bluuebunny/crossref_metadata_2025 huggingface dataset:
Avances en el estudio histórico de la mina de galena de Bunyola (isla de Mallorca)
Authors: Hermanns Marcus Heinrich
Published: February 2015

Se presentan en este trabajo los resultados de la analítica (química y isotópica) realizada para determinar la huella dactilar de la zona minera de Bunyola (Isla de Mallorca), uno de los yacimientos de galena que presenta el archipiélago Balear. Estos trabajos se realizaron para contextualizar tanto los restos mineros de la zona como para contextualizar también algunos conjuntos de material arqueológico de plomo, cuya materia prima se atribuía a este yacimiento minero. Sin embargo, gran parte de los restos en el terreno pertenecen a la mineria de finales del siglo XIX y principios del siglo XX. Las consideraciones acerca de una posible explotación en época antigua deben quedar abiertas hasta que se pueda concretar con más datos arqueológicos y/o analíticos.
Estado de la cuestión sobre la vivienda urbana romana en el área valenciana
Authors: Peñalver Carrascosa Tamara
Published: February 2015

En el siguiente artículo pretendemos realizar un estado de la cuestión del conjunto de hallazgos arqueológicos pertenecientes a la arquitectura doméstica romana de carácter urbano en territorio valenciano, siendo objeto de estudio los núcleos urbanos de Lesera, Saguntum, Edeta, Valentia, Lucentum e Ilici. Para ello pretendemos definir el tipo de plantas y articulación espacial de las domus, estableciendo las funcionalidades de las diversas estancias, así como la secuencia cronológica de las mismas, para llegar a establecer patrones que nos permitan indicar rasgos de afinidad local.
De la prospección sistemática al laboratorio GIS en La Canal de Navarrés
Authors: García Puchol Oreto , Barton Michael , Bernabeu Aubán Joan , Diez Castillo Agustín , Pardo Gordò Salvador
Published: February 2015

El trabajo que presentamos se ha desarrollado en el marco del proyecto NSF “The Emergence of Coupled Natural and Human Landscapes in the Western Mediterranean”, en el área comprendida por la actual comarca de La Canal de Navarres. Este espacio se convierte en uno de las áreas elegidas para un programa de recogida de datos centrado en la prospección sistemática “off site “  o “patch-based” (Barton et al. 2004; Dunnell 1992). Los datos relativos a la cultura material se combinan con la información espacial y ecológica, lo cual permite una comprensión dinámica de los mismos.
Regulation of EGFR signal transduction by analogue-to-digital conversion in endosomes
Authors: Villaseñor Roberto , Nonaka Hidenori , Del Conte-Zerial Perla , Kalaidzidis Yannis , Zerial Marino
Published: February 2015

An outstanding question is how receptor tyrosine kinases (RTKs) determine different cell-fate decisions despite sharing the same signalling cascades. Here, we uncovered an unexpected mechanism of RTK trafficking in this process. By quantitative high-resolution FRET microscopy, we found that phosphorylated epidermal growth factor receptor (p-EGFR) is not randomly distributed but packaged at constant mean amounts in endosomes. Cells respond to higher EGF concentrations by increasing the number of endosomes but keeping the mean p-EGFR content per endosome almost constant. By mathematical modelling, we found that this mechanism confers both robustness and regulation to signalling output. Different growth factors caused specific changes in endosome number and size in various cell systems and changing the distribution of p-EGFR between endosomes was sufficient to reprogram cell-fate decision upon EGF stimulation. We propose that the packaging of p-RTKs in endosomes is a general mechanism to ensure the fidelity and specificity of the signalling response.
Drosophila sessile hemocyte clusters are true hematopoietic tissues that regulate larval blood cell differentiation
Authors: Leitão Alexandre B , Sucena Élio
Published: February 2015

Virtually all species of coelomate animals contain blood cells that display a division of labor necessary for homeostasis. This functional partition depends upon the balance between proliferation and differentiation mostly accomplished in the hematopoietic organs. In Drosophila melanogaster, the lymph gland produces plasmatocytes and crystal cells that are not released until pupariation. Yet, throughout larval development, both hemocyte types increase in numbers. Mature plasmatocytes can proliferate but it is not known if crystal cell numbers increase by self-renewal or by de novo differentiation. We show that new crystal cells in third instar larvae originate through a Notch-dependent process of plasmatocyte transdifferentiation. This process occurs in the sessile clusters and is contingent upon the integrity of these structures. The existence of this hematopoietic tissue, relying on structure-dependent signaling events to promote blood homeostasis, creates a new paradigm for addressing outstanding questions in Drosophila hematopoiesis and establishing further parallels with vertebrate systems.
Database of ion temperature maps during geomagnetic storms
Authors: Keesee Amy M. , Scime Earl E.
Published: February 2015

Ion temperatures as a function of the x and y axes in the geocentric solar magnetospheric (GSM) coordinate system and time are available for 76 geomagnetic storms that occurred during the period July 2008 to December 2013 on CDAWeb. The method for mapping energetic neutral atom data from the Two Wide‐angle Imaging Spectrometers (TWINS) mission to the GSM equatorial plane and subsequent ion temperature calculation are described here. The ion temperatures are a measure of the average thermal energy of the bulk ion population in the 1–40 keV energy range. These temperatures are useful for studies of ion dynamics, for placing in situ measurements in a global context, and for establishing boundary conditions for models of the inner magnetosphere and the plasma sheet.
The Swarm Initial Field Model for the 2014 geomagnetic field
Authors: Olsen Nils , Hulot Gauthier , Lesur Vincent , Finlay Christopher C. , Beggan Ciaran , Chulliat Arnaud , Sabaka Terence J. , Floberghagen Rune , Friis‐Christensen Eigil , Haagmans Roger , Kotsiaros Stavros , Lühr Hermann , Tøffner‐Clausen Lars , Vigneron Pierre
Published: February 2015

