bluuebunny/crossref_metadata_2025 huggingface dataset:
tert‐Butyl Hydroperoxide and Tetrabutylammonium Iodide‐Promoted Free Radical Cyclization of α‐Imino‐N‐arylamides and α‐Azido‐N‐arylamides
Authors: Li Dianjun , Yang Tonghao , Su Hailin , Yu Wei
Published: July 2015

The oxidizing system of tert‐butyl hydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) is capable of generating α‐(arylaminocarbonyl)iminyl radicals from ethyl 2‐(N‐arylcarbamoyl)‐2‐iminoacetates. These iminyl radicals preferably undergo intramolecular ipso attack on the benzene ring to give azaspirocyclohexadienyl radicals, which are readily captured by molecular oxygen under an oxygen atmosphere to yield azaspirocyclohexadienones. In the absence of oxygen, the reaction affords quinoxalin‐2‐one products. This oxidizing system is also effective to convert α‐aryl‐α‐azido‐N‐arylamides to the corresponding iminyl radicals under basic conditions (sodium tert‐butoxide, t‐BuONa), and the subsequent cyclization of these iminyl radicals results in the formation of azaspirocyclohexadienone products in high yields under an oxygen atmosphere. Plausible mechanisms are proposed to rationalize the experimental results, and factors influencing the reactions are discussed.

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Response to long‐term growth hormone therapy in patients affected by RASopathies and growth hormone deficiency: Patterns of growth, puberty and final height data
Authors: Tamburrino Federica , Gibertoni Dino , Rossi Cesare , Scarano Emanuela , Perri Annamaria , Montanari Francesca , Fantini Maria Pia , Pession Andrea , Tartaglia Marco , Mazzanti Laura
Published: July 2015

RASopathies are developmental disorders caused by heterozygous germline mutations in genes encoding proteins in the RAS‐MAPK signaling pathway. Reduced growth is a common feature. Several studies generated data on growth, final height (FH), and height velocity (HV) after growth hormone (GH) treatment in patients with these disorders, particularly in Noonan syndrome, the most common RASopathy. These studies, however, refer to heterogeneous cohorts in terms of molecular information, GH status, age at start and length of therapy, and GH dosage. This work reports growth data in 88 patients affected by RASopathies with molecularly confirmed diagnosis, together with statistics on body proportions, pubertal pattern, and FH in 33, including 16 treated with GH therapy for proven GH deficiency. Thirty‐three patients showed GH deficiency after pharmacological tests, and were GH‐treated for an average period of 6.8 ± 4.8 years. Before starting therapy, HV was −2.6 ± 1.3 SDS, and mean basal IGF1 levels were −2.0 ± 1.1 SDS. Long‐term GH therapy, starting early during childhood, resulted in a positive height response compared with untreated patients (1.3 SDS in terms of height‐gain), normalizing FH for Ranke standards but not for general population and Target Height. Pubertal timing negatively affected pubertal growth spurt and FH, with IGF1 standardized score increased from −2.43 to −0.27 SDS. During GH treatment, no significant change in bone age velocity, body proportions, or cardiovascular function was observed. © 2015 Wiley Periodicals, Inc.
Genetic analysis of SNPs in CACNA1C and ANK3 gene with schizophrenia: A comprehensive meta‐analysis
Authors: Nie Fayi , Wang Xiaoli , Zhao Panpan , Yang Hao , Zhu Wenhua , Zhao Yaling , Chen Bo , Valenzuela Robert K. , Zhang Rui , Gallitano Amelia L. , Ma Jie
Published: July 2015

Recently, genome‐wide association studies (GWAS), meta‐analyses, and replication studies focusing on bipolar disorder (BD) have implicated the α‐1C subunit of the L‐type voltage‐dependent calcium channel (CACNA1C) and ankyrin 3 (ANK3) genes in BD. Based on the hypothesis that both schizophrenia (SZ) and BD may share some common genetic risk factors, we investigated the association of CACNA1C and ANK3 with SZ using meta‐analytic techniques, combining all published data up to April 2015. Nine teams, including four European decent samples and five Asian samples, contributed 14,141 cases and 30,679 controls for the analysis of CACNA1C rs1006737 and SZ. A significant difference was identified between patients and controls for the A‐allele of rs1006737 in combined studies (Z = 6.02, P = 1.74E‐09), in European studies (Z = 4.08, P = 4.50E‐05), and in Asian studies (Z = 4.60, P = 4.22E‐06). Meanwhile, for the T‐allele of ANK3 rs10761482 (1,794 cases versus 1,395 controls), a significant association was observed in combined samples (Z = 2.06, P = 0.04) and in Asian samples (Z = 3.10, P = 0.002). In summary, our study provides further evidence for the positive association of CACNA1C and ANK3 with SZ. These results support the hypothesis that both SZ and BD share common genetic risk factors. Further research is needed to examine the functions of CACNA1C and ANK3, and their interacting partners in the molecular, developmental, and pathophysiological processes in SZ. © 2015 Wiley Periodicals, Inc.
A magnetic resonance imaging family study of cortical thickness in schizophrenia
Authors: Goghari Vina M. , Truong Wanda , Spilka Michael J.
Published: July 2015

