Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-OH)₂]reacts with 2,3,4,5,6-pentafluoro benzenamine (C₆F₅-NH₂), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC₆H₄, 4-MeOC₆H₄), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-C₆F₅NH)₂] ( 1 ) and (Bu₄N)₂[{Ni(C₆F₅)₂} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu₄N[Ni(C₆F₅)2(ArN₃Ar)] ( 3 – 5 ), Bu₄N[Ni(C₆F₅)₂(pyNPh)] ( 6 ), and Bu₄N[Ni(C₆F₅)₂(pyCONPh)] ( 7 ). The hydroxo.complex (Bu₄N)₂[{Ni(C₆F₅)2-(μ-OH)}₂] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, ¹H and ¹⁹F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu₄N)₂[{Ni(C₆F₅)₂}₂(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°.     

Determination of propazine by differential pulse polarography in micellar and emulsified media

An electroanalytical study of the herbicide propazine's reduction process in micellar solutions and oil-in-water emulsions is reported. The anionic surfactant sodium pentanesulphonate was chosen as the most suitable. The differential pulse polarograms of micellar solutions had two reduction peaks below pH 2.0, whereas only one peak was obtained above pH 2.O. Ethyl acetate was chosen as the organic solvent to form propazine emulsions. Unlike in micellar solutions, the DPP polarograms of propazine emulsions showed only one peak even at pH < 2.0, suggesting that propazine hydrolysis was hindered in the emulsified medium. The limiting current is diffusion-controlled and the electrode process is irreversible. Propazine can be determined by differential pulse polarography over the 1.0 × 10^–1 – 1.0 × 10^–1moll^–1 and 1.0 × 10^–15 – 4.0 × 10^–1 moll^–1 concentration ranges and the limit of detection was 2.8 × 10^–1 moll^–1. Of the potential interferents simazine, methoprotryne and terbutryn (alls-triazines), thiram (a dithiocarbamate), dinoseb (nitrophenolic), and heptachlor (chlorinated cyclo-diene herbicide), only the first two were significant (10% error for equimolar concentrations). The method was applied to the determination of propazine in spiked drinking water. At a concentration level of 2.0 × 10^–1 moll^–1 a recovery of 94 ± 6% was obtained, after tenfold concentration on Sep-Pak.     

Two-plane sub-bundles of nonorientable real vector-bundles

Let be a nonorientable m-plane bundle over a CW complex X of dimension m or less. Given a 2-plane bundle over X, we wish to know whether can be embedded as a sub-bundle of . The bundle need not be orientable. When is even-dimensional there is the added complication of twisted coefficients. In that case, we use Postnikov decomposition of certain nonsimple fibrations in order to describe the obstructions for the embedding problem. Emery Thomas [11] and [12] treated this problem for and both orientable. The results found here are applied to the tangent bundle of a closed, connected, nonorientable smooth manifold, as a special case.The writing of this paper was partially supported by CNPq grant     

Cochlear power flux as an indicator of mechanical activity

The question of whether one can conclude just from basilar membrane (BM) vibration data that the cochlea is an active mechanical system is addressed. To this end, a method is developed which computes the power flux through a channel cross section of a short-wave cochlear model from a given BM vibration pattern. The power flux is an important indicator of mechanical activity because a rise in this function corresponds to creation of mechanical energy. The power flux method is applied to BM velocity patterns as measured by Johnstone and Yates [J. Acoust. Soc. Am. 55, 584-587 (1974)] and by Sellick et al. [Hear. Res. 10, 101-108 (1983)] in the guinea pig and by Robles et al. [Peripheral Auditory Mechanisms, edited by J.B. Allen, J.L. Hall, A.E. Hubbard, S.T. Neely, and A. Tubis (Springer, New York, 1986a), pp. 121-128, and J. Acoust. Soc. Am. 80, 1364-1374 (1986b)] in the chinchilla. Before the calculations are performed, the BM data are interpolated and smoothed in order to avoid numerical errors as a result of too few and noisy data points. The choice of the smoothing method influences the computed power flux function considerably. Nevertheless, the calculations appear to make a clear distinction between the "old" data, showing broad BM tuning (Johnstone and Yates, 1974), and the "new" data, in which the response is much more peaked (Sellick et al., 1983; Robles et al., 1986a, b). The former do not give rise to a significant increase of the power flux; the latter do, although less convincingly for the Sellick et al. (1983) data than for the Robles et al. (1986a,b) data. It is thus concluded that the recently obtained, sharply tuned BM responses reflect the presence of mechanical activity in the cochlea.