Defects in divided zinc-copper aluminate spinels: structural features and optical absorption properties

Zn1-xCuxAl2O4 (0 < or = x < 0.30) compounds have been synthesized by polyesterification using metallic salts and annealing at low temperatures as well as by conventional solid state. XRD-powder data refinements (Rietveld method) have demonstrated that both compound series crystallize in the spinel structure (Fd3m) and exhibit similar inversion rates. This low-temperature route lead to metastable phases with crystallite sizes around 40 nm whereas particle sizes are larger than 1 moicrom in the case of solid-state route. This preparative method largely described in the literature allows stabilizing reduced copper states thanks to the presence of reductive organic species, which are decomposed below T = 700 degrees C. The absorption spectra of the x = 0.15 composition exhibit strong differences depending on the synthesis route. These differences can be explained by the occurrence of Cu2+/Cu+ mixed valencies in compounds prepared by the low-temperature route; 33% of monovalent copper has been identified in the x = 0.15 composition prepared by low-temperature process, whereas the solid-state compound contains only divalent copper. Reductive properties of polyesterification reaction implying citric acid and low annealing temperature (T = 700 degrees C) are mainly responsible of the occurrence of the Cu2+/Cu+ mixed valencies. Actually, the annealing under air at T = 1000 degrees C of divided zinc-copper aluminates prepared at low temperatures (T = 700 degrees C) leads to the oxidation reaction Cu+ --> Cu2+ + e- confirmed by the evolution of magnetic measurements, ESR spectra, and optical absorption properties. Defects such as oxygen vacancies in the anionic network leading to reduction in the cations coordination number could also explain the strong evolution of optical absorption spectra especially around lambda = 700 nm where intervalencies transfer (Cu+/Cu2+) as well as intra-atomic d-d transitions (Cu2+ in a 5-fold coordination) can occur. Finally the occurrence of monovalent and divalent copper at the surface of such divided oxides, probably in tetrahedral sites, has been demonstrated by FTIR spectroscopy using the co-adsorption of CO and NO as probe molecules.     

Theoretical elastic moduli for disordered packings of interconnected spheres

A theoretical model has been developed which provides analytical expressions for the elastic moduli of disordered isotropic ensembles of spheres interconnected by physical bonds. Young's and shear moduli have been derived assuming an ideal random isotropic network and the radial distribution function for disordered packings of spheres. The interparticle interactions are accounted for in terms of surface forces for the two distinct cases of perfectly rigid spheres and spheres deformable at contact. A theoretical expression is also derived in a similar way for the bulk or compressibility modulus. In this case, an atomistic approach has been followed based on the analogy with noble gas solids and colloidal crystals. Also in this case, disordered spatial distribution of the spheres is described statistically. For the case of colloidal aggregates, a total two-body mean-field interaction potential is used which includes the Born repulsion energy. This latter contribution plays an essential role in determining the compression behavior of systems of particles aggregated in the primary minimum of the potential well and, therefore, must not be neglected. Both the expression of the Young's modulus and that of the compressibility modulus derived in this work are found to be consistent with two distinct sets of experimental data which recently appeared in the literature.     

1,2,3-triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M=FeIII, CrIII and VIII/IV) and related compounds: ground-state spins ranging from S=0 to S=25 and spin-enhanced magnetocaloric effect

We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe)18Cl6] (M=FeIII, CrIII) and [V14(L)6O6(OMe)18Cl6-xOx] (L=anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe14(C2H2N3)6O6(OMe)18Cl6], [Cr14(bta)6O6(OMe)18Cl6] (btaH=benzotriazole), [V14O6(Me2bta)6(OMe)18Cl6-xOx] [Me2btaH=5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-Cl}2+ and {VIV=O}2+] and for the distorted [FeIII14O9(OH)(OMe)8(bta)7(MeOH)5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S相似文献   

Simultaneous determination of multiple intracellular metabolites in glycolysis, pentose phosphate pathway and tricarboxylic acid cycle by liquid chromatography-mass spectrometry

A highly selective and sensitive method for identification and quantification of intracellular metabolites involved in central carbon metabolism (including glycolysis, pentose phosphate pathway and tricarboxylic acid cycle) by means of liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS) was developed. The volatile ion pair modifier tributylammonium acetate (TBAA) was employed in the mobile phase for simultaneously separation of 29 negatively charged compounds including sugar phosphates, nucleotides, and carboxylic acids on a common C18 reversed-phase column. Method validation results displayed that limits of detection (LODs) calculated according to DIN (German Institute for Standardization) 32645 are mostly below 60 nM, only with the exception of pyruvate and malate. The calibration curves showed excellent linearity mainly over three orders of magnitude with correlation coefficients R(2)>0.9982. This LC-MS/MS method was successfully applied to determine these metabolites in cell extracts of Escherichia coli. Most of the intracellular metabolites were found within the detection range and the relative standard deviations of the measurements were smaller than 5.65% (n=5) for a cell extract sample.     

