bluuebunny/crossref_metadata_2025 huggingface dataset:
Atomic Mechanism of Predictable Phase Transition in Dual‐Phase H2Ti3O7/TiO2 (B) Nanofiber: An In Situ Heating TEM Investigation
Authors: Lei Yimin , Sun Jie , Liu Hongwei , Cheng Xuan , Chen Fuyi , Liu Zongwen
Published: July 2014

The phase transition from H2Ti3O7 to TiO2 (B) in a 1D single nanocrystal of H2Ti3O7 was observed by in situ heating in a transmission electron microscope experimentally. The results indicate a typical monoclinic‐to‐monoclinic crystallographic orientation relationship between the two phases. Moreover, the fundamental building blocks and invariant deformation element model were both adopted to reveal the atomic mechanism and predict the crystallographic orientation relationship quantitatively for the phase transition. The prediction was precisely consistent with TEM results.
Towards Molecular Construction Platforms: Synthesis of a Metallotricyclic Spirane Based on Bis(2,2′:6′,2“‐Terpyridine)RuII Connectivity
Authors: Xie Ting‐Zheng , Guo Kai , Huang Mingjun , Lu Xiaocun , Liao Sheng‐Yun , Sarkar Rajarshi , Moorefield Charles N. , Cheng Stephen Z. D. , Wesdemiotis Chrys , Newkome George R.
Published: July 2014

The design and construction of the first multicomponent stepwise assembly of a ‐based (tpy=terpyridine), three‐dimensional, propeller‐shaped trismacrocycle, 8, are reported. Key steps in the synthesis involve the preparation of a hexaterpyridinyl triptycene and its reaction with dimeric, 60°‐directional, bisterpyridine‐RuII building blocks. Characterization includes ESI‐ and ESI‐TWIM‐MS and TEM, along with 1D and 2D 1H NMR spectroscopy.
Conjugation to Albumin‐Binding Molecule Tags as a Strategy to Improve Both Efficacy and Pharmacokinetic Properties of the Complement Inhibitor Compstatin
Authors: Huang Yijun , Reis Edimara S. , Knerr Patrick J. , van der Donk Wilfred A. , Ricklin Daniel , Lambris John D.
Published: July 2014

The compstatin family of complement inhibitors has shown promise in various immuno‐inflammatory disorders. Although recent analogues show beneficial pharmacokinetics, further extension of the plasma half‐life is expected to benefit systemic application of these peptidic inhibitors. We therefore synthesized conjugates of compstatin analogues and albumin‐binding molecules (ABM) to increase circulatory residence. Equilibrium dialysis in complement‐depleted serum showed a marked increase in plasma protein binding from <8 % to >99 % for a resulting chimera (ABM2‐Cp20). Further analysis confirmed interaction with albumin from different species, primarily via site II. Importantly, ABM2‐Cp20 bound 20‐fold stronger to its target protein C3b (KD=150 pM) than the parent peptide. Kinetic and in silico analysis suggested that ABM2 occupies a secondary site on C3b and improves the dissociation rate via additional contacts. Addition of an ABM modifier thereby not only improved plasma protein binding but also produced the most potent compstatin analogue to date with potential implications for the treatment of systemic complement‐related diseases.
Management of patients with HER2‐positive metastatic breast cancer: Is there an optimal sequence of HER2‐directed approaches?
Authors: Zelnak Amelia B. , Wisinski Kari B.
Published: July 2014

The successful development of therapies targeting the human epidermal growth factor receptor 2 (HER2) has altered the natural progression of disease among patients with HER2‐positive metastatic breast cancer. The monoclonal antibody trastuzumab was the first HER2‐directed agent and it was associated with significantly improved outcomes for patients. Subsequently, other HER2‐directed agents such as the monoclonal antibody pertuzumab, the tyrosine kinase receptor inhibitor lapatinib, and the immunoconjugate trastuzumab emtansine were developed to overcome resistance to trastuzumab and provide additional treatment options for patients. Recent data have demonstrated that the use of these HER2‐directed agents improves outcomes. However, with the emergence of new HER2‐targeted agents, the optimal sequencing of treatment remains unclear. Ongoing research is investigating new HER2 combinations, the role of sequencing, novel HER2‐directed agents, and combinations with other targeted agents to overcome resistance. Cancer 2015;121:17–24. © 2014 American Cancer Society.
Complications of pelvic radiation in patients treated for gynecologic malignancies
Authors: Viswanathan Akila N. , Lee Larissa J. , Eswara Jairam R. , Horowitz Neil S. , Konstantinopoulos Panagiotis A. , Mirabeau‐Beale Kristina L. , Rose Brent S. , von Keudell Arvind G. , Wo Jennifer Y.
Published: July 2014

Radiation therapy is a critical treatment modality in the management of patients with gynecologic tumors. New highly conformal external‐beam and brachytherapy techniques have led to important reductions in recurrence and patient morbidity and mortality. However, patients who receive pelvic radiation for gynecologic malignancies may experience a unique constellation of toxicity because of the anatomic locations, combination with concurrent chemotherapy and/or surgery, as well as potential surgical interventions. Although side effects are often categorized into acute versus late toxicities, several late toxicities represent continuation and evolution of the same pathologic process. Comorbidities and radiation dose can significantly increase the risk of morbidity. Current understanding of the incidence of various morbidities in patients treated with current radiation techniques for gynecologic malignancies, the impact of chemotherapy and surgery, treatment options for those effects, and future areas of research are highlighted. Cancer 2014;120:3870–3883. © 2014 American Cancer Society.
Hydrogen Transport in Non‐Ideal Crystalline Materials
Authors: Auinger Michael
Published: July 2014

