bluuebunny/crossref_metadata_2025 huggingface dataset:
Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations
Authors: Sadeh Saeid , Bhattacharjee Hridaynath , Khozeimeh Sarbisheh Elaheh , Quail J. Wilson , Müller Jens
Published: October 2014

A series of new boron‐bridged [1]ferrocenophanes ([1]FCPs) was prepared by salt‐metathesis reactions between enantiomerically pure dilithioferrocenes and amino(dichloro)boranes (Et2NBCl2, iPr2NBCl2, or tBu(Me3Si)NBCl2). The dilithioferrocenes were prepared in situ by lithium–bromine exchange from the respective planar‐chiral dibromides (Sp,Sp)‐[1‐Br‐2‐(HR2C)H3C5]2Fe (R=Me or Et). In most of the cases, mixtures of the targeted [1]FCPs 4 and the unwanted 1,1′‐bis(boryl)ferrocenes 5 were formed. The product ratio depends on the bulkiness of the amino group, the speed of addition of the amino(dichloro)borane, the alkyl group on Cp rings, and in particular on the reaction temperature. The formation of strained [1]FCPs is strongly favored by increased reaction temperatures. Secondly, CHEt2 groups at Cp rings favored the formation of the targeted [1]FCPs stronger than CHMe2 groups. These discoveries open up new possibilities to further suppress the formation of unwanted byproducts by a careful choice of the reaction temperature and through tailoring the bulkiness of CHR2 groups on ferrocene. Thermal ring‐opening polymerizations of selected boron‐bridged [1]FCPs gave metallopolymers with a Mw of 10 kDa (GPC).
Platinum Complexes of a Borane‐Appended Analogue of 1,1′‐Bis(diphenylphosphino)ferrocene: Flexible Borane Coordination Modes and in situ Vinylborane Formation
Authors: Cowie Bradley E. , Emslie David J. H.
Published: October 2014

A bis(phosphine)borane ambiphilic ligand, [Fe(η5‐C5H4PPh2)(η5‐C5H4PtBu{C6H4(BPh2)‐ortho})] (FcPPB), in which the borane occupies a terminal position, was prepared. Reaction of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)] (1) in which the arylborane is η3BCC‐coordinated. Subsequent reaction with CO and CNXyl (Xyl=2,6‐dimethylphenyl) afforded [PtL(FcPPB)] {L=CO (2) and CNXyl (3)} featuring η2BC‐ and η1B‐arylborane coordination modes, respectively. Reaction of 1 or 2 with H2 yielded [PtH(μ‐H)(FcPPB)] in which the borane is bound to a hydride ligand on platinum. Addition of PhC2H to [Pt(FcPPB)] afforded [Pt(C2Ph)(μ‐H)(FcPPB)] (5), which rapidly converted to [Pt(FcPPB′)] (6; FcPPB′=[Fe(η5‐C5H4PPh2)(η5‐C5H4PtBu{C6H4(BPh‐CPh=CHPh‐Z)‐ortho}]) in which the newly formed vinylborane is η3BCC‐coordinated. Unlike arylborane complex 1, vinylborane complex 6 does not react with CO, CNXyl, H2 or HC2Ph at room temperature.
Exploiting Supramolecular Synthons in Designing Gelators Derived from Multiple Drugs
Authors: Roy Rajdip , Deb Jolly , Jana Siddhartha Sankar , Dastidar Parthasarathi
Published: October 2014

A simple strategy for designing salt‐based supramolecular gelators comprised of various nonsteroidal anti‐inflammatory drugs (NSAIDs) and amantadine (AMN) (an antiviral drug) has been demonstrated using a supramolecular synthon approach. Single‐crystal and powder X‐ray diffraction established the existence of the well‐studied gel‐forming 1D supramolecular synthon, namely, primary ammonium monocarboxylate (PAM) synthon in all the salts. Remarkably five out of six salts were found to be capable of gelling methyl salicylate (MS)—an important ingredient in commercially available topical gels; one such selected biocompatible salt displayed an anti‐inflammatory response in prostaglandin E2 (PGE2) assay, thereby indicating their plausible biomedical applications.
A Phosphine‐Catalyzed Novel Asymmetric [3+2] Cycloaddition of C,N‐Cyclic Azomethine Imines with δ‐Substituted Allenoates
Authors: Wang De , Lei Yu , Wei Yin , Shi Min
Published: October 2014

Catalytic asymmetric [3+2] cycloadditions of C,N‐cyclic azomethine imines with δ‐substituted allenoates have been developed in the presence of (S)‐Me‐f‐KetalPhos, affording functionalized tetrahydroquinoline frameworks in good yields with high diastereo‐ and good enantioselectivities under mild condition. The substrate scope has been also examined. This is the first time that δ‐substituted allenoates have been applied as a δ,γ‐CC bond participated C2 synthon in asymmetric synthesis.
Conjugation of Cisplatin Analogues and Cyclooxygenase Inhibitors to Overcome Cisplatin Resistance
Authors: Neumann Wilma , Crews Brenda C. , Sárosi Menyhárt B. , Daniel Cristina M. , Ghebreselasie Kebreab , Scholz Matthias S. , Marnett Lawrence J. , Hey‐Hawkins Evamarie
Published: October 2014

Cyclooxygenase (COX) is an enzyme involved in tumorigenesis and is associated with tumor cell resistance against platinum‐based antitumor drugs. Cisplatin analogues were conjugated with COX inhibitors (indomethacin, ibuprofen) to study the synergistic effects that were previously observed in combination treatments. The conjugates ensure concerted transport of both drugs into cells, and subsequent intracellular cleavage enables a dual‐action mode. Whereas the platinum(II) complexes showed cytotoxicities similar to those of cisplatin, the platinum(IV) conjugates revealed highly increased cytotoxic activities and were able to completely overcome cisplatin‐related resistance. Although some of the complexes are potent COX inhibitors, the conjugates appear to execute their cytotoxic action via COX‐independent mechanisms. Instead, the increased lipophilicity and kinetic inertness of the conjugates seem to facilitate cellular accumulation of the platinum drugs and thus improve the efficacy of the antitumor agents. These conjugates are important tools for the elucidation of the direct influence of COX inhibitors on platinum‐based anticancer drugs in tumor cells.
A cytomorphometric analysis of pulmonary and mediastinal granulomas: Differentiating histoplasmosis from sarcoidosis by fine‐needle aspiration
Authors: Gailey Michael P. , Keeney Matthew E. , Jensen Chris S.
Published: October 2014

BACKGROUND

Histoplasmosis and sarcoidosis are commonly included in the differential diagnosis of mass lesions at lung and mediastinal sites. Once cancer is excluded on aspiration biopsy, further classification is essential for proper treatment.