Novel naphthalene diimides as activatable precursors of bisalkylating agents, by reduction and base catalysis

Mild activation of water-soluble naphthalene diimides (NDIs) as bisalkylating agents has been achieved by base catalysis and by chemical and electrochemical reductions. NDI activation by a single electron reduction represents a novelty in the field of activatable electrophiles. Under mild reduction, induced by S2O4(2-) in aqueous solution, the resulting NDI radical anion (NDI*-) undergoes a monomolecular fragmentation to yield a new transient species, where the NDI radical anion is tethered to a quinone methide moiety. The latter still retains electrophilic properties, reacting with amines, thiols, and ethyl vinyl ether. Owing to the NDI recognition properties, these results represent the first step toward selective and bioactivatable cross-linking agents.     

A practical synthesis of 2,4(5)-diarylimidazoles from simple building blocks

A simple and efficient approach to selectively obtain 2,4(5)-diarylimidazoles suppressing formation of 2-aroyl-4(5)-arylimidazoles is described. The yield of each of the two products strongly depends on the reaction conditions employed. This reaction provides a simple method to prepare small libraries of biologically active compounds by parallel synthesis.     

Ionization and tautomerization of 2-nitrocyclohexanone in aqueous solution

The keto-enol tautomerism of 2-nitrocyclohexanone (2-NCH) was studied in aqueous solution under different experimental conditions. Ketonization rate constants were measured spectrophotometrically at 25 degrees C at an ionic strength of 0.4 mol dm-3 (NaCl) in diluted hydrochloric acid, in diluted sodium hydroxide, and in several buffers by using NaHSO3 as the scavenger of the keto form. A value of pK(a)(EH) = 4.78 for the enol form was obtained from the rate-pH profile of the reaction. A value of pK(a)(KH) = 5.97 for the keto form was directly obtained from the UV-vis spectra of 2-NCH recorded at different pHs. The equilibrium constant for the keto-enol tautomerism, pK(T) = -log([enol]/[ketone]) = 1.19, was obtained by combining the two pKa values (pK(T) = pK(a)(KH) - pK(a)(EH)). A comparison of these results with the corresponding values (Keefe, J. R.; Kresge, A. J. In The Chemistry of Enols; Rappoport, Z., Ed.; Wiley & Sons: New York, 1990; pp 399-480) for cyclohexanone shows the dramatic effects of an alpha-nitro substituent on the keto-enol acidities and the tautomerization constant of alicyclic ketones. Rates and equilibria were discussed in the light of the Br?nsted equation, the principle of nonperfect synchronization, and the Marcus theory. It turns out that, on passing from nitroalkanes to nitroketones, the resonance contribution to pKa and deprotonation rate decreases, being overwhelmed by steric and inductive effects.     

Interactions at the surface of organophilic-modified laponites: a multinuclear solid-state NMR study

Organically modified clays are largely employed in the preparation of nanostructured materials. The structural and dynamic characterization of the clay surface appears very important in the perspective of understanding the molecular mechanisms determining the improvement of the material properties. To this aim, in this work, a synthetic clay, Laponite, was studied in its untreated hydrophilic Na+-form, after ion exchange with alkylammonium cations and after subsequent grafting reaction with an alkoxysilane. These three samples were characterized by IR, SEM, TGA, and X-ray techniques and were deeply investigated by means of a wide combination of 29Si, 13C, and 1H high- and low-resolution solid-state NMR experiments. The grafting reaction with alkoxysilanes, occurring at the clay platelet edges, resulted in a reduction of the clay inter-platelet distances, and in an increased disorder in both the arrangement of the platelets and the conformational structure of the intercalated organic cation chains, probably due to the relative twisting of adjacent platelets.     

Violation of distribution symmetry in statistical evaluation of absolute enantioselective synthesis

Enantiomeric excesses obtained in absolute enantioselective synthesis by chiral autocatalysis (Soai-reaction) were statistically analyzed. Two sets of parallel experiments, which were performed under chemically different conditions, are available. One group contains 37, while the other contains 84 preparative results. The former group shows some interesting tendencies but does not give conclusive statistical results. The sample of 84 parallel experiments, providing 39 R- and 45 S-excesses have shown that these data represent two distinct, non-symmetric sets with different non-Gaussian distributions. Clear S preference was found.     

Computational clues for a new mechanism in the glycosylase activity of the human DNA repair protein hOGG1. A generalized paradigm for purine-repairing systems?

A theoretical density functional theory (DFT, B3LYP) investigation has been carried out on the catalytic cycle responsible for the glycosylase activity of the human DNA repair protein hOGG1: enzyme activation, cleavage of the glycosidic bond, and expulsion of the damaged base. An unprecedented large quantum mechanics (QM) model system has been used, which includes a complete oxoG molecule, the deoxyribose ring bonded to the phosphate groups, and most of the surrounding residues that simulate the protein binding pocket. It has been found that Asp268 does not play any role in Lys249 activation and that the oxoG basis acts as a coenzyme, triggering nucleophile activation by Lys249 deprotonation. An SN2 nucleophilic attack by Lys249 on the anomeric carbon then follows. This is the rate-determining step of the process with an activation barrier of 16.7 kcal mol(-1) in good agreement with the experimental value of 17.1 kcal mol(-1). The expelled oxoG plays again as an enzyme cofactor at the end of the process by activating (via proton transfer) ribose ring opening and Schiff base formation. This study suggests a recurring catalytic strategy in the enzymatic cleavage of purine nucleoside where the activation of the leaving group by protonation of the nucleoside base (via an enzymatic general acid) triggers the cleavage of the glycosidic bond.