bluuebunny/crossref_metadata_2025 huggingface dataset:
Manganese deposits on Mars suggest a highly oxidized past
Authors: Rosen Julia
Published: November 2014

As the Curiosity rover picks its way across the Martian surface, sampling rocks and snapping photos, it searches for signs that the dusty craters and ridges under its treads may once have supported life or, at least, that they might have been habitable. Now, using measurements of manganese abundances in Martian rocks, Lanza et al. provide new evidence that Mars may have hosted liquid water and a more strongly oxygenated atmosphere at some point in its past.
Changes in Earth's radiation balance between 1985 and 2012
Authors: Orwig Jessica
Published: November 2014

Since the turn of the century, surface temperatures on Earth have continued to increase, but at a slower rate than between 1985 and 1999. This is despite increasing greenhouse gas emissions due to human activity. Consistent with the steadily increasing strength of the greenhouse effect, Allan et al. find that heating of the planet—measured as the difference between the amount of sunlight absorbed by Earth and the longwave radiative energy emitted to space—was greater between 2000 and 2012 than during the earlier time period, 1985–1999, despite the slowing rate of surface warming.
The ability of rock physics models to infer marine in situ pore pressure
Authors: Hornbach Matthew J. , Manga Michael
Published: November 2014

Pore fluid pressure is an important parameter defining the mechanical strength of marine sediments. Obtaining high spatial resolution in situ pore pressure measurements in marine sediments, however, is a challenge, and as a result, only a handful of in situ pore pressure measurements exist at scientific drill sites. Integrating rock physics models with standard IODP/ODP measurements provides a potentially widely applicable approach for calculating in situ pore pressure. Here we use a rock physics approach to estimate in situ pore pressure at two Scientific Ocean Drill Sites where in situ pressure is well constrained: ODP Site 1173, used as reference for normal (hydrostatic) fluid pressures, and ODP Site 948, where previous studies infer high fluid pressures (λ* ∼ 0.45–0.95, where the pore pressure ratio λ* is defined as the pore pressure above hydrostatic divided by the difference between the largest principal stress and hydrostatic stress). Our analysis indicates that the rock physics method provides an accurate, low‐precision method for estimating in situ pore pressure at these drill sites, and sensitivity analysis indicates this method can detect modestly high (λ* > 0.6) pore pressure at the 95% confidence level. This approach has broad applicability because it provides an inexpensive, high‐resolution (meter‐scale) method for retrospectively detecting and quantifying high pore pressure at any drill site where quality wireline logs and ocean drilling data exist.
A trial estimation of frictional properties, focusing on aperiodicity off Kamaishi just after the 2011 Tohoku earthquake
Authors: Ariyoshi Keisuke , Uchida Naoki , Matsuzawa Toru , Hino Ryota , Hasegawa Akira , Hori Takane , Kaneda Yoshiyuki
Published: November 2014

Motivated by the fact that temporal earthquake aperiodicity was observed off Kamaishi just after the 2011 Tohoku earthquake, we performed numerical simulations of chain reactions due to the postseismic slip of large earthquakes by applying rate‐ and state‐dependent friction laws. If the repeater is composed of single asperity, our results show that, (i) a mixture of partial and whole rupturing of a single asperity can explain some of the observed variability in timing and size of the repeating earthquakes off Kamaishi; (ii) the partial rupturing can be reproduced with moderate frictional instability with the aging‐law and not the slip or Nagata laws; (iii) the perturbation of the activated earthquake hypocenters observed mostly in the ESE‐WNW direction may reflect the fact that the large postseismic slip of the 2011 Tohoku earthquake propagated from ESE to WNW off Kamaishi; (iv) the observed region of repeating earthquake quiescence may reflect the strong plate coupling of megathrust earthquakes.
Azimuthal anisotropy of Rayleigh waves in the crust in southern Tohoku area, Japan
Authors: Ikeda Tatsunori , Tsuji Takeshi
Published: November 2014

To reveal seismic anisotropy within the crust in the southern Tohoku area, Japan, we analyze the azimuthal anisotropy of Rayleigh waves in the frequency range of 40–65 mHz. Rayleigh wave anisotropy is estimated by array analysis of 102 teleseismic events that occurred between 2007 and 2014. The frequency variation of the estimated azimuthal anisotropy indicates depth variation of the seismic anisotropy within the crust: (1) north‐south fast velocity direction around the upper crust and (2) trench‐normal fast velocity direction in the deeper crust. We also conduct a time‐lapse analysis of Rayleigh wave anisotropy to demonstrate the stability of the estimated anisotropy in time and to estimate possible changes in seismic anisotropy associated with the 2011 Tohoku‐oki earthquake. We demonstrate that the azimuthal location of teleseismic events influences the accuracy of time‐lapse analysis. Moreover, a decrease of azimuthal anisotropic ratio in time‐lapse results might be related to changes in the velocity structure associated with release of crustal stress during the Tohoku‐oki earthquake.
Woody plant encroachment into grasslands leads to accelerated erosion of previously stable organic carbon from dryland soils
Authors: Puttock Alan , Dungait Jennifer A. J. , Macleod Christopher J. A. , Bol Roland , Brazier Richard E.
Published: November 2014

