Photodissociation of isomeric dichloroethylenes in the ultraviolet: Effect of the second chlorine atom substitution on the dynamics

We report the Cl-*(P-2(1/2)) production dynamics in the near-UV dissociation of three isomers (cis-, gem-, and trans-) of dichloroethylene using the conventional resonance enhanced multiphoton ionization technique. Substantial amounts of Cl-* are produced in the wavelength range 222-304 nm. The Cl-* quantum yield (phi(*)) i maximum at 304 nm for all the isomers and phi(*)(cis) is markedly higher than phi(*)(gem) and phi(*)(trans) except at 222 nm. Existence of both direct and indirect dissociation pathways at these wavelengths complicates the Cl* production dynamics. The higher value of phi(*)(cis) originates from a large contribution from direct dissociation via the (n, sigma(*)) state.

Dynamics of zeolite cage and its effect on the diffusion properties of sorbate: persistence of diffusion anomaly in NaA zeolite

Recent computer simulations on zeolites Y and A have found that the diffusion coefficient and the rate of intercage diffusion exhibit, apart from a linear dependence on the reciprocal of the square of the sorbate diameter, an anomalous peak as sorbate diameter approaches the window diameter. Here we report molecular dynamics simulations of zeolite NaA incorporating framework flexibility as a function