METHODS

A search identified patients with histoplasmosis and sarcoidosis for whom the diagnosis was made by clinicopathologic correlation. Cases were reviewed for various cytologic parameters along with patient demographic, clinical, and laboratory data.

RESULTS

Fifty‐eight cases of histoplasmosis and 44 cases of sarcoidosis were reviewed. Thirty‐seven of 58 (64%) Histoplasma cases exhibited abundant, bland necrosis, and 76% of cases contained <2 angular and ragged granulomas per slide. Yeasts were identified in 36 of 37 (97%) specimens with necrosis and in 44 of 58 (76%) cases overall. These cases had an acute (14%) and/or chronic (67%) inflammatory component and uncommonly had a giant cell infiltrate (12%). Sarcoid granulomas were round with crisp, sharp borders: 80% of these granulomas contained >3 granulomas per slide, and 32% contained >10 granulomas per slide. All sarcoid granulomas had a chronic inflammatory background without acute inflammatory cells, and 50% contained giant cell infiltrates.

CONCLUSIONS

Differentiation between histoplasmosis and sarcoidosis is possible in the majority of cases. Histoplasmosis usually exhibits few angular, ragged granulomas (<2 granulomas per slide) in a background of bland necrosis. Yeasts are identified on special stains performed in aspirate smears. Sarcoidosis typically contains many more granulomas (often >10 per slide) than histoplasmosis and has a rounded morphology with crisp and sharp borders. Typically, there is no necrosis or acute inflammation, and giant cell infiltrates are frequent. Cancer (Cancer Cytopathol) 2015;123:51–8. © 2014 American Cancer Society.
Computational generation of the Purkinje network driven by clinical measurements: The case of pathological propagations
Authors: Palamara Simone , Vergara Christian , Catanzariti Domenico , Faggiano Elena , Pangrazzi Cesarino , Centonze Maurizio , Nobile Fabio , Maines Massimiliano , Quarteroni Alfio
Published: October 2014

To properly describe the electrical activity of the left ventricle, it is necessary to model the Purkinje fibers, responsible for the fast and coordinate ventricular activation, and their interaction with the muscular propagation. The aim of this work is to propose a methodology for the generation of a patient‐specific Purkinje network driven by clinical measurements of the activation times related to pathological propagations. In this case, one needs to consider a strongly coupled problem between the network and the muscle, where the feedback from the latter to the former cannot be neglected as in a normal propagation. We apply the proposed strategy to data acquired on three subjects, one of them suffering from muscular conduction problems owing to a scar and the other two with a muscular pre‐excitation syndrome (Wolff–Parkinson–White). To assess the accuracy of the proposed method, we compare the results obtained by using the patient‐specific Purkinje network generated by our strategy with the ones obtained by using a non‐patient‐specific network. The results show that the mean absolute errors in the activation time is reduced for all the cases, highlighting the importance of including a patient‐specific Purkinje network in computational models. Copyright © 2014 John Wiley & Sons, Ltd.
A finite strain nonlinear human mitral valve model with fluid‐structure interaction
Authors: Gao Hao , Ma Xingshuang , Qi Nan , Berry Colin , Griffith Boyce E. , Luo Xiaoyu
Published: October 2014

A computational human mitral valve (MV) model under physiological pressure loading is developed using a hybrid finite element immersed boundary method, which incorporates experimentally‐based constitutive laws in a three‐dimensional fluid‐structure interaction framework. A transversely isotropic material constitutive model is used to characterize the mechanical behaviour of the MV tissue based on recent mechanical tests of healthy human mitral leaflets. Our results show good agreement, in terms of the flow rate and the closing and opening configurations, with measurements from in vivo magnetic resonance images. The stresses in the anterior leaflet are found to be higher than those in the posterior leaflet and are concentrated around the annulus trigons and the belly of the leaflet. The results also show that the chordae play an important role in providing a secondary orifice for the flow when the valve opens. Although there are some discrepancies to be overcome in future work, our simulations show that the developed computational model is promising in mimicking the in vivo MV dynamics and providing important information that are not obtainable by in vivo measurements. © 2014 The Authors. International Journal for Numerical Methods in Biomedical Engineering published by John Wiley & Sons Ltd.
Polymeric Foaming with Nanoscale Nucleants: A Surface Nanobubble Mechanism
Authors: Kumar Dadi Niranjan , Roy Anik , Jha Amarkant , Sambasivan Arvind , Harikrishnan G.
Published: October 2014

