995 resultados para Molé, Mathieu


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The binding of a 14 kDa beta-galactoside animal lectin to splenocytes has been studied in detail. The binding data show that there are two classes of binding sites on the cells for the lectin: a high-affinity site with a K-a ranging from 1.1 x 10(6) to 5.1 x 10(5) M-1 and a low affinity binding site with a K-a ranging from 7.7 x 10(4) to 3.4 x 10(4) M-1 The number of receptors per cell for the high- and low-affinity sites is 9 +/- 3 x 10(6) and 2.5 +/- 0.5 x 10(6) respectively. The temperature dependence of the K value yielded the thermodynamic parameters. The energetics of this interaction shows that, although this interaction is essentially enthalpically driven (Delta H - 21 kJ lambda mol(-1)) for the high-affinity sites, there is a very favorable entropy contribution to the free energy of this interaction (-T Delta S - 17.5 Jmol(-1)), suggesting that hydrophobic interaction may also be playing a role in this interaction. Lactose brought about a 20% inhibition of this interaction, whereas the glycoprotein asialofetuin brought about a 75 % inhibition, suggesting that complex carbohydrate structures are involved in the binding of galectin-1 to splenocytes, Galectin-1 also mediated the binding and adhesion of splenocytes to the extracellular matrix glycoprotein laminin, suggesting a role for it in cell-matrix interactions. Copyright (C) 2000 John Wiley & Sons, Ltd.

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The effect of temperature and stoichiometry on the polarization switching rate in lithium niobate is presented. An increased polarization switching rate in congruent and near-stoichiometric lithium niobate (CLN and SLN) and SLN doped with 1.6 mol% Zn (SLN:Zn(1.6)) is observed using a pulsed field switching technique near the transition temperature (TO. Compared to CLN, the observed switching rate and domain wall mobility for SLN and SLN:Zn(1.6) are higher. The extra charge flow was observed during switching at high temperatures,and is attributed to the creation of defect dipoles and increase in ionic conductivity. Forward domain motion is expected to be the mechanism involved in switching. (C) 2010 Elsevier Ltd. All rights reserved.

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Two series of glasses were prepared, xNa2O, yZnO, 100 - x - yB2O3 and 30 - xNa2O, xZnO, 70B2O3 (mol%). The temperature dependence of the direct current resistivity was measured from room temperature to about 700 K and in both series of glasses we observed a simple Arrhenius type of temperature dependence. However, the resistivity of the binary alkali glass increased steeply by as much as two orders of magnitude with the addition of even a small quantity of ZnO and remained virtually unaffected by further addition of ZnO. The resistivity decreases gradually with increasing pressure in Na2O-B2O3 but increases with increasing pressure with the addition of ZnO.

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The standard Gibbs energies of formation of RuO2 and OsO2 at high temperature have been determined with high precision, using a novel apparatus that incorporates a buffer electrode between the reference and working electrodes, The buffer electrode absorbs the electrochemical flux of oxygen through the solid electrolyte from the electrode with higher oxygen chemical potential to the electrode with lower oxygen potential, The buffer electrode prevents polarization of the measuring electrode and ensures accurate data, The standard Gibbs energies of formation (Delta(f)G degrees) of RuO2, in the temperature range of 900-1500 K, and OsO2, in the range of 900-1200 K, can be represented by the equations Delta(f)G degrees(RuO2)(J/mol) = -324 720 + 354.21T - 23.490T In T Delta(f)G degrees(OsO2)(J/mol) = -304 740 + 318.80T - 18.444T In T where the temperature T is given in Kelvin and the deviation of the measurement is +/- 80 J/mol, The high-temperature heat ;capacities of RuO2 and OsO2 are measured using differential scanning calorimetry. The information for both the low- and high-temperature heat rapacity of RuO2 is coupled with the Delta(f)G degrees data obtained in this study to evaluate the standard enthalpy of formation of RuO2 at 298.15 K (Delta(f)H degrees(298.15K)). The low-temperature heat capacity of OsO2 has not been measured: therefore, the standard enthalpy and entropy of formation of OsO2 at 298.15 K (Delta(f)H degrees(298.15K) and S degrees(298.15K), respectively) are derived simultaneously through an optimization procedure from the high-temperature heat capacity and the Gibbs energy of formation. Both Delta fH degrees(298.15K) and S degrees(298.15K) are treated as variables in the optimization routine, For RuO2, the standard enthalpy of formation at 298.15 K is Delta fH degrees(298.15K) (RuO2) -313.52 +/- 0.08 kJ/mol, and that for OsO2 is Delta(f)H degrees(298.15K) (OSO2) = -295.96 +/- 0.08 kJ/mol. The standard entropy of OsO2 at 298.15 K that has been obtained from the optimization is given as S degrees(298.15K) (OsO2) = 49.8 +/- 0.2 J (mol K)(-1).

