Charly Mayeux

Towards the Discrimination of Carboxylates by Hydrogen-Bond Donor Anion Receptors

The binding constants (log Kass ) of small synthetic receptor molecules based on indolocarbazole, carbazole, indole, urea and some others, as well as their combinations were measured for small carboxylate anions of different basicity, hydrophilicity and steric demands, that is, trimethylacetate, acetate, benzoate and lactate, in 0.5 % H2 O/[D6 ]DMSO by using the relative NMR-based measurement method. As a result, four separate binding affinity scales (ladders) including thirty-eight receptors were obtained with the scales anchored to indolocarbazole. The results indicate that the binding strength is largely, but not fully, determined by the strength of the primary hydrogen-bonding interaction. The latter in turn is largely determined by the basicity of the anion. The higher is the basicity of the anion the stronger in general is the binding, leading to the approximate order of increasing binding strength, lactate<benzoate<acetate≤trimethylacetate, which holds with all investigated receptors. Nevertheless, there are a number of occasions when the binding order changes with changing of the carboxylate anion, sometimes quite substantially. Principal component analysis (PCA) reveals that this is primarily connected to preferential binding of trimethylacetate, supposedly caused by an additional hydrophobic/solvophobic interaction. These findings enable making better predictions, which receptor framework or cavity is best suited for carboxylate anions in receptor design.

Computational Study of Cesium Cation Interactions with Neutral and Anionic Compounds Related to Soil Organic Matter

The gas-phase cesium cation affinities (CsCAs) and basicities (CsCBs) for 56 simple neutral compounds (mostly aromatic molecules) and 41 anions (carboxylates and phenolates) were calculated using density functional theory (DFT), in the context of the interaction of Cs(+) with soil organic matter (SOM). The B3LYP/def2-TZVP method gives in general CsCAs and CsCBs in a good agreement with experimental data. The strong deviations in case of NO(3)(-) and CsSO(4)(-) anions need further experimental investigations as the high-level CCSD(T) calculations support B3LYP results. Different cesium cation complexation patterns between Cs(+) and the neutral and anionic systems are discussed. As expected, the strongest CsCAs are observed for anions. The corresponding quantities are approximately by 4-5 times higher than for the neutral counterparts, being in the range 90-118 kcal/mol. The weakest cesium cation bonding is observed in the case of unsubstituted aromatic systems (11-15 kcal/mol).

Evaluation of alkali metal cation affinities and basicities using extrapolation to the complete basis set limit.

The complete basis set (CBS) extrapolation is used at Hartree-Fock and second-order Møller-Plesset perturbation theory levels and with the def2-xZVP x-ζ basis set (x = 2-4). This approach leads to general, robust, and well-calibrated methods, especially when Hartree-Fock energy (E(HF)) and correlation energies (E(CE)) are extrapolated separately. Indeed, the absolute deviations between theoretical and experimental data are usually smaller than the reported experimental errors. We also point out the need to change usual parameters utilized in CBS methods when calculations involve atoms from third and subsequent rows. The best CBS scheme studied in the current work for obtaining energies for the estimation of alkali metal cation affinities and basicities is E(CBS)[∞] = 1.10529·E(HF)[4] - 0.10529·E(HF)[2] + 0.92703·E(CE)[4] - 0.07297·E(CE)[2], where E(HF)[2], E(HF)[4], E(CE)[2], and E(CE)[4] are the Hartree-Fock energy (E(HF)) and MP2 correlation energies (E(CE)) obtained with def2-QZVP (x = 4) and def2-SV(p) (x = 2) basis sets.

A study of the cesium cation bonding to carboxylate anions by the kinetic method and quantum chemical calculations.

Collision-induced dissociation (CID) of the Cs(+) heterodimer adducts of the nitrate anion (NO(3)(-)) and a variety of substituted benzoates (XBenz(-)) [(XBenz(-))(Cs(+))(NO(3)(-))](-) produces essentially nitrate and benzoate ions. A plot of the natural logarithm of their intensity ratio, ln[I (NO(3)(-))/I(XBenz(-))], versus the calculated cesium cation affinity (DFT B3LYP) of the substituted benzoate ions (equivalent to the enthalpy of heterolytic dissociation of the salt) is reasonably linear. This suggests that the kinetic method can be used as a source of data on the intrinsic interaction between the anionic and the cationic moieties in a salt.

Interaction of the Cesium Cation with Mono-, Di-, and Tricarboxylic Acids in the Gas Phase. A Cs+ Affinity Scale for Cesium Carboxylates Ion Pairs

Humic substances (HS), including humic and fulvic acids, play a significant role in the fate of metals in soils. The interaction of metal cations with HS occurs predominantly through the ionized (anionic) acidic functions. In the context of the effect of HS on transport of radioactive cesium isotopes in soils, a study of the interaction between the cesium cation and model carboxylic acids was undertaken. Structure and energetics of the adducts formed between Cs+ and cesium carboxylate salts [Cs+RCOO−] were studied by the kinetic method and density functional theory (DFT). Clusters generated by electrospray ionization mass spectrometry from mixtures of a cesium salt (nitrate, iodide, trifluoroacetate) and carboxylic acids were quantitatively studied by CID. By combining the results of the kinetic method and the energetic data from DFT calculations, a scale of cesium cation affinity, CsCA, was built for 33 cesium carboxylates representing the first scale of cation affinity of molecular salts. The structural effects on the CsCA values are discussed.

Catalytic Effect of Cesium Cation Adduct Formation on the Decarboxylation of Carboxylate Ions in the Gas Phase

The effect of Cs(+) ligation on the decarboxylation of malonic acids (unsubstituted and methyl-, dimethyl-, ethyl-, and phenyl-substituted) in their carboxylate form was studied in the gas phase using tandem mass spectrometry. The study is based on the comparison of the decarboxylation of the bare monoanion (hydrogen malonates) and of the cesium adduct of the cesium salt (Cs(+) [cesium hydrogen malonates]) under collisional activation. Energy-resolved dissociation curves of the negative and positive ions exhibit major differences. Decarboxylation of the cationic adducts of substituted malonic acid salts occurs at significantly lower collisional activation than for the corresponding bare hydrogen malonate anions. The conclusions from these experiments are supported by DFT calculations. The calculated activation parameters (enthalpy and Gibbs energy) confirm that the cesium cation coordination assists the decarboxylation of the carboxylate form.