The dimensionally restricted, diffusion‐driven volumetric change of almost flat nucleated surface nanobubbles hosted on dispersed nanoscale surfaces is proposed as the probable mechanism of heterogeneous bubble generation during polymer–nanoscale‐nucleant suspension foaming. By conducting numerical simulations, this hypothesis is used to predict the final bubble sizes upon polymeric foaming with nanoscale nucleants and to compare them with reported experimentally determined values. The volumetric change in the bubble hosted on the miniscule surface is envisaged to occur due to two parallel diffusion processes: 1) through the contact line of the bubble cap with the surface, and 2) through the curved gas–polymer interface. The foaming conditions determine the direction and molar rate of both these diffusions. The mechanism explains the relative nucleating efficiency of nanoscale surfaces experimentally observed during reactive and nonreactive polymeric foaming by predicting the growth or dissolution of the bubble. In the case of nonreactive thermoplastic foaming, the size of the bubbles released to the bulk from the nanoscale surface varies in a near linear fashion with respect to the size of the nucleants, limited to a maximum nucleant size. Beyond this maximum, the size of bubble generated is independent of the nucleant size. However, increase in the initial nanoscopic contact angle does not significantly affect the bubble size upon detachment from the surface.
Effects of Hydrophobicity of Diffusion Layer on the Electroreduction of Biomass Derivatives in Polymer Electrolyte Membrane Reactors
Authors: Chen Wei , He Gaohong , Ge Feilong , Xiao Wu , Benziger Jay , Wu Xuemei
Published: October 2014

For the first time, the hydrophobicity design of a diffusion layer based on the volatility of hydrogenation reactants in aqueous solutions is reported. The hydrophobicity of the diffusion layer greatly influences the hydrogenation performance of two model biomass derivatives, namely, butanone and maleic acid, in polymer electrolyte membrane reactors operated at atmospheric pressure. Hydrophobic carbon paper repels aqueous solutions, but highly volatile butanone can permeate in vapor form and achieve a high hydrogenation rate, whereas, for nonvolatile maleic acid, great mass transfer resistance prevents hydrogenation. With a hydrophilic stainless‐steel welded mesh diffusion layer, aqueous solutions of both butanone and maleic acid permeate in liquid form. Hydrogenation of maleic acid reaches a similar level as that of butanone. The maximum reaction rate is 340 nmol cm−2 s−1 for both hydrogenation systems and the current efficiency reaches 70 %. These results are better than those reported in the literature.
High Shear Homogenization of Lignin to Nanolignin and Thermal Stability of Nanolignin‐Polyvinyl Alcohol Blends
Authors: Nair Sandeep S. , Sharma Sudhir , Pu Yunqiao , Sun Qining , Pan Shaobo , Zhu J. Y , Deng Yulin , Ragauskas Art J.
Published: October 2014

A new method to prepare nanolignin using a simple high shear homogenizer is presented. The kraft lignin particles with a broad distribution ranging from large micron‐ to nano‐sized particles were completely homogenized to nanolignin particles with sizes less than 100 nm after 4 h of mechanical shearing. The 13C nuclear magnetic resonance (NMR) and 31P NMR analysis showed that there were no major changes in the chemical composition between the starting kraft lignin particles and the nanolignin obtained after 4 h of mechanical treatment. The nanolignin particles did not show any change in molecular weight distribution and polydispersity compared to the original lignin particles. The nanolignin particles when used with polyvinyl alcohol (PVA) increased the thermal stability of nanolignin/PVA blends more effectively compared to the original lignin/PVA blends.
Mesoporous TiN as a Noncarbon Support of Ag‐Rich PtAg Nanoalloy Catalysts for Oxygen Reduction Reaction in Alkaline Media
Authors: Cui Zhiming , Yang Minghui , Chen Hao , Zhao Mengtian , DiSalvo Francis J.
Published: October 2014

There has been growing interest in noncarbon supports for fuel cell reactions, especially for the oxygen reduction reaction (ORR) in alkaline media. Herein, we report a robust mesoporous titanium nitride (TiN) which is not only kinetically stable in alkaline media, but also electrochemically stable in the potential range of fuel cell operation. This binary nitride exhibits an order of magnitude higher electronic conductivity than carbon black. Bimetallic Ag‐rich PtAg nanoalloy is selected as the catalyst for the ORR in alkaline media due to their superior activity and relatively low cost. TiN‐supported Pt1Ag9 nanoalloy catalysts are synthesized by a new and efficient approach with KEt3BH as reducing agent and THF as solvent. Pt1Ag9/TiN exhibits much higher mass activity and durability for the ORR in alkaline media than Pt1Ag9/C, Pt/C and Ag/C catalysts, suggesting that mesoporous TiN is a very promising support in alkaline media.
Opportunities and challenges for repair of macrovascular disease using circulating blood‐derived progenitor cells
Authors: Loeken Mary R.
Published: October 2014

There are currently few solutions for diabetic vascular disease that involve repair of damaged tissues. The manuscript by Porat et al. in this issue, suggests a possible method to use a patient's own circulating blood cells to provide progenitors to repair damaged vascular tissues. Copyright © 2014 John Wiley & Sons, Ltd.
Neuroimmunological communication via CGRP promotes the development of a regulatory phenotype in TLR4‐stimulated macrophages
Authors: Baliu‐Piqué Mariona , Jusek Gabriela , Holzmann Bernhard
Published: October 2014

Environmental signals shape the phenotype and function of activated macrophages. Here, we show that the neuropeptide calcitonin gene‐related peptide (CGRP), which is released from sensory nerves, modulates the phenotype of TLR4‐activated murine macrophages by enhancing expression of the regulatory macrophage markers IL‐10, sphingosine kinase 1 (SPHK1), and LIGHT (lymphotoxin‐like, exhibits inducible expression and competes with HSV glycoprotein D for herpesvirus entry mediator, a receptor expressed by T lymphocytes). In contrast, CGRP inhibits production of cytokines characteristic of inflammatory macrophages and does not affect expression of wound‐healing macrophage markers upon TLR4 engagement. In IL‐4‐stimulated macrophages, CGRP increased LIGHT expression, but failed to induce IL‐10 and SPHK1. The stimulatory effect of CGRP on IL‐10 production required activation of protein kinase A and was linked to prolonged phosphorylation of CREB and sustained nuclear accumulation of CRTC2 and CRTC3 (where CRTC is CREB‐regulated transcriptional cofactor). CGRP enhanced expression of regulatory macrophage markers during the early, but not late, phase of LPS‐stimulation and this effect was independent of autocrine type‐I IFN activity. In contrast, autocrine type‐I IFN activity and treatment of macrophages with IFN‐β promoted late‐phase IL‐10 production, but had only minor influence on LIGHT and SPHK1 expression. Together, the results identify neuroimmunological communication through CGRP as a novel costimulatory pathway promoting the development of a regulatory phenotype of TLR4‐stimulated macrophages. CGRP appears to act through a mechanism that involves sustained activation of CREB‐dependent gene transcription.
IFN‐λ‐mediated IL‐12 production in macrophages induces IFN‐γ production in human NK cells
Authors: de Groen Rik A. , Boltjes Arjan , Hou Jun , Liu Bi‐Sheng , McPhee Fiona , Friborg Jacques , Janssen Harry L. A. , Boonstra André
Published: October 2014

