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  • Articles  (18,163)
  • Wiley  (18,163)
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  • Articles  (18,163)
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  • Wiley  (18,163)
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  • 1
    Publication Date: 2014-12-07
    Description: Although catchment storage is an intrinsic control on the rainfall-runoff response of streams, direct measurement remains a major challenge. Coupled models that integrate long-term hydrometric and isotope tracer data are useful tools that can provide insights into the dynamics of catchment storage and the volumes of water involved. In this study, we use a tracer-aided hydrological model to characterize catchment storage as a dynamic control on system function related to streamflow generation, which also allows direct estimation of the non-stationarity of water ages. We show that in a wet Scottish upland catchment dominated by runoff generation from riparian peats (histosols) with high water storage, non-stationarity in water age distributions are only clearly detectable during more extreme wet and dry periods. This is explained by the frequency and longevity of hydrological connectivity and the associated relative importance of flow paths contributing younger or older waters to the stream. Generally, these saturated riparian soils represent large mixing zones that buffer the time variance of water age and integrate catchment-scale partial mixing processes. Although storage simulations depend on model performance, which is influenced by input variability and the degree of isotopic damping in the stream, a longer-term storage analysis of this model indicates a system which is only sensitive to more extreme hydroclimatic variability. This article is protected by copyright. All rights reserved.
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  • 2
    Publication Date: 2014-12-13
    Description: 2-Pivaloylpterin, an acylated derivative of the biochemically relevant pterin [2-amino-4-oxo-(3 H )pteridine] heterocyclus, undergoes stepwise metallation by the 1, 1′-bis(diphenylphosphanyl)ferrocene-copper(I) cation, [(dppf)Cu] + . The final product obtained, [Cu 3 (dppf)(μ 2 -dppf)(PP)(PP-H + )] 2 (BF 4 ) 4 , could be structurally characterized to reveal coordinative saturation with binding of central Cu + ions to N 1 ,N 3 ,O 4 ,N 5 ,N 8 and pivaloyl-O donor atoms.
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  • 3
    Publication Date: 2014-12-13
    Description: Abstract . Two coordination polymers, namely, {[Cd(cdpc)(hmt)(H 2 O)] · H 2 O} n ( 1 ), and [Mn(Hcdpc) 2 (4, 4′-bpy)(H 2 O)] n ( 2 ), were constructed by synergistic assembly through the mixed-ligand synthetic strategy (H 2 cdpc = 1-carboxymethyl-3, 5-dimethyl-1H-pyrazole-4-carboxylic acid, hmt = hexamethylenetetramine, and 4, 4′-bpy = 4, 4′-dipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X-ray diffraction analysis reveals that complex 1 is a 2D 4-connected sql sheet, and complex 2 is an interesting 1D loop chain. The two complexes are further expanded to 3D supramolecular structure through non-covalent bonds. Besides, luminescent properties of two complexes in the solid state and magnetic property of 2 were also investigated.
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  • 4
    Publication Date: 2014-12-17
    Description: Secreted phosphoprotein 24 kDa (Spp24) is an apatite- and BMP/TGF-β cytokine-binding phosphoprotein found in serum and many tissues, including bone. N-terminally intact degradation products ranging in size from 14 kDa to 23 kDa have been found in bone. The cleavage sites in Spp24 that produce these short forms have not been definitively identified, and the biological activities and mechanisms of action of Spp24 and its degradation products have not been fully elucidated. We found that the C-terminus of Spp24 is labile to proteolysis by furin, kallikrein, lactoferrin, and trypsin, indicating that both extracellular and intracellular proteolytic events could account for the generation of biologically-active Spp18, Spp16, and Spp14. We determined the effects of these truncation products on kinase-mediated signal transduction, gene expression, and osteoblastic differentiation in W-20-17 bone marrow stromal cells cultured in basal or pro-osteogenic media. After culturing for five days, all forms inhibited BMP-2-stimulated osteoblastic differentiation, assessed as induction of alkaline phosphatase activity, in basal, but not pro-osteogenic media. After 10 days, they also inhibited BMP-2-stimulated mineral deposition in pro-osteogenic media. Spp24 had no effect on Erk1/2 phosphorylation, but Spp18 stimulated short-term Erk1/2, MEK 1/2, and p38 phosphorylation. Pertussis toxin and a MEK1/2 inhibitor ablated Spp18-stimulated Erk 1/2 phosphorylation, indicating a role for G i proteins and MEK1/2 in the Spp18-stimulated Erk1/2 phosphorylation cascade. Truncation products, but not full-length Spp24, stimulated RUNX2, ATF4, and CSF1 transcription. This suggests that Spp24 truncation products have effects on osteoblastic differentiation mediated by kinase pathways that are independent of exogenous BMP/TGF-β cytokines. This article is protected by copyright. All rights reserved
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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  • 5
    Publication Date: 2014-12-18
    Description: Sarcopenia and osteoporosis have recently been noted for their relationship with locomotive syndrome and increased number of older people. Sarcopenia is defined by decreased muscle mass and impaired muscle function, which may be associated with frailty. Several clinical data have indicated that increased muscle mass is related to increased bone mass and reduced fracture risk. Genetic, endocrine and mechanical factors as well as inflammatory and nutritional states concurrently affect muscle tissues and bone metabolism. Several genes, including myostatin and α-actinin 3, have been shown in a genome-wide association study (GWAS) to be associated with both sarcopenia and osteoporosis. Vitamin D, growth hormone and testosterone as well as pathological disorders, such as an excess in glucocorticoid and diabetes, affect both muscle and bone. Basic and clinical research of bone metabolism and muscle biology suggests that bone interacts with skeletal muscle via signaling from local and humoral factors in addition to their musculoskeletal function. However, the physiological and pathological mechanisms related to muscle and bone interactions remain unclear. We found that Tmem119 may play a critical role in the commitment of myoprogenitor cells to the osteoblast lineage. We also reported that osteoglycin and FAM5C might be muscle-derived humoral osteogenic factors. Other factors, including myostatin, osteonectin, insulin-like growth factor I, irisin and osteocalcin, may be associated with the interactions between muscle tissues and bone metabolism. This article is protected by copyright. All rights reserved
    Electronic ISSN: 0091-7419
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  • 6
    Publication Date: 2014-12-17
    Description: The chemical preparation, structure, luminescence, and electronic properties are given for a new potassium holmium cyclotetraphosphate KHoP 4 O 12 , a promising optics material for applications. Single-crystal X-ray diffraction analysis shows that the newly synthesized compound crystallizes in the monoclinic system with space group C 2/ c and Z = 4. [P 4 O 12 ] 4– anionic rings and HoO 8 polyhedra display a three-dimensional (3D) framework by corner-sharing. The ten-coordinated potassium atoms are located in the delimited tunnels. KHoP 4 O 12 exhibits the blue light emission under the excitation of 330 nm. To gain further insights into electronic properties of crystal KHoP 4 O 12 , theoretical calculation based on density functional theory (DFT) was performed using the total-energy code CASTEP with the LDA + U approach. The calculated bandgap with U = 3.0–3.5 eV is in good agreement with the experimental measurement.
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  • 7
    Publication Date: 2014-11-04
    Description: The facile synthesis, molecular structure, and reactivity of [Cu(C 7 H 7 NH 2 )Cl] 4 ( 1 ) towards dioxygen and derivatives is reported. The compound could easily be prepared in good yields by mixing CuCl and benzylamine under inert conditions in dichloromethane. Surprisingly this copper(I) compound, a copper(I) tetramer with Cu I ··· Cu I interactions of 2.89 Å, was formed instead of an expected cubane cluster. Oxidation reactions led to formation of μ-oxido-species as intermediates, however 1 did not show any catalytic activity in the activation of CH bonds. In contrast it turned out that 1 was quite stable towards oxidation. Analogous reactions with CuBr or CuI were different and neither cluster units or polynuclear copper(I) complexes were obtained.
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  • 8
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    Publication Date: 2014-12-16
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  • 9
    Publication Date: 2014-12-16
    Description: The effect of different factors, such as pH of the medium (1.5 〈 pH 〈 4.0; 1 × 10 –4 mol · L –1 〈 [SO 4 2– ] 〈 1 × 10 –1 mol · L –1 ), the concentration of extracting agent, temperature and the type of the solvent, on the extraction of vanadium(V) by trioctylamine was studied. It was shown that the extraction of vanadium(V) by trioctylamine at 25 ± 0.5 °C takes place in the pH range 2.0–3.5 and the extracting complex contains decavanadate anion H 2 V 10 O 28 4– and four molecules of the extracting agent. This allows the reaction of vanadium(V) extraction by trioctylamine to be described by the following equation: 2( R 3 NH) 2 SO 4 + H 2 V 10 O 28 4– ( R 3 NH) 4 H 2 V 10 O 28 + 2SO 4 . The effect of the length of the alkyl chain of alcohol (propyl, butyl, isododecyl alcohol) on the homogeneity of the system V V -TOA-toluene-alcohol was investigated. It was established that the solubility of the extracting complexes of vanadium(V) with trioctylamine can be increased by using isododecyl alcohol C 12 H 25 OH as a modifying agent. It was shown that under optimal conditions in the presence of isododecyl alcohol at temperatures above 25 °C in the pH interval 2.0–3.5 trioctylamine extracts vanadium(V) with a high distribution coefficient (lg D V V 〉 2).
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  • 10
    Publication Date: 2014-12-17
    Description: Tumor cells display different bioenergetic profiles when compared to normal cells. In the present work we showed metabolic reprogramming by means of inhibitors of histone deacetylase (HDACis), sodium butyrate and trichostatin A in breast cancer cells representing different stages of aggressiveness and metabolic profile. When testing the effect of NaB and TSA on viability of cells, it was shown that non-tumorigenic MCF-10A cells were less affected by increasing doses of the drugs than the tumorigenic, hormone dependent, tightly cohesive MCF-7, T-47D and the highly metastatic triple-negative MDA-MB 231 cells. T-47D cells were the most sensitive to treatment with both, NaB and TSA. Experiments measuring anchorage- independent growth of tumor cells showed that MCF-7, T-47D, and MDA-MB-231 cells were equally sensitive to the treatment with NaB. The NaB induced an attenuation of glycolysis, reflected by a decrease in lactate release in MCF-7 and T47D lines. Pyruvate kinase activity was significantly enhanced by NaB in MDA-MB-231 cells only. In contrast, the inhibitor enhanced lactate dehydrogenase activity specifically in T-47 D cells. Glucose-6-phosphate dehydrogenase activity was shown to be differentially modulated by NaB in the cell lines investigated: the enzyme was inhibited in MCF-7 cells, whereas in T-47D and MDA-MB-231 cells, G6PDH was activated. NaB and TSA were able to significantly increase the oxygen consumption by MDA-MB-231 and T-47D cells. Collectively the results show that epigenetic changes associated to acetylation of proteins in general affect the energy metabolism in all cancer cell lines and that mitochondria may occupy a central role in metastasis. This article is protected by copyright. All rights reserved
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  • 11
    Publication Date: 2014-12-06
    Description: The tetraalkyldigallium(II) compound R 2 Ga–Ga R 2 ( 1 ) [ R = CH(SiMe 3 ) 2 ] reacted with amino and hydroxo functionalized carboxylic acids by retention of the Ga–Ga bond and release of CH 2 (SiMe 3 ) 2 . New heterocyclic or cage-like compounds were formed with three, two, or six Ga–Ga bonds in a single molecule. The latter dodecagallium compounds encapsulated THF or dioxane molecules in their molecular cavities (carcerands), the other compounds have up to six THF molecules coordinated by N–H ··· O hydrogen bonds.
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  • 12
    Publication Date: 2014-11-28
    Description: Reduction of chalcogen-rich Pb:Ch (1:2) phases in ethane-1,2-diamine ( en ) by elemental alkali metals results in the formation of solutions of [Pb 2 Ch 3 ] 2– of high purity and abundance. In contrast, application of the same reaction conditions to a binary Bi:Te (1:2) phase yields the mononuclear [BiTe 3 ] 3– anion. Instead of the expected [Tl 2 Te 3 ] 4– or [Tl 2 Te 2 ] 2– anions, analogous reactions with a Tl:Te (1:1) phase end up with a C–C-bond cleavage of the solvent en with formation of a salt of the telluridocyanate (N≡C–Te) – anion. Side reactions of en and elemental cesium are presented and metalate solutions are investigated with NMR spectroscopy.
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  • 13
    Publication Date: 2014-11-28
    Description: Seven lanthanide containing strand-like coordination polymers and dimeric complexes were obtained in a reversible reaction from 1, 3-thiazole (thz) and Ln Cl 3 ( Ln = La, Ce, Pr, Nd). The reactions do not require activation and render coordination polymers accessible at room temperature, already. The product constitutions depend on the lanthanide and the thiazole-to-halide ratio. For lanthanum and cerium formation of the coordination polymers 1 ∞ [ Ln Cl 3 (thz) 3 ] · thz as well as dimeric complexes [ Ln 2 Cl 6 (thz) 8 ] · 3thz were observed. For praseodymium and neodymium dimeric complexes were observed with and without non-coordinating thz. Upon heating, the compounds release thiazole under re-formation of Ln Cl 3 , the formation reaction thus being a thermally reversible reaction. Compounds and conversion processes were characterized by temperature dependent X-ray powder and single-crystal X-ray diffraction, in-situ temperature dependent gas phase IR spectroscopy, DTA/TG, and elemental analysis.
