Search results for " bonding"
showing 10 items of 934 documents
Homogeneous mixtures of polybetaines with low molecular weight salts
1996
The prepaparation of amorphous, homogeneous blends of zwitterionic polymers with various low molecular weight salts, and in particular with ionic dyes was studied. Homogeneous miscibility was achieved in many cases up to equimolar amounts of salt, even for bulky compounds. Whether miscibility is achieved, or not, depends in a subtle way on the chemical structure of the salt, but no obvious correlation between structure and miscibility could yet be revealed. Spectral shifts of the dye UV/Vis spectra in solution as well as in bulk suggest strong interactions between the polybetaines and the admired salts.
Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate
2014
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ] n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attri…
Ion pair association in isodielectric mixtures at 25�C
1974
Conductance measurements of potassium perchlorate and iodide have been carried out on the following mixtures: methanol-ethylene carbonate, acetone-ethylene carbonate, acetonitrile-ethylene carbonate, sulfolane-ethylene carbonate, isodielectric with water; and in benzene-sulfolane, benzene-acetonitrile, ethanol-sulfolane, isodielectric with methanol. The extent of ionic association at a given concentration in two solvents of the same dielectric constant is greater in the aprotic solvent.
7-Amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid as the dimethylformamide and water monosolvates at 293 K.
2010
The molecular structure of 7-amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid is reported in two crystal environments, viz. as the dimethylformamide (DMF) monosolvate, C(7)H(7)N(5)O(2)S·C(3)H(7)NO, (I), and as the monohydrate, C(7)H(7)N(5)O(2)S·H(2)O, (II), both at 293 (2) K. The triazolo[1,5-a]pyrimidine molecule is of interest with respect to the possible biological activity of its coordination compounds. While the DMF solvate exhibits a layered structural arrangement through N...O hydrogen-bonding interactions, the monohydrate displays a network of intermolecular O...O and N...O hydrogen bonds assisted by cocrystallized water molecules and weak π-π stacking intera…
The skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite
2001
The complete mechanism for the skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite was investigated theoretically by means of DFT calculations, and the influence of the local geometry of the active site and of electrostatic effects on the geometries of the species involved and on activation and reaction energies were analyzed. It was found that whereas the geometry and stability of alkoxide intermediates are strongly influenced by the local geometry of the active site, the ionic transition states are mainly stabilized by electrostatic effects. Both aspects result in a lowering of the activation energies of the elementary steps that form the mechanism and therefore in enhanced r…
Molecular “Floppyness” and the Lewis Acidity of Silanes: A Density Functional Theory Study
2001
A comprehensive set of Lewis acid-base adducts of silanes was investigated by means of the density functional theory geometry optimization [B3LYP/6−31G(d)], and thermochemical calculations, [B3LYP/6−311+G(2d,p)//B3LYP/6−31G(d)]. Complex formation was found to weaken Si−Cl and Si−Br bonds more than Si−F or Si−H bonds. Comparable distances between Si and a Lewis base L (L = NH3, OH2, F−) are shorter in hexa- than in pentacoordinated complexes. The molecular structures of the pentacoordinated Si complexes allowed for a mapping of an SN2 reaction pathway by correlating the lengths of the Si−X and Si−L bonds. Complex formation was found to be exothermic for most of the coordination compounds, an…
FT-IR and dielectric study of water/AOT liquid crystals
2000
Abstract In order to explore the influence of microwave radiation on highly viscous microheterogeneous systems, the evolution of structural and dynamical properties of the water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT) liquid crystals as a function of the molar ratio R (R=[water]/[AOT]) has been investigated by FT-IR spectroscopy and time domain reflectometry. The study emphasises how the progressive hydration of the surfactant head groups is mainly responsible for the structural and dynamical evolution of water/AOT liquid crystals. In particular, it has been found that the state of water at lower R values is strongly perturbed, bulk-like water appears only at R>23 and the water/AOT in…
Modification of commercial UF membranes by electrospray deposition of polymers for tailoring physicochemical properties and enhancing filtration perf…
2020
Abstract The main challenge for a widespread use of nanoporous membranes in the removal of ionic contaminants lies in the adjustment of their physicochemical properties to allow adequate ion rejection and mitigate fouling based on the targeted application. Most of the commercial membranes are negatively charged and their use is thus not necessarily relevant for divalent cation rejection. The main objective for researchers is therefore to provide novel tailored membranes by developing specific synthesis or modifying available membranes. It is proposed here to tailor physicochemical properties of a commercial low molecular weight cut-off ultrafiltration membrane by electrospray deposition of …
Interactions between cationic amylose derivatives and a pulp fiber model surface studied by molecular modelling
2007
This study was performed in order to obtain more information about the interactions between pulp fibers and acetylated cationic starch derivatives on a molecular scale. The adsorption of the polymers on the fiber surface was studied by simulating polymers on a fiber model surface at 300 K. Fractional atomic coordinates of regenerated cellulose II were used to generate a cellulose fiber surface model. Carboxylate groups were added on the cellulose surface to represent the anionic charge of pulp fiber which originates from hemicelluloses. Amylose chains cationized and acetylated atom by atom were chosen to represent four different starch derivatives. Atomic charges used in simulations were ca…
ChemInform Abstract: Synthesis, Structures and DFT Calculations on Alkaline-Earth Metal Azide-Crown Ether Complexes.
2008
The first examples of azide complexes of calcium, strontium or barium with crown ethers have been prepared and fully characterised, notably [Ba([18]crown-6)(N3)2(MeOH)], [Sr([15]crown-5)(N3)2(H2O)], [Ca([15]crown-5)(N3)2(H2O)] and [Sr([15]crown-5)(N3)(NO3)]. Crystal structures reveal the presence of a variety of coordination modes for the azide groups including 1-, -1,3- and linkages via H-bonded water molecules, in addition to azide ions. The [Ba([18]crown-6)(N3)2(MeOH)]1/3 MeOH contains dinuclear cations with three -1,3-NNN bridges, the first example of this type in main group chemistry. The structures obtained have been compared with molecular structures computed by density functional th…