bluuebunny/crossref_metadata_2025 huggingface dataset:
PEG/PVDF membranes for separating organosulphur compounds from n‐heptane: Effect of PEG molecular weight
Authors: Hu Wenling , Han Xiaolong , Liu Liangliang , Zhang Xin , Xue Juanqin , Wang Baoyi , Zhang Peng , Cao Xingzhong
Published: September 2016

Polyethylene glycol (PEG) of three different molecular weights was used to prepare PEG/PVDF composite membranes for separating organosulphur compounds from n‐heptane by pervaporation. All the composite membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X‐ray diffraction (XRD), and positron annihilation spectroscopy (PAS). The effects of operating temperature, feed sulphur content, and organosulphur species on performance of PEG/PVDF composite membranes with different molecular weights were investigated. When the feed organosulphur was thiophene, the fluxes decreased with an increase in PEG molecular weight, however, the enrichment factors were in a different order: PEG membrane with molecular weight of 35 000 exhibited the highest enrichment factor of 12.59 for thiophene at 85 °C. When the feed organosulphur was 2‐methylthiophene or 2,5‐dimethylthiophene, it was found that the PEG membrane with molecular weight of 100 000 showed the highest enrichment factor. The results showed that PEG molecular weight has a considerable effect on separation performance for pervaporation desulphurization.
Genetic Ancestry using Mitochondrial DNA in patients with Triple‐negative breast cancer (GAMiT study)
Authors: Rao Roshni , Rivers Aeisha , Rahimi Asal , Wooldridge Rachel , Rao Madhu , Leitch Marilyn , Euhus David , Haley Barbara B.
Published: September 2016

BACKGROUND

Triple‐negative breast cancer (TNBC) lacks estrogen, progesterone, and human epidermal growth factor receptor 2 (HER2)/neu receptors, and is aggressive and therapeutically challenging. Genetic ancestry testing is an emerging medical field. Mitochondrial DNA (mtDNA), which is distinct from nuclear DNA, is maternally inherited and allows for origin determination. Patients with TNBC tend to be younger and are more likely to be African American, making this an ideal disease for mtDNA exploration. To the authors' knowledge, the current study is the first to perform mtDNA for self‐described African American, White, and Hispanic patients with TNBC to identify mtDNA patterns.

METHODS

Patients with TNBC who were at any stage of therapy/survivorship were included. Self‐reported ethnicity was confirmed at the time of the prospective buccal swab. Haplogroup prediction was performed on sequencing of hypervariable region 1. Using sequence similarity scores and lineage databases, sequence patterns were determined. Data regarding presentation and treatment, tumor features, and outcomes was collected.

RESULTS

A total of 92 patients were included: 31 self‐described African American, 31 White, and 30 Hispanic individuals. Hispanic patients were found to have the largest tumor size (4.5 cm; P = .01) and youngest age (41 years; P<.0001). Eight patients were BRCA1/2 mutation carriers. There were no differences noted among groups with regard to surgery, lymph node metastases, or survival. Analysis revealed Nigerian, Cameroon, or Sierra Leone ancestry and haplogroups A, U, H, or B to be the most common mtDNA patterns. Twelve discordances (13%) between mtDNA analysis and self‐described ethnicity were identified among the 92 patients. The highest discordance (26%; 8 patients) was noted in self‐described Hispanic patients: 3 had Nigerian ancestry, and 1 individual demonstrated haplogroup K mtDNA (Ashkenazi Jewish ancestry).

CONCLUSIONS

Discordance between self‐reported ethnicity and mtDNA analysis was identified in 13% of patients with TNBC. The identification of mtDNA patterns with a predisposition toward TNBC may allow for risk stratification. Cancer 2017;107–113. © 2016 American Cancer Society.
Design of a numerical model of lung by means of a special boundary condition in the truncated branches
Authors: Tena Ana F. , Fernández Joaquín , Álvarez Eduardo , Casan Pere , Walters D. Keith
Published: September 2016

Background

The need for a better understanding of pulmonary diseases has led to increased interest in the development of realistic computational models of the human lung.

Methods

To minimize computational cost, a reduced geometry model is used for a model lung airway geometry up to generation 16. Truncated airway branches require physiologically realistic boundary conditions to accurately represent the effect of the removed airway sections. A user‐defined function has been developed, which applies velocities mapped from similar locations in fully resolved airway sections. The methodology can be applied in any general purpose computational fluid dynamics code, with the only limitation that the lung model must be symmetrical in each truncated branch.

Results

Unsteady simulations have been performed to verify the operation of the model. The test case simulates a spirometry because the lung is obliged to rapidly perform both inspiration and expiration. Once the simulation was completed, the obtained pressure in the lower level of the lung was used as a boundary condition. The output velocity, which is a numerical spirometry, was compared with the experimental spirometry for validation purposes.

Conclusions

This model can be applied for a wide range of patient‐specific resolution levels. If the upper airway generations have been constructed from a computed tomography scan, it would be possible to quickly obtain a complete reconstruction of the lung specific to a specific person, which would allow individualized therapies.
Molecular Engineering of Somatostatin Analogue with Minimal Dipeptide Motif Induces the Formation of Functional Nanoparticles
Authors: Shekhter Zahavi Talia , Oron‐Herman Mor , Kostenich Genady , Rub Eyal , Salitra Yoseph , Buzhansky Ludmila , Orenstein Arie , Gazit Ehud , Adler‐Abramovich Lihi
Published: September 2016