Hydrogen‐transport behaviour under (non‐)isothermal conditions is discussed. An extended modelling approach based on the effective diffusion coefficient is outlined for arbitrary temperature programmes, defect properties and hydrogen‐loading pressures. The influence of mathematical terms, such as the trap equilibrium reaction or microstructural changes, is critically discussed and examples of thermal desorption spectra and isothermal diffusion behaviour are given.
Dynamics of Methanol in Ionic Liquids: Validity of the Stokes–Einstein and Stokes–Einstein–Debye Relations
Authors: Herold Elisabeth , Strauch Matthias , Michalik Dirk , Appelhagen Andreas , Ludwig Ralf
Published: July 2014

The validity of Stokes–Einstein (SE) and Stokes–Einstein–Debye (SED) relations for methanol in the physical environment of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide is studied by means of nuclear magnetic resonance (NMR) relaxation time experiments, viscosity measurements and molecular dynamics (MD) simulations. The reorientational correlation times of the hydroxyl groups of pure methanol and of methanol in the IL/methanol mixtures were determined. For that purpose an approach for estimating NMR deuteron quadrupole coupling constants, presented by Wendt and Farrar (Mol. Phys.­ 1998, 95, 1077–1081), was confirmed. The self‐diffusion coefficients of methanol were taken from the MD simulations. The viscosities of all systems were then measured and the SE and SED relations validated. For pure methanol both relations are valid, whereas they become increasingly invalid with increasing IL concentration, as indicated by effective volumes and radii that are too low. The deviation from the SE and SED relations could be related to dynamical heterogeneities described by the non‐Gaussian parameter α(t) obtained from MD simulations. For pure methanol, α(t) is close to zero in accord with the validity of both relations. With increasing IL concentration the dynamical heterogeneities of methanol increase strongly. The times t* at the maximum of α(t) increase linearly with the relative number of methanol monomers in the mixtures. Thus, the dynamical heterogeneities are largest for single methanol molecules fully embedded in the IL environment. In their own environment methanol molecules are highly mobile, whereas in the IL‐rich region the mobility is strongly reduced leading to the non‐validity of SE and SED relations.
Tuning Hydrogen Storage in Lithium‐Functionalized BC2N Sheets by Doping with Boron and Carbon
Authors: Qiu Nian‐xiang , Zhang Cheng‐hua , Xue Ying
Published: July 2014

First‐principles calculations are used to explore the strong binding of lithium to boron‐ and carbon‐doped BC2N monolayers (BC2NBC and BC2NCN, respectively) without the formation of lithium clusters. In comparison to BC2N and BC2NCB, lithium‐decorated BC2NBC and BC2NCN systems possess stronger s–p and p–p hybridization and, hence, the binding energy is higher. Lithium becomes partially positively charged by donating electron density to the more electronegative atoms of the sheet. Attractive van der Waals interactions are responsible for binding hydrogen molecules around the lithium atoms. Each lithium atom can adsorb three hydrogen molecules on both sides of the sheet, with an average hydrogen binding energy of approximately 0.2 eV, which is in the range required for practical applications. The BC2NBC–Li and BC2NCN–Li complexes can serve as high‐capacity hydrogen‐storage media with gravimetric hydrogen capacities of 9.88 and 9.94 wt %, respectively.
Protein Structure Prediction: Assembly of Secondary Structure Elements by Basin‐Hopping
Authors: Hoffmann Falk , Vancea Ioan , Kamat Sanjay G. , Strodel Birgit
Published: July 2014

The prediction of protein tertiary structure from primary structure remains a challenging task. One possible approach to this problem is the application of basin‐hopping global optimization combined with an all‐atom force field. In this work, the efficiency of basin‐hopping is improved by introducing an approach that derives tertiary structures from the secondary structure assignments of individual residues. This approach is termed secondary‐to‐tertiary basin‐hopping and benchmarked for three miniproteins: trpzip, trp‐cage and ER‐10. For each of the three miniproteins, the secondary‐to‐tertiary basin‐hopping approach successfully and reliably predicts their three‐dimensional structure. When it is applied to larger proteins, correctly folded structures are obtained. It can be concluded that the assembly of secondary structure elements using basin‐hopping is a promising tool for de novo protein structure prediction.
Conformational Equilibria and Large‐Amplitude Motions in Dimers of Carboxylic Acids: Rotational Spectrum of Acetic Acid–Difluoroacetic Acid
Authors: Gou Qian , Feng Gang , Evangelisti Luca , Caminati Walther
Published: July 2014

We report the rotational spectra of two conformers of the acetic acid–difluoroacetic acid adduct (CH3COOH–CHF2COOH) and supply information on its internal dynamics. The two conformers differ from each other, depending on the trans or gauche orientation of the terminal CHF2 group. Both conformers display splittings of the rotational transitions, due to the internal rotation of the methyl group of acetic acid. The corresponding barriers are determined to be V3(trans)=99.8(3) and V3(gauche)=90.5(9) cm−1 (where V3 is the methyl rotation barrier height). The gauche form displays a further doubling of the rotational transitions, due to the tunneling motion of the CHF2 group between its two equivalent conformations. The corresponding B2 barrier is estimated to be 108(2) cm−1. The increase in the distance between the two monomers upon OH→OD deuteration (the Ubbelohde effect) is determined.
Organic Superhalogens
Authors: Giri Santanab , Child Brandon Z. , Jena Puru
Published: July 2014

Using first‐principles calculations with predictive capability we show that organic molecules having negative electron affinity can be transformed to superhalogens with electron affinities far exceeding that of chlorine, once its core and ligand atoms are suitably replaced. The discovery of organic superhalogens could have significant impact in chemistry, allowing the synthesis of new materials and compounds.
Synthesis of Bright Alkenyl‐1H‐1,2,4‐triazoles: A Theoretical and Photophysical Study
Authors: Cebrián Cristina , de Mata Muñoz Juan , Strassert Cristian Alejandro , Prieto Pilar , Díaz‐Ortiz Ángel , De Cola Luisa , de la Hoz Antonio
Published: July 2014

