The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Measurement of the neutron (^3He) spin structure function at low Q^2 : a connection between the Bjorken and Drell-Hearn-Gerasimov sum rules

The spin dependent cross sections, σT_1/2 and σT_3/2 , and asymmetries, A_∥ and A_⊥ for ³He have been measured at the Jefferson Lab's Hall A facility. The inclusive scattering process ³He(e,e)X was performed for initial beam energies ranging from 0.86 to 5.1 GeV, at a scattering angle of 15.5°. Data includes measurements from the quasielastic peak, resonance region, and the deep inelastic regime. An approximation for the extended Gerasimov-Drell-Hearn integral is presented at a 4-momentum transfer Q² of 0.2-1.0 GeV².

Also presented are results on the performance of the polarized ³He target. Polarization of ³He was achieved by the process of spin-exchange collisions with optically pumped rubidium vapor. The ³He polarization was monitored using the NMR technique of adiabatic fast passage (AFP). The average target polarization was approximately 35% and was determined to have a systematic uncertainty of roughly ±4% relative.

Mass transfer from a cylinder to an air stream in axisymmetrical flow (an experimental study)

Mass transfer from wetted surfaces on one-inch cylinders with unwetted approach sections was studied experimentally by means of the evaporation of n-octane and n-heptane into an air stream in axisymmetrical flow, for Reynolds numbers from 5,000 to 310,000. A transition from the laminar to the turbulent boundary layer was observed to occur at Reynolds numbers from 10,000 to 15,000. The results were expressed in terms of the Sherwood number as a function of the Reynolds number, the Schmidt number, and the ratio of the unwetted approach length to the total length. Empirical formulas were obtained for both laminar and turbulent regimes. The rates of mass transfer obtained were higher than theoretical and experimental results obtained by previous investigators for mass and heat transfer from flat plates.

Effect of surface roughness on rarefied-gas heat transfer in microbearings

In this Letter, the rarefaction and roughness effects on the heat transfer process in gas microbearings are investigated. A heat transfer model is developed by introducing two-variable Weierstrass-Mandelbrot (W-M) function with fractal geometry. The heat transfer problem in the multiscale self-affine rough microbearings at slip flow regime is analyzed and discussed. The results show that rarefaction has more significant effect on heat transfer in rough microbearings with lower fractal dimension. The negative influence of roughness on heat transfer found to be the Nusselt number reduction. The heat transfer performance can be optimized with increasing fractal dimension of the rough surface. © 2012 Elsevier B.V. All rights reserved.

Turbine blade tip heat transfer in low speed and high speed flows

In this paper, high and low speed tip flows are investigated for a high-pressure turbine blade. Previous experimental data are used to validate a CFD code, which is then used to study the tip heat transfer in high and low speed cascades. The results show that at engine representative Mach numbers the tip flow is predominantly transonic. Thus, compared to the low speed tip flow, the heat transfer is affected by reductions in both the heat transfer coefficient and the recovery temperature. The high Mach numbers in the tip region (M>1.5) lead to large local variations in recovery temperature. Significant changes in the heat transfer coefficient are also observed. These are due to changes in the structure of the tip flow at high speed. At high speeds, the pressure side corner separation bubble reattachment occurs through supersonic acceleration which halves the length of the bubble when the tip gap exit Mach number is increased from 0.1 to 1.0. In addition, shock/boundary-layer interactions within the tip gap lead to large changes in the tip boundary-layer thickness. These effects give rise to significant differences in the heat-transfer coefficient within the tip region compared to the low-speed tip flow. Compared to the low speed tip flow, the high speed tip flow is much less dominated by turbulent dissipation and is thus less sensitive to the choice of turbulence model. These results clearly demonstrate that blade tip heat transfer is a strong function of Mach number, an important implication when considering the use of low speed experimental testing and associated CFD validation in engine blade tip design. Copyright © 2009 by ASME.

Thin film coil design considerations for wireless power transfer in flat panel display

Wireless power transfer is experimentally demonstrated by transmission between an AC power transmitter and receiver, both realised using thin film technology. The transmitter and receiver thin film coils are chosen to be identical in order to promote resonant coupling. Planar spiral coils are used because of the ease of fabrication and to reduce the metal layer thickness. The energy transfer efficiency as a function of transfer distance is analysed along with a comparison between the theoretical and the experimental results. © 2012 Materials Research Society.