Functionalized nanoparticles decorated with functional biological entities serve as preferred vehicles for numerous theranostic applications. Here we offer an alternative strategy in which the targeting moieties also act as building blocks for the formation of functional nanoassemblies. Diphenylalanine, a small, highly potent self‐assembling module, was incorporated with a somatostatin analogue, a modified hormone which preferentially binds to cancer cells. The co‐assembly of the engineered hormone together with the structurally diverse diphenylalanine derivative allowed the formation of bioactive homogenous spherical nanostructures. Significant internalization capacity of the loaded co‐assembled nanospheres into cancer cells in vitro, as well as selective in vivo accumulation in tumors, were demonstrated. These findings present a new method for the molecular engineering of bioactive peptide molecules by minor modifications with a remarkably potent association motif.
Homogeneous Photocatalytic H2 Production Using a RuII Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer
Authors: Khnayzer Rony S. , Olaiya Babatunde S. , El Roz Karim A. , Castellano Felix N.
Published: September 2016

Invited for this month's cover are the research groups of Prof. Rony S. Khnayzer at Lebanese American University and Prof. Felix (Phil) N. Castellano at North Carolina State University. The cover picture illustrates the absorption of visible light by a ruthenium bathophenanthroline MLCT chromophore followed by a sequence of electron transfer steps that ultimately leads to the efficient production of hydrogen gas from water. Read the full text of the article at 10.1002/cplu.201600227.
Telomere‐Mediated Chromosomal Truncation for Generating Engineered Minichromosomes in Maize
Authors: Swyers Nathan C. , Cody Jon P. , McCaw Morgan E. , Graham Nathaniel D. , Zhao Changzeng , Gaeta Robert T. , Birchler James A.
Published: September 2016

Minichromosomes have been generated in maize using telomere‐mediated truncation. Telomere DNA, because of its repetitive nature, can be difficult to manipulate. The protocols in this unit describe two methods for generating the telomere DNA required for the initiation of telomere‐mediated truncation. The resulting DNA can then be used with truncation cassettes for introduction into maize via transformation. © 2016 by John Wiley & Sons, Inc.
Architecture of the Interface between the Perovskite and Hole‐Transport Layers in Perovskite Solar Cells
Authors: Moriya Masahiro , Hirotani Daisuke , Ohta Tsuyoshi , Ogomi Yuhei , Shen Qing , Ripolles Teresa S. , Yoshino Kenji , Toyoda Taro , Minemoto Takashi , Hayase Shuzi
Published: September 2016

The interface between the perovskite (PVK, CH3NH3PbI3) and hole‐transport layers in perovskite solar cells is discussed. The device architecture studied is as follows: F‐doped tin oxide (FTO)‐coated glass/compact TiO2/mesoporous TiO2/PVK/2,2′,7,7′‐tetrakis‐(N,N‐di‐4‐methoxyphenylamino)‐9,9′‐spirobifluorene (Spiro‐MeOTAD)/Au. After a thin layer of 4,4,4‐trifluorobutylammonium iodide (TFBA) was inserted at the interface between PVK and Spiro‐MeOTAD, the photovoltaic efficiency increased from 11.6–14.5 % to 15.1–17.6 %. TFBA (10 ppm) was added in the PVK solution before coating. Owing to the low surface tension of TFBA, TFBA rose to the surface of the PVK layer spontaneously during spin‐coating to make a thin organic layer. The PVK grain boundaries also seemed to be passivated with the addition of TFBA. However, large differences in Urbach energies and valence band energy level were not observed for the PVK layer with and without the addition of TFBA. The charge recombination time constant between the PVK and the Spiro‐MeOTAD became slower (from 8.4 to 280 μsec) after 10 ppm of TFBA was added in the PVK. The experimental results using TFBA conclude that insertion of a very thin layer at the interface between PVK and Spiro‐MeOTAD is effective for suppressing charge recombination and increasing photovoltaic performances.
Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal–Cubic Structural Phase Transition
Authors: Hoque Md Nadim Ferdous , Islam Nazifah , Li Zhen , Ren Guofeng , Zhu Kai , Fan Zhaoyang
Published: September 2016

Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal–cubic structural phase transition of methylammonium lead iodide (MAPbI3). However, the ionic and optical properties of MAPbI3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 °C in the ionic/electrical properties of MAPbI3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. These observations can be explained by the “continuous” nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal–cubic structural phase transition occurs.
Pharmacokinetics of dextromethorphan and its metabolites in horses following a single oral administration
Authors: Corado Carley R. , McKemie Daniel S. , Knych Heather K.
Published: September 2016

Dextromethorphan is an N‐methyl‐D‐aspartate (NMDA) non‐competitive antagonist commonly used in human medicine as an antitussive. Dextromethorphan is metabolized in humans by cytochrome P450 2D6 into dextrorphan, which is reported to be more potent than the parent compound. The goal of this study is to describe the metabolism of and determine the pharmacokinetics of dextromethorphan and its major metabolites following oral administration to horses. A total of 23 horses received a single oral dose of 2 mg/kg. Blood samples were collected at time 0 and at various times up to 96 h post drug administration. Urine samples were collected from 12 horses up to 120 h post administration. Plasma and urine samples were analyzed using liquid chromatography‐mass spectrometry, and the resulting data analyzed using non‐compartmental analysis. The Cmax, Tmax, and the t1/2 of dextromethorphan were 519.4 ng/mL, 0.55 h, and 12.4 h respectively. The area under the curve of dextromethorphan, free dextrorphan, and conjugated dextrorphan were 563.8, 2.19, and 6,691 h*ng/mL respectively. In addition to free and glucuronidated dextrorphan, several additional glucuronide metabolites were identified in plasma, including hydroxyl‐desmethyl dextrorphan, desmethyl dextrorphan, and three forms of hydroxylated dextrorphan. Dextromethorphan was found to be eliminated from the urine predominately as the O‐demethylated metabolite, dextrorphan. Several additional metabolites including several novel hydroxy‐dextrorphan metabolites were also detected in the urine in both free and glucuronidated forms. No significant undesirable behavioural effects were noted throughout the duration of the study. Copyright © 2016 John Wiley & Sons, Ltd.
Bacteria‐type‐specific biparental immune priming in the pipefish Syngnathus typhle
Authors: Beemelmanns Anne , Roth Olivia
Published: September 2016