Schizophrenia is associated with abnormalities in cortical thickness, including both thicker and thinner cortices than controls. Although less reliably than in patients, non‐psychotic relatives of schizophrenia patients have also demonstrated both thicker and thinner cortices than controls, suggesting an effect of familial or genetic liability. We investigated cortical thickness in 25 schizophrenia patients, 26 adult non‐psychotic first‐degree biological relatives, and 23 community controls using the automated program FreeSurfer. Contrary to hypotheses, we found relatives of schizophrenia patients had greater cortical thickness in all lobes compared to patients and controls; however, this finding was not as widespread when compared to controls. In contrast, schizophrenia patients only demonstrated a thinner right fusiform region than controls and relatives. Our finding of greater thickness in adult biological relatives could represent a maladaptive abnormality or alternatively, a compensatory mechanism. Previous literature suggests that the nature of abnormalities in relatives can vary by the age of relatives and change across the developmental period. Abnormalities in patients may depend on lifestyle factors and on current and previous anti‐psychotic medication use. Our results speak to the need to study various populations of patients and relatives across the lifespan to better understand different developmental periods and the impact of environmental factors. © 2015 Wiley Periodicals, Inc.
Biosynthesis‐Assisted Structural Elucidation of the Bartolosides, Chlorinated Aromatic Glycolipids from Cyanobacteria
Authors: Leão Pedro N. , Nakamura Hitomi , Costa Margarida , Pereira Alban R. , Martins Rosário , Vasconcelos Vitor , Gerwick William H. , Balskus Emily P.
Published: July 2015

The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C‐glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural‐elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR‐forming ketosynthase and aromatase. Bioinformatic analysis also revealed a novel potential halogenase. Knowledge of the bartoloside biosynthesis constrained the DAR core structure by defining key pathway intermediates, ultimately allowing us to determine the full structures of the bartolosides. This work illustrates the power of genomics to enable the use of biosynthetic information for structure elucidation.
Finely Tuned Polymer Interlayers Enhance Solar Cell Efficiency
Authors: Liu Yao , Page Zachariah A. , Russell Thomas P. , Emrick Todd
Published: July 2015

Three conjugated polymer zwitterions (CPZs), containing thiophene‐, diketopyrrolopyrrole‐ (DPP), and naphthalene diimide (NDI) backbones, were synthesized with pendant zwitterions, specifically sulfobetaine groups. Diboronate‐ester‐functionalized bithiophene and benzothiadiazole monomers were copolymerized with zwitterion‐substituted dibromothiophene, DPP, and NDI monomers by A2+B2 Suzuki polymerization. The CPZs were incorporated into polymer solar cells (PSCs) as interlayers between the photoactive layer and Ag cathode. The thiophene‐based CPZs gave power conversion efficiencies (PCEs) of about 5 %, while the narrow‐energy‐gap DPP‐ and NDI‐based CPZs performed exceptionally well, giving PCEs of 9.49 % and 10.19 %, respectively. The interlayer thickness had only a minor impact on the device performance for the DPP‐ and NDI‐CPZs, a finding attributed to their electron‐transport properties. Ultraviolet photoelectron and reflectance spectroscopies, combined with external quantum efficiency measurements, provided structure–property relationships that lend insight into the function of CPZ interlayers in PSCs. NDI‐based CPZ interlayers provide some of the best performing organic solar cells reported to date, and prove useful in conjunction with high‐performing polymer‐active layers and stable, high‐work‐function, metal cathodes.
Palladium(II)‐Catalyzed Allylic CH Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation
Authors: Xing Xiangyou , O'Connor Nicholas R. , Stoltz Brian M.
Published: July 2015

The use of Oxone and a palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered α‐quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for CH activation allows for unusual tunable selectivity between a two‐electron oxidation to the allylic acetates and a four‐electron oxidation to the corresponding enals, with the dominant product depending on the presence or absence of water. The versatile synthetic utility of both the allylic acetate and enal products accessible through this methodology is also demonstrated.
Sodium Salts of Anionic Chiral Cobalt(III) Complexes as Catalysts of the Enantioselective Povarov Reaction
Authors: Yu Jie , Jiang Hua‐Jie , Zhou Ya , Luo Shi‐Wei , Gong Liu‐Zhu
Published: July 2015

The sodium salts of anionic chiral cobalt(III) complexes (CCC−Na+) have been found to be efficient catalysts of the asymmetric Povarov reaction of easily accessible dienophiles, such as 2,3‐dihydrofuran, ethyl vinyl ether, and an N‐protected 2,3‐dihydropyrrole, with 2‐azadienes. Ring‐fused tetrahydroquinolines with up to three contiguous stereogenic centers were thus obtained in high yields, excellent diastereoselectivities (endo/exo up to >20:1), and high enantioselectivities (up to 95:5 e.r.).
Highly Ordered Nanoporous Films from Supramolecular Diblock Copolymers with Hydrogen‐Bonding Junctions
Authors: Montarnal Damien , Delbosc Nicolas , Chamignon Cécile , Virolleaud Marie‐Alice , Luo Yingdong , Hawker Craig J. , Drockenmuller Eric , Bernard Julien
Published: July 2015

We designed efficient precursors that combine complementary associative groups with exceptional binding affinities and thiocarbonylthio moieties enabling precise RAFT polymerization. Well defined PS and PMMA supramolecular polymers with molecular weights up to 30 kg mol−1 are synthesized and shown to form highly stable supramolecular diblock copolymers (BCPs) when mixed, in non‐polar solvents or in the bulk. Hierarchical self‐assembly of such supramolecular BCPs by thermal annealing affords morphologies with excellent lateral order, comparable to features expected from covalent diblock copolymer analogues. Simple washing of the resulting materials with protic solvents disrupts the supramolecular association and selectively dissolves one polymer, affording a straightforward process for preparing well‐ordered nanoporous materials without resorting to crosslinking or invasive chemical degradations.
One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes
Authors: Burroughs Laurence , Eccleshare Lee , Ritchie John , Kulkarni Omkar , Lygo Barry , Woodward Simon , Lewis William
Published: July 2015

