Photochemistry of acetylacetone isolated in parahydrogen matrices upon 266 nm irradiation

The photochemistry of the chelated enol form of acetylacetone (AcAc) was investigated by UV excitation of the S(2) state at 266 nm in parahydrogen matrices, complemented by experiments in neon and normal hydrogen matrices. Infrared (IR) spectroscopy, combined with theoretical calculations, was used to identify the photoproducts. Isomerization towards various non-chelated forms (no intramolecular H-bond) of AcAc is the dominant channel whereas fragmentation is very minor. The isomerization kinetics is monitored by IR spectroscopy. Among the seven non-chelated conformers of AcAc, only three are formed in parahydrogen matrices, whereas four are observed in normal hydrogen matrices. This difference suggests that an active tunnelling process between conformers occurs in parahydrogen but is quenched in normal hydrogen where guest-host interactions are stronger. Fragmentation and isomerization of excited AcAc are discussed in the light of these new data. The role of the intermediate triplet state in the S(2)→ S(0) relaxation is confirmed, as the importance of phonons in the condensed phase.     

One‐, two‐, and three‐electron bonding: An “in vitro” theoretical study using noninteger nuclear charges evidences the crucial role of electronegativity in the strength of symmetrical bonds

Fictitious hydrogen atoms H*_A of variable nuclear charge 0.5 ≤ Z_A ≤ 2 (and thus of variable electronegativity) are used to study the intrinsic dependency of chemical bonding on electronegativity. Dissociation energy and equilibrium distance are reported for symmetrical 1‐, 2‐ and 3‐electron H*_AH*_A systems and 2‐electron dissymmetrical H*_A‐H ones. Dealing with symmetrical systems, the strongest two‐electron bonds are found for Z_A ≈ 1.2. Oneelectron and three‐electron strongest bonds occur respectively with low (ca. 0.7) and high (ca. 1.7) Z_A values and can become stronger than the corresponding 2‐electron system. Comparison with data on real systems leads to conclude that electronegativity is a prevailing atomic property in the control of the dissociation energy of symmetrical 1‐, 2‐ and 3‐electron bonds. A simplified mathematical model at Hartree‐Fock or Heitler‐London level with a minimal basis set reproduces these trends semi‐quantitatively and provides the overall shape of the dissociation curves. Finally some points are qualitatively discussed from MO analysis, which emphasize the dependence of the bonding/antibonding properties on the nucleus charge Z_A and their occupancy number. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Electrosynthesis of structured derivated polythiophenes: Application to electrodeposition of latex particles on these substrates

Synthesis of super-structured polymers is a great challenge because these entities could present a large choice of applications. Synthesis and electropolymerisation of thiophene derivatives are reported. Star-shaped 3D molecules are chosen because these structures ensure a high electronic conductivity. Three-dimensional structures could also assist the conductivity. 1,3,5-tris[5-(2,2′-dithienyl)]benzene 1, tris(2,2′-dithienyl)methylcarbinol 2, tris(5(2,2′:5′2″-terthienyl)methylcarbinol 3 are synthetised by different ways. UV and IR analysis are reported along with an AFM examination of the film. The first attempt of latex particle deposition on the film is also reported showing promising results in view of surface functionalisation.     

Chronopotentiometry as a Sensitive Interfacial Characterisation Tool for Peptide Aptamer Monolayers

Constant current chronopotentiometry is employed in conjunction with cyclic voltammetry and ac voltammetry to present in‐depth interfacial characterisations of the adsorption behaviour of a peptide affinity probe (Cys‐p53), of a thiolated hepta(ethylene glycol) (t‐OEG) and of mixed monolayers of these at mercury electrodes. The peptide sequence is derived from the interaction site of the protein p53 with the protein Mdm2. The adsorbed Cys‐p53 peptide is catalytically active towards the hydrogen evolution reaction, giving rise to very intense peaks in chronopotentiometry, whereas the oligo(ethylene glycol) is not. This difference enables one to monitor the presence of the peptide within mixed monolayers. It is shown that in the binary layers, the adsorption of t‐OEG is kinetically favoured while Cys‐p53 is thermodynamically more strongly adsorbed.     