The transfer of acquired and specific immunity against previously encountered bacteria from mothers to offspring boosts the immune response of the next generation and supports the development of a successful pathogen defense. While most studies claim that the transfer of immunity is a maternal trait, in the sex‐role‐reversed pipefish Syngnathus typhle, fathers nurse the embryos over a placenta‐like structure, which opens the door for additional paternal immune priming. We examined the potential and persistence of bacteria‐type‐specific parental immune priming in the pipefish S. typhle over maturation time using a fully reciprocal design with two different bacteria species (Vibrio spp. and Tenacibaculum maritimum). Our results suggest that S. typhle is able to specifically prime the next generation against prevalent local bacteria and to a limited extent even also against newly introduced bacteria species. Long‐term protection was thereby maintained only against prevailing Vibrio bacteria. Maternal and paternal transgenerational immune priming can complement each other, as they affect different pathways of the offspring immune system and come with distinct degree of specificity. The differential regulation of DNA‐methylation genes upon parental bacteria exposure in premature pipefish offspring indicates that epigenetic regulation processes are involved in transferring immune‐related information across generations. The identified trade‐offs between immune priming and reproduction determine TGIP as a costly trait, which might constrain the evolution of long‐lasting TGIP, if parental and offspring generations do not share the same parasite assembly.
Summer streamflow deficits from regenerating Douglas‐fir forest in the Pacific Northwest, USA
Authors: Perry Timothy D. , Jones Julia A.
Published: September 2016

Despite controversy about effects of plantation forestry on streamflow, streamflow response to forest plantations over multiple decades is not well understood. Analysis of 60‐year records of daily streamflow from eight paired‐basin experiments in the Pacific Northwest of the United States (Oregon) revealed that the conversion of old‐growth forest to Douglas‐fir plantations had a major effect on summer streamflow. Average daily streamflow in summer (July through September) in basins with 34‐ to 43‐year‐old plantations of Douglas‐fir was 50% lower than streamflow from reference basins with 150‐ to 500‐year‐old forests dominated by Douglas‐fir, western hemlock, and other conifers. Study plantations are comparable in terms of age class, treatments, and growth rates to managed forests in the region. Young Douglas‐fir trees, which have higher sapwood area, higher sapflow per unit of sapwood area, higher concentration of leaf area in the upper canopy, and less ability to limit transpiration, appear to have higher rates of evapotranspiration than old trees of conifer species, especially during dry summers. Reduced summer streamflow in headwater basins with forest plantations may limit aquatic habitat and exacerbate stream warming, and it may also alter water yield and timing in much larger basins. Legacies of past forest management or extensive natural disturbances may be confounded with effects of climate change on streamflow in large river basins. Continued research is needed using long‐term paired‐basin studies and process studies to determine the effects of forest management on streamflow deficits in a variety of forest types and forest management systems.
Plasmacytoid dendritic cells induce tolerance predominantly by cargoing antigen to lymph nodes
Authors: Kohli Karan , Janssen Anika , Förster Reinhold
Published: September 2016

Plasmacytoid dendritic cells (pDCs) have been shown to induce tolerance to innocuous antigens. Their migratory properties allow them to take up antigens from the periphery and transport them to the draining lymph nodes or to the thymus. However, pDC‐T‐cell interaction in the primary and secondary lymphoid organs still remains poorly defined. In this study, we show that resting pDCs loaded with exogenous antigen could induce tolerance when transferred intralymphatically into a single lymph node of wild‐type C57BL/6 mice. However, this was a result of antigen transfer from pDCs to endogenous antigen presenting cells and subsequent abortive proliferation of cognate CD4+ T cells. pDCs could not directly induce the proliferation of CD4+ T cells, as observed in mice lacking MHC class II gene. Moreover, pDCs failed to make physical contacts with OT‐II cells as revealed by two‐photon imaging. Thus, the role of resting pDCs in tolerance induction seems to be independent of its direct interaction with cognate CD4+ T cells.
pH‐Controlled Luminescence Turn‐On Behaviour of a Water‐Soluble Europium‐Based Molecular Complex
Authors: Singha Debal Kanti , Majee Prakash , Mondal Sudip Kumar , Mahata Partha
Published: September 2016

We have successfully synthesized a new europium metal–organic complex (MOC) [Eu2(pydcH)6]·3H2O (1, H2pydc = 2,6‐pyridinedicarboxylic acid) by the hydrothermal technique as well as simple solvent evaporation in water. Single‐crystal X‐ray crystallographic data of 1 confirms a molecular complex of tricapped trigonal prismatic Eu3+ ions with a free carboxylic acid site of each 2,6‐pyridinedicarboxylic acid ligand. Complex 1 is water‐soluble and remains stable in a broad pH range of 2–11. Upon excitation at 280 nm 1 shows a characteristic ligand‐sensitized metal‐centred visible red luminescence. The luminescence of complex 1 can be further enhanced by changing the pH of the solution in the range of 2–6. Besides, the luminescence response is completely reversible in the range of pH 2–6. The mechanism of the pH‐dependent luminescence behaviour is successfully explained and supported by UV/Vis absorption and IR spectroscopic experiments.
Chiral and Redox‐Active Room‐Temperature Ionic Liquids Based on Ferrocene and l‐Proline
Authors: Bouvet Carola B. , Krautscheid Harald
Published: September 2016