Drylands worldwide are experiencing rapid and extensive environmental change, concomitant with the encroachment of woody vegetation into grasslands. Woody encroachment leads to changes in both the structure and function of dryland ecosystems and has been shown to result in accelerated soil erosion and loss of soil nutrients. Covering 40% of the terrestrial land surface, dryland environments are of global importance, both as a habitat and a soil carbon store. Relationships between environmental change, soil erosion, and the carbon cycle are uncertain. There is a clear need to further our understanding of dryland vegetation change and impacts on carbon dynamics. Here two grass‐to‐woody ecotones that occur across large areas of the southwestern United States are investigated. This study takes a multidisciplinary approach, combining ecohydrological monitoring of structure and function and a dual‐proxy biogeochemical tracing approach using the unique natural biochemical signatures of the vegetation. Results show that following woody encroachment, not only do these drylands lose significantly more soil and organic carbon via erosion but that this includes significant amounts of legacy organic carbon which would previously have been stable under grass cover. Results suggest that these dryland soils may not act as a stable organic carbon pool, following encroachment and that accelerated erosion of carbon, driven by vegetation change, has important implications for carbon dynamics.
Five‐year‐olds punish antisocial adults
Authors: Kenward Ben , Östh Therese
Published: November 2014

The human tendency to impose costs on those who have behaved antisocially towards third parties (third‐party punishment) has a formative influence on societies, yet very few studies of the development of this tendency exist. In most studies where young children have punished, participants have imposed costs on puppets, leaving open the question as to whether young children punish in real third‐party situations. Here, five‐year‐olds were given the opportunity to allocate desirable or unpleasant items to antisocial and neutral adults, who were presented as real and shown on video. Neutral individuals were almost always allocated only desirable items. Antisocial individuals were instead usually allocated unpleasant items, as long as participants were told they would give anonymously. Most participants who were instead told they would give in person did not allocate unpleasant items, although a minority did so. This indicates that the children interpreted the situation as real, and that whereas they genuinely desired to punish antisocial adults, they did not usually dare do so in person. Boys punished more frequently than girls. The willingness of preschoolers to spontaneously engage in third‐party punishment, occasionally even risking the social costs of antagonizing an anti‐social adult, demonstrates a deep‐seated early‐developing punitive sentiment in humans. Aggr. Behav. 41:413–420, 2015. © 2014 Wiley Periodicals, Inc.
Human brain arteriovenous malformations express lymphatic‐associated genes
Authors: Shoemaker Lorelei D. , Fuentes Laurel F. , Santiago Shauna M. , Allen Breanna M. , Cook Douglas J. , Steinberg Gary K. , Chang Steven D.
Published: November 2014

Objective

Brain arteriovenous malformations (AVMs) are devastating, hemorrhage‐prone, cerebrovascular lesions characterized by well‐defined feeding arteries, draining vein(s) and the absence of a capillary bed. The endothelial cells (ECs) that comprise AVMs exhibit a loss of arterial and venous specification. Given the role of the transcription factor COUP‐TFII in vascular development, EC specification, and pathological angiogenesis, we examined human AVM tissue to determine if COUP‐FTII may have a role in AVM disease biology.

Methods

We examined 40 human brain AVMs by immunohistochemistry (IHC) and qRT‐PCR for the expression of COUP‐TFII as well as other genes involved in venous and lymphatic development, maintenance, and signaling. We also examined proliferation and EC tube formation with human umbilical ECs (HUVEC) following COUP‐TFII overexpression.

Results

We report that AVMs expressed COUP‐TFII, SOX18, PROX1, NFATC1, FOXC2, TBX1, LYVE1, Podoplanin, and vascular endothelial growth factor (VEGF)‐C, contained Ki67‐positive cells and heterogeneously expressed genes involved in Hedgehog, Notch, Wnt, and VEGF signaling pathways. Overexpression of COUP‐TFII alone in vitro resulted in increased EC proliferation and dilated tubes in an EC tube formation assay in HUVEC.

Interpretation

This suggests AVM ECs are further losing their arterial/venous specificity and acquiring a partial lymphatic molecular phenotype. There was significant correlation of gene expression with presence of clinical edema and acute hemorrhage. While the precise role of these genes in the formation, stabilization, growth and risk of hemorrhage of AVMs remains unclear, these findings have potentially important implications for patient management and treatment choice, and opens new avenues for future work on AVM disease mechanisms.
Prognostic factors for outcome in patients with refractory and relapsed acute lymphocytic leukemia treated with inotuzumab ozogamicin, aCD22 monoclonal antibody
Authors: Jabbour Elias , O'Brien Susan , Huang Xuelin , Thomas Deborah , Rytting Michael , Sasaki Koji , Cortes Jorge , Garcia‐Manero Guillermo , Kadia Tapan , Ravandi Farhad , Pierce Sherry , Kantarjian Hagop
Published: November 2014

