Synthesis and structural characterization of integrally oxidized, metal-free phthalocyanine compounds: [H(2)(pc)][IBr(2)] and [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br

The first integrally oxidized metal-free phthalocyanine compounds have been synthesized by chemical oxidation. Phthalocyanine (H(2)(pc), pc = phthalocyaninato) was oxidized with IBr to afford the compounds [H(2)(pc)][IBr(2)] (1) and [H(2)(pc)](2)[IBr(2)]BrAC(10)H(7)Br (2), whose structures were determined by means of single-crystal X-ray diffraction methods: [H(2)(pc)][IBr(2)], P2(1)/c, a = 8.0272(9) A, b = 21.258(2) A, c = 18.1439(2) A, beta = 113.975(2) degrees, V = 2828.8(5) A(3), T = 153 K, Z = 4; [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br, P, a = 8.4724(6) A, b = 13.5794(10) A, c = 13.8403(10) A, alpha = 90.854(1) degrees, beta = 103.417(1) degrees, gamma = 97.049(1)E degrees, V = 1535.61(19) A(3), T = 153 K, Z = 1. The extended structure of [H(2)(pc)][IBr(2)] comprises slipped columns of pc rings stacked along the a axis in adjacent columns at approximately 70 degrees to one another. IBr(2-) ions occupy the interstitial columns. The extended structure of [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br comprises slant stacks of pc rings along the crystallographic a axis with IBr(2-) ions, Br(-) ions, and disordered 1-bromonaphthalene molecules in the adjacent, parallel columns. The overall reaction for the formation of 1 is 2H(2)(pc) + 4IBr --> 2[H(2)(pc)][IBr(2)] + I(2), and the overall reaction for the formation of 2 (not including solvent) is 2H(2)(pc) + 3IBr --> [H(2)(pc)](2)Br[IBr(2)] + I(2).     

Nuclear magnetic resonance studies of sulfur inversion in bis(cyclopentadienyl)-molybdenum and -tungsten complexes with dithioethers

The metallocene thioether derivatives [Cp₂M(MeSCH₂CH₂SMe)][PF₆]₂ (1, M = MO; 2, M = W), [Cp₂Mo(SCH₂CH₂SMe)][PF₆] (3) and [Cp₂M(SCH₂CH₂S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol⁻¹), 2 (51.2 ± 4.6 kJ mol⁻¹) and 3 (30.0 ± 3.1 kJ mol⁻¹). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour.     

Anion-pi interactions in cyanuric acids: a combined crystallographic and computational study

Several structures of pi complexes of isocyanuric acid and of several thio derivatives with anions have been computed by using high level ab initio calculations. The nature of the complexes has been studied by means of the method of molecular interaction potential with polarization (MIPp) and Bader's theory of atoms-in-molecules. These molecules form favorable complexes with anions and can be used as binding units for building receptors for the molecular recognition of anions. In several cases, the anion-pi interaction has been demonstrated experimentally by means of X-ray crystallography.     

Untersuchungen an Kristallhydraten anorganischer Salze, 8. Mitt. Interpretation der Schwingungsspektren vonM(BF4)2·6H2O fürM=Fe2+, Co2+, Ni2+

The infrared and Raman spectra were recorded in the range 4000–160 cm^–1 forM(BF₄)₂·6 H₂O whereM=Fe²⁺, Co²⁺, Ni²⁺. The spectroscopic data support the X-ray structural data in showing that in the crystal hydrates studied two kinds of hydrogen bonds are present: H₂O...H₂O and OH₂... F₄B^–. The energies and molecular force constants (f _OH and fH₂O) andr _OH for OH₂...F₄B^– were calculated for the three crystal hydrates. It was found that the bond OH₂... F₄B^– is comparatively weak, with mean energy 3.7–3.3 kcal/mol. Two types of water molecule with different structures are existing as the first are participating in H₂O...H–O–H...F₄B^– and the second in BF₄ ^–...H–O–H...F₄B^–.     

Analysis of conformational equilibria in aplidine using selective excitation 2D NMR spectroscopy and molecular mechanics/dynamics calculations

Aplidine (dehydrodidemnin B), a natural product with potent antitumor activity currently in multicenter phase II clinical trials, exists in DMSO as a mixture of four slowly interconverting conformations in a ratio of 47:33:13:7. NMR spectroscopy shows that these arise as a consequence of cis/trans isomerization about the NMe-Leu(7)-Pro(8) and Pro(8)-Pyr amide bonds of the molecule's side chain. Two major conformations account for 47% and 33% of the total population, a ratio of 60:40 between the two. They correspond to the cis- and trans-isomers, respectively, about the Pro(8)-Pyr amide bond. Two minor conformers arise as a consequence of similar isomerism about the Pro(8)-Pyr amide bond, but in structures in which the NMe-Leu(7)-Pro(8) amide bond is cis rather than trans. These account for approximately 13% and 7% of the total population, corresponding to a ratio of 65:35 cis/trans, respectively. Molecular dynamics simulations show that the three-dimensional structures of all four conformational isomers are similar in the macrocycle and that all are essentially unchanged with respect to the macrocycle of didemnin B. Significant differences in the conformation of the molecule's side chain are, however, observed between major and minor pairs. Analysis of hydrogen-bonding patterns shows that each major conformer exhibits a beta-turn like structure and is stabilized by hydrogen bonding between a different carbonyl group of the pyruvyl unit of the molecule's side chain and the NH of the Thr(6) residue. The minor isomers have a cis-amide bond between the NMe-Leu(7) and Pro(8) residues that obliges the side chain to adopt an extended disposition where hydrogen bonding to the macrocycle is absent. These results suggest that the ability of the molecule's side chain to adopt a beta-turn-like conformation may not be a prerequisite for biological activity in the didemnins and that conformations having an extended side-chain may play a role in the biological activity of aplidine.     