The syntheses of room‐temperature ionic liquids (RTILs) combining the naturally occurring amino acid l‐proline and ferrocene (Fc) building blocks are reported. After quaternization of ({[(2S)‐N‐methylpyrrolidine‐2‐yl]methyleneoxy}carbonyl)ferrocene (1) with alkyl iodides and anion exchange, the resulting diastereomeric (1S,2S)‐ and (1R,2S)‐[(ferrocenylcarbonyl)oxy]methylene‐N,N‐dialkylpyrrolidine‐1‐ium RTILs are redox‐active and air‐ and water‐stable. They are also thermally stable up to 263 °C. The electrochemical FeII/FeIII potential is shifted to +0.28 V versus Fc/Fc+. Before anion exchange, several iodide derivatives were obtained as crystalline products, and their crystal structures are reported. According to the NMR spectroscopic data cation–anion aggregates are present in the non‐coordinating solvent CDCl3. In contrast, in the polar solvent [D6]dimethyl sulfoxide ([D6]DMSO), the ion pairs are separated.
Formation of NH,NR N‐Heterocyclic Carbene Complexes through Mercuration of Mono‐N‐substituted Benzimidazoles
Authors: Yu Ming‐Hung , Yang Hsueh‐Hui , Naziruddin Abbas Raja , Kanne Shanker , Wang Bo‐Han , Liu Fu‐Chen , Lin Ivan J. B. , Lee Gene‐Hsiang
Published: September 2016

A simple two‐step method to prepare NH,NR N‐heterocyclic carbene (NHC) complexes is described herein. In the first step, the reactions of N‐substituted benzimidazoles (R‐BimH) with Hg(OAc)2 in the presence of NaBr rendered 12‐membered mercuramacrocycles [Hg4(R‐Bim)4Br4] [R = Me, pyridyl (Py), Bn]. These complexes consist of four HgII ions bridged by four benzimidazolyl anions through N and C atoms. This reaction presumably proceeds through an initial N‐complexation of the benzimidazole to the HgII ion. Consequently, C2‐H becomes more acidic, and even an acetate anion can promote the deprotonation at C2 to form the C‐metalated products. The second step involves the protonation of these mercuramacrocycles with HBF4·OEt2 to give the protic complexes featuring the NH,NR–NHC ligands of general formula [(R‐BimH)2Hg][BF4]2 (R = Me, Py, Bn).
C–N Bond Coupling Reactions of Ammonia with Acetone Promoted by Iridium and Rhodium Complexes: Experimental and DFT Studies
Authors: Pilar Betoré M. , García‐Orduña Pilar , Lahoz Fernando J. , Casado Miguel A. , Polo Víctor , Oro Luis A.
Published: September 2016

Treatment of acetone solutions of the known chlorido‐bridged complexes [{M(µ‐Cl)(cod)}2] (M = Ir, Rh; cod = 1,5‐cyclooctadiene) under an ammonia atmosphere afforded the cationic complexes {M(cod)[κN,κN‐NH2–C(CH3)2–CH2–C(CH3)=NH]}Cl [M = Ir (3), Rh (4)]. The molecular structures of 3 and 4 showed the formation of six‐membered metallacycles due to the presence of a 4‐imino‐2‐methylpentan‐2‐amine‐κN,κN‐chelated ligand. Alternatively, the cations [M(cod)(NCCH3)2]BF4 (M = Ir, Rh) reacted with gaseous ammonia at atmospheric pressure affording bis(ammine) complexes [M(cod)(NH3)2]BF4 [M = Ir (5), Rh (6)], which were found to react with acetone, forming cations [M(cod)(κN,κN‐NH2–C(CH3)2–CH2–C(CH3)=NH)]BF4 [M = Ir (7), Rh (8)]. DFT studies reveal that the transformation of 6 into 8 is mediated by NH3 molecules acting as an external base. The reaction is triggered by deprotonation of an ammonia ligand forming a amido–metal intermediate, which further transforms into an acetimino ligand through aldol condensation. The terminal methyl group of one acetimino ligand is deprotonated by NH3 yielding an enamine ligand, which can react with the imine ligand through concerted nucleophilic addition to afford the metallacycle, which is stabilized by protonation.
Well‐Dispersed Fe2O3 Nanoparticles on g‐C3N4 for Efficient and Stable Photo‐Fenton Photocatalysis under Visible‐Light Irradiation
Authors: Zhou Liang , Wang Lingzhi , Zhang Jinlong , Lei Juying , Liu Yongdi
Published: September 2016

In this study, a highly efficient heterogeneous photo‐Fenton system (Fe2O3/g‐C3N4/H2O2/visible light) has been developed. The heterogeneous catalyst Fe2O3/g‐C3N4 in this system was successfully prepared by growing Fe2O3 nanoparticles on the surface of g‐C3N4. The Fe2O3 nanoparticles could achieve high dispersion on the surface of g‐C3N4 and form a heterojunction with g‐C3N4 to improve the charge separation. In addition, the combination of the Fenton's reagent Fe2O3/H2O2 and the photocatalyst g‐C3N4 greatly enhances the rate of the Fenton's reaction with the assistance of the photocatalytic process. The results showed that the Fe2O3/g‐C3N4 catalyst had a superior catalytic activity as compared with the single component of Fe2O3 or g‐C3N4 and the mechanical mixture of Fe2O3 and g‐C3N4. The catalyst prepared with 3 mL of FeCl3 aqueous solution shows the best photo‐Fenton photocatalytic efficiency with a reaction rate constant of 0.02461 mg L–1 min–1, which is about 45.4, 8.4 and 7.2 times larger than that of pure Fe2O3 (0.0005418 mg L–1 min–1), pure g‐C3N4 (0.00294 mg L–1 min–1) and the mechanically mixed Fe2O3/g‐C3N4 (0.0034 mg L–1 min–1), respectively. A possible mechanism for the visible‐light‐irradiated photo‐Fenton photocatalysis is proposed, and the Fe2O3/g‐C3N4 catalyst exhibited stable performance without obvious loss of catalytic activity after four successive runs, showing a good application prospect for the photo‐oxidative degradation of organic contaminants in wastewater.
Synthesis of Fluorescent 1,3‐Diarylpropynones by Carbonylative Alkynylation Reaction Using (Phosphine) (1,2,3‐triazol‐5‐ylidene)palladium Complexes as Catalysts
Authors: Dasgupta Ayan , Ramkumar Venkatachalam , Sankararaman Sethuraman
Published: September 2016

