bluuebunny/crossref_metadata_2025 huggingface dataset:
Detection and characterization of urinary metabolites of boldione by LC‐MS/MS. Part I: Phase I metabolites excreted free, as glucuronide and sulfate conjugates, and released after alkaline treatment of the urine
Authors: Gómez C. , Pozo O. J. , Fabregat A. , Marcos J. , Deventer K. , Van Eenoo P. , Segura J. , Ventura R.
Published: October 2012

Boldione (1,4‐androstadien‐3,17‐dione) is included in the list of prohibited substances, issued by the World Anti‐Doping Agency (WADA). Endogenous production of low concentrations of boldione has also been reported. The objective of this study was to assess boldione metabolism in humans. Detection of boldione metabolites was accomplished by analysis by liquid chromatography coupled to tandem mass spectrometry of urine samples obtained after administration of the drug and subjected to different sample preparation procedures to analyze the different metabolic fractions (free, glucuronides, sulpfates and released in basic media). In addition to boldione, eight metabolites were detected in the free fraction. Four of them were identified by comparison with standards: 6β‐hydroxy‐boldenone (M3), androsta‐1,4,6‐triene‐3,17‐dione (M5), (5α)‐1‐androstenedione (M6) and (5α)‐1‐testosterone (M8). Metabolite M7 was identified as the 5β‐isomer of 1‐androstenedione, and metabolites M1, M2 and M4 were hydroxylated metabolites and tentative structures were proposed based on mass spectrometric data. After β‐glucuronidase hydrolysis, five additional metabolites excreted only as conjugates with glucuronic acid were detected: boldenone, (5β)‐1‐testosterone (M9), and three metabolites resulting from reduction of the 3‐keto group. Boldenone, epiboldenone, and hydroxylated metabolites of boldione, boldenone and 1‐testosterone were detected as conjugates with sulfate. In addition, boldione and seven metabolites (boldenone, M2, M3, M4, M5, M7 and M9) increased their concentration in urine after treatment of the urine in alkaline conditions. In summary, 15 boldione metabolites were detected in all fractions. The longer detection time was observed for metabolite M4 after alkaline treatment of the urine, which was detected up to 5 days after boldione administration. Copyright © 2012 John Wiley & Sons, Ltd.
Microevolution of symbiotic Bradyrhizobium populations associated with soybeans in east North America
Authors: Tang Jie , Bromfield E. S. P. , Rodrigue N. , Cloutier S. , Tambong J. T.
Published: October 2012

Microevolution and origins of Bradyrhizobium populations associated with soybeans at two field sites (A and B, 280 km apart in Canada) with contrasting histories of inoculation was investigated using probabilistic analyses of six core (housekeeping) gene sequences. These analyses supported division of 220 isolates in five lineages corresponding either to B. japonicum groups 1 and 1a or to one of three novel lineages within the genus Bradyrhizobium. None of the isolates from site A and about 20% from site B (the only site with a recent inoculation history) were attributed to inoculation sources. The data suggest that most isolates were of indigenous origin based on sequence analysis of 148 isolates of soybean‐nodulating bacteria from native legumes (Amphicarpaea bracteata and Desmodium canadense). Isolates from D. canadense clustered with B. japonicum group 1, whereas those from A. bracteata were placed in two novel lineages encountered at soybean field sites. One of these novel lineages predominated at soybean sites and exhibited a significant clonal expansion likely reflecting selection by the plant host. Homologous recombination events detected in the 35 sequence types from soybean sites had an effect on genetic diversification that was approximately equal to mutation. Interlineage transfer of core genes was infrequent and mostly attributable to gyrB that had a history of frequent recombination. Symbiotic gene sequences (nodC and nifH) of isolates from soybean sites and native legumes clustered in two lineages corresponding to B. japonicum and B. elkani with the inheritance of these genes appearing predominantly by vertical transmission. The data suggest that soybean‐nodulating bacteria associated with native legumes represent a novel source of ecologically adapted bacteria for soybean inoculation.
A three‐dimensional multifunctional compound‐eye endoscopic system with extended depth of field
Authors: Kagawa Keiichiro , Yamada Kenji , Tanaka Eiji , Tanida Jun
Published: October 2012

A focusing‐free and multispectral three‐dimensional endoscope based on a compact compound‐eye camera is proposed. A prototype TOMBO endoscope with 3 ×2 aspherical lenses using a wavefront coding technique and a 640 ×480‐pixel color imager demonstrates extended depth of field and registration of multispectral images based on an estimated depth map. © 2012 Wiley Periodicals, Inc. Electron Comm Jpn, 95(11): 14–27, 2012; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ecj.11431
Analysis of possible introduction of PV systems considering output power fluctuations and battery technology, employing an optimal power generation mix model
Authors: Komiyama Ryoichi , Shibata Saeko , Nakamura Yosuke , Fujii Yasumasa
Published: October 2012