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  • 14
    Publication Date: 2014-12-03
    Description: The structural and vibrational data for the CF 3 XX CF 3 ( X = O, S, Se, Te) molecules were compared using DFT quantum chemistry calculations. The experimental vibrational frequencies and their assignments to the different normal modes of vibration could be confirmed. The data was also used to define a scaled quantum mechanics force field and sets of derived internal force constants for each molecule. A linear relationship between the experimental X – X bond lengths and the corresponding force constants was found. Additionally, some calculations for the mixed molecule CF 3 SOCF 3 were made.
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  • 15
    Publication Date: 2014-01-11
    Description: Transient abnormal myelopoiesis (TAM) in neonates with Down syndrome, which spontaneously resolves within several weeks or months after birth, may represent a very special form of leukemia arising in the fetal liver (FL). To explore the role of the fetal hematopoietic microenvironment in the pathogenesis of TAM, we examined the in vitro influences of stromal cells of human FL and fetal bone marrow (FBM) on the growth of TAM blasts. Both FL and FBM stromal cells expressed mesenchymal cell antigens (vimentin, α-smooth muscle actin, CD146 and nestin), being consistent with perivascular cells/mesenchymal stem cells that support hematopoietic stem cells. In addition, a small fraction of the FL stromal cells expressed an epithelial marker, cytokeratin 8, indicating that they could be cells in epithelial-mesenchymal transition (EMT). In the coculture system, stromal cells of the FL, but not FBM, potently supported the growth of TAM blast progenitors, mainly through humoral factors. High concentrations of hematopoietic growth factors were detected in culture supernatants of the FL stromal cells and a neutralizing antibody against granulocyte-macrophage colony-stimulating factor (GM-CSF) almost completely inhibited the growth-supportive activity of the culture supernatants. These results indicate that FL stromal cells with unique characteristics of EMT cells provide a pivotal hematopoietic microenvironment for TAM blasts and that GM-CSF produced by FL stromal cells may play an important role in the pathogenesis of TAM.
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  • 16
    Publication Date: 2014-01-11
    Description: Because of the biological relevance of thiols and sulfides such as cysteine, homocysteine, glutathione and hydrogen sulfide, their detection has attracted a great deal of research interest. Fluorescent probes are emerging as a new strategy for thiol and hydrogen sulfide analysis due to their high sensitivity, low cost, and ability to detect and image thiols in biological samples. In this short review we have summarized recent advances in the development of thiol and hydrogen sulfide reactive fluorescent probes. These probes are compared and contrasted with regard to their designing strategies, mechanisms, photophysical properties, and/or reaction kinetics. Biological applications of these probes are also discussed. J. Cell. Biochem. 9999: XX–XX, 2014. © 2013 Wiley Periodicals, Inc.
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  • 17
    Publication Date: 2014-01-11
    Description: Liraglutide, a modified form of glucagon-like peptide-1 (GLP-1), has been found to improve beta cell function in type 2 diabetes (T2DM). However, the effect of liraglutide on beta cell function under lipotoxic stress and the underlying molecular mechanisms remain unclear. In the present study, we investigated the role of PI3K/Akt/FoxO1 signaling in liraglutide-involved beta cell protection in high free fatty acids (FFAs) condition. The apoptosis, proliferation, and insulin secretion capability of MIN6 cells and islets from C57BL/6J mice were evaluated when exposed to FFAs with/without liraglutide. The expression of effectors involved in PI3K/Akt/FoxO1signalling pathway was detected by real-time PCR and western blotting in MIN6 cells and islets from C57BL/6J mice. Liraglutide substantially inhibited the lipoapoptosis and improved the proliferation and insulin secretion of beta cells in high FFAs condition. Western blot revealed that the phosphorylation of Akt and FoxO1 was markedly decreased under lipid stress but was elevated when treated with liraglutide. Moreover, FFAs could up-regulate the expression levels of p27, Bax, Cidea but down-regulate the expression levels of Pdx-1, MafA, and NeuroD in beta cells, which was canceled by the addition of liraglutide. Moreover, LY294002, a PI3K inhibitor, could significantly abrogate all the protective actions of liraglutide against lipotoxicity. We concluded that liraglutide markedly improved beta cell function under lipid stress and that the protective action of liraglutide was mediated by activation of PI3K/Akt, which resulted in inactivation of FoxO1 along with the down-regulation of p27, Bax, Cidea and up-regulation of Pdx-1, MafA, and NeuroD expressions.
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  • 18
    Publication Date: 2014-01-15
    Description: The coordination polymer [Zn(bpdc)(bimb)(H 2 O)] n ( 1 ) [H 2 bpdc = biphenyl-3,4′-di carboxylate, bimb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene] was constructed under hydrothermal conditions. The structure of complex 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, XRD, IR spectroscopy, and TG analysis. Complex 1 shows an exceptional self-penetrating 4-connected net derived from a threefold interpenetrating 6 3 -hcb subnet. Furthermore, the luminescent property of complex 1 is investigated
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  • 19
    Publication Date: 2014-01-16
    Description: The new dithiophosphate anion P 2 S 6 (OEt) 2 2– was obtained from the reaction of commercially available P 4 S 10 with Na 2 S in pyridine, subsequent ethanolysis and isolated as the stable bis(pyridinium) salt 1 . The molecular structure of 1 in the crystal was determined by single-crystal X-ray diffraction and reveals a PSSP dihedral angle of 87.3(1)° within the anion. The compound is a rare representative of a thiodiphosphate anion with a disulfide bridge between the two phosphorus atoms.
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  • 20
    Publication Date: 2014-01-16
    Description: The ureates of the alkali metals Na – Cs were synthesized from urea and the metals in liquid ammonia at temperatures below 50 °C. The crystal structures were determined using single-crystal X-ray diffraction. NaCN 2 H 3 O crystallizes in the monoclinic system [ P 2 1 / c , Z = 16, a = 17.529(1) Å, b = 6.4784(5) Å, c = 10.8211(9) Å, β = 96.938(1)°]. All other ureates are orthorhombic, with KCN 2 H 3 O and RbCN 2 H 3 O being isotypic [ Pbca , Z = 8, KCN 2 H 3 O: a = 7.102(4) Å, b = 7.221(4) Å, c = 13.533(8) Å; RbCN 2 H 3 O: a = 7.1973(8) Å, b = 7.3531(8) Å, c = 13.921(2) Å]. CsCN 2 H 3 O adopts a smaller unit cell [ P 2 1 2 1 2 1 , Z = 4, a = 6.3520(3) Å, b = 7.1645(4) Å, c = 9.0911(5) Å]. The ureates of K, Rb, and Cs contain hydrogen-bond networks, the imino nitrogen atom acting as the hydrogen-bond acceptor in CsCN 2 H 3 O. In KCN 2 H 3 O and RbCN 2 H 3 O, however, the carbonyl oxygen atom accepts the hydrogen bonds.
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  • 21
    Publication Date: 2014-01-19
    Description: Phosphorus (P) is one of the major limiting nutrient in many freshwater ecosystems. During the last decade, attention has been focused on the fluxes of suspended sediment and particulate P through freshwater drainage systems because of severe eutrophication effects in aquatic ecosystems. Hence, the analysis and prediction of phosphorus and sediment dynamics constitutes an important element for ecological conservation and restoration of freshwater ecosystems. In that sense, the development ofa suitable prediction model is justified and the present work is devoted to the validation and application of a predictive Soluble Reactive Phosphorus (SRP) uptake and sedimentation models, to a real riparian system of the middle Ebro river floodplain. Both models are coupled to a fully distributed 2D shallow water flow numerical model. The SRP uptake model is validated using data from three field experiments. The model predictions show a good accuracy for SRP concentration, where the linear regressions between measured and calculated of the three experiments were significant ( r 2  ≥ 0.62; p  ≤ 0.05), and a Nash-Sutcliffe coefficient (E) that ranged from 0.54 to 0.62. The sedimentation model is validated using field data collected during 2 real flooding events within the same river reach. The comparison between calculated and measured sediment deposition showed a significant linear regression ( p  ≤ 0.05; r 2  = 0.97) and an E that ranged from 0.63 to 0.78. Subsequently, the complete model that includes flow dynamics, solute transport, SRP uptake and sedimentation is used to simulate and analyze floodplain sediment deposition, river nutrient contribution and SRP uptake. According to this analysis, the main SRP uptake process appears to be the sediment sorption. The analysis also reveals the presence of a lateral gradient of hydrological connectivity that decreases with distance from the river, and controls the river matter contribution to the floodplain. This article is protected by copyright. All rights reserved.
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  • 22
    Publication Date: 2014-01-19
    Description: The inherent effects of global sea surface temperature (SST) anomalies on hydrological cycle and vegetation cover complicate the structure of tropical climate at the regional scale. Assessing hydrological processes related to climate forcing is important in Central America because it is surrounded by both the Pacific and Atlantic oceans and two continental landmasses. In this study, the use of high-resolution remote sensing imagery in wavelet analysis helps identify nonstationary characteristics of hydrological and ecological responses. The wavelet-based empirical orthogonal function (WEOF) further reflects the nonlinear relationship between the Atlantic and Pacific SST and the greenness of a pristine forested site in Panama, La Amistad International Park. Integrated WEOF and descriptive statistics for data analysis reveal a higher temporal variability in terrestrial precipitation relative to in-situ land surface temperature and its probable effects on the presence of dry periods. Such teleconnection signals of SST were identified as a driving force of decline in tropical forest greenness during dry periods. The results of our remote sensing-based wavelet analysis showed intrannual high frequency and biennial to triennial low frequency signals between enhanced vegetation index (EVI)/precipitation datasets and SST indices in both Atlantic and Pacific oceans. A spatiotemporal priority search further confirmed the importance of the effects of the El Niño-Southern Oscillation (ENSO) over terrestrial responses in the selected study site. Coincidence of the effect of ENSO teleconnection patterns on precipitation and vegetation suggest possible impacts of El Niño-associated droughts in Central America, accompanied by reduced rainfall, especially during the first months of rainy season (June, July and August), and decline in vegetation cover during the dry season (March and April). This article is protected by copyright. All rights reserved.
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  • 23
    Publication Date: 2014-01-19
    Description: Chromium tricarbonyl η 6 complexes of 3 cyclacene are considered quantum chemically at the levels of B3LYP/6-31G(d), B3LYP/6-31++G(d, p), B3LYP/LANL2DZ, and RF/6-31G(d, p)//B3LYP/6-31++G(d, p). One of the complexes involves the top ring (A-type) and the other one (B-type) makes use of ring of the acene belt of the cyclacene in the complex formation. Energy calculations reveal that B-type complex is more stable than A-type. Some geometrical and quantum chemical properties were obtained. Additionally, vibrational and UV/Vis spectra of the complexes were produced.
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  • 24
    Publication Date: 2014-01-19
    Description: Three mononuclear copper(II) complexes of copper nitrate with 2, 6-bis(pyrazol-1-yl)pyridine ( bPzPy ) and 2, 6-bis(3′,5′-dimethylpyrazol-1-yl)pyridine ( bdmPzPy ), [Cu(bPzPy)(NO 3 ) 2 ] ( 1 ), [Cu(bPzPy)(H 2 O)(NO 3 ) 2 ] ( 2 ) and [Cu(bdmPzPy)(NO 3 ) 2 ] ( 3 ) were synthesized by the reaction of copper nitrate with the ligand in ethanol solution. The complexes have been characterized through analytical, spectroscopic and EPR measurements. Single crystal X-ray structure analysis of complexes 1 and 2 revealed a five-coordinate copper atom in 1 , whereas 2 contains a six-coordinate (4+2) Cu II ion with molecular units acting as supramolecular nodes. These neutral nodes are connected through O–H ··· O(nitrate) hydrogen bonds to give couples of parallel linear strips assembled in 1D-chains in a zipper-like motif.
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  • 25
    Publication Date: 2014-01-19
    Description: The organic-inorganic hybrid compounds, [Cu 2 Cl 6 ] 2– ( 1 ), [Fe 2 Cl 6 O] 2– ( 2 ), and [FeCl 4 ] – ( 3 ), based on [(C 8 H 12 NO)(18-crown-6)] + (C 8 H 12 NO = 4-methoxybenzylammonium) supramolecular cations, were synthesized and structurally characterized. Crystal structure analyses and thermal and dielectric studies showed that compounds 1 and 2 have similar crystal packings and undergo reversible phase transitions at 230 K and 358 K, respectively. Compound 3 shows a phase transition at 361 K, though its crystal structure is remarkably different from 1 and 2 . These results indicate that the phase transitions may arise from the [(C 8 H 12 NO)(18-crown-6)] + supramolecular cations. The role of the chlorometalate anions is to tune the crystal packings and thus the phase transition points and types.
