Search results for "BOND"
showing 10 items of 3527 documents
Tin compounds interaction with membranes of egg lecithin liposomes.
2007
This work is a continuation of earlier research concerning the influence of tin compounds on the dynamic properties of liposome membranes produced with lecithin hen egg yolks (EYL). The experiments were carried out at room temperature (about 25 ∞C). Four tin compounds were chosen, including three organic ones, (CH3)4Sn, (C2H5)4Sn and (C3H7)3SnCl, and one inorganic, SnCl2. The investigated compounds were admixed to water dispersions of liposomes. The content of the admixture changed within the range 0 mol-% to 11mol-% in proportion to EYL. Two spin probes were used in the experiment: 2,2,6,6-tetramethylpiperidine- 1-oxyl (TEMPO) and 2-ethyl-2-(15-methoxy-15-oxopentadecyl)-4,4-dimethyl-3-oxaz…
A very simple one-pot electrosynthesis of nitrones starting from nitro and aldehyde components
2018
The cathodic treatment of nitroarenes in the presence of aldehydes yields directly and selectively nitrones. Electrolysis can be conducted on a very simple undivided beaker-type cell under constant current conditions. The conversion tolerates multiple bonds, a variety of functional groups and heterocyclic moieties. Competing reductive conversions such as pinacolization are not observed. The green aspects of this electro-conversion are avoidance of metals, an environmentally benign solvent mixture, and stable as well as sustainable carbon electrodes.
In situ UV-visible spectroelectrochemistry in the course of oxidative monomer electrolysis
2015
Abstract Novel method to characterize the macromolecuar structure of an electroactive polymer deposited via electrooxidation of the corresponding monomer on the electrode surface has been proposed. It is based on experimental determination of the number of electrons spent for oxidation of an initially solute monomer species which is used to calculate the number of covalent bonds linking each monomer unit with neighboring units inside the polymer. The former parameter is found by tracing simultaneously the variations of instantaneous values of the solute monomer concentration and of the passed charge in the course of the monomer oxidation electrolysis. This monomer concentration is establish…
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…
A new C–C bond formation model based on the quantum chemical topology of electron density
2014
ELF topological analyses of bonding changes in non-polar, polar and ionic organic reactions involving the participation of CC(X) double bonds make it possible to establish a unified model for C–C bond formation. This model is characterised by a C-to-C coupling of two pseudoradical centers generated at the most significant atoms of the reacting molecules. The global electron density transfer process that takes place along polar and ionic reactions favours the creation of these pseudoradical centers at the most nucleophilic/electrophilic centers of the reacting molecules, decreasing activation energies. The proposed reactivity model based on the topological analysis of the changes in electron…
ChemInform Abstract: A New C-C Bond Formation Model Based on the Quantum Chemical Topology of Electron Density
2014
ELF topological analyses of bonding changes in non-polar, polar and ionic organic reactions involving the participation of CC(X) double bonds make it possible to establish a unified model for C–C bond formation. This model is characterised by a C-to-C coupling of two pseudoradical centers generated at the most significant atoms of the reacting molecules. The global electron density transfer process that takes place along polar and ionic reactions favours the creation of these pseudoradical centers at the most nucleophilic/electrophilic centers of the reacting molecules, decreasing activation energies. The proposed reactivity model based on the topological analysis of the changes in electron…
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.
Dissociation energies within selected configuration interaction and perturbation theory
1993
Abstract Selected configuration interaction (CI) calculations and second-order perturbational theory are used to truncate systematically multireference single and double excitation CI (MRCI) expansions in the calculation of the bond dissociation energies of several systems like the single-bonded LiF molecule or the multiple-bonded N2, NO and O2 diatomic systems. The method is extended to compute the CH bond dissociation energy ofethene C2H4. It is shown how the proposed scheme (perturbation-selected MRCI (MRCI-PS)) is able to reproduce the accuracy of complete MRCI expansions with only a small number of configurations variationally evaluated.
Encapsulation of secondary and tertiary ammonium salts by resorcinarenes and pyrogallarenes: the effect of size and charge concentration
2015
The binding of different categories of alkyl ammonium (secondary and tertiary mono- and di-ammonium) salts with resorcinarenes and a pyrogallarene through weak interactions was analysed in all phases. 1H NMR spectroscopy and electrospray ionisation mass spectrometry were utilized in analysing the complexes in solution and in the gas phase, respectively. The 1H NMR titration studies in methanol-d4 reveal that the association constants for the 1:1 complexes vary according to the electronic properties of the hosts as well as the size, geometric orientation and charge concentration of the guest cations with binding constants of up to 950 M−1 in some cases. Mass spectrometry reveals 1:1 monomeri…
ChemInform Abstract: Lithium Enediolates and Dienediolates of Carboxylic Acids in Synthesis: Alkylation with Secondary Halides.
2010
Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.