The synthesis of a variety of 1,3‐diarylpropynones that contain not only substituted phenyl groups but also fluorophoric 1‐pyrenyl, 3‐carbazolyl, and 1‐naphthyl groups was achieved in good to excellent yields by using a carbonylative alkynylation reaction in the presence of cis‐(Tz)Pd(Cl)2(PPh3) (Tz = 1,2,3‐triazol‐5‐ylidene) as a precatalyst under 1.0 atm of CO. Products resulting from competing Sonogashira coupling reactions, namely 1,2‐diarylacetylenes, were not observed. The synthesized ynones exhibit fluorescence not only in solution but also in the solid state. The catalytically active palladium species was recovered and reused for up to three cycles by adsorbing the cis‐(Tz)Pd(Cl)2(PPh3) precatalyst onto silica gel and carrying out the reaction under heterogeneous conditions.
Oxaenediynes through the Nicholas‐Type Macrocyclization Approach
Authors: Lyapunova Anna G. , Danilkina Natalia A. , Khlebnikov Alexander F. , Köberle Beate , Bräse Stefan , Balova Irina A.
Published: September 2016

The Nicholas‐type macrocyclization has been used for the first time for the synthesis of 10‐ and 11‐membered oxaenediynes fused to a benzothiophene. The acyclic starting materials were easily synthesized by electrophilic cyclization of o‐(buta‐1,3‐diynyl)thioanisoles followed by a Sonogashira coupling of the resulting 2‐ethynyl‐3‐iodobenzothiophenes with functionalized alkynes. A high reactivity of the 10‐membered oxacycles in the Bergman cyclization was predicted by DFT calculations and confirmed by differential scanning calorimetry. The ability of enediynes to induce single‐strand PM2 DNA scissions was also found.
Helical‐Shaped Bis‐1,4‐benzoxathiines through an Inverse‐Electron‐Demand Hetero‐Diels–Alder Reaction of ortho‐Thioquinones
Authors: Viglianisi Caterina , Menichetti Stefano , Piantini Sara , Tofani Lorenzo
Published: September 2016

The reaction of transient ortho‐thioquinones, which act as electron‐poor dienes, with properly designed bis‐dienophiles leads to the formation of helical‐shaped bis‐benzoxathiine cycloadducts with complete control of the regiochemistry and the relative stereochemistry. Bis‐benzoxathiines were the result of two consecutive inverse‐electron‐demand cycloaddition processes with stereospecific approach of the diene anti to the bis‐dienophile. The helical‐shaped structure of the final products was demonstrated spectroscopically and confirmed by single‐crystal X‐ray analysis.
Cu/Ag‐Cocatalyzed Aerobic Oxidative Amination and CuCl2‐Mediated Aerobic Oxidative Chloroamination of Maleimides
Authors: An Yu‐Long , Zhang He‐Hui , Yang Zhen‐Hua , Lin Long , Zhao Sheng‐Yin
Published: September 2016

An efficient Cu(OAc)2/Ag2CO3‐cocatalyzed approach for the synthesis of 3‐aminomaleimides and 3‐amino‐4‐indolylmaleimides has been developed with satisfactory yields. A series of primary and secondary amines are compatible with this reaction. In addition, treatment of maleimides with primary amines using 1 equiv. of CuCl2 leads to the formation of chloroamination products such as 3‐amino‐4‐chloromaleimides by a radical‐type mechanism.
Nickel‐Catalyzed Allylic C(sp2)–H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes
Authors: Wu Qiang , Wang Lanlan , Jin Rizhe , Kang Chuanqing , Bian Zheng , Du Zhijun , Ma Xiaoye , Guo Haiquan , Gao Lianxun
Published: September 2016

Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp2)–H activation by in‐situ‐formed Ni0, which is inserted into the C–H bond at the 2‐position of the allyl moiety without a directing group. The isomerization of allylarene to 1‐propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross‐coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp2)–H activation and represents a new method for the synthesis of 1,1‐disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp2)–H activation and multiple intermolecular 1,2‐, 1,3‐, and 2,3‐hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.
Facile and Diverse Synthesis of Benzo[b]fluorenone Derivatives through a Copper/Selectfluor‐Catalyzed Tandem Annulation of 1,6‐Enynes
Authors: Zhang Jian , Zhang Haifeng , Shi Dongdong , Jin Hongwei , Liu Yunkui
Published: September 2016