Data from the first year of ESA's Swarm constellation mission are used to derive the Swarm Initial Field Model (SIFM), a new model of the Earth's magnetic field and its time variation. In addition to the conventional magnetic field observations provided by each of the three Swarm satellites, explicit advantage is taken of the constellation aspect by including east‐west magnetic intensity gradient information from the lower satellite pair. Along‐track differences in magnetic intensity provide further information concerning the north‐south gradient. The SIFM static field shows excellent agreement (up to at least degree 60) with recent field models derived from CHAMP data, providing an initial validation of the quality of the Swarm magnetic measurements. Use of gradient data improves the determination of both the static field and its secular variation, with the mean misfit for east‐west intensity differences between the lower satellite pair being only 0.12 nT.
Evaluation of CMIP5 upper troposphere and lower stratosphere geopotential height with GPS radio occultation observations
Authors: Ao Chi O. , Jiang Jonathan H. , Mannucci Anthony J. , Su Hui , Verkhoglyadova Olga , Zhai Chengxing , Cole Jason , Donner Leo , Iversen Trond , Morcrette Cyril , Rotstayn Leon , Watanabe Masahiro , Yukimoto Seiji
Published: February 2015

We present a detailed comparison of geopotential height fields between the Coupled Model Inter‐Comparison Project phase 5 (CMIP5) models and satellite observations from GPS radio occultation (RO). Our comparison focuses on the annual mean, seasonal cycle, and interannual variability of 200 hPa geopotential height in the years 2002–2008. Using a wide sample of atmosphere‐only model runs (AMIP) from the CMIP5 archive, we find that most models agree well with the observations and weather reanalyses in the tropics in both the annual means and interannual variabilities. However, the agreement is poor over the extratropics with the largest model spreads in the high latitudes and the largest bias in the southern middle to high latitudes that persist all seasons. The models also show excessive seasonal variability over the Northern midlatitude land areas as well as the Southern Ocean but insufficient variability over the tropics and Antarctica. While the underlying causes for the model discrepancies require further analyses, this study demonstrates that global observations from GPS RO provide accurate benchmark‐quality measurements in the upper troposphere and lower stratosphere through which biases in climate models as well as weather reanalyses can be identified.
Validation of the summertime surface energy budget of Larsen C Ice Shelf (Antarctica) as represented in three high‐resolution atmospheric models
Authors: King J. C. , Gadian A. , Kirchgaessner A. , Kuipers Munneke P. , Lachlan‐Cope T. A. , Orr A. , Reijmer C. , van den Broeke M. R. , van Wessem J. M. , Weeks M.
Published: February 2015

We compare measurements of the turbulent and radiative surface energy fluxes from an automatic weather station (AWS) on Larsen C Ice Shelf, Antarctica with corresponding fluxes from three high‐resolution atmospheric models over a 1 month period during austral summer. All three models produce a reasonable simulation of the (relatively small) turbulent energy fluxes at the AWS site. However, biases in the modeled radiative fluxes, which dominate the surface energy budget, are significant. There is a significant positive bias in net shortwave radiation in all three models, together with a corresponding negative bias in net longwave radiation. In two of the models, the longwave bias only partially offsets the positive shortwave bias, leading to an excessive amount of energy available for heating and melting the surface, while, in the third, the negative longwave bias exceeds the positive shortwave bias, leading to a deficiency in calculated surface melt. Biases in shortwave and longwave radiation are anticorrelated, suggesting that they both result from the models simulating too little cloud (or clouds that are too optically thin). We conclude that, while these models may be able to provide some useful information on surface energy fluxes, absolute values of modeled melt rate are significantly biased and should be used with caution. Efforts to improve model simulation of melt should initially focus on the radiative fluxes and, in particular, on the simulation of the clouds that control these fluxes.
Simulating vegetation controls on hurricane‐induced shallow landslides with a distributed ecohydrological model
Authors: Hwang Taehee , Band Lawrence E. , Hales T. C. , Miniat Chelcy F. , Vose James M. , Bolstad Paul V. , Miles Brian , Price Katie
Published: February 2015

