Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

An experimental study of reverse transition in two-dimensional channel flow

An experimental investigation on reverse transition from turbulent to laminar flow in a two-dimensional channel was carried out. The reverse transition occurred when Reynolds number of an initially turbulent flow was reduced below a certain value by widening the duct in the lateral direction. The experiments were conducted at Reynolds numbers of 625, 865, 980 and 1250 based on half the height of the channel and the average of the mean velocity. At all these Reynolds numbers the initially turbulent mean velocity profiles tend to become parabolic. The longitudinal and vertical velocity fluctuations ($\overline{u^{\prime 2}}$ and $\overline{v^{\prime 2}}$) averaged over the height of the channel decrease exponentially with distance downstream, but $\overline{u^{\prime}v^{\prime}} $ tends to become zero at a reasonably well-defined point. During reverse transition $\overline{u^{\prime}}\overline{v^{\prime}}/\sqrt{\overline{u^{\prime 2}}}\sqrt{\overline{v^{\prime 2}}}$ also decreases as the flow moves downstream and Lissajous figures taken with u’ and v’ signals confirm this trend. There is approximate similarly between $\overline{u^{\prime 2}} $ profiles if the value of $\overline{u^{\prime 2}_{\max}} $ and the distance from the wall at which it occurs are taken as the reference scales. The spectrum of $\overline{u^{\prime 2}} $ is almost similar at all stations and the non-dimensional spectrum is exponential in wave-number. All the turbulent quantities, when plotted in appropriate co-ordinates, indicate that there is a definite critical Reynolds number of 1400±50 for reverse transition.

Transition to turbulence in the free convection boundary layers on an inclined heated plate

An experimental study has been made of transition to turbulence in the free convective flows on a heated plate. Observations have been made with the plate vertical and inclined at angles up to about 50° to the vertical, both above and below the plate. A fibre anemometer was used to survey the region of intermittent turbulence. Information has thus been obtained about the range of Grashof numbers over which transition takes place. Even when the plate is vertical the region of intermittent turbulence is long. When it is inclined, this region becomes still longer in the flow below the plate as a result of the stabilizing stratification, a Richardson number effect. It is possible to have a whole flow such that it should be described as transitional, not laminar or turbulent. It was noticed that in this flow and the vertical plate one, the velocity during the laminar periods could be either of two characteristic values, one of them close to zero. The behaviour above an inclined plate could be interpreted largely as a trend towards the behaviour described in a preceding paper.

Some properties of boundary layer flow during the transition from laminar to turbulent motion

Transition in the boundary layer on a flat plate is examined from the point of view of intermittent production of turbulent spots. On the hypothesis of localized laminar breakdown, for which there is some expermental evidence, Emmons’ probability calculations can be extended to explain the observed statistical similarity of transition regions. Application of these ideas allows detailed calculations of the boundary layer parameters including mean velocity profiles and skin friction during transition. The mean velocity profiles belong to a universal one-parameter family with the intermittency factor as the parameter. From an examination of experimental data the probable existence of a relation between the transition Reynolds number and the rate of production of the turbulent spots is deduced. A simple new technique for the measurement of the intermittency factor by a Pitot tube is reported.

A dynamical instability due to fluid–wall coupling lowers the transition Reynolds number in the flow through a flexible tube