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The coexisting phases in the pseudobinary system BaO-Y2O3 have been identified by equilibrating samples containing different amounts of component oxides at 1173, 1273 and 1373 K. Only two ternary oxides, BaY2O4 and Ba3Y4O9, have been found to be stable in the temperature range of investigation. Solid state galvanic cells: Pt, O2+BaO+BaF2double vertical barBaF2+2mol%Al2O3double vertical barBaF2+BaY2O4+Y2O3+O2, Pt and Pt, O2+BaO+BaF2double vertical barBaF2+2mol% Al2O3double vertical barBaF2+BaY2O4+Ba3Y4O9+O2, Pt have been employed for determining the Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from the component oxides in the range 850 to 1250 K. A composite solid electrolyte incorporating Al2O3-dispersed BaF2 was used in the cells. To prevent interaction between the Al2O3 powder and electrode materials, the solid electrolyte was coated with pure BaF2. The Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from component oxides are given by: Δf0 (BaY2O4, s)=−128,310+5.211T (±580) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K) and ΔGfo(Ba3Y4O9, s)= −317,490 −24.704T (±1100) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K).

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CaSiO3 : Dy3+ (1-5 mol. %) nanophosphors were synthesized by a simple low-temperature solution combustion method. Powder X-ray diffraction patterns revealed that the phosphors are crystalline and can be indexed to a monoclinic phase. Scanning electron micrographs exhibited faceted plates and angular crystals of different sizes with a porous nature. Photoluminescence properties of the Dy3+-doped CaSiO3 phosphors were observed and analyzed. Emission peaks at 483, 573 and 610 nm corresponding to Dy3+ were assigned as F-4(9/2)-> H-6(15/2), F-4(9/2) -> H-6(13/2) and F-4(9/2) -> H-6(11/2) transitions, respectively, and dominated by the Dy3+ F-4(9/2) -> H-6(13/2) hyperfine transition. Experimental results revealed that the luminescence intensity was affected by both heat treatment and the concentration of Dy3+ (1-5 mol. %) in the CaSiO3 host. Optimal luminescence conditions were achieved when the concentration of Dy3+ was 2 mol. %. UV-visible absorption features an intense band at 240 nm, which corresponds to an O-Si ligand-to-metal charge transfer band in the SiO32- group. The optical energy band gap for the undoped sample was found to be 5.45 eV, whereas in Dy3+-doped phosphors it varies in the range 5.49-5.65 eV. The optical energy gap widens with increase of Dy3+ ion dopant.

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Sintered, polycrystalline ZnO ceramics with copper as the only additive exhibit highly nonlinear current‐voltage characteristics. Increasing nonlinearity index (α=4–45) with Cu concentration of 0.01–1 mol % is also variable with respect to ceramic processing methods. Incorporation of Cu in the ZnO lattice is indicated from the electron probe microanalysis and the photoluminescence spectra. Cu acceptors are compensated by holes in the grain boundary layers, whereas the concentration of intrinsic donors is higher in the grain interior. The presence of positive charges leads to thinning of the depletion region, resulting in nonlinear characteristics.

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In 1-cyclo-hexyl-6,6,8a-trimethyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C19H27NO3, (I), and the isomorphous compounds 6,6,8a-trimethyl-1-phenyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C19H21NO3, (II), and 6,6,8a-trimethyl-1-(3-pyridyl)-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C18H20N2O3, (III), the tetra-hydro-benzo-dihydro-furo-pyrrolidine ring systems are folded at the cis junction of the five-membered rings, giving rise to a non-planar shape of the tricyclic cores. The dihydro-furan and pyrrolidine rings in (I) are puckered and adopt an envelope conformation. The cyclo-hexene rings adopt a half-chair conformation in all the mol-ecules, while the substituent N-cyclo-hexyl ring in (I) assumes a chair form. Short intra-molecular C-HcO contacts form S(5) and S(6) motifs. The isomorphous compounds (II) and (III) are effectively isostructural, and aggregate into chains via inter-molecular C-HcO hydrogen bonds.