Structure-function analysis of the inverted terminal repeats of the Sleeping Beauty transposon

Translocation of Sleeping Beauty (SB) transposon requires specific binding of SB transposase to inverted terminal repeats (ITRs) of about 230 bp at each end of the transposon, which is followed by a cut-and-paste transfer of the transposon into a target DNA sequence. The ITRs contain two imperfect direct repeats (DRs) of about 32 bp. The outer DRs are at the extreme ends of the transposon whereas the inner DRs are located inside the transposon, 165-166 bp from the outer DRs. Here we investigated the roles of the DR elements in transposition. Although there is a core transposase-binding sequence common to all of the DRs, additional adjacent sequences are required for transposition and these sequences vary in the different DRs. As a result, SB transposase binds less tightly to the outer DRs than to the inner DRs. Two DRs are required in each ITR for transposition but they are not interchangeable for efficient transposition. Each DR appears to have a distinctive role in transposition. The spacing and sequence between the DR elements in an ITR affect transposition rates, suggesting a constrained geometry is involved in the interactions of SB transposase molecules in order to achieve precise mobilization. Transposons are flanked by TA dinucleotide base-pairs that are important for excision; elimination of the TA motif on one side of the transposon significantly reduces transposition while loss of TAs on both flanks of the transposon abolishes transposition. These findings have led to the construction of a more advanced transposon that should be useful in gene transfer and insertional mutagenesis in vertebrates. (C) 2002 Elsevier Science Ltd. All rights reserved.

A partially incoherent rate theory of long-range charge transfer in deoxyribose nucleic acid

A quantum chemistry based Green's function formulation of long-range charge transfer in deoxyribose nucleic acid (DNA) double helix is proposed. The theory takes into account the effects of DNA's electronic structure and its incoherent interaction with aqueous surroundings. In the implementation, the electronic tight-binding parameters for unsolvated DNA molecules are determined at the HF/6-31G* level, while those for individual nucleobase-water couplings are at a semiempirical level by fitting with experimental redox potentials. Numerical results include that: (i) the oxidative charge initially at the donor guanine site does hop sequentially over all guanine sites; however, the revealed rates can be of a much weaker distance dependence than that described by the ordinary Ohm's law; (ii) the aqueous surroundings-induced partial incoherences in thymine/adenine bridge bases lead them to deviate substantially from the superexchange regime; (iii) the time scale of the partially incoherent hole transport through the thymine/adenine pi stack in DNA is about 5 ps. (C) 2002 American Institute of Physics.

On detection wavelength and electron-hole wave function overlap of type II InAs/In-x Ga1-x Sb superlattice infrared photodetector

In this paper, the detection wavelength and the electron-hole wave function overlap of InAs/IrxGa1-xSb type II superlattice photodetectors are numerically calculated by using the envelope function and the transfer matrix methods. The band offset is dealt with by employing the model solid theory, which already takes into account the lattice mismatch between InAs and InxGa1-xSb layers. Firstly, the detection wavelength and the wave function overlap are investigated in dependence on the InAs and InxGa1-xSb layer thicknesses, the In mole fraction, and the periodic number. The results indicate that the detection wavelength increases with increasing In mole fraction, InAs and InxGa1-xSb layer thicknesses, respectively. When increasing the periodic number, the detection wavelength first increases distinctly for small periodic numbers then increases very slightly for large period numbers. Secondly, the wave function overlap diminishes with increasing InAs and InxGa1-xSb layer thicknesses, while it enhances with increasing In mole fraction. The dependence of the wave function overlap on the periodic number shows the same trend as that of the detection wavelength on the periodic number. Moreover, for a constant detection wavelength, the wave function overlap becomes greater when the thickness ratio of the InAs over InxGa1-xSb is larger.

Experimental investigation on TBAB clathrate hydrate slurry flows in a horizontal tube: Forced convective heat transfer behaviors

Tetra-n-butyl-ammonium bromide (TBAB) clathrate hydrate slurry (CHS) is one kind of secondary refrigerants, which is promising to be applied into air-conditioning or latent-heat transportation systems as a thermal storage or cold carrying medium for energy saving. It is a solid-liquid two phase mixture which is easy to produce and has high latent heat and good fluidity. In this paper, the heat transfer characteristics of TBAB slurry were investigated in a horizontal stainless steel tube under different solid mass fractions and flow velocities with constant heat flux. One velocity region of weakened heat transfer was found. Moreover, TBAB CHS was treated as a kind of Bingham fluids, and the influences of the solid particles, flow velocity and types of flow on the forced convective heat transfer coefficients of TBAB CHS were investigated. At last, criterial correlations of Nusselt number for laminar and turbulent flows in the form of power function were summarized, and the error with experimental results was within 20%.

A transfer matrix approach to conductance in quantum waveguides

A transfer matrix approach is presented for the study of electron conduction in an arbitrarily shaped cavity structure embedded in a quantum wire. Using the boundary conditions for wave functions, the transfer matrix at an interface with a discontinuous potential boundary is obtained for the first time. The total transfer matrix is calculated by multiplication of the transfer matrix for each segment of the structure as well as numerical integration of coupled second-order differential equations. The proposed method is applied to the evaluation of the conductance and the electron probability density in several typical cavity structures. The effect of the geometrical features on the electron transmission is discussed in detail. In the numerical calculations, the method is found to be more efficient than most of the other methods in the literature and the results are found to be in excellent agreement with those obtained by the recursive Green's function method.

