984 resultados para Fractions.
Resumo:
We study the dynamical properties of the homogeneous shear flow of inelastic dumbbells in two dimensions as a first step towards examining the effect of shape on the properties of flowing granular materials. The dumbbells are modelled as smooth fused disks characterized by the ratio of the distance between centres (L) and the disk diameter (D), with an aspect ratio (L/D) varying between 0 and 1 in our simulations. Area fractions studied are in the range 0.1-0.7, while coefficients of normal restitution (e(n)) from 0.99 to 0.7 are considered. The simulations use a modified form of the event-driven methodology for circular disks. The average orientation is characterized by an order parameter S, which varies between 0 (for a perfectly disordered fluid) and 1 (for a fluid with the axes of all dumbbells in the same direction). We investigate power-law fits of S as a function of (L D) and (1 - e(n)(2)) There is a gradual increase in ordering as the area fraction is increased, as the aspect ratio is increased or as the coefficient of restitution is decreased. The order parameter has a maximum value of about 0.5 for the highest area fraction and lowest coefficient of restitution considered here. The mean energy of the velocity fluctuations in the flow direction is higher than that in the gradient direction and the rotational energy, though the difference decreases as the area fraction increases, due to the efficient collisional transfer of energy between the three directions. The distributions of the translational and rotational velocities are Gaussian to a very good approximation. The pressure is found to be remarkably independent of the coefficient of restitution. The pressure and dissipation rate show relatively little variation when scaled by the collision frequency for all the area fractions studied here, indicating that the collision frequency determines the momentum transport and energy dissipation, even at the lowest area fractions studied here. The mean angular velocity of the particles is equal to half the vorticity at low area fractions, but the magnitude systematically decreases to less than half the vorticity as the area fraction is increased, even though the stress tensor is symmetric.
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Two new cyclohexadepsipeptides have been isolated from the fungus Isaria. Fungal growth in solid media yielded hyphal strands from which peptide fractions were readily isolable by organic-solvent extraction. Two novel cyclodepsipeptides, isaridin A and isaridin B, have been isolated by reverse-phase HPLC, and characterized by ESI-MS and 1H-NMR. Single crystals of both peptides have been obtained, and their 3D structures were elucidated by X-ray diffraction. The isaridins contain several unusual amino acid residues. The sequences are cyclo(β-Gly-HyLeu-Pro-Phe-NMeVal-NMePhe) and cyclo(β-Gly-HyLeu-β-MePro-Phe-NMeVal-NMePhe), where NMeVal is N-methylvaline, NMePhe N-methylphenylalanine, and HyLeu hydroxyleucine (=2-hydroxy-4-methylpentanoic acid). The two peptides differ from one another at residue 3, isaridin A having an (S)-proline at this position, while β-methyl-(S)-proline (=(2S,3S)-2,3,4,5-tetrahydro-3-methyl-1H-pyrrole-2-carboxylic acid) is found in isaridin B. The solid-state conformations of both cyclic depsipeptides are characterized by the presence of two cis peptide bonds at HyLeu(2)-Pro(3)/HyLeu(2)-β-MePro(3) and NMeVal(5)-NMePhe(6), respectively. In isaridin A, a strong intramolecular H-bond is observed between Phe(4)CO⋅⋅⋅HNβ-Gly(1), and a similar, but weaker, interaction is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4). In contrast, in isaridin B, only a single intramolecular H-bond is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4