The spatial distribution of shallow landslides in steep forested mountains is strongly controlled by aboveground and belowground biomass, including the distribution of root cohesion. While remote sensing of aboveground canopy properties is relatively advanced, estimating the spatial distribution of root cohesion at the forest landscape scale remains challenging. We utilize canopy height information estimated using lidar (light detecting and ranging) technology as a tool to produce a spatially distributed root cohesion model for landslide hazard prediction. We characterize spatial patterns of total belowground biomass based on the empirically derived allometric relationship developed from soil pit measurements in the Coweeta Hydrologic Laboratory, North Carolina. The vertical distribution of roots and tensile strength were sampled at soil pits allowing us to directly relate canopy height to root cohesion and use this model within a distributed ecohydrological modeling framework, providing transient estimates of runoff, subsurface flow, soil moisture, and pore pressures. We tested our model in mountainous southern Appalachian catchments that experienced a number of landslides during the 2004 hurricane season. Slope stability estimates under the assumption of spatially uniform root cohesion significantly underpredicted both the total number of landslides and the number of “false positives,” unfailed areas of the landscape that were predicted to fail. When we incorporate spatially distributed root cohesion, the accuracy of the slope stability forecast improves dramatically. With the growing availability of lidar data that can be used to infer belowground information, these methods may provide a wider utility for improving landslide hazard prediction and forecasting.
High‐Efficiency Dielectric Huygens’ Surfaces
Authors: Decker Manuel , Staude Isabelle , Falkner Matthias , Dominguez Jason , Neshev Dragomir N. , Brener Igal , Pertsch Thomas , Kivshar Yuri S.
Published: February 2015

Optical metasurfaces have developed as a breakthrough concept for advanced wave‐front engineering enabled by subwavelength resonant nanostructures. However, reflection and/or absorption losses as well as low polarization‐conversion efficiencies pose a fundamental obstacle for achieving high transmission efficiencies that are required for practical applications. Here, for the first time to our knowledge, highly efficient all‐dielectric metasurfaces are demonstrated for NIR frequencies using arrays of silicon nanodisks as metaatoms. The main features of Huygens' sources are employed, namely, spectrally overlapping crossed electric and magnetic dipole resonances of equal strength, to demonstrate Huygens' surfaces with full transmission‐phase coverage of 360° and near‐unity transmission. Full‐phase coverage combined with high efficiency in transmission are experimentally confirmed. Based on these key properties, all‐dielectric Huygens' metasurfaces can become a new paradigm for flat optical devices, including beam‐steering, beam‐shaping, and focusing, as well as holography and dispersion control.
Asymmetric Hydroalkoxylation of Non‐Activated Alkenes: Titanium‐Catalyzed Cycloisomerization of Allylphenols at High Temperatures
Authors: Schlüter Johannes , Blazejak Max , Boeck Florian , Hintermann Lukas
Published: February 2015

The asymmetric catalytic addition of alcohols (phenols) to non‐activated alkenes has been realized through the cycloisomerization of 2‐allylphenols to 2‐methyl‐2,3‐dihydrobenzofurans (2‐methylcoumarans). The reaction was catalyzed by a chiral titanium–carboxylate complex at uncommonly high temperatures for asymmetric catalytic reactions. The catalyst was generated by mixing titanium isopropoxide, the chiral ligand (aS)‐1‐(2‐methoxy‐1‐naphthyl)‐2‐naphthoic acid or its derivatives, and a co‐catalytic amount of water in a ratio of 1:1:1 (5 mol % each). This homogeneous thermal catalysis (HOT‐CAT) gave various (S)‐2‐methylcoumarans with yields of up to 90 % and in up to 85 % ee at 240 °C, and in 87 % ee at 220 °C.
Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines, Quinolines, and Phenanthridines
Authors: Jiang Heng , An Xiaode , Tong Kun , Zheng Tianyi , Zhang Yan , Yu Shouyun
Published: February 2015

A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)3] as a photoredox catalyst, the acyl oximes were converted by 1 e− reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids.
Observation of Diastereotopic Signals in 15N NMR Spectroscopy
Authors: Alkorta Ibon , Dardonville Christophe , Elguero José
Published: February 2015

The first example in the literature of a compound showing anisochronous 15N atoms resulting from diastereotopicity is described. Racemic 1,3‐dimethyl‐2‐phenyloctahydro‐1H‐benzimidazole was prepared and studied by 1H, 13C and 15N NMR spectroscopy. If convenient conditions were used (monitored by theoretical calculations of 2JN‐H spin–spin coupling constants), two 15N NMR signals were observed and corresponded to the diastereotopic atoms. GIAO/density‐functional calculations of chemical shifts were not only in good agreement with the experimental values but also served as prediction tools. This study suggests that 15N NMR spectroscopy could be used to probe chirality.
Active Sites and Mechanisms for Direct Oxidation of Benzene to Phenol over Carbon Catalysts
Authors: Wen Guodong , Wu Shuchang , Li Bo , Dai Chunli , Su Dang Sheng
Published: February 2015

The direct oxidation of benzene to phenol with H2O2 as the oxidizer, which is regarded as an environmentally friendly process, can be efficiently catalyzed by carbon catalysts. However, the detailed roles of carbon catalysts, especially what is the active site, are still a topic of debate controversy. Herein, we present a fundamental consideration of possible mechanisms for this oxidation reaction by using small molecular model catalysts, Raman spectra, static secondary ion mass spectroscopy (SIMS), DFT calculations, quasi in situ ATR‐IR and UV spectra. Our study indicates that the defects, being favorable for the formation of active oxygen species, are the active sites for this oxidation reaction. Furthermore, one type of active defect, namely the armchair configuration defect was successfully identified.
Identification of Structure–Activity Relationships from Screening a Structurally Compact DNA‐Encoded Chemical Library
Authors: Franzini Raphael M. , Ekblad Torun , Zhong Nan , Wichert Moreno , Decurtins Willy , Nauer Angela , Zimmermann Mauro , Samain Florent , Scheuermann Jörg , Brown Peter J. , Hall Jonathan , Gräslund Susanne , Schüler Herwig , Neri Dario
Published: February 2015