An intramolecular Cannizzaro‐type hydride transfer to an in situ prepared allene enables the synthesis of ortho‐fused 4‐substituted cycloocta‐2,5‐dien‐1‐ones with unprecedented technical ease for an eight‐ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields.
Protein Delivery System Containing a Nickel‐Immobilized Polymer for Multimerization of Affinity‐Purified His‐Tagged Proteins Enhances Cytosolic Transfer
Authors: Postupalenko Viktoriia , Desplancq Dominique , Orlov Igor , Arntz Youri , Spehner Danièle , Mely Yves , Klaholz Bruno P. , Schultz Patrick , Weiss Etienne , Zuber Guy
Published: July 2015

Recombinant proteins with cytosolic or nuclear activities are emerging as tools for interfering with cellular functions. Because such tools rely on vehicles for crossing the plasma membrane we developed a protein delivery system consisting in the assembly of pyridylthiourea‐grafted polyethylenimine (πPEI) with affinity‐purified His‐tagged proteins pre‐organized onto a nickel‐immobilized polymeric guide. The guide was prepared by functionalization of an ornithine polymer with nitrilotriacetic acid groups and shown to bind several His‐tagged proteins. Superstructures were visualized by electron and atomic force microscopy using 2 nm His‐tagged gold nanoparticles as probes. The whole system efficiently carried the green fluorescent protein, single‐chain antibodies or caspase 3, into the cytosol of living cells. Transduction of the protease caspase 3 induced apoptosis in two cancer cell lines, demonstrating that this new protein delivery method could be used to interfere with cellular functions.
Giant Magnetoresistance in the Half‐Metallic Double‐Perovskite Ferrimagnet Mn2FeReO6
Authors: Li Man‐Rong , Retuerto Maria , Deng Zheng , Stephens Peter W. , Croft Mark , Huang Qingzhen , Wu Hui , Deng Xiaoyu , Kotliar Gabriel , Sánchez‐Benítez Javier , Hadermann Joke , Walker David , Greenblatt Martha
Published: July 2015

The first transition‐metal‐only double perovskite compound, Mn2+2Fe3+Re5+O6, with 17 unpaired d electrons displays ferrimagnetic ordering up to 520 K and a giant positive magnetoresistance of up to 220 % at 5 K and 8 T. These properties result from the ferrimagnetically coupled Fe and Re sublattice and are affected by a two‐to‐one magnetic‐structure transition of the Mn sublattice when a magnetic field is applied. Theoretical calculations indicate that the half‐metallic state can be mainly attributed to the spin polarization of the Fe and Re sites.
Ultrathin Co3S4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions
Authors: Liu Youwen , Xiao Chong , Lyu Mengjie , Lin Yue , Cai Weizheng , Huang Pengcheng , Tong Wei , Zou Youming , Xie Yi
Published: July 2015

Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co3S4 under neutral conditions can be enhanced by exposed octahedral planes and self‐adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn–Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co3+ in the octahedral self‐adapt from low‐spin to high‐spin states. As a result, the synergistic effect endow the Co3S4 nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state‐of‐the‐art among inorganic non‐noble metal compounds.
Vinylation of Unprotected Phenols Using a Biocatalytic System
Authors: Busto Eduardo , Simon Robert C. , Kroutil Wolfgang
Published: July 2015

Readily available substituted phenols were coupled with pyruvate in buffer solution under atmospheric conditions to afford the corresponding para‐vinylphenol derivatives while releasing only one molecule of CO2 and water as the by‐products. This transformation was achieved by designing a biocatalytic system that combines three biocatalytic steps, namely the CC coupling of phenol and pyruvate in the presence of ammonia, which leads to the corresponding tyrosine derivative, followed by deamination and decarboxylation. The biocatalytic transformation proceeded with high regioselectivity and afforded exclusively the desired para products. This method thus represents an environmentally friendly approach for the direct vinylation of readily available 2‐, 3‐, or 2,3‐disubstituted phenols on preparative scale (0.5 mmol) that provides vinylphenols in high yields (65–83 %).
Boronic acid‐based thin films that show saccharide‐responsive multicolor changes
Authors: Iwami Yuto , Yokozawa Takenori , Yamamoto Hiroki , Kanekiyo Yasumasa
Published: July 2015

A novel saccharide sensor that displays a distinct color change resembling a “traffic signal” was developed. By copolymerizing boronic acid and amine monomers on a glass plate, a boronic acid‐containing thin film was obtained. Anionic blue and yellow dyes were adsorbed on the thin film, and the film was immersed in aqueous saccharide solutions containing a cationic red dye. With increase in the saccharide concentration in the solution, the thin film changes color from green to red via yellow. The observed distinct changes in color were attributed to a stepwise release and binding of dyes. The sensitivity of the saccharide sensor was dependent on the monomer composition of the thin film and increased with increasing the boronic acid content. The pH of the saccharide solution was another key factor affecting the sensing behavior, and glucose‐responsive color changes were significantly enhanced at pH 7.8. By optimizing these conditions, significant color changes in response to glucose were achieved. Saccharide selectivity was found to be in the following order: fructose > glucose > galactose = mannose > sucrose. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42679.
Controlled electrochemical synthesis of conductive nanopolypyrrole and its application in the design of a solid‐state ion sensor
Authors: Das Ishwar , Agrawal Namita Rani , Pandey Avinash Kumar , Choudhary Rinki , Pandey P. C.
Published: July 2015