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Present in situ chemical treatment technologies for mitigation of petroleum hydrocarbon contamination are in the developmental stage or being tested. To devise efficient strategies for restricting the movement of petroleum hydrocarbon (PHC) molecules in the contaminated soil, it is proposed to utilize the sorption–interaction relationships between the petroleum contaminants and the soil substrate. The basic questions addressed in this paper are as follows (i) What are the prominent chemical constituents of the various petroleum fractions that interact with the soil substrate? (ii) What are the functional groups of a soil that interact with the contaminants? (iii) What are the bonding mechanisms possible between the soil functional groups and the PHC contaminants? (iv) What are the consequent changes brought about the soil physical properties on interaction with PHC's? (v) What are the factors influencing the interactions between PHC molecules and clay particles of the soil substrate? (vi) What is the possibility of improving the soil's attenuation ability for PHC's? The development of answers to the basic questions reveal that petroleum hydrocarbons comprise a mixture of nonpolar alkanes and aromatic and polycyclic hydrocarbons, that have limited solubility in water. The bonding mechanism between the nonpolar PHC's and the clay surface is by way of van der Waals attraction. The adsorption of the nonpolar hydrocarbons by the clay surface occurs only when their (i.e., the hydrocarbon molecules) solubility in water is exceeded and the hydrocarbons exist in the micellar form. Dilute solutions of hydrocarbons in water, i.e., concentrations of hydrocarbons at or below the solubility limit, have no effect on the hydraulic conductivity of clay soils. Permeation with pure hydrocarbons invariably influences the clay hydraulic conductivity. To improve the attenuation ability of soils towards PHC's, it is proposed to coat the soil surface with "ultra" heavy organic polymers. Adsorption of organic polymers by the clay surface may change the surface properties of the soil from highly hydrophilic (having affinity for water molecules) to organophilic (having affinity for organic molecules). The organic polymers attached to the clay surface are expected to attenuate the PHC molecules by van der Waals attraction, by hydrogen bonding, and also by adsorption into interlayer space in the case of soils containing swelling clays.
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Ten new cyclic hexadepsipeptides, six isariins and four isaridins, from the fungus Isaria have been identified and characterized by high-performance liquid chromatography, coupled to tandem electrospray ionization mass spectrometry (LC-ESIMS/MS). The isariins possess a beta-hydroxy acid residue and five alpha-amino acids, while isaridins contain a beta-amino acid, an alpha-hydroxy acid, and four alpha-amino acids. One- and two-dimensional NMR spectroscopy confirmed the chemical identity of some of the isariin fractions. Mass spectral fragmentation patterns of [M + H](+) ions reveal clear diagnostic fragment ions for the isariins and isaridins. Previously described cyclic depsipeptides, isarfelins from Isaria felina (Guo, Y. X.; Liu, Q. H.; Ng, T. B.; Wang H. X. Peptides 2005, 26, 2384), are now reassigned as members of the isaridin family. Examination of isaridin sequences revealed significant similarities with cyclic hexadepsipeptides such as destruxins and roseotoxins. The structure of an isariin (isariin A) investigated by NMR spectroscopy indicated the presence of a hybrid alpha beta C-11 turn, formed by the beta-hydroxy acid and glycine residues and a (D)Leu-(L)Ala type II' beta-turn. Additionally, the inhibitory effect of isariins and an isaridin on the intra-erythrocytic growth of Plasmodium falciparum is presented.