Inotuzumab ozogamicin was found to be highly active in patients with refractory‐relapsed acute lymphocytic leukemia (ALL), with an overall response rate of 58% and a median survival of 6.3 months. Identifying factors associated with different outcomes on inotuzumab therapy may help select patients for this treatment and advice of prognosis. A total of 89 patients treated with inotuzumab on previous studies were analyzed. Inotuzumab was given at 1.3–1.8 mg/m2intravenously (IV) × 1 every 3–4 weeks or weekly (0.8 mg/m2day 1, 0.5 mg/m2days 8 and 15) every 3–4 weeks. Pretreatment factors associated with achieving marrow complete response (CR) and with survival were analyzed using standard statistical methods. The median survival of patients with at least marrow CR was 9.2 months versus 3.4 months for those without marrow CR (P < 0.001). By multivariate analysis, a high peripheral blood absolute blast count and low platelet count were independently associated with a lower likelihood of achieving at least marrow CR. Baseline characteristics independently associated with worse survival included adverse cytogenetics [complex karyotype, translocation (4;11), translocation (9;22), abnormal chromosome 17], disease beyond first salvage, and high peripheral blood absolute count. Patients with 0, 1–2, or 3 adverse factors had a median survival of 39+, 7.5, and 2.4 months, respectively. Our current analyses identified a subset of adult patients with ALL in whom outcome of therapy with inotuzumab ozogamicin can be differentially predicted. Am. J. Hematol. 90:193–196, 2015. © 2014 Wiley Periodicals, Inc.
Green and effective route for the synthesis of monodispersed palladium nanoparticles using herbal tea extract (Stachys lavandulifolia) as reductant, stabilizer and capping agent, and their application as homogeneous and reusable catalyst in Suzuki coupling reactions in water
Authors: Veisi Hojat , Ghorbani‐Vaghei Ramin , Hemmati Saba , Aliani Majid Haji , Ozturk Turan
Published: November 2014

A simple and eco‐friendly procedure has been devised for the green synthesis of palladium nanoparticles, using the aqueous extract of herbal tea (Stachys lavandulifolia), a renewable and nontoxic natural phyto‐exudate. The water‐soluble components of the extract act as reducing agent and stabilizer. This green route does not require a surfactant or capping agent for the growth of palladium nanoparticles. The generated nanoparticles were analysed using UV–visible spectroscopy, transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X‐ray analysis and inductively coupled plasma. The palladium nanoparticles having spherical shape and dimensions of between 5 and 7 nm were employed as a homogeneous catalyst for Suzuki coupling reactions conducted in water under mild conditions. Good yields of products, a facile work‐up, no evidence of leached palladium from the catalyst surface and smooth recovery of the catalysis by adding ethyl acetate, which could be reused at least eight times, confirm the very good efficiency of the catalytic reaction. Copyright © 2014 John Wiley & Sons, Ltd.
Synergistic effect of graphite nanoplatelets and glass fibers in polypropylene composites
Authors: Pedrazzoli Diego , Pegoretti Alessandro , Kalaitzidou Kyriaki
Published: November 2014

In this study, polypropylene (PP) composites reinforced with short glass fibers (GF) and exfoliated graphite nanoplatelets were obtained by melt compounding followed by injection molding. Morphological observations and quasi‐static tensile tests were carried out in order to investigate how the morphology and the mechanical properties of the composites were affected by the combined effect of two fillers of rather different size scales (i.e., micro‐ and nanoscale). The results indicate that the dispersion of the nanofiller in the PP matrix promoted the formation of a stronger interface between the matrix and GF, as indicated by the increase of the interfacial shear strength determined by the single‐fiber microdebonding test. Concurrently, a significant improvement of the tensile modulus and impact strength of the composites was observed, with small changes in the processability of hybrid composites compared to that of GF composites, as confirmed by rheological measurements. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41682.
Morphogenesis of the Spleen During the Human Embryonic Period
Authors: Endo Aya , Ueno Saki , Yamada Shigehito , Uwabe Chigako , Takakuwa Tetsuya
Published: November 2014

We aimed to observe morphological changes in the spleen from the emergence of the primordium to the end of the embryonic period using histological serial sections of 228 samples. Between Carnegie stages (CSs) 14 and 17, the spleen was usually recognized as a bulge in the dorsal mesogastrium (DM), and after CS 20, the spleen became apparent. Intrasplenic folds were observed later. A high‐density area was first recognized in 6 of the 58 cases at CS 16 and in all cases examined after CS 18. The spleen was recognized neither as a bulge nor as a high‐density area at CS 13. The mesothelium was pseudostratified until CS 16 and was replaced with high columnar cells and then with low columnar cells. The basement membrane was obvious after CS 17. The mesenchymal cells differentiated from cells in the DM, and sinus formation started at CS 20. Hematopoietic cells were detected after CS 18. The vessels were observed at CS 14 in the DM. Hilus formation was observed after CS 20. The parallel entries of the arteries and veins were observed at CS 23. The rate of increase in spleen length in relation to that of stomach length along the cranial‐caudal direction was 0.51 ± 0.11, which remained constant during CSs 19 and 23, indicating that their growths were similar. These data may help to better understand the development of normal human embryos and to detect abnormal embryos in the early stages of development. Anat Rec, 298:820–826, 2015. © 2014 Wiley Periodicals, Inc.
The Musculature That Drives Active Touch by Vibrissae and Nose in Mice
Authors: Haidarliu Sebastian , Kleinfeld David , Deschênes Martin , Ahissar Ehud
Published: November 2014

Coordinated action of facial muscles during whisking, sniffing, and touching objects is an important component of active sensing in rodents. Accumulating evidence suggests that the anatomical schemes that underlie active sensing are similar across the majority of whisking rodents. Intriguingly, however, muscle architecture in the mystacial pad of the mouse was reported to be different, possessing only one extrinsic vibrissa protracting muscle (M. nasalis) in the rostral part of the snout. In this study, the organization of the muscles that move the nose and the mystacial vibrissae in mice was re‐examined and compared with that reported previously in other rodents. We found that muscle distribution within the mystacial pad and around the tip of the nose in mice is isomorphic with that found in other whisking rodents. In particular, in the rostral part of the mouse snout, we describe both protractors and retractors of the vibrissae. Nose movements are controlled by the M. dilator nasi and five subunits of the M. nasolabialis profundus, with involvement of the nasal cartilaginous skeleton as a mediator in the muscular effort translation. Anat Rec, 298:1347–1358, 2015. © 2014 Wiley Periodicals, Inc.
Plentiful PtdIns5P from scanty PtdIns(3,5)P2 or from ample PtdIns? PIKfyve‐dependent models: Evidence and speculation (response to: DOI 10.1002/bies.201300012)
Authors: Shisheva Assia , Sbrissa Diego , Ikonomov Ognian
Published: November 2014

