Action des bromures de perfluoroalkylmagnésiums sur les aldéhydes α,βéthyléniques

Perfluoroalkylmagnesium bromide, C_nF_2n+1MgBr (n = 2, 6, 8), reacts with α,β-unsaturated aldehydes to give allylic alcohols as the sole products. No attack on the β-carbon atom of the carbonyl was detected, even when the reaction was carried out in the presence of CuCl. Part of the Grignard reagent decomposes to trans-R_FCFCFBr and trans-R_FCFCFI. Neither a mechanism involving dissociation into R⁺_F MgX^- nor the formation of a carbene intermediate is capable of explaining the thermal decomposition of the Grignard reagent.     

Motion of foam films in diverging-converging channels

Existing theories of the motion of foam films in capillaries often assimilate the pressure drop over the foam films to the static capillary pressure obtained from the Young-Laplace equation. Hence, they ignore the contribution of dynamic effects associated with the rapid stretching and contraction of the foam films to the overall viscous dissipation. This paper reports an investigation of the motion of foam films in axisymmetric diverging-converging channels, taking into account surface viscosity and elasticity. First, a phenomenological theory for the motion of the foam films is developed using simple physical arguments. We show that the displacement of the film obeys a nonlinear second-order differential equation, which can be solved numerically for the (dimensionless) distance from the inlet and the pressure drop as a function of time. Experiments with foam film motion, conducted using glass diverging-converging channels (minimum radius = 3.00 +/- 0,01 mm, maximum diameter = 7,98 +/- 0,01 mm) and nitrogen foam stabilized with sodium dodecyl sulfate (SDS) in brine, are discussed. For a single film motion in the diverging channel, we find that (a) the static pressure drop is a concave-upward function of distance and decreases from 1.0 to about 0.3, whereas (b) the dynamic pressure drop is concave downward and increases from 1 to a maximum of 1.3 and then decreases to 0.7. In the converging channel both the static and dynamic pressure drops are concave-downward functions, but the dynamic pressure drop values are always higher than the static ones. For two films the motions were found to be rather sensitive to the initial arrangement in the channel. The experiments are found to be in excellent agreement with the theoretical predictions. These observations imply that the large flow resistance obtained during foam flow in granular porous media, where converging-diverging channels are abundant, is largely due to the surface elasticity and viscosity of the films.     

Synthesis of a model system for the preparation of phloroglucinol containing natural products

A model system for the synthesis of phloroglucinol containing natural products was synthesized. Key steps include a manganic acetate-mediated cyclization and the facile conversion of an alkene into a β-bromoenone.     

Synthesis, structural characterization and ferrimagnetic property of MnPS3 intercalated with nickel(II) cyclopolyamine complex cations

Two new intercalation compounds were prepared by the reactions of Ni(II) cyclopolyamine complex cations with a preintercalate Mn_1−xPS₃K_2x(H₂O)_y, respectively, through “ion exchange” process. Their structures were characterized by elemental analysis, X-ray powder diffraction and infrared spectroscopy. The lattice spacing increased 0.567 and 1.093 nm with respect to the pristine MnPS₃. Ferrimagnetism of the intercalates was confirmed by SQUID experiment with T_c at 40 and 33 K, respectively.     

1,4-双(4''''-溴苯酰基)苯的合成工艺改进

以对苯二甲酰氯和溴苯为原料,无水氯化铝粉末为催化剂,合成了1,4-双(4'-溴苯酰基)苯,其结构经1H NMR,IR和DSC表征.     

钯镁基体改进剂对铅,铋,锗在石墨炉中原子化影响的研究

通过原子吸收和X-射线衍射分析证明,加入钯镁基体改进剂在预热处理后对Pb、Bi和Ge三个元素分别生成金属间化合物PbPd_3、BiPd_3、Ge_9Pd_(23)和其他化合物,从而提高了最高允许灰化温度,改变了原子化机理。在原子化阶段这些金属间化合物直接分解为金属原子,结果提高测定灵敏度。     

Theoretical study on the structure and property relationship of the cationic conjugated polyelectrolytes

A theoretical study using density functional theory was performed to understand the structure/property relationship of the cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined.     

Chemical activation of carbon nanofibers and nanotubes

Method of thermodynamic simulation was used to calculate the equilibrium parameters of reactions of graphite with anhydrous LiOH, NaOH, and KOH and with the alkalis in the presence of water vapor. The change in the specific surface area and mass loss were used to analyze the interaction of carbon nanofibers and multilayer carbon nanotubes produced by catalytic pyrolysis of CH₄ with the alkalis.     

Domino "[3+3]-cyclization-homo-Michael" reactions of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes

The Lewis acid mediated domino "[3+3]-cyclization-homo-Michael" reaction of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes allows an efficient one-pot synthesis of functionalized salicylates containing a halogenated side chain. A great variety of substitution patterns could be realized by variation of the starting materials and of the Lewis acid. The mechanism of the domino process was studied.     

Synthesis of model long-chain ω-alkenyltrichlorosilanes and triethoxysilanes for the formation of self-assembled monolayers

The synthesis of model long-chain hydrocarbons (C₁₃ and C₁₉) carrying a vinyl group and a trichloro- or a triethoxysilyl group at each end is reported. These compounds are suitable for linkage to a hydroxylated silicon surface and at the other end with vinyl group for further functionalization and multilayer formation.