Influence of the Absorbed Water on the Tensile Strength of Flax Fibers

The complex structure of flax fibres involves many chemical biomolecules located in an amorphous matrix in which cellulose micrifibrils are embbeded. The drying of flax fibres influences significantly their tensile strength. This result can be explained by the creation of damages within the fibre and by the modification of the chemical composition of the matrix components. This loss of water involves a modification of the adhesion between the cellulose microfibrils and the matrix. This modification is due to the evolution of the components ensuring the transfer of load between the microfibrils and thus conditioning the strength of the cellular wall.     

Numerical Prediction of Two-Phase Flow through a Tube Bundle Based on Reduced-Order Model and a Void Fraction Correlation

Predicting the void fraction of a two-phase flow outside of tubes is essential to evaluate the thermohydraulic behaviour in steam generators. Indeed, it determines two-phase mixture properties and affects two-phase mixture velocity, which enable evaluating the pressure drop of the system. The two-fluid model for the numerical simulation of two-phase flows requires interaction laws between phases which are not known and/or reliable for a flow within a tube bundle. Therefore, the mixture model, for which it is easier to implement suitable correlations for tube bundles, is used. Indeed, by expressing the relative velocity as a function of slip, the void fraction model of Feenstra et al. and Hibiki et al. developed for upward cross-flow through horizontal tube bundles is introduced and compared. With the method suggested in this paper, the physical phenomena that occur in tube bundles are taken into consideration. Moreover, the tube bundle is modelled using a porous media approach where the Darcy–Forchheimer term is usually defined by correlations found in the literature. However, for some tube bundle geometries, these correlations are not available. The second goal of the paper is to quickly compute, in quasi-real-time, this term by a non-intrusive parametric reduced model based on Proper Orthogonal Decomposition. This method, named Bi-CITSGM (Bi-Calibrated Interpolation on the Tangent Subspace of the Grassmann Manifold), consists in interpolating the spatial and temporal bases by ITSGM (Interpolation on the Tangent Subspace of the Grassmann Manifold) in order to define the solution for a new parameter. The two developed methods are validated based on the experimental results obtained by Dowlati et al. for a two-phase cross-flow through a horizontal tube bundle.     

Synthesis with immobilized enzyme of the most important sialic acid.

Starting from a crude mixture of N-acetylmannosamine and N-acetylglucosamine, N-acetylneuraminic acid has been easily synthesized on 2.8 millimoles scale, with one immobilized enzyme.     

Isolation and structure (x-ray analysis) of karinolide,a new quassinoid from Simaba Multiflora

Karinolide $\text{1}$ is a structurally novel C₂₀ quassinoid isolated from the French Guyanan Simaroubaceae, Simaba multiflora A.Juss. whose structure was established by X-ray diffraction analysis. 6α-Senecioyloxychaparrin $\text{2}$, the known 6α-senecioloyxychaparrinone $\text{3}$ and 9-methoxycanthin-6-one $\text{5}$ were also isolated ; their structure were determined by spectral means.     

Integer linear programming as a tool for constructing trees from quartet data

The task of the quartet puzzling problem is to find a best-fitting binary X-tree for a finite n-set from confidence values for the 3n4 binary trees with exactly four leaves from X, its fitness being measured by the sum of the confidence values of all "induced" four-leaves subtrees. We describe a method for finding an exact solution of this problem by integer linear programming. Similar procedures can also be used for finding, e.g. best-fitting "circular" networks. A crucial problem in this context is, of course, how to obtain the input confidence values for the quartet trees. We propose to use inner products of rate-matrix diagonals calculated for pairs of taxa and present the trees resulting from applying our approach to two data sets of up to 36 mitochondrial sequences of mammals including an outgroup.