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The influence of the pedogenic and climatic contexts on the formation and preservation of pedogenic carbonates in a climosequence in the Western Ghats (Karnataka Plateau, South West India) has been studied. Along the climosequence, the current mean annual rainfall (MAR) varies within a 80 km transect from 6000 mm at the edge of the Plateau to 500 mm inland. Pedogenic carbonates occur in the MAR range of 500-1200 mm. In the semi-arid zone (MAR: 500-900 mm), carbonates occur (i) as rhick hardpan calcretes on pediment slopes and (ii) as nodular horizons in polygenic black soils (i.e. vertisols). In the sub-humid zone (MAR: 900-1500 mm), pedogenic carbonates are disseminated in the black soil matrices either as loose, irregular and friable nodules of millimetric size or as indurated botryoidal nodules of centimetric to pluricentimetric size. They also occur at the top layers of the saprolite either as disseminated pluricentimetric indurated nodules or carbonate-cemented lumps of centimetric to decimetric size. Chemical and isotopic (Sr-87/Sr-86) compositions of the carbonate fraction were determined after leaching with 0.25 N HCl. The corresponding residual fractions containing both primary minerals and authigenic clays were digested separately and analyzed. The trend defined by the Sr-87/Sr-86 signatures of both labile carbonate fractions and corresponding residual fractions indicates that a part of the labile carbonate fraction is genetically linked to the local soil composition. Considering the residual fraction of each sample as the most likely lithogenic source of Ca in carbonates, it is estimated that from 24% to 82% (55% on average) of Ca is derived from local bedrock weathering, leading to a consumption of an equivalent proportion of atmospheric CO2. These values indicate that climatic conditions were humid enough to allow silicate weathering: MAR at the time of carbonate formation likely ranged from 400 to 700 mm, which is 2- to 3-fold less than the current MAR at these locations. The Sr, U and Mg contents and the (U-234/U-238) activity ratio in the labile carbonate fraction help to understand the conditions of carbonate formation. The relatively high concentrations of Sr, U and Mg in black soil carbonates may indicate fast growth and accumulation compared to carbonates in saprolite, possibly due to a better confinement of the pore waters which is supported by their high (U-234/U-238) signatures, and/or to higher content of dissolved carbonates in the pore waters. The occurrence of Ce, Mn and Fe oxides in the cracks of carbonate reflects the existence of relatively humid periods after carbonate formation. The carbonate ages determined by the U-Th method range from 1.33 +/- 0.84 kyr to 7.5 +/- 2.7 kyr and to a cluster of five ages around 20 kyr, i.e. the Last Glacial Maximum period. The young occurrences are only located in the black soils, which therefore constitute sensitive environments for trapping and retaining atmospheric CO2 even on short time scales. The maximum age of carbonates depends on their location in the climatic gradient: from about 20 kyr for centimetric nodules at Mule Hole (MAR = 1100 mm/yr) to 200 kyr for the calcrete at Gundlupet (MAR = 700 mm/yr, Durand et al., 2007). The intensity of rainfall during wet periods would indeed control the lifetime of pedogenic carbonates and thus the duration of inorganic carbon storage in soils. (C) 2010 Elsevier Ltd. All rights reserved.
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The effect of thiocarbamates (S-ethyldipropylthiocarbamate and diallate), substituted ureas (monuron and diuron), and uracils (bromacil and terbacil) on lipid metabolism in groundnut (Arachis hypogaea) leaves was investigated under nonphotosynthetic conditions. The uptake of [1-14C]acetate by leaf disks was inhibited by the thiocarbamates and marginally by the substituted ureas, but not by the uracil herbicides. The uptake of [methyl-14C]choline was inhibited to a lesser extent by thiocarbamates, while the other herbicides showed a slight stimulation. The thiocarbamates almost completely inhibited uptake of [32P]orthophosphate at 1.0 mM concentration, while diuron and terbacil showed significant inhibition. [1-14C]Acetate incorporation into lipids was inhibited only by diallate. [methyl-14C]Choline incorporation into the choline phosphoglycerides was inhibited by diallate, diuron, and bromacil. The incorporation of [32P]orthophosphate into phospholipids was substantially inhibited (over 90% at 1.0 mM) by the thiocarbamates, but not by the other herbicides. [35S]Sulfate incorporation into sulfoquinovosyl diglycerides was markedly inhibited only by the thiocarbamates. Fatty acid synthesis by isolated chloroplasts was inhibited 40–85% by thiocarbamates, substituted ureas, and bromacil, but not by terbacil. The inhibitory effect of the urea derivatives was reversible, but that of thiocarbamates was irreversible. sn-Glycerol-3-phosphate acyltransferase(s) of the chloroplast and microsomal fractions were profoundly inhibited by thiocarbamates, but not by the other two groups of herbicides. Phosphatidic acid phosphatase was insensitive to all the herbicides tested.
