Molecular interpretation of the linear relationship between the entropy and the enthalpy of activation of charge transfer reactions in polar liquids

The well-known linear relationship (T?S# =??H# +?, where 1 >? > 0,? > 0) between the entropy (?S#) and the enthalpy (?H#) of activation for reactions in polar liquids is investigated by using a molecular theory. An explicit derivation of this linear relation from first principles is presented for an outersphere charge transfer reaction. The derivation offers microscopic interpretation for the quantities? and?. It has also been possible to make connection with and justify the arguments of Bell put forward many years ago.

Correlation between conductivity or diffusivity and activation energy in amorphous solids

There exist many investigations of ionic transport in a variety of glasses. These studies exhibit strong correlation between ionic conductivity and activation energy: Typically, it is found that higher conductivity is associated with lower activation energies and vice versa. Although there are explanations for this at a phenomenological level, there is no consistent physical picture to explain the correlation between conductivity and activation energy. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a host amorphous matrix. We find that there is a maximum in self-diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has been previously found in other condensed phases, such as confined fluids and dense liquids, and has its origin in the levitation effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our results suggest that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity, and activation energy. The nature of this relationship is discussed in terms of the levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results of Nascimento et al. [Braz. J. Phys. 35, 626 (2005)] that structural features of the glass are important in determining the ionic conductivity.

Endoplasmic Reticulum Stress-Mediated Activation of p38 MAPK, Caspase-2 and Caspase-8 Leads to Abrin-Induced Apoptosis

Abrin from Abrus precatorius plant is a potent protein synthesis inhibitor and induces apoptosis in cells. However, the relationship between inhibition of protein synthesis and apoptosis is not well understood. Inhibition of protein synthesis by abrin can lead to accumulation of unfolded protein in the endoplasmic reticulum causing ER stress. The observation of phosphorylation of eukaryotic initiation factor 2 alpha and upregulation of CHOP (CAAT/enhancer binding protein (C/EBP) homologous protein), important players involved in ER stress signaling by abrin, suggested activation of ER stress in the cells. ER stress is also known to induce apoptosis via stress kinases such as p38 MAPK and JNK. Activation of both the pathways was observed upon abrin treatment and found to be upstream of the activation of caspases. Moreover, abrin-induced apoptosis was found to be dependent on p38 MAPK but not JNK. We also observed that abrin induced the activation of caspase-2 and caspase-8 and triggered Bid cleavage leading to mitochondrial membrane potential loss and thus connecting the signaling events from ER stress to mitochondrial death machinery.

Tyrosine kinases and calcium dependent activation of endothelial cell phospholipase D by diperoxovanadate

Reactive oxygen species (ROS) mediated modulation of signal transduction pathways represent an important mechanism of cell injury and barrier dysfunction leading to the development of vascular disorders. Towards understanding the role of ROS in vascular dysfunction, we investigated the effect of diperoxovanadate (DPV), derived from mixing hydrogen peroxide and vanadate, on the activation of phospholipase D (PLD) in bovine pulmonary artery endothelial cells (BPAECs). Addition of DPV to BPAECs in the presence of .05% butanol resulted in an accumulation of [P-32] phosphatidylbutanol (PBt) in a dose- and time-dependent manner. DPV also caused an increase in tyrosine phosphorylation of several protein bands (Mr 20-200 kD), as determined by Western blot analysis with antiphosphotyrosine antibodies. The DPV-induced [P-32] PBt-accumulation was inhibited by putative tyrosine kinase inhibitors such as genistein, herbimycin, tyrphostin and by chelation of Ca2+ with either EGTA or BAPTA, however, pretreatment of BPAECs with the inhibitor PKC bisindolylmaleimide showed minimal inhibition. Also down-regulation of PKC alpha and epsilon, the major isotypes of PKC in BPAECs, by TPA (100 nM, 18 h) did not attenuate the DPV-induced PLD activation. The effects of putative tyrosine kinase and PKC inhibitors were specific as determined by comparing [P-32] PBt formation between DPV and TPA. In addition to tyrosine kinase inhibitors, antioxidants such as N-acetylcysteine and pyrrolidine dithiocarbamate also attenuated DPV-induced protein tyrosine phosphorylation and PLD stimulation. These results suggest that oxidation, prevented by reduction with thiol compounds, is involved in DPV-dependent protein tyrosine phosphorylation and PLD activation.