A sustainable synthesis of alkenyl‐1H‐1,2,4‐triazoles through the Hiyama reaction is reported, which employs water as solvent and sodium hydroxide to activate the silyl group under microwave irradiation, thereby leading to high product yields (51–93 %) in very short reaction times. Two substitution patterns were attained owing to the different reactivity of the third and fifth positions of the 1H‐1,2,4‐triazole unit, as evidenced by calculated condensed Fukui functions. Moreover, all compounds are good blue emitters (ΦF up to 0.69) in THF solution, although they exhibit an optical behavior dependent on the substitution. Excited‐state theoretical investigations by the configuration interaction singles method and time‐dependent density functional theory were performed not only to support and elucidate the studied photophysical properties, but also to create a predictive model to reduce the cost and optimize the search for new blue emitters based on this class of alkenyl‐1H‐1,2,4‐triazoles.
Stabilization for a class of nonlinear networked control systems via polynomial fuzzy model approach
Authors: Li Hongyi , Chen Ziran , Sun Yiyong , Karimi Hamid Reza
Published: July 2014

This article is concerned with the stabilization problem for nonlinear networked control systems which are represented by polynomial fuzzy models. Two communication features including signal transmission delays and data missing are taken into account in a network environment. To solve the network‐induced communication problems, a novel sampled‐data fuzzy controller is designed to guarantee that the closed‐loop system is asymptotically stable. The stability and stabilization conditions are presented in terms of sum of squares (SOS), which can be numerically solved via SOSTOOLS. Finally, a simulation example is provided to demonstrate the feasibility of the proposed method. © 2014 Wiley Periodicals, Inc. Complexity 21: 74–81, 2015
Enhancing Dye‐Sensitized Solar Cell Performances by Molecular Engineering: Highly Efficient π‐Extended Organic Sensitizers
Authors: Grisorio Roberto , De Marco Luisa , Agosta Rita , Iacobellis Rosabianca , Giannuzzi Roberto , Manca Michele , Mastrorilli Piero , Gigli Giuseppe , Suranna Gian Paolo
Published: July 2014

This study deals with the synthesis and characterization of two π‐extended organic sensitizers (G1 and G2) for applications in dye‐sensitized solar cells. The materials are designed with a D–A–π–A structure constituted by i) a triarylamine group as the donor part, ii) a dithienyl‐benzothiadiazole chromophore followed by iii) a further ethynylene‐thiophene (G1) or ethynylene‐benzene (G2) π‐spacer and iv) a cyano‐acrylic moiety as acceptor and anchoring part. An unusual structural extension of the π‐bridge characterizes these structures. The so‐configured sensitizers exhibit a broad absorption profile, the origin of which is supported by density functional theory. The absence of hypsochromic shifts as a consequence of deprotonation as well as notable optical and electrochemical stabilities are also observed. Concerning the performances in devices, electrochemical impedance spectroscopy indicates that the structural modification of the π‐spacer mainly increases the electron lifetime of G2 with respect to G1. In devices, this feature translates into a superior power conversion efficiency of G2, reaching 8.1 %. These results are comparable to those recorded for N719 and are higher with respect to literature congeners, supporting further structural engineering of the π‐bridge extension in the search for better performing π‐extended organic sensitizers.
Innate IFN‐γ promotes development of experimental autoimmune encephalomyelitis: A role for NK cells and M1 macrophages
Authors: Dungan Lara S. , McGuinness Niamh C. , Boon Louis , Lynch Marina A. , Mills Kingston H. G.
Published: July 2014

The role of IFN‐γ in the pathogenesis of autoimmune diseases is controversial. Although Th1 cells can induce experimental autoimmune encephalomyelitis (EAE), IFN‐γ can suppress Th17 cells that are pathogenic in EAE. Here we show that NK cells provide an early source of IFN‐γ during development of EAE. Depletion of NK cells or neutralization of IFN‐γ delayed the onset of EAE and was associated with reduced infiltration of IL‐17+ and GM‐CSF+ T cells into the CNS. In the passive transfer model, immune cells from myelin oligodendrocyte glycoprotein (MOG)‐immunized IFN‐γ−/− mice failed to induce EAE, despite producing IL‐17 and GM‐CSF. The macrophages expressed markers of M2 activation and the T cells had low very late antigen‐4 (VLA‐4) expression and failed to infiltrate the CNS. Addition of recombinant IFN‐γ to immune cells from the IFN‐γ−/− mice activated M1 macrophages and restored VLA‐4 expression, migratory, and encephalitogenic activity of T cells. Furthermore, treatment of recipient mice with anti‐VLA‐4 neutralizing antibody abrogated EAE induced by transfer of T cells from WT mice. Our findings demonstrate IFN‐γ‐producing T cells are not required for development of EAE, but NK cell‐derived IFN‐γ has a key role in promoting M1 macrophage expansion and VLA‐4‐mediated migration of encephalitogenic T cells into the CNS.
Compositionally Controlled Self‐Assembly of Hierarchical Pd–Ni Bimetallic Chains
Authors: Jin Peiyu , Liang Xin , He Yeheng , Liu Sijia , Zhu Xiaolin
Published: July 2014

