Über peroxoverbindungen XI. Nichtradikalische substitions- und redoxreaktionen des bis(trimethylsilyl)peroxyds

The reactivity of bis(trimethylsilyl)peroxide with a variety of nucleophilic, electrophilic, oxidizing, and reducing agents has been investigated.     

Localized surface modes and resonances for vicinal surfaces: The (117) face of fcc crystals

Considering the (117) face of an fcc crystal, the dispersion relations of localized surface modes and resonances have been calculated using the method of generating coefficients of Green functions. The force between atoms are limited to the central force between the nearest neighbours. In the direction of propagation orthogonal to a step, for each wavevector value, a localized surface mode and two resonances have been found. Their polarization amplitude and width have been calculated. It is shown that these results can be qualitatively understood by folding three times the dispersion relation of the (001) face which is the crystallographic plane of the terrace. In the direction parallel to the step, the dispersion relations are obtained by the superposition of the sagittal and transverse dispersion relation of the (001) face. The (117) configuration introduces a coupling between these two polarizations and some resonances appear. A general rule which enables one to predict qualitatively the shape of the dispersion relation for any vicinal surface of type (11m) is expressed.     

The loss of a methyl radical and the retro diels—Alder reaction in the electron impact mass spectrometry of 2-cyclohexen-1-ol and related compounds

The electron impact mass spectra of 2-cyclohexen-1-ol and of several of its ²H and ¹³C labelled analogues show that the molecular ions lose a methyl radical by a completely different means from the mechanism described previously. Moreover, the retro Diels–Alder reaction also proceeds in a non-classical way; in addition to the elimination of an olefinic molecule from unrearranged molecular ions, a second more important route implies a formal 1,3 allylic rearrangement prior to the retro Diels–Alder reaction. The mass spectra of a series of alkyl substituted homologues show that the competition between the two processes is closely related to the size of the olefinic moiety that is expelled.     

Interaction between the type-3 copper protein tyrosinase and the substrate analogue p-nitrophenol studied by NMR

The interaction of the monooxygenating type-3 copper enzyme Tyrosinase (Ty) from Streptomyces antibioticus with its inhibitor p-nitrophenol (pnp) was studied by paramagnetic NMR methods. The pnp binds to oxidized Ty (Ty(met)) and its halide (F(-), Cl(-)) bound derivatives with a dissociation constant in the mM range. The Cu(2) bridging halide ion is not displaced upon the binding of pnp showing that the pnp does not occupy the Cu(2) bridging position. The binding of pnp to Ty(met) or Ty(met)Cl leads to localized changes in the type-3 (Cu-His(3))(2) coordination geometry reflecting a change in the coordination of a single His residue that, still, remains coordinated to Cu. The binding of pnp to Ty(met)Cl causes a decrease in the Cu(2) magnetic exchange parameter -2J from 200 cm(-)(1) in the absence to 150 +/- 10 cm(-)(1) in the presence of pnp. From the (1)H and (2)D NMR relaxation parameters of pnp bound to Ty(met), a structural model of pnp coordination to the Ty type-3 center could be derived. The model explains the absence of hydroxylase activity in the closely related type-3 copper protein catechol oxidase. The relevance of the experimental findings toward the Ty catalytic mechanism is discussed.     

Titanium(III) chloride and electrochemical reduction of pyrazine,quinoxaline and triazine derivatives and of their salts

The reduction of pyrazine, quinoxaline and triazine derivatives by titanium(III) chloride leads to di- or tetrahydrogenated compounds. High yields of tetrahydro compounds are also obtained through the reduction of quinoxalinium salts. These results are compared with those obtained by electrochemical reduction.     

Comparison of ferroelectric domain delineation in triglycine sulphate by the etching technique and the pyroelectric laser technique. Application to the study of polarization reversal

It is shown that the well-known etch technique and the newly developed pyroelectric laser technique can reveal similar domains. However the latter technique is so fast that it appears as the best one to study problems such as nucleation and domain wall motion.

In the case of an alanine doped TGS crystal it is shown that domain wall motions started at a given nucleation field E₁ stop at some characteristic boundary lines in the crystal. To carry on the polarization reversal, we have to increase the electric field up to some higher value E₂ which is the minimum value of the nucleation field in the next area. Then a new domain is growing very rapidly by wall motions until the characteristic boundary lines of this area are reached. These lines are probably dislocation lines. It is shown that a direct side observation of domains is possible. Conical and cylindrical domains are clearly visible.     

Analyse du titane et de ses alliages par spectrométrie d'émission dans l'ultraviolet-vide

The large ultraviolet spectrograph for analysis in vacuum (VUV spectrograph) developed by ONERA and described in a previous article, has been used for multielements quantitative analysis: in pure titanium, concentrations of oxygen, nitrogen, hydrogen and carbon have been determined as well as silicon and iron impurities; in titanium-based alloys, addition metals at high concentration, Al, V, Mo, Zr, Si, have also been determined simultaneously with the gaseous elements and impurities. The analytical lines located between 200 and 2600 Å and corresponding to highly ionized atoms (II to VI) have been selected. The stability of the equipment has been tested and the repeatability of results has been investigated. This new analytical technique allows the study of various surface phenomena such as the variations in oxygen, nitrogen and carbon concentrations with a resolution in depth of a few microns. The method allows it to envisage the quantitative analysis of surface phenomena on metal films with a thickness below one micron.