Gas phase derivatization of endohedral metallofullerenes R@C-82 and R-2@C-80 (R = Nd, Ce)

Endohedral metallofullerenes Ce@C-82, Ce-2@C-80, Nd@C-82 and Nd-2@C-80 undergo gas phase ion/molecule reactions with the ion system from self-chemical ionization of vinyl acetate, and exohedral derivatives are thus generated, A new heterocycle is formed from metallofullerenes and a C2H3O+ cation, Endohedral metallofullerenes show much higher reactivities than empty fullerenes during the association and the charge and proton transfer processes, The strong electron-donating character of endohedral metallofullerenes is due to their unique super-atom-like electronic structures. (C) 1997 by John Wiley & Sons, Ltd.

Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

STUDY OF THE ELECTRODE PROCESS OF HEMOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode is reported. The resulting film on a platinum electrode surface was analyzed with electron spectroscopy for chemical analysis (ESCA). The heterogeneous electron transfer processes of hemoglobin at the polymerized azure A film electrode have been investigated using in situ UV-visible spectroelectrochemistry. The formal potential (E-degrees') and electron transfer number (n) of hemoglobin were calculated as E = 0.088 V versus NHE (standard deviation +/- 0.5, N = 4) and n = 1.8 (standard deviation +/- 0.5, N = 4). Exhaustive reduction and oxidation electrolysis are achieved in 80 and 380 seconds, respectively, during a potential step between -0.3 and +0.3 V. A formal heterogeneous electron-transfer rate constant (k(sh)) of 3.54(+/- 0.12) X 10(-6) cm/s and a transfer coefficient (alpha) of 0.28(+/- 0.01) were obtained by cyclic voltabsorptometry, which indicated that the poly-azure A film electrode is able to catalyze the direct reduction and oxidation of hemoglobin.

Shell effect on stabilization processes following multi-electron transfer in slow Arq+-Ar (g=6-9, 11) collisions

We experimentally investigate the shell effect on the stabilization processes following the multi-electron transfer in slow collisions of Arq+-Ar (q = 6-9, It) The relative cross-section ratios of multi-electron transfer and of the subsequent stabilization with respect to single-electron capture are measured meanwhile compared with the theoretical results predicted by the classical over-barrier model. Our result indicates that the multi-electron transfer is dominant when the projectile charge is large and the subsequent stabilization shows a dramatic variation if the projectile L-shell configuration becomes open. It shows that the subsequent stabilization processes of multiply excited scattering ions have a strong dependence on the projectile shell. (C) 2010 Elsevier BV All rights reserved.

Enhancements of the simulation method on the edge effect in resin transfer molding processes

In resin transfer molding processes, small clearances exist between the fiber preform and the mold edges, which result in a preferential resin flow in the edge channel and then disrupt the flow patterns during the mold filling stage. A mathematical model including the effect of cavity thickness on resin flow was developed for flow behavior involving the interface between an edge channel and a porous medium. According to the mathematical analysis of momentum equations in a fully developed rectangular duct and formulations of the equivalent edge permeability, comparing with three-dimensional Navier-Stokes equations, the governing equations were modified in the edge channel. The volume of fluid (VOF) method was applied to track the flow front. A simple case is numerically simulated using the modified governing equations. The effects of edge channel width and cavity thickness on flow front and inlet pressure are analyzed, and the evolution characteristics of simulated results are in agreement with the experimental results. (c) 2007 Elsevier B.V. All rights reserved

Reactive Mold Filling in Resin Transfer Molding Processes with Edge Effects

Reactive mold filling is one of the important stages in resin transfer molding processes, in which resin curing and edge effects are important characteristics. On the basis of previous work, volume-averaging momentum equations involving viscous and inertia terms were adopted to describe the resin flow in fiber preform, and modified governing equations derived from the Navier-Stokes equations are introduced to describe the resin flow in the edge channel. A dual-Arrhenius viscosity model is newly introduced to describe the chemorheological behavior of a modified bismaleimide resin. The influence of the curing reaction and processing parameters on the resin flow patterns was investigated.

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)(6)(3-) in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA(+), IPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

Mixed ion transfer analysis in redox processes of electroactive thin films

Electrochemical quartz crystal microbalance (EQCM) technique was used to measure the ion transfer in redox processes in electroactive organic thin films, such as self-assembled monolayer (SAM) (4-pyridyl hydroquinone, abbr. 4PHQ), multilayer based on SAM and conducting polymer film (here poly-(3,4-ethylenedioxythiophene), abbr. PEDOT). A mechanism of mixed ion transfer is developed and presented. Analysis of mixed ion transfer during redox processes successfully elucidates the deviation of oscillation frequency of the quartz crystal from theoretical expectation.

A coupling model for terrestrial processes in arid areas and its application

In this paper, the importance of investigation on terrestrical processes in arid areas for mankind's living environment protection and local economy development as well as its present state of the art are elucidated. A coupling model, which evaluates heat, mass, momentum and radiative fluxes in the SPAC system, is developed for simulating microclimate over plant and bare soil. Especially, it is focussed on the details of turbulence transfer. For illustration, numerical simulation of the water-heat exchange processes at Shapotou Observatory, GAS, Ninxia Province are conducted, and the computational results show that the laws of land-surface processes are rather typical in the arid areas.