Magnetic Pd–Ni bimetals with various compositions were synthesized by a one‐pot reaction, in which chain‐like Pd–Ni bimetals formed through the self‐assembly of Pd–Ni nanoparticles. The self‐assembly behaviour of the Pd–Ni bimetals gradually changes with the changes in composition. The Pd–Ni nanoparticles form simple chains at lower Pd content, while the Pd–Ni bimetals take on a beads‐on‐string structure composed of sphere‐shaped Pd–Ni‐nanoparticle assemblies at higher Pd content. Magnetic hysteresis loops show that Ni‐rich assemblies have a higher saturation magnetization than Pd‐rich assemblies. The formation mechanism for these Pd–Ni assemblies is proposed, in which the self‐assembly behaviours are controlled by the competition of the surfactant interaction and the magnetic dipole interaction. The catalytic activity and selectivity of the hydrogenation of acetophenone over these Pd–Ni bimetals depend on their compositions.
X‐ray Crystallographic Analysis of a Tailor‐Made Bis(phthalocyaninato)‐TbIII Single‐Molecule Magnet as a Fundamental Unit for Supramolecular Spintronic Devices
Authors: Klyatskaya Svetlana , Eichhöfer Andreas , Wernsdorfer Wolfgang
Published: July 2014

The single‐crystal X‐ray diffraction analysis of the title compound, the pyrene‐substituted unsymmetrical bis(phthalocyaninato)terbium(III) Single‐Molecule Magnet (SMM) [Pc–Tb–Pc*]0 (1) (Pc = dianion of phthalocyanine, P* = dianion of phthalocyanine decorated with six flexible hexyl chains and one 4‐pyren‐1yl‐butoxy group), was carried out. Both phthalocyaninato ligands in 1 are distorted from planarity and, therefore, adopt a biconcave shape. Effective π–π interactions between the molecules lead to the formation of head‐to‐tail π dimers. These dimers are stacked in the crystal, forming adjacent, parallel columns, the axes of which are tilted by 30° with respect to the C4 axes of the macrocycles. Herein, we also report the synthesis and characterization of the new isostructural Dy (compound 2) and Ho (compound 3) analogues of 1.
Photoluminescence of Zinc Complexes: Easily Tunable Optical Properties by Variation of the Bridge Between the Imido Groups of Schiff Base Ligands
Authors: Dumur Frédéric , Contal Emmanuel , Wantz Guillaume , Gigmes Didier
Published: July 2014

A series of organic–metal chelate complexes of symmetric tetradentate Schiff base ligands derived from salicylaldehyde and 2‐hydroxy‐1‐naphthaldehyde were designed and investigated. The combination of five nonconjugated flexible spacers and five conjugated rigid spacers with four salicylaldehyde derivatives provided a series of forty complexes. The series of blue to red photoluminescent complexes was investigated by UV/Vis absorption and luminescence spectroscopy in solution and in the solid state as well as cyclic voltammetry. The nature of the bridge in the ligand scaffold was determined to be the main parameter that influences the absorption and the emission color of the investigated zinc(II) complexes.
Time course of Algerian Azeradj extra‐virgin olive oil quality during olive ripening
Authors: Bakhouche Abdelhakim , Lozano‐Sánchez Jesús , Bengana Mohamed , Fernández‐Gutiérrez Alberto , Segura‐Carretero Antonio
Published: July 2014

The aim of this work was the chemical characterization of Algerian Azeradj extra‐virgin olive oil (EVOO) at different harvest dates in terms of oil yield, quality indices, fatty acids, pigments, polyphenols, and oxidative stability, in order to establish the best harvesting period for this variety. For this purpose, Azeradj EVOO samples were taken at three harvest dates corresponding to three ripening stages. Except for K270, the analysis of EVOOs showed a significant increase in the values of all quality parameters as olive ripening progresses (free fatty acids, peroxide index, and K232), while no significant variation was found for oil yield. Moreover, a significant decrease was observed for the monounsaturated fatty acid:polyunsaturated fatty acid (MUFA:PUFA) ratio, chlorophyll, carotenoids, total phenols, and oxidative stability in EVOOs produced at the advanced ripening stage. For better monitoring of the behavior of the phenolic fraction in EVOOs during ripening, for the first time in this work, individual phenolic compounds of Azeradj EVOOs was characterized using HPLC‐ESI‐TOF/MS. A total of 21 phenolic compounds belonging to different families were identified in Azeradj EVOOs. The highest concentrations of secoiridoids and phenolic alcohols were found at the beginning of November (D1); however, lignans and flavones concentrations were higher at the end of November (D2). EVOO obtained at the last harvest date (D3) showed the lowest content on all phenolic families. Finally, according to the results of the analyses performed in this work, early harvesting provides Azeradj EVOO with excellent chemical characteristics.

Practical applications: The Algerian olive oil sector is one of the least competitive in the Mediterranean region even if the Algerian olive oil displays some potential assets. Therefore, the chemical characterization of olive oil from one of the main varieties (Azeradj) cultivated in Algeria is of a great importance. The results will be available to all Algerian olive oil producers, and should be helpful in choosing the optimal harvest period to obtain Azeradj EVOO of high chemical quality.

Olive ripeness affects the chemical composition of Azeradj extra‐virgin olive oil.
Intravenous lipid microspheres loaded with alkylated norcantharidin derivative norcantharimide: Improved stability and prolonged half‐life
Authors: Pan Zhendong , Niu Yantao , Wang Yueqi , Tang Yilin , Tang Xing , Cai Cuifang
Published: July 2014

To facilitate the preparation of lipid microspheres, norcantharimide, a C14 alkyl chain derivative of norcantharidin, was synthesized and its physicochemical properties were investigated. The N‐14NCTDA loaded lipid microspheres (N‐14NCTDA LMs) were prepared by a high‐pressure homogenization method and characterized in terms of size, zeta‐potential, encapsulation efficiency and stability. The apparent oil–water partition coefficient of N‐14NCTDA (Log P > 2) was considerably enhanced in comparison to NCTD (Log P (−1.06), pH = 7.4). After optimization of the lipid microsphere formulation, the particle size distribution, zeta‐potential and entrapment efficacy were determined to be 189.2 ± 49.8 nm, −26.78 ± 1.03 mV, and 98.4 ± 0.38%, respectively. High physical and chemical stability was demonstrated in accelerated stability test. A pharmacokinetic study was carried out in rats after intravenous administration of N‐14NCTDA LMs and N‐14NCTDA solution. Their pharmacokinetic profiles were similar with no significant differences in main parameters. Nevertheless, it was noteworthy that a greatly prolonged half‐life and higher Vss was obtained for N‐14NCTDA LMs compared with NCTD loaded lipid microspheres (NCTD LMs). Therefore, the N‐14NCTDA LMs with high encapsulation efficiency and high stability are superior for the treatment of cancer, not only due to reduced venous irritation, but also due to prolonged half‐life.