A facile synthesis of a diverse array of benzo[b]fluorenone derivatives has been developed. The method involves a Cu0/Selectfluor‐catalyzed tandem annulation of 1,6‐enynes, which takes place under mild reaction conditions. For tert‐butylethynyl‐substituted 1,6‐enynes, the major reaction pathway was a tandem annulation/C–C‐bond‐cleavage/fluorination process leading to fluorinated benzo[b]fluorenones as the major products; tert‐butyl‐substituted benzo[b]fluorenones were obtained as the minor products. For arylethynyl‐substituted 1,6‐enynes, the substrates underwent tandem annulations to give 5‐aryl‐substituted benzo[b]fluorenones in moderate to excellent yields. For (trimethylsilyl)ethynyl‐substituted 1,6‐enynes, the reaction involved a tandem annulation/C–Si‐bond‐cleavage process to deliver 11H‐benzo[b]fluoren‐11‐ones in moderate yields.
Electrochemical Characteristics of 4‐oxo‐4H‐pyran‐dicarboxylic Acid (Chelidonic Acid) and some of its Metal Complexes
Authors: Jadreško Dijana , Kakša Matija , Popović Zora
Published: September 2016

A few novel metal complexes of chelidonic acid (chelH2), namely [Ca(chel)(H2O)3] (1), [Cu(chel)(H2O)5] ⋅ 2H2O (2) and [VO(chel)(H2O)3] ⋅ 2H2O (3) were prepared, identified by elemental analysis and characterized by electrochemical methods. IR‐spectra and thermal stability in solid state are discussed as well. The electrochemical characteristics of the free chelidonic acid and its complexes 1–3 were studied by (cyclic) square‐wave voltammetry, on static mercury drop electrode (SMDE) and paraffin‐impregnated graphite electrode (PIGE), in aqueous media over a wide pH range. The reduction of chelidonic acid on SMDE is a kinetically controlled electrode reaction, occurring with the transfer of one electron and two protons for 1<pH<6, whereas in very alkaline media the electron transfer is pH independent, i.e. the mechanism of electro‐reduction of chelH2 is proposed. The experimental parameters of the electroanalytical procedure were optimized and the method was applied for the investigation of the metal ion coordination preferences toward chelidonic acid. For the direct determination of solid complexes 1–3, SW voltammetry of microparticles was used.
A population study using the human erythrocyte PIG‐A assay
Authors: Cao Yiyi , Yang Li , Feng Nannan , Shi Oumin , Xi Jing , You Xinyue , Yin Chunrong , Yang Huan , Horibata Katsuyoshi , Honma Masamitsu , Qian Biyun , Weng Wei , Luan Yang
Published: September 2016

Erythrocyte‐based PIG‐A assay is sensitive and reliable in detecting exposure to mutagenetic agents in animal studies, but there are few data from human populations. In this study, we employed a method for detecting CD59 phenotypic variants, resulting from mutation in the PIG‐A gene, in human red blood cells (RBCs), and determined the CD59‐deficient RBC (RBCCD59−) frequencies in 217 subjects from general population. The majority of subjects had a relatively low mutant frequencies (MFs) (average, 5.25 ± 3.6 × 10−6, median, 4.38 × 10−6, for all subjects), but with males having a significantly greater MFs (5.97 ± 4.0 × 10−6) than females (4.19 ± 2.5 ×10−6). There was no correlation between MFs and age. In addition, MFs showed no difference between smoker and nonsmoker, and also no association with smoke duration in male subjects. However, there was a significant correlation between cigarette‐pack‐years which indicated that the MF was only slightly elevated with the increase of cigarette‐pack‐years. Moreover, intraindividual variations were investigated in three volunteer subjects over 300 days, and the MFs were relatively stable and repeatable. Furthermore, a pilot study by using white blood cell (WBC) assay based on labeling with FLAER was performed in volunteer subjects. The MFs of FLAER‐deficient WBC (WBCFLAER−) and RBCCD59− were consistently elevated in two subjects. Our findings provide baseline data that will be helpful in designing further studies using the PIG‐A assay to monitor the genotoxic effects of carcinogens in human populations. Environ. Mol. Mutagen. 57:589–604, 2016. © 2016 Wiley Periodicals, Inc.
Characteristics of Avoidant/Restrictive Food Intake Disorder in a Cohort of Adult Patients
Authors: Nakai Yoshikatsu , Nin Kazuko , Noma Shun'ichi , Teramukai Satoshi , Wonderlich Stephen A.
Published: September 2016

Objective

To assess and compare clinical symptoms and psychometric analysis of adult patients with avoidant/restrictive food intake disorder (ARFID) with those with anorexia nervosa (AN).

Method

We completed a retrospective review of adult patients with a feeding and eating disorder assessed between 1990 and 2005 that qualified for a diagnosis of ARFID. Patients with ARFID were compared with those with AN, with respect to the demographics, clinical symptoms and psychometric analysis.

Results

Using the criteria of the fifth edition of the Diagnostic and Statistical Manual, 95 (9.2%) of 1029 patients with a feeding and eating disorder met the criteria for ARFID. All patients with ARFID were women. The ARFID group had a significantly shorter duration of illness, lower rates of hospital admission history and less severe psychopathology than the AN group.

Conclusions

Adult patients with ARFID in this study were clinically distinct from those with AN and somewhat different from paediatric patients with ARFID in previous studies. Copyright © 2016 John Wiley & Sons, Ltd and Eating Disorders Association.
MoS2 as a co‐catalyst for photocatalytic hydrogen production from water
Authors: Han Bing , Hu Yun Hang
Published: September 2016

Solar‐to‐hydrogen conversion based on photocatalytic water splitting is a promising pathway for sustainable hydrogen production. The photocatalytic process requires highly active, inexpensive, and earth‐abundant materials as photocatalysts. As a presentative layer‐structured transition metal dichalcogenides, molybdenum disulfide (MoS2) is attracting intensive attention due to its unique electro and photo properties. In this article, we comprehensively review the recent research efforts of exploring MoS2 as a co‐catalyst for photocatalytic hydrogen production from water, with emphasis on its combination with CdS, CdSe, graphene, carbon nitride, TiO2, and others. It is shown that MoS2–semiconductor composites are promising photocatalysts for hydrogen evolution from water under visible light irradiation.
Effects of clay minerals on transport of graphene oxide in saturated porous media
Authors: Lu Taotao , Xia Tianjiao , Qi Yu , Zhang Chengdong , Chen Wei
Published: September 2016