With increasing interest in alternative options to interferon‐alpha‐based treatments, IFN‐λ has shown therapeutic promise in a variety of diseases. Although the antiviral activity of IFN‐λ has been extensively studied, there is limited knowledge regarding the immunological functions of IFN‐λ and how these differ from those of other classes of IFNs. In this study, we investigated the effects of IFN‐λ on primary human NK cells, both in a direct and indirect capacity. We demonstrate that in contrast to interferon‐alpha, IFN‐λ is unable to directly stimulate NK cells, due to the absence of IFN‐λ receptor chain 1 (IFN‐λR1) on NK cells. However, IFN‐λ, in combination with TLR4 challenge, is able to induce the production of select members of the IL‐12 family of cytokines in monocyte‐derived macrophages. We further show that through macrophage‐mediated IL‐12 production, IFN‐λ is able to indirectly affect NK cells and ultimately induce IFN‐γ production.
Lithium Complexes of Asymmetric Hydrogen Tetraimido Sulfate
Authors: Matussek Julia , Herbst‐Irmer Regine , Stalke Dietmar
Published: October 2014

Two novel monolithiated complexes, [(thf)2Li(NtBu)2(NHtBu)S(Ndipp)] (3) and [(thf)2Li(NtBu)2(NHtBu)S(Ndmp)] (4), are presented from the reaction of the neutral tri(tert‐butyl)sulfur triimide S(NtBu)3 (1), nBuLi, and diisopropylaniline and dimethylaniline, respectively. These asymmetrically substituted hydrogen tetraimido sulfate complexes of lithium provide the opportunity to switch the metal in a transmetalation reaction and to introduce another substituent at the protonated imide function.
1D Heterometallic Oxalate Compounds as Precursors for Mixed Ca–Cr Oxides – Synthesis, Structures, and Magnetic Studies
Authors: Androš Lidija , Jurić Marijana , Popović Jasminka , Pajić Damir , Zadro Krešo , Molčanov Krešimir , Žilić Dijana , Planinić Pavica
Published: October 2014

The heterodimetallic compounds {[CaCr2(L)2(C2O4)4]·xH2O}n [L = 2,2′‐bipyridine (bpy), x = 0.83 (1); L = 1,10‐phenanthroline (phen), x = 0.33 (2)] were synthesized and characterized by IR spectroscopy, X‐ray diffraction and magnetic measurements. The crystal structure of 2 is reported: the chelation of a [Cr(phen)(C2O4)2]– units towards Ca cations results in 1D double zigzag chains. The ability of 1 and 2 to act as single‐source precursors for the formation of Ca–Cr oxides is explored by thermal analysis, powder X‐ray diffraction and IR spectroscopy. The thermal processing of 1 and 2 at 1100 °C in air led to the appearance of the β‐CaCr2O4 phase as the major crystalline oxide. By heating the samples up to 1100 °C in nitrogen, only the β‐CaCr2O4 phase formed, whereas heating at 1400 °C caused the crystallization of two polymorphs, α‐ and β‐CaCr2O4. The magnetic behaviour of β‐CaCr2O4 pointed to the freezing of magnetic moments in coexistence with a weak ferromagnetic order.
Generation of Group VI Piano‐Stool and Triple‐Decker Complexes from [(IMes)2PtH(Cl‐boratabenzene)] Species
Authors: Pérez Viridiana , Barnes Stephanie S. , Fontaine Frédéric‐Georges
Published: October 2014

Species [(IMes)2Pt(H)(1‐Cl‐2‐SiMe3–BC5H4)] (1) was used as the source of the Cl‐boratabenzene anion for coordination to group VI transition metals, resulting in the formation of piano‐stool complexes [(η6‐1‐Cl‐2‐SiMe3–BC5H4)M(CO)3]– [M = Cr (2), Mo (4), W (5)] and a homodimetallic triple‐decker complex [(CO)3Cr(η6‐1‐Cl‐2‐SiMe3–BC5H4)Cr(CO)3]– (3). All species were spectroscopically characterized and the first X‐ray structure of a Cl‐boratabenzene species is reported.
Mechanistic Study of a Complementary Reaction System that Easily Affords Quinazoline and Perimidine Derivatives
Authors: Wang Zerong Daniel , Eilander Joshua , Yoshida Motoko , Wang Tianzhi
Published: October 2014

A new reaction between 2‐aminobenzophenone and thiourea in dimethyl sulfoxide (DMSO) has been developed that primarily affords 4‐phenylquinazoline as a single product. This reaction is also applicable, in general, to the reactions between thiourea and conformation‐restricted β‐amino ketones, such as 1‐aminoanthracene‐9,10‐dione and 1‐amino‐9H‐fluoren‐9‐one, to prepare perimidine derivatives. Experimental data is consistent with our computational study on the thermal decomposition of thiourea to form hydrogen sulfide and carbodiimide. This reaction involves a coupling between 2‐aminobenzophenone and carbodiimide generated in situ from thiourea to form 4‐phenylquinazolin‐2(1H)‐imine intermediate, and the generation of sulfur‐containing reducing agent from hydrogen sulfide and DMSO, which reduces 4‐phenylquinazolin‐2(1H)‐imine to 4‐phenyl‐1,2‐dihydroquinazolin‐2‐amine. Elimination of ammonia from the latter yields 4‐phenylquinazoline.
Heterocycle‐to‐Heterocycle Route to Quinoline‐4‐amines: Reductive Heterocyclization of 3‐(2‐Nitrophenyl)isoxazoles
Authors: Coffman Keith C. , Duong Vy , Bagdasarian Alex L. , Fettinger James C. , Haddadin Makhluf J. , Kurth Mark J.
Published: October 2014