Practical applications: Norcantharidin (NCTD) has been shown to be effective against cancer, especially against primary hepatic carcinoma, but its application is limited by severe renal toxicity and short half‐life. Compared to common injection preparations, lipid microspheres loaded with NCTD lead to greatly reduced venous irritation but problems with low encapsulation efficiency, short half‐life and high kidney toxicity have not been solved. N‐14NCTDA is a new synthetic chemotherapeutic agent, which displayed good broad spectrum cytotoxicity compared with NCTD. In this preformulation study we show that N‐14NCTDA is a promising alternative to NCTD.

Significantly enhanced stability and prolonged half‐life were obtained for N‐14NCTDA LMs compared with NCDT LMs.
Ethyl rhamnolipids as a renewable source to produce biopolyurethanes
Authors: Miao Shida , Callow Nicholas V. , Ju Lu‐Kwang
Published: July 2014

Responding to increasing environmental concerns, lipids are attractive feedstock to produce bio‐based polyurethanes. In this study, ethyl rhamnolipids were used to synthesize polyurethanes by reacting with 1,6‐hexane diisocyanate (HDI). Rhamnolipids were produced by microbial fermentation, providing a novel source for biopolyurethanes. FTIR and gel content analyses confirmed that the hydroxyl groups on rhamnose residues were reacted with isocyanates. DSC analysis revealed an adjustable glass transition temperature (Tg) from 19 to 50°C. Ethyl rhamnolipids are liquid at 50°C, presumably because rhamnose is connected with fatty acid at a mid‐chain position and the unique structure decreases the tendency to crystallize. The liquid polyols were found to have good mixing and reaction properties. The study may inspire future synthesis of novel lipid‐based polyols.

Practical applications: Use of vegetable oil‐based polyols for polyurethane production had been extensively investigated. However, synthesis of these polyols mostly involved introduction of petroleum‐based chemicals such as methanol and 1,2‐propanediol. Rhamnolipids are natural glycolipids. Using ethyl rhamnolipids to prepare polyurethanes provides an alternative, more renewable route. In addition, it inspires synthesis of vegetable oil polyols by introducing natural sugars.

Bio‐based polyurethanes were prepared from ethyl rhamnolipids, by reaction with 1,6‐hexane diisocyanate (HDI). Rhamnolipids, obtained from fermentation, are an alternative renewable source of reactants for polyurethane production. The unique structure of rhamnolipids may also inspire future synthesis of novel lipid‐based polyols.
Phytotoxicity of trace metals in spiked and field-contaminated soils: Linking soil-extractable metals with toxicity
Authors: Hamels Fanny , Malevé Jasmina , Sonnet Philippe , Kleja Dan Berggren , Smolders Erik
Published: July 2014

Soil tests have been widely developed to predict trace metal uptake by plants. The prediction of metal toxicity, however, has rarely been tested. The present study was set up to compare 8 established soil tests for diagnosing phytotoxicity in contaminated soils. Nine soils contaminated with Zn or Cu by metal mining, smelting, or processing were collected. Uncontaminated reference soils with similar soil properties were sampled, and series of increasing contamination were created by mixing each with the corresponding soil. In addition, each reference soil was spiked with either ZnCl2 or CuCl2 at several concentrations. Total metal toxicity to barley seedling growth in the field-contaminated soils was up to 30 times lower than that in corresponding spiked soils. Total metal (aqua regia–soluble) toxicity thresholds of 50% effective concentrations (EC50) varied by factors up to 260 (Zn) or 6 (Cu) among soils. For Zn, variations in EC50 thresholds decreased as aqua regia > 0.43 M HNO3 > 0.05 M ethylenediamine tetraacetic acid (EDTA) > 1 M NH4NO3 > cobaltihexamine > diffusive gradients in thin films (DGT) > 0.001 M CaCl2, suggesting that the last extraction is the most robust phytotoxicity index for Zn. The EDTA extraction was the most robust for Cu-contaminated soils. The isotopically exchangeable fraction of the total soil metal in the field-contaminated soils markedly explained the lower toxicity compared with spiked soils. The isotope exchange method can be used to translate soil metal limits derived from soils spiked with metal salts to site-specific soil metal limits. Environ Toxicol Chem 2014;33:2479–2487. © 2014 SETAC
Depuration of metals by the green-colored oyster Crassostrea sikamea
Authors: Wang Lei , Wang Wen-Xiong
Published: July 2014

