Search results for "Method"
showing 10 items of 13253 documents
1,6-π-Electrocyclization of 3-Vinyl-FunctionalizedN,N-Dimethyl-2,2′-Bisindolyl: Some analysis of the educt transformation process
1998
The thermally and photochemically induced 1,6-π-electrocyclization reaction of 3-vinyl-functionalized N, N'-dimethyl-2,2′-bisindolyls 4 has been analysed and some reactivity aspects are presented. On the basis of time dependent 1H nmr and uv spectroscopic measurements the educt transformations can be observed in detail. Some results of the isomerization process of the educts are also given.
Hydration of agarose double helix: A monte carlo simulation
2009
The structure of the water around agarose double helix is analyzed with ab initio quantum mechanical calculations and Monte Carlo simulations. The potential surface is sampled by computing the interaction energy between fragments of agarose and a water molecule placed at 221 different orientations and/or positions. These energy values are fitted to a simple analytical expression representing atom-atom pair potentials for a water molecule interacting with agarose. A preliminary understanding of the agarose-water interaction is obtained from isoenergy contour maps at planar cross sections, perpendicular to the long axis of the double helix, and for cylindrical surfaces enclosing the double he…
Theoretical Study on the Structures and Electronic Spectra of TCNE2−
2006
Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) compiles have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE 2- has D 2d symmetry in vacuum as well as in the solvents dichloromethane and cicetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoreitcal results, are compared to the experimental data and good agreement is achieved.
DSC study on hyaluronan drying and hydration
2011
Abstract The processes of hyaluronan (HYA) drying and hydration were studied using differential scanning calorimetry. In the first approach the isoconversional Kissinger–Akahita–Sunose (KAS) method was applied in order to determine actual activation energies of evaporation of pure water and water from concentrated HYA solutions. Since the evaporation is a single-step process, the activation energies for pure water provided results consistent with tabulated values of evaporation enthalpies. In the course of water evaporation from hyaluronan solution a break in increasing enthalpy followed by a decrease below 0.34 g of water per 1 g of HYA was observed. This result confirmed earlier observati…
Micellization in Model Surfactant Systems
1999
Formation of micelles in model lattice surfactant systems was studied by a novel methodology based on grand-canonical Monte Carlo simulations. The methodology involves combining free-energy information from a series of simulations in small systems by histogram reweighting. The solution osmotic pressure as a function of overall volume fraction of surfactant shows a sharp break at the critical micelle concentration (cmc) at sufficiently low temperatures. Studies in larger systems at appropriate values of the surfactant chemical potential are used to investigate the size distribution of micellar aggregates. The methodology allows for a clear distiction between micellization and macroscopic pha…
Ab initio study of rotational isomerism and electronic structure of isomeric bipyrroles
1985
Abstract Ab initio calculations using STO-3G and 4-31G basis sets have been performed on the internal rotation barriers and conformational stabilities for 2,3′- and 3,3′-bipyrrole. The twofold rotation potential predicted for both isomers at minimal basis level becomes a more involved fourfold potential when the split-valence basis set is employed, because it takes into account more properly the nonbonded interannular interactions. A transoid-gauche minimum is predicted to have the minimal absolute conformational energy in both isomers. The electronic structure of the highest occupied MOs of 2,2′-, 2,3′- and 3,3′-bipyrrole are analyzed in terms of the single pyrrole MO pattern and a similar…
Static and Dynamic Properties of the Nonframework Cations in Na-Mordenites Zeolite
2004
This work consists of exploring the effect of Si/Al ratio and water content on both the static and dynamic properties of the extra-framework cations in a typical zeolite system Na+-Mordenites. Atomistic simulations based on interatomic potentials and minimisation techniques have been used to determine the location of the cations as a function of the Si/Al ratio and the hydration level. Our calculations showed two different cation behaviours depending on the type of channels that they occupy, the positions of the cations in the main channels being substantially perturbed upon the sorption of water molecules whereas those of the cations located in the small side channels being only slightly s…
Flow-through voltammetry (FTV) with the hanging mercury drop electrode (HMDE)
1995
A flow-through cell with integrated hanging mercury drop electrode for voltammetric, inverse voltammetric, adsorptive voltammetric, and chronoamperometric methods is described. HMDE droplets are automatically formed and renewed. By optimizing the flow-channel the sensitivity could be increased approximately five times in comparison with batch methods using the same deposition conditions.
Hartree–Fock study of adhesion and charge redistribution on the Ag/MgO(0 0 1) interface
2001
Abstract Ab initio study of the Ag/MgO(0 0 1) interfaces based on a quantitative analysis of the bonding in the interfacial region is provided in the framework of Hartree–Fock approach. We are describing the way interfacial electronic and other properties evolve as a function of metal coverage. General conclusion that could be drawn from our calculations is that chemical bond formation is not important for the Ag/MgO(0 0 1) perfect interface. Physisorption of Ag atoms over surface O 2− ions associated with atomic polarization and charge redistribution in the metal planes are the dominant effects. The adhesion energy is enhanced by the interaction of the substrate Mg 2+ ions with the surplus…
Application of fast solvent extraction processes to studies of exotic nuclides
1998
Fast solvent extraction is a chemical separation method, which can be applied to study exotic nuclides. Since about 1970 the SISAK technique, which is an on-line method based on multi-stage solvent extraction separations, has been successfully used to investigate the nuclear properties of β-decaying nuclides with half-lives down to about one second. During the last decade it has become possible to produce transactinide elements in high enough yields to investigate their chemical properties on a one-atom-at-a-time scale. For this purpose it was necessary to improve and change the detection part of the SISAK system in order to be capable to detect spontaneously fissioning and α-decaying nucli…