A polypyrrole (PPy) conductive polymer was electrochemically synthesized from pyrrole–cupric chloride (CuCl2)–H2O (system A) and pyrrole–CuCl2–sodium dodecyl sulfate–H2O (system B). Their morphologies and growth behavior were studied, and their aggregates were characterized by powder X‐ray diffraction, scanning electron microscopy, transmission electron spectroscopy, thermogravimetry, and Fourier transform infrared studies. The powder X‐ray diffraction pattern showed only one peak characteristic of PPy. In system B, the dimensions of the fractal patterns were calculated and found to be very close to the theoretical value of diffusion‐limited aggregation. Various morphological transitions were observed at different field intensities and CuCl2 concentrations. Transmission electron spectroscopy studies revealed the formation of nanosized spherical particles 5–10 nm in size. For system B, a potassium‐ion‐selective electrode was constructed on the basis of a dibenzo‐18‐crown‐6 impregnated poly(vinyl chloride) matrix membrane over a synthesized polymer‐modified electrode. The electrode showed Nernstian behavior with a slope of 57 mV; this revealed the potential application of the as‐synthesized material in the design of a solid‐state ion‐selective electrode. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42729.
Calcium Carbonate Mineralized Nanoparticles as an Intracellular Transporter of Cytochrome c for Cancer Therapy
Authors: Koo Ahn Na , Min Kyung Hyun , Lee Hong Jae , Jegal Jun Ho , Lee Jae Won , Lee Sang Cheon
Published: July 2015

A new intracellular delivery system based on an apoptotic protein‐loaded calcium carbonate (CaCO3) mineralized nanoparticle (MNP) is described. Apoptosis‐inducing cytochrome c (Cyt c) loaded CaCO3 MNPs (Cyt c MNPs) were prepared by block copolymer mediated in situ CaCO3 mineralization in the presence of Cyt c. The resulting Cyt c MNPs had a vaterite polymorph of CaCO3 with a mean hydrodynamic diameter of 360.5 nm and exhibited 60 % efficiency for Cyt c loading. The Cyt c MNPs were stable at physiological pH (pH 7.4) and effectively prohibited the release of Cyt c, whereas, at intracellular endosomal pH (pH 5.0), Cyt c release was facilitated. The MNPs enable the endosomal escape of Cyt c for effective localization of Cyt c in the cytosols of MCF‐7 cells. Flow cytometry showed that the Cyt c MNPs effectively induced apoptosis of MCF‐7 cells. These findings indicate that the CaCO3 MNPs can meet the prerequisites for delivery of cell‐impermeable therapeutic proteins for cancer therapy.
Resolution of enantiomers of bupropion and its metabolites by liquid chromatography
Authors: Batra Sonika , Bhushan Ravi
Published: July 2015

Bupropion, a tricyclic aminoketone, is used primarily in the treatment of depression, the management of patients with bipolar and schizo‐affective disorder, and the treatment of Parkinson's disease. Bupropion is marketed as a racemate, but the racemic mixture is known to have several disadvantages while the two isomers of bupropion and its metabolite differ significantly in their pharmacological activities. Therefore, the stereoselective determination of the drug enantiomers in pharamaceutical dosages, plasma or urine is of potential clinical and analytical importance. Different chromatographic methods have been employed for the separation of the two enantiomers. This is the first attempt to review the methods of enantiosepartion of bupropion using both direct and indirect approaches in both HPLC and TLC. The review presents a detailed discussion on the use of chiral stationary phase (based on polysaccharide, α1 acid glycoprotein and ovomucoid column) and chiral derivatizing reagents (based on isothiocyanate and cyanuric chloride) along with TLC separation of bupropion enantiomers using ligand exchange and impregnation methods. The focus is also on the separation mechanism for enantioresolution using the various methods described herein. Copyright © 2015 John Wiley & Sons, Ltd.
Quantitative analysis of 3‐OHB[a]P and (+)‐anti‐BPDE as biomarkers of B[a]P exposure in rats
Authors: Lin Qi , Xiao‐Chen Liu , Bo Yang , Na Liu , Min Shi , Gang Chen , Hui Liu , Jie Zhou , Fa‐Sheng Li
Published: July 2015

The aim of this study was to develop an analytical method for the determination the levels of metabolites of benzo[a]pyrene (B[a]P), 3‐hydroxybenzo(a)pyrene (3‐OHB[a]P) and (+)‐anti‐benzo(a)pyrene diol‐epoxide [(+)‐anti‐BPDE, combined with DNA to form adducts], in rat blood and tissues exposed to B[a]P exposure by high‐performance liquid chromatography with fluorescence detection (HPLC/FD), and to investigate the usefulness of 3‐OHB[a]P and (+)‐anti‐BPDE as markers of intragastrical exposure to B[a]P in rats. The levels of 3‐OH‐B[a]P and B[a]P‐tetrol I‐1 released after acid hydrolysis of (+)‐anti‐BPDE in the samples were measured by HPLC/FD. The calibration curves were linear (r2 > 0.9904), and the lower limit of quantification ranged from 0.34 to 0.45 ng/mL for 3‐OHB[a]P and from 0.43 to 0.58 ng/mL for (+)‐anti‐BPDE. The intra‐ and inter‐day stability assay data suggested that the method is accurate and precise. The recoveries of 3‐OHB[a]P and (+)‐anti‐BPDE were in the ranges of 73.6 ± 5.0 to 116.5 ± 6.3% and 73.3 ± 8.5 to 141.2 ± 13.8%, respectively. A positive correlation was found between the concentration of intragastrical B[a]P and the concentrations of 3‐OH‐B[a]P and (+)‐anti‐BPDE in the blood and in most of the tissues studied, except for the brain and kidney, which showed no correlation between B[a]P and 3‐OHB[a]P and between B[a]P and (+)‐anti‐BPDE, respectively. A sensitive, reliable and rapid HPLC/FD was developed and validated for analysis of 3‐OHB[a]P and (+)‐anti‐BPDE in rat blood and tissues. There was a positive correlation between the concentration of 3‐OHB[a]P or (+)‐anti‐BPDE in the blood and the concentration of 3‐OHB[a]P or (+)‐anti‐BPDE in the most other tissues examined. The concentration of 3‐OHB[a]P or (+)‐anti‐BPDE in the blood could be used as an indicator of the concentration of 3‐OHB[a]P or (+)‐anti‐BPDE in the other tissues in response to B[a]P exposure. These results demonstrate that 3‐OHB[a]P and (+)‐anti‐BPDE are potential biomarkers of B[a]P exposure, which would also be useful to assess the carcinogenic risks from B[a]P exposure. Copyright © 2015 John Wiley & Sons, Ltd.
Determination of the chemical constituents of the different processed products of Anemarrhena asphodeloides Rhizomes by high‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry
Authors: Peng Ying , Zhao Lulu , Lin Dongju , Liu Yuyang , Zhang Mengyu , Song ShaoJiang
Published: July 2015