A flow-induced instability in a tube with flexible walls is studied experimentally. Tubes of diameter 0.8 and 1.2 mm are cast in polydimethylsiloxane (PDMS) polymer gels, and the catalyst concentration in these gels is varied to obtain shear modulus in the range 17–550 kPa. A pressure drop between the inlet and outlet of the tube is used to drive fluid flow, and the friction factor $f$ is measured as a function of the Reynolds number $Re$. From these measurements, it is found that the laminar flow becomes unstable, and there is a transition to a more complicated flow profile, for Reynolds numbers as low as 500 for the softest gels used here. The nature of the $f$–$Re$ curves is also qualitatively different from that in the flow past rigid tubes; in contrast to the discontinuous increase in the friction factor at transition in a rigid tube, it is found that there is a continuous increase in the friction factor from the laminar value of $16\ensuremath{/} Re$ in a flexible tube. The onset of transition is also detected by a dye-stream method, where a stream of dye is injected into the centre of the tube. It is found that there is a continuous increase of the amplitude of perturbations at the onset of transition in a flexible tube, in contrast to the abrupt disruption of the dye stream at transition in a rigid tube. There are oscillations in the wall of the tube at the onset of transition, which is detected from the laser scattering off the walls of the tube. This indicates that the coupling between the fluid stresses and the elastic stresses in the wall results in an instability of the laminar flow.

Steady compressible flow of cohesionless granular materials through a wedge-shaped bunker

A continuum model based on the critical-state theory of soil mechanics is used to generate stress, density, and velocity profiles, and to compute discharge rates for the flow of granular material in a mass flow bunker. The bin–hopper transition region is idealized as a shock across which all the variables change discontinuously. Comparison with the work of Michalowski (1987) shows that his experimentally determined rupture layer lies between his prediction and that of the present theory. However, it resembles the former more closely. The conventional condition involving a traction-free surface at the hopper exit is abandoned in favour of an exit shock below which the material falls vertically with zero frictional stress. The basic equations, which are not classifiable under any of the standard types, require excessive computational time. This problem is alleviated by the introduction of the Mohr–Coulomb approximation (MCA). The stress, density, and velocity profiles obtained by integration of the MCA converge to asymptotic fields on moving down the hopper. Expressions for these fields are derived by a perturbation method. Computational difficulties are encountered for bunkers with wall angles θw [gt-or-equal, slanted] 15° these are overcome by altering the initial conditions. Predicted discharge rates lie significantly below the measured values of Nguyen et al. (1980), ranging from 38% at θw = 15° to 59% at θw = 32°. The poor prediction appears to be largely due to the exit condition used here. Paradoxically, incompressible discharge rates lie closer to the measured values. An approximate semi-analytical expression for the discharge rate is obtained, which predicts values within 9% of the exact (numerical) ones in the compressible case, and 11% in the incompressible case. The approximate analysis also suggests that inclusion of density variation decreases the discharge rate. This is borne out by the exact (numerical) results – for the parameter values investigated, the compressible discharge rate is about 10% lower than the incompressible value. A preliminary comparison of the predicted density profiles with the measurements of Fickie et al. (1989) shows that the material within the hopper dilates more strongly than predicted. Surprisingly, just below the exit slot, there is good agreement between theory and experiment.

On the criteria for reverse transition in a two-dimensional boundary layer flow

Experiments on reverse transition were conducted in two-dimensional accelerated incompressible turbulent boundary layers. Mean velocity profiles, longitudinal velocity fluctuations $\tilde{u}^{\prime}(=(\overline{u^{\prime 2}})^{\frac{1}{2}})$ and the wall-shearing stress (TW) were measured. The mean velocity profiles show that the wall region adjusts itself to laminar conditions earlier than the outer region. During the reverse transition process, increases in the shape parameter (H) are accompanied by a decrease in the skin friction coefficient (Cf). Profiles of turbulent intensity (u’2) exhibit near similarity in the turbulence decay region. The breakdown of the law of the wall is characterized by the parameter \[ \Delta_p (=\nu[dP/dx]/\rho U^{*3}) = - 0.02, \] where U* is the friction velocity. Downstream of this region the decay of $\tilde{u}^{\prime}$ fluctuations occurred when the momentum thickness Reynolds number (R) decreased roughly below 400.