Ultrafast dynamics of dye molecules in solution as a function of temperature

Femtosecond time-resolved studies using fluorescence depletion spectroscopy were performed on Rhodamine 700 in acetone solution and on Oxazine 750 in acetone and formamide solutions at different temperatures. The experimental curves that include both fast and slow processes have been fitted using a biexponential function. Time constants of the fast process, which corresponds to the intramolecular vibrational redistribution (IVR) of solute molecules, range from 300 to 420 fs and increase linearly as the temperature of the environment decreases. The difference of the average vibrational energy of solute molecules in the ground state at different temperatures is a possible reason that induces this IVR time-constant temperature dependence. However, the time constants of the slow process, which corresponds to the energy transfer from vibrational hot solute molecules to the surroundings occurred on a time scale of 1-50 ps, changed dramatically at lower temperature, nonlinearly increasing with the decrease of temperature. Because of the C-H...O hydrogen-bond between acetone molecules, it is more reasonable that acetone molecules start to be associated, which can influence the energy transfer between dye molecules and acetone molecules efficiently, even at temperatures far over the freezing point.

Affinity and Specificity of Levamlodipine-Human Serum Albumin Interactions: Insights into Its Carrier Function

The affinity and specificity of drugs with human serum albumin (HSA) are crucial factors influencing the bioactivity of drugs. To gain insight into the carrier function of HSA, the binding of levamlodipine with HSA has been investigated as a model system by a combined experimental and theoretical/computational approach. The fluorescence properties of HSA and the binding parameters of levamlodipine indicate that the binding is characterized by one binding site with static quenching mechanism, which is related to the energy transfer. As indicated by the thermodynamic analysis, hydrophobic interaction is the predominant force in levamiodipine-HSA complex, which is in agreement with the computational results. And the hydrogen bonds can be confirmed by computational approach between levamlodipine and HSA. Compared to predicted binding energies and binding energy spectra at seven sites on HSA, levamlodipine binding HSA at site I has a high affinity regime and the highest specificity characterized by the largest intrinsic specificity ratio (ISR). The binding characteristics at site I guarantee that drugs can be carried and released from HSA to carry out their specific bioactivity.

Study of facilitated potassium ion transfer across a water vertical bar 1,2-dichloroethane interface using different phase volume ratio systems

A study of potassium ion transfer across a water \ 1,2-dichloroethane (W \ DCE) interface facilitated by dibenzo-18-crown-6 (DB18C6) with various phase volume ratio systems is presented. The key point was that a droplet of aqueous solution containing a redox couple, Fe(CN)(6)(3-)/Fe(CN)(6)(4-), with equal molar ratio, was first attached to a platinum electrode surface, and the resulting droplet electrode was then immersed into the organic solution containing a hydrophobic electrolyte to construct a platinum electrode/aqueous phase/organic phase system. The interfacial potential of the W \ DCE within the series could be externally controlled because the specific compositions in the aqueous droplet make the Pt electrode function like a reference electrode as long as the concentration ratio of Fe(CN)(6)(3-)/Fe(CN)(6)(4-) remains constant. In this way, a conventional three-electrode potentiostat can be used to study the ion transfer process at a liquid \ liquid (L \ L) interface facilitated by an ionophore with variable phase volume ratio (r = V-o/V-w). The effect of r on ion transfer and facilitated ion transfer was studied in detail experimentally. We also demonstrated that as low as 5 x 10(-8) M DB18C6 could be determined using this method due to the effect of the high phase volume ratio.

Studies on extraction and mass transfer of samarium and neodymium in hollow fiber membrane (HFM) with HEH/EHP

The membranes of polyvinylidene fluoride, which were synthesized by our laboratory, were used to study the transfer and extraction performances of Nd(III) and Sm(III) with the extraction system of HEH/EHP-kerosene. The results show that the membrane material was suitable to the study on membrane extraction, and could offer a good transfer performance in the membrane construction parameters selected, The extraction reaction in the membrane module was the same as that in liquid-liquid process, HEH/EHP ammoniated for increasing the mass transfer coefficient was almost the same with increasing the concentration of HEH/EHP, and H+ was still transferred first at higher pH range of feed solution when HEH/EHP was ammoniated, The controlling model of the membrane extraction process was the diffusion model accompanied by interfacial reaction, The controlling function of interfacial reaction would increase gradually with the increasing of the membrane pore size. The mass transfer coefficient increased when extraction and stripping were carried out simultaneously.