The origin of the surprising stabilities of highly charged self-assembled polymetallic complexes in solution

The thermodynamics of electrochemical and complexation reactions involving the heterobimetallic triple-stranded helicates [MA(L5)3]n+ (M=Ru(II), Cr(III) and A=Ca(II), Lu(III)) reveal that solvation processes mask intramolecular intermetallic repulsions in solution, a phenomenon at the origin of the surprising stabilities of highly charged self-assembled polymetallic complexes in solution. A judicious combination of Born-Haber cycles and the Born equation restores the expected electrostatic trend in the gas phase, in which intermetallic interactions can be simply modeled using a standard Coulombic approach. Semiquantitative estimation and prediction of the contribution of the intermetallic repulsion to the total free energy of the formation of discrete polymetallic assemblies in solution become thus accessible. This point is crucial for programming stable metallosupramolecular architectures in solution.     

A comparison of two methods for selecting vibrational configuration interaction spaces on a heptatomic system: ethylene oxide

Two recently developed methods for solving the molecular vibrational Schrodinger equation, namely, the parallel vibrational multiple window configuration interaction and the vibrational mean field configuration interaction, are presented and compared on the same potential energy surface of ethylene oxide, c-C(2)H(4)O. It is demonstrated on this heptatomic system with strong resonances that both approaches converge towards the same fundamental frequencies. This confirms their ability to tackle the vibrational problem of large molecules for which full configuration interaction calculations are not tractable.     

Spectroscopic and kinetic evidence for an accumulating intermediate in an SNV reaction with amine nucleophiles. Reaction of methyl beta-methylthio-alpha-nitrocinnamate with piperidine and morpholine

A spectroscopic and kinetic study of the reaction of methyl beta-methylthio-alpha-nitrocinnamate (4-SMe) with morpholine, piperidine, and hydroxide ion in 50% DMSO/50% water (v/v) at 20 degrees C is reported. The reactions of 4-SMe with piperidine in a pH range from 10.12 to 11.66 and those with morpholine at pH 12.0 are characterized by two kinetic processes when monitored at lambdamax (364 nm) of the substrate, but by only one process when monitored at lambdamax (388) nm of the product. The rate constants obtained at 388 nm were the same as those determined for the slower of the two processes at 364 nm. These rate constants refer to product formation, whereas the faster process observed at 364 nm is associated with the loss of reactant to form an intermediate. In contrast, for the reaction of 4-SMe with morpholine at pH 8.62 the rates of product formation and disappearance of the substrate were the same, i.e., there is no accumulation of an intermediate. Likewise, the reaction of 4-SMe with OH- did not yield a detectable intermediate. The factors that allow the accumulation of intermediates in certain SNV reactions but not in others are discussed in detail, and structure-reactivity comparisons are made with reactions of piperidine and morpholine with other highly activated vinylic substrates.     

Charge state effect on the zwitterion influence on stability of non-covalent interaction of single-stranded DNA with peptides

Negative ion ESI mass spectrometry was used to study the gas-phase stability and dissociation pathways of peptide-DNA complexes. We show that bradykinin and three modified peptides containing the basic residue arginine or lysine form stable interactions with single-stranded oligonucleotides. ESI-MS/MS of complexes of T(8) with PPGFSPFRR resulted in a major dissociation pathway through cleavage of the peptide covalent bond. The stability of the complex is due to electrostatic interaction between the negatively charged phosphate group and the basic side chain of the arginine and lysine residues as demonstrated by Vertes et al. and Woods et al. In fact, the present work establishes the role played by zwitterions on complex stabilisation. The presence of protons in nucleobase and/or amino acid contributes in reinforcing the strength of the salt bridge (SB) interaction. The zwitterionic form of the most basic of amino acid residues, arginine, is assumed to form a strong SB interaction to the negatively charged phosphate groups of DNA. This non-covalent complex is stable enough to withstand disruption of the non-covalent interaction and to first break the covalent bond. Moreover, the dependence of fragmentation patterns upon the complex charge state is explained by the fact that the net number of negative charges modulates the number of zwitterionic sites, which stabilise the complexes. Finally, the weak influence of the nucleobase is assumed by the existence of competition for proton addition between the nucleobase and the R/K side chain leading to a decrease in the stabilisation of the SB interaction.     