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  • 26
    Publication Date: 2014-01-23
    Description: This paper evaluates the IBIS land surface model using daily soil moisture data over a three-year period (2005–2007) at a semi-arid site in southeastern Australia, the Stanley catchment, using the Monte-Carlo GLUE approach. The model was satisfactorily calibrated for both the surface 30 cm and full profile 90 cm. However, full-profile calibration was not as good as that for the surface, which results from some deficiencies in the evapotranspiration component in IBIS. Relatively small differences in simulated soil moisture were associated with large discrepancies in the predictions of surface runoff, drainage and evapotranspiration. We conclude that while land surface schemes may be effective at simulating heat fluxes they may be ineffective for prediction of hydrology unless the soil moisture is accurately estimated. Sensitivity analyses indicated that the soil moisture simulations were most sensitive to soil parameters, and the wilting point was the most identifiable parameter. Significant interactions existed between three soils parameters: porosity, saturated hydraulic conductivity and Campbell “b” exponent so they could not be identified independent of each other. There were no significant differences in parameter sensitivity and interaction for different hydroclimatic years. Even though the data record contained a very dry year and another year with a very large rainfall event, this indicated that the soil model could be calibrated without the data needing to explore the extreme range of dry and wet conditions. IBIS was much less sensitive to vegetation parameters. The leaf area index (LAI) could affect the mean of daily soil moisture time series when LAI 〈 1, while the variance of the soil moisture time series was sensitive to LAI 〉 1. IBIS was insensitive to the Jackson rooting parameter, suggesting that the effect of the rooting depth distribution on predictions of hydrology was insignificant. This article is protected by copyright. All rights reserved.
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  • 27
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    Publication Date: 2014-01-24
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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  • 28
    Publication Date: 2014-01-15
    Description: The chemical bonding in the intermetallic compounds ZnPd and ZnPt with the tetragonal CuTi type of structure, and in the chemically related intermetallic compounds ZnNi, ZnCu, ZnAg, and ZnAu with the cubic CsCl type of structure, is examined applying the electron localizability approach. The analysis of the chemical bonding reveals charge transfer from zinc to the transition metal ( TM ), in line with the respective electronegativities. While in ZnNi, ZnCu, and ZnAg as well as ZnPd and ZnPt the Zn– TM interactions are described by multi-center bonding and ionic interactions, mainly ionic interactions are found in the intermetallic compound ZnAu. Going from ZnNi over ZnPd to ZnPt, a gradual change from isotropic to more and more anisotropic distribution of the atomic interactions is detected, resulting in a more pronounced tetragonal distortion.
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  • 29
    Publication Date: 2014-01-15
    Description: Two new three-dimensional frameworks with zeolite-like channels were prepared in the presence of 1,6-diaminohexane. Cu 1.5 (H 3 N–(CH 2 ) 6 –NH 3 ) 0.5 [C 6 H 2 (COO) 4 ] · 5H 2 O ( 1 ) crystallizes in the triclinic space group P with a = 772.56(7), b = 1110.36(7), c = 1111.98(8) pm, α = 98.720(7)°, β = 108.246(9)°, and γ = 95.559(7)°. Cu 2 (H 3 N–(CH 2 ) 6 –NH 3 ) 0.5 (OH)[C 6 H 2 (COO) 4 ] · 3H 2 O ( 2 ) crystallizes in the monoclinic space group P2 / c with a = 1159.34(11), b = 1059.44(7), c = 1582.2(2) pm, and β = 106.130(11)°. The Cu 2+ coordination polyhedra are connected by [C 6 H 2 (COO) 4 ] 4– anions to yield three-dimensional frameworks with wide centrosymmetric channel-like voids. Complex 1 reveals voids extending along [100] with diagonals of 900 pm and 300 pm, whereas in complex 2 the diagonal of the nearly rectangular crossection of the channels extending parallel to [001] is 900 pm. The negative excess charges of the frameworks are compensated by [H 3 N–(CH 2 ) 6 –NH 3 ] 2+ cations, which occupy the voids along with water molecules. The [H 3 N–(CH 2 ) 6 –NH 3 ] 2+ cations are not connected to Cu 2+ and have served as templates.
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  • 30
    Publication Date: 2014-01-15
    Description: The molecular alumosiloxanes (O-SiPh 2 -O-SiPh 2 -O) 3 Al 2 and (O-SiPh 2 -O-SiPh 2 -O) 4 [Al(OH)] 4 react either with water in diethyl ether, or with 1,4-butane-diol to form the new macro-cyclic compounds Al 6 (OH) 8 (O-SiPh 2 -O-SiPh 2 -O) 4 (O-SiPh 2 -O-SiPh 2 -OH) 2 ·6H 2 O ( 2 ) or Al 6 (OH) 8 (O-SiPh 2 -O-SiPh 2 -O) 4 (O-SiPh 2 -O-SiPh 2 -O-CH 2 –CH 2 –CH 2 –CH 2 –OH) 2 ( 3 ). As shown by single crystal structure analyses, both compounds 2 and 3 have a center of symmetry, resemble each other structurally and display in their center an [Al 2 (OH) 8 ] 2– unit, which is coordinated in a similar fashion to a 24-membered [Al 4 (O-SiPh 2 -O-SiPh 2 -O) 4 ] 2+ cycle branched at two aluminum atoms displaying either two (O-SiPh 2 -O-SiPh 2 -OH) ( 2 ) or two (O-SiPh 2 -O-SiPh 2 -O-CH 2 –CH 2 –CH 2 –CH 2 –OH) ( 3 ) arms. The [Al 2 (OH) 8 ] 2– groups are connected to the cycles through oxygen atoms of their hydroxide groups which link to the aluminum atoms of the ring (of the four aluminum atoms in the ring two have a double contact and two a single). Parallel to this bonding, the aluminum atoms of [Al 2 (OH) 8 ] 2– have either a water molecule in their coordination sphere, which is incorporated in a complex hydrogen bridged network including the silanol function ( 2 ), or are bonded to the –CH 2 -OH group of the siloxane-alcohol arm of the cycle ( 3 ). The aluminum atoms of the central part are in both compounds in the centers of two distorted edge sharing oxygen octahedra (mean Al–O = 1.881(7) Å ( 2 ), 1.893(7) Å ( 3 )), while the other four aluminum atoms display a tetrahedral oxygen environment (Al–O = 1.752(8) Å ( 2 ), 1.754(8) Å ( 3 )). Whereas all hydroxy groups of the [Al 2 (OH) 8 ] 2– unit in 2 are engaged in hydrogen bonding including further water molecules which make part of the network, the [Al 2 (OH) 8 ] 2– unit in 3 shows fewer hydrogen bridges. We have here a rare example of the same chemical species in a more hydrophilic and a less hydrophilic surrounding. This allows a detailed study of the impact of secondary hydrogen bonding on the structure.
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  • 31
    Publication Date: 2014-01-15
    Description: The mechanochemical synthesis offers an easy access to obtain alkaline earth metal terephthalates M (C 8 H 4 O 4 ) · n H 2 O ( M = Ca, Sr, Ba). In the presented study we describe for the first time the mechanochemical synthesis of powders of Ca(C 8 H 4 O 4 ) · 3H 2 O, Ca(C 8 H 4 O 4 ), Sr(C 8 H 4 O 4 ) · H 2 O, and Ba(C 8 H 4 O 4 ), which so far were only synthesized as single crystals from aqueous solutions or by reactions in an autoclave. Furthermore, a new hydrate Ba(C 8 H 4 O 4 ) · 2(1.5)H 2 O, not described so far in the literature, was prepared. All compounds were characterized by X-ray powder diffraction, thermal analysis, elemental analysis, FT-IR, and MAS NMR spectroscopic measurements.
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  • 32
    Publication Date: 2014-01-18
    Description: The aim of this study is to determine the efficacy of tumor-targeting Salmonella typhimurium A1-R (A1-R) on a pancreatic cancer patient-derived orthotopic xenografts (PDOX). The PDOX model was originally established from a pancreatic cancer patient in SCID-NOD mice. The pancreatic cancer PDOX was subsequently transplanted by surgical orthotopic implantation (SOI) in transgenic nude red fluorescent protein (RFP) mice in order that the PDOX stably acquired red fluorescent protein (RFP)-expressing stroma for the purposes of imaging the tumor after passage to non-transgenic nude mice in order to visualize tumor growth and drug efficacy. The nude mice with human pancreatic PDOX were treated with A1-R or standard chemotherapy, including gemcitabine (GEM), which is first-line therapy for pancreatic cancer, for comparison of efficacy. A1-R treatment significantly reduced tumor weight, as well as tumor fluorescence area, compared to untreated control ( P  = 0.011), with comparable efficacy of GEM, CDDP, and 5-FU. Histopathological response to treatment was defined according to Evans’s criteria and A1-R had increased efficacy compared to standard chemotherapy. The present report is the first to show that A1-R is effective against a very low-passage patient tumor, in this case, pancreatic cancer. The data of the present report suggest A1-1 will have clinical activity in pancreatic cancer, a highly lethal and treatment-resistant disease and may be most effectively used in combination with other agents.
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  • 33
    Publication Date: 2014-01-19
    Description: Over the past few decades ground water has become an essential commodity due to increased demand as a result of growing population, industrialization, urbanization etc. The water supply situation is expected to become more severe in the future because of continued unsustainable water use and projected change in hydro-meteorological parameters due to climate change. This study is based on the integrated approach of Remote Sensing (RS), Geographical Information System (GIS) and Multi-Criteria Decision Making (MCDM) techniques to determine the most important contributing factors that affect the ground water resources and to delineate the ground water potential zones. Ten thematic layers viz. geomorphology, geology, soil, topographic elevation (DEM), land use/land cover, drainage density, lineament density, proximity of surface water bodies, surface temperature and post-monsoon ground water depth were considered for the present study. These thematic layers were selected for ground water prospecting based on literature, discussion with the experts of Central Ground Water Board (CGWB), Government of India, field observations, geophysical investigation and multivariate techniques. The thematic layers and their features were assigned suitable weights on the Saaty's scale according to their relative significance for ground water occurrence. The assigned weights of the layers and their features were normalized by using Analytic Hierarchy Process (AHP) and eigenvector method. Finally, the selected thematic maps were integrated using weighted linear combination method to create the final ground water potential zone map. The final output map shows different zones of ground water potential, viz., very good (16%), good (35%), moderate (28%) low (17%) and very low (2.1%). The ground water potential zone map was finally validated using the discharge and ground water depth data from 28 and 98 pumping wells respectively which showed good correlation. This article is protected by copyright. All rights reserved.
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  • 34
    Publication Date: 2014-01-19
    Description: Bank erosion is the main source of suspended sediment (SS) and diffuse total phosphorus (TP) in many lowland catchments. This study compared a physically based sediment routing method (Physical method), which distinguishes between stream bed and bank erosion, with the original sediment routing method (Original method) within the Soil and Water Assessment Tool (SWAT) version 2009, for simulating SS and TP losses from a lowland catchment. A SWAT model was set up for the lowland River Odense catchment in Denmark and calibrated against observed stream flow and phosphate (PO 4 ) loads. Based on an initial calibration of hydrological and PO 4 parameters, the SWAT model with the Original method (Original model) and the SWAT model with the Physical method (Physical model) were calibrated separately against observed SS and TP loads. The SWAT model simulated daily stream flow well, but underestimated PO 4 loads. The Physical model simulated daily SS and TP better than the Original model. The simulated contribution of bank erosion to SS in the Physical model (99%) was close to the estimated contribution from in-situ erosion measurements (90-94%). Compared with the Original method, the Physical method is not only more conceptually correct, but also improves model performance. This article is protected by copyright. All rights reserved.
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  • 35
    Publication Date: 2014-01-19
    Description: This paper focuses on surface-subsurface water exchange in a steep coarse-bedded stream with step-pool morphology. We use both flume experiments and numerical modelling to investigate the influence of stream discharge, channel slope and sediment hydraulic conductivity on hyporheic exchange. The model step-pool reach, whose topography is scaled from a natural river, consists of 3 step-pool units with 0.1 m step heights, discharges ranging between base and over bankfull flows (scaled values of 0.3-4.5 L/s) and slopes of 4 and 8%. Results indicate that the deepest hyporheic flow occurs with the steeper slope and at moderate discharges and downwelling fluxes at the base of steps are highest at the largest stream discharges. In contrast to pool-riffle morphology, these findings show that steep slopes cause deeper surface-subsurface exchanges than gentle slopes. Numerical simulation results show that the portion of the hyporheic zone influenced by surface water temperature increases with sediment hydraulic conductivity. These experiments and numerical simulations emphasize the importance of topography, sediment permeability and roughness elements along the channel surface in governing the locations and magnitude of downwelling fluxes and hyporheic exchange. Our results show that hyporheic zones in these steep streams are thicker than previously expected by extending the results from streams with pool-riffle bed forms. This article is protected by copyright. All rights reserved.
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  • 36
    Publication Date: 2014-01-20
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  • 37
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    Publication Date: 2014-01-15
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  • 38
    Publication Date: 2014-01-19
    Description: The objective of this analysis is to demonstrate the feasibility of using a composite L2 SMOS soil moisture product for determining drought conditions by taking advantage of its spatial and temporal resolution. The work investigates the potential relationships between soil moisture anomalies and two drought indices, the Standardized Precipitation Index (SPI) and the Standardized Precipitation Evapotranspiration Index (SPEI), both calculated on a ten-day basis. As the two drought indices can be applied to different time scales for precipitation series, the influence of time scale on the drought definition is also studied. The anomalies were calculated both for the in situ soil moisture by REMEDHUS (Soil Moisture Measurement Stations Network, Spain) and from the SMOS L2 soil moisture product. In general, in situ anomalies exhibit higher correlation coefficients for the drought indices than those of SMOS, except for the shortest time scale. As expected, the short-term remotely sensed anomalies have a high response to precipitation events. This effect may be due to the greater sensitivity of SMOS data to rainfall, as well as to the spatial averaged nature of its observations. The optimal time scale was one month for the SMOS values and ranged between 30 and 50 days for the in situ values. The use of evapotranspiration in the calculation of the indices did not improve the description of the anomalies. The relationship between indices and soil moisture conditions provides encouraging results. Indeed, this method generates preliminary but valuable insights for future satellite products. This article is protected by copyright. All rights reserved.
