有机硅活性中间体的研究 II. 一些含环丙基的有机硅化合物的合成及其结构

用锂有机物的方法合成了四种含有环丙基有机硅化合物,对上述每种化合物中可能存在着的立体异构进行了分离和和构型测定。     

Investigation of low-voltage on-resonance ion selection for Fourier transform mass spectrometry

Low-voltage on-resonance ion selection (LOIS) was recently introduced as an alternative technique for ion selection and storage. Under high pressure conditions and similar to the technique of quadrupolar axialization, unwanted (unselected) trapped ions are eliminated from the analysis cell through collisions with cell plates following orbital expansion. The ions remaining after tens of seconds of mass selection can be detected with better coherence, leading to improvements in ion detection and sensitivity. Here, experiments designed to test ion remeasurement and ion transfer capabilities are presented. Simulations of ion motion give insight into the possible mechanism of ion cooling, which does not appear to be the same as that of the axialization process. Because of its ease of use, lack of need for additional hardware devices, and comparable ion selection results, LOIS is an attractive alternative for trapped ion experiments.     

Sonoelectrochemistry at highly boron-doped diamond electrodes: silver oxide deposition and electrocatalysis in the presence of ultrasound

The use of boron-doped diamond has a considerable impact in electrochemistry owing to the wide potential range accessible, low background currents, extreme hardness, and the ease of chemical modification of diamond surfaces. It is shown here that, although the electrodeposition of silver metal is known to yield very poorly adhering films with a poor electrical contact, a silver oxysalt deposit formed on anodically pre-treated diamond surfaces adheres strongly with good electrical contact. The deposit is stable even in the presence of ultrasound. Voltammetric and XPS studies reveal that the silver oxide deposit, in contrast to the silver metal deposit, is efficiently stripped from the diamond surface by applying a sufficiently negative potential. The silver oxysalt Ag₇O₈NO₃, deposited onto two types of boron-doped diamond electrodes, a 50 μm thick polycrystalline thin film deposited on a tungsten substrate and a polished free standing diamond plate, is shown to act as an electrocatalyst for oxygen evolution and for the oxidation of toluene. This development opens up the possibility of boron-doped diamond being applied as an inert and conducting substrate material for a wide range of oxidic materials, which can then be utilised as active electrocatalysts at high applied potentials. Received: 17 March 2000 / Accepted: 10 April 2000     

Direct observation of orbital ordering in La0.5Sr1.5MnO4 using soft x-ray diffraction

We report the first direct resonant soft x-ray scattering observations of orbital ordering. We have studied the low temperature phase of La0.5Sr1.5MnO4, a compound that displays charge and orbital ordering. Previous claims of orbital ordering in such materials have relied on observations at the manganese K edge. These claims have been questioned in several theoretical studies. Instead we have employed resonant soft x-ray scattering at the manganese L(III) and L(II) edges which probes the orbital ordering directly. Energy scans at constant wave vector are compared to theoretical predictions and suggest that at all temperatures there are two separate contributions to the scattering: direct orbital ordering and strong cooperative Jahn-Teller distortions of the Mn3+ ions.     

New mechanism for the alpha to omega martensitic transformation in pure titanium

We propose a new direct mechanism for the pressure driven alpha-->omega martensitic transformation in pure titanium. A systematic algorithm enumerates all possible pathways whose energy barriers are evaluated. A new, homogeneous pathway emerges with a barrier at least 4 times lower than other pathways. The pathway is shown to be favorable in any nucleation model.     

Pentacene disproportionation during sublimation for field-effect transistors

At moderate temperatures in flowing gas, pentacene undergoes a disproportionation reaction to produce 6,13-dihydropentacene (DHP) and a series of polycondensed aromatic hydrocarbons, including the previously unknown peripentacene (PP). The process requires activation by heating to 320 degrees C and is possibly catalyzed by impurities such as DHP, 6,13-pentacenequinone (PQ), Al, or Fe found in the starting materials. These impurities also result in a decrease in the intrinsic field-effect mobility (FEM) of pentacene crystals. Subsequent purifications remove such impurities, thus inhibiting the formation of the disproportionation products and increasing the FEM of pentacene (2.2 cm(2)/Vs). These results clarify the importance of purification of semiconductive materials for measurements of intrinsic mobility and optimal device performance.     

Charge stripe glasses in La<Subscript>2-x</Subscript>Sr<Subscript>x</Subscript>NiO<Subscript>4</Subscript> for 0.20 < x < 0.25

We present high resolution X-ray measurements characterising the charge stripe order state in the La_2-xSr_xNiO₄ system with x = 0.20, 0.225 and 0.25. We find that in the x = 0.20, 0.225 and 0.25 systems the charge stripe order exists in a charge stripe glass characterised by weak, poorly correlated incommensurate charge stripes in contrast to the strong well correlated charge stripes in the commensurate x = 1/3 system. No stabilisation of the charge order was observed at the next possible commensurate value of ε= 0.25. A comparison with high energy X-ray measurements suggested that the charge order may exist in a charge stripe glass in the bulk in the doping region x = 0.20 - 0.33. Finally at low temperature there was an initial increase in the intensity and correlation not observed with neutron measurements and it appears to be an effect that X-rays are sensitive to but neutrons are not.     

Pauson-Khand reaction of 2-ethynyl aniline: Synthesis of fused ring indoles by organocuprate conjugate addition followed by spontaneous dehydration

The Pauson-Khand reaction of 2-ethynyl aniline gives the expected cyclopentenone product, with the aniline alpha to the ketone. Treatment with organocuprates gives not the simple conjugate addition product, but the indole derived from an addition-cyclisation-nucleophilic attack sequence.     

A study of the photochemical response of o-nitrobenzyl cholate derivatives in P(MMA-MAA) matrices

Ortho-nitrobenzyl cholate esters have been successfully used as photosensitive components in solution inhibition deep UV photoresists. The photochemical behavior of a variety of substituted o-nitrobenzyl cholate derivaties has been examined and resist sensitivity is related to the quantum yield of the reaction. The most efficient system examined is o, o′-dinitrobenzyl cholate/P(MMA-MMA), where the quantum yield of photoreaction is 0.2 and resist sensitivity is ca. 150 mJ/cm² for a 1.5 μm film. The mode of resist behaviour on irradiation and development is also reported.