Methods for the rapid and inexpensive discovery of hit compounds are essential for pharmaceutical research and DNA‐encoded chemical libraries represent promising tools for this purpose. We here report on the design and synthesis of DAL‐100K, a DNA‐encoded chemical library containing 103 200 structurally compact compounds. Affinity screening experiments and DNA‐sequencing analysis provided ligands with nanomolar affinities to several proteins, including prostate‐specific membrane antigen and tankyrase 1. Correlations of sequence counts with binding affinities and potencies of enzyme inhibition were observed and enabled the identification of structural features critical for activity. These results indicate that libraries of this type represent a useful source of small‐molecule binders for target proteins of pharmaceutical interest and information on structural features important for binding.
A highly efficient heterogeneous rhodium(I)‐catalyzed C–S coupling reaction of thiols with polychloroalkanes or alkyl halides under mild conditions
Authors: Xia Jianhui , Yao Ruiya , Cai Mingzhong
Published: February 2015

Heterogeneous C–S coupling reaction of thiols with polychloroalkanes or alkyl halides was achieved at 30 or 80 °C in the presence of 5 mol% of an MCM‐41‐immobilized bidentate phosphine rhodium complex (MCM‐41‐2P‐RhCl(PPh3)) and triethylamine, yielding a variety of formaldehyde dithioacetals, ethylenedithioethers and unsymmetric thioethers in good to excellent yields. This heterogeneous rhodium catalyst can be easily recovered and recycled by simple filtration of the reaction solution and used for at least 10 consecutive trials without significant loss of activity. Copyright © 2015 John Wiley & Sons, Ltd.
Palladium‐catalyzed three‐component cyclization of 2‐bromocyclohex‐1‐enecarboxylic acids with carbon monoxide and arylhydrazines leading to 2‐anilinohydroisoindoline‐1,3‐diones
Authors: Yoon Il Chul , Cho Chan Sik
Published: February 2015

2‐Bromocyclohex‐1‐enecarboxylic acids are carbonylatively cyclized with arylhydrazines or their hydrochlorides in tetrahydrofuran at 120 °C under carbon monoxide pressure in the presence of a catalytic amount of PdCl2 and 1,3‐bis(diphenylphosphino)propane along with Et3N to give 2‐anilinohydroisoindoline‐1,3‐diones. Copyright © 2015 John Wiley & Sons, Ltd.
N‐methyliminodiacetic acid as a simple and highly efficient ligand for palladium‐catalyzed Suzuki–Miyaura cross‐coupling of aryl chlorides
Authors: Qi Liang , Zhou Xiuling , Li Xiaogang , Li Wei , Lv Meiyun , Guo Mengping
Published: February 2015

A simple, air‐stable, inexpensive and easily prepared molecule, N‐methyliminodiacetic acid (MIDA), is reported as a ligand for palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction of phenylboronic acid with aryl chlorides. The yield of the corresponding Suzuki coupling reaction is up to around 90% at both high temperature of 80°C and room temperature under ambient atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.
NiS Hollow Spheres for High‐Performance Supercapacitors and Non‐Enzymatic Glucose Sensors
Authors: Wei Chengzhen , Cheng Cheng , Zhao Junhong , Wang Yan , Cheng Yanyan , Xu Yazhou , Du Weimin , Pang Huan
Published: February 2015

α‐NiS and β‐NiS hollow spheres were successfully synthesized via the Kirkendall effect under different hydrothermal conditions. The obtained α‐NiS and β‐NiS hollow spheres were evaluated as electrode materials for supercapacitors. Importantly, the α‐NiS hollow sphere electrode has a large specific capacitance (562.3 F g−1 at 0.60 A g−1) and good cycling property (maintaining about 97.5 % at 2.4 A g−1 after 1000 cycles). Furthermore, the as‐prepared α‐NiS and β‐NiS hollow spheres were successfully applied to construct electrochemical glucose sensors. Especially, the α‐NiS hollow spheres exhibit a good sensitivity (155 μA mM−1 cm−2), low detection limit (0.125 μM), and a wide linear range.
Micro sequential injection system as the interfacing device for process analytical applications
Authors: Wu Chao‐Hsiang “Richard” , Wee Siowfong
Published: February 2015

It is an important and desirable capability to be able to control the quality and quantity of biological product by maintaining and adjusting bioreactor performance throughout its production duration. Amino acids are the building blocks of proteins. Scientists will need to ensure sufficient supply of amino acids as the substrates in the bioreactors as well as to control the excess level of undesirable free amino acid byproducts to maintain an optimum growth environment for cell culture. We have developed a compact and robust sample preparation platform capable of interfacing with analytical instruments to achieve bioreactor amino acids monitoring. We demonstrated the feasibility of this concept by incorporating an automatic amino acid sample preparation protocol to a micro sequential injection (μSI) system connected to an ultra‐performance liquid chromatography system for real‐time, at‐line amino acid separation, and quantitation. The μSI system was configured into a “platform‐like” sample preparation system that is able to accommodate future wet chemistry‐type sample preparations. Its real‐time amino acid results can be readily available to bioprocess scientists for quick decision making and design of their next experiment. Potential automatic feedback control mechanisms can be established through trigger events based on predetermined analytical signal thresholds so the system can communicate with facility infrastructure to control bioreactors in near real‐time fashion. The proposed μSI system described in this paper can be widely used as an automatic sample preparation system connected to the front‐end of analytical instruments to enable process analytical technology applications. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:607–613, 2015
Paravalvular leak closure after transcatheter aortic valve replacement: Technical challenges and clinical utility
Authors: Feldman Ted
Published: February 2015

Key Points

Post TAVR PVL closure with low profile vascular plugs is feasible, even for the relatively longer frame of the CoreValve device.