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  • 39
    Publication Date: 2014-01-19
    Description: The cage compound Ba 3 Ge 16 Ir 4 crystallizes with the Ba 3 Ge 16 Rh 4 type of crystal structure, which represents a hierarchical derivative of the BaAl 4 type. The crystal structure [Pearson symbol tI 46, space group I 4/ mmm ; a = 6.5312(2) Å, c = 22.2845(6) Å] was refined from single-crystal X-ray diffraction data. The phase was obtained after 10 d at 910 °C with small impurities of clathrate-I, BaGe 7 Ir 2 and α-Ge remaining at the grain boundaries. Ba 3 Ge 16 Ir 4 is a Pauli-paramagnetic metal, which becomes superconducting below T c = 5.1 K. Electronic structure and analysis of the chemical bonding were performed based on density functional theory calculations. The physical properties are discussed in comparison to the isotypic phase Ba 3 Ge 16 Rh 4 .
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  • 40
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    Publication Date: 2014-01-20
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  • 41
    Publication Date: 2014-01-23
    Description: Remote estimation of river discharge from river width variations is an intriguing method for gauging rivers without conventional measurements. Entirely cloud-free imagery of an entire river reach is often rare, but partial coverage is more frequent. Discharge is estimated from spatially discontinuous imagery via construction of multiple width-discharge rating curves within a 62 km reach of the Tanana River, Alaska. The resulting discharge error is as low as 6.7% RMSE. Imagery covering 〈20% of the study reach can be used. This article is protected by copyright. All rights reserved.
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  • 42
    Publication Date: 2014-03-13
    Description: Reports of abruptly declining flows of Canada's Athabasca River have prompted concern because this large, free-flowing river could be representative for northern North America, provides water for the massive Athabasca oil-sands projects, and flows to the extensive and biodiverse Peace-Athabasca, Slave and Mackenzie River deltas. To investigate historic hydrology along the river and its major tributaries we expanded the time series with interpolations for short data gaps; calculations of annual discharges from early, summer-only records; and by splicing records across sequential hydrometric gauges. These produced composite, century-long records (1913 to 2011) and trend detection with linear Pearson correlation provided similar outcomes to non-parametric Kendall τ−b tests. These revealed that the mountain and foothills reaches displayed slight increases in winter discharges versus larger declines in summer discharges, and consequently declining annual flows (~0.16%/yr at Hinton; p 〈 0.01). Conversely, with contrasting boreal contributions, the Athabasca River at Athabasca displayed no overall trend in monthly or annual flows, but there was correspondence with the Pacific Decadal Oscillation (PDO) that contributed to a temporary flow decline from 1970 to 2000. These findings from century-long records contrast with interpretations from numerous shorter-term studies, and emphasize the need for sufficient time series for hydrologic trend analyses. For Northern Hemisphere rivers, the study interval should be at least 80 years to span two PDO cycles and dampen the influence from phase transitions. Most prior trend analyses considered only a few decades and this weakens interpretations of the hydrologic consequences of climate change. This article is protected by copyright. All rights reserved.
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  • 43
    Publication Date: 2014-03-13
    Description: Parthenolide is the main bioactive component in feverfew, a common used herbal medicine, and has been extensively studied in relation to its anti-cancer properties. However there have been very few in-depth studies of the activities of this compound at the molecular level. Here, we showed that parthenolide increased reactive oxygen species (ROS), induced cell death, activated AMPK and autophagy, and led to M phase cell cycle arrest in breast cancer cells. Removal of ROS inhibited all parthenolide-associated events, such as cell death, AMPK activation, autophagy induction and cell cycle arrest. Blockade of autophagy relieved cell cycle arrest, whereas inhibition of AMPK activity significantly repressed the induction of both autophagy and cell cycle arrest. These observations clearly showed that parthenolide-driven ROS activated AMPK-autophagy pathway. Furthermore, inhibition of either AMPK or autophagy significantly potentiated parthenolide-induced apoptosis. Therefore, our results show that parthenolide activates both apoptosis pathway and AMPK-autophagy survival pathway through the generation of ROS, and that suppression of AMPK or autophagy can potentially enhance the anti-cancer effect of parthenolide on breast cancer cells. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
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  • 44
    Publication Date: 2014-03-13
    Description: Polycomb repressive complex 2 (PRC2) is a critical epigenetic regulator in many biological processes, including maintenance of cell identity, stem cell self-renewal, differentiation, and deregulation of PRC2 is often observed in human cancers and diseases. Here we report that KDM5B (PLU-1/JARID1B), a histone lysine demethylase of Jumonji family, associates with PRC2 and colocalizes with PRC2 in nuclear bodies, and their physical association is dependent on direct interaction between KDM5B and the SUZ12 component of PRC2. Interestingly, co-occupancy of KDM5B and PRC2 was evidenced at the conserved cis -regulatory DNA element on retinoic acid (RA) responsive genes. Transcription readout and in vitro pull-down experiments suggest that KDM5B is an essential co-activator, but not a co-repressor, for the RA signaling, and the interface between KDM5B's JMJC domain and retinoic acid receptor α (RARα) is crucial for RA-mediated gene expression. Detailed chromatin immunoprecipitation assays addressed the seemingly paradox by revealing a biphasic effect of KDM5B on RA-induced gene activation through decoupled H3K4me3 demethylation and PRC2-antagonizing activities. These results demonstrate that KDM5B and PRC2 regulate RA signaling cascade in a cooperative and orchestrated fashion. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
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  • 45
    Publication Date: 2014-03-13
    Description: Four zinc(II) complexes, namely, Zn(Hdmpz) 2 (L1) 2 ( 1 ) (Hdmpz = 3, 5-dimethylpyrazole, HL1 = trichloroacetic acid), Zn(Hdmpz) 2 (L2) 2 ( 2 ) (HL2 = 2, 4-dichlorophenoxyacetic acid), [Zn 2 (μ-dmpz) 2 (Hdmpz) 2 (L3) 2 ] ( 3 ) (HL3 = 1-naphthylacetic acid), and [Zn(Hdmpz) 2 (L4) 2 ] · H 2 O ( 4 ) (HL4 = indole-3-acetic acid) were prepared and structurally characterized by different techniques including elemental analysis, IR spectroscopy, TG, and single-crystal X-ray diffraction analysis. The complexes display 2D to 3D structures with tetrahedral to pentagonal coordination around the central zinc atom. The X-ray studies suggested that 1 , 2 , and 4 are mononuclear complexes, whereas 3 is a centrosymmetric dinuclear complex. The pyrazole ligand is coordinated in both terminal as well as a bridging fashion in the dinuclear moiety but the pyrazole ligand in the mononuclear complexes is coordinated only in monodentate terminal fashion with its neutral N group. The carboxylate groups behave as monodentate ligands in 1 – 3 , whereas the carboxylate in 4 functioned as both monodentate and chelating bidentate ligand. On the basis of X-ray crystallographic study the rich intra- and intermolecular weak interactions such as classical hydrogen bonds, C–H ··· O, CH 3 ··· O, CH–Cl, Cl–Cl, C–H ··· π, CH 2 –π, CH 3 –π, O–π, and π–π are analyzed. All these noncovalent interactions help to assemble the discrete complexes into high-dimensional ordered superamolecular structures.
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  • 46
    Publication Date: 2014-03-13
    Description: Acetate trinuclear metal complexes of Zn II and Co II with the potentially tridentate Schiff base ligand, having mixed phenolate, imine, and pyridine donor groups, HL, were synthesized. The complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV/Vis spectroscopy, and magnetic measurements. Crystal structures of [ M 3 L 2 (OAc) 4 ] ( M = Zn II , Co II ) complexes, were also determined. The X-ray structures show the presence of trinuclear complexes with metal ions joined by phenolate and acetate bridging groups. The ligands coordinate to the metal ions through the imine nitrogen and their corresponding attached pyridyl and phenolate groups. The coordination environment for the metal ions is completed by bridging acetate anions to generate an octahedral coordination arrangement for the Co II complex and mixed distorted, bipyramidal trigonal and octahedral arrangements for the Zn II complex.
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  • 47
    Publication Date: 2014-03-14
    Description: Recent studies have suggested that the hydrologic connectivity of northern headwater catchments is likely controlled by antecedent moisture conditions and land cover patterns. A water storage model ( EWS ), based on water levels ( WLs ), specific yield ( Sy ) and surface elevation ( SE ) changes was compared to a basic water budget of a small, boreal, patterned fen (13 ha) during the ice-free period. Results showed that the EWS model reproduced well storage variations derived from the water budget. These results suggest that storage variations can be properly represented by the fluctuations of WLs when we consider the heterogeneous soil properties. However, storage deviations occurred at the daily scale and could be explained by a lack of information on water retention in unsaturated layers, canopy interceptions and preferential flows. Despite the significant impact of SE changes on the different peatland cover storage budgets (strings and lawns), using Sy mean values had low impact on storage estimations. This can be explained by the large proportion of pools and high WLs throughout the fen. At the fen scale, high storage in the pools seemed to reduce the Sy difference between strings and lawns. The results of this study provide new insights about the complex hydrological behaviour of northern catchments and allow for conceiving new hydrological modeling perspectives. This article is protected by copyright. All rights reserved.
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  • 48
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    Publication Date: 2014-03-14
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  • 49
    Publication Date: 2014-03-14
    Description: Starting from a flexible tri-carboxylic acid ligand H 3 L {H 3 L = 2,4,6-tris[(4′-carboxyphenoxy)methyl]-1,3,5-trimethylbenzene}, a 3D metal-organic framework [Zn(HL)(H 2 O)] n ( 1 ) and a 2D polymeric layered solid {[(CH 3 ) 2 NH 2 )] 2 [Cd 2 L 2 (DMA) 2 ]} n ( 2 ) were hydrothermally synthesized. The complexes were characterized by elemental analyses, FT-IR spectroscopy, TGA, and single-crystal X-ray diffraction. The X-ray structural analyses reveal that the complex 1 is an example of a doubly interpenetrated 3D helical MOF with mutually entwined right- and left-handed helices to form an overall racemic framework. Complex 2 is made up of fourfold interwoven 2D nets in the solid state.
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  • 50
    Publication Date: 2014-03-14
    Description: Oxidovanadium(IV) complexes, [VO(acac)(L)Cl] ( 1 ), [VO(cur)(L)Cl] ( 2 ), and [VO(scur)(L)Cl] ( 3 ) {acac = acetylacetonate, cur = curcumin monoanion, scur = diglucosylcurcumin monoanion, L = 11-(9-acridinyl)dipyrido[3, 2-a:2',3'-c]phenazine (acdppz)}, were prepared and characterized. The complexes are non-electrolytic in DMF and 1:1 electrolytic in aqueous DMF. The one-electron paramagnetic complexes showed a d-d band near 725 nm in aqueous DMF and green emission near 520 nm in aqueous DMSO. The complexes exhibited an irreversible V IV /V III redox response near –0.85 V versus SCE in aqueous DMF. The complexes showed good binding strengths to calf thymus DNA ( K b : 3.1 × 10 5 –9.6 × 10 5 M –1 ) and efficient pUC19 DNA photocleavage activity in red light of 705 and 785 nm by singlet oxygen ( 1 O 2 ) pathway. Complexes 1 and 2 exhibited significant photocytotoxicity (IC 50 : 0.1–1.0 μM) in visible light (400–700 nm) with low dark toxicity (IC 50 : 〉20 μM) in HeLa and HaCaT cells. Complex 3 was cytotoxic in both light and dark. DNA ladder formation experiments indicated cell death via apoptotic pathway. Confocal microscopy done with 1 and 2 revealed primarily cytosolic localization of the complexes with significant presence of the complex in the mitochondria as evidenced from the imaging data using mitotracker red.
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  • 51
    Publication Date: 2014-03-14
    Description: The coordination polymer [Cd(HL)(BPDA)] n · n H 2 O ( 1 ) based on 3-(5-(pyridin-4-yl)-1 H -1,2,4-triazol-3-yl)pyridine (HL) and 1,1′-biphenyl-4,4′-dicarboxylic acid (H 2 BPDA) was hydrothermally synthesized and characterized by single-crystal X-ray diffraction, XRPD, IR spectroscopy, and elemental analysis. The asymmetric unit of compound 1 consists of one crystallographically independent Cd II ion, one HL ligand, “two half” BPDA 2– ligand, and one lattice water molecule. There are two crystallographically different BDPA 2– moieties, but each of them is placed in a symmetry element. The BPDA 2– ligands and Cd II ions connected to2D sheet, and the 2D sheets are connected to a 3D MOF by the HL ligands. Each dimeric Cd II unit links six nearest neighbors through the BPDA 2– and HL ligands, and the dimeric Cd II units are centrosymmetric. Two parallel HL ligands connect two dimeric Cd II units, generating long Cd2–HL–Cd2–HL rings, also centrosymmetric. So we can define the dimeric Cd II unit as a 6-connected node. Thus, the 3D structure can be described as a threefold parallel interpenetrated bsn beta-Sn topology. In addition, the optical properties of compound 1 and the free ligand H L were investigated.