Recently, we have presented data supporting the notion that PIKfyve not only produces the majority of constitutive phosphatidylinositol 5‐phosphate (PtdIns5P) in mammalian cells but that it does so through direct synthesis from PtdIns. Another group, albeit obtaining similar data, suggests an alternative pathway whereby the low‐abundance PtdIns(3,5)P2 undergoes hydrolysis by unidentified 3‐phosphatases, thereby serving as a precursor for most of PtdIns5P. Here, we review the experimental evidence supporting constitutive synthesis of PtdIns5P from PtdIns by PIKfyve. We further emphasize that the experiments presented in support of the alternative pathway are also compatible with a direct mechanism for PIKfyve‐catalyzed synthesis of PtdIns5P. While agreeing with the authors that constitutive PtdIns5P could theoretically be produced from PtdIns(3,5)P2 by 3‐dephosphorylation, we argue that until direct evidence for such an alternative pathway is obtained, we should adhere to the existing experimental evidence and quantitative considerations, which favor direct PIKfyve‐catalyzed synthesis for most constitutive PtdIns5P.
Temperature‐dependent control of Staphylococcus aureus biofilms and virulence by thermoresponsive oligo(N‐vinylcaprolactam)
Authors: Lee Jin‐Hyung , Kim Yong‐Guy , Lee Kayeon , Kim Seong‐Cheol , Lee Jintae
Published: November 2014

Bacterial biofilms are associated with persistent infections because they are highly tolerant of antimicrobial agents, and in the case of Staphylococcus aureus, which is a leading cause of nosocomial infections because of its resistance to diverse antibiotics, biofilm formation is a known mechanism of drug resistance. In the present study, we investigated the ability of thermoresponsive oligo (N‐vinylcaprolactam) (OVCL) to control biofilm formation by and the virulence of S. aureus. One synthetic and four commercial OVCLs (MW ≤ 240,000) at 50 µg/mL were found to increase S. aureus biofilm formation 7‐fold at 25 °C, but to markedly inhibit S. aureus biofilm formation at 37 °C. Confocal and scanning electron microscopy confirmed the temperature‐dependent effect of OVCL on S. aureus biofilms. It was found that the addition of OVCL to S. aureus culture caused cells to become dramatically more hydrophilic at 37 °C, which partially supports the biofilm reduction. Also, transcriptional analysis showed that OVCL temperature‐dependently regulated biofilm‐related genes (aur, agrA, and icaA) in S. aureus. In addition, it was found surface coatings containing OVCL effectively controlled S. aureus biofilm formation on solid glass surfaces. Furthermore, OVCL inhibited the hemolysis of human red blood cells by S. aureus at 37 °C and attenuated S. aureus virulence in the nematode Caenorhabditis elegans. These results suggest that OVCL has potential use for controlling bacterial biofilm formation and virulence. Biotechnol. Bioeng. 2015;112: 716–724. © 2014 Wiley Periodicals, Inc.
Synthesis and Olfactory Characterization of Silicon‐Containing Derivatives of the Acyclic Lily‐of‐the‐Valley Odorant 5,7,7‐Trimethyl‐4‐methylideneoctanal
Authors: Dörrich Steffen , Mahler Christoph , Tacke Reinhold , Kraft Philip
Published: November 2014

5‐Methyl‐4‐methylidene‐6‐(trimethylsilyl)hexanal (1b), a sila analog of the acyclic lily‐of‐the‐valley odorant 5,7,7‐trimethyl‐4‐methylideneoctanal (1a), and the Si‐containing derivatives 2–6 were prepared in multistep syntheses, starting from Cl3SiH and Cl2SiMe2, respectively. Compounds 1b, 2–6, and their new precursors were characterized by elemental analyses (C, H, N) and NMR spectroscopic studies (1H, 13C, 15N, and 29Si). To gain more information about the structureodor correlation in the family of lily‐of‐the‐valley or ‘muguet’ odorants, C/Si analogs 1a/1b and derivatives 2–6 were evaluated for their olfactory properties.
Development of New Natural Extracts
Authors: Lavoine‐Hanneguelle Sophie , Périchet Christine , Schnaebele Nicolas , Humbert Marina
Published: November 2014

For over the past 20 years, a remarkable development in the study and search of natural products has been observed. This is linked to a new market trend towards ecology and also due to new regulations. This could be a rupture, but also a real booster for creativity. Usually, in the flavor and fragrance field, creativity was boosted by the arrival of new synthetic molecules. Naturals remained the traditional, century‐old products, protected by secrecy and specific know‐how from each company. Regulatory restrictions or eco‐friendly certification constraints like hexane‐free processes triggered an important brainstorming in the industry. As a result, we developed new eco‐friendly processes including supercritical CO2 extraction, allowing fresh plants to be used to obtain industrial flower extracts (Jasmine Grandiflorum, Jasmine Sambac, Orange blossom). These extracts are analyzed by GC, GC/MS, GCO, and HPTLC techniques. New or unusual raw materials can also be explored, but the resulting extracts have to be tested for safety reasons. Some examples are described.
Defining the Potential of Aglycone Modifications for Affinity/Selectivity Enhancement against Medically Relevant Lectins: Synthesis, Activity Screening, and HSQC‐Based NMR Analysis
Authors: Rauthu Subhash R. , Shiao Tze Chieh , André Sabine , Miller Michelle C. , Madej Élodie , Mayo Kevin H. , Gabius Hans‐Joachim , Roy René
Published: November 2014

