35 research outputs found
Interpretation of experimental hydrogen-bond enthalpies and entropies from COSMO polarisation charge densities
In this work, experimental hydrogen-bond (HB) enthalpies measured in previous works for a wide range of acceptor molecules in dilute mixtures of 4-fluorophenol in non-polar solvents are quantified from COSMO polarisation charge densities σ of HB acceptors (HBA). As well as previously demonstrated for quantum chemically calculated HB enthalpies, a good correlation of the experimental data with the polarisation charge densities is observed, covering an extended range of HBA (O, N, S, π systems and halogens) ranging from very weak to strong hydrogen bonds. Furthermore, for the first time, a quantitative analysis of experimental HB entropies is performed for such a chemical diversity of HBA. A good quantification of these entropies is achieved using the polarisation charge density σ as a descriptor in combination with the logarithm of a directional partition function ΩHB. This partition function covers the directional and multiplicity entropy of HBA and is based on the σ-proportional HB enthalpy expression taken from COSMO-RS. As a result, the experimental HB enthalpies and free energies of the ∼300 HB complexes are quantified with an accuracy of ∼2 kJ mol−1 based on COSMO polarisation charge densities
Pretreatment of the cockroach cercal afferent/giant interneuron synapses with nicotinoids and neonicotinoids differently affects acetylcholine and nicotine-induced ganglionic depolarizations
We have recently demonstrated that neonicotinoid insecticides were able to act as agonists of postsynaptic nicotinic acetylcholine receptors (nAChRs) expressed at the synapse between the cercal nerve XI and the giant interneurons, in the sixth abdominal ganglion. In this work, we demonstrated that nicotinoids such as nornicotine acted as an agonist of nicotinic acetylcholine receptors expressed at cercal afferent/giant interneurons while cotinine was a poor agonist. Indeed, nornicotine induced a ganglionic depolarization which was blocked by the nicotinic antagonist mecamylamine. In addition, we found that pretreatment of the sixth abdominal ganglion with 1 and 10 muM nornicotine and cotinine had no significant effect on acetylcholine and nicotine-induced depolarization. But pretreatment with 1 and 10 muM acetamiprid and imidacloprid had a strong effect. 1 and 10 muM acetamiprid completely blocked acetylcholine-induced depolarization, whereas imidacloprid had a partial effect. The present work therefore suggests, in agreement with previous studies, that nornicotine and cotinine bind to distinct cockroach postsynaptic nAChRs, whereas acetamiprid and imidacloprid have competitive effects with acetylcholine and nicotine on ganglionic depolarization
Orientational Effects and Random Mixing in 1‑Alkanol + Nitrile Mixtures
1-Alkanol + alkanenitrile or + benzonitrile systems have been investigated by means of the molar excess
functionsenthalpies (Hm E ), isobaric heat capacities (Cp,m
E ), volumes (Vm E ), and entropiesand using the Flory model and the
concentration−concentration structure factor (SCC(0)) formalism. From the analysis of the experimental data available in the
literature, it is concluded that interactions are mainly of dipolar type. In addition, large Hm E values contrast with rather low Vm E
values, indicating the existence of strong structural effects. Hm E measurements have been used to evaluate the enthalpy of the
hydroxyl−nitrile interactions (ΔHOH−CN). They are stronger in methanol systems and become weaker when the alcohol size
increases. In solutions with a given short chain 1-alkanol (up to 1-butanol), the replacement of ethanenitrile by butanenitrile
weakens the mentioned interactions. Application of the Flory model shows that orientational effects exist in methanol or 1-
nonanol, or 1-decanol + ethanenitrile mixtures. In the former solution, this is due to the existence of interactions between unlike
molecules. For mixtures including 1-nonanol or 1-decanol, the systems at 298.15 K are close to their UCST (upper critical
solution temperature), and interactions between like molecules are dominant. Orientational effects also are encountered in
methanol or ethanol + butanenitrile mixtures because self-association of the alcohol plays a more important role. Aromaticity
effect seems to enhance orientational effects. For the remainder of the systems under consideration, the random mixing
hypothesis is attained to a rather large extent. Results from the application of the SCC(0) formalism show that homocoordination
is the dominant trend in the investigated solutions, and are consistent with those obtained from the Flory model
Quantum calculations of At-mediated halogen bonds: on the influence of relativistic effects
International audienc
Structural features and protonation site of epibatidine in the gas phase: an investigation through infrared multiphoton dissociation spectroscopy and computational chemistry
International audienc
Theoretical investigation of the AtO<sup>+</sup> hydrolyzed species in ligand-exchange reactions including solvation effects
National audienc
The role of water molecules of the first solvation shell in modelling ligand-exchange reactions leading to AtO+ hydrolyzed species
International audienc
CCDC 764884: Experimental Crystal Structure Determination
Related Article: A.Tabatchnik-Rebillon, C.Aube, H.Bakkali, T.Delaunay, G.T.Manh, V.Blot, C.Thobie-Gautier, E.Renault, M.Soulard, A.Planchat, J.-Y.Le Questel, R.Le Guevel, C.Guguen-Guillouzo, B.Kauffmann, Y.Ferrand, I.Huc, K.Urgin, S.Condon, E.Leonel, M.Evain, J.Lebreton, D.Jacquemin, M.Pipelier, D.Dubreuil|2010|Chem.-Eur.J.|16|11876|doi:10.1002/chem.201000859,Related Article: A.Tabatchnik, V.Blot, M.Pipelier, D.Dubreuil, E.Renault, J.-Y.Le Questel|2010|J.Phys.Chem.A|114|6413|doi:10.1021/jp101394t,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.