2014

Polydopamine nanoparticles are prepared and tested as catalyst for the reaction of oxirans and CO2.
ChemInform Abstract: A Highly Active and Magnetically Recoverable Tris(triazolyl)—CuI Catalyst for Alkyne—Azide Cycloaddition Reactions.
Authors: Wang Dong , Etienne Laetitia , Echeverria Maria , Moya Sergio , Astruc Didier
Published: September 2014

The tris(triazole) (MRC) is found to be a highly efficient catalyst for the title reaction.
ChemInform Abstract: Synthesis of 2‐Aryl‐5‐nitropyridines by Three‐Component Ring Transformation of 3,5‐Dinitro‐2‐pyridone.
Authors: Le Thi Song , Asahara Haruyasu , Kobiro Kazuya , Sugimoto Ryuichi , Saigo Kazuhiko , Nishiwaki Nagatoshi
Published: September 2014

The amount of NH4OAc is crucial to prepare exclusively the pyridine derivatives in high yields.
ChemInform Abstract: Organocatalytic Cascade Reactions: Diversity‐Oriented Synthesis for the Construction of Hydroisoquinoline Scaffolds.
Authors: Gomez Clarisa Villegas , Cruz David Cruz , Mose Rasmus , Joergensen Karl Anker
Published: September 2014

An organocatalytic cascade reaction mediated trienamine [4 + 2]‐cycloaddition/nucleophilic ring‐closing sequence is developed.