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We reported the presence of a 80 kDa polypeptide in porcine follicular fluid that inhibited the binding of 125I-radiolabelled hFSH as well as hCG to the rat ovarian gonadotropin receptors. In the present study, the biological activity of the receptor binding inhibitor is determined using an in vitro bioassay procedure. Granulosa cells isolated from PMSG primed immature rat ovaries respond to exogenously added gonadotropins in terms of progesterone production. Addition of fractions containing the gonadotropin receptor binding inhibitory activity inhibited progesterone production stimulated by the gonadotropins in a dose-dependent fashion. The receptor binding inhibitory activity was also capable of inhibiting progesterone production stimulated by PMSG, which has both FSH- and LH-like activities in rats. In contrast, progesterone production stimulated by dbcAMP was not inhibited by the receptor binding inhibitor. This result indicates that the site of action of the inhibitor is proximal to the formation of the cAMP. The above observations point out to a possible role for this factor in modulating gonadotropin activity at the ovarian level.
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The major heat-stable shrimp allergen (designated as Sa-II), capable of provoking IgE-mediated immediate type hypersensitivity reactions after the ingestion of cooked shrimp, has been shown to be a 34-kDa heat- stable protein containing 300 amino acid residues. Here, we report that a comparison of amino acid sequences of different peptides generated by proteolysis of Sa-II revealed an 86% homology with tropomyosin from Drosophila melanogaster, suggesting that Sa-II could be the shrimp muscle protein tropomyosin. To establish that Sa-II is indeed tropomyosin, the latter was isolated from uncooked shrimp (Penaeus indicus) and its physicochemical and immunochemical properties were compared with those of Sa-II. Both tropomyosin and Sa-II had the same molecular mass and focused in the isoelectric pH range of 4.8 to 5.4. In the presence of 6 M urea, the mobility of both Sa-II and shrimp tropomyosin shifted to give an apparent molecular mass of 50 kDa, which is a characteristic property of tropomyosins. Shrimp tropomyosin bound to specific IgE antibodies in the sera of shrimp-sensitive patients as assessed by competitive ELISA inhibition and Western blot analysis. Tryptic maps of both Sa-II and tropomyosin as obtained by reverse phase HPLC were superimposable. Dot-blot and competitive ELISA inhibition using sera of shrimp-sensitive patients revealed that antigenic as well as allergenic activities were associated with two peptide fractions. These IgE-binding tryptic peptides were purified and sequenced. Mouse anti-anti-idiotypic antibodies raised against Sa-II specific human idiotypic antibodies recognized not only tropomyosin but also the two allergenic peptides, thus suggesting that these peptides represent the major IgE binding epitopes of tropomyosin. A comparison of the amino acid sequence of shrimp tropomyosin in the region of IgE binding epitopes (residues 50-66 and 153-161) with the corresponding regions of tropomyosins from different vertebrates confirmed lack of allergenic cross-reactivity between tropomyosins from phylogenetically distinct species.
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Fast protein liquid chromatography (FPLC) system using Mono Q (HR 5/5) anion-exchange column chromatography followed by highly cross-linked urea-polyacrylamide gel electrophoresis (urea-PAGE) was used for the purification of lysine-specific tRNA (tRNA(Lys)) from rat liver. Crude tRNA from rat liver was fractionated with a linear gradient of NaCl (0.3-0.8 M) in triethanolamine-HCl buffer, pH 4.5, and the activity of tRNA(Lys) was found to elute between 0.51 and 0.57 M NaCl. Using this concentration range of NaCl, tRNA(Lys) was refractionated on the same column with a shallow gradient, where a single peak of tRNA(Lys) activity was obtained. tRNA(Lys)-rich fractions recovered from the second run were electrophoretically separated on 16% polyacrylamide-7 M urea gel into one major band and three minor bands. The major band showed a specific activity of 997 pmols/A260 U for tRNALys with a 43-fold purification and approximately 17% recovery. The minor bands displayed negligible or no activity for lysine. tRNA(Lys) obtained by this method was found to be homogeneous by competitive aminoacylation. The advantages of FPLC followed by urea-PAGE in the purification of an amino acid-specific tRNA over conventional column chromatography are discussed.
