Improved procedure for the reductive acetylation of acyclic esters and a new synthesis of ethers

An optimized protocol for the DIBALH reductive acetylation of acyclic esters and diesters is described. This reductive acetylation procedure allows a wide variety of esters to be converted into the corresponding alpha-acetoxy ethers in good to excellent yields. It was found that, under mild acidic conditions, many alpha-acetoxy ethers can be further reduced to the corresponding ethers. This net two-step ester deoxygenation is an attractive alternative to the classical Williamson synthesis for certain ethers.     

Steam Plasma Treatment of Organic Substances for Hydrogen and Syngas Production

Gasification of several organic materials in steam plasma generated in a special plasma torch with a water-stabilized arc was investigated. Thermal plasma with very high enthalpy and low mass flow rate is produced in an arc discharge which is in direct contact with water. Biomass and several types of solid and liquid organic waste were gasified by plasma aided reactions of materials with water, carbon dioxide and oxygen. Composition of produced gas, energy balance of gasification process and gasification efficiency were determined from measured data. Synthesis gas with high content of hydrogen and carbon monoxide and very low content of carbon dioxide, light hydrocarbons and tar was obtained for all tested materials. Comparison of measured data with results of theoretical computations confirmed that steam plasma gasification produces syngas with composition which is close to the one obtained from thermodynamic equilibrium calculations.     

Processes and properties of electric arc stabilized by water vortex

Experimental investigation of an electric arc stabilized by a water vortex was carried out in a DC arc plasma torch for the power range 90-200 kW. Volt-ampere characteristics of the arc as well as the power balance were determined separately for the part of the arc column stabilized by water and for the remaining part between the nozzle exit and the external anode. The temperature of arc plasma close to the nozzle exit was determined by emission spectroscopy. Negatively biased electric probes in the ion collecting regime were used for determination of the plasma flow velocity. The measured temperatures up to 27000 K, and velocities up to 7 km/s are higher than the values commonly reported for plasma torches with DC arcs stabilized by a gas flow. Mass and energy balances within the arc chamber were determined from the experimental results. The radial transport of the energy by radiation was identified as a decisive process controlling the arc and plasma properties. The balance of radial energy transport was studied. The ratio of energy spent for evaporation of the water to the energy absorbed in the evaporated mass is very low in the water stabilized arc. This is the principal cause of high plasma temperatures and velocities found by the measurements     

Resonance neutron capture in 52Cr

Neutron capture γ-ray measurements have been performed upon a natural sample of Cr. Twenty-six γ-rays were observed from the 1626 eV resonance of the ⁵²Cr(n, γ)⁵³Cr reaction, and twenty-four of them were assigned to a level scheme. A value of $\text{3}\text{2}$^? was determined for the spin-parity of this resonance. The neutron separation energy, derived from a separate thermal measurement with an enriched (99.9 %) ⁵²Cr sample was determined to be 7939.1 ± 0.2 keV. The high (n, γ) (d, p) correlation found for thermal capture is absent for the p-resonance, however the γ-ray intensities from thermal and resonance capture are correlated, with r = 0.86_?0.11^+0.06.     

Influence of aggregation on interaction of lipophilic, water-insoluble azaphthalocyanines with DOPC vesicles

Dioleoylphosphatidylcholine unilamellar vesicles made by extrusion technique (LUVETs) were studied as the delivery system for lipophilic water-insoluble potential photosensitizers for photodynamic therapy (PDT). Two azaphthalocyanines (AzaPcs) with hydrophobic substituents only and two also possessing two charged amino groups were introduced into the study. All compounds are insoluble in water and form aggregates in PBS with tetrahydrofuran as cosolvent. The size of these aggregates depends on the concentration of AzaPc in solution. AzaPcs with tert-butyl substituents were found to be incorporated into the lipid bilayer of vesicles in the monomeric form even at high concentrations. The stability of LUVETs with incorporated AzaPc was excellent for at least 4 weeks. Therefore, they are suitable for use as a delivery system for these water-insoluble photosensitizers. Very low amount of AzaPc with n-octyl substituents incorporated into LUVETs due to its stronger self-aggregation. Values of binding constants determined for all AzaPcs showed inverse order than expected from their lipophilicities. However, the binding constants followed the order of the strength of aggregation forces. Aggregation of AzaPcs in water medium plays a very important role in the interaction of AzaPcs with LUVETs.     

2,2':6',2'-terpyridine substituted in the 4'-position by the solubilizing and sterically demanding tert-butyl group: a surprisingly new ligand

We describe the synthesis and characterization of 4'-tert-butyl-2,2':6',2'-terpyridine (4'-(t)Butpy, 1), a convergent tpy ligand that exhibits both a sterically demanding and solubilizing 4'-substituent. In the solid state, molecules of 1 pack with alternating tpy and tert-butyl domains, and the bulky alkyl substituents prevent the molecules from engaging in the face-to-face π-interactions which are typical of simple tpy ligands. Instead, the predominant packing forces involve CH···N hydrogen bonds and weak CH···π contacts. The syntheses of the homoleptic complexes [M(1)(2)][PF(6)](2) (M = Fe, Co, Zn and Ru) and the heteroleptic [Ru(tpy)(1)][PF(6)](2) are described. The complexes have been fully characterized in solution, including the (1)H NMR spectroscopic characterization of the paramagnetic [Co(1)(2)][PF(6)](2). Cyclic voltammetric data are consistent with the tert-butyl substituent being slightly electron releasing. The single crystal structures of [Zn(1)(2)][PF(6)](2) and [Ru(1)(2)][PF(6)](2) have been determined; the compounds are essentially isomorphous. The packing of the cations is such that the tert-butyl substituents are accommodated in pockets between the tpy domains of adjacent cations, and as a consequence, the {M(tpy)(2)}-embrace that is a ubiquitous feature of many related structures is not observed.