The presence of kaolinite, montmorillonite, and illite in packed quartz sand inhibited the transport of graphene oxide to different degrees. Transport inhibition was exerted mainly by the presence of positively charged sites on clay edges (which served as favorable deposition sites), whereas the effects on the overall particle–collector interaction energy and flow path were small. Kaolinite exhibited the most significant transport-inhibition effects because of its high percentage of edge area. Environ Toxicol Chem 2017;36:655–660. © 2016 SETAC
Captive pandas are at risk from environmental toxins
Authors: Chen Yi‐ping , Maltby Lorraine , Liu Qiang , Song Yi , Zheng Ying‐juan , Ellison Aaron M , Ma Qing‐yi , Wu Xiao‐min
Published: September 2016

Ex situ conservation efforts are the last resort for many critically endangered species, and captive breeding centers are thought to provide a safe environment for producing individuals for eventual re‐introduction to the wild. The giant panda (Ailuropoda melanoleuca) is one of the world's most endangered animals and is a widely recognized symbol for conservation. Here, we report that captive pandas in China experience environmental and dietary exposures to high concentrations of persistent organic pollutants (polychlorinated dibenzo‐p‐dioxins, dibenzofurans, and biphenyls) and heavy metals (arsenic, cadmium, chromium, and lead). In the short term, those animals exhibiting elevated levels of such toxins should be relocated to breeding centers in less contaminated areas. Ensuring the long‐term survival of both captive and wild pandas depends in part on reducing atmospheric emissions of toxic pollutants throughout China.
A novel high mobility group box 1 neutralizing chimeric antibody attenuates drug‐induced liver injury and postinjury inflammation in mice
Authors: Lundbäck Peter , Lea Jonathan D. , Sowinska Agnieszka , Ottosson Lars , Fürst Camilla Melin , Steen Johanna , Aulin Cecilia , Clarke Joanna I. , Kipar Anja , Klevenvall Lena , Yang Huan , Palmblad Karin , Park B. Kevin , Tracey Kevin J. , Blom Anna M. , Andersson Ulf , Antoine Daniel J. , Erlandsson Harris Helena
Published: September 2016

Acetaminophen (APAP) overdoses are of major clinical concern. Growing evidence underlines a pathogenic contribution of sterile postinjury inflammation in APAP‐induced acute liver injury (APAP‐ALI) and justifies development of anti‐inflammatory therapies with therapeutic efficacy beyond the therapeutic window of the only current treatment option, N‐acetylcysteine (NAC). The inflammatory mediator, high mobility group box 1 (HMGB1), is a key regulator of a range of liver injury conditions and is elevated in clinical and preclinical APAP‐ALI. The anti‐HMGB1 antibody (m2G7) is therapeutically beneficial in multiple inflammatory conditions, and anti‐HMGB1 polyclonal antibody treatment improves survival in a model of APAP‐ALI. Herein, we developed and investigated the therapeutic efficacy of a partly humanized anti‐HMGB1 monoclonal antibody (mAb; h2G7) and identified its mechanism of action in preclinical APAP‐ALI. The mouse anti‐HMGB1 mAb (m2G7) was partly humanized (h2G7) by merging variable domains of m2G7 with human antibody‐Fc backbones. Effector function‐deficient variants of h2G7 were assessed in comparison with h2G7 in vitro and in preclinical APAP‐ALI. h2G7 retained identical antigen specificity and comparable affinity as m2G7. 2G7 treatments significantly attenuated APAP‐induced serum elevations of alanine aminotransferase and microRNA‐122 and completely abrogated markers of APAP‐induced inflammation (tumor necrosis factor, monocyte chemoattractant protein 1, and chemokine [C‐X‐C motif] ligand 1) with prolonged therapeutic efficacy as compared to NAC. Removal of complement and/or Fc receptor binding did not affect h2G7 efficacy. Conclusion: This is the first report describing the generation of a partly humanized HMGB1‐neutralizing antibody with validated therapeutic efficacy and with a prolonged therapeutic window, as compared to NAC, in APAP‐ALI. The therapeutic effect was mediated by HMGB1 neutralization and attenuation of postinjury inflammation. These results represent important progress toward clinical implementation of HMGB1‐specific therapy as a means to treat APAP‐ALI and other inflammatory conditions. (Hepatology 2016;64:1699‐1710).
Methylparaben stimulates tumor initiating cells in ER+ breast cancer models
Authors: Lillo M. Angeles , Nichols Cydney , Perry Chanel , Runke Stephanie , Krutilina Raisa , Seagroves Tiffany N. , Miranda‐Carboni Gustavo A. , Krum Susan A.
Published: September 2016

