Preparation and Eh--pH diagrams of Fe(II)--Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

Fe(II)--Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E_h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing “green rust one” (GR1) from “green rust two” (GR2). Since green rusts (GRs) are of a pyroaurite-sjögrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH)₂, their chemical formulae can be determined from the Mössbauer spectra. Three quadrupole doublets are observed: D₁ and D₂ correspond to a ferrous state with isomershift IS of about 1.27 mm s^-1 and quadrupole splittings QS of about 2.85 and 2.60 mm s^-1, respectively, whereas D₃ corresponds to a ferric state with IS and QS of about 0.4 mm s^-1. The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E_h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed.     

High-Performance Thin-Layer Chromatographic Determination of Satranidazole in its Dosage Form

JPC – Journal of Planar Chromatography – Modern TLC - A high-performance thin-layer chromatographic method has been developed for determination of a new antiamoebic drug, satranidazole,...     

Dislocation driven chromium precipitation in Fe-9Cr binary alloy: a positron lifetime study

The influence of initial heat treatment on anomalous Cr precipitation within high temperature solubility region of the Fe–9Cr alloy has been investigated using positron lifetime studies. Air-quenched samples with pre-existing dislocations exhibited a distinct annealing stage in positron lifetime between 800 and 1100?K corresponding to Cr-precipitation. During this stage, Transmission Electron Microscopy showed fine precipitates of average size 4 nm, dispersed throughout the sample and from Energy-dispersive X-ray spectroscopy (EDS) analysis they are found to be Cr-enriched. The presence of dislocations is found to be responsible for Cr precipitation.     

Acid–Base‐Controlled Stereoselective Metalation of Overhanging Carboxylic Acid Porphyrins: Consequences for the Formation of Heterobimetallic Complexes

Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so‐called hanging‐atop (HAT) Pb^II cation to regular Pb^II porphyrin complexes allowed a stereoselective incorporation of the N‐core bound cation, and an allosterically controlled Newton’s cradle‐like motion of the two Pb^II ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT Pb^II coordination. The nature of the N‐core bound metal ion (Zn^II, Cd^II), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through ¹H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis‐strap ligands have been considered. They all incorporate a COOH group hung over the N‐core on one side. For the bis‐strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear Zn^II or Cd^II complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT Pb^II. An allosteric effector (e.g., 4‐dimethylaminopyridine (DMAP), in the case of a single‐strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO^?, is required to switch the N‐core bound cation to the opposite side with concomitant release of the COO^?, thereby allowing HAT Pb^II complexation. In the absence of a base, Zn^II or Cd^II binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the overhanging COOH fully available, is responsible for a stronger binding of the HAT Pb^II. Thus, either allosteric or acid–base control is achieved through stereoselective metalation of Zn^II or Cd^II. In the latter case, according to the deprotonation state of the COOH group, the best electron‐donating ligand is located on one or the other side of the porphyrin (COO^?>CONHR>COOR>COOH): the lower affinity of COOH for Zn^II and Cd^II, the higher for a HAT Pb^II. These insights provide new opportunities for the elaboration of innovative bimetallic molecular switches.     

Physico-Chemical and Phytochemical Characterization of Moroccan Wild Jujube “Zizyphus lotus (L.)” Fruit Crude Extract and Fractions

Wild jujube “Ziziphus lotus (L.) Desf.” belongs to the Rhamnaceae family and is a traditionally herbaceous medicinal plant. It is very common in arid and semi-arid regions and is currently used for its antidiabetic, sedative, analgesic, anti-inflammatory and hypoglycemic activities. The aim of the present work was to characterize the physico-chemical properties and the phytochemical profile of wild jujube sample collected from the Guercif region, in order to determine the polyphenolic compounds and the antioxidant ability Analyses were carried out directly after the harvest for the determination of pH, refractive index, total soluble solid (°Brix), dry matter, sugar/acidity, total sugars, reducing sugars, as well as lipid and protein content. Results showed that the investigated fruit is acidic (pH 4.9 ± 0.23) and rich in sugars (80.2 g/100 g ± 3.81). The GC-MS analysis of the fruit revealed a number of volatile compounds, as many as 97, belonging to different chemical classes. The HPLC-DAD-ESI/MS analysis showed the presence of a total of 20 polyphenolic compounds in both EtOAc and MeOH-water extracts. Among them, p-Hydroxybenzoic acid was the most abundant in the EtOAc extract (185.68 µg/100 mg ± 0.5) whereas Quercetin 3-O-rhamnoside-7-O-glucoside was found in higher amounts in the MeOH-water extract (25.40 µg/100 mg ± 0.5). These components have medical interest, notably for human nutrition, as well as health benefits and therapeutic effects. Therefore, Moroccan jujube “Zizyphus lotus (L.)” fruit may have potential industrial applications for food formulations.     

Elements with generalized bounded conjugation orbits

For a pair of linear bounded operators and on a complex Banach space , if commutes with then the orbits of under are uniformly bounded. The study of the converse implication was started in the 1970s by J. A. Deddens. In this paper, we present a new approach to this type of question using two localization theorems; one is an operator version of a theorem of tauberian type given by Katznelson-Tzafriri and the second one is on power-bounded operators by Gelfand-Hille. This improves former results of Deddens-Stampfli-Williams.     

Monte Carlo simulation of magnetic phase transitions in Mn-doped ZnO

The magnetic properties of Mn-doped ZnO semiconductor have been investigated using the Monte Carlo method within the Ising model. The temperature dependences of the spontaneous magnetization, specific heat and magnetic susceptibility have been constructed for different concentrations of magnetic dopant Mn and different carrier concentrations. The exact values of Mn concentration and carrier concentration at which high temperature transition occurs are determined. An alternative for the explanation of some controversies concerning the existence and the nature of magnetism in Mn diluted in ZnO systems is given. Other features are also studied.     

Unprecedented incorporation of α-emitter radioisotope 213Bi into porphyrin chelates with reference to a daughter isotope mediated assistance mechanism

For the first time, α-emitter radioisotope (213)Bi has been incorporated into porphyrin chelates, with rates matching with the short period of the radionuclide. An in situ transmetalation mechanism involving the daughter isotope (209)Pb is expected to boost the (213)Bi radiolabeling process.     

Withanolides from Withania adpressa

From the leaves of Withania adpressa, a plant endemic to Sahara of Morocco and Algeria, the novel steroidal lactone (22R)‐14α,15α,17β,20β‐tetrahydroxy‐1‐oxowitha‐2,5,24‐trien‐26,22‐olide (= (15S,17S)‐14,15,17,20‐tetrahydroxy‐22,26‐epoxyergosta‐2,5,24‐triene‐1,26‐dione; 1 ), was isolated, along with three known compounds, withanolides F ( 2 ), J ( 3 ), and oleanolic acid. Their structures were mainly solved by in‐depth 1D‐ and 2D‐NMR (including ADEQUATE) experiments, as well as by HR‐MS analyses and chemical evidence.