In this work, high‐performance liquid chromatography (HPLC) coupled with a hybrid quadrupole time of‐flight mass spectrometry (Q‐TOF‐MS/MS) was used to study chemical compositions of different processed products of Rhizoma Anemarrhenae (RA). A Grace AlltimaTM C18 column (250 × 4.6 mm, 5 µm) was used for separation. Mobile phase consisted of 0.1% formic acid and acetonitrile, using gradient elution. ESI‐MS data was acquired in both positive and negative mode. The experiment was established on the basis of a series of reference substances (two xanthone and seven saponins) to qualitatively identify the chemical compounds of different processed products of RA by MS analysis. There was no difference in the type of chemical constituents between different processed products of RA. A total of 25 compounds were identified, including four xanthones, 21 steroidal saponins and eight pairs of isomers. Copyright © 2015 John Wiley & Sons, Ltd.
Engaging Employees in Sustainable Development – a Case Study of Environmental Education and Awareness Training in Hong Kong
Authors: Law Michelle Man Suet , Hills Peter , Hau Billy Chi Hang
Published: July 2015

Environmental education and awareness training can help to develop and encourage a transition to a greener corporate culture. A series of environmental education and awareness training programmes of The Hongkong and Shanghai Banking Corporation Limited (HSBC) (Hong Kong) was used as a case study to assess how learning transfers through nature‐based environmental education and awareness training and to investigate the possible outcomes of providing nature‐based training to employees. Evaluation of the training outcomes, in terms of changes in employees’ environmental knowledge, attitudes and behaviour, was surveyed by using retrospective post‐ and then‐test questionnaires. Results showed that employees who joined these programmes gained knowledge and changed their values and behaviour towards the environment significantly. The study also indicated the establishment of trust in and satisfaction with the organization among employees through the training, which in turn promoted employees’ organizational commitment towards corporate sustainability. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
A Retrospective Analysis of Children's Assessment Reports: What Helps Children Tell?
Authors: McElvaney Rosaleen , Culhane Maebh
Published: July 2015

This paper explores a retrospective analysis of children's file data as a research method of gathering information on children's experiences of informal disclosure of child sexual abuse. This study extracted data from files where children were seen for a child sexual abuse evaluation in Ireland and the children were deemed to have given a credible account of abuse by the professionals concerned. A content analysis was conducted using themes identified in previously published research, based on direct interviews with children about their experiences of informal disclosure. The paper discusses the relative merits and limitations of this method, through reporting on the findings of the file analysis and comparing these findings with findings obtained from a smaller sub‐sample of this sample of children, who were interviewed about their experiences of disclosure. It is suggested that this method is worth exploring with a larger sample size which would enable statistical analysis and thus explore the predictive factors influencing early informal disclosure. Frontline services can contribute to the knowledge base on what helps children tell through service‐based research that uses data already collected from evaluation interviews with children, thus eliminating the need to interview children for research purposes. Copyright © 2015 John Wiley & Sons, Ltd.

‘A content analysis was conducted using themes identified in previously published research’

Key Practitioner Messages

Frontline professionals gather useful data on a daily basis on informal disclosures of child sexual abuse.

Practitioners can contribute to the knowledge base on informal disclosure by systematically gathering information from service users.

We need more information on what helps children tell. We therefore need to explore innovative methods of gathering such information directly from children in ways that do not rely on interviewing children repeatedly yet include the child's voice.

‘We need more information on what helps children tell’
The Relationship between Maternal Childhood Emotional Abuse/Neglect and Parenting Outcomes: A Systematic Review
Authors: Hughes Mary , Cossar Jill
Published: July 2015

This paper reviews the evidence concerning the association between reported maternal childhood experience of emotional abuse and/or neglect and subsequent parenting outcomes. Relevant studies were identified through a systematic search of four electronic databases using a pre‐determined keyword search. Reference lists of included papers were reviewed and key authors in the field contacted to ascertain whether other papers were available. Twelve studies which met our eligibility criteria were included for review. Tentative support was found for a relationship between maternal childhood emotionally abusive/neglectful experiences and a range of adverse parenting outcomes, including increased parenting stress and maltreatment potential, lower empathy and greater psychological control. However, limitations within the research (e.g. small sample sizes, retrospective designs) reduce the confidence with which we can draw firm conclusions. Recommendations are offered for future research together with an outline of clinical implications arising from this review. Copyright © 2015 John Wiley & Sons, Ltd.

