Effects of the doping and the number of planes on the shadow bands of Bi-based cuprates

Angle resolved photoemission spectroscopy (ARPES) has been used to investigate the shadow bands present at the Fermi surface of bismuth based superconductors. Bi₂Sr₂CaCu₂O_8+δ (Bi2212) single crystals with different doping levels and Bi₂Sr₂CuO_6+δ (Bi2201) thin films have been studied by means of momentum distribution curves along the ΓY high symmetry direction in two different Brillouin zones and for an extensive photon energy range. The results show an enhancement of the shadow band intensity in the second Brillouin zone for photon energies around hν=30 eV. Furthermore, the ratio Shadow Bands/Main Band is shown to be constant as a function of both the doping level and the number of CuO₂ planes. An interpretation of this observation on the basis of the current theoretical models will be provided.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

Hétérocycles contenant du phosphore: XXVIII—Etude par Résonance Magnétique Nucléaire et analyse conformationnelle de quelques oxazaphosphorinanes-1,3,2 (II)

The ¹H n.m.r. spectra of some new 1,3,2-oxazaphosphorinanes are analysed. The stereochemistry and the ring conformation is discussed. The free energy and the torsional angle of the C-4? C-5 and C-5? C-6 fragments are calculated for some of these 1,3,2-oxazaphosphorinanes.     

QM/MM determination of kinetic isotope effects for COMT-catalyzed methyl transfer does not support compression hypothesis

Secondary alpha-D3 kinetic isotope effects calculated by the hybrid AM1/TIP3P/CHARMM method for the reaction of S-adenosylmethionine with catecholate anion in aqueous solution and catalyzed by rat liver catechol O-methyltransferase at 298 K are 0.94 and 0.85, respectively, in good accord with experiment. The large inverse effect for the enzymatic reaction is not due to compression but arises from significant increases in the stretching and bending force constants involving the isotopically substituted atoms of the transferring methyl group as between the reactant complex and the transition structure, larger than for the reaction in water.     

Theoretical insights in enzyme catalysis

In this tutorial review we show how the methods and techniques of computational chemistry have been applied to the understanding of the physical basis of the rate enhancement of chemical reactions by enzymes. This is to answer the question: Why is the activation free energy in enzyme catalysed reactions smaller than the activation free energy observed in solution? Two important points of view are presented: Transition State (TS) theories and Michaelis Complex (MC) theories. After reviewing some of the most popular computational methods employed, we analyse two particular enzymatic reactions: the conversion of chorismate to prephenate catalysed by Bacillus subtilis chorismate mutase, and a methyl transfer from S-adenosylmethionine to catecholate catalysed by catechol O-methyltransferase. The results and conclusions obtained by different authors on these two systems, supporting either TS stabilisation or substrate preorganization, are presented and compared. Finally we try to give a unified view, where a preorganized enzyme active site, prepared to stabilise the TS, also favours those reactive conformations geometrically closer to the TS.     

Physicochemical study of solid-state benznidazole–cyclodextrin complexes

Although not being the ideal drug due to its low solubility and high toxicity, the benznidazole is the drug currently chosen for Chagas disease treatment. The deep knowledge about the characteristics of the drug in addition to the knowledge of more effective vectorization techniques of drugs in pharmaceutical forms allows a faster and cheaper development of a new therapeutic alternative in comparison to the introduction of a new molecule in the treatment. The aim of this study is the characterization of inclusion complexes Benznidazole and cyclodextrins in solid state. The interactions between Benznidazole (BNZ) and β-cyclodextrins (β-CD) modified: randomly methylated β-CD (RMβCD) and sulfobutylether β-CD (SBβCD) were studied by differential scanning calorimetry (DSC), fourier transform-infrared spectroscopy, RAMAN, and scanning electron microscopy. The preparation of solid-state binary systems by different techniques, namely, kneading, evaporated, and freeze-drying. The results suggest the formation of inclusion complexes of the drug with both CDs types in solid state by the techniques which were used, based on physicochemical data of interaction compared to the drug or the CDs/drug physical mixture. Thus, the preparation technique played an important role in the BNZ and modified CDs.     

Single‐Step Sulfo‐Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu₂ZnSn(S_ySe_1?y)₄ (kesterite) photovoltaic absorbers are synthesized by a one‐step annealing process from copper‐poor and zinc‐rich precursor metallic stacks prepared by direct‐current magnetron sputtering deposition. Depending on the chalcogen source—mixtures of sulfur and selenium powders, or selenium disulfide—as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur‐rich to selenium‐rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as‐grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single‐step sulfo‐selenization method, pentenary kesterite‐based devices with conversion efficiencies up to 4.4 % are obtained.     

Gamma-ray multiplicity measurements in the28Si+64Ni reaction at 163.8 MeV

The²⁸Si+⁶⁴Ni reaction at 163.8 MeV incident energy is studied by measuring in coincidenceγ-rays and charged particles identified from Z=2 to Z=16. The transition from quasi-elastic to more damped reactions is observed when the difference between the detected charge and the projectile one is increased. The strong influence of the particle decay on the measuredγ-ray multiplicity is evidenced with the help of the statistical model computer code CASCADE. Dissipative events are well described in the rolling limit with excitation energy equally shared between the fragments. The overall agreement is lost for the fragments with the projectile charge which show a small value of theγ-multiplicity even for dissipative events. This is probably connected with the previously observed non statistical behavior of gamma rays emitted in coincidence with projectile-like fragments. In the alpha-spectrum measured in coincidence with gamma-rays, the deexcitation of fused systems is clearly separated from in flight emission of deep inelastic fragments. The low measured gamma-ray multiplicity for fusion events is qualitatively explained taking into account the effect of alpha-emission in the statistical decay.