Device closure for PVL may be successful even after post‐dilatation and valve‐in‐valve have failed.

The low profile of the AVP4, which can pass through 4‐5F diagnostic catheters, makes this approach practical.

© 2014 Wiley Periodicals, Inc.
Bifunctional Cyclam‐Based Ligands with Phosphorus Acid Pendant Moieties for Radiocopper Separation: Thermodynamic and Kinetic Studies
Authors: Paúrová Monika , Havlíčková Jana , Pospíšilová Aneta , Vetrík Miroslav , Císařová Ivana , Stephan Holger , Pietzsch Hans‐Jürgen , Hrubý Martin , Hermann Petr , Kotek Jan
Published: February 2015

Two macrocyclic ligands based on cyclam with trans‐disposed N‐methyl and N‐(4‐aminobenzyl) substituents as well as two methylphosphinic (H2L1) or methylphosphonic (H4L2) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)—K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H4L2, probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an “out‐of‐cage” complex and thus accelerate its “in‐cage” binding. The rate of CuII complexation by the phosphinate ligand H2L1 is comparable to that of cyclam itself and its derivatives with non‐coordinating substituents. Acid‐assisted decomplexation of the copper(II) complexes is relatively fast (τ1/2=44 and 42 s in 1 M aq. HClO4 at 25 °C for H2L1 and H4L2, respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion‐selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non‐carrier‐added 64Cu in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60–70 % recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900‐fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation.
Design, Synthesis and Biological Evaluation of Novel N‐(4‐([2,2′:5′,2′′‐Terthiophen]‐5‐yl)‐2‐methylbut‐3‐yn‐2‐yl) Benzamide Derivatives
Authors: Zhu Youquan , Zhang Haili , Wang Danyang , Li Lei , Xu Han , Li Huabin , Ma Yuan
Published: February 2015

On the basis of the principle of combination of active groups, a series of novel N‐(4‐([2,2′:5′,2′′‐terthiophen]‐5‐yl)‐2‐methylbut‐3‐yn‐2‐yl) benzamide derivatives were designed, synthesized and systematically evaluated for their antiviral activity against tobacco mosaic virus (TMV). The bioassay results showed that most of these compounds displayed good anti‐TMV activity, and some of them exhibited higher antiviral activity than commercial Ningnanmycin. Especially, compound 8e with excellent anti‐TMV activity (inactivation activity, 92.3%/500 µg·mL−1; curative activity, 85.7%/500 µg·mL−1 and protection activity, 64.7%/500 µg·mL−1) emerged as a potential inhibitor of plant virus TMV. Quantitative structure‐activity relationship studies proved that the van der Waals volume (V) and electronic parameter (∑(∑σo+σp) and ∑σm) for the substituent R1 were very important for antiviral activities in this class of compounds.
Infertility in reproductive‐age female cancer survivors
Authors: Levine Jennifer M. , Kelvin Joanne Frankel , Quinn Gwendolyn P. , Gracia Clarisa R.
Published: February 2015

Improved survival rates among reproductive‐age females diagnosed with cancer have increased the focus on long‐term quality of life, including maintenance of the ability to conceive biological children. Cancer‐directed therapies such as high‐dose alkylating agents and radiation to the pelvis, which deplete ovarian reserve, radiation to the brain, which affects the hypothalamic‐pituitary‐gonadal axis, and surgical resection of reproductive structures can decrease the likelihood of having biological children. Standard fertility preservation strategies such as embryo and oocyte cryopreservation before the onset of therapy offer the opportunity to conserve fertility, but they may not be feasible because of the urgency to start cancer therapy, financial limitations, and a lack of access to reproductive endocrinologists. Ovarian tissue freezing is considered experimental, with limited data related to pregnancies, but it minimizes treatment delay. Studies evaluating gonadotropin‐releasing hormone analogues have had mixed results, although a recent randomized, prospective study in women with breast cancer demonstrated a protective effect. Fertility preservation programs are increasingly being developed within cancer programs. In this article, we describe risks to infertility and options for preservation, raise psychosocial and ethical issues, and propose elements for establishing an effective fertility preservation program. Cancer 2015;121:1532–1539. © 2015 American Cancer Society.
Ephrin‐as are required for the topographic mapping but not laminar choice of physiologically distinct RGC types
Authors: Sweeney Neal T. , James Kiely N. , Sales Emily C. , Feldheim David A.
Published: February 2015