Kinetics of oxygen exchange over CeO2-ZrO2 fluorite-based catalysts

The kinetics of 18O/16O isotopic exchange over CeO2-ZrO2-La2O3 and Pt/CeO2-ZrO2 catalysts have been investigated under the conditions of dynamic adsorption-desorption equilibrium at atmospheric pressure and a temperature range of 650-850 degrees C. The rates of oxygen adsorption-desorption on Pt sites, support surface, oxygen transfer (spillover) from Pt to the support as well as the amount of oxygen accumulated in the oxide bulk, and oxygen diffusion coefficient were estimated. The nanocrystalline structure of lanthana-doped ceria-zirconia prepared via the Pechini route with a developed network of domain boundaries and specific defects guarantees a high oxygen mobility in the oxide bulk (D = (1.5 / 2.0).10-18 m2 s-1 at 650 degrees C) and allows accumulation of over-stoichiometric/excess oxygen. For Pt/CeO2-ZrO2, oxygen transfer from Pt to support (characteristic time < 10-2 s) was shown to be responsible for the fast exchange between the gas-phase oxygen and oxygen adsorbed on the mixed oxide surface. The rate of direct exchange between the gas phase and surface oxygen is increased as well due to the increased concentration (up to 2 monolayers) of surface/near subsurface oxygen species accumulated on the oxygen vacancies (originated from the incorporation of highly dispersed Pt atoms). The characteristic time of diffusion of the oxygen localized in the subsurface layers is about 1 s. The overall quantity of over-stoichiometric oxygen and/or hydroxyl groups accumulated in the bulk can reach the equivalent of 10 monolayers, and characteristic time of oxygen diffusion within the bulk is about 20 s. All these kinetic data are required for the further step of modeling partial oxidation of hydrocarbons under steady- and unsteady-state conditions.     

Characterisation of the supramolecular structure of malonamides by application of pulsed field gradients in NMR spectroscopy

Malonamides are known and extensively studied for their lanthanide and actinide extracting properties. Those studies have also highlighted aggregated phenomena and a splitting of the organic phase, in some particular experimental conditions. To explain this behaviour of extractants, (1)H NMR was used to study micellar phenomena by the determination of the self-diffusion coefficients of two malonamides only different by the length of their alkyl chain (DMDBTDMA and DMDBPMA), in presence of n-dodecane and for systems saturated with water or anhydrous. Several information on the aggregates and on the malonamide supramolecular structure were obtained by fitting the curves of self-diffusion coefficient vs. concentration and by conjugated NMR experimental data to potentiometric titrations and physical measurements.     

Design and Implementation of a Novel Quench Flow Reactor for the Study of Nascent Olefin Polymerisation

A novel stopped flow reactor system is described in the current work, along with the underlying design philosophy. While the concept of stopped flow technology is not recent, this system is the first to be designed with the objective of studying particle morphology, and to work at extremely short (40 ms) residence times. It is shown that traditional chemical engineering principles are required to properly design and operate this type of reactor, and that when correctly design, it is a very flexible tool for the study of nascent polymerisation of olefins.

     

Allergenic α-methylene-γ-lactones. A simple method for the introduction of deuterium in sesquiterpenic α-methylene-γ-butyrolactones.

Sodium borohydride reduction of sesquiterpene lactone vinylic sulfoxides in a deuterated solvent lead to ²H-Iabeled natural allergens ; the mechanism of hydride addition is discussed.     

Décomposition du percarbonate de O,O-t-butyle et O-isopropényle en solution: Acétonylation des esters,acides et nitriles

The Free-Radical Decomposition of O,O-t-Butyl and O-Isopropenyl Peroxycarbonate in Solution: the Acetonylation of Esters, Acides and Nitriles The free-radical decomposition of O, O-t-butyl and O-isopropenyl peroxycarbonate in substratres possessing mobile H-atoms (S? H) consists mainly in an induced chain process leading to acetonylated derivatives of the solvent. Fairly good yields are obtained but teh acetonylation of functional substrates often gives mixtures of isomers. In the case of methyl acetate, the acetonylation occurs on the C-atoms adjacent to the carbonyl (acylox moiety) and to the O-atom (alkox moiety). However, the relative amounts of the isomeric products depend on the concentration of the peroxycarbonate solutions; at lowest concentration, methyl 4-oxopentanoate (acyloxy moiety) is obtained selectively. It is assumed that the free radicals issued from the solvent are able to abstract H-atoms of other molecules of solvent before adding to the double bond of the peroxycarbonate; the more the peroxycarbonate solution is diluted the more the transfers from the C-atom adjacent to the carbonyl to the radicals adjacent to the O-atom are favoured. In the case of methyl alkanoates, H-transfers from the α-C-atoms to β-radicals of teh acyloxy moiety may account for the orientation of the process. Owing to similar H-transfer processes, the acetonylation of functional esters, of acids and nitriles is selective in most cases.