The emerging significance of lectins for pathophysiological processes provides incentive for the design of potent inhibitors. To this end, systematic assessment of contributions to affinity and selectivity by distinct types of synthetic tailoring of glycosides is a salient step, here taken for the aglyconic modifications of two disaccharide core structures. Firstly we report the synthesis of seven N‐linked‐lactosides and of eight O‐linked N‐acetyllactosamines, each substituted with a 1,2,3‐triazole unit, prepared by copper‐catalyzed azide–alkyne cycloaddition (CuAAC). The totally regioselective β‐D‐(1→4) galactosylation of a 6‐O‐TBDPSi‐protected N‐acetylglucosamine acceptor provided efficient access to the N‐acetyllactosamine precursor. The resulting compounds were then systematically tested for lectin reactivity in two binding assays of increasing biorelevance (inhibition of lectin binding to a surface‐presented glycoprotein and to cell surfaces). As well as a plant toxin, we also screened the relative inhibitory potential with adhesion/growth‐regulatory galectins (total of eight proteins). This type of modification yielded up to 2.5‐fold enhancement for prototype proteins, with further increases for galectins‐3 and ‐4. Moreover, the availability of 15N‐labeled proteins and full assignments enabled 1H,15N HSQC‐based measurements for hu‐ man galectins‐1, ‐3, and ‐7 against p‐nitrophenyl lactopyranoside, a frequently tested standard inhibitor containing an aromatic aglycone. The measurements confirmed the highest affinity against galectin‐3 and detected chemical shift differences in its hydrophobic core upon ligand binding, besides common alterations around the canonical contact site for the lactoside residue. What can be accomplished in terms of affinity/selectivity by this type of core extension having been determined, the applied combined strategy should be instrumental for proceeding with defining structure–activity correlations at other bioinspired sites in glycans and beyond the tested lectin types.
Rigidified Clicked Dimeric Ligands for Studying the Dynamics of the PDZ1‐2 Supramodule of PSD‐95
Authors: Eildal Jonas N. N. , Bach Anders , Dogan Jakob , Ye Fei , Zhang Mingjie , Jemth Per , Strømgaard Kristian
Published: November 2014

PSD‐95 is a scaffolding protein of the MAGUK protein family, and engages in several vital protein–protein interactions in the brain with its PDZ domains. It has been suggested that PSD‐95 is composed of two supramodules, one of which is the PDZ1‐2 tandem domain. Here we have developed rigidified high‐affinity dimeric ligands that target the PDZ1‐2 supramodule, and established the biophysical parameters of the dynamic PDZ1‐2/ligand interactions. By employing ITC, protein NMR, and stopped‐flow kinetics this study provides a detailed insight into the overall conformational energetics of the interaction between dimeric ligands and tandem PDZ domains. Our findings expand our understanding of the dynamics of PSD‐95 with potential relevance to its biological role in interacting with multivalent receptor complexes and development of novel drugs.
A Route to Stereochemically Pure Benzyllithium Reagents by Stereocontrolled Epimerisation
Authors: Koller Stephan G. , Kroesen Ulrike , Strohmann Carsten
Published: November 2014

Alkyllithium compounds are not generally stable at room temperature, therefore strategies were established to overcome this limitation. We present a systematic approach to obtain a stereochemically enriched benzyllithium compound, starting with the simple addition of a chiral auxiliary and ending by incorporation of the auxiliary in the substrate. Thereby, a very unusual dimer of a lithiated benzylsilane was obtained, which could be split into stereochemically enriched monomers by the addition of Lewis bases. Furthermore, we were able to understand the factors responsible for this stereochemical enrichment by using quantum chemical calculations and clarify the configuration of the lithiated compound and the corresponding trapping product by crystallisation. This enabled us to determine the stereochemical course of the deprotonation and the subsequent metathesis reaction.
ISAC's classification results file format
Authors: Spidlen Josef , Bray Chris ,   ISAC Data Standards Task Force, Brinkman Ryan R.
Published: November 2014

Identifying homogenous sets of cell populations in flow cytometry is an important process for sorting and selecting populations of interests for further data acquisition and analysis. Many computational methods are now available to automate this process, with several algorithms partitioning cells based on high‐dimensional separation versus the traditional pairwise two‐dimensional visualization approach of manual gating. ISAC's classification results file format was developed to exchange the results of both manual gating and algorithmic classification approaches in a standardized way based on per event based classifications, including the potential for soft classifications expressed as the probability of an event being a member of a class. © 2014 International Society for Advancement of Cytometry
Generation of storm runoff and the role of animals in a small upland headwater stream
Authors: Meijles Erik W. , Dowd John F. , Williams Andrew G. , Heppell Catherine M.
Published: November 2014