In the retinocollicular projection, the axons from functionally distinct retinal ganglion cell (RGC) types form synapses in a stereotypical manner along the superficial to deep axis of the superior colliculus (SC). Each lamina contains an orderly topographic map of the visual scene but different laminae receive inputs from distinct sets of RGCs, and inputs to each lamina are aligned with the others to integrate parallel streams of visual information. To determine the relationship between laminar organization and topography of physiologically defined RGC types, we used genetic and anatomical axon tracing techniques in wild type and ephrin‐A mutant mice. We find that adjacent RGCs of the same physiological type can send axons to both ectopic and normal topographic locations, supporting a penetrance model for ephrin‐A independent mapping cues. While the overall laminar organization in the SC is unaffected in ephrin‐A2/A5 double mutant mice, analysis of the laminar locations of ectopic terminations shows that the topographic maps of different RGC types are misaligned. These data lend support to the hypothesis that the retinocollicular projection is a superimposition of a number of individual two‐dimensional topographic maps that originate from specific types of RGCs, require ephrin‐A signaling, and form independently of the other maps. © 2015 Wiley Periodicals, Inc. Develop Neurobiol 75: 584–593, 2015
Probing diversity within subpopulations of locomotor‐related V0 interneurons
Authors: Griener Anna , Zhang Wei , Kao Henry , Wagner Christine , Gosgnach Simon
Published: February 2015

The V0 interneuronal population is derived from Dbx1 expressing progenitors. Initial studies on these interneurons in the mouse spinal cord demonstrated that they project commissural axons and are involved in coordinating left‐right alternation during locomotion. Subsequent work has indicated that the V0 population can be divided into genetically distinct ventral (V0V) and dorsal (V0D) subpopulations, and experimental evidence suggests that each is responsible for left‐right alternation at different locomotor speeds. In this study, we perform a series of experiments to probe the location and connectivity of these subpopulations in neonatal mice and demonstrate that they are more diverse than previously predicted. While the distribution of either subpopulation remains consistent along the extent of the lumbar spinal cord, a cluster of V0D cells lateral to the central canal receive substantial input from primary afferents. Retrograde tracing and activity dependent labeling experiments demonstrate that a group of V0 interneurons located in this same region preferentially project axons towards contralateral motoneurons via an oligosynaptic pathway, and are active during fictive locomotion. Our results suggest that this subset of V0 interneurons may be primarily responsible for coordination of left‐right alternation during locomotion. Furthermore these experiments indicate that while genetic identity is one determinant of the function of a neuron during locomotion, the specific position in which the cell is located may also play a key role. © 2015 Wiley Periodicals, Inc. Develop Neurobiol 75: 1189–1203, 2015
Aqueous Complexation of YIII, LaIII, NdIII, SmIII, EuIII, and YbIII with Some Heterocyclic Substituted β‐Diketones
Authors: Petrov Alexander I. , Lutoshkin Maxim A. , Taydakov Ilya V.
Published: February 2015

This paper deals with spectrophotometric investigation on complexation of YIII, LaIII, NdIII, SmIII, EuIII, and YbIII metal ions with six heterocyclic substituted β‐diketones. The stability constants of 36 monocomplex species was determined in aqueous solutions at 298 K and I = 0.25; it lay in the range from 5.14 to 9.76 logarithmic units. The influence of the natures of the metal and ligand on the stability constant along with the dependence of the stability constant on an ionic potential (z/r) was studied and is discussed. The acid–base, tautomeric, and dimeric equilibriums of the studied substituted β‐diketones have been investigated using UV/Vis and 1H NMR spectroscopy. Also, ab initio calculations of electronic structures of metal aquacomplex species, anions of β‐diketones, and their complex species have been carried out.
Beyond diazomethane: Alternative approaches to analyzing non‐esterified fatty acids
Authors: Potter Greg , Budge Suzanne M. , Speers R. Alex
Published: February 2015

In many branches of lipid science, researchers are interested in non‐esterified fatty acid (NEFA) content and composition. For many years, diazomethane was the reagent of choice to selectively derivatize and then detect NEFA due to its highly specific methylation of the carboxylic acid functional group. While the activity of this derivatizing reagent is very defined, it is dangerous and can be difficult to obtain. In this brief review, we have compiled a collection of methods which allow for the detection of NEFA and hydroxy NEFA without the use of diazomethane. We have concentrated on methods that employ three distinct approaches of selective quantification/extraction, purification from total lipids and derivatization techniques.

Chemical reactions that occur during selective extraction of NEFA using a quaternary ammonium salt (a) and the later pyrolytic derivatization when the mixture is placed in the hot injection port of a GC (b).
Protectin DX, a double lipoxygenase product from DHA, inhibits the production of both inflammatory cytokines and reactive oxygen species in human retinal pigment epithelium cells
Authors: Dai Yining , Zhao Chan , Liang Xiaofang , Dai Rongping , Dong Fangtian
Published: February 2015

Oxidative stress and inflammation in retinal pigment epithelium (RPE) play important roles in the development of age‐related macular degeneration (AMD). Docosahexaenoic acid (22:6, n‐3, DHA) is highly concentrated in RPE and can be converted into the active oxygenate derivative protectin DX (PDX). The current study explored the effects of PDX on RPE cells under oxidative stress. Pretreatment with PDX significantly inhibited t‐BH‐induced reactive oxygen species (ROS) production and increased intracellular total antioxidant capability (T‐AOC) and superoxide dismutase (SOD) activity in RPE cells. Furthermore, PDX pretreatment greatly suppressed the t‐BH‐induced excessive secretion of tumor necrosis factor‐α (TNF‐α) and vascular endothelial growth factor‐A (VEGF‐A). Interestingly, peroxisome proliferator‐activated receptor‐γ coactivator‐1α (PGC‐1α), a key regulator of enzymes that detoxify ROS, was induced by PDX pretreatment, suggesting a possible mechanism that explains the antioxidant effects of PDX in RPE cells.