‘Twelve studies which met our eligibility criteria were included for review’

Key Practitioner Messages

There is tentative evidence that maternal childhood experience of emotional abuse/neglect may be associated with subsequent deficits in parenting.

Maternal childhood experiences of being parented should be considered when attempting to make sense of children's difficulties and/or problems in the parent-child relationship.

Further research is required to explore these relationships and to build on our knowledge about contextual risk and protective factors.

‘Maternal childhood experiences of being parented should be considered’
Minority Identity Strategies Bound by Prejudice: Restricted Perspectives of People Categorized as Gypsies in Hungary
Authors: Bigazzi Sára , Csertő István
Published: July 2015

In this study, we explored the identity strategies of Hungarian Gypsies with different socialization backgrounds, including the degree of majority and minority identifications, the contents of Gypsy identity as well as coping with threatening social situations. Sampling was based on external social categorization: majority members were asked for contacts to Gypsy acquaintances. Questionnaire data were used to assess socialization background, group identification and preferred coping strategies at different levels, while contents of Gypsy identity were explored in an associative network. Results suggest that subjects make an exclusive choice between national and ethnic identities. While all subjects prefer ethnic identity, subjects with different socialization backgrounds follow different identity strategies. In sum, large‐family subjects are emotionally attached to their ethnic group, avoid interaction with the majority and prefer the idea of a multicultural society. Small‐family subjects are emotionally detached from their ethnic group and vote for a homogeneous society. Results are interpreted in terms of integration‐related social policies. While these are aimed at the foundation of a recognized active minority, members of these new generations find the way of recognition in individual assimilation due to the threat of prejudice. Copyright © 2015 John Wiley & Sons, Ltd.
Potential‐Induced Segregation Phenomena in Bimetallic PtAu Nanoparticles: An In Situ Near‐Ambient‐Pressure Photoelectron Spectroscopy Study
Authors: Papaefthimiou Vasiliki , Diebold Morgane , Ulhaq‐Bouillet Corinne , Doh Won Hui , Blume Raoul , Zafeiratos Spyridon , Savinova Elena R.
Published: July 2015

The surface properties of a model membrane electrode assembly of a high‐temperature proton‐exchange‐membrane fuel cell with a nanostructured PtAu working electrode were studied under operando conditions (polarization, humidified H2 atmosphere, 150 °C) using near‐ambient‐pressure photoelectron spectroscopy (NAP–XPS). NAP–XPS proved to be a powerful tool for the in situ investigation of the changes in the chemical composition, the segregation of the two metals, and the changes in their oxidation state. Nondestructive depth profiling revealed the influence of the polarization and the gas ambient on the distribution of the two metals in the near‐surface region. The results suggest that the surface of the electrode is covered by a thin layer of gold, which is stable at potentials below the onset of surface‐oxide formation. Anodic oxidation of the PtAu electrode pulls Pt to the surface, leading to intermixing of Pt and Au atoms and the formation of an interfacial alloy.
Tailoring Diverse Microwave Properties of High Magnetic Moment FeCo Nanofilms through Different Atom Arrangements
Authors: Zong Baoyu , Phuoc Nguyen Nguyen , Wu Yuping , Ho Pin , Ma Fusheng , Han Guchang , Yang Yi , Li Zhengwen , He Shikun , Wu Yihong
Published: July 2015

The application of a pure FeCo film directly to devices is limited by the intrinsic properties of a homogeneous monolayer of the alloy, despite it having the highest saturation magnetization. A feasible methodology based on alternating current‐density electrodeposition to tune the microwave properties of FeCo films through diverse atom‐stacking arrangements is reported. The properties range from a large relative resonance permeability (up to 728 in the real part) to ultrahigh resonant frequency (up to 5.2 GHz), and extremely wide frequency dispersion (1.5–6.0 GHz); these are not observed in other materials or as a result of conventional doping methods. They are attained using different single‐layer, semi‐multilayer, and multilayer FeCo nanofilms, fabricated by diverse stacking arrangements of Fe and Co atoms during deposition in a single bath. This technique firstly exemplifies the significant effect of atom arrangement on magnetic inhomogeneity, nanoscale morphology, composition, crystal texture, stress, and damping, which in turn largely alters both the static and dynamic magnetic properties of the ferromagnetic film. These thin FeCo films might be used directly in various devices operating in the gigahertz frequency range.
Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT
Authors: Borgogno Andrea , Rastrelli Federico , Bagno Alessandro
Published: July 2015

The relative energies of spin states of several iron(IV)–oxo complexes and related species have been calculated with DFT methods by employing the B3LYP* functional. We show that such calculations can predict the correct ground spin state of FeIV complexes and can then be used to determine the 1H NMR spectra of all spin states; the spectral features are remarkably different, hence calculated paramagnetic 1H NMR spectra can be used to support the structure elucidation of numerous paramagnetic complexes. Applications to a number of stable and reactive iron(IV)–oxo species are described.
Bioinorganic Nanocomposite Hydrogels Formed by HRP–GOx‐Cascade‐Catalyzed Polymerization and Exfoliation of the Layered Composites
Authors: Liao Chuan‐An , Wu Qing , Wei Qing‐Cong , Wang Qi‐Gang
Published: July 2015