This paper presents an evaluation of the impact of extensive introduction of photovoltaic (PV) systems and stationary battery technology into the optimal power generation mix in the Kanto and Kinki regions. The introduction of solar PV systems is expected to be extensively deployed in the Japanese household sector and utility companies in order to address the concerns of energy security and climate change. Considering this expected large‐scale deployment of PV systems in electric power systems, it is necessary to investigate the optimal power generation mix which is technologically capable of controlling and accommodating the intermittent output‐power fluctuations inherent in PV systems. Against this background, we develop both a solar photovoltaic power generation model and an optimal power generation mix model, including stationary battery technology, which can be used to explicitly analyze the impact of PV output fluctuations at a detailed time interval resolution such as 10 minutes for 365 consecutive days. Simulation results reveal that PV introduction does not necessarily increase battery technology due to the cost competitiveness of thermal power plants in the load‐following requirement caused by PV systems. Additionally, on the basis of sensitivity analysis on PV system cost, dramatic cost reduction proves to be indispensable for PV to supply bulk electricity similarly to thermal and nuclear power plants. © 2012 Wiley Periodicals, Inc. Electr Eng Jpn, 182(2): 9–19, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.22329
3‐(2‐Pyridyl)‐5‐(2‐thienyl)pyrazole and Complexes of Its Anion with Lithium, Magnesium, Calcium, and Zinc Ions
Authors: Kloubert Tobias , Müller Christoph , Krieck Sven , Schlotthauer Tina , Görls Helmar , Westerhausen Matthias
Published: October 2012

5‐(2‐Furanyl)‐3‐(2‐pyridyl)pyrazole (1) and 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazole (2) oligomerize through hydrogen bridges in the solid state to yield tetramers and dimers, respectively. The pyrazole units are very acidic and, therefore, deprotonation of 2 with the organometallic reagents LiN(SiMe3)2, PhLi, ZnMe2, and ZnEt2 allows the synthesis of (tetrahydrofuran)lithium 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate (3a), bis[methylzinc 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate] (4a), and bis[ethylzinc 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate] (4b). Recrystallization of 3a in the presence of 1,4‐dioxane yields catena‐[(1,4‐dioxane)lithium 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate] (3b). Magnesiation of 2 yields different products depending on the organometallic magnesium reagent applied. The use of butylmagnesium chloride gives tris(tetrahydrofuran)magnesium chloride 3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate (5). Employment of the diphenylmagnesium–1,4‐dioxane complex leads to the formation of bis(tetrahydrofuran)magnesium bis[3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate] (6), whereas the more aggressive diethylmagnesium–1,4‐dioxane complex also metalated the thienyl substituent to yield bis[bis(tetrahydrofuran)magnesium 3‐(2‐pyridyl)‐5‐(2‐thienyl‐5‐ide)pyrazolate] (7). A trinuclear calcium complex, tris(tetrahydrofuran)tricalcium μ3‐hydroxide iodide tetrakis[3‐(2‐pyridyl)‐5‐(2‐thienyl)pyrazolate] (8), is isolated after calciation of 2 and inadvertent hydrolysis during recrystallization.
Complexation of Paraquat and Diazapyrenium Derivatives with Dipyrido[30]crown‐10
Authors: Li Shijun , Weng Guan‐Huan , Zheng Bo , Yan Xuzhou , Wu Jing , Lin Wei , Chen Huan‐Xin , Zhang Xi‐Chang
Published: October 2012

A new pyridine‐containing crown ether, dipyrido[30]crown‐10 (DP30C10), has been synthesized and has been shown to form [2]pseudorotaxanes spontaneously with paraquat derivatives in solution, as demonstrated by proton NMR spectroscopy and mass spectrometry, and in the solid state, as proved by single‐crystal X‐ray analysis. The complexation between DP30C10 and N,N′‐dimethyl‐2,7‐diazapyrenium bis(hexafluorophosphate) was also investigated, and was found to have an association constant of 8.2 × 103 M–1 in acetonitrile. Based on this recognition motif, a dual‐action acid/base and base/acid‐controllable molecular switch was demonstrated.
Design and Synthesis of Janus‐Type Chiral Dendritic Diphosphanes and Their Applications in Asymmetric Hydrogenation
Authors: Liu Ji , Feng Yu , Ma Baode , He Yan‐Mei , Fan Qing‐Hua
Published: October 2012

A series of chiral diphosphane‐functionalized Janus dendrimers (up to 16 BINAP units) have been readily synthesized by using liquid‐phase organic synthesis with the third‐generation Fréchet‐type poly(aryl ether) dendron as the soluble support. The resulting dendritic ligands were purified by simple solvent precipitation without the need for chromatographic separation at the end of reaction. Complete functionalization of the dendrimers with BINAP moieties was confirmed by 1H NMR, MALDI‐TOF mass spectroscopy, and elemental analyses. Their ruthenium complexes were applied to the asymmetric hydrogenation of 2‐arylacrylic acids. It was found that only slightly lower enantioselectivities were achieved than the corresponding small‐molecular Ru catalyst. Interestingly, a clear increase in activity of the dendritic catalysts was observed on going to the higher generations. In addition, the third‐generation catalyst could be recycled without significant loss of catalytic activity or enantioselectivity before the fifth catalytic run.
Dynamic changes in myelin aberrations and oligodendrocyte generation in chronic amyloidosis in mice and men
Authors: Behrendt Gwendolyn , Baer Kristin , Buffo Annalisa , Curtis Maurice A. , Faull Richard L. , Rees Mark I. , Götz Magdalena , Dimou Leda
Published: October 2012