Practical applications: DHA is highly concentrated in human RPE and photoreceptor cells. It remains controversial whether DHA can reduce the risk of progression to advanced AMD. The current study investigated the anti‐inflammatory and antioxidant effects of PDX on oxidative stress‐induced RPE cells. These results suggest the potential application of active oxygenated DHA derivatives in the prevention and treatment of AMD and other oxidative stress‐related retina diseases, such as diabetic retinopathy.

DHA is highly concentrated in RPE and can be converted into the active oxygenate derivative protectin DX (PDX). Pretreatment with PDX significantly inhibited production of t‐BH‐induced reactive oxygen species (ROS) and increased capability of intracellular total antioxidant (T‐AOC) and activity of superoxide dismutase (SOD) in RPE cells. Furthermore, PDX pretreatment greatly suppressed t‐BH‐induced excessive secretion of tumor necrosis factor‐α (TNF‐α) and vascular endothelial growth factor‐A (VEGF‐A). Interestingly, peroxisome proliferator‐activated receptor‐γ coactivator‐1α (PGC‐1α), a key regulator of enzymes that detoxify ROS, was shown to be up‐regulated by PDX pretreatment, suggesting a possible mechanism underlying the antioxidant effects of PDX in RPE cells.
Development of zero trans/low sat fat systems structured with sorbitan monostearate and fully hydrogenated canola oil
Authors: de Oliveira Glazieli Marangoni , Stahl Marcella Aparecida , Ribeiro Ana Paula Badan , Grimaldi Renato , Cardoso Lisandro Pavie , Kieckbusch Theo Guenter
Published: February 2015

Currently, lipid scientists are searching for alternatives or solutions to a concern widely discussed by health organizations around the world, namely, the demand to limit the amount of saturated fat intake by the population. The present work considers the development of a lipid system with zero trans fat and low contents of saturated fatty acids (low sat). Palm oil (PO) was used as zero trans fat basis and canola oil (CO) as a source of low sat lipids. The functional attributes of these mixtures were adjusted by the incorporation of a structuring agent (sorbitan monostearate—SMS) and a crystallization modifier (fully hydrogenated canola oil—FHCO). Blends of PO with CO were formulated and the effects of adding 6% of a mixture of FHCO and SMS (50:50 w/w) to the samples were evaluated measuring the solid fat content by NMR, the thermal events by DSC and the polymorphism by XRD. Result for the oil blend (50:50 PO:CO) indicated a reduction of 40.52% in the content of saturated fatty acids compared to the original sample (100:0 PO:CO). The additives increased the consistency and the thermal resistance of the samples and proved to be effective in forming a homogeneous structural network, ensuring the continuity of the liquid oil inside the lipid matrix.

Practical applications: This research on oleogels systems has demonstrated the great potential of structuring agents for a wide variety of applications. The oil‐based fats development can be used to replace high saturated fats or hydrogenated oils in formulation of margarines, shortenings, spreads, and other specific applications.

Blends of palm oil and canola oil (100:0, 75:25 and 50:50) and these mixtures adjusted by the incorporation of 6% of a 50:50 (w/w) mixture of fully hydrogenated canola oil and sorbitan monostearate (100:0S, 75:25S and 50:50S) at 25°C. Polarized light micrograph of crystals structure were obtained under static isothermal crystallization. The additives proved to be effective in forming a homogeneous structural network, ensuring the continuity of the liquid oil inside the lipid matrix.
Comprehensive and quantitative profiling of lipid species in human milk, cow milk and a phospholipid‐enriched milk formula by GC and MS/MSALL
Authors: Sokol Elena , Ulven Trond , Færgeman Nils J. , Ejsing Christer S.
Published: February 2015

Here we present a workflow for in‐depth analysis of milk lipids that combines gas chromatography (GC) for fatty acid (FA) profiling and a shotgun lipidomics routine termed MS/MSALL for structural characterization of molecular lipid species. To evaluate the performance of the workflow we performed a comparative lipid analysis of human milk, cow milk, and Lacprodan® PL‐20, a phospholipid‐enriched milk protein concentrate for infant formula. The GC analysis showed that human milk and Lacprodan have a similar FA profile with higher levels of unsaturated FAs as compared to cow milk. In‐depth lipidomic analysis by MS/MSALL revealed that each type of milk sample comprised distinct composition of molecular lipid species. Lipid class composition showed that the human and cow milk contain a higher proportion of triacylglycerols (TAGs) as compared to Lacprodan. Notably, the MS/MSALL analysis demonstrated that the similar FA profile of human milk and Lacprodan determined by GC analysis is attributed to the composition of individual TAG species in human milk and glycerophospholipid species in Lacprodan. Moreover, the analysis of TAG molecules in Lacprodan and cow milk showed a high proportion of short‐chain FAs that could not be monitored by GC analysis. The results presented here show that complementary GC and MS/MSALL analysis is a powerful approach for characterization of molecular lipid species in milk and milk products.

Practical applications: Milk lipid analysis is routinely performed using gas chromatography. This method reports the total fatty acid composition of all milk lipids, but provides no structural or quantitative information about individual lipid molecules in milk or milk products. Here we present a workflow that integrates gas chromatography for fatty acid profiling and a shotgun lipidomics routine termed MS/MSALL for structural analysis and quantification of molecular lipid species. We demonstrate the efficacy of this complementary workflow by a comparative analysis of molecular lipid species in human milk, cow milk, and a milk‐based supplement used for infant formula.