The mild preparation of multifunctional nanocomposite hydrogels is of great importance for practical applications. We report that bioinorganic nanocomposite hydrogels, with calcium niobate nanosheets as cross‐linkers, can be prepared by dual‐enzyme‐triggered polymerization and exfoliation of the layered composite. The layered HRP/calcium niobate composites (HRP=horseradish peroxidase) are formed by the assembly of the calcium niobate nanosheets with HRP. The dual‐enzyme‐triggered polymerization can induce the subsequent exfoliation of the layered composite and final gelation through the interaction between polymer chains and inorganic nanosheets. The self‐immobilized HRP‐GOx enzymes (GOx=glucose oxidase) within the nanocomposite hydrogel retain most of enzymatic activity. Evidently, their thermal stability and reusability can be improved. Notably, our strategy could be easily extended to other inorganic layered materials for the fabrication of other functional nanocomposite hydrogels.
Cu‐Catalyzed Cyanation of Arylboronic Acids with Acetonitrile: A Dual Role of TEMPO
Authors: Zhu Yamin , Li Linyi , Shen Zengming
Published: July 2015

The cyanation of arylboronic acids by using acetonitrile as the “CN” source has been achieved under a Cu(cat.)/TEMPO system (TEMPO=2,2,6,6‐tetramethylpiperidine N‐oxide). The broad substrate scope includes a variety of electron‐rich and electron‐poor arylboronic acids, which react well to give the cyanated products in high to excellent yields. Mechanistic studies reveal that TEMPOCH2CN, generated in situ, is an active cyanating reagent, and shows high reactivity for the formation of the CN− moiety. Moreover, TEMPO acts as a cheap oxidant to enable the reaction to be catalytic in copper.
Synthesis, Aromaticity and Photophysical Behaviour of Ferrocene‐ and Ruthenocene‐Appended Semisynthetic Chlorin Derivatives
Authors: Nikkonen Taru , Moreno Oliva María , Taubert Stefan , Melchionna Michele , Kahnt Axel , Helaja Juho
Published: July 2015

Two novel synthetic strategies to covalently link a metallocene electron‐donor unit to a chlorin ring are presented. In one approach, pyropheophorbide a is readily converted into its 131‐ferrocenyl dehydro derivative by nucleophilic addition of the ferrocenyl anion to the 131‐carbonyl group. In another approach, the corresponding 131‐pentamethylruthenocenyl derivative is synthesised from 131‐fulvenylchlorin by a facile ligand exchange/deprotonation reaction with the [RuCp*(cod)Cl] (Cp*=pentamethylcyclopentadienyl; cod=1,5‐cyclooctadiene) complex. The resulting metallocene–chlorins exhibit reduced aromaticity, which was unequivocally supported by ring‐current calculations based on the gauge‐including magnetically induced current (GIMIC) method and by calculated nucleus‐independent chemical shift (NICS) values. The negative ring current in the isocyclic E ring suggests the antiaromatic character of this moiety and also clarifies the spontaneous reactivity of the complexes with oxygen. The oxidation products were isolated and their electrochemical and photophysical properties were studied. The ruthenocene derivatives turned out to be stable under light irradiation and showed photoinduced charge transfer with charge‐separation lifetimes of 152–1029 ps.
Intramolecular Formal anti‐Carbopalladation/Heck Reaction: Facile Domino Access to Carbo‐ and Heterooligocyclic Dienes
Authors: Pawliczek Martin , Milde Bastian , Jones Peter G. , Werz Daniel B.
Published: July 2015

An intramolecular domino process consisting of a formal anti‐carbopalladation followed by Heck reaction is realized. Complex oligo(hetero)cyclic scaffolds are efficiently obtained in one synthetic step from easily obtainable enyne precursors. In contrast to common syn‐carbopalladation reactions of alkyne units, the carbopalladation employed here is designed to afford an anti‐arrangement of the two new substituents across the emerging double bond. A prerequisite is that the residues next to the alkyne should lack any β‐hydrogen atoms. The method paves the way to tri‐ and tetrasubstituted double‐bond systems that have not been accessible by conventional Pd catalysis.
Non‐Uniform Sampling and J‐UNIO Automation for Efficient Protein NMR Structure Determination
Authors: Didenko Tatiana , Proudfoot Andrew , Dutta Samit Kumar , Serrano Pedro , Wüthrich Kurt
Published: July 2015

High‐resolution structure determination of small proteins in solution is one of the big assets of NMR spectroscopy in structural biology. Improvements in the efficiency of NMR structure determination by advances in NMR experiments and automation of data handling therefore attracts continued interest. Here, non‐uniform sampling (NUS) of 3D heteronuclear‐resolved [1H,1H]‐NOESY data yielded two‐ to three‐fold savings of instrument time for structure determinations of soluble proteins. With the 152‐residue protein NP_372339.1 from Staphylococcus aureus and the 71‐residue protein NP_346341.1 from Streptococcus pneumonia we show that high‐quality structures can be obtained with NUS NMR data, which are equally well amenable to robust automated analysis as the corresponding uniformly sampled data.
Gynecologic cancer outcomes in the elderly poor: A population‐based study
Authors: Doll Kemi M. , Meng Ke , Basch Ethan M. , Gehrig Paola A. , Brewster Wendy R. , Meyer Anne‐Marie
Published: July 2015

BACKGROUND

Adults aged ≥65 years who are dually enrolled in Medicare and Medicaid are an at‐risk group in health care. However, to the best of the authors' knowledge, the outcomes of women with gynecologic cancers in this population are unknown.

METHODS

The current study was a population‐based cohort study of North Carolina state cancer registry cases of uterine, ovarian, cervical, and vulvar/vaginal cancers (2003‐2009), with linked enrollment in Medicare and state Medicaid. Outcomes of all‐cause mortality and stage of disease at the time of diagnosis were analyzed as a function of enrollment status using multivariate analysis and survival curves.