The accumulation of metals (especially copper) in oysters has led to green-color now being found in Chinese estuaries. In the present study, the authors quantified the depuration of 8 metals (Ag, Cd, Co, Cr, Cu, Ni, Pb, and Zn) in green-colored oysters (Crassostrea sikamea) collected from an estuary that is heavily contaminated by metals as a result of industrial effluent releases. The oysters were depurated under laboratory conditions for 4 mo; the accumulated concentrations and the subcellular distribution of metals were measured at different time intervals. Results showed that the green color of oysters faded to light yellow (nearly normal) after 4 mo of depuration. Depuration of metals could be described by a first-order kinetic process. The calculated overall depuration rate constants of metals were in the range of 0.008 d−1 to 0.024 d−1, with a biological retention half-life of 30 d to 70 d. The depuration rates of green-colored contaminated oysters were significantly higher for Cd, Cu, Cr, and Ni than the rates of oysters from a less contaminated site, whereas the depuration rates of Ag, Co, Pb, and Zn were comparable between the 2 populations. When corrected for the change of oyster tissue weight, the actual efflux rate constants of the metals (0.0708–0.1014 d−1) were much higher than the overall depuration rate constants. Cellular debris and metallothionein-like proteins were the important fractions binding with the metals in the oysters. Significant changes in metal subcellular distribution were observed during the 4-mo depuration for Ag, Cd, Cu, and Zn. Metallothionein-like protein became more important in sequestering the metals during the depuration period, with a concomitant decrease in metals associated with the cellular debris fraction. Environ Toxicol Chem 2014;33:2379–2385. © 2014 SETAC
Development of a strontium chronic effects benchmark for aquatic life in freshwater
Authors: McPherson Cathy A. , Lawrence Gary S. , Elphick James R. , Chapman Peter M.
Published: July 2014

There are no national water-quality guidelines for strontium for the protection of freshwater aquatic life in North America or elsewhere. Available data on the acute and chronic toxicity of strontium to freshwater aquatic life were compiled and reviewed. Acute toxicity was reported to occur at concentrations ranging from 75 mg/L to 15 000 mg/L. The majority of chronic effects occurred at concentrations above 11 mg/L; however, calculation of a representative benchmark was confounded by results from 4 studies indicating that chronic effects occurred at lower concentrations than all other studies, in 2 cases below background concentrations reported for US and European streams. Two of these studies, including 1 reporting effects below background concentrations, were repeated and found not to be reproducible; chronic effects occurred at considerably higher strontium concentrations than in the original studies. Studies with narrow-mouthed toad and goldfish were not repeated; both studies reported chronic effects below background concentrations, and both studies had been conducted by the authors of 1 of the 2 studies that were repeated and shown to be nonreproducible. Studies by these authors (3 of the 4 confounding studies), conducted over 30 yr ago, lacked detail in reporting of methods and results. It is thus likely that repeating the toad and goldfish studies would also have resulted in a higher strontium effects concentration. A strontium chronic effects benchmark of 10.7 mg/L that incorporates the results of additional testing summarized in the present study is proposed for freshwater environments. Environ Toxicol Chem 2014;33:2472–2478. © 2014 SETAC
Stability of limonene and monitoring of a hydroperoxide in fragranced products
Authors: Kern Susanne , Granier Thierry , Dkhil Hafida , Haupt Tina , Ellis Graham , Natsch Andreas
Published: July 2014

Upon prolonged exposure to air, limonene is prone to oxidation. Hydroperoxides formed upon oxidation are strong skin sensitizers in animal tests and give positive patch tests in human dermatitis patients. However, there is no analytical evidence indicating potential sources from which the public can be exposed to sufficient quantities of limonene hydroperoxide for induction of skin sensitization to occur. It has been proposed that fragranced products might lead to such exposure. Here, we developed analytical methods using mass spectrometry (MS) in combination with gas chromatography (GC)‐MS and liquid chromatography (LC)‐MS to detect limonene‐2‐OOH. GC‐MS has a low sensitivity, whereas LC‐MS was found to be a sensitive method to detect this hydroperoxide. However, selectivity of LC‐MS is low in complex fine fragrances owing to limited separation and unspecific ions. We developed an additional method based on selective reduction of limonene‐2‐OOH to carveol by triphenylphosphine (PPh3). Quantitative carveol formation from the hydroperoxide in the presence of PPh3 could be verified in hydroperoxide‐spiked fragrances. These methods were then applied to stability studies. We found a high stability of limonene in eaux de toilette and the PPh3‐reduction assay gave no indication of hydroperoxide formation in repeatedly opened, half‐empty bottles stored for 9 months. Aged fine fragrances retrieved from consumers contained an average of 1990 µg/g limonene, but only traces of carveol were formed in a minority of the samples in the presence of PPh3. Control samples were spiked with trans‐limonene‐2‐OOH. Quantitative trans‐carveol formation in the presence of PPh3 indicated that the method would detect the hydroperoxide in these consumer products if it was present at higher concentrations. In conclusion, limonene‐2‐OOH may be detected in complex fragrance samples by selective reduction followed by GC‐MS. However, we could not find evidence for significant limonene‐2‐OOH formation in aged fine fragrance samples. Copyright © 2014 John Wiley & Sons, Ltd.
A mesenchymal‐like phenotype and expression of CD44 predict lack of apoptotic response to sorafenib in liver tumor cells
Authors: Fernando Joan , Malfettone Andrea , Cepeda Edgar B. , Vilarrasa‐Blasi Roser , Bertran Esther , Raimondi Giulia , Fabra Àngels , Alvarez‐Barrientos Alberto , Fernández‐Salguero Pedro , Fernández‐Rodríguez Conrado M. , Giannelli Gianluigi , Sancho Patricia , Fabregat Isabel
Published: July 2014