A variety of quinoline‐4‐amines were synthesized from substituted 3‐(2‐nitrophenyl)isoxazoles utilizing Zn0 or Fe0 dust and HOAc using a reductive heterocyclization process. The starting isoxazoles were synthesized from readily available starting materials. A brief survey of functional groups tolerated in this reductive heterocyclization was performed and several 10‐amino‐3,4‐dihydrobenzo[b][1,6]naphthyridin‐1(2H)‐one and 9‐amino‐3,4‐dihydroacridin‐1(2H)‐one examples were synthesized.
Women with dysmenorrhoea are hypersensitive to experimentally induced forearm ischaemia during painful menstruation and during the pain‐free follicular phase
Authors: Iacovides S. , Avidon I. , Baker F.C.
Published: October 2014

Background

Monthly primary dysmenorrhoeic pain is associated with increased sensitivity to painful stimuli, particularly in deep tissue. We investigated whether women with dysmenorrhoea, compared with controls, have increased sensitivity to experimentally induced deep‐tissue muscle ischaemia in a body area distant from that of referred menstrual pain.

Methods

The sub‐maximal effort tourniquet test was used to induce forearm ischaemia in 11 women with severe dysmenorrhoea and in nine control women both during menstruation and in the follicular phase of the menstrual cycle. Von Frey hair assessments confirmed the presence of experimental ischaemia. Women rated the intensity of menstrual and ischaemic pain on a 100‐mm visual analogue scale.

Results

Women with dysmenorrhoea [mean (SD): 68 (20) mm] reported significantly greater menstrual pain compared with controls [mean (SD): 2 (6) mm; p = 0.0001] during the menstruation phase. They also rated their forearm ischaemic pain as significantly greater than the controls during the menstruation [dysmenorrhoeics vs. controls mean (SD): 58 (19) mm vs. 31 (21) mm, p < 0.01] and follicular [dysmenorrhoeics vs. controls mean (SD): 60 (18) mm vs. 40 (14) mm, p < 0.01] phases of the menstrual cycle.

Conclusions

These data show that compared with controls, women who experience severe recurrent dysmenorrhoea have deep‐tissue hyperalgesia to ischaemic pain in muscles outside of the referred area of menstrual pain both during the painful menstruation phase and pain‐free follicular phase. These findings suggest the presence of long‐lasting changes in muscle pain sensitivity in women with dysmenorrhoea. Our findings that dysmenorrhoeic women are hyperalgesic to a clinically relevant, deep‐muscle ischaemic pain in areas outside of referred menstrual pain confirm other studies showing long‐lasting changes in pain sensitivity outside of the painful period during menstruation.
A Novel Non‐Enzymatic Glucose Sensor Based on Cobalt Nanoparticles Implantation‐Modified Indium Tin Oxide Electrode
Authors: Wang Tong , Yu Yanan , Tian Huifeng , Hu Jingbo
Published: October 2014

A new type of cobalt nanoparticles modified indium tin oxide electrode (CoNPs/ITO) was fabricated using ion implantation technique. This method is low‐cost, facile and environmentally friendly without the use of any other chemicals. Electrochemical oxidation of glucose with this sensor was examined by cyclic voltammetry (CV) and chronoamperometry in alkaline aqueous solutions. The proposed sensor exhibited prominent electrocatalytic activity toward the oxidation of glucose with a low limit of detection of 0.25 µM. Furthermore, the fabricated electrode showed excellent selectivity, good reproducibility and long‐term stability. Thus CoNPs/ITO electrode is a promising candidate in the development of non‐enzymatic glucose sensors.
Methanol Synthesis from CO2 Hydrogenation over CuO–ZnO–TiO2 Catalysts: The Influence of TiO2 Content
Authors: Xiao Jie , Mao Dongsen , Guo Xiaoming , Yu Jun
Published: October 2014

A series of CuO–ZnO–TiO2 catalysts with various TiO2 loadings were prepared by using a co‐precipitation method. The prepared catalysts were characterized by using X‐ray diffraction (XRD), N2 adsorption, reactive N2O adsorption, X‐ray photoelectron spectroscopy (XPS), temperature‐programmed reduction (TPR), hydrogen temperature programmed desorption (H2‐TPD), and CO2‐TPD techniques, and tested the extent of methanol synthesis from carbon dioxide (CO2) hydrogenation. The results indicate that the addition of TiO2 to the CuO–ZnO catalyst makes the copper species exist in an amorphous‐like structure or in much smaller crystallites, which promotes the reduction of CuO. Upon increasing the TiO2 loading, the metallic Cu surface area (SCu) of the catalyst rises first and then decreases, exhibiting a maximum at a TiO2 loading of 10 %. The results of the catalytic experiments reveal that the addition of TiO2 favors the production of methanol, and an optimum catalytic activity is obtained at a TiO2 loading of 10 %. Moreover, the methanol yield increases linearly with the SCu of the catalysts, thereby indicating that the addition of TiO2 enhances the SCu but not the intrinsic activity.
Maternal repeated oral exposure to microcystin-LR affects neurobehaviors in developing rats
Authors: Li XiaoBo , Zhang Xin , Ju Jingjuan , Li Yunhui , Yin Lihong , Pu Yuepu
Published: October 2014