RESULTS

Of 4522 women aged ≥65 years (3702 of whom were enrolled in Medicare [82%] and 820 of whom were dually enrolled [18%]), there were 2286 cases of uterine (51%), 1587 cases of ovarian (35%), 302 cases of cervical (7%), and 347 cases of vulvar/vaginal (8%) cancers. Dual enrollees had increased all‐cause mortality overall (adjusted hazard ratio [aHR], 1.34; 95% confidence interval [95% CI], 1.19‐1.49), and within each cancer site (uterine: aHR, 1.22 [95% CI, 1.02‐1.47]; ovarian: aHR, 1.25 [95% CI, 1.05‐1.49]; cervical: aHR, 1.34 [95% CI, 0.96‐1.87]; and vulvar/vaginal: aHR, 1.93 [95% CI, 1.36‐2.72]). Increased odds of advanced‐stage disease at the time of diagnosis among dual enrollees was only present in patients with uterine cancer (adjusted odds ratio, 1.38; 95% CI, 1.06‐1.79). Stratified survival curves demonstrated the strongest disparities among women with early‐stage uterine and early‐stage vulvar/vaginal cancers.

CONCLUSIONS

Women aged ≥65 years who were dually enrolled in Medicare and Medicaid were found to have an overall 34% increase in all‐cause mortality after diagnosis with a gynecologic cancer compared with the non‐dually enrolled Medicare population. Women with early‐stage uterine and vulvar/vaginal cancers appeared to have the most disparate outcomes. Because these malignancies are generally curable, they have the most potential for benefit from targeted interventions. Cancer 2015;121:3591–3599. © 2015 American Cancer Society.
Uncommon BRAF mutations in the follicular variant of thyroid papillary carcinoma: New insights
Authors: Rossi Esther Diana , Martini Maurizio , Bizzarro Tommaso , Capodimonti Sara , Cenci Tonia , Lombardi Celestino Pio , Pontecorvi Alfredo , Fadda Guido , Larocca Luigi Maria
Published: July 2015

BACKGROUND

Mutational analysis is reshaping the practice of fine‐needle aspiration cytology for the diagnosis of thyroid nodules. The v‐Raf murine sarcoma viral oncogene homolog B1 (BRAF) valine (V) to glutamic acid (E) substitution at codon 600 (BRAFV600E) is the most effective diagnostic/prognostic marker and is used mainly for papillary thyroid carcinomas (PTCs). Although BRAFV600E represents 95% of all BRAF mutations, uncommon BRAF mutations have been identified in thyroid carcinomas. For the current study, the authors evaluated morphologic (plump pink cells and sickle‐shaped nuclei) anti‐BRAFV600E antibody (VE1) immunocytochemical and molecular findings of BRAF mutations in PTCs and in the follicular variant of PTC (FVPC).

METHODS

Between January 2013 and June 2014, there were 150 cytologic samples with surgical follow‐up at the authors' institution. BRAF mutations, which were identified using liquid‐based cytology, were classified into wild‐type BRAF, BRAFV600E, and uncommon BRAF mutations. All clinicopathologic correlations between BRAF and FVPCs were analyzed.

RESULTS

Forty‐four of 150 samples were identified as benign histologic lesions, and the authors focused on the 106 cytologic samples from patients who had malignant outcomes (60 PTCs and 46 FVPCs). The series included 16 follicular neoplasms, 36 samples diagnosed as suspicious of malignancy, and 54 samples diagnosed as positive for malignancy. The BRAFV600E mutation was detected in 17.4% of FVPCs and in 66.6% of PTCs, whereas uncommon BRAF mutations were detected only in FVPCs. Plump pink cells and VE1 expression were not identified in samples that had uncommon BRAF mutations. VE1 immunocytochemistry yielded positive results in all 36 samples that had the BRAFV600E mutation.

CONCLUSIONS

Uncommon BRAF mutations were observed only in FVPCs and were linked to less aggressive behavior. Negative/weak VE1 expression was observed in both wild‐type and uncommon BRAF mutations. The current investigation did not reveal any plump cells or morphologic BRAF findings in samples that had uncommon BRAF mutations. In the authors' experience, BRAF mutations detected by DNA methods were more accurate in identifying FVPCs. Cancer (Cancer Cytopathol) 2015;123:593–602. © 2015 American Cancer Society.
Efficient privacy‐preserving temporal and spacial data aggregation for smart grid communications
Authors: Dong Xiaolei , Zhou Jun , Cao Zhenfu
Published: July 2015

Smart grid is ever‐increasingly adopted by nations and governments for its grand development with the underlying technologies of power management and information communications. The real‐time electricity usage can be monitored and aggregated by the smart meters deployed in the household for further analysis, control, and pricing. However, the existing solutions mainly depend on Paillier's additive homomorphic encryptions taking high computational complexity, and the aggregation mainly focused on the time series data generated by one single user. In this paper, we propose an efficient privacy‐preserving temporal and spacial data aggregation from one‐way functions in smart grid communications, which also allows spacial data aggregation from multiple users. The proposed construction can guarantee the unconditional security of users' metering power data privacy from the community gateway and the operation center, and the Adaptive Chosen Ciphertext Attack (CCA2) security of the aggregation result that can only be accessed by the authorized operating center. Both temporal and spacial data aggregation only require computing the underlying one‐way function once. The formal security proof and performance evaluations demonstrate the efficiency and the practicability of our scheme. Copyright © 2015 John Wiley & Sons, Ltd.