Chemical and radiochemical characterization of depleted uranium (DU) in Kosovo soils

As is well known ammunitions containing depleted uranium (DU) were used by NATO during the Balkan war. The paper deals with the determination of uranium alpha emitting radiosotopes in Kosovo soils by chemical separation and alpha spectrometry. The samples were collected by CISAM (Centro Interforze Studi ed Applicazioni Militari, S. Piero a Grado, Livorno) in the period November 1999-April 2000. The DU distribution in soil appeared very disomogeneous; the isotope weight percentages for U-238, U-235 and U-234 resulted 99.76, 0.24 and 7.24.10(-4) respectively; consequently the activity distribution was 86.42%, 1.31%, 11.63% and the isotope ratios were 1.52.10(-2) and 0.134 for U-235/U-238 and U-234/U-238 showing clearly the presence of DU. A small peak at 4.49 MeV (U-236) in the alpha spectrum indicated that the used DU was the by-product of exhausted uranium reprocessing. In order to determine the chemical and physiological solubility of uranium a fractionation study was carried out by using the Tessier method: 55% of uranium showed a fair solubility, but 45% was solubilized only by 8 M HNO3.     

The reaction Yb+O2 → YbO + O in a crossed molecular beam experiment

Dissociation energy (D_o = 4.29 ± 0.05 eV), threshold energy (E = 0.83 ± 0.05 eV) and forward scattering at a collision-al energy E_c = 1.1 cV have been found by crossing beam of Yb atoms with a supersonic seeded beam of He + O₂ at collisional energies up to E_c = 1.4 eV.     

A New Complex of Europium(II) with edta – Structure and Spectroscopy

A new complex of europium(II) with ethylenediaminetetraacetic acid was obtained by electrochemical reduction. The compound is composed of polymeric chains, guanidinium cations and water molecules. The Eu²⁺ cation is eight‐coordinate (two nitrogen atoms and six carboxylate oxygen atoms), and contrary to europium(III) complexes with edta, does not contain water molecules in the first coordination sphere. Relationships between the coordination mode and IR as well as UV–Vis spectra are discussed.     

The Selection of the Optimal Impregnation Conditions of Vegetable Matrices with Iodine

This study aimed to determine the use of selected vegetables (pumpkin, cauliflower, broccoli, carrot) as carriers of potassium iodide (KI) and potassium iodate (KIO₃) by determining changes in iodine content under various conditions of impregnation as the degree of hydration, impregnated sample temperature, and impregnation time. The influence of these conditions on iodine contents in vegetables after their fortification and storage (21 °C/230 days) was analyzed. The results showed that all selected vegetables could be efficient iodine carriers. However, the conditions of the impregnation process are crucial for fortification efficiency, particularly the degree of hydration and the temperature of the impregnated samples before drying. The results showed that the lowest iodine content was in samples fortified at 4 °C and 1:4 hydration. On the other hand, the highest reproducibility of iodine was for the following fortification conditions: temperature of −76 °C and hydration of 1:1. The studies confirmed the higher stability of iodine in KIO₃ form compared to KI. To increase recovery of the introduced iodine in the product after drying, using the conditioning step at 4 °C is not recommended. We recommend freezing vegetables immediately after the impregnation process     

Monitoring of Spirulina Flakes and Powders from Italian Companies

Microalgae and microalgae-derived compounds have great potential as supplements in the human diet and as a source of bioactive products with health benefits. Spirulina (Arthrospira platensis (Nordstedt) Gomont, or Spirulina platensis) belongs to the class of cyanobacteria and has been studied for its numerous health benefits, which include anti-inflammatory properties, among others. This work was aimed at comparing some spirulina products available on the Italian market. The commercial products here analyzed consisted of spirulina cultivated and processed with different approaches. Single-component spirulina products in powder and flake form, free of any type of excipient produced from four different companies operating in the sector, have been analyzed. The macro- and micromorphological examination, and the content of pigments, phycobiliproteins, phenols, and proteins have shown differences regarding the morphology and chemical composition, especially for those classes of particularly unstable compounds such as chlorophylls and carotenoids, suggesting a great influence of both culture conditions and processing methods.