Progress In Modeling Of Fluid Flows In Crystal Growth Processes

Modeling of fluid flows in crystal growth processes has become an important research area in theoretical and applied mechanics. Most crystal growth processes involve fluid flows, such as flows in the melt, solution or vapor. Theoretical modeling has played an important role in developing technologies used for growing semiconductor crystals for high performance electronic and optoelectronic devices. The application of devices requires large diameter crystals with a high degree of crystallographic perfection, low defect density and uniform dopant distribution. In this article, the flow models developed in modeling of the crystal growth processes such as Czochralski, ammonothermal and physical vapor transport methods are reviewed. In the Czochralski growth modeling, the flow models for thermocapillary flow, turbulent flow and MHD flow have been developed. In the ammonothermal growth modeling, the buoyancy and porous media flow models have been developed based on a single-domain and continuum approach for the composite fluid-porous layer systems. In the physical vapor transport growth modeling, the Stefan flow model has been proposed based on the flow-kinetics theory for the vapor growth. In addition, perspectives for future studies on crystal growth modeling are proposed. (c) 2008 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

Observation and modeling for terrestrial processes in alpine meadow

The water-heat transfer process between land and atmosphere in Haibei alpine meadow area has been systematically observed. A multi-layer coupling model for land-atmosphere interaction was presented with special attention paid to the moisture transfer in leaf stomata under unsaturated condition. A profound investigation on the physical process of turbulent transfer inside the vegetation has been performed with a revised formula of water absorption for root system. The present model facilitates the study of vertically distributed physical variables in detail. Numerical simulation was conducted according to the transfer process of Kinesia humility meadow in the area of Haibei Alpine Meadow Ecosystem Station, CAS. The calculated results agree well with observation.

Two bifurcation processes for onset of oscillatory thermocapillary convection in a floating half zone

An overview on the onset of thermocapillary oscillatory convection in a floating half zone is provided, and it is a typical subject in the microgravity sciences related to the space materials science, especially the floating zone processing, and also to the microgravity fluid physics. The main interests are focused around the process for onset of oscillatory thermocapillary convection, which is known also as the bifurcation transition from quasi-steady convection to oscillatory convection. The onset of oscillation depends on a set of critical parameters, such as the Marangoni number, Prandtl number, geometrical parameters, and heat transfer parameters. Recent studies show that, there exists the bifurcation transition from steady and axial symmetric convection to the steady and axial non-symmetric convection before the onset of oscillation in cases of small Prandtl number fluids and in cases of larger Prandtl number fluids of fat liquid bridge with small aspect ratio. The transition process is a strong non-linear process because the velocity deviation has the same order of magnitude as that of an average flow after the onset of oscillation, and unsteady 3-D numerical simulation is suitable to do in depth analysis on strong non-linear process, and leads generally to a better comparison with the experimental results.

Verification of EL2 electronic absorption effect on charge transfer in semi-insulating GaAs

The electronic absorption of EL2 centers has been clarified to be related to the electron acid hole photoionizations, and the transition from its ground state to metastable state, respectively. Under an illumination with a selected photon energy in the near infrared region, these three processes with different optical cross sections will show different kinetics against the illumination time. It has recently been shown that the photosensitivity (measured under 1.25 eV illumination) of the local vibrational mode absorption induced by some deep defect centers in SI-GaAs is a consequence of the electron and hole photoionizations of EL2. This paper directly measures the kinetics of the electronic transition associated with EL2 under 1.25 eV illumination, which implies the expected charge transfer among different charge states of the EL2 center. A calculation based on a simple rate equation model is in good agreement with the experimental results.

Modeling study on the flow, heat transfer and energy conversion characteristics of low-power arc-heated hydrogen/nitrogen thrusters

A modeling study is conducted to investigate the effect of hydrogen content in propellants on the plasma flow, heat transfer and energy conversion characteristics of low-power (kW class) arc-heated hydrogen/nitrogen thrusters (arcjets). 1:0 (pure hydrogen), 3:1 (to simulate decomposed ammonia), 2:1 (to simulate decomposed hydrazine) and 0:1 (pure nitrogen) hydrogen/nitrogen mixtures are chosen as the propellants. Both the gas flow region inside the thruster nozzle and the anode-nozzle wall are included in the computational domain in order to better treat the conjugate heat transfer between the gas flow region and the solid wall region. The axial variations of the enthalpy flux, kinetic energy flux, directed kinetic-energy flux, and momentum flux, all normalized to the mass flow rate of the propellant, are used to investigate the energy conversion process inside the thruster nozzle. The modeling results show that the values of the arc voltage, the gas axial-velocity at the thruster exit, and the specific impulse of the arcjet thruster all increase with increasing hydrogen content in the propellant, but the gas temperature at the nitrogen thruster exit is significantly higher than that for other three propellants. The flow, heat transfer, and energy conversion processes taking place in the thruster nozzle have some common features for all the four propellants. The propellant is heated mainly in the near-cathode and constrictor region, accompanied with a rapid increase of the enthalpy flux, and after achieving its maximum value, the enthalpy flux decreases appreciably due to the conversion of gas internal energy into its kinetic energy in the divergent segment of the thruster nozzle. The kinetic energy flux, directed kinetic energy flux and momentum flux also increase at first due to the arc heating and the thermodynamic expansion, assume their maximum inside the nozzle and then decrease gradually as the propellant flows toward the thruster exit. It is found that a large energy loss (31-52%) occurs in the thruster nozzle due to the heat transfer to the nozzle wall and too long nozzle is not necessary. Modeling results for the NASA 1-kW class arcjet thruster with hydrogen or decomposed hydrazine as the propellant are found to compare favorably with available experimental data.