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Genistein and daidzein, the major isoflavones present in soybeans, possess a wide spectrum of physiological and pharmacological functions. The binding of genistein to human serum albumin (HSA) has been investigated by equilibrium dialysis, fluorescence measurements, CD and molecular visualization. One mole of genistein is bound per mole of HSA with a binding constant of 1.5 +/- 0.2 X 10(5) m(-1). Binding of genistein to HSA precludes the attachment of daidzein. The ability of HSA to bind genistein is found to be lost when the tryptophan residue of albumin is modified with N-bromosuccinimide. At 27 degrees C (pH 7.4), van't Hoff's enthalpy, entropy and free energy changes that accompany the binding are found to be -13.16 kcal.mol(-1), -21 cal.mol(-1)K(-1) and -6.86 kcal.mol(-1), respectively. Temperature and ionic strength dependence and competitive binding measurements of genistein with HSA in the presence of fatty acids and 8-anilino-1-naphthalene sulfonic acid have suggested the involvement of both hydrophobic and ionic interactions in the genistein-HSA binding. Binding measurements of genistein with BSA and HSA, and those in the presence of warfarin and 2,3,5-tri-iodobenzoic acid and Forster energy transfer measurements have been used for deducing the binding pocket on HSA. Fluorescence anisotropy measurements of daidzein bound and then displaced with warfarin, 2,3,5-tri-iodobenzoic acid or diazepam confirm the binding of daidzein and genistein to subdomain IIA of HSA. The ability of HSA to form ternery complexes with other neutral molecules such as warfarin, which also binds within the subdomain IIA pocket, increases our understanding of the binding dynamics of exogenous drugs to HSA.

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Gd2O3:Eu3+ (0.5-8.0 mol%) nanophosphors have been prepared by low temperature solution combustion method using metal nitrates as oxidizers and oxalyl dihydrazide (ODH) as a fuel. The phosphors are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence (PL) techniques. PXRD patterns of as-formed and calcined (800 degrees C, 3 h) Gd2O3 powders exhibit monoclinic phase with mean crystallite sizes ranging from 20 to 50 nm. Eu3+ doping changes the structure from monoclinic to mixed phase of monoclinic and cubic. SEM micrographs shows the products are foamy, agglomerated and fluffy in nature due to the large amount of gases liberated during combustion reaction. Upon 254 nm excitation the photoluminescence of the Gd2O3:Eu3+ particles show red emission at 611 nm corresponding to D-5(0)-> F-7(2) transition. It is observed that PL intensity increases with calcination temperature. This might be attributed to better crystallization and eliminates the defects, which serve as centers of non-radiative relaxation for nanomaterials. It is observed that the optical energy gap (E-g) is widened with increase Eu3+ content. (C) 2010 Elsevier B.V. All rights reserved.

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Phase diagram studies show that at ambient pressure only one ternary oxide, Cu(2)Ln(2)O(5), is stable in the ternary systems Cu-Ln-O (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu) at high temperatures. The crystal structure of Cu(2)Ln(2)O(5) can be described as a zig-zag arrangement of one-dimensional Cu2O5 chains parallel to-the a-axis with Ln atoms occupying distorted octahedral sites between these chains. Four sets of emf measurements on Gibbs energy of formation of Cu(2)Ln(2)O(5) (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu; Y) from component binary oxides and one set of high-temperature solution calorimetric data on enthalpy of formation have been reported in the literature. Except for Cu2Y2O5, the measured values for the Gibbs energies of formation of all other Cu(2)Ln(2)O(5) compounds fall in a narrow band (+/-1 kJ mol(-1)) and indicate a regular increase in stability with decreasing ionic radius of the lanthanide ion. The values for the second law enthalpy of formation, derived from the temperature dependence of emf obtained in different studies, show larger differences, as high as 25 kJ mol(-1) for Cu2Tm2O5. Though associated with an uncertainty of +/-4 kJ mol(-1), the calorimetric measurements help to identify the best set of emf data. The trends in thermodynamic data correlate well with the global instability index (GII) based on the overall deviation from the valence sum rule. Low values for the index calculated from crystallographic information indicate higher stability. Higher values are indicative of the larger stress in the structure.