This paper illustrates the hillslope storm runoff mechanisms and the effects of livestock in upland areas. The research site was a small upland catchment area on Dartmoor (Southwest England). It was shown that overland flow on the tracks and paths created by animals in the area responded very rapidly to rainfall, in the same order of magnitude as stream runoff. Livestock stocking densities were significantly different in different vegetation compositions. The topsoil bulk density values, moisture content and spatial track densities were significantly higher in areas associated with higher stocking rates. These areas reach a wetness threshold at an earlier state than surrounding, drier areas. When isolated, the wetter areas start discharging water only locally into downslope drier areas, but are not contributing to storm runoff in the stream. In areas with a high density of animal tracks, water is being discharged onto the track directly. The tracks comprised an ephemeral hydrological network contributing storm runoff to the stream quickly after rainfall. They transmit water rapidly downhill, short‐circuiting local areas, reducing runoff lag time and increasing storm stream runoff. The runoff producing mechanism, in which soil conditions, vegetation types and path networks are a complex interplay of contributing factors, may be relevant to other uplands, especially when they act as water reservoir or source area for possible flooding events. Therefore, upland management policies need to take into account that the heterogeneity of hillslopes at local scales has implications for storm runoff at the catchment scale. Copyright © 2014 John Wiley & Sons, Ltd.
Glycine–Nitrate Process for the Elaboration of Eu3+‐Doped Gd2O3 Bimodal Nanoparticles for Biomedical Applications
Authors: Goglio Graziella , Kaur Gaganpreet , Pinho Sonia L. C. , Penin Nicolas , Blandino Alexia , Geraldes Carlos F. G. C. , Garcia Alain , Delville Marie‐Helene
Published: November 2014

Monoclinic and cubic europium‐doped Gd2O3 structures were selectively synthesized by the glycine–nitrate process by fine control of the synthesis temperature through the crucial fuel/oxidant ratio. The cubic phase is obtained under fuel‐rich conditions, whereas stoichiometric conditions induce the simultaneous formation of cubic and monoclinic polymorphs. The samples were subjected to appropriate sintering to obtain highly crystalline and carbon‐free materials. The average nanoparticle (NP) size determined by TEM for these nanopowders (23 nm) agrees with the average crystallite sizes obtained from XRD Rietveld analysis; therefore, the particles are monocrystalline. Both electron energy loss spectroscopy (EELS) and photoluminescence studies showed that the europium‐doped NPs are highly luminescent, and the Eu3+ ions are homogeneously distributed over the whole material as well as over the two gadolinium crystallographic sites of the cubic phase. These fluorescent NPs exhibit relaxivities that define them as potential T1 contrast agents for further biomedical applications.
Docosahexaenoic acid purification from fish processing industry by‐products
Authors: Rincón Cervera Miguel Ángel , Venegas Elena , Ramos Bueno Rebeca Pilar , Suárez Medina Maria Dolores , Guil Guerrero José Luis
Published: November 2014

Docosahexaenoic acid (DHA) is a well‐known dietary n‐3 polyunsaturated fatty acid (PUFA) found in marine fish and organisms whose beneficial effects for human health are widely reported. However, the supply of food containing DHA is currently becoming critical due to the overexploitation of fisheries worldwide. Consequently, searching for alternative sources of DHA is a relevant issue nowadays. Viscera from cultured fishes is considered a by‐product by the fishery industry and therefore discarded after fish processing. In this work, viscera from farmed marine fish (Sparus aurata and Dicentrarchus labrax) and also oil extracted from such by‐products have been studied to assess their suitability as DHA sources by obtaining their fatty acid profiles. Viscera oil was used as a source for DHA purification by a simple and easily scalable chromatographic method. As a result, a highly purified DHA fraction (>99.0% DHA on total fatty acids) was obtained.

Practical applications: This DHA concentrate obtained from viscera oil could be potentially used for alimentary or pharmaceutical purposes due to its lower cholesterol content compared with other known marine sources and also because only safe and legally allowed food‐grade solvents have been used throughout the whole process. This way, by obtaining a high added‐value product, a revaluation is given to fish by‐products which are usually discarded.

Fatty acid profile of whole viscera oil (11.1% DHA of total FA) (left) and chromatogram of the DHA fraction after chromatographic purification (>99.0% DHA of total FA) (right) by using food‐grade solvents as the mobile phase.
Molecular crowding‐based imprinted monolithic column for capillary electrochromatography
Authors: Zong Hai‐Yan , Liu Xiao , Liu Zhao‐Sheng , Huang Yan‐Ping
Published: November 2014

Molecular crowding is a new approach to stabilizing binding sites and improving molecular recognition. In this work, the concept was applied to the preparation of imprinted monolithic columns for CEC. The imprinted monolithic column was synthesized using a mixture of d‐zopiclone (d‐ZOP)(template), methacrylic acid, ethylene glycol dimethacrylate, and poly(methyl methacrylate) (PMMA) (molecular crowding agent). The resulting PMMA‐based imprinted capillary was able to separate ZOP enantiomers in CEC mode. The resolution of enantiomer separation achieved on the d‐ZOP‐imprinted monolithic column was up to 2.09. Some polymerization factors, such as template‐monomer molar ratio, functional monomer‐cross‐linker molar ratio and the composition of the porogen, on the imprinting effect of resulting molecularly imprinted polymer (MIP) monolithic column were systematically investigated. Chromatographic parameters, including pH values, the content of acetonitrile and the salt concentration on chiral separation were also studied. The results indicated the addition of PMMA resulted in MIPs with superior retention properties and excellent selectivity for d‐ZOP, as compared to the MIPs prepared without addition of the crowding‐inducing agent. The results revealed that molecular crowding is an effective method for the preparation of a highly efficient MIP stationary phase for chiral separation in CEC.
Iterative process acceleration of calculation of unsteady, viscous, compressible, and heat‐conductive gas flows
Authors: Shterev K. S.
Published: November 2014

