Search results for "Constants"
showing 10 items of 150 documents
Formation and Stability of Cadmium(II)/Phytate Complexes by Different Electrochemical Techniques. Critical Analysis of Results
2010
In the present work the stability constants of various cadmium(II)/phytate (Phy) species were determined at T = 298.15 K in NaNO3(aq) at I = 0.1 mol·L−1 by DP-ASV (Differential Pulse Anodic Stripping Voltammetry) and by potentiometric titrations using an ISE-Cd2+. Cyclic voltammograms were also recorded to check the electrochemical behavior of cadmium in the presence of phytate. The results were analyzed together with previous data determined by ISE-H+ measurements. Data obtained were used to provide an exhaustive speciation scheme for the phytate/cadmium(II) system at different conditions, as well as a comprehensive representation of the binding ability of phytate toward cadmium(II). Diffe…
Calibrations and isoperimetric profiles
2007
We equip many noncompact nonsimply connected surfaces with smooth Riemannian metrics whose isoperimetric profile is smooth, a highly nongeneric property. The computation of the profile is based on a calibration argument, a rearrangement argument, the Bol-Fiala curvature dependent inequality, together with new results on the profile of surfaces of revolution and some hardware know-how.
DFT calculation of 1J(119Sn,13C) and 2J(119Sn,1H) coupling constants in di- and trimethyltin(IV) compounds
2008
We have tested several computational protocols, at the nonrelativistic DFT level of theory, for the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) spin-spin coupling constants in di- and trimethyltin(IV) derivatives with various ligands. Quite a good agreement with experimental data has been found with several hybrid functionals and a double-zeta basis set for a set of molecules comprising tetra-, penta-, and hexa-coordinated tin(IV). Then, some of the protocols have been applied to the calculation of the 2J(119Sn, 1H) of the aquodimethyltin(IV) ion and dimethyltin(IV) complex with D-ribonic acid and to the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) of the dimethyltin(IV)-glycylglycin…
8-Hydroxyquinoline-2-Carboxylic Acid as Possible Molybdophore: A Multi-Technique Approach to Define Its Chemical Speciation, Coordination and Sequest…
2020
8-hydroxyquinoline-2-carboxylic acid (8-HQA) has been found in high concentrations (0.5&ndash
The Effect of Metal Cations on the Aqueous Behavior of Dopamine. Thermodynamic Investigation of the Binary and Ternary Interactions with Cd2+, Cu2+ a…
2021
The interactions of dopamine [2-(3,4-Dihydroxyphenyl)ethylamine, (Dop−)] with cadmium(II), copper(II) and uranyl(VI) were studied in NaCl(aq) at different ionic strengths (0 ≤ I/mol dm−3 ≤ 1.0) and temperatures (288.15 ≤ T/K ≤ 318.15). From the elaboration of the experimental data, it was found that the speciation models are featured by species of different stoichiometry and stability. In particular for cadmium, the formation of only MLH, ML and ML2 (M = Cd2+; L = dopamine) species was obtained. For uranyl(VI) (UO22+), the speciation scheme is influenced by the use of UO2(acetate)2 salt as a chemical; in this case, the formation of ML2, MLOH and the ternary MLAc (Ac = acetate) species in a …
Speciation of Al3+ in fairly concentrated solutions (20 to 200 mmol L-1) at I = 1 mol L-1 (NaNO3), in the acidic pH range, at different temperatures.
2011
AbstractThe hydrolysis of Al3+ was studied in aqueous 1 mol L−1 NaNO3 solution at different concentrations (20–200 mmol L−1) and temperatures (283.15–343.15 K) by potentiometry (ISE-H+, glass electrode). Many different speciation models were considered in the calculations and it was found that the best model is represented by the following species: Al(OH)2+, Al(OH)45+, Al13(OH)327+. Hydrolysis constants and enthalpy changes at different temperatures are reported.
Evaluation of molecular mass and tacticity of polyvinyl alcohol by non-equilibrium capillary electrophoresis of equilibrium mixtures of a polymer and…
2011
Non-equilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) has been used to characterize polyvinyl alcohol (PVA). Commercial PVA samples with different molecular masses, from M(w)=15 up to 205 kDa, were used. According to the (13)C NMR spectra, the samples also differed in tacticity (stereoregularity). Mixtures of PVA and the anionic azo-dye Congo Red (CR) were injected in the presence of a borate buffer. The electropherograms gave a band and a peak due to the residual PVA-CR complex and the excess dye, respectively, plus a superimposed exponential decay due to the partial dissociation of the complex during migration. The stoichiometry of the PVA-CR complex, q=[monomer]/[dye…
A DFT study of the Karplus-type dependence of vicinal 3J(Sn-C-X- C), X=N,O,S, in organotin(iv) compounds: Application to conformationally flexible sy…
2010
ZORA relativistic and non-relativistic DFT protocols have been used to investigate vicinal coupling constants, (3)J(Sn-C-X-C), in several organotin(iv) compounds, with particular emphasis on cyclic alpha-aminoorganostannanes. The dependence of the coupling constant on the heteroatom X (X = N,O,S) in the coupling path, and, for X = N, its substituents, has been studied in detail. The electron-withdrawing strength of the N-substituents has been found to strongly affect the magnitude and shape of the Karplus-type curve. The results obtained for the simple model systems, having no or little conformational flexibility, have helped in rationalizing the data concerning real flexible cyclic systems…
One-bond 1 J (15 N,H) coupling constants at sp2 -hybridized nitrogen of Schiff bases, enaminones and similar compounds: A theoretical study
2020
1 J(15 N,H) coupling constants for enaminones and NH-forms of intramolecularly hydrogen-bonded Schiff bases as model compounds for sp2 -hybridized nitrogen atoms are evaluated using density functional theory (DFT) to find the optimal functionals and basis sets. Ammonia is used as a test molecule and its one-bond coupling constant is compared with experiment. A methylamine Schiff base of a truncated molecule of gossypol is used for checking the performance of selected B3LYP, O3LYP, PBE, BHandH, and APFD density functionals and standard, modified, and dedicated basis sets for coupling constants. Both in vacuum and in chloroform, modeled by the simple continuum model of solvent, the modified b…
Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polariz…
2009
Density functional theory (DFT) was used to estimate water's isotropic nuclear shieldings and indirect nuclear spin-spin coupling constants (SSCCs) in the Kohn-Sham (KS) complete basis set (CBS) limit. Correlation-consistent cc-pVxZ and cc-pCVxZ (x = D, T, Q, 5, and 6), and their modified versions (ccJ-pVxZ, unc-ccJ-pVxZ, and aug-cc-pVTZ-J) and polarization-consistent pc-n and pcJ-n (n = 0, 1, 2, 3, and 4) basis sets were used, and the results fitted with a simple mathematical formula. The performance of over 20 studied density functionals was assessed from comparison with the experiment. The agreement between the CBS DFT-predicted isotropic shieldings, spin-spin values, and the experimenta…