Search results for "computational"

Binding equilibria between beta-cyclodextrin and p-nitro-aniline derivatives: the first systematic study in mixed water-methanol solvent systems.

2009

Abstract Complexation equilibria, in mixed water–methanol solvent media, between native β-cyclodextrin and a set of suitably selected p -nitro-aniline derivatives were studied by means of polarimetry. The effects exerted by the organic co-solvent on the conditional inclusion free energies Δ G cond 0 and the differential molar optical rotations Δ Θ were thoroughly analyzed under the perspective of the enthalpy–entropy compensation effect. Experimental data suggest an intimate participation (‘dynamic co-inclusion’) of solvent molecules in the formation and in the conformational dynamics of the host–guest inclusion complex.

Polarimetry as a useful tool for the determination of binding constants between cyclodextrins and organic guest molecules

2006

Binding constants for cyclodextrin inclusion complexes can be easily estimated by means of simple polarimetric measurements. Determinations are as reliable and accurate as those obtained by means of other more sophisticated techniques, and take advantage by the limited waste of material required. Our results are briefly compared with literature values obtained by means of different techniques.

pH-Dependent ligands as carriers in transport experiments

2004

Abstract Conformationally pH-regulated ligands have been used as carriers in transport experiments. The experiments were carried out through bulky membranes and the pH at the source phase and at the receiving phase were modified to study the ability of ligands to act as pH-regulated carriers. The influence of pH on transport efficiency seems to be related to its influence on conformational equilibrium. X-ray determination of one precursor compound has been useful for determining the stereochemistry of one of the carriers. To cite this article: A.M. Costero et al., C. R. Chimie 7 (2004).

Solvation chemistry of water-soluble thiol-protected gold nanocluster Au102 from DOSY NMR spectroscopy and DFT calculations

2014

The hydrodynamic diameter of Aum(pMBA)n [(m, n) = (102, 44) and (144, 60)] clusters in aqueous media was determined via DOSY NMR spectroscopy. The apparent size of the same (n, m) cluster depends on the counter ion of the deprotonated pMBA− ligand as explained by the competing ion-pair strength and hydrogen bonding interactions studied in DFT calculations. The choice of the counter ion affects the surface chemistry and molecular structure at the organic/water interface, which is relevant for biological applications.

The nature of the chemical bond in (CH3)3N-BCl3 and (CH3)3N-AlCl3

1994

1,2-Dipolar addition model for the cytoprotective activity of selected α,β-unsaturated compounds with CO functionality: an ab initio study

2001

Abstract The mechanism of the addition of a nucleophile (an alkylthiol group) to a double bond of α,β-unsaturated systems in the gas phase was explored. In this study, intermediates of the reaction were also investigated using ab initio calculations (RHF/6-31G ∗ and MP2/6-31+G ∗ ). Our results indicate that direct dipolar attack of the S–H group of an alkylthiol on the CC double bond is a reasonable reaction path. The present results represent, therefore, additional support for our hypothesis. This suggests that the mechanism of cytoprotection might be mediated, at least in part, by a reaction between the olefinic acceptor and the sulfhydryl-containing groups of the mucosa.

The transformation of aromatic molecules into the subspace of their double bonds

1975

A model of new submolecules is presented. As an application some absorptions of aromatic radicals are interpreted in UV and visible spectra. Extension of the model to biological systems is prejudged.

A theoretical study of neutral and reduced tetracyano-p-quinodimethane (TCNQ)

2004

Abstract The molecular structure of neutral, anionic, and dianionic tetracyano- p -quinodimethane (TCNQ), as well as the electron affinity of TCNQ, have been studied with HF, MP2, and different density functional theory (DFT) procedures. The optimized geometries compare well with the available experimental data, although the C N bond distance is not correctly described at the MP2 level. The calculated parameters are rather insensitive to the basis set employed, and the addition of diffuse functions does not yield significant changes. When the extra electrons are added, the central ring of TCNQ progressively becomes more aromatic. Compared with the CCSD(T) estimate, the value of the adiabati…

Can Experimental Electron-Density Studies be Used as a Tool to Predict Biologically Relevant Properties of Low-Molecular Weight Enzyme Ligands?

2013

The case of protease inhibitor model compounds incorporating an aziridine or epoxide ring is used to exemplify how application of experimental electron-density techniques can be used to explain the biological properties of low-molecular weight enzyme ligands. This is furthermore seen in the light of a comparison of crystal and enzyme environments employing QM/MM computations to elucidate to which extent the properties in the crystal can be used to predict behavior in the biological surrounding.

Binding and isomerization energies for the Cu/CN and Cu(I)CN interactions

1993

Abstract Binding and isomerization energies of the CuCN, CuNC, CuCN+, and CuNC+ systems were investigated by means of a multireference CI perturbatively selected, MRCI-PS approach. The inclusion of the main dynamical correlation effects are evaluated. The binding energies for CuCN and CuNC are 4.37 and 4.03 eV, respectively, and those for CuCN+ and CuNC+ are 0.08 and 1.61 eV. Calculated isomerization energies are 7.86 and 35.98 kcal/mol for CuCN and Cu(I)CN isomerizations, respectively.