α,α'-二氧代烯酮环二硫代缩醛的NMR研究

报道了7种新的α,α'-二氧代烯酮环二硫代缩醛化合物的NMR谱.应用¹H、¹³C NMR谱等确定了这7种新化合物的分子结构,并对全部谱峰进行了归属,初步探讨了分子结构对化学位移的影响.     

Synthesis of poly(1.4.-benzamide) in solutions of randomly coiled polymers

The polycondensation of p-aminobenzoic acid by the use of triphenylphospine and hexachloroethane is described. One way to obtain a mixed solution of rigid rod and flexible coil polymers is the polycondensation of the rigid chains in a solution of a flexible polymer matrix. Results on matrix polycondensation of poly(p-benzamide) in solutions of poly(methyl methacrylate), poly(methyl methacrylate-co-styrene), polystyrene and polyacrylonitrile are reported. It is shown that there exists an interrelation between the phase behavior of the mixed polymer solutions and the influence of the matrix polymer on the synthesis of poly(1.4.-benzamide). The ternary phase diagrams of the rigid rod/flexible coil polymer solutions were determined.     

Collisions between electrostatically confined linear polar molecules

Collisions between linear polar molecules that were electrostatically trapped were investigated. The collisional transition from a low to a high field seeking state (inelastic collision) causes trap loss. The efficiency of evaporative cooling is improved at higher elastic collision rates. We calculated cross-sections of inelastic and elastic collision using a semi-classical treatment. Received 6 December 2001 / Received in final form 26 February 2002 Published online 28 June 2002     

Towards conformationally dependent redox-responsive molecular switches. New polyferrocene bis benzo crown ether receptors

New polyferrocene bis benzo-15-crown-5 ligands have been prepared and shown to form 1:1 intramolecular sandwich complexes with the potassium cation. Electrochemical investigations reveal that both receptors undergo small anodic perturbations of the respective ferrocene-ferrocenium redox couples in the presence of alkali metal cations.     

Asymmetric molecular sieve carbon membranes

An asymmetric molecular sieve carbon membrane is obtained by conventional pyrolysis of a thermosetting polymeric film, followed by unequal oxidation. Morphology, pore size distribution, and gas separation characteristics of the membrane are discussed. The transport mechanism for gas permeation is clearly non-Knudsen diffusion since heavier oxygen permeates faster than lighter nitrogen. The proposed mass transfer mechanism is that of a molecular sieve.     

Palladium island growth on Ni(111) Stochastic classical trajectory — ghost atom calculations

We generalize previous stochastic classical trajectory-ghost atom calculations for describing palladium deposition onto the Ni(111) surface between 0.1 and 0.5 monolayers. The growth evolves through two-dimensional islands. The islands are formed following the downward funneling mechanism. Surface temperature does not affect the island growth.     

Monte Carlo simulation for temperature dependence of Ga diffusion length on GaAs(0 0 1)

Diffusion length of Ga on the GaAs(0 0 1)-(2×4)β2 is investigated by a newly developed Monte Carlo-based computational method. The new computational method incorporates chemical potential of Ga in the vapor phase and Ga migration potential on the reconstructed surface obtained by ab initio calculations; therefore we can investigate the adsorption, diffusion and desorption kinetics of adsorbate atoms on the surface. The calculated results imply that Ga diffusion length before desorption decreases exponentially with temperature because Ga surface lifetime decreases exponentially. Furthermore, Ga diffusion length L along and [1 1 0] on the GaAs(0 0 1)-(2×4)β2 are estimated to be and L_[110]200 nm, respectively, at the incorporation–desorption transition temperature (T860 K).     

On the dynamics of electrochemical ion-transfer reactions

A model electrochemical ion-transfer reaction is investigated by molecular dynamics simulations. Non-equilibrium solvation effects can lead to barrier recrossings when the ion passes the transition state. The resulting transmission coefficient, which measures the deviation of the rate from the predictions of the transition state theory, is in good agreement with the Grote–Hynes theory. By contrast, Kramers theory predicts a much lower rate constant. The reaction occurs in the polarization caging regime of Grote–Hynes theory, in which the solvent motion controls the advance of the reaction. Furthermore, the molecular friction depends strongly on the distance from the electrode.     

Gas source MBE grown wavelength extended 2.2 and 2.5 μm InGaAs PIN photodetectors

Using homo-junction structure and relative thin linear graded In_xGa_1−xAs as the buffer layer, extended wavelength InGaAs PIN photodetectors with cut-off wavelength of 2.2 and 2.5 μm at room temperature have been grown by using GSMBE, and their performance over a wide temperature range have been extensively investigated. For those 2.2 or 2.5 μm detectors with 100 μm diameter, the typical dark current (V_R = 10 mV) and R₀A are 57 nA/10.3 Ω cm² or 67 nA/12.7 Ω cm² at 290 K, and 84 pA/4.70 kΩ cm² or 161 pA/3.12 kΩ cm² at 210 K respectively. The thermal activation energies of the dark current are 0.447 eV or 0.404 eV for 2.2 or 2.5 μm detectors respectively.