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We propose a model for concentrated emulsions based on the speculation that a macroscopic shear strain does not produce an affine deformation in the randomly close-packed droplet structure. The model yields an anomalous contribution to the complex dynamic shear modulus that varies as the square root of frequency. We test this prediction using a novel light scattering technique to measure the dynamic shear modulus, and directly observe the predicted behavior over six decades of frequency and a wide range of volume fractions.
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We have carried out Brownian dynamics simulations of binary mixtures of charged colloidal suspensions of two different diameter particles with varying volume fractions phi and charged impurity concentrations n(i). For a given phi, the effective temperature is lowered in many steps by reducing n(i) to see how structure and dynamics evolve. The structural quantities studied are the partial and total pair distribution functions g(tau), the static structure factors, the time average g(<(tau)over bar>), and the Wendt-Abraham parameter. The dynamic quantity is the temporal evolution of the total meansquared displacement (MSD). All these parameters show that by lowering the effective temperature at phi = 0.2, liquid freezes into a body-centered-cubic crystal whereas at phi = 0.3, a glassy state is formed. The MSD at intermediate times shows significant subdiffusive behavior whose time span increases with a reduction in the effective temperature. The mean-squared displacements for the supercooled liquid with phi = 0.3 show staircase behavior indicating a strongly cooperative jump motion of the particles.
Resumo:
Purine nucleotide synthesis in Plasmodium falciparum takes place solely by the purine salvage pathway in which preformed purine base(s) are salvaged from the host and acted upon by a battery of enzymes to generate AMP and GMP. Inhibitors of this pathway have a potent effect on the in vitro growth of P. falciparum and are hence, implicated as promising leads for the development of new generation anti-malarials. Here, we describe the mechanism of inhibition of the intraerythrocytic growth of P. falciparum by the purine nucleoside precursor, 5-aminoimidazole-4-carboxamide ribonucleoside (AICAR). Our results show that AICAR toxicity is mediated through the erythrocyte in which AICAR is phosphorylated to its nucleotide, ZMP. Further, purine metabolite labeling of the parasitized erythrocytes by H-3]-hypoxanthine, in the presence of AICAR, showed a significant decrease in radioactive counts in adenylate fractions but not in guanylate fractions. The most dramatic effect on parasite growth was observed when erythrocytes pretreated with AICAR were used in culture. Pretreatment of erythrocytes with AICAR led to significant intracellular accumulation of ZMP and these erythrocytes were incapable of supporting parasite growth. These results implicate that in addition to the purine salvage pathway in P. falciparum, AICAR alters the metabolic status of the erythrocytes, which inhibits parasite growth. As AICAR and ZMP are metabolites in the human serum and erythrocytes, our studies reported here throw light on their possible role in disease susceptibility, and also suggests the possibility of AICAR being a potential prophylactic or chemotherapeutic anti-malarial compound. (C) 2011 Elsevier B.V. All rights reserved.
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A monotonic decrease in viscosity with increasing shear stress is a known rheological response to shear flow in complex fluids in general and for flocculated suspensions in particular. Here we demonstrate a discontinuous shear-thickening transition on varying shear stress where the viscosity jumps sharply by four to six orders of magnitude in flocculated suspensions of multiwalled carbon nanotubes (MWNT) at very low weight fractions (approximately 0.5%). Rheooptical observations reveal the shear-thickened state as a percolated structure of MWNT flocs spanning the system size. We present a dynamic phase diagram of the non-Brownian MWNT dispersions revealing a starting jammed state followed by shear-thinning and shear-thickened states. The present study further suggests that the shear-thickened state obtained as a function of shear stress is likely to be a generic feature of fractal clusters under flow, albeit under confinement. An understanding of the shear-thickening phenomena in confined geometries is pertinent for flow-controlled fabrication techniques in enhancing the mechanical strength and transport properties of thin films and wires of nanostructured composites as well as in lubrication issues.
