The di-iron subsite of all-iron hydrogenase: mechanism of cyanation of a synthetic [2Fe3S]-carbonyl assembly

This paper describes the kinetics and intimate mechanisms associated with cyanation of [2Fe3S] assemblies to give species structurally related to the subsite of all-iron hydrogenase. Stopped-flow FTIR spectroscopy has enabled the quantitation of the dynamics of five well-defined steps that experimentally illustrate the role of bridging carbonyls in the assembly of the dicyanide species, how on-off sulfur ligation can have a dramatic effect on cyanation kinetics and how the [2Fe3S] core stabilises bridging carbonyl species.     

Transient FTIR spectroelectrochemical and stopped-flow detection of a mixed valence (Fe(I)-Fe(II)) bridging carbonyl intermediate with structural elements and spectroscopic characteristics of the di-iron sub-site of all-iron hydrogenase

Iron(I) in biology?: one-electron oxidation of an (Fe(I)-Fe(I)) carbonyl cyanide precursor bearing a proximal thioether group leads to an (Fe(I)-Fe(II)) bridging carbonyl transient with spectral features similar to the di-iron sub-site of the CO inhibited paramagnetic centre of all-iron hydrogenase.     

Lithiation of 2-heterosubstituted pyridines with BuLi-LiDMAE: evidence for regiospecificity at C-6.

The determination of the initial deprotonation site of 2-chloro- and 2-methoxypyridine during reaction with BuLi-LiDMAE has been investigated. A series of experiments on deuterated regioisomers revealed a direct lithiation at C-6 excluding a potential first classical ortholithiation and lithium equilibration in the reaction medium. These results suggested that the formation of lithium aggregates at the neighboring of the pyridinic nitrogen atom favored BuLi delivery at C-6 as well as 6-lithio intermediate stabilization.     

Supramolecular cluster catalysis: facts and problems

By checking the chemistry underlying the concept of “supramolecular cluster catalysis” we identified two major errors in our publications related to this topic, which are essentially due to contamination problems. (1) The conversion of the “closed” cluster cation [H₃Ru₃(C₆H₆)(C₆Me₆)₂(O)]⁺ (1) into the “open” cluster cation [H₂Ru₃(C₆H₆)(C₆Me₆)₂(O)(OH)]⁺ (2), which we had ascribed to a reaction with water in the presence of ethylbenzene is simply an oxidation reaction which occurs in the presence of air. (2) The higher catalytic activity observed with ethylbenzene, which we had erroneously attributed to the “open” cluster cation [H₂Ru₃(C₆H₆)(C₆Me₆)₂(O)(OH)]⁺ (2), was due to the formation of RuO₂ · nH₂O, caused by a hydroperoxide contamination present in ethylbenzene.     

Magnesium substitution in Nd0.7Sr0.3MnO3

Magnesium substitution in Nd_0.7Sr_0.3MnO₃ has been studied by neutron powder diffraction. Polycrystalline samples of nominal compositions Nd_0.7Sr_0.3Mn_1−yMg_yO₃ with y=0.0, 0.1, 0.2 and 0.3 were synthesized by the standard solid-state reaction method. Rietveld refinements of the neutron powder diffraction data showed that all samples had distorted perovskite structure of orthorhombic symmetry. Mg initially preferred to substitute for Nd and only at Mg concentration greater than 0.1, a substantial substitution for Mn occurred. Our study also showed that Mg-substitution did not change the crystal structure of Nd_0.7Sr_0.3MnO₃.     

Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX^th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV‐visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.     

Setting local rank constraints by orthogonal projections for image resolution analysis: Application to the determination of a low dose pharmaceutical compound

Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.     

Distribution of free amino acids,polyphenols and sugars of Ziziphus jujuba pulps harvested from plants grown in Tunisia

Ziziphus jujuba pulps are very much appreciated by the inhabitants and have been recently exported. This article reports on the chemical composition (amino acids, polyphenols and sugars) of the pulps of four Z. jujuba ecotypes (Choutrana, Mahdia, Mahres and Sfax). The major amino acids identified were proline, aspartic acid and glutamic acid. Among these, proline was the most abundant amino acid (17.4 mol). Considerable differences in total phenolic contents (15.85 mg/L) were found. Predominant phenols identified by using HPLC were rutin (1.09 mg/L) and chlorogenic acid (2.57 mg/100 g). Sugars isolated from Ziziphus pulps were found at a rate of 43.52%. Using HPLC method, three sugars from the pulp extract were identified: glucose, galactose and sucrose. The Mahdia ecotype was the richest in these sugars with 0.45, 136.51 and 113.28 mg/L, respectively.     

Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.