Microcystins are toxic peptides secreted by certain water blooms of toxic cyanobacteria. The most widely studied microcystin is microcystin-LR (MC-LR), which exhibits hepatotoxicity and neurotoxicity. However, limited information is available regarding the effects on offspring following maternal exposure. The present study was conducted to observe the effects of progestational exposure to MC-LR on postnatal development in rats. Female Sprague-Dawley rats (28 d old) were randomly divided into a control group and 3 treatment groups (1.0 µg MC-LR/kg body wt, 5.0 µg MC-LR/kg body wt, and 20.0 µg MC-LR/kg body wt), with 7 rats per group. The MC-LR was administered through gavage once every 48 h for 8 wk. Pure water was used as control. Each female rat was mated with an unexposed adult male rat. Motor development, behavioral development, and learning ability of pups were detected using surface righting reflex, negative geotaxis, and cliff avoidance tests on postnatal day 7. Open-field and Morris water maze tests were performed on postnatal day 28 and day 60. The levels of lipid peroxidation products and antioxidant indices in the rat hippocampus were also detected. Pups from the MC-LR-treated groups had significantly lower scores than controls in the cliff avoidance test (p < 0.05). Cognitive impairment, malondialdehyde level, and total superoxide dismutase activity significantly increased in MC-LR–exposed pups compared with controls (p < 0.05). Therefore, the present study reveals that maternal exposure to MC-LR has adverse effects on neurodevelopment in rat offspring. Environ Toxicol Chem 2015;34:64–69. © 2014 SETAC
A time-course transcriptional kinetics of the hypothalamic–pituitary–gonadal and hypothalamic–pituitary–adrenal axes in zebrafish eleutheroembryos after exposure to norgestrel
Authors: Liang Yan-Qiu , Huang Guo-Yong , Ying Guang-Guo , Liu Shuang-Shuang , Jiang Yu-Xia , Liu Shan , Peng Feng-jiao
Published: October 2014

The objective of the present study was to investigate the effects of norgestrel on the hypothalamic–pituitary–gonadal (HPG) and hypothalamic–pituitary–adrenal (HPA) axes in zebrafish eleutheroembryos. Zebrafish embryos were exposed to different concentrations of norgestrel (0 ng L−1, 5 ng L−1, 50 ng L−1, and 100 ng L−1) for 144 h post fertilization (hpf), and the transcriptional profiles of the HPG and HPA axes were examined every day. Norgestrel modulated the expression of Pgr and Vtg1 messenger (m)RNAs mainly at 96 hpf for all treatment groups. In addition, norgestrel strongly altered the expression of Cyp11a1 mRNA above 5 ng L−1 (significant upregulation from 48 hpf to 120 hpf and significant downregulation for 144 hpf). Norgestrel treatment could significantly induce expression of Cyp19a1a, Cyp11b, Gnrh2, Gnrh3, and Lhb mRNAs but inhibit transcripts of Hsd11b2 and Crh genes above 5 ng L−1 at different time points. The transcriptional expression levels of Esr1, Ar, Star, Hsd17b3, Fshb, and Pomc were also mediated by 5 ng L−1 norgestrel or higher during different exposure periods. Taken together, the overall results imply that the transcriptional changes in zebrafish eleutheroembryos may pose a potential effect on embryonic development, in particular in the brain and gonadogenesis. Environ Toxicol Chem 2015;34:112–119. © 2014 SETAC
Effects of tannin source and concentration from tree leaves on two species of tadpoles
Authors: Earl Julia E. , Semlitsch Raymond D.
Published: October 2014

Vegetation in and around freshwater ecosystems can affect aquatic organisms through the production of secondary compounds, which are retained in leaves after senescence and are biologically active. Tannins can be toxic to tadpoles, but the plant source of tannins and tannin concentration have been confounded in experimental designs in previous studies. To examine the effects of the concentration and source of tannins (tree species), we examined the effects of 4 factors on tadpole survival, growth, and development: tannin source (red oak [Quercus rubra], white oak [Quercus alba], or sugar maple [Acer saccharum]); tannin concentration (including a control); diet protein level; and tadpole species (American toad [Anaxyrus americanus] and spring peepers [Pseudacris crucifer]). Tannin source and concentration affected spring peeper survival, but American toads had uniformly high survival. Spring peepers had a lower survival rate in high tannin concentrations of oak leachate but a high survival rate in both concentrations of sugar maple leachate. These differences in survival did not correspond with changes in dissolved oxygen, and no effect of dietary protein level on tadpole performance was observed. The presence of plant leachate resulted in increased tadpole growth in both species, but the mechanism for this finding is unclear. The results of the present study show that tannin concentration and source are important factors for tadpole performance, adding further evidence that plant chemistry can affect aquatic organisms. Environ Toxicol Chem 2015;34:120–126. © 2014 SETAC
Mowing mitigates bioactivity of neonicotinoid insecticides in nectar of flowering lawn weeds and turfgrass guttation
Authors: Larson Jonathan L. , Redmond Carl T. , Potter Daniel A.
Published: October 2014

Systemic neonicotinoid insecticides are used to control turfgrass insect pests. The authors tested their transference into nectar of flowering lawn weeds or grass guttation droplets, which, if high enough, could be hazardous to bees or other insects that feed on such exudates. The authors applied imidacloprid or clothianidin to turf with white clover, followed by irrigation, and used liquid chromatography-tandem mass spectrometry (LC-MS/MS) to analyze residues in clover blooms that were directly sprayed during application or that formed after the first mowing. Imidacloprid residues in guttation fluid from field-grown creeping bentgrass were assessed similarly. The authors used Orius insidiosus, a small anthrocorid bug that is sensitive to dietary neonicotinoids, as a bioindicator of the exudates' toxicity. Nectar from directly sprayed clover blooms contained 5493 ng/g to 6588 ng/g imidacloprid or 2882 ng/g to 2992 ng/g clothianidin and was acutely toxic to Orius. Residues were 99.4% to 99.8% lower in nectar of blooms formed after mowing, and nontoxic to Orius. Imidacloprid residues in turfgrass guttation averaged 88 ng/g at 1 wk after treatment, causing some intoxication of Orius, but declined to 23 ng/g within 3 wk. Systemic transference of neonicotinoids into white clover nectar and creeping bentgrass guttation appears relatively low and transitory. The hazard to nontarget insects via nectar of flowering weeds in treated lawns can be mitigated by adhering to label precautions and mowing to remove blooms if they are inadvertently sprayed. Environ Toxicol Chem 2015;34:127–132. © 2014 SETAC
Effects of bisphenol A on mineral nutrition in soybean seedling roots
Authors: Nie Lijun , Wang Lihong , Wang Qingqing , Wang Shengman , Zhou Qing , Huang Xiaohua
Published: October 2014