The multikinase inhibitor sorafenib is the only effective drug in advanced cases of hepatocellular carcinoma (HCC). However, response differs among patients and effectiveness only implies a delay. We have recently described that sorafenib sensitizes HCC cells to apoptosis. In this work, we have explored the response to this drug of six different liver tumor cell lines to define a phenotypic signature that may predict lack of response in HCC patients. Results have indicated that liver tumor cells that show a mesenchymal‐like phenotype, resistance to the suppressor effects of transforming growth factor beta (TGF‐β) and high expression of the stem cell marker CD44 were refractory to sorafenib‐induced cell death in in vitro studies, which correlated with lack of response to sorafenib in nude mice xenograft models of human HCC. In contrast, epithelial‐like cells expressing the stem‐related proteins EpCAM or CD133 were sensitive to sorafenib‐induced apoptosis both in vitro and in vivo. A cross‐talk between the TGF‐β pathway and the acquisition of a mesenchymal‐like phenotype with up‐regulation of CD44 expression was found in the HCC cell lines. Targeted CD44 knock‐down in the mesenchymal‐like cells indicated that CD44 plays an active role in protecting HCC cells from sorafenib‐induced apoptosis. However, CD44 effect requires a TGF‐β‐induced mesenchymal background, since the only overexpression of CD44 in epithelial‐like HCC cells is not sufficient to impair sorafenib‐induced cell death. In conclusion, a mesenchymal profile and expression of CD44, linked to activation of the TGF‐β pathway, may predict lack of response to sorafenib in HCC patients.
Autotaxin Downregulates LPS‐Induced Microglia Activation and Pro‐Inflammatory Cytokines Production
Authors: Awada Rana , Saulnier‐Blache Jean Sébastien , Grès Sandra , Bourdon Emmanuel , Rondeau Philippe , Parimisetty Avinash , Orihuela Ruben , Harry G. Jean , d'Hellencourt Christian Lefebvre
Published: July 2014

Inflammation is essential in defense against infection or injury. It is tightly regulated, as over‐response can be detrimental, especially in immune‐privileged organs such as the central nervous system (CNS). Microglia constitutes the major source of inflammatory factors, but are also involved in the regulation of the inflammation and in the reparation. Autotaxin (ATX), a phospholipase D, converts lysophosphatidylcholine (LPC) into lysophosphatidic acid (LPA) and is upregulated in several CNS injuries. LPA, a pleiotropic immunomodulatory factor, can induce multiple cellular processes including morphological changes, proliferation, death, and survival. We investigated ATX effects on microglia inflammatory response to lipopolysaccharide (LPS), mimicking gram‐negative infection. Murine BV‐2 microglia and stable transfected, overexpressing ATX‐BV‐2 (A +) microglia were treated with LPS. Tumor necrosis factor α (TNFα), interleukin (IL)‐6, and IL‐10 mRNA and proteins levels were examined by qRT‐PCR and ELISA, respectively. Secreted LPA was quantified by a radioenzymatic assay and microglial activation markers (CD11b, CD14, B7.1, and B7.2) were determined by flow cytometry. ATX expression and LPA production were significantly enhanced in LPS treated BV‐2 cells. LPS induction of mRNA and protein level for TNFα and IL‐6 were inhibited in A+ cells, while IL‐10 was increased. CD11b, CD14, and B7.1, and B7.2 expressions were reduced in A+ cells. Our results strongly suggest deactivation of microglia and an IL‐10 inhibitory of ATX with LPS induced microglia activation. J. Cell. Biochem. 115: 2123–2132, 2014. © 2014 Wiley Periodicals, Inc.
Molecular Mechanisms Associated With PTHrP‐Induced Proliferation of Colon Cancer Cells
Authors: Martín María Julia , Calvo Natalia , de Boland Ana Russo , Gentili Claudia
Published: July 2014

Parathyroid Hormone‐related Protein (PTHrP) is normally produced in many tissues and is recognized for its endocrine, paracrine, autocrine and intracrine modes of action. PTHrP is also implicated in different types of cancer and its expression correlates with the severity of colon carcinoma. Using the human colon cell line Caco‐2 we recently obtained evidence that PTHrP, through a paracrine pathway, exerts a protective effect under apoptotic conditions. However, if exogenous PTHrP is able or not to induce the proliferation of these intestinal tumor cells is not known. We found that PTHrP treatment increases the number of live Caco‐2 cells. The hormone induces the phosphorylation and nuclear translocation of ERK 1/2, α p38 MAPK, and Akt, without affecting JNK phosphorylation. In addition, PTHrP‐dependent ERK phosphorylation is reverted when PI3K activity was inhibited. Following MAPKs nuclear translocation, the transcription factors ATF‐1 and CREB were activated in a biphasic manner. In addition PTHrP induces the translocation into the nucleus of β‐catenin, protein that plays key role in maintaining the growth and proliferation of colorectal cancer, and increases the amount of both positive cell cycle regulators c‐Myc and Cyclin D. Studies with ERK1/2, α p38 MAPK, and PI3K specific inhibitors showed that PTHrP regulates Caco‐2 cell proliferation via these signaling pathways. In conclusion, the results obtained in this work expand our knowledge on the role of exogenous PTHrP in intestinal tumor cells and identify the signaling pathways that are involved in the mitogenic effect of the hormone on Caco‐2 cells. J. Cell. Biochem. 115: 2133–2145, 2014. © 2014 Wiley Periodicals, Inc.
The accuracy of self‐reported drug ingestion histories in emergency department patients
Authors: Monte Andrew A. , Heard Kennon J. , Hoppe Jason A. , Vasiliou Vasilis , Gonzalez Frank J.
Published: July 2014