Myelin loss is frequently observed in human Alzheimer's disease (AD) and may constitute to AD‐related cognitive decline. A potential source to repair myelin defects are the oligodendrocyte progenitor cells (OPCs) present in an adult brain. However, until now, little is known about the reaction of these cells toward amyloid plaque deposition neither in human AD patients nor in the appropriate mouse models. Therefore, we analyzed cells of the oligodendrocyte lineage in a mouse model with chronic plaque deposition (APPPS1 mice) and samples from human patients. In APPPS1 mice defects in myelin integrity and myelin amount were prevalent at 6 months of age but normalized to control levels in 9‐month‐old mice. Concomitantly, we observed an increase in the proliferation and differentiation of OPCs in the APPPS1 mice at this specific time window (6–8 months) implying that improvements in myelin aberrations may result from repair mechanisms mediated by OPCs. However, while we observed a higher number of cells of the oligodendrocyte lineage (Olig2+ cells) in APPPS1 mice, OLIG2+ cells were decreased in number in postmortem human AD cortex. Our data demonstrate that oligodendrocyte progenitors specifically react to amyloid plaque deposition in an AD‐related mouse model as well as in human AD pathology, although with distinct outcomes. Strikingly, possible repair mechanisms from newly generated oligodendrocytes are evident in APPPS1 mice, whereas a similar reaction of oligodendrocyte progenitors seems to be strongly limited in final stages of human AD pathology. © 2012 Wiley Periodicals, Inc.
Synthesis and Properties of the Alkyl/Aryl Germanium Dioximates Containing Ge─O Bond: Stability Factors—A Theoretical Approach
Authors: Thomas Raji , Joseph P. Nelson , Pardasani Pushpa , Mukherjee T.
Published: October 2012

The reactions of R2GeCl2 and R3GeCl with 9,10‐phenanthrenequinone dioxime in 1:1 and 1:2 molar ratios to form a series of organogermanium complexes of the general formula R2GeL and (R3Ge)2L [R=Me, Et, Ph] have been investigated. The physical and spectral properties of all derivatives are described. In addition, the nature of Ge─O bond has been studied by using the DFT/B3LYP method.
One‐Pot Halogen‐Free Synthesis of 2,3‐Dihydro‐1H‐inden‐2‐yl‐phosphinic Acid from 1H‐indene and Elemental Phosphorus via the Trofimov–Gusarova Reaction
Authors: Artem'ev Alexander V. , Malysheva Svetlana F. , Korocheva Anastasiya O. , Bagryanskaya Irina Yu.
Published: October 2012

1H‐Indene reacts with red phosphorus in the superbasic KOH/DMSO(H2O) suspension at 120°C for 2.5 h to give (after acidification) 2,3‐dihydro‐1H‐inden‐2‐yl‐phosphinic acid in 55% isolated yield.
MULTIDIMENSIONAL DISTANCE‐TO‐COLLAPSE POINT AND SOVEREIGN DEFAULT PREDICTION
Authors: Savona Roberto , Vezzoli Marika
Published: October 2012

By focusing on sovereign defaults, this paper introduces a multidimensional distance‐to‐collapse point based on a two‐step procedure. The first step is nonparametric and provides an early warning system that signals a potential crisis whenever preselected leading indicators exceed specific thresholds. The second is parametric and incorporates the first‐step country default predictors within a probit specification. Such a two‐step procedure generalizes the distance‐to‐default à la Merton within a multidimensional setting, wherein we care about the distance of each indicator from its threshold. Empirical evidence about debt crises of emerging markets over the period 1975–2002 proves that our methodology predicts 80% of the total defaults and non‐defaults in and out of sample. Copyright © 2012 John Wiley & Sons, Ltd.
GA/GB fold switching may modulate fatty acid transfer from human serum albumin to bacteria
Authors: Polticelli Fabio , Caprari Silvia , Gianni Stefano , Ascenzi Paolo
Published: October 2012

Human serum albumin (HSA) accounts for most of the functions of plasma. Among others, HSA serves as a carrier and a solubilizer for many endogenous and exogenous ligands, including fatty acids (FAs) as well as peptides and proteins such as the GA module of the bacterial poly(A)‐binding (PAB) protein. Although the biological function(s) of the GA module of the bacterial PAB protein is unknown, the acquisition of the GA module adds selective advantages to the bacterium in terms of growth rate and increase in virulence, probably by providing the bacteria with FAs and, possibly, other nutrients transported by HSA. Here, we hypothesize that the GA module may undergo a structural transition from the all‐α form to the 4β+α form typical of the GB domains upon binding of a FA molecule, as part of the mechanism which allows the bacterial PAB protein to extract FAs from HSA. © 2012 IUBMB. IUBMB Life, 64(11): 885–888, 2012
Adipose tissue engineering with human adipose tissue‐derived adult stem cells and a novel porous scaffold
Authors: Wang Wei , Cao Bin , Cui Lei , Cai Jinglong , Yin Jingbo
Published: October 2012

We investigated the effect of a novel porous scaffold composed with water‐soluble poly(L‐glutamic acid) (PLGA) and chitosan (CS) on the attachment, proliferation, and adipogenic differentiation of human adipose tissue‐derived adult stem cells (ADSCs) in vitro and in vivo. Scanning electron microscope and fluorescent Dil labeling were used to reveal the attachment and growth of ADSCs on scaffolds; cell proliferation was detected by DNA assay. The adipogenic differentiation potential of ADSCs on the scaffolds was assayed by Oil‐red O staining and further confirmed by reverse transcriptase polymerase chain reaction (RT‐PCR) for adipogenic gene markers (peroxisome proliferator‐activated receptor γ2, lipoprotein lipase, fatty acid‐binding protein, adiponectin). Cell‐seeded constructs exposed to adipogenic medium for 2 weeks in vitro were implanted in severe combined immunodeficient (SCID) mice for 6 weeks. It was shown that ADSCs attached and spread well on scaffolds with good proliferation behaviors and abundance of extracellular matrix deposition. Oil‐red O staining and RT‐PCR showed adipogenic differentiation potential of ADSCs on scaffolds. Newly formed adipose‐like tissue was confirmed in vivo in SCID mice by Oil‐red O staining. PLGA/CS porous scaffolds exhibit good compatibility to ADSCs and can be promising biomaterials for adipose tissue engineering. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 68–75, 2013.
A new radiopaque embolizing agent for the treatment of endoleaks after endovascular repair: Influence of contrast agent on chitosan thermogel properties
Authors: Coutu Jean‐Michel , Fatimi Ahmed , Berrahmoune Saoussen , Soulez Gilles , Lerouge Sophie
Published: October 2012