Bisphenol A (BPA) is a ubiquitous chemical in the environment and potentially harmful to plants. However, relevant studies of the effects of BPA on plants are relatively scarce. In the present work, the effects of BPA on the biomass (fresh wt and dry wt), absorptive function (activity and absorptive area), and mineral element levels in soybean (Glycine max L.) seedling roots treated with 1.5 mg L−1, 3.0 mg L−1, 6.0 mg L−1, 12.0 mg L−1, 24.0 mg L−1, 48.0 mg L−1, and 96.0 mg L−1 BPA were investigated. Treatment with 1.5 mg L−1 BPA increased the levels of nitrate and other mineral elements (P, K, Mg, Mn, Zn, and Mo) in the roots, whereas treatments with BPA at higher concentrations decreased the levels of these elements in the roots. All treatments with BPA caused increases in the levels of ammonium, Ca, Fe, and Cu in the roots. Moreover, treatment with 1.5 mg L−1 BPA increased the fresh weight, dry weight, activity, and absorptive area of the roots, whereas treatments with BPA at higher concentrations decreased these indices in a dose-dependent manner. Furthermore, correlation analysis data showed that BPA affected the levels of mineral elements and absorptive function of soybean seedling roots, which may be the physiological basis of BPA action on plants. Environ Toxicol Chem 2015;34:133–140. © 2014 SETAC
Improving the relationship between soil characteristics and metal bioavailability by using reactive fractions of soil parameters in calcareous soils
Authors: de Santiago-Martín Ana , van Oort Folkert , González Concepción , Quintana José R. , Lafuente Antonio L. , Lamy Isabelle
Published: October 2014

The contribution of the nature instead of the total content of soil parameters relevant to metal bioavailability in lettuce was tested using a series of low-polluted Mediterranean agricultural calcareous soils offering natural gradients in the content and composition of carbonate, organic, and oxide fractions. Two datasets were compared by canonical ordination based on redundancy analysis: total concentrations (TC dataset) of main soil parameters (constituents, phases, or elements) involved in metal retention and bioavailability; and chemically defined reactive fractions of these parameters (RF dataset). The metal bioavailability patterns were satisfactorily explained only when the RF dataset was used, and the results showed that the proportion of crystalline Fe oxides, dissolved organic C, diethylene-triamine-pentaacetic acid (DTPA)-extractable Cu and Zn, and a labile organic pool accounted for 76% of the variance. In addition, 2 multipollution scenarios by metal spiking were tested that showed better relationships with the RF dataset than with the TC dataset (up to 17% more) and new reactive fractions involved. For Mediterranean calcareous soils, the use of reactive pools of soil parameters rather than their total contents improved the relationships between soil constituents and metal bioavailability. Such pool determinations should be systematically included in studies dealing with bioavailability or risk assessment. Environ Toxicol Chem 2015;34:37–44. © 2014 SETAC
Testing WHAM-FTOX with laboratory toxicity data for mixtures of metals (Cu, Zn, Cd, Ag, Pb)
Authors: Tipping Edward , Lofts Stephen
Published: October 2014

The Windermere humic aqueous model using the toxicity function (WHAM-FTOX) describes cation toxicity to aquatic organisms in terms of 1) accumulation by the organism of metabolically active protons and metals at reversible binding sites, and 2) differing toxic potencies of the bound cations. Cation accumulation (νi, in mol g−1) is estimated through calculations with the WHAM chemical speciation model by assuming that organism binding sites can be represented by those of humic acid. Toxicity coefficients (αi) are combined with νi to obtain the variable FTOX (= Σ αiνi) which, between lower and upper thresholds (FTOX,LT, FTOX,UT), is linearly related to toxic effect. Values of αi, FTOX,LT, and FTOX,LT are obtained by fitting toxicity data. Reasonable fits (72% of variance in toxic effect explained overall) were obtained for 4 large metal mixture acute toxicity experiments involving daphnids (Cu, Zn, Cd), lettuce (Cu, Zn, Ag), and trout (Zn, Cd, Pb). Strong nonadditive effects, most apparent in results for tests involving Cd, could be explained approximately by purely chemical competition for metal accumulation. Tentative interpretation of parameter values obtained from these and other experimental data suggests the following order of bound cation toxicity: H < Al < (Cu Zn Pb UO2) < (Cd Ag). Another trend is a strong increase in Cd toxicity relative to that of Zn as organism complexity increases (from bacteria to fish). Environ Toxicol Chem 2015;34:788–798. © 2014 SETAC
Rapid differentiation of in vitro cellular responses to toxic chemicals by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
Authors: Chiu Norman H.L. , Jia Zhenquan , Diaz Reynaldo , Wright Petra
Published: October 2014

Changes in protein expression as a cellular response to chemical exposure have been well established. Current methods for monitoring cellular responses usually require the use of specific reagents and/or labor-intensive procedures. The present study demonstrates the concept of using mass spectral pattern to distinguish different cellular responses. The concept is based on the ability to acquire a unique mass spectral pattern directly from a specific cell culture by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The results demonstrate that distinguishable and reproducible spectral patterns can be obtained from different cellular responses. Environ Toxicol Chem 2015;34:161–166. © 2014 SETAC
Tradeoff between storage cost and repair cost in heterogeneous distributed storage systems
Authors: Yu Quan , Shum Kenneth W. , Sung Chi Wan
Published: October 2014