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Only a small amount (<= 3.5 mol%) of Ge can be doped in Ga2O3, Ga1.4In0.6O3 and In2O3 by means of solid state reactions at 1400 degrees C. All these samples are optically transparent in the visible range, but Ge-doped Ga2O3 and Ga1.4In0.6O3 are insulating. Only Ge-doped In2O3 exhibits a significant decrease in resistivity, the resistivity decreasing further on thermal quenching and H-2 reduction.The resistivity of 2.7% Ge-doped In2O3 after H-2 reduction shows a metallic behavior, and a resistivity of similar to 1 m Omega cm at room temperature, comparable to that of Sn-doped In2O3. (C) 2010 Elsevier Ltd. All rights reserved.

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The creep behaviour of a creep-resistant AE42 magnesium alloy has been examined in the temperature range of 150 to 240 degrees C at the stress levels ranging from 40 to 120 MPa using impression creep technique. A normal creep behaviour, i.e., strain rate decreasing with strain and then reaching a steady state, is observed at all the temperatures and stresses employed The stress exponent varies from 5.1 to 5.7 and the apparent activation energy varies from 130 to 140 kJ/mol, which suggests the high temperature climb of dislocation controlled by lattice self-diffusion being the dominant creep mechanism in the stress and temperature range employed The creep behaviour of the AE42 alloy has also been compared with its composites reinforced with Saffil short fibres and SiC particles in four combinations. All the composites exhibited a lower creep rate than the monolithic AE42 alloy tested at the same temperature and stress levels and the decrease in creep rate was greater in the longitudinal direction than in the transverse direction, as expected. All the hybrid composites, i.e., the composites reinforced with a combination of Saffil short fibres and SiC particles, exhibited creep rates comparable to the composite reinforced with 20% Saffil short fibres alone at all the temperature and stress levels employed, which is beneficial from the commercial point of view.

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A thermodynamic study of the Ti-O system at 1573 K has been conducted using a combination of thermogravimetric and emf techniques. The results indicate that the variation of oxygen potential with the nonstoichiometric parameter delta in stability domain of TiO2-delta with rutile structure can be represented by the relation, Delta mu o(2) = -6RT In delta - 711970(+/-1600) J/mol. The corresponding relation between non-stoichiometric parameter delta and partial pressure of oxygen across the whole stability range of TiO2-delta at 1573 K is delta proportional to P-O2(-1/6). It is therefore evident that the oxygen deficient behavior of nonstoichiometric TiO2-delta is dominated by the presence of doubly charged oxygen vacancies and free electrons. The high-precision measurements enabled the resolution of oxygen potential steps corresponding to the different Magneli phases (Ti-n O2n-1) up to n = 15. Beyond this value of n, the oxygen potential steps were too small to be resolved. Based on composition of the Magneli phase in equilibrium with TiO2-delta, the maximum value of n is estimated to be 28. The chemical potential of titanium was derived as a function of composition using the Gibbs-Duhem relation. Gibbs energies of formation of the Magneli phases were derived from the chemical potentials of oxygen and titanium. The values of -2441.8(+/-5.8) kJ/mol for Ti4O7 and -1775.4(+/-4.3) kJ/mol for Ti3O5 Obtained in this study refine values of -2436.2(+/-26.1) kJ/mol and-1771.3(+/-6.9) kJ/mol, respectively, given in the JANAF thermochemical tables.

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The combustion technique produces ionically dispersed Ag on a nano-crystalline CeO2 surface. The catalysts thus produced were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic properties towards NO reduction, CO and hydrocarbon oxidation have been investigated using the temperature programmed reaction technique in a packed bed tubular reactor. These results are compared with alpha-Al2O3 supported finely divided Ag metal particles synthesized by the same method. Both oxidation and reduction reactions over Ag/CeO2 have been observed to occur at lower temperatures compared to Ag/Al2O3. The rate and turnover frequency of the NO+CO reaction over 1% Ag/CeO2 are 56.3 mu mol g(-1) s(-1) and 0.97 s(-1) at 225 degrees C respectively. Activation energy (E-a) values are 71 and 67 kJ mol(-1) for CO+O-2 and NO+CO reactions, respectively, over 1% Ag/CeO2 catalyst.