A workflow for milk lipid analysis based on combined gas chromatography and high‐resolution shotgun lipidomics. In‐depth structural characterization and quantification of molecular lipid species in milk and milk products.
Interaction between extra virgin olive oil phenolic compounds and mucin
Authors: Quintero‐Flórez Angélica , Sánchez‐Ortiz Araceli , Gaforio Martínez José Juan , Jiménez Márquez Antonio , Beltrán Maza Gabriel
Published: February 2015

Extra virgin olive oil (EVOO) phenolic compounds provide nutritional benefits because of their antioxidant capacity. The interaction between phenolic compounds and proteins may reduce their bioavailability and antioxidant capacity. The objective of this project was to evaluate the interaction between phenolic compounds from EVOO and mucin (protein produced by epithelial tissues). EVOO phenolic extract and a number of commercially available pure phenolics present in EVOO were also used in this study: cinnamic, p‐coumaric, caffeic, vanillic and protocatechuic acids, tyrosol, hydroxytyrosol and oleuropein. The interaction between polyphenols and proteins was measured by monitoring the increasing turbidity of the reaction mixture and expressed in nephelometric turbidity units. Polyphenol solutions at different concentrations were mixed with mucin solutions. Reaction mixtures were measured after 1, 30, 60, 90 and 180 min at 37°C. The results suggest that EVOO polyphenols interact with the mucin solution forming an insoluble complex after 1 min of reaction. The highest interaction between polyphenols and proteins was observed for the EVOO phenolic extract and cinnamic, p‐coumaric and caffeic acids. The interaction between polyphenols and mucin varied depending on the phenol concentration and chemical structure. The importance of the results is to evaluate the possible consequences of EVOO phenolic–protein interactions in the bioavailability and antioxidant capacity of the polyphenols present in the EVOO.

Practical applications: Nephelometry is a simple method for the evaluation of the interaction between phenolic extract from EVOO and mucin. Phenolic compounds interact with mucin and this could provide information about possible negative consequences for the bioavailability of polyphenols and finally for the health benefits of EVOO. Additionally, this method could complement sensorial analysis for evaluation of the astringency of EVOOs, according to their polyphenol profiles.

Schematic representation of the stages occurring in binding and precipitation of polyphenol by mucin. Adapted from [30, 45].
Kinetics of the epoxidation of soybean oil with H2O2 catalyzed by phosphotungstic heteropoly acid in the presence of polyethylene glycol
Authors: Cheng Weiwei , Liu Guoqin , Wang Xuede , Liu Xinqi , Jing Lu
Published: February 2015

In this work, the kinetics of “in situ” epoxidation of soybean oil with H2O2 (30% w/w), catalyzed by phosphotungstic heteropoly acid [π‐C5H5N(CH2)15CH3]3[PW4O16] (PHA) phase transfer catalyst and polyethylene glycol (PEG) as interfacial agent in dichloroethane, were investigated at 40, 50, 60, and 70°C. Assuming that the epoxidation reaction occurred in the pseudo‐homogeneous catalytic system and the side reaction of epoxy ring cleavage was negligible, the results appeared that the epoxidation reaction of soybean oil in the presence of PEG was a second‐order with respect to double bond concentration and a first‐order to the H2O2 concentration. The corresponding apparent activation energy (42.12 kJ/mol) was lower than that of PHA alone (49.23 kJ/mol), indicating that PEG could decrease the activation energy and speed up the epoxidation reaction of soybean oil.

Practical applications: An environmentally friendly catalyst is eagerly needed to produce peroxided soybean oil for low yield and to prevent polluting the environment through the epoxidation of soybean oil with peracid. Phosphotungstic heteropoly acid phase transfer catalyst and polyethylene glycol improve the conversion and selectivity of the epoxidation reaction of soybean oil, and enhance its production efficiency.

The activation energy of the soybean oil epoxidation reaction with H2O2 catalyzed by phosphotungstic heteropoly acid (PHA) in the presence of polyethylene glycol (PEG) was lower than that of PEG alone, accounting for the results showing that the epoxy group band of the former (PHA + PEG) appeared quicker than the latter (PHA) in IR spectra.
Synthesis and characterization of novel trialdehyde, tribenzylamine, and triamine from triolein
Authors: Yang Jian , Yue Jin , Zha Baoping , Zhao Yanyun
Published: February 2015

Considering the energy crisis and environmental pollution, more attention has been focused on the synthesis of bio‐based monomers and polymers. In this study, novel trialdehyde, tribenzylamine, and triamine were synthesized from triolein, a major component of rapeseed oil, and their structures were characterized by FT‐IR, 1H NMR, 13C NMR, and mass spectrometry. The produced tribenzylamine and triamine could be utilized as potential bio‐monomers to produce polymers, such as polyurea and polyamide. The developed synthetic methodology could be employed on other unsaturated triacyglycerols and plant oils.

Practical applications: A practical method to synthesize three novel compounds from the vegetable oil feedstock has been developed. These compounds are of interest for the synthesis of polymers such as hyperbranched polyurea, which have some potential use as optical, electronic, magnetic, and nano‐materials.

The polyamine could be utilized as potential bio‐monomers to produce polymers, such as polyurea and polyamide. In this study, a novel tribenzylamine, and triamine were synthesized from triolein, a major component of rapeseed oil. The developed synthetic methodology could be employed on other unsaturated triacyglycerols and plant oils.