In distributed storage systems (DSS), the storage costs and download costs with different storage nodes, in general, can be different. In such heterogeneous storage systems, how to establish a fundamental tradeoff between system storage cost and system repair cost is investigated. We formulate the problem of establishing the tradeoff between system storage cost and system repair cost as a bi‐objective linear programming problem subject to the min‐cut constraint of information flow graphs. We give a tight min‐cut bound for heterogeneous DSSs with general setting. Moreover, we show that the tradeoff between system storage cost and system repair cost of some special heterogeneous DSSs can be established in polynomial time. Copyright © 2014 John Wiley & Sons, Ltd.
Appetite loss and neurocognitive deficits in late‐life depression
Authors: Potter Guy G. , McQuoid Douglas R. , Steffens David C.
Published: October 2014

Objectives

This study aimed to examine the association of appetite loss symptoms to neurocognitive performance in late‐life depression (LLD).

Methods

This study used cross‐sectional data from individuals aged 60+ years with major depressive disorder (N = 322). Participants received clinical assessment of depression and neuropsychological testing. Factor analysis was used to characterize depression symptom factors, and composite scales were developed for episodic memory, psychomotor–executive functions, verbal fluency, and working memory span.

Results

Factor analysis produced a five‐factor solution: (1) anhedonia/sadness; (2) suicidality/guilt; (3) appetite/weight loss; (4) sleep disturbance; and (5) anxiety/tension. In separate multivariate models for each neurocognitive domain and including all five depression factors, higher appetite‐loss‐related symptoms were associated with lower performance in episodic memory, psychomotor–executive functions, and verbal fluency; results were significant with covariates of age, education, race, sex, age of depression onset, and illness burden. No other depression factors were associated with neurocognitive performance in these models. In an additional set of models, the appetite factor mediated the association between global depression severity and neurocognitive performance.

Discussion

A factor of appetite and weight loss symptoms in LLD was uniquely associated with neurocognitive performance, in contrast to lack of association among other depression symptom factors.

Conclusion

Cognitive deficits are a major adverse outcome of LLD, and prominent appetite loss during acute depression may be a marker for these deficits, independent of overall depression severity. Research is needed to understand the mechanisms that may explain this association, and how it is related to the cognitive and symptomatic course of LLD. Copyright © 2014 John Wiley & Sons, Ltd.
Access and utilisation of health services by domestic helpers in Cyprus
Authors: Kantaris Marios , Theodorou Mamas , Galanis Petros , Kaitelidou Daphne
Published: October 2014

Background

Immigrants have always been a very vulnerable group with severe inequalities in the access and utilisation of health services. The aim of this study was to investigate the conditions of access and utilization of health services from domestic helpers in Cyprus.

Methods

A cross‐sectional study with 625 domestic helpers was carried out during October 2010–April 2011. The sampling method was snowball sampling. Statistical analysis included x2 test, x2 trend test, Mann‐Whitney test, t‐test and multivariate logistic regression analysis.

Results

The main reasons of health service utilization were blood tests, short‐term illnesses and injuries/poisonings. Eighteen percent of domestic helpers reported a need for health services, which was not met. Ten percent responded that there was a need for pharmaceuticals that remained unmet. Sixty‐two percent reported that their first action in case of a health problem is seeking advice and assistance from their employer. After adjustment, only increased length of stay in Cyprus was associated with increased use of health services (p < 0.001).

Conclusion

The barriers of language and communication, ignorance of the system and the different culture are largely evident in Cyprus. The role of the employers is very important with regard to the access and use of health services. Copyright © 2014 John Wiley & Sons, Ltd.
Perceived Parental Protectiveness Promotes Positive Friend Influence
Authors: Laursen Brett , Žukauskienė Rita , Raižienė Saulė , Hiatt Cody , Dickson Daniel J.
Published: October 2014

Friend influence over prosocial behaviour and delinquent behaviour was examined as a function of relative parental protectiveness in a community sample of Lithuanian high school students (M = 16.5 years old). Participants completed self‐reports describing commitment to personal values, delinquent behaviours, prosocial behaviours, and perceived parental protectiveness. Mutual friends (158 male dyads, 241 female dyads) were identified from peer nominations. Distinguishable dyad Actor–Partner Interdependence Model analyses illustrate how parenting promotes positive peer influence. The results indicate that friend influence is greatest in the context of protective parenting: Adolescents who perceived more parental protectiveness were positively influenced by the strength of their friend's personal values, whereas adolescents who perceived less parental protectiveness were not. Copyright © 2014 John Wiley & Sons, Ltd.
Assessment of ALA‐induced PpIX production in porcine skin pretreated with microneedles
Authors: Rodrigues Phamilla Gracielli Sousa , Campos de Menezes Priscila Fernanda , Fujita Alessandra Keiko Lima , Escobar André , Barboza de Nardi Andrigo , Kurachi Cristina , Bagnato Vanderlei S.
Published: October 2014

Photodynamic therapy (PDT) is used for skin treatments of premalignant and cancer lesions and recognized as a non‐invasive technique that combines tissue photosensitization and subsequent exposure to light to induce cell death. However, it is limited to the treatment of superficial lesions, mainly due to the low cream penetration. Therefore, the improvement of transdermal distribution of aminolevulinic acid (ALA) is needed. In this study, the kinetics and homogeneity of production of ALA‐induced PpIX after the skin pre‐treatment with microneedles rollers of 0.5, 1.0 and 1.5 mm length were investigated. An improvement in homogeneity and production of PpIX was shown in a porcine model.

Widefield fluorescence imaging three hours after the topical application of ALA‐cream in the combined treatment with microeedles rollers.

magnified image

Widefield fluorescence imaging three hours after the topical application of ALA‐cream in the combined treatment with microeedles rollers.