A new injectable radiopaque embolizing agent has been developed, based on chitosan thermogelling properties. Different commercial contrast agents (Isovue®, Visipaque®, and Conray®) were associated with chitosan‐β‐glycerophosphate. Their impact on gelation kinetic, mechanical properties, radiopacity, and cytotoxicity was tested to evaluate the best candidate and its feasibility for the treatment of endoleaks after endovascular aneurysm repair (EVAR). Addition of contrast agents did not prevent gelation at body temperature, but it significantly increased the viscosity of the solution before gelation, delayed gelation, and reduced the gelation rate. However, using chitosan with a high degree of deacetylation and 20 vol % contrast agent made it possible to obtain a gel with rapid gelation that was visible during X‐ray based guided intervention. Hydrogels exhibit relatively low mechanical properties, which are only slightly modified by the addition of contrast agents. In vitro studies have demonstrated rapid release of contrast agents from hydrogels when immersed in a saline solution (>50% within 4 h). This is suitable for embolization, as radiopacity is required only to follow the embolization procedure, while long‐term radiopacity would hamper further imaging and endoleak detection. Cytotoxicity and osmolality testing of extracts demonstrated some toxicity of products released by the gel during the first few hours, which is mainly related to their hypertonicity. After the first 24 h incubation, hydrogels released no more cytotoxic compounds, suggesting that the hydrogel rapidly becomes biocompatible. Altogether, this study suggests that the new radiopaque thermogels present interesting characteristics as embolizing agents for EVAR, although their mechanical properties require improvement. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 153–161, 2013.
Growth of calcium phosphates on magnesium substrates for corrosion control in biomedical applications via immersion techniques
Authors: Shadanbaz Shaylin , Walker Jemimah , Staiger Mark P. , Dias George J. , Pietak Alexis
Published: October 2012

Magnesium (Mg) has been suggested as a revolutionary biodegradable replacement for current permanent metals used in orthopedic applications. Current investigations concentrate on the control of the corrosion rate to match bone healing. Calcium phosphate coatings have been a recent focus of these investigations through various coating protocols. Within this investigation, an in situ crystallization technique was utilized as an inexpensive and relatively simple method to produce a brushite and monetite coating on pure Mg. Coatings were characterized using energy dispersive spectroscopy, glancing angle X‐ray diffraction and field emission scanning electron microscopy. Corrosion protection properties of the coatings were assessed in physiological buffers, Earles balanced salt solution, minimum essential media, and minimum essential media containing serum albumin, over a 4‐week period. Using this novel coating protocol, our findings indicate brushite and monetite coated Mg to have significant corrosive protective effects when compared with its uncoated counterpart whilst maintaining high coating substrate adhesion, homogeneity, and reproducibility. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 162–172, 2013.
Structure and strength of the distal radius in female patients with rheumatoid arthritis: A case-control study
Authors: Zhu Tracy Y , Griffith James F , Qin Ling , Hung Vivian WY , Fong Tsz-Ning , Au Sze-Ki , Tang Xiao Lin , Kwok Anthony W , Leung Ping-Chung , Li Edmund K , Tam Lai-Shan
Published: October 2012

The purpose of this work was to investigate the volumetric bone mineral density (vBMD), bone microstructure, and mechanical indices of the distal radius in female patients with rheumatoid arthritis (RA). We report a cross-sectional study of 66 middle-aged female RA patients and 66 age-matched healthy females. Areal BMD (aBMD) of the hip, lumbar spine, and distal radius was measured by dual-energy X-ray absorptiometry (DXA). High-resolution peripheral quantitative computed tomography (HR-pQCT) was performed at the distal radius, yielding vBMD, bone microstructure, and mechanical indices. Cortical and trabecular vBMD were 3.5% and 10.7% lower, respectively, in RA patients than controls, despite comparable aBMD. Trabecular microstructural indices were –5.7% to –23.1% inferior, respectively, in RA patients compared to controls, with significant differences in trabecular bone volume fraction, separation, inhomogeneity, and structural model index. Cortical porosity volume and percentage were 128% and 93% higher, respectively, in RA patients, with stress being distributed more unevenly. Fourteen RA patients had exaggerated periosteal bone apposition primarily affecting the ulnovolar aspect of the distal radius. These particular patients were more likely to have chronic and severe disease and coexisting wrist deformity. The majority of the differences in density and microstructure between RA patients and controls did not depend on menstrual status. Recent exposure to glucocorticoids did not significantly affect bone density and microstructure. HR-pQCT provides new insight into inflammation-associated bone fragility in RA. It detects differences in vBMD, bone microstructure, and mechanical indices that are not captured by DXA. At the distal radius, deterioration in density and microstructure in RA patients involved both cortical and trabecular compartments. Excessive bone resorption appears to affect cortical more than trabecular bone at distal radius, particularly manifested as increased cortical porosity. Ulnovolar periosteal apposition of the distal radius is a feature of chronic, severe RA with wrist deformity. © 2013 American Society for Bone and Mineral Research.
A Total Solution to Baseline Separation of 20 Brominated Flame Retardant Additives in Electronic Products with Automated Soxhlet Hot Extraction and Gas Chromatography‐Mass Spectrometry
Authors: Zhang Shuai , Zhao Tian‐Bo , Luo Guan , Huang Hui , Wang Jia , Cai Zhong‐Zhan
Published: October 2012