In this paper, extrapolation technique is introduced in the Semi‐Implicit Method for Pressure‐Linked Equations ‐ Time Step (SIMPLE‐TS) finite volume iterative algorithm for calculation of compressible Navier–Stokes–Fourier equations subject of slip and jump boundary conditions. The initial state, required by the iterative solver in simulation of unsteady flow problems, is approximated in time by Lagrange polynomial extrapolation in each node. The approach is applicable to a parallel code in a straightforward way due to algorithmic independence of the neighboring nodes in the computational grid. A criterion is proposed to determine the order of extrapolation polynomial and stop the extrapolation execution, when the local steady state is reached. The approach is tested on different microflow problems: Couette flow, flow past a square in a microchannel at subsonic and supersonic speeds, and convective Rayleigh–Bénard flow of a rarefied gas. The acceleration varies from 1.14‐fold to 2.8‐fold. Copyright © 2014 John Wiley & Sons, Ltd.
Synthesis of Furo[2,3‐d]pyridazin‐4(5H)‐one and Its N(5)‐Substituted Derivatives
Authors: Karahan Emrah , Koza Gani , Balci Metin
Published: November 2014

We report the efficient preparation of furo[2,3‐d]pyridazin‐4(5H)‐one and its N‐substituted derivatives starting from methyl 2‐methylfuran‐3‐carboxylate. The Me group was converted to the aldehyde group, which was then condensed with hydrazine derivatives. Then, the ester functionalities were hydrolyzed to the corresponding acids, followed by treatment with SOCl2 to give N‐substituted furopyridazinone derivatives.
Synthesis of ortho‐Phenylenebis(guanidine) Derivatives with Potential Chirality
Authors: Fukuzumi Masahiro , Nakanishi Waka , Ishikawa Tsutomu , Kumamoto Takuya
Published: November 2014

We report the synthesis and potential chirality of ortho‐phenylenebisguanidines (BGs) with substituents at C(3) and C(6). Guanidinylation of 3,6‐disubstituted benzene‐1,2‐diamines with 2‐chloro‐4,5‐dihydro‐1,3‐dimethyl‐1H‐imidazolium chloride gave the corresponding BGs. X‐Ray crystallography showed that the two guanidine moieties occupy different faces of the benzene ring, creating potential chirality, although optical resolution of tBu‐substituted BG by chiral HPLC failed. However, a methylated acyclic bisguanidinium salt (BGms) was obtained as a chiral crystal with a space group of P212121.
Solar elastosis and cutaneous melanoma: A site‐specific analysis
Authors: Kvaskoff Marina , Pandeya Nirmala , Green Adèle C. , Perry Susan , Baxter Catherine , Davis Marcia B. , Mortimore Rohan , Westacott Lorraine , Wood Dominic , Triscott Joe , Williamson Richard , Whiteman David C.
Published: November 2014

Cutaneous melanomas are postulated to arise through at least two causal pathways, namely the “chronic sun exposure” and “nevus” pathways. While chronic sun exposure probably causes many head/neck melanomas, its role at other sites is unclear. In a population‐based, case‐case comparison study conducted in Brisbane, Australia, we determined the prevalence and epidemiologic correlates of chronic solar damage in skin adjacent to invasive, incident melanomas on the trunk (n = 418) or head/neck (n = 92) among patients aged 18–79 in 2007–2010. Participants self‐reported information about environmental and phenotypic factors, and a dermatologist counted nevi and actinic keratoses. Dermatopathologists assessed solar elastosis adjacent to each melanoma using a four‐point scale (nil, mild, moderate, marked), and noted the presence or absence of adjacent neval remnants. We measured associations between various factors and solar elastosis using polytomous logistic regression. Marked or moderate solar elastosis was observed in 10% and 27%, respectively, of trunk melanomas, and 60% and 17%, respectively, of head/neck melanomas. At both sites, marked elastosis was positively associated with age (ptrend < 0.0001) and inversely associated with neval remnants (ptrend < 0.001). For trunk melanomas, marked elastosis was associated with highest quartiles of total sun exposure [odds‐ratio (OR) = 5.47, 95% confidence interval (CI) = 1.08–27.60] and facial freckling (OR = 2.98, 95% CI = 1.17–7.56), and inversely associated with deeply tanning skin (OR = 0.29, 95% CI = 0.08–1.11) and high nevus counts (OR = 0.08, 95% CI = 0.01–0.66). Mostly similar associations were observed with moderate solar elastosis. About one in three trunk melanomas in Queensland have evidence of moderate‐to‐marked sun damage, and they differ in risk associations from those without.
MUC5AC hypomethylation is a predictor of microsatellite instability independently of clinical factors associated with colorectal cancer
Authors: Renaud Florence , Vincent Audrey , Mariette Christophe , Crépin Michel , Stechly Laurence , Truant Stéphanie , Copin Marie‐Christine , Porchet Nicole , Leteurtre Emmanuelle , Van Seuningen Isabelle , Buisine Marie‐Pierre
Published: November 2014

