Efficient and sustainable V-catalyzed oxidative desulfurization of fuels assisted by ionic liquids

Fuel desulfurization is an appealing topic for the chemical industry since severe environmental regulations regarding SO₂ emissions have been legislated in many countries. In order to reduce the amount of sulfur-containing compounds in fuels, responsible for high SO_x emission levels, a green chemistry approach is compulsory. In this paper, vanadium salen and salophen complexes were used in the oxidation of a model aromatic sulfide, such as dibenzothiophene (DBT), in the presence of H₂O₂ as green oxidant. The oxidative process was successfully coupled with the extraction of the oxidized compounds by ionic liquids. The system resulted highly selective for sulfide oxidation, showing poor reactivity toward the oxidation of alkenes and allowing a significant reduction of S content in a model benzine. To note, the use of microwave in place of standard heating allowed to obtain 98% of DBT oxidation and almost complete sulfur extraction in the model fuel in 1000 s. For these reasons, this system was considered an easy, rapid and clean process to achieve fuel desulfurization.     

Influence of constant magnetic field on electrodeposition of metals,alloys, conductive polymers,and organic reactions

The paper presents and summarizes some research on constant magnetic field effects in chemistry. Metals and alloys electrodeposited under constant magnetic field have greater thickness and smoother surface with finest grains. Metallic materials deposited under the influence of uniform magnetic field may have stronger corrosion resistance, than those obtained without the presence of magnetic field. Constant magnetic field also causes an increase of the electropolymerization rate and yield of some organic reactions. Our research also shows that the presence of constant magnetic field affects the electrodeposition process of alloys and their morphology to a great extent. The effects of magnetic field on metals, alloys, composites, polymers and other materials are due to the Lorentz force and the magnetohydrodynamic effect. It is possible that the further development of magnetoelectrodeposition will allow for using the constant magnetic field to improve the properties of metal coatings, alloys, polymers, and other materials in the industry.     

Can Coordination‐Driven Supramolecular Self‐Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

The reaction between a preassembled Cu^I bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano‐capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano‐capped linkers with two other types of preassembled Cu^I bimetallic molecular clips that also had short intermetallic distances.     

Asymmetric synthesis and structure-activity studies of the fungal metabolites colletorin A,colletochlorin A and their halogenates analogues

The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature.     

A decanuclear oxomolybdenum(V,VI) cluster with 4-isopropylpyridine

The title centrosymmetric cluster octakis(4-iso­propyl­pyridine-N)-di-μ₄-oxo-hexa-μ₃-oxo-octa-μ₂-oxo-deca­oxo­octa­molyb­denum(V)­dimolybdenum(VI), [Mo₁₀O₂₆(C₈H₁₁N)₈], consists of ten Mo atoms connected together by bridging oxo groups. Pentavalent Mo atoms are linked into four Mo₂^V pairs by metal–metal single bonds with lengths of 2.5637 (6) and 2.6132 (6) Å.     

Surface and bulk modification of polyolefins by functional aryl nitrenes as highly reactive intermediates

Aromatic azides with hindered amine light stabilizer (HALS) residues or hydrophilic groups such as glucose, sucrose and dextrine residues were synthesized and used for surface modification of polyolefins. By UV‐irradiation nitrenes were formed, which are able to react with polyolefin surfaces. By photochemical immobilization of the carbohydrates hydrophilicity of PE and PP was strongly increased (surface tensions > 44mN/m). Light stability of PP surfaces modified with HALS azides was comparable with PP, stabilised with Tinuvin 770. Bulk modification of ethylene‐propylene and ethylene‐octene copolymers was achieved by grafting nitrenes formed by thermal decomposition of azido benzoic acid. In a circulating air oven up to 1.55 wt% amino benzoic acid residues could be bonded covalently to ethylene‐propylene‐copolymers, less than half of it to ethylene‐octene‐copolymers. Reactive extrusion resulted in grafting yields of more than 50% for both types of copolymers.     

Die Struktur des Pentaphenyldisilans

Structure of Pentaphenyldisilane For the first time Pentaphenyldisilane was prepared by Gilman and Goodman. It is produced by the reaction of Ph₃SiLi with Ph₂ClSiH. The crystal structure presents an ideally staggered conformation. The distance d(Si? Si) = 235.7 pm corresponds to a normal single bond length. This emphasizes the complete relief of the central Si? Si bond by the insertion of only one hydrogen atom.     

Temperature-controlled 'breathing' of carbon dioxide bubbles

We report a microfluidic (MF) approach to studies of temperature mediated carbon dioxide (CO(2)) transfer between the gas and the liquid phases. Micrometre-diameter CO(2) bubbles with a narrow size distribution were generated in an aqueous or organic liquid and subsequently were subjected to temperature changes in the downstream channel. In response to the cooling-heating-cooling cycle the bubbles underwent corresponding contraction-expansion-contraction transitions, which we term 'bubble breathing'. We examined temperature-controlled dissolution of CO(2) in four exemplary liquid systems: deionized water, a 0.7 M aqueous solution of NaCl, ocean water extracted from Bermuda coastal waters, and dimethyl ether of poly(ethylene glycol), a solvent used in industry for absorption of CO(2). The MF approach can be extended to studies of other gases with a distinct, temperature-dependent solubility in liquids.