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Silane (SiH4) was used as an n-type dopant in GaAs grown by low pressure metalorganic vapor phase epitaxy using trimethylgallium (TMGa) and arsine (AsH3) as source materials. The electron carrier concentrations and silicon (Si) incorporation efficiency are studied by using Hall effect, electrochemical capacitance voltage profiler and low temperature photoluminescence (LTPL) spectroscopy. The influence of growth parameters, such as SiH4 mole fraction, growth temperature, TMGa and AsH3 mole fractions on the Si incorporation efficiency have been studied. The electron concentration increases with increasing SIH4 mole fraction, growth temperature, and decreases with increasing TMGa and AsH3 mole fractions. The decrease in electron concentration with increasing TMGa can be explained by vacancy control model. The PL experiments were carried out as a function of electron concentration (10(17) - 1.5 x 10(18) cm(-3)). The PL main peak shifts to higher energy and the full width at half maximum (FWHM) increases with increasing electron concentrations. We have obtained an empirical relation for FWHM of PL, Delta E(n) (eV) = 1.4 x 10(-8) n(1/3). We also obtained an empirical relation for the band gap shrinkage, Delta E-g in Si-doped GaAs as a function of electron concentration. The value of Delta E-g (eV) = -2.75 x 10(-8) n(1/3), indicates a significant band gap shrinkage at high doping levels. These relations are considered to provide a useful tool to determine the electron concentration in Si-doped GaAs by low temperature PL measurement. The electron concentration decreases with increasing TMGa and AsH3 mole fractions and the main peak shifts to the lower energy side. The peak shifts towards the lower energy side with increasing TMGa variation can also be explained by vacancy control model. (C) 1999 Elsevier Science S.A. All rights reserved.
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This paper presents an assessment of the flexural behavior of 15 fully/partially prestressed high strength concrete beams containing steel fibers investigated using three-dimensional nonlinear finite elemental analysis. The experimental results consisted of eight fully and seven partially prestressed beams, which were designed to be flexure dominant in the absence of fibers. The main parameters varied in the tests were: the levels of prestressing force (i.e, in partially prestressed beams 50% of the prestress was reduced with the introduction of two high strength deformed bars instead), fiber volume fractions (0%, 0.5%, 1.0% and 1.5%), fiber location (full depth and partial depth over full length and half the depth over the shear span only). A three-dimensional nonlinear finite element analysis was conducted using ANSYS 5.5 [Theory Reference Manual. In: Kohnke P, editor. Elements Reference Manual. 8th ed. September 1998] general purpose finite element software to study the flexural behavior of both fully and partially prestressed fiber reinforced concrete beams. Influence of fibers on the concrete failure surface and stress-strain response of high strength concrete and the nonlinear stress-strain curves of prestressing wire and deformed bar were considered in the present analysis. In the finite element model. tension stiffening and bond slip between concrete and reinforcement (fibers., prestressing wire, and conventional reinforcing steel bar) have also been considered explicitly. The fraction of the entire volume of the fiber present along the longitudinal axis of the prestressed beams alone has been modeled explicitly as it is expected that these fibers would contribute to the mobilization of forces required to sustain the applied loads across the crack interfaces through their bridging action. A comparison of results from both tests and analysis on all 15 specimens confirm that, inclusion of fibers over a partial depth in the tensile side of the prestressed flexural structural members was economical and led to considerable cost saving without sacrificing on the desired performance. However. beams having fibers over half the depth in only the shear span, did not show any increase in the ultimate load or deformational characteristics when compared to plain concrete beams. (C) 2002 Published by Elsevier Science Ltd.