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  • 52
    Publication Date: 2014-03-14
    Description: The 4-connected dmp -type cadmium(II)-isonicotinate framework [Cd(isonic) 2 (H 2 O)] n · n (DMA) ( 1 ) (isonic = isonicotinate, DMA = N , N ′-dimethylacetamide) was obtained by the solvothermal reactions of Cd(NO 3 ) 2 and isonicotinic acid (Hisonic). Compound 1 features a 3D porous framework with the opened channels occupied by the lattice DMA molecules. Thermal analysis reveals that such framework remains much stable after removal the free DMA molecules. CO 2 adsorption measurement shows that such framework exhibits notable CO 2 adsorption behavior.
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  • 53
    Publication Date: 2014-03-14
    Description: The reaction of the basic bismuth nitrate [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ] · H 2 O with either thiosalicylic acid or sulfuric acid gave the novel bismuth hydrogen sulfate [Bi 2 (SO 4 ) 2 (dmso) 8 ](HSO 4 ) 2 ( 1 ) (DMSO = dimethyl sulfoxide). The formation of sulfate ions is observed in the presence of either Bi 3+ or [Bi 6 O 4 (OH) 4 ] 6+ indicating bismuth-induced oxidation of thiosalicylic acid. Compound 1 was characterized by elemental analysis, infrared spectroscopy, thermal analysis (TGA), and temperature dependent in situ X-ray powder diffraction. Crystals suitable for single crystal structure analysis were obtained from a DMSO/acetone solution. The title compound 1 crystallizes in the triclinic space group P with the following lattice parameters: a = 9.5240(4) Å, b = 9.9535(4) Å, c = 12.6620(5) Å, α = 109.943(4)°, β = 93.952(3)°, γ = 102.868(3)°, V = 1086.17(8) Å 3 , and Z = 1. Analysis of the thermally induced decomposition revealed the formation of Bi 2 O(SO 4 ) 2 and Bi 2 O 2 (SO 4 ) as intermediate products and Bi 28 O 32 (SO 4 ) 10 as final product.
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  • 54
    Publication Date: 2014-03-14
    Description: Recently, the synthesis of hexadentate ligands based on N , N ′-bis-(2,2′-bipyridine-6-ylmethyl)-2,2′-biphenylenediamine ( 1a – d ) and the corresponding iron(II) complexes ( 3a – d ) was reported by our group. In this contribution we present the synthesis of the analogous cobalt(II) complexes 4a – d . Together with the iron(II) complex the electrochemical behavior of the complexes 3 and 4 was investigated by cyclic voltammetry (CV). The aminomethyl substructure was identified as the main source of ligand degradation caused by chemical oxidation with air. Upon exposure to air the amine group in complexes 3 and 4 is oxidized to imine and even amide groups. Some examples ( 8 , 9 ) of the oxidation products were characterized by X-ray structure analysis. In order to increase the robustness of the Fe II and Co II complexes towards oxidation, the ligand scaffold of 1a was modified by N -methylation of the amino group yielding the tertiary amine 2 . The corresponding iron(II) and cobalt(II) complexes employing 2 as ligand were synthesized {[Fe( 2 )][PF 6 ] 2 ( 5 ), [Co( 2 )][PF 6 ] 2 ( 6 )} and fully characterized, their redox behavior and spin-state was investigated by CV and Evans' method. It was found, that the introduced N -methyl group leads to a substantial anodic shift of the M II – M III redox potential and the stabilization of Fe II and Co II high-spin state. By means of X-ray structure analysis these effects could be explained by repulsive steric effects of the methyl group.
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  • 55
    Publication Date: 2014-03-14
    Description: The intermetallic compounds Y 2 RuB 6 , Y 2 ReB 6 , Y 2 RhSi 3 , YRh 2 Si, and YPdSi were synthesized from the elements by arc-melting and subsequent annealing in sealed silica ampoules. The samples were studied by X-ray diffraction on powders. The structures of Y 2 RuB 6 and Y 2 RhSi 3 were refined from single crystal diffraction data: Y 2 ReB 6 type, Pbam , a = 916.3(2) pm, b = 1150.3(3) pm, c = 364.37(9) pm, wR 2 = 0.1056, 942 F 2 values, 38 variables for Y 2 RuB 6 and Er 2 RhSi 3 type, a = 812.6(2), c = 787.2(1) pm, wR 2 = 0.0682, 369 F 2 values, 17 variables for Y 2 RhSi 3 . The five compounds are characterized by two or three (YPdSi), crystallographically independent yttrium sites, which were all well resolved in 89 Y solid state NMR spectra. The NMR signal shifts were correlated with the density of states of the s electrons at the Fermi level, resulting in a non-ambiguous assignment of the NMR signals to the various sites in the crystal structures.
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  • 56
    Publication Date: 2014-03-14
    Description: The title complexes were obtained by reactions of [(η 5 -C 5 H 5 )(CO) 2 Fe] – , [(η 5 -C 5 H 4 CH 3 )(CO) 2 Fe] – , [Re(CO) 5 ] – , or [Mn(CO) 5 ] – with the mixed anhydride from the respective pyridine carboxylic acid and pivalic acid or with isonicotinic acid chloride, and were characterized by spectroscopic data and elemental analysis.
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  • 57
    Publication Date: 2014-05-03
    Description: The N -(2, 6-diisopropylphenyl)- N ′-benzoylthiourea ligand (shown as L ) ( 1 ) was synthesized and characterized. Reactions of 1 with CuCl 2 and CuBr 2 afforded the monomeric L 2 CuCl ( 2 ) and dimeric [ L BrCu(μ- L )] 2 ( 3 ), respectively, due to the reduction of Cu II . The reaction of 1 and CuCl gave the same product L 2 CuCl ( 2 ), while the treatment of 1 with CuBr led to the formation of a rare example of adamantanoid cage ( L Cu) 2 (μ- L ) 2 Cu 2 (μ-Br) 4 ( 4 ) containing enantiomeric couple. The product of 1 and CuI was found to be dimeric [ L ICu(μ- L )] 2 ( 5 ), which is isomorphous to 3 . All compounds obtained were fully characterized by elemental analysis, IR, 1 H NMR and 13 C NMR spectroscopy, and single-crystal X-ray diffraction.
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  • 58
    Publication Date: 2014-05-03
    Description: Thermodynamic data for gaseous SiF 2 and SiCl 2 known from literature show that these binary subhalides are formed nearly quantitatively at 1376 °C and 1076 °C, respectively, as products of the reaction of elemental silicon with SiF 4 or SiCl 4 at 1 × 10 –2 mbar. Applying the co-condensation technique SiF 2 as well as SiCl 2 can be trapped at –196 °C and prepared in synthetic scale. Herein, first analysis of metastable SiF 2 and SiCl 2 solutions are presented, showing that SiF 2 is more reactive than SiCl 2 leading to compounds of low boiling point of so far unknown composition. The metastable SiCl 2 solution can be used as a SiCl 2 source, which is shown by the trapping reaction with Idipp [Idipp = 1, 3-bis(2, 6- i Pr 2 -C 6 H 3 )imidazol-2-ylidene] leading to Idipp-SiCl 2 . The reactivity of the solution might be fine-tuned by changing the donor opening the door for further applications.
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  • 59
    Publication Date: 2014-04-29
    Description: Cleavage of the cell–cell adhesion molecule, PTPµ, occurs in human glioblastoma multiforme brain tumor tissue and glioma cell lines. PTPµ cleavage is linked to increased cell motility and growth factor independent survival of glioma cells in vitro. Previously, PTPµ was shown to be cleaved by furin in the endoplasmic reticulum to generate membrane associated E- (extracellular) and P- (phosphatase) subunits, and by ADAMs and the gamma secretase complex at the plasma membrane. We also identified the presence of additional extracellular and intracellular PTPµ fragments in brain tumors. We set out to biochemically analyze PTPµ cleavage in cancer cells. We determined that, in addition to the furin-processed form of PTPµ, a pool of 200 kDa full-length PTPµ exists at the plasma membrane that is cleaved directly by ADAM to generate a larger shed form of the PTPµ extracellular segment. Notably, in glioma cells, full-length PTPµ is also subject to calpain cleavage, which generates novel PTPµ fragments not found in other immortalized cells. We also observed glycosylation and phosphorylation differences in the cancer cells. Our data suggest that an additional serine protease also contributes to PTPµ shedding in glioma cells. We hypothesize that a “protease storm” occurs in cancer cells whereby multiple proteases converge to reduce the presence of cell–cell adhesion molecules at the plasma membrane and to generate protein fragments with unique biological functions. As a consequence, the “protease storm” could promote the migration and invasion of tumor cells. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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  • 60
    Publication Date: 2014-05-07
    Description: Mesenchymal stem cells (MSCs) have shown a great potential for cell-based therapy and many different therapeutic purposes. Despite the recent advances in the knowledge of MSCs biology, their biochemical and molecular properties are still poorly defined. Ecto-nucleoside triphosphate diphosphohydrolases (E-NTPDases) and ecto-5′-nucleotidase (eNT/CD73) are widely expressed enzymes that hydrolyze extracellular nucleotides, generating an important cellular signaling cascade. Currently, studies have evidenced the relationship between the purinergic system and the development, maintenance, and differentiation of stem cells. The objective of this study is to identify the NTPDases and eNT/CD73 and compare the levels of nucleotide hydrolysis on MSCs isolated from different murine tissues (bone marrow, lung, vena cava, kidney, pancreas, spleen, skin, and adipose tissue). MSCs from all tissues investigated expressed the ectoenzymes at different levels. In MSCs from pancreas and adipose tissue, the hydrolysis of triphosphonucleosides was significantly higher when compared to the other cells. The diphosphonucleosides were hydrolyzed at a higher rate by MSC from pancreas when compared to MSC from other tissues. The differential nucleotide hydrolysis activity and enzyme expression in these cells suggests that MSCs play different roles in regulating the purinergic system in these tissues. Overall MSCs are an attractive adult-derived cell population for therapies, however, the fact that ecto-nucleotide metabolism can affect the microenvironment, modulating important events, such as immune response, makes the assessment of this metabolism an important part of the characterization of MSCs to be applied therapeutically. J. Cell. Biochem. 9999: XX–XX, 2014. © 2014 Wiley Periodicals, Inc.
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  • 61
    Publication Date: 2014-05-02
    Description: Minor changes to seasonal air temperature and precipitation can have a substantial impact on the availability of water resources within large watersheds. Two such watersheds, the north-flowing Mackenzie and east-flowing Saskatchewan Basins have been identified as highly vulnerable to such changes, and, therefore, selected for study as part of the Climatic Redistribution of western Canadian Water Resources (CROCWR) project. CROCWR aims to evaluate spatial and temporal changes to water resource distribution through the analysis of a suite of hydroclimatic and streamflow variables. As part of this analysis, dominant summer (May-Oct) circulation patterns at 500-hPa for 1950-2011 are identified using the method of Self-Organizing Maps (SOM). Surface climate variables associated with these patterns are then identified, including both daily air temperature and precipitation, and seasonal Standardized Precipitation-Evapotranspiration Index (SPEI) values. Statistical methods are applied to assess the relationships between dominant circulation patterns and the Southern Oscillation Index (SOI) and Pacific Decadal Oscillation (PDO). Results indicate that mid-summer (Jul-Aug) is dominated by a split-flow blocking pattern, resulting in cool (warm), wet (dry) conditions in the southern (northern) portion of the study area. By contrast, the shoulder season (May and Oct) is dominated by a trough of low-pressure over the North Pacific Ocean. The frequency of weak split-flow blocking is higher during positive SOI and negative PDO, while ridging over the western continent is more frequent during negative SOI and positive PDO. Results from this analysis increase our knowledge of processes controlling the distribution of summer water resources in western Canada. This article is protected by copyright. All rights reserved.
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  • 62
    Publication Date: 2014-05-03
    Description: Lithium transition metal silicates, Li 2 M SiO 4 ( M = Fe, Mn, Co), have attracted much interest as positive electrodes for Li-ion batteries due to their high theoretical capacities and their rich crystal chemistry. Low (β) and high (γ) temperature forms of these tetrahedral structures differ in the ordering/distribution of cations within tetrahedral sites of an hcp based packing of oxygen. We have carried out VT powder neutron and X-ray diffraction on Li 2 M SiO 4 ( M = Fe, Mn) to characterize the rich polymorphism observed across the Li 2 M SiO 4 ( M = Fe, Mn) system as a function of temperature. For Li 2 FeSiO 4 below 500 °C a β II phase was observed with slight Li/Fe disorder. Above this temperature there was a sluggish transition to the γ s phase, which was observed up to ca. 820 °C, with the γ II polymorph seen at highest temperatures. Excellent agreement with phases obtained by quenching was observed, except that the γ phases exhibit a statistical distribution of Li/Fe, in contrast to the well-ordered structures of quenched phases. The Li 2 MnSiO 4 polymorphism is less complex, the β II phase is stable from room temperature to 750 °C, at which temperature it transforms to the γ structure with disordered Li/Mn.
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  • 63
    Publication Date: 2014-05-03
    Description: Ag@Au core-shell nanoparticles were synthesized by using a fluorescent dipeptide β -Ala-Trp in water medium and at a room temperature without using any external reducing and stabilizing agents. The shell thickness of gold in core-shell Ag@Au nanoparticles has also been varied by changing the concentration of the gold(III) precursor keeping the other conditions same. The optical property of these core-shell nanoparticles varies with the shell thickness. Interestingly, these core-shell nanoparticles exhibit good catalytic property for the reduction of nitrophenols to aminophenols and nitroanilines to aminoanilines. A series of nitrophenol and nitroaniline compounds were taken as substrates for reduction. Moreover, this core-shell nanoparticle displays remarkable difference in catalytic property for reduction of nitro group with the variation of shell thickness. This catalyst (Ag@Au core-shell nanoparticle) can also be recycled for several times indicating its reusability.