A body of epidemiological evidence implicates exposure to endocrine disrupting chemicals (EDCs) with increased susceptibility to breast cancer. To evaluate the physiological effects of a suspected EDC in vivo, we exposed MCF‐7 breast cancer cells and a patient‐derived xenograft (PDX, estrogen receptor positive) to physiological levels of methylparaben (mePB), which is commonly used in personal care products as a preservative. mePB pellets (4.4 μg per day) led to increased tumor size of MCF‐7 xenografts and ER+ PDX tumors. mePB has been thought to be a xenoestrogen; however, in vitro exposure of 10 nM mePB failed to increase MCF‐7 cell proliferation or induction of canonical estrogen‐responsive genes (pS2 and progesterone receptor), in contrast to 17β‐estradiol (E2) treatment. MCF‐7 and PDX‐derived mammospheres exhibited increased size and up‐regulation of canonical stem cell markers ALDH1, NANOG, OCT4 and SOX2 when exposed to mePB; these effects were not observed for MDA‐MB‐231 (ER−) mammospheres. As tumor‐initiating cells (TICs) are also believed to be responsible for chemoresistance, mammospheres were treated with either tamoxifen or the pure anti‐estrogen fulvestrant in the presence of mePB. Blocking the estrogenic response was not sufficient to block NANOG expression in mammospheres, pointing to a non‐classic estrogen response or an ER‐independent mechanism of mePB promotion of mammosphere activity. Overall, these results suggest that mePB increases breast cancer tumor proliferation through enhanced TIC activity, in part via regulation of NANOG, and that mePB may play a direct role in chemoresistance by modulating stem cell activity. Copyright © 2016 John Wiley & Sons, Ltd.
Ethics and Relationship: From Risk Management to Relational Engagement
Authors: Birrell Pamela J. , Bruns Cindy M.
Published: September 2016

In this article, the underlying assumptions of the current ACA Code of Ethics () are examined as they are embedded in historical and cultural contexts. A relational ethic situated within relational‐cultural theory that provides an alternative framework for understanding ethics in a relational and compassionate way is presented.
Improving the Ring‐opening Polymerization of l‐Lactide Using n‐Butyl Lithium with Various Bidentate Ligands
Authors: Chen Hsuan‐Ying , Huang Yen‐Tzu , Vandavasi Jaya Kishore , Chen Yu‐Hsieh , Kuei Chia‐Hao
Published: September 2016

A series of bidentate ligands were examined to improve the catalytic activity of
l
‐lactide (LA) polymerization by using n‐butyl lithium and BnOH. For LA polymerization, n‐butyl lithium with tetraisopropyl methylenebis(phosphonate) (L8
) showed the greatest catalytic activity but with poor controllability of the polymer molecular weight. The polydispersity indices (PDIs) could be improved without BnOH addition, but Mn
GPC
was much different from the Mn
Cal
. 1H NMR spectra confirmed that the cyclized PLA was obtained, thus implying that active chain‐end mechanisms were operative in LA polymerization.
Comparison of Three Different Hepatitis C Virus Genotyping Methods: 5′NCR PCR‐RFLP, Core Type‐Specific PCR, and NS5b Sequencing in a Tertiary Care Hospital in South India
Authors: Daniel Hubert D.‐J. , David Joel , Raghuraman Sukanya , Gnanamony Manu , Chandy George M. , Sridharan Gopalan , Abraham Priya
Published: September 2016

Background

Based on genetic heterogeneity, hepatitis C virus (HCV) is classified into seven major genotypes and 64 subtypes. In spite of the sequence heterogeneity, all genotypes share an identical complement of colinear genes within the large open reading frame. The genetic interrelationships between these genes are consistent among genotypes. Due to this property, complete sequencing of the HCV genome is not required. HCV genotypes along with subtypes are critical for planning antiviral therapy. Certain genotypes are also associated with higher progression to liver cirrhosis.

Methods

In this study, 100 blood samples were collected from individuals who came for routine HCV genotype identification. These samples were used for the comparison of two different genotyping methods (5′NCR PCR‐RFLP and HCV core type‐specific PCR) with NS5b sequencing.

Results

Of the 100 samples genotyped using 5′NCR PCR‐RFLP and HCV core type‐specific PCR, 90% (κ = 0.913, P < 0.00) and 96% (κ = 0.794, P < 0.00) correlated with NS5b sequencing, respectively. Sixty percent and 75% of discordant samples by 5′NCR PCR‐RFLP and HCV core type‐specific PCR, respectively, belonged to genotype 6. All the HCV genotype 1 subtypes were classified accurately by both the methods.

Conclusion

This study shows that the 5′NCR‐based PCR‐RFLP and the HCV core type‐specific PCR‐based assays correctly identified HCV genotypes except genotype 6 from this region. Direct sequencing of the HCV core region was able to identify all the genotype 6 from this region and serves as an alternative to NS5b sequencing.
The Evolutionary Origin of Female Orgasm
Authors: PAVLIČEV MIHAELA , WAGNER GÜNTER
Published: September 2016

The evolutionary explanation of female orgasm has been difficult to come by. The orgasm in women does not obviously contribute to the reproductive success, and surprisingly unreliably accompanies heterosexual intercourse. Two types of explanations have been proposed: one insisting on extant adaptive roles in reproduction, another explaining female orgasm as a byproduct of selection on male orgasm, which is crucial for sperm transfer. We emphasize that these explanations tend to focus on evidence from human biology and thus address the modification of a trait rather than its evolutionary origin. To trace the trait through evolution requires identifying its homologue in other species, which may have limited similarity with the human trait. Human female orgasm is associated with an endocrine surge similar to the copulatory surges in species with induced ovulation. We suggest that the homolog of human orgasm is the reflex that, ancestrally, induced ovulation. This reflex became superfluous with the evolution of spontaneous ovulation, potentially freeing female orgasm for other roles. This is supported by phylogenetic evidence showing that induced ovulation is ancestral, while spontaneous ovulation is derived within eutherians. In addition, the comparative anatomy of female reproductive tract shows that evolution of spontaneous ovulation is correlated with increasing distance of clitoris from the copulatory canal. In summary, we suggest that the female orgasm‐like trait may have been adaptive, however for a different role, namely for inducing ovulation. With the evolution of spontaneous ovulation, orgasm was freed to gain secondary roles, which may explain its maintenance, but not its origin.