Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes

Summary The reaction of ()-(tetren)CoOH²⁺ with S₂O ₃ ^2- in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH²⁺,S₂O ₃ ^2- ] formation. Replacement of coordinated OH^- by S₂O ₃ ^2- is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH²⁺ (tetren-H)CoOH ₂ ²⁺ , the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S₂O₃)⁺ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS₂O₃]⁺ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S₂O ₃ ^2- .     

The growth of crystalline vapor deposited carbon-60 thin films

Thin films (25-2500 Å) of C₆₀ molecules have been deposited on both (001) NaCl and mica substrates at varying temperatures by resistive evaporation. Both electron diffraction and high resolution microscopy have been used to assess the degree of crystallinity, the orientational ordering and the nature of the defects present in these face-centered-cubic films. For NaCl, optimum conditions yielded polycrystalline films with a tendency towards a 110 orientation, while for mica, extended single crystal films have been fabricated which exhibit a 111 direction normal to the film surface.     

Shape-tunable polymer nodules grown from liposomes via ring-opening metathesis polymerization

A new inisurf (acting as surfactant and initiator) molecule for ring-opening metathesis polymerization (ROMP) was synthesized and used in aqueous solution in order to control the size and shape of polymer nodules grown from liposomes. Nodules were observed to grow in size with conversion of monomer, and depending on the monomer used, they adopted either a spherical or comet-like shape. Here, we investigate polymer production from a liposome surface. We use a hydrophobic derivative of the Grubbs catalyst positioned at the liposome surface to allow for ROMP of monomers dissolved in the aqueous outer phase. We obtain nodules of polymer that can grow up to tens of micrometers, unveiling new efficient possibilities of polymerization from a membrane in an aqueous solution.     

Importance of REP values when comparing the CALUX bioassay results with chemoanalyses results Example with spiked vegetable oils

Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).The CALUX results were compared with the concentrations of the congeners’ spiked into the oil.     

Carbene chemistry. Part 13 [1]. Preparation of sole fluoroallenes by a carbene route,and the reaction of allenes with halogenocarbenes

Fluoroallene and 1, 3-difluoroallene are prepared in good overall yield by the addition of dichlorocarbene to vinyl fluoride and 1, 2-difluoroethylene respectively, followed by pyrolysis of the dichlorocyclopropanes and treatment of the resulting dichloropropenes with zinc. Pyrolysis of 1, 1-dichloro-2-fluorocyclopropane over zinc gives fluoroallene directly.The reaction of allene with 2, 2, 3-trifluoro-3-trifluoro- methyloxiran at 180°C as a source of difluorocarbene gives both 1, 1-difluoro-2-methylenecyclopropane and its rearrangement product 1-(difluoromethylene)cyclopropane, the latter reacting more readily with a second difluorocarbene to give 2, 2, 3, 3- tetrafluorospiropentane. In an analogous way, fluoroallene reacts with dichlorocarbene, generated from trifluoro(trichloromethyl) silane at 140°C, to give $\text{E}$- and $\text{Z}$-1, 1-dichloro-2- (fluoromethylene)cyclopropane, 1-(dichloromethylene)-2-fluorocyclopropane, and 2, 2, 3, 3-tetrachloro-4-fluorospiropentane.