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  • 64
    Publication Date: 2014-05-03
    Description: Two coordination polymers, namely {[Mn(2,4′-bpdc)(bimb)(H 2 O) 0.5 ] · 0.5H 2 O} n ( 1 ) and [Mn(4,4′-bpdc)(bimb)] n · 2.5H 2 O ( 2 ) [2,4′-bpdc = biphenyl-2,4′-dicarboxylate, 4,4′-bpdc = biphenyl-4,4′-dicarboxylate, and bimb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene], were hydrothermally synthesized by reactions of manganese(II) salt with the rigid ligand 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene and isomeric biphenyl dicarboxylate ligands. Complex 1 has an unusual 6-connected three-dimensional (3D) architecture with point symbol (4 4 .6 11 ). Complex 2 has also a 3D structure with two-interpenetrated pcu topology with point symbol (4 12 .6 3 ). Structural comparisons show that the positions of the carboxylate groups in the ligand backbone play an important role in governing the structural topologies of these complexes.
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  • 65
    Publication Date: 2014-03-05
    Description: Little research has examined whether forests reduce stream water eutrophication in agricultural areas during spring snowmelt periods. This study evaluated the role of forests in ameliorating deteriorated stream water quality in agricultural areas, including pasture, during snowmelt periods. Temporal variation in stream water quality at a mixed land-use basin (565 ha: pasture 13%, forestry 87%), northern Japan, was monitored for 7 years. Synoptic stream water sampling was also conducted at 16 sites across a wide range of forest and agricultural areas in a basin (18.3 km 2 ) in spring, summer, and fall. Atmospheric nitrogen (N) and phosphorus (P) deposition were measured for 4 years. The results showed that concentration pulses of nitrate (NO 3 – ), organic N (ON), and total P (TP) in stream water were observed when discharge increased during spring snowmelt. Their concentrations were high when silicate concentrations were low, suggesting surface water exported from pasture largely contributed to stream water pollution during snowmelt. Atmospheric N and P deposition (4.1 kg N ha –1 y –1 ; 0.09 kg P ha –1 y –1 , respectively) was too low to affect the background concentrations of N and P in streams from forested areas. Reduction of eutrophication caused by nutrients from pasture was mainly due to dilution by water containing low concentrations of N and P exported from forested areas, while in-stream reduction were not dominant processes. Results indicate that forests have a limited capacity to reduce the concentration pulses of N and P in stream water during snowmelt in this study basin. This article is protected by copyright. All rights reserved.
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  • 66
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    Publication Date: 2014-03-05
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  • 67
    Publication Date: 2014-03-20
    Description: The semirigid exo -bidentate ligand 1, 4-bis{[(2′-picolylaminoformyl)phenoxyl]methyl}-2, 5-bismethylbenzene (L) was designed, synthesized, and used as building blocks for constructing luminescent lanthanide polymers. Two new lanthanide coordination polymers were characterized by elemental analysis, X-ray diffraction analysis, and IR spectroscopy. The coordination polymers exhibit the metal-to-ligand molar ratio of 1:1 and the semirigid exo -bidentate ligand bridges lanthanide nitrates forming a zigzag chain, which further interconnected to three dimensional supramolecular structure in aid of cooperative C–H ··· O hydrogen bonds. The luminescence properties of the europium(III) complex are discussed in detail.
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  • 68
    Publication Date: 2014-03-20
    Description: Lung development follows a stereotypic program orchestrated by key interactions among epithelial and mesenchymal tissues. Deviations from this developmental program can lead to pulmonary diseases including bronchopulmonary dysplasia and pulmonary hypertension. Significant efforts have been made to examine the cellular and molecular basis of the tissue interactions underlying these stereotypic developmental processes. Genetically engineered mouse models, lung organ culture, and advanced imaging techniques are a few of the tools that have expanded our understanding of the tissue interactions that drive lung development. Intimate crosstalk has been identified between the epithelium and mesenchyme, distinct mesenchymal tissues, and individual epithelial cells types. For interactions such as the epithelial-mesenchymal crosstalk regulating lung specification and branching morphogenesis, the key molecular players, FGF, BMP, WNT, and SHH, are well established. Additionally, VEGF regulation underlies the epithelial-endothelial crosstalk that coordinates airway branching with angiogenesis. Recent work also discovered a novel role for SHH in the epithelial-to-mesenchymal (EMT) transition of the mesothelium. In contrast, the molecular basis for the crosstalk between upper airway cartilage and smooth muscle is not yet known. In this review we examine current evidence of the tissue interactions and molecular crosstalk that underlie the stereotypic patterning of the developing lung and mediate injury repair. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
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  • 69
    Publication Date: 2014-03-20
    Description: The epithelial lining of the respiratory system originates from a small group of progenitor cells in the ventral foregut endoderm of the early embryo. Research in the last decade has revealed a number of paracrine signaling pathways that are critical for the development of these respiratory progenitors. In the post genomic era the challenge now is to figure out at the genome wide level how these different signaling pathways and their downstream transcription factors interact in a complex “gene regulatory network” (GRN) to orchestrate early lung development. In this prospective we review our growing understanding of the GRN governing lung specification. We discuss key gaps in our knowledge and describe emerging opportunities that will soon provide an unprecedented understanding of lung development and accelerate our ability to apply this knowledge to regenerative medicine. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
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  • 70
    Publication Date: 2014-03-05
    Description: In NLDAS-2 Noah simulation, the NLDAS team introduced an intermediate “fix” to constrain the surface exchange coefficient when the atmospheric boundary layer is stable. In the current NLDAS-2 Noah version, this fix is used for all stable cases including snow-free grid cells. In this study, we simply apply this fix to the grid cells in which both stable atmospheric boundary layer and snow exist simultaneously, excluding the snow-free grid cells as we recognize that the fix in NLDAS-2 is too strong. We conduct a 31-year (1979-2009) NLDAS-2 Noah interim (Noah-I) run, and use observed streamflow, evapotranspiration, land surface temperature, soil temperature, and ground heat flux to evaluate the results, including comparisons with the original NLDAS-2 Noah run. The results show that Noah-I has the same performance as NLDAS-2 Noah for snow water equivalent; however, Noah-I significantly improved the simulation of other hydrometeorological products as noted above when compared to NLDAS-2 Noah and the observations. This simple modification is being included in the next Noah version used in NLDAS. The hydrometeorological products from the improved NLDAS-2 Noah-I are being staged on the NCEP public server. This article is protected by copyright. All rights reserved.
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  • 71
    Publication Date: 2014-04-26
    Description: Large-scale watershed modelling presents a unique challenge in terms of physiographic and climatological heterogeneity and spatially varied hydrologic responses. In particular, the spatial variability in hydrologic processes may introduce a high degree of uncertainty in the modelling of a large watershed. This study assessed the uncertainties in annual/seasonal streamflow and annual peak flow simulations with respect to selection of climate data and model parameter sets for the Variable Infiltration Capacity (VIC) model of the Athabasca River Basin (ARB) in Alberta, Canada. Two high-resolution gridded climate data sets over the 1979 to 2010 period, and six different model parameter sets calibrated corresponding to different time periods and various hydrologic patterns, were employed to quantify the uncertainty in VIC simulations. Moreover, the possibility of an ensemble approach to predict hydrologic responses in the ARB has been investigated. The results indicated that stramflow simulations near the headwater and along the Athabasca River mainsteam have high uncertainty corresponding to selection of climate data mainly due to greater difference of precipitation between the two climate data sets, whereas sub-basin stations at low-elevations were more sensitive to the selection of parameter set for interflow-dominated runoff cycle. All stations showed higher uncertainty corresponding to the selection of parameter set for annual peak flows. In addition, this study confirmed that the ensemble means can provide more accurate and consistent hydrologic information for the low-elevation area where higher internal variability exists. This article is protected by copyright. All rights reserved.
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  • 72
    Publication Date: 2014-04-26
    Description: Multilayer covers are widely accepted reclamation designs in the oil sands region of northern Alberta, Canada, with an ultimate goal of revegetating to species characteristic of predisturbance native plant communities. To determine the optimal depth of reclamation material required to reclaim overburden shale from an oil sands mine, an evaluation was made of the long-term performance of six reclamation soil cover depths all placed over overburden. The measured soil water contents from different cover thicknesses at South Bison Hills located at the Syncrude Mine site north of Fort McMurray, Alberta were used to calibrate and validate a dual-porosity model in HYDRUS-1D. The calibrated and validated model was then used to evaluate the influence of cover thickness and climatic variability on plant available water for forest growth. The frequency distributions of actual transpiration (T r ) for six cover treatments with a range of leaf area index (LAI) cases were developed. These T r frequency distributions were then modified by coupling T r and LAI. The modified frequency distributions for annual T r for the six simulated cover thickness highlight the strong non-linearity between the distribution of T r over a long-term (60 year) climate cycle in that incremental increases in cover thickness do not produce proportional increases in T r . The results indicated that, once the cover thickness exceeds 100 cm, there is little incremental increase in the median value of T r over the 60 year climate cycle. This article is protected by copyright. All rights reserved.
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  • 73
    Publication Date: 2014-04-26
    Description: Within peatland ecosystems small deviations in surface elevation result in microforms that differ in depth to water-table, plant type and rate of biogeochemical cycling, possibly leading to differences in peat physical and hydrological properties that could feed back to whole ecosystem hydrological and biogeochemical function. However, hydrological parameters for peatland microforms have not been quantified. This study determined bulk density, pore size distribution and saturated hydraulic conductivity (K sat ) at hummocks and hollows of four, Sphagnum -dominated Canadian peatlands. Study sites included both a bog and poor fen in each of Alberta and Quebec allowing for investigation of differences in peat hydrophysical properties between microforms across a range of Sphagnum -dominated peatlands. Hydraulic conductivity was determined in the laboratory on peat from the surface (0.03-0.08 m) and the saturated zone (0.20 m below the local water-table position). Peatland type, climate region, microform and depth of peat were all significant descriptors of variation in K sat . Deeper peat was less conductive than surface peat. Hummocks generally had higher K sat than hollows at both surface and saturated zones, although differences between microforms varied between sites. Differences in K sat between samples were correlated with bulk density, von Post humification and macroporosity. These results indicate that there are microtopographical differences in peat hydrophysical properties; however, the strong decline in K sat with depth indicates that differences in the local water-table, resulting in a change in depth of water flow, is likely a stronger control on local K sat than microform type. This article is protected by copyright. All rights reserved.
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  • 74
    Publication Date: 2014-04-28
    Description: A regional, or pooled, approach to frequency analysis is explored in the context of the estimation of rainfall quantiles required for the formation of Intensity-Duration-Frequency (IDF) curves. Resampling experiments are used, in conjunction with two rainfall data sets with long record lengths, to explore the merits of a pooled approach to the estimation of extreme rainfall quantiles. The width of the 95% confidence interval for quantile estimates is used as the primary basis to evaluate the relative merits of pooled and single site estimates of rainfall quantiles. Recommendations are formulated for applying the regional approach to frequency analysis and these recommendations are used in the application of the regional approach to 40 sites with IDF data in southern Ontario, Canada. The results demonstrate that the regional approach is preferred to single site analysis for estimating extreme rainfall quantiles for conditions and data availability commonly encountered in practice. This article is protected by copyright. All rights reserved.
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  • 75
    Publication Date: 2014-03-20
    Description: Integrated river basin models should provide a spatially distributed representation of basin hydrology and transport processes to allow for spatially implementing specific management and conservation measures. To accomplish this, the Soil and Water Assessment Tool (SWAT) was modified by integrating a landscape routing model to simulate water flow across discretized routing units. This paper presents a grid-based version of the SWAT landscape model that has been developed to enhance the spatial representation of hydrology and transport processes. The modified model uses a new flow separation index that considers topographic features and soil properties to capture channel and landscape flow processes related to specific landscape positions. The resulting model is spatially fully distributed and includes surface, lateral, and groundwater fluxes in each grid cell of the watershed. Furthermore it more closely represents the spatially heterogeneous distributed flow and transport processes in a watershed. The model was calibrated and validated for the Little River Watershed (LRW) near Tifton, Georgia (USA). Water balance simulations as well as 30 the spatial distribution of surface runoff, subsurface flow and evapotranspiration are examined. Model results indicate that groundwater flow is the dominant landscape process in the LRW. Results are promising and satisfactory output was obtained with the presented grid-based SWAT landscape model. Nash-Sutcliffe model efficiencies for daily stream flow were 0.59 and 0.63 for calibration and validation periods and the model reasonably simulates the impact of the landscape position on surface runoff, subsurface flow and evapotranspiration. Additional revision of the model will likely be necessary to adequately represent temporal variations of transport and flow processes in a watershed. This article is protected by copyright. All rights reserved.