Stress induced phase transition in a monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Transcription factors that mediate epithelial-mesenchymal transition lead to multidrug resistance by upregulating ABC transporters

Development of multidrug resistance (MDR) is a major deterrent in the effective treatment of metastatic cancers by chemotherapy. Even though MDR and cancer invasiveness have been correlated, the molecular basis of this link remains obscure. We show here that treatment with chemotherapeutic drugs increases the expression of several ATP binding cassette transporters (ABC transporters) associated with MDR, as well as epithelial-mesenchymal transition (EMT) markers, selectively in invasive breast cancer cells, but not in immortalized or non-invasive cells. Interestingly, the mere induction of an EMT in immortalized and non-invasive cell lines increased their expression of ABC transporters, migration, invasion, and drug resistance. Conversely, reversal of EMT in invasive cells by downregulating EMT-inducing transcription factors reduced their expression of ABC transporters, invasion, and rendered them more chemosensitive. Mechanistically, we demonstrate that the promoters of ABC transporters carry several binding sites for EMT-inducing transcription factors, and overexpression of Twist, Snail, and FOXC2 increases the promoter activity of ABC transporters. Furthermore, chromatin immunoprecipitation studies revealed that Twist binds directly to the E-box elements of ABC transporters. Thus, our study identifies EMT inducers as novel regulators of ABC transporters, thereby providing molecular insights into the long-standing association between invasiveness and MDR. Targeting EMT transcription factors could hence serve as novel strategies to curb both metastasis and the associated drug resistance. Cell Death and Disease (2011) 2, e179; doi:10.1038/cddis.2011.61; published online 7 July 2011

Conformational basis for substrate recognition and regulation of catalytic activity in Staphylococcus aureus nucleoside di-phosphate kinase

Nucleoside diphosphate kinases (NDK) are characterized by high catalytic turnover rates and diverse substrate specificity. These features make this enzyme an effective activator of a pro-drug an application that has been actively pursued for a variety of therapeutic strategies. The catalytic mechanism of this enzyme is governed by a conserved histidine that coordinates a magnesium ion at the active site. Despite substantial structural and biochemical information on NDK, the mechanistic feature of the phospho-transfer that leads to auto-phosphorylation remains unclear. While the role of the histidine residue is well documented, the other active site residues, in particular the conserved serine remains poorly characterized. Studies on some homologues suggest no role for the serine residue at the active site, while others suggest a crucial role for this serine in the regulation and quaternary association of this enzyme in some species. Here we report the biochemical features of the Staphylococcus aureus NDK and the mutant enzymes. We also describe the crystal structures of the apo-NDK, as a transition state mimic with vanadate and in complex with different nucleotide substrates. These structures formed the basis for molecular dynamics simulations to understand the broad substrate specificity of this enzyme and the role of active site residues in the phospho-transfer mechanism and oligomerization. Put together, these data suggest that concerted changes in the conformation of specific residues facilitate the stabilization of nucleotide complexes thereby enabling the steps involved in the ping-pong reaction mechanism without large changes to the overall structure of this enzyme. (C) 2011 Elsevier B.V. All rights reserved.

Study of Brittle-to-ductile-transition in Pt-aluminide bond coat using micro-tensile testing method

The Brittle-to-ductile-transition-temperature (BDTT) of free-standing Pt-aluminide (PtAl) coating specimens, i.e. stand-alone coating specimens without any substrate, was determined by micro-tensile testing technique. The effect of Pt content, expressed in terms of the thickness of initial electro-deposited Pt layer, on the BDTT of the coating has been evaluated and an empirical correlation drawn. Increase in the electrodeposited Pt layer thickness from nil to 10 mu m was found to cause an increase in the BDTT of the coating by about 100 degrees C.

Performance Analysis of TCP Uploads in WLANs with Multiple Rates

Throughput analysis of bulk TCP downloads in cases where all WLAN stations are associated at the same rate with the AP is available in the literature. In this paper,we extend the analysis to TCP uploads for the case of multirate associations. The approach is based on a two-dimensional semi- Markov model for the number of backlogged stations. Analytical results are in excellent agreement with simulations performed using QUALNET 4.5.