Inaccuracies in self‐reports may lead to duplication of therapy, failure to appreciate non‐compliance leading to exacerbation of chronic medical conditions, or inaccurate research conclusions. Our objective is to determine the accuracy of self‐reported drug ingestion histories in patients presenting to an urban academic emergency department (ED). We conducted a prospective cohort study in ED patients presenting for pain or nausea. We obtained a structured drug ingestion history including all prescription drugs, over‐the‐counter medication (OTC) drugs, and illicit drugs for the 48 hours prior to ED presentation. We obtained urine comprehensive drug screens (CDS) and determined self‐report/CDS concordance. Fifty‐five patients were enrolled. Self‐reported drug ingestion histories were poor in these patients; only 17 (30.9%) of histories were concordant with the CDS. For the individual drug classes, prescription drug‐CDS was concordant in 32 (58.2%), OTC‐CDS was concordant in 33 (60%), and illicit drug‐CDS was concordant in 45 (81.8%) of subjects. No demographic factors predicted an accurate self‐reported drug history. Sixteen patients had drugs detected by CDS that were unreported by history. Nine of these 16 included an unreported opioid. In conclusion, self‐reported drug ingestion histories are often inaccurate and resources are needed to confirm compliance and ensure unreported drugs are not overlooked.
On the homology of the shoulder girdle in turtles
Authors: Nagashima Hiroshi , Sugahara Fumiaki , Takechi Masaki , Sato Noboru , Kuratani Shigeru
Published: July 2014

The shoulder girdle in turtles is encapsulated in the shell and has a triradiate morphology. Due to its unique configuration among amniotes, many theories have been proposed about the skeletal identities of the projections for the past two centuries. Although the dorsal ramus represents the scapular blade, the ventral two rami remain uncertain. In particular, the ventrorostral process has been compared to a clavicle, an acromion, and a procoracoid based on its morphology, its connectivity to the rest of the skeleton and to muscles, as well as with its ossification center, cell lineage, and gene expression. In making these comparisons, the shoulder girdle skeleton of anurans has often been used as a reference. This review traces the history of the debate on the homology of the shoulder girdle in turtles. And based on the integrative aspects of developmental biology, comparative morphology, and paleontology, we suggest acromion and procoracoid identities for the two ventral processes. J. Exp. Zool. (Mol. Dev. Evol.) 324B: 244–254, 2015. © 2014 Wiley Periodicals, Inc.
Ontogenetic development and sexual dimorphism of franciscana dolphin skull: A 3D geometric morphometric approach
Authors: del Castillo Daniela L. , Flores David A. , Cappozzo Humberto L.
Published: July 2014

The aim of this work was to study the postnatal ontogenetic development of Pontoporia blainvillei skull, identifying major changes on shape, and relating them to relevant factors in the life history of the species. We analyzed a complete ontogenetic series (73♂, 83♀) with three‐dimensional geometric morphometric techniques. Immature dolphins showed a very well‐developed braincase and a poorly developed rostrum, and the principal postnatal changes affected the rostrum and the temporal fossa, both structures implied functionally to the feeding apparatus, thus suggesting a specialized mode for catch fast prey in P. blainvillei. Osseous elements associated with sound production were already well developed on immature dolphins, suggesting the importance of this apparatus since the beginning of postnatal life. Sexual dimorphism was detected on both shape and size variables. Females were bigger than males, in accordance with previous studies. Shape differences between sexes were found on the posterior part of premaxillaries and external bony nares (P < 0.01), suggesting that this sexual dimorphism is related to differences on vocalization capabilities. J. Morphol. 275:1366–1375, 2014. © 2014 Wiley Periodicals, Inc.
Surface‐enhanced Raman scattering of N‐acetylneuraminic acid on silver nanoparticle surface
Authors: Vinogradova Ekaterina , Tlahuice‐Flores Alfredo , Velazquez‐Salazar J. Jesus , Larios‐Rodriguez Eduardo , Jose‐Yacaman Miguel
Published: July 2014

N‐Acetylneuraminic acid (sialic acid, Neu5Ac) has recently gained interest as a potential marker for a variety of pathophysiological processes, although no Raman study has been reported for this important biomolecule. In this paper, the vibrational properties of Neu5Ac were studied by means of Raman, surface‐enhanced Raman scattering (SERS), and density functional theory calculations. By adsorption of Neu5Ac on silver nanoparticle surface, strongly enhanced Raman intensities are obtained, allowing easy measurement of small amounts of aqueous Neu5Ac (10 µl of a 10−7 m solution) utilizing low laser power and short exposure time. The mechanism of adsorption of Neu5Ac on the silver surface is discussed on the basis of the experimental and theoretical results. This study demonstrates that SERS can provide an effective tool for development of a label‐free, rapid, and sensitive optical platform for identification of Neu5Ac. Copyright © 2014 John Wiley & Sons, Ltd.
Vineyards in Terraced Landscapes: New Opportunities from Lidar Data
Authors: Tarolli Paolo , Sofia Giulia , Calligaro Simone , Prosdocimi Massimo , Preti Federico , Dalla Fontana Giancarlo
Published: July 2014

Vineyard landscapes are a relevant part of the European culture, and several authors concluded that they are the agricultural practice that causes the highest soil loss. Grape quality depends on the availability of water, and soil erosion is an important parameter dictating the vineyard sustainability; therefore, soil and water conservation measures are often implemented. Among them, the construction of terraces is the most widely used system. However, while favouring agricultural activities, terraces if not properly maintained can lead to local instabilities creating hazards for settlements and cultivations, and for the related economy. Terraced fields are also served by agricultural roads that can have deep effects on water flows triggering surface erosion. The goal of this research is to use lidar elevation data for a hydro‐geomorphological analysis of terraced vineyards. The work is divided in two parts. At first, the Relative Path Impact Index is tested in two vineyards to identify terrace‐induced and road‐induced erosions. Statistical thresholds of the Relative Path Impact Index are then defined to label the most critical areas. On the second step, using the index and the defined thresholds, we simulate different scenarios of soil conservation measures, establishing the optimal solution to reduce erosion. The results highlight the effectiveness of high‐resolution topography in the analysis of surface erosion in terraced vineyards, when the surface water flow is the main factor triggering the instabilities. The proposed analysis can help in scheduling a suitable planning to mitigate the consequences of the anthropogenic alterations induced by the terraces and agricultural roads. Copyright © 2014 John Wiley & Sons, Ltd.