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  • 76
    Publication Date: 2014-04-29
    Description: Direct sediment inputs from forest roads at stream crossings are a major concern for water quality and aquatic habitat. Legacy road-stream crossing approaches, or the section of road leading to the stream, may have poor water and grade control upon reopening, thus increasing the potential for negative impacts to water quality. Rainfall simulation experiments were conducted on the entire running surface area associated with six reopened stream crossing approaches in the southwestern Virginia Piedmont physiographic region, USA. Event-based surface runoff and associated total suspended solids (TSS) concentrations were compared among a succession of gravel surfacing treatments that represented increasing intensities of best management practice (BMP) implementation. The three treatments were No Gravel (10-19% cover), Low Gravel (34-60% cover), and High Gravel (50-99% cover). Increased field hydraulic conductivity was associated with maximized surface cover, and ranged from 7.2 to 41.6, 11.9 to 46.3, and 16.0 to 58.6 mm h -1 , respectively, for the No Gravel, Low Gravel, and High Gravel treatments. Median TSS concentration of surface runoff for the No Gravel treatment (2.84 g L -1 ) was greater than Low Gravel (1.10 g L -1 ) and High Gravel (0.82 g L -1 ) by factors of 2.6 and 3.5, respectively. Stream crossing approaches with 90-99% surface cover had TSS concentrations below 1 g L -1 . Reducing the length of road segments that drain directly to the stream can reduce the costs associated with gravel surfacing. This research demonstrates that judicious and low-cost BMPs can ameliorate poor water control and soil erosion associated with reopening legacy roads. This article is protected by copyright. All rights reserved.
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  • 77
    Publication Date: 2014-01-26
    Description: Leukemia inhibitory factor (LIF) is a pleiotropic cytokine that belongs to the interleukin-6 family and is expressed by multiple tissue types. This study analyzed the effect of LIF on osteoblast differentiation using primary murine bone marrow stromal cells (BMSCs). Colony-forming unit-osteoblast formation by BMSCs was significantly suppressed by LIF treatment. To clarify the mechanism underlying the LIF suppressive effect on osteoblast differentiation, we analyzed the downstream signaling pathway of LIF. LIF/signal transducer and activator of transcription 3 (STAT3) signaling induces the expression of suppressor of cytokine signaling 3 (SOCS3). SOCS3 knockdown experiments have previously demonstrated that short-hairpin SOCS3-BMSCs reversed the LIF suppressive effect. Our results demonstrated that LIF suppresses osteoblast differentiation through the LIF/STAT3/SOCS3 signaling pathway. J. Cell. Biochem. © 2013 Wiley Periodicals, Inc.
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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  • 78
    Publication Date: 2014-02-01
    Description: The following study discusses the synthesis of macroporous glass beads, featuring variable pore sizes, and their application as starting material for a double templating route according to the nanocasting principle. In the first step, the initial porous glass was filled with the carbon precursor, a mesophase pitch, which after the subsequent carbonization and dissolution of the glass matrix results in an inverse macroporous carbon replica. Afterwards, the carbon beads were filled with amorphous silica by a typical sol-gel-process. The next step can be divided into two phases. The silica gel phase was first “structured” inside the macropores of the inverse carbon replica by converting it into an ordered mesoporous phase via pseudomorphic transformation. This process demanded alkaline conditions and a surfactant, that finally converts the silica into hierarchically structured beads with the dimension and the pores of the initial glass and MCM-41 pores inside the walls. The final step comprised the template removal via calcination. The obtained materials were characterized by mercury intrusion, nitrogen adsorption, scanning electron microscopy, x-ray powder diffraction and particle size analysis. In comparison to the previously reported approaches, the new method allows a higher flexibility in the texture properties of the resulting hierarchically structured materials including a variable ratio between ordered mesopores and additional macropores by parallel control of the total porosity and wall thickness in the starting porous glass.
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  • 79
    Publication Date: 2014-02-01
    Description: New periodic mesoporous organosilicas were synthesized using [bis(triethoxysilyl)vinyl]aniline (BTEVA) and [bis(triethoxysilyl)vinyl]benzene (BTEVB) as precursors and by functionalizing the BTEVA PMO with aminopropyl groups. All PMO materials showed a high degree of hexagonal order in the respective P-XRDs as well as high surface areas with narrow pore size distributions. The PMOs together with activated carbon were investigated with regards to their hexanal adsorption capacity in a gravimetric apparatus with an attached GC-MS. For the amine PMOs two different regions during adsorption were found. In the first region loadings in the range of 30 wt% were reached by a fast adsorption process. In the second region the loading reached 50 wt% but with slower kinetics. In desorption experiments up to 150 °C the loading decreased from 50 wt% to 30 wt%, where an equilibrium state was observed. With GC-MS and NMR the first region could be assigned to a chemisorption process, where the hexanal forms an imine group with the amine function in a Schiff base reaction. The subsequent second region can be assigned to weaker and thus reversible physisorption. The total capacity (first and second region) is substantially higher for the amine PMOs than for the activated carbon. Due to the chemical bonding in the chemisorption process, the desorption behavior is completely different: compared to the activated carbon the bonding of hexanal is much stronger for the amine PMOs.
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  • 80
    Publication Date: 2014-02-04
    Description: The cover picture shows a section of the crystal structure of the coordination polymer Cu 1.5 (H 3 N-(CH 2 ) 6 -NH 3 ) 0.5 [C 6 H 2 (COO) 4 ]·5H 2 O( 1 ), which features channel-like voids accommodating hexane-1,6-diammonium cations that compensate for the negative charge of the three-dimensional framework. A space-filling view of the framework is inserted. The compound can be dehydrated to a trihydrate and rehydrated to the starting composition retaining the crystal structure. Cu 2 (H 3 N-(CH 2 ) 6 -NH 3 ) 0.5 (OH)[C 6 H 2 (COO) 4 ]·3H 2 O ( 2 ) has a similar framework structure with channels of different dimensions accommodating hexane-1,6-diammonium cations as well. The different compounds have been obtained from aqueous solution by employing the same method, however, at different temperatures. More details are discussed in the article by R. Köferstein and C. Robl on page 310ff.
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  • 81
    Publication Date: 2014-02-05
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  • 82
    Publication Date: 2014-02-05
    Description: Groundwater modeling has emerged as a powerful tool to develop a sustainable management plan for efficient groundwater utilization and protection of this vital resource. This study deals with the development of five hybrid artificial neural network (ANN) models and their critical assessment for simulating spatio-temporal fluctuations of groundwater in an alluvial aquifer system. Unlike past studies, in this study, all the relevant input variables having significant influence on groundwater have been considered and the hybrid ANN technique (ANN-cum-Genetic Algorithm) has been used to simulate groundwater levels at 17 sites over the study area. The parameters of the ANN models were optimized using Genetic Algorithm (GA) optimization technique. The predictive ability of the five hybrid ANN models developed for each of the 17 sites was evaluated using six goodness-of-fit criteria and graphical indicators, together with adequate uncertainty analyses. The analysis of the results of this study revealed that the MLP-LM model is the most efficient in predicting monthly groundwater levels at almost all the 17 sites, while the RBF model is the least efficient. The GA technique was found to be superior to the commonly used trial-and-error method for determining optimal ANN architecture and internal parameters. Of the goodness-of-fit statistics used in this study, only RMSE, r 2 and NSE were found to be more powerful and useful in assessing the performance of the ANN models. It can be concluded that the hybrid ANN modeling approach can be effectively used for predicting spaio-temporal fluctuations of groundwater at basin or sub-basin scales. This article is protected by copyright. All rights reserved.
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  • 83
    Publication Date: 2014-02-24
    Description: Phosphorus (P) loss from agricultural watersheds has long been a critical water quality problem, the control of which has been the focus of considerable research and investment. Preventing P loss depends on accurately representing the hydrological and chemical processes governing P mobilization and transport. The Soil and Water Assessment Tool (SWAT) is a watershed model commonly used to predict runoff and non-point source pollution transport. SWAT simulates runoff employing either the curve number ( CN ) or Green and Ampt methods, both assume infiltration excess runoff, although shallow soils underlain by a restricting layer commonly generate saturation excess runoff from variable source areas (VSA). In this study, we compared traditional SWAT to a re-conceptualized version, SWAT-VSA, which represents VSA hydrology, in a complex agricultural watershed in east central Pennsylvania. The objectives of this research were to provide further evidence of SWAT-VSA's integrated and distributed predictive capabilities against measured surface runoff and stream P loads and to highlight the model's ability to drive sub-field management of P. Thus, we relied on a detailed field management database to parameterize the models. SWAT and SWAT-VSA predicted discharge similarly well (daily Nash-Sutcliffe Efficiencies of 0.61 and 0.66, respectively), but SWAT-VSA outperformed SWAT in predicting P export from the watershed. SWAT estimated lower P loss (0.0 - 0.25 kg ha -1 ) from agricultural fields than SWAT-VSA (0.0 - 1.0+ kg ha -1 ), which also identified critical source areas - those areas generating large runoff and P losses at the sub field level. These results support the use of SWAT-VSA in predicting watershed-scale P losses and identifying critical source areas of P loss in landscapes with VSA hydrology. This article is protected by copyright. All rights reserved.
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  • 84
    Publication Date: 2014-02-24
    Description: This article presents results of mercury in surface waters from Hunza River basin, Northern Areas, Pakistan. Small-scale gold mining activities along Hunza and Gilgit rivers are long known to be discharging mercury in the amalgamation and roasting processes. Previous studies reported high mercury concentrations in soils close to mining operations as well as serious health problems for miners. However, none of the studies have focused on the level of contamination in aqueous environments. This is the first study on the investigation of source and fate of sediment and river-borne mercury in Hunza River. Samples collected near panning sites showed higher mercury concentrations than critical levels established by the U.S. Environmental Protection Agency. The observed dissolved mercury concentrations ranged from 5.10 to 25.25 ng/L, whereas particulate-bound mercury ranged from 4.85 to 154.62 ng/L. Particulate phase mercury corresponded to more than 75% of the total observed mercury concentrations for all of the sampled rivers. Thus, suspended sediments represented the major pathway of the riverine mercury transport. A mass balance calculation suggested a 48.6 g/km 2 of annual mercury flux into Hunza River basin. The samples collected from the most affected river, Shimsal River, averaged to have 108 ng/L total mercury concentration. This number was close to the average soil mercury data from PMDC (2001) of 151 ng/L. The dominant source of contamination was shown to be the leaching of large quantities of mercury from the Hg-rich sediment and flood plain soil into the rivers rather than the direct release from mining activities. Significant decrease in both dissolved and particulate-bound mercury concentration downstream of Attabad Lake suggested that mercury is being accumulated or consumed in the lake. Although minimization or elimination of mercury loses from mining process seems important for the wellbeing of the miners, preventing remobilization of accumulated mercury is equally important in mercury control in this region. This article is protected by copyright. All rights reserved.
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  • 85
    Publication Date: 2014-02-24
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  • 86
    Publication Date: 2014-02-26
    Description: Perovskite-type LaVO 2.78 N 0.10 powder was synthesized by thermal ammonolysis of the oxide precursor LaVO 4 . By X-ray, neutron, and electron diffraction an orthorhombic crystal structure with space group Pnma was identified. XANES spectra showed that the oxidation state of vanadium changes from 5+ in LaVO 4 to approximately 3+ in LaVO 2.78 N 0.10 . The temperature dependence of the electrical conductivity revealed an Arrhenius-type behavior with an activation energy of 0.103 eV in the temperature range of 119–302 K indicating that the conduction process is thermally activated band transition. Based on the positive Seebeck coefficient, holes were identified as the dominant charge carriers in the temperature range of 100–302 K. Both the Seebeck coefficient and the thermal conductivity showed an anomaly at 138 K, which is attributed to the Néel temperature for antiferromagnetic ordering according to magnetic susceptibility measurements.
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  • 87
    Publication Date: 2014-02-27
    Description: The study of the multiannual thermal dynamics of Lake Iseo, a deep lake in the Italian pre-alpine area, is presented. Interflow was found to be the dominant river entrance mode, suggesting future susceptibility of the lake thermal structure to the overall effects of climate change expected in the upstream alpine watershed. A lake model employed the results of a long-term hydrologic model to simulate the effects of a climate change scenario on the lake's thermal evolution for the period 2012-2050. The model predicts an overall average increase in the lake water temperature of 0.012 °C/year and a reinforced Schmidt thermal stability of the water column in winter up to 800 Jm -2 . Both these effects may further prevent the deep circulation process, which is vital for the oxygenation of deep water. This article is protected by copyright. All rights reserved.
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  • 88
    Publication Date: 2014-02-27
    Description: Changes in water temperature can have important consequences for aquatic ecosystems, with some species being sensitive even to small shifts in temperature during some or all of their lifecycle. While many studies report increasing regional and global air temperatures, evidence of changes in river water temperature has thus far been site-specific and often from sites heavily influenced by human activities that themselves could lead to warming. Here we present a tiered assessment of changing river water temperature, covering England and Wales with data from 2,773 locations. We use novel statistical approaches to detect trends in irregularly sampled spot measurements taken between 1990 and 2006. During this 17 year period, on average, mean water temperature increased by 0.03 °C per year (± 0.002 °C) and positive changes in water temperature were observed at 2,385 (86%) sites. Examination of catchments, where there has been limited human influence on hydrological response, shows that changes in river flow have had little influence on these water temperature trends. In the absence of other systematic influences on water temperature, it is inferred that anthropogenically-driven climate change is driving some of this trend in water temperature. This article is protected by copyright. All rights reserved.