An efficient and reliable separation technique based on automated Soxhlet hot extraction (AHSE) was developed and validated. It can be applied to rapid separations of 20 persistent organic pollutants, including two types of brominated flame retardants (BFRs), polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) contained in nonmetallic component parts of electronic products. The qualitative chromatographic analyses were carried out by using a gas chromatography coupled with a mass spectrometry detector (GC‐MS). The 20 persistent organic pollutants were simultaneously and completely separated by a 15 meter HP‐5MS short capillary column in 25 minutes. Through the tests of extraction performance, effects of solvent and extraction time on selected BFRs were investigated; toluene and 120 min extraction time were chose as the optimum conditions. Besides, this article examines the influence of temperature on the chromatographic analysis, the optimum temperature parameters were 280 °C and 320 °C for injector and column, respectively. The ASHE‐GCMS method was validated for the analysis of the certified reference material of CRM8110‐a and IRMM310. The limits of detection (LOD) for polymer sample was 0.55‐4.50 μg mL−1; linearity range from 0.11 to 16 μg mL−1. The proposed methodology can fully meet the requirement of relational directives.
Enhancing Device Performance of Small Molecular Organic Photovoltaic Cells by Controlling the Deposition Rate of Fullerene
Authors: Liu Shun‐Wei , Lee Chih‐Chien , Su Wei‐Cheng , Lin Chi‐Feng , Chou Chia‐Chang
Published: October 2012

To improve the power conversion efficiency (PCE) of small molecular weight organic photovoltaic cells (OPVs) it is proposed to use a simple fabrication method by controlling the deposition rate of the acceptor material fullerene (C60) in planar heterojunction OPV structures of ITO/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/copper phthalocyanine (CuPc)/C60/bathocuproine (BCP)/Ag. In our optimised device, the highest PCE of 1.7% was obtained through a deposition rate of C60 equal to 0.3 nm/s due to the superior charge balance in the CuPc/C60 heterojunction. Such a charge balance condition increased the fill factor from 52.4% to 56.1% by reducing the carrier accumulation in the OPV device. The electron only device was fabricated with the purpose of analysing the electron mobility of C60 as a function of the deposition rate. In addition, the effects of the deposition rates on the performance of planar OPV devices were exhaustively analysed by examining the absorption properties and the surface morphologies.
Synthesis, Crystal Structure, Photophysical and Electrochemical Properties of rac‐6,13‐Dihydro‐6,13‐methanopentacene
Authors: Tsai Hsing‐Yang , Luo Ming‐Hui , Fang Tzu‐Chien , Chang Ming‐Jen , Chen Kew‐Yu
Published: October 2012

The title compound, rac‐6,13‐dihydro‐6,13‐methanopentacene (1), has been synthesized and characterized by elemental analysis, FT‐IR, 1H NMR, UV‐Vis, HRMS spectra, cyclic voltammetry and single‐crystal X‐ray diffraction. The crystal belongs to orthorhombic, space group P212121, with Z = 4 and cell dimensions a = 6.0185(4), b = 8.1914(6), c = 31.4080(19) Å. In the crystal structure, two types of intermolecular C–H···π hydrogen bonds are observed, and further stabilize the crystal structure. Its photophysical and electrochemical properties and complementary density functional theory (DFT) calculations are reported.
The Electrochemical Behavior of p‐tert‐Butyl‐sulfonylcalix[4]arene and Its Selective Complexation with Metal Ions at Water‐Air Interface
Authors: Wang Fei , Jiang Xin‐Zhong , Gao Lin , Zhao Long‐Tao
Published: October 2012

The electrochemical behavior of p‐tert‐butyl‐sulfonylcalix[4]arene (SCA) has been investigated by cyclic voltammetry. The results show that there is an irreversible electrochemical oxidative wave when the potential ranges from 0.9 to 1.9 V versus saturated calomel electrode (SCE) in CH2Cl2 at a glassy carbon electrode. The kinetic parameters of the andic wave, such as α,n, ks, D and the diffusion activation energy (Ed), were discussed. In addition, the interaction of SCA with metal ions at the water‐air interface was also discussed by Langmuir‐Blodgett (LB) techniques. The results confirm that the selectivity of SCA as ligand for Pb2+ in monomolecular film is very high by complexation action, which provide the foundation that LB film of SCA modified glassy carbon electrode (GCE) as voltammetric sensor to detect trace amounts of Pb2+.
4D flow MRI
Authors: Markl Michael , Frydrychowicz Alex , Kozerke Sebastian , Hope Mike , Wieben Oliver
Published: October 2012