Determination of diffusion parameters and activation energy of diffusion in V3Si phase with A15 crystal structure

Diffusion such is the integrated diffusion coefficient of the phase, the tracer diffusion coefficient of species at different temperatures and the activation energy for diffusion, are determined in V3Si phase with A15 crystal structure. The tracer diffusion coefficient of Si Was found to be negligible compared to the tracer diffusion coefficient of V. The calculated diffusion parameters will help to validate the theoretical analysis of defect structure of the phase, which plays an important role in the superconductivity.

On the relationship between finger width, velocity, and fluxes in thermohaline convection

Double-diffusive finger convection occurs in many natural processes.The theories for double-diffusive phenomena that exist at present consider systems with linear stratification in temperature and salinity. The double-diffusive systems with step change in salinity and temperature are, however, not amenable to simple stability analysis. Hence factors that control the width of the finger, velocity, and fluxes in systems that have step change in temperature and salinity have not been understood so far. In this paper we provide new physical insight regarding factors that influence finger convection in two-layer double-diffusive system through two-dimensional numerical simulations. Simulations have been carried out for density stability ratios (R-rho) from 1.5 to 10. For each density stability ratio, the thermal Rayleigh number (Ra-T) has been systematically varied from 7x10(3) to 7x10(8). Results from these simulations show how finger width, velocity, and flux ratios in finger convection are interrelated and the influence of governing parameters such as density stability ratio and the thermal Rayleigh number. The width of the incipient fingers at the time of onset of instability has been shown to vary as Ra-T-1/3. Velocity in the finger varies as Ra(T)1/3/R-rho. Results from simulation agree with the scale analysis presented in the paper. Our results demonstrate that wide fingers have lower velocities and flux ratios compared to those in narrow fingers. This result contradicts present notions about the relation between finger width and flux ratio. A counterflow heat-exchanger analogy is used in understanding the dependence of flux ratio on finger width and velocity.

Approximate potential-distance relationship for clays

The conventional procedure of determining the surface potential of clay platelet and the variation of potential with distance is lengthy and time consuming. Simplified graphical procedures using Gouy theory have been developed and presented. The new procedures are simple, accurate and very much less time consuming.

New temperature fluctuation method for direct determination of thermal activation energy of deep levels in semiconductors

A new method is suggested where the thermal activation energy is measured directly and not as a slope of an Arrhenius plot. The sample temperature T is allowed to fluctuate about a temperature T0. The reverse-biased sample diode is repeatedly pulsed towards zero bias and the transient capacitance C1 at time t1 is measured The activation energy is obtained by monitoring the fluctuations in C1 and T. The method has been used to measure the activation energy of the gold acceptor level in silicon.

Graphical method to include temperature variation of activation energy in Hall data analysis

A graphical method is presented for Hall data analysis, including the temperature variation of activation energy due to screening. This method removes the discrepancies noted in the analysis of recently reported Hall data on Si(In).

Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

GEODERM: geometric shape design system using an entity-relationship model

GEODERM, a microcomputer-based solid modeller, which incorporates the parametric object model, is discussed. The entity-relationship model, which is used to describe the conceptual schema of the geometric database, is also presented. Three of the four modules of GEODERM, which have been implemented are described in some detail. They are the Solid Definition Language (SDL), the Solid Manipulation Language (SML) and the User-System Interface.

Fractional power dependence of rate on activation energy for reactions with very low internal barriers

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate,kI, are obtained by solving the associated first passage time problems. Both the average rate constant, kI, and the numerically calculated long-time rate constant, kL, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.

Isomerization Dynamics In Solution In The Absence Of An Activation Barrier - Evaluation Of The Potential Parameters

We analyze recent experimental results of Sundström and Gillbro by using the theory of Bagchi, Fleming and Oxtoby. The experimental results are in good agreement with this theory, but not with the earlier theory of Förster and Hoffmann. By fitting the new experimental results to the theory, we obtain approximate estimates of the frequency of the excited surface (assumed harmonic) and the width of the sink function.

Interdiffusion and activation energy in Ti3Au phase with A15 crystal structure

The knowledge of diffusion parameters, such as integrated diffusion coefficient and the activation energy for diffusion is important to understand the growth rate of the product phase and the atomic mechanism of diffusion. These parameters are determined in Ti3Au phase with A15 crystal structure. The calculated diffusion parameters will help in validating the theoretical analysis on defect structure of the phase.

Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.