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  • 89
    Publication Date: 2014-02-27
    Description: Parametric method of flood frequency analysis (FFA) involves fitting of a probability distribution to the observed flood data at the site of interest. When record length at a given site is relatively longer and flood data exhibits skewness, a distribution having more than three parameters is often used in FFA such as Log Pearson Type 3 distribution. This paper examines the suitability of a 5-paramter Wakeby distribution for the annual maximum flood data in eastern Australia. We adopt a Monte Carlo simulation technique to select an appropriate plotting position formula and to derive a probability plot correlation coefficient (PPCC) test statistic for Wakeby distribution. The Weibull plotting position formula has been found to be the most appropriate for the Wakeby distribution. Regression equations for the PPCC tests statistics associated with the Wakeby distribution for different levels of significance have been derived. Furthermore, a power study to estimate the rejection rate associated with the derived PPCC test statistics has been undertaken. Finally, an application using annual maximum flood series data from 91 catchments in eastern Australia has been presented. Results show that the developed regression equations can be used with a high degree of confidence to test whether the Wakeby distribution fits the annual maximum flood series data at a given station. The methodology developed in this paper can be adapted to other probability distributions and to other study areas. This article is protected by copyright. All rights reserved.
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  • 90
    Publication Date: 2014-02-28
    Description: From the reaction of 2,3-dihydro-1,3,4,5-tetraisopropylimidazol-2-ylidene ( 4 ) (Carb) with iodine a compound of composition Carb · I 2 was obtained. Crystals were isolated from dichloromethane and the X-ray structure analysis revealed the presence of both Carb-I 2 ( 6 ) and [Carb–I 3 –Carb]I ( 7 ) moieties including disordered solvent according to the composition of {[Carb–I 3 –Carb]I · 2Carb-I 2 · 2CH 2 Cl 2 } ( 5 ).
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  • 91
    Publication Date: 2014-02-28
    Description: The isovalent substitution of strontium for barium in CaBaCo 4 O 7 destroys the ferrimagnetism in a striking way though it keeps the same orthorhombic crystal symmetry and cobalt valence as the parent phase. The gradual weakening of ferrimagnetism in CaBa 1– x Sr x Co 4 O 7 (0 〈 x ≤ 0.10) leaves place to magnetic frustration together with antiferrimagnetism. The phase separation that appears, due to the strong competition between long range ferrimagnetic ordering and magnetic frustration, is interpreted by local melting of charge ordering. The latter originates from local structural distortion around the Ba(Sr) site. The dynamic scaling theory, τ = τ 0 ( T f / T g – 1) – zv , suggests that the frustrated magnetic phase is cluster glass in nature with strongly interacting spins. This finding reveals that the orthorhombic symmetry in CaBaCo 4 O 7 is not a sufficient condition to manifest ferrimagnetic ordering.
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  • 92
    Publication Date: 2014-02-28
    Description: Three iron(II)-2-aminophenolate complexes [(L 1 )Fe II (4- t Bu-HAP)] ( 2 ), [(L 1 )Fe II (HAP)] ( 3 ), and [(L 1 )Fe II (4-NO 2 -HAP)] ( 4 ) [L 1 = tris(2-pyridylthio)methanido anion, 4- t Bu-HAP = 2-amino-4- tert -butylphenolate, HAP = 2-aminophenolate, and 4-NO 2 -HAP = 2-amino-4-nitrophenolate] were isolated and characterized to study their reactivity towards dioxygen. The complexes were synthesized from the iron(II)-acetonitrile complex [(L 1 )Fe II (CH 3 CN) 2 ] + ( 1 ) using substituted 2-aminophenolates. Single crystal structure of 4 reveals that the mononuclear central iron atom is coordinated by a tetradentate N 3 C ligand and a monoanionic bidentate 4-NO 2 -HAP giving rise to a distorted octahedral coordination arrangement. The six-coordinate iron(II) complexes, 2 and 4 , react with dioxygen to form the corresponding iron(III)-2-iminobenzosemiquinonato radical complexes, [(L 1 )Fe III (4- t Bu-ISQ)] + ( 2 Ox ) and [(L 1 )Fe III (4-NO 2 -ISQ)] ( 4 Ox ). Complex 3 , on the other hand, undergoes an oxidative C–S bond forming reaction between HAP and pyridine-2-thiolate (PyS) to afford [(L 1 )Fe III (ISQ′)] + ( 3 Ox ) [ISQ′ = 5-(2-thiopyridyl)-2-iminobenzosemiquinonato radical]. In each case, the reaction proceeds via a low-spin iron(III)-2-amidophenolate intermediate species. All the complexes exhibit strong iron–carbon bonding interaction. The bond parameters of the oxidized complexes, obtained from the single crystal structures, clearly establish the presence of ligand-centered radical.
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  • 93
    Publication Date: 2014-02-28
    Description: Two coordination compounds of the ligand tetrazolate-5-carboxylate (tzc) with zinc(II), namely, [Zn 2 (tzc) 2 (bpp)] ( 1 ) and [Zn 2 (tzc) 2 (bpea)] ( 2 ) [bpp = 1,3-bis(4-pyridyl)propane, bpea = 1,2-bis(4-pyridyl)ethane] were synthesized by hydrothermal methods involving the in situ generation of the ligand from sodium ethyl tetrazolate-5-carboxylate. Both compounds 1 and 2 exhibit a three-dimensional structure with 3,4-connected self-penetrating net topology in which two-dimensional Zn II -tzc layers are interlinked by the bpp or bpea spacers, with the tzc ligand being in the μ 3 -N1,O1:N4,O2:N2 coordination mode. The luminescence properties of 1 and 2 were also investigated.
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  • 94
    Publication Date: 2014-02-28
    Description: Soft metal-organic grafting of periodic mesoporous silica (PMS) has recently been demonstrated to give gadolinium-loaded nanostructured hybrid materials with interesting 1 H relaxometric properties. Here, the sterically demanding alkoxide and aryloxide complexes, [ Ln (OCH 2 CMe 3 ) 3 ] 4 and Ln (OC 6 H 3 t Bu 2 -2,6) 3 ( Ln = La, Gd), respectively, were grafted onto PMS materials MCM-41, SBA-15, and SBA-1. Support materials with distinct topology and pore diameters were utilized in order to direct the metal precursors towards the PMSs internal or external surfaces. All hybrid materials were examined by N 2 physisorption, Diffuse Reflectance Infrared Fourier Transform (DRIFT) and solid-state NMR spectroscopy, as well as elemental analysis. The characterization data demonstrated the successful silica attachment of the alk(aryl)oxide complexes via the surface silanol groups. Careful design of the hybrid materials based on findings in our previous studies resulted in Gd III loaded materials with particularly high 1 H longitudinal relaxivities at high magnetic field strength (400 MHz). The highest relaxivity of r 1 = 31 mM –1 s –1 was found for material [Gd(OCH 2 CMe 3 ) 3 ] 4 @SBA-1 showing no intrapore metal loading. This value is amongst the highest relaxivities reported for Gd III loaded mesoporous nanomaterials so far at such high field strength. The metal loading, localization of metal centers (directed by the topology of the PMS), and the particular properties of the metal-organic precursor are factors found to influence r 1 .
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  • 95
    Publication Date: 2014-03-01
    Description: A need for more accurate flood inundation maps has recently arisen due to the increasing frequency and extremity of flood events. The accuracy of flood inundation maps is determined by the uncertainty propagated from all of the variables involved in the overall process of flood inundation modeling. Despite our advanced understanding of flood progression, it is impossible to eliminate the uncertainty due to the constraints involving cost, time, knowledge, and technology. Nevertheless, uncertainty analysis in flood inundation mapping can provide useful information for flood-risk management. The twin objectives of this study were firstly to estimate the propagated uncertainty rates of key variables in flood inundation mapping by using the first-order approximation (FOA) method and secondly to evaluate the relative sensitivities of the model variables by using the Hornberger–Spear–Young (HSY) method. Monte Carlo simulations using the Hydrologic Engineering Center's River Analysis System (HEC–RAS) and triangle-based interpolation were performed to investigate the uncertainty arising from discharge, topography, and Manning's n in the East Fork of the White River near Seymour, Indiana, and in Strouds Creek in Orange County, North Carolina. We found that the uncertainty of a single variable is propagated differently to the flood inundation area depending on the effects of other variables in the overall process. The uncertainty was linearly/nonlinearly propagated corresponding to valley shapes of the reaches. In addition, the HSY sensitivity analysis revealed the topography of Seymour reach and the discharge of Strouds Creek to be major contributors to the change of flood inundation area. This article is protected by copyright. All rights reserved.
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  • 96
    Publication Date: 2014-02-09
    Description: This paper provides evidence of the recovery of a small, moorland catchment to a severe drought, the most extreme on record in the UK. We present a detailed water quality time series for the post-drought recovery period, from the first significant storm event at the end of the drought through three very wet months during which time the catchment fully wetted up. High-frequency observations were obtained using pump water samplers, at 15-minute intervals for storm events and 2-hourly at other times. There are significant shifts in discharge-concentration response as the catchment wets up; initial behaviour is very different to later storms. Extreme drought may become more common in a warmer world, so it is increasingly important to understand water quality response during and after such episodes, if their impact on water resources and in-stream ecology is to be better anticipated. This article is protected by copyright. All rights reserved.
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    Electronic ISSN: 1099-1085
    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 97
    Publication Date: 2014-02-09
    Description: Based on interactions between landscape characteristics and precipitation inputs, watersheds respond differently to different climatic inputs. The objective of this study was to quantitatively characterize controls on runoff generation from two first order micro-catchments in the Amazonia region. The study investigated the variation of hydrological signatures at micro-catchment scale, and relates these to landscape and land cover differences and weather descriptors that control the observed responses. One catchment is a pasture cleared of all natural vegetation in the early 1980's and the second catchment is a primary tropical forest with minor signs of disturbance. Water levels and meteorological variables were continuously monitored during the study period (December 2012-May 2013). Water level measurements were converted to discharge, evapotranspiration was quantified using Penman-Monteith equation and catchment pedohydrological properties were also determined. During the study period, mean total rainfall was 1200 mm and direct runoff ratios were 0.29 and 0.12 for the pasture and forest catchments, respectively. Base flow index was relatively higher in the forest catchment (0.76) compared to pasture catchment (0.63). Results from this study showed that the pasture catchment had a 35% higher mean stream flow. Analysis of selected individual rainstorm events also showed peak discharges were attained much faster in the pasture catchment compared to the forest catchment. At both sites, rainfall-runoff responses were highly dependent on surface and subsurface flow generation. Overland flow was observed in the pasture site during intense rainfall events. The pasture catchment exhibited higher event water contribution than the forest catchment. Findings from this research suggest that shallow lateral pathways play a significant role in controlling runoff generation processes in the forest catchment, while infiltration excess runoff generation processes dominate in the pasture catchment. The findings in this study suggest that the conversion of forest to pasture may lead to important changes in runoff generation processes and water storage in these head water catchments. This article is protected by copyright. All rights reserved.
    Print ISSN: 0885-6087
    Electronic ISSN: 1099-1085
    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 98
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    Wiley
    Publication Date: 2014-02-12
    Print ISSN: 0885-6087
    Electronic ISSN: 1099-1085
    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 99
    Publication Date: 2014-02-13
    Description: To investigate the expressional alternation of microRNAs (miRNA) during the malignant transformation and development of human glioma, we measured miRNA expression profile as well as mRNA expression profile in normal human neural stem cells (hNSCs) and human glioma stem cells (hGSCs). We found 116 miRNA up-regulated and 62 miRNA down-regulated in GSCs. On the other hand, we identified 1,372 mRNA down-regulated, and 1,501 mRNA up-regulated in GSCs compared to those in NSCs. We then analyzed the pathways and the predicted target genes of the miRNAs which differ significantly in expression between GSCs and NSCs using the statistical enrichment methods. These target mRNAs are involved in many cancer-related signaling pathways, such as cell cycle, axon guidance, glioma development, adhesion junction, MAPK and Wnt signaling. Furthermore, we obtained the differently expressed miRNA-target relationships according to the θ value which is used to calculate the regulation extent of miRNA-target and using the databases of miRanda, Targetscans and Pictar. Among the top 10 miRNA-target relationships, hsa-miR-198 and its potential targeted gene DCX and NNAT were selected for validation, and NNAT was found to be the direct target of miR-198. Finally, the functional roles of miR-155–5p and miR-124–3p whose expressions altered significantly between GSCs and NSCs were addressed. Our results provide new clues for the potential mechanisms involved in the origin and development of glioma. Clinically, the altered miRNAs may serve as potential targets and diagnostic tools for novel therapeutic strategies of glioblastoma. J. Cell. Biochem. © 2013 Wiley Periodicals, Inc.
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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  • 100
    Publication Date: 2014-02-13
    Description: Satellite cell migration is critical for skeletal muscle growth and regeneration. Controlled cell migration is dependent on the formation of mature focal adhesions between the cell and the underlying extracellular matrix (ECM). These cell-ECM interactions trigger the activation of signalling events such as the Rho/ROCK pathway. We have previously identified a specific role for ROCK-2 during myoblast migration. In this study we report that ROCK inhibition with Y-27632 increases C2C12 myoblast velocity, but at the expense of directional migration. In response to Y-27632 an increased number of smaller focal adhesions were distributed across adhesion sites that in turn were clearly larger than sites in untreated cells, suggesting a reduction in focal adhesion maturation. We also confirm ROCK-2 localization to the focal adhesion sites in migrating myoblasts and demonstrate a change in the distribution of these ROCK-2 containing adhesions in response to Y-27632. Taken together, our observations provide further proof that ROCK-2 regulates directional myoblast migration through focal adhesion formation and maturation. J. Cell. Biochem. © 2014 Wiley Periodicals, Inc.
    Electronic ISSN: 0091-7419
    Topics: Biology , Chemistry and Pharmacology , Medicine
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