Traditionally, magnetic resonance imaging (MRI) of flow using phase contrast (PC) methods is accomplished using methods that resolve single‐directional flow in two spatial dimensions (2D) of an individual slice. More recently, three‐dimensional (3D) spatial encoding combined with three‐directional velocity‐encoded phase contrast MRI (here termed 4D flow MRI) has drawn increased attention. 4D flow MRI offers the ability to measure and to visualize the temporal evolution of complex blood flow patterns within an acquired 3D volume. Various methodological improvements permit the acquisition of 4D flow MRI data encompassing individual vascular structures and entire vascular territories such as the heart, the adjacent aorta, the carotid arteries, abdominal, or peripheral vessels within reasonable scan times. To subsequently analyze the flow data by quantitative means and visualization of complex, three‐directional blood flow patterns, various tools have been proposed. This review intends to introduce currently used 4D flow MRI methods, including Cartesian and radial data acquisition, approaches for accelerated data acquisition, cardiac gating, and respiration control. Based on these developments, an overview is provided over the potential this new imaging technique has in different parts of the body from the head to the peripheral arteries. J. Magn. Reson. Imaging 2012;. © 2012 Wiley Periodicals, Inc.
MRI of cardiac iron overload
Authors: Chu Winnie C.W. , Au Wing Y. , Lam Wynnie W.M.
Published: October 2012

Transfusion therapy has greatly improved the survival of transfusion dependent thalassemia major (TM) patients; however, the resultant iron load damages tissues including the heart, liver and endocrine organs. Among these, heart complication still remains the leading cause of mortality. Myocardial iron deposition can occur independently of other solid organ involvement; conversely, the heart may be spared despite heavy siderosis in other tissues. Iron chelation treatment diminishes the risk of hemosiderosis; however, the chelation treatment has its own toxicities and might not be available to all patients due to costs. Close monitoring of individual organ iron concentration and function is thus important for optimization of individual patient care. This review outlines the importance and clinical significance of recently available MRI techniques for monitoring cardiac iron load. J. Magn. Reson. Imaging 2012;36:1052–1059. © 2012 Wiley Periodicals Inc.
4D flow MRI
Authors: Markl Michael , Frydrychowicz Alex , Kozerke Sebastian , Hope Mike , Wieben Oliver
Published: October 2012

Traditionally, magnetic resonance imaging (MRI) of flow using phase contrast (PC) methods is accomplished using methods that resolve single‐directional flow in two spatial dimensions (2D) of an individual slice. More recently, three‐dimensional (3D) spatial encoding combined with three‐directional velocity‐encoded phase contrast MRI (here termed 4D flow MRI) has drawn increased attention. 4D flow MRI offers the ability to measure and to visualize the temporal evolution of complex blood flow patterns within an acquired 3D volume. Various methodological improvements permit the acquisition of 4D flow MRI data encompassing individual vascular structures and entire vascular territories such as the heart, the adjacent aorta, the carotid arteries, abdominal, or peripheral vessels within reasonable scan times. To subsequently analyze the flow data by quantitative means and visualization of complex, three‐directional blood flow patterns, various tools have been proposed. This review intends to introduce currently used 4D flow MRI methods, including Cartesian and radial data acquisition, approaches for accelerated data acquisition, cardiac gating, and respiration control. Based on these developments, an overview is provided over the potential this new imaging technique has in different parts of the body from the head to the peripheral arteries. J. Magn. Reson. Imaging 2012;36:1015–1036. © 2012 Wiley Periodicals, Inc.
Glucocorticoid‐induced fetal brain growth restriction is associated with p73 gene activation
Authors: Mouihate Abdeslam , Al‐Bader Maie D.
Published: October 2012

Fetal exposure to excessive amounts of glucocorticoids (GCs) hampers proper brain development. The molecular mechanism(s) underlying these GCs effects are not well understood. We explored the impact of fetal exposure to maternal GCs on fetal brain expression of p63 and p73 transactivation (TA) and dominant negative (ΔN) gene variants that promote neural cell death (TA) and cell survival programs (ΔN). The fetoplacental enzyme 11β‐hydroxysteroid dehydrogenase 2, which shields fetuses from maternal glucocorticoids, was inhibited throughout pregnancy by daily injection of carbenoxolone to pregnant dams. The expression of p63 and p73 gene variants and proteins was monitored by real‐time rtPCR and Western blot in the brains of male and female fetuses. Carbenoxolone administration led to an overall enhanced level of corticosterone in the amniotic fluid of both male and female fetuses at late pregnancy. These enhanced corticosterone levels were associated with a significant reduction in fetal brain weights and a significant increase in TAp73 mRNA and p73 protein levels. However, the expression levels of TAp63 mRNA and p63 proteins were either suppressed or unaffected. The pro‐neural survival gene variant ΔNp73 was significantly reduced in female and enhanced in male fetal brains, whereas ΔNp63 was significantly reduced in the brains of both genders. These data suggest that the GCs‐induced negative impact on fetal brain development likely is due, at least in part, to their action of the pro‐neural cell death gene variant TAp73 and to the modulation of the pro‐survival ΔNp63 and ΔNp73 gene variants in a gender‐dependent fashion. © 2012 Wiley Periodicals, Inc.
Training old rats selectively modulates synaptosomal protein synthesis
Authors: Eyman Maria , Cefaliello Carolina , Mandile Paola , Piscopo Stefania , Crispino Marianna , Giuditta Antonio
Published: October 2012

We have previously shown that the local synthesis of two synaptic proteins of 66.5‐kDa and 87.6‐kDa is selectively enhanced in male adult rats trained for a two‐way active avoidance task. We report here that a comparable but not identical response occurs in 2‐year‐old male rats trained for the same task. In the latter age group, the local synthesis of the 66.5‐kDa protein markedly increases in cerebral cortex, brainstem, and cerebellum, with a somewhat lower increment in synthesis of the 87.6‐kDa protein. On the other hand, the newly synthesized 87.6‐kDa protein correlates with avoidances and escapes and inversely correlates with freezings in cerebral cortex and brainstem, whereas the correlations of the newly synthesized 66.5‐kDa protein remain below significance. These correlative patterns are sharply at variance with those present in trained adult rats. Our data confirm that the local system of synaptic protein synthesis is selectively modulated by training and show that the synaptic response of old rats differs from that of adult rats as reflected in behavioral responses. © 2012 Wiley Periodicals, Inc.
Climatology of precipitation over the Iberian Central System mountain range
Authors: Durán L. , Sánchez E. , Yagüe C.
Published: October 2012

An analysis of the observed precipitation for the last 22 years (1989–2010) over Sierra de Guadarrama (centre of Iberian Central System) has been performed. Since this area has received less attention compared with other mountain ranges in Europe and the rest of the world, an exhaustive compilation of literature on precipitation main characteristics on Central Iberia (SW Europe) has been done. The analysis, based on both rain gauges and reanalysis, is focused on the search of the atmospheric mechanisms and moisture sources that lead to precipitation. Also, emphasis has been made in the role played by orography conditioning, the complex spatial patterns observed in the region. This work shows how it behaves as an orographic island that rises over an extensive plateau with a marked Atlantic forcing despite the distance these masses have to travel inlands, with mostly of wet days due to advection of moisture from the ocean and small amount of rain due to local sources of humidity and convective precipitation. It also shows the great enhancement of precipitation caused by the range due to orographic precipitation and the big differences found at the downwind and upwind side of the mountain leading to marked spatial patterns seasonal dependent, complex vertical gradients and high wind direction dependency. Finally, statistically significant mean conditions of variables related with orographic precipitation are given in order to be used as boundary conditions for orographic precipitation modelling exercises. This works gives a climatic framework for future precipitation assessments that could be conducted combining measurements and such models.
Nanostructured thin films as surface‐enhanced Raman scattering substrates
Authors: Mura Stefania , Greppi Gianfranco , Innocenzi Plinio , Piccinini Massimo , Figus Cristiana , Marongiu Maria Laura , Guo Cunlan , Irudayaraj Joseph
Published: October 2012

Nanoporous thin films with silver nanoparticles were synthesized with a bottom–up approach, and its potential as effective surface‐enhanced Raman scattering (SERS) substrates was demonstrated. The use of mesoporous titania films as substrates allowed to control the growth of nanoparticles on the film surface. Atomic force microscopy measurements, Ultraviolet‐visible and X‐ray diffraction analysis confirmed the photoreduction of Ag+ to Ag0 with the formation of nanoparticles with crystallite dimensions of 32 to 36 nm. The new substrates allowed the detection of two analytes (rhodamine B isothiocyanate and cytochrome c), present in solutions at very low concentrations, highlighting their potential in SERS sensing. Reproducibility, homogeneity, enhancement factor of the substrate, consistency of results and detection limits were also assessed. Copyright © 2012 John Wiley & Sons, Ltd.
Follow‐up of early stage melanoma: Specialist clinician perspectives on the functions of follow‐up and implications for extending follow‐up intervals
Authors: Rychetnik Lucie , McCaffery Kirsten , Morton Rachael L , Thompson John F , Menzies Scott W , Irwig Les
Published: October 2012

Background

There is limited evidence on the relative effectiveness of different follow‐up schedules for patients with AJCC stage I or II melanoma, but less frequent follow‐up than is currently recommended has been proposed.

Objectives

To describe melanoma clinicians' perspectives on the functions of follow‐up, factors that influence follow‐up intervals, and important considerations for extending intervals.

Methods

Qualitative interviews with 16 clinicians (surgical oncologists, dermatologists, melanoma unit physicians) who conduct follow‐up at two of Australia's largest specialist centers.

Results

Follow‐up is conducted for early detection of recurrences or new primary melanomas, to manage patient anxiety, support patient self‐care, and as part of shared care. Recommended intervals are based on guidelines but account for each patient's clinical risk profile, level of anxiety, patient education requirements, capacity to engage in skin self‐examination, and how the clinician prefers to manage any suspicious lesions.

Conclusions

To revise guidelines and implement change it is important to understand the rationale underpinning existing practice. Extended follow‐up intervals for early stage melanoma are more likely to be adopted after the first year when patients are less anxious and sufficiently prepared to conduct self‐examination. Clinicians may retain existing schedules for highly anxious patients or those unable to examine themselves. J. Surg. Oncol. 2013;107:463–468. © 2012 Wiley Periodicals, Inc.
Optimization of a refolding step for a therapeutic fusion protein in the quality by design (QbD) paradigm
Authors: Bade Pratap D. , Kotu Susmitha P. , Rathore Anurag S.
Published: October 2012

Production of biotech therapeutics in Escherichia coli involves protein expression as insoluble inclusion bodies that need to be denatured and the resulting protein refolded into the native structure. In this paper, we apply a Quality by Design approach using Design of Experiments for optimization of the refolding process for a recombinant biotech therapeutic, granulocyte colony stimulating factor. First, risk analysis was performed to identify process parameters that require experimental examination. Next, the chosen parameters were examined using a fractional factorial screening design. Based on the results of this study, parameters that have significant effect on refold yield and product quality were identified and examined using a full factorial Design of Experiments for their interactions. The final model was statistically significant and delivered a refolding yield of 77%. Further, kinetics of refolding was evaluated under optimal conditions and was found to be of first order with a rate constant of 0.132/min. Design space was established for the three parameters for a given permissible range of yield, protein concentration, and purity. The primary objective of this paper is to provide a roadmap for implementing Quality by Design for development of a protein refolding step.
Tunable Surface Nanoporosity by Electropolymerization of N‐Alkyl‐3,4‐ethylenedioxypyrroles With Different Alkyl Chain Lengths
Authors: Darmanin Thierry , Guittard Frédéric
Published: October 2012

The tuning of the surface morphology is crucial in the development of superhydrophobic surfaces with various wetting properties. Here, we report the synthesis and electrodeposition of poly(3,4‐ethylenedioxypyrrole) (PEDOP) derivatives containing hydrocarbon chains (ethyl to tetradecyl). Surprisingly, the alkyl chain length has a very important influence on the surface morphology and as a consequence on the water‐repellency properties. The amount of the nanoporosity and the water‐repellency properties can be controlled with alkyl chain length. Moreover, it seems the presence of surface nanoporosity is in correlation with the steric hindrances induced by the alkyl chains during the electrodeposition. This paper uses bioinspired approaches (fluorocarbon free) to reach superhydrophobic surfaces.
Covalent Attachment of Gold Nanoparticles to Surfaces and Polymeric Substrates Using UV Light
Authors: Roth Peter J. , Theato Patrick
Published: October 2012

Uniform benzophenone‐covered AuNP (Bph‐AuNP) were prepared in a two‐phase ethyl acetate/water reduction of auric acid employing a benzophenone‐functionalized disulfide. Upon UV irradiation, the benzophenone carbonyl bond was excited allowing for insertion into a nearby C–H bond and thus a covalent attachment of the AuNP onto a substrate exhibiting C–H bonds. Using this technique, polycarbonate–gold core–shell particles were easily obtained, providing a simple synthetic pathway toward AuNP hybrids with polycondensation polymers. Bph‐AuNP were also covalently attached to alkylated silica microspheres or cellulose paper. UV irradiation through a photo mask enabled a photolithographic surface patterning.
Evaluation of Spectroscopic and Morphological Properties of PMMA Modified with ILs
Authors: de Oliveira Viviane B. , Pereira Nizamara S. , Andrade Carlos Kleber Z. , Sales Maria José A.
Published: October 2012

Summary: In recent years, an important class of new compounds, ionic liquids (ILs), has been investigated as additives for polymers. In this work, we carried out the synthesis of 4 different ILs: 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIM.BF4), 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM.PF6), and the chiral ILs acetyl‐(−)menthol‐1‐buthylimidazole tetrafluoroborate ([amebim]BF4) and acetyl‐(−)menthol‐1‐buthylimidazole hexafluorophosphate ([amebim]PF6). These ILs were added to poly(methyl methacrylate) (PMMA) in 10, 20 and 30% ratios by weight and the ILs, PMMA and the obtained materials (PMMA:ILs) were characterized by infrared, visible spectroscopy and atomic force microscope. The ILs added to PMMA did not provide significant changes in the infrared spectra, compared to pure PMMA. However, the absorption spectra in the visible region of the PMMA:ILs materials showed differences, compared to the spectrum of pure PMMA.
Conductive Nanocomposites Based on Cellulose Nanofibrils Coated with Polyaniline‐DBSA Via In Situ Polymerization
Authors: Silva Michael J. , Sanches Alex O. , Malmonge Luiz F. , Medeiros Eliton S. , Rosa Morsyleide F. , McMahan Colleen M. , Malmonge José A.
Published: October 2012

Summary: Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI‐DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet‐visible‐near infrared (UV‐Vis ‐ NIR) and Fourier‐transform infrared (FTIR) spectroscopies and X‐ray diffraction (XRD). FTIR and UV‐Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10−1 S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X‐ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils.
Effect of Organoclay Mixture on the Rheological Properties of ABS‐Clay Nanocomposites
Authors: Galvan Danieli , Carneiro Fábio , Mazzucco Mateus , Bartoli Julio Roberto , d'Ávila Marcos Akira , Morales Ana Rita , Fernandes Elizabeth Grillo
Published: October 2012

Summary: In this work, poly(acrylonitrile‐butadiene‐styrene) (ABS) and different organically modified montmorillonite clay nanocomposites were prepared by melt intercalation in a co‐rotating twin screw extruder. The influence of the screw torque during processing and of the mixture of the modified organoclays in the intercalation/exfoliation of the clay in the polymeric matrix was evaluated through low angle X‐ray diffraction range and capillary and parallel plate‐plate rheometry.
Preparation and Characterization of PVA Hidrogels Nanofibers
Authors: Almeida Rosemeire S. , Rodriguez Geraldine N. , Lima Lonetá L. , Bavaresco Vanessa P. , Zavaglia Cecília A. C. , d'Ávila Marcos A.
Published: October 2012

Summary:Poly(vinyl alcohol) (PVA) is a biomaterial that has interesting features for applications in soft tissue replacement due to its similarities in the mechanical properties of such tissues. This paper describes the preparation and characterization of PVA fibers obtained by electrospinning and crosslinked with potassium persulfate as thermoinitiator. These PVA fibers were characterized by Scanning Electron Microscopy (SEM) and Optical Microscopy (OM) to analyze the morphology of the spun samples. Finally, Fourier Transform Infrared Spectroscopy (FTIR) and differential scanning calorimetry (DSC) were performed and the results showed that the biomaterial was partially cross‐linked, which indicates a potential use for dermal regeneration applications. The morphology of the fibers indicated that structural changes occurred in the biomaterial after thermal crosslinking.