Colorectal cancers (CRC) with microsatellite instability (MSI) display unique clinicopathologic features including a mucinous pattern with frequent expression of the secreted mucins MUC2 and MUC5AC. The mechanisms responsible for this altered pattern of expression remain largely unknown. We quantified DNA methylation of mucin genes (MUC2, MUC5AC, MUC4) in colonic cancers and examined the association with clinicopathological characteristics and molecular (MSI, KRAS, BRAF, and TP53 mutations) features. A control cohort was used for validation. We detected frequent hypomethylation of MUC2 and MUC5AC in CRC. MUC2 and MUC5AC hypomethylation was associated with MUC2 and MUC5AC protein expression (p = 0.004 and p < 0.001, respectively), poor differentiation (p = 0.001 and p = 0.007, respectively) and MSI status (p < 0.01 and p < 0.001, respectively). Interestingly, MUC5AC hypomethylation was specific to MSI cancers. Moreover, it was significantly associated with BRAF mutation and CpG island methylator phenotype (p < 0.001 and p < 0.001, respectively). All these results were confirmed in the control cohort. In the multivariate analysis, MUC5AC hypomethylation was a highly predictive biomarker for MSI cancers. MUC5AC demethylation appears to be a hallmark of MSI in CRC. Determination of MUC5AC methylation status may be useful for understanding and predicting the natural history of CRC.
A complete automated algorithm for segmentation of tissues and identification of tumor region in T1, T2, and FLAIR brain images using optimization and clustering techniques
Authors: Govindaraj Vishnuvarthanan , Murugan Pallikonda Rajasekaran
Published: November 2014

Tissues in brain are the most complicated parts of our body, a clear examination and study are therefore required by a radiologist to identify the pathologies. Normal magnetic resonance (MR) scanner is capable of producing brain images with bounded tissues, where unique and segregated views of the tissues are required. A distinguished view upon the images is manually impossible and can be subjected to operator errors. With the assistance of a soft computing technique, an automated unique segmentation upon the brain tissues along with the identification of the tumor region can be effectively done. These functionalities assist the radiologist extensively. Several soft computing techniques have been proposed and one such technique which is being proposed is PSO‐based FCM algorithm. The results of the proposed algorithm is compared with fuzzy C‐means (FCM) and particle swarm optimization (PSO) algorithms using comparison factors such as mean square error (MSE), peak signal to noise ratio (PSNR), entropy (energy function), Jaccard (Tanimoto Coefficient) index, dice overlap index and memory requirement for processing the algorithm. The efficiency of the PSO‐FCM algorithm is verified using the comparison factors.
POSTERIOR‐PREDICTIVE EVIDENCE ON US INFLATION USING EXTENDED NEW KEYNESIAN PHILLIPS CURVE MODELS WITH NON‐FILTERED DATA
Authors: Baştürk Nalan , Çakmakli Cem , Ceyhan S. Pinar , Van Dijk Herman K.
Published: November 2014

Changing time series properties of US inflation and economic activity, measured as marginal costs, are modeled within a set of extended New Keynesian Phillips curve (NKPC) models. It is shown that mechanical removal or modeling of simple low‐frequency movements in the data may yield poor predictive results which depend on the model specification used. Basic NKPC models are extended to include structural time series models that describe typical time‐varying patterns in levels and volatilities. Forward‐ and backward‐looking expectation components for inflation are incorporated and their relative importance is evaluated. Survey data on expected inflation are introduced to strengthen the information in the likelihood. Use is made of simulation‐based Bayesian techniques for the empirical analysis. No credible evidence is found on endogeneity and long‐run stability between inflation and marginal costs. Backward‐looking inflation appears stronger than forward‐looking inflation. Levels and volatilities of inflation are estimated more precisely using rich NKPC models. The extended NKPC structures compare favorably with existing basic Bayesian vector autoregressive and stochastic volatility models in terms of fit and prediction. Tails of the complete predictive distributions indicate an increase in the probability of deflation in recent years. Copyright © 2014 John Wiley & Sons, Ltd.
Development and steroidogenic properties of the Bidder's organ of the tadpole of Rhinella arenarum (Amphibia, Anura)
Authors: Sassone Alina Grisel , Regueira Eleonora , Scaia Maria Florencia , Volonteri Maria Clara , Ceballos Nora Raquel
Published: November 2014

Several studies suggested that in anuran amphibians steroidogenic enzymes are critical for gonadal differentiation, proposing that the amount of sex steroids would adjust this differentiation. Among anurans, bufonids are important for the study of sex differentiation due to the presence of Bidder's organ (BO) that differentiates as a rudimentary ovary in the cephalic portion of the genital ridge. Considering that in adult males of Rhinella arenarum, the BO synthesizes estradiol, the main purpose of this work is to examine, in this species, the morphogenesis of BO and the steroidogenic capacity of this organ during larval development. BO and the proper gonads are distinguished from Gosner stage 26. During metamorphosis, BO primary oogonia develop in oogonia in nests, early previtellogenic oocytes and late previtellogenic oocytes in follicles while proper gonads remain undifferentiated. Aromatase was detected by immunohistochemistry in almost all the largest follicles of the BOs while the cytochrome P450 side‐chain cleavage was observed in only few oocytes. The proper gonad was not immunoreactive in any stage. The determination of aromatase and 5α‐reductase activities showed that the population of tadpoles between stages 36–41 is not homogeneous in terms of aromatase activity. In addition, from stage 26 to the end of metamorphosis, all the stages were able to produce estradiol from endogenous substrate but stages 40–41, corresponding to the end of pro‐metamorphosis, produced the highest values. In conclusion, BO is able to synthesize estradiol from endogenous precursors and proper gonad remains undifferentiated at least until the end of the metamorphosis. J. Exp. Zool. 323A: 137–145, 2015. © 2014 Wiley Periodicals, Inc.