Search results for "CONST"
showing 10 items of 7706 documents
Increased Acid Dissociation at the Quartz/Water Interface.
2018
As shown by a quite significant amount of literature, acids at the water surface tend to be “less” acid, meaning that their associated form is favored over the conjugated base. What happens at the solid/liquid interface? In the case of the silica/water interface, we show how the acidity of adsorbed molecules can instead increase. Using a free energy perturbation approach in combination with electronic structure-based molecular dynamics simulations, we show how the acidity of pyruvic acid at the quartz/water interface is increased by almost two units. Such increased acidity is the result of the specific microsolvation at the interface and, in particular, of the stabilization of the deprotona…
Proteolytic cleavage of soybean Bowman-Birk inhibitor monitored by means of high-performance capillary electrophoresis. Implications for the mechanis…
1996
The hydrolysis of the soybean Bowman-Birk inhibitor in the presence of catalytic amounts of bovine trypsin and the formation of the non-covalent enzyme-inhibitor complex with an equimolar amount of enzyme are monitored by means of high-performance capillary electrophoresis (HPCE). The inhibitor is cleaved in the trypsin-reactive and more slowly in the chymotrypsin-reactive subdomain. HPCE proves itself as the only reliable analytical tool to monitor these reactions in clear contrast to classical electrophoretic, chromatographic and enzymatic methods. The most efficient separation of the intact and the two active site cleaved forms of the inhibitor was achieved in borate buffer at pH 10.0. T…
Chemical speciation of organic matter in natural waters. Interaction of nucleotide 5′ mono-, di- and triphosphates with major components of seawater
2004
AbstractThe interactions of nucleotide 5’ mono-, di- and triphosphates in a multicomponent ionic medium simulating the macro-composition of seawater (Na+, K+, Ca2+, Mg2+, Cl-, SO42-, Synthetic Sea Water, SSW) have been investigated at different ionic strengths and at T= 25°C. A chemical speciation model, according to which all the internal interactions between the components of the ionic medium are taken into account, was applied to determine the effective formation constants of species in the nucleotide-seawater system. The results were compared to protonation parameters calculated from single electrolyte systems. A simpler model (SSW considered as a single salt BA, with Bz+ and Az-), repr…
Equilibrium studies in natural fluids: interactions of -PO43−, -P2O74−and -P3O105−with the major constituents of sea water
1998
AbstractThe interaction of PiO(i+2)−(3i+1) (i = 1,2,3) with the major components of seawater has been studied potentiometrically, at 25°C, in an artificial seawater (Na+, K, Ca2+, Mg2+, Cl− and SO42−) at different salinities (5—45%o). Apparent protonation constants have been calculated, from potentiometric data, and estimated, using an appropriate complex formation model. Formation constants of complexes formed by phosphates and the cation of seawater (the inorganic content of seawater being considered as a single 1:1 salt) have been determined. The comparison between experimental and estimated results showed that a suitable complexation model can be used with a fairly good accuracy in pred…
Coil overlap in moderately concentrated polyelectrolyte solutions: effects of self-shielding as compared with salt-shielding as a function of chain l…
2016
The generalized intrinsic viscosity {η} (hydrodynamic volume of the solute at arbitrary polymer concentration c) – introduced by analogy to the intrinsic viscosity [η] – provides access to the degree of coil overlap Ω for polyelectrolyte solutions in pure water or in saline water. The experimental basis of this investigation consists in viscosity measurements as a function of c for a large number of sodium polystyrene sulfonate (Na-PSS) samples covering the molecular weight range from 0.91 to 1000 kg mol−1. The accurate modeling of these dependencies with a maximum of three parameters yields detailed information on Ω as a function of (c[η]) in the absence and in the presence of extra salt. …
Thermodynamic Properties of Sodium n-Alkanecarboxylates in Water and in Water + Cyclodextrins Mixtures
1998
Densities and heat capacities of water−substrate, water−cyclodextrin, and water−substrate−cyclodextrin systems were determined at 298 K. The substrates studied are sodium n-alkanecarboxylates (CnCOONa) (from sodium acetate to sodium decanoate) and the cyclodextrins are hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin, (HP-β-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD). The apparent molar volumes and heat capacities of CnCOONa in water were calculated as functions of concentration. The standard partial molar properties agree with those obtained by using the additivity rule. HP-β-CD essentially does not affect the thermodynamic properties of C1COON…
Chemical Constituents of Urospermum picroides
1992
Seven phenolic compounds were isolated from the aerial parts of U. picroides. They were identified by UV spectra, TLC and HPLC-DAD as luteolin, luteolin-7-glucoside, quercetin, quercetin-3-galactoside, kaempferol-3-galactoside, chlorogenic and isochlorogenic acids. Other phenolics were characterized by HPLC-DAD analysis: gallic, protocatechuic, caffeic, ferulic and isoferulic acids, quercetin-3-glucoside and luteolin-4′-glucoside.
Phase separation of blends of polydisperse polymers: Comparison between experiment and theory for the system poly(dimethylsiloxane)/poly(ethylmethyls…
1996
Cloud point curves were measured turbidimetrically for blends (upper critical solution temperatures ; UCSTs) of poly(ethylmethylsiloxane) (PEMS) and four different samples of poly(dimethylsiloxane) (PDMS) ; the weight average molar masses in kg/mol are 31.2 for PEMS and 10.4, 15.5, 18.1 and 24.0 for PDMS ; all components have polydispersity indices D (= M w /M n ) within the range from 1.82 to 2.67. Corresponding calculations on the basis of the Flory-Huggins theory (three adjustable parameters) account for the polydispersity; molecular weight distributions are represented by the generalized Schulz-Flory equation. Calculated cloud point curves agree very well with those measured, if individ…
Contour-Variable Model of Constitutive Equations for Polymer Melts
2009
Based on a modified expression of the rate of the convective constraint release, we present a new contour-variable model of constitutive equations in which the non-uniform segmental stretch and the non-Gaussian chain statistical treatment of the single chain are considered to describe the polymer chain dynamics and the rheological behavior of an entangled system composed of linear polymer chains. The constitutive equations are solved numerically in the cases of steady shear and transient start-up of steady shear. The results indicate that the orientation and stretch, as well as the tube survival probability, have strong dependence on the chain contour variable, especially in the high-shear-…
1H,13C and17O NMR study of chlorovanillins and some related compounds
1992
1H, 13C and 17O NMR chemical shifts and nJ(H,H), 1J(C,H) and 3J(C-6, H-formyl) spin—spin coupling constants of chlorinated vanillins (3-methoxy-4-hydroxybenzaldehydes) were determined. The variation in the long-range 4J(H,H) value between the formyl proton and an ortho-proton suggests that the ortho-substituent strongly forces the formyl group out of the aromatic plane. This can also be observed by considering the 3J(C-6,H-formyl) values and the 13C and 17O NMR chemical shifts. The 17O NMR chemical shifts show a linear correlation with the torsion angle of the formyl group calculated by molecular mechanics. The 13C and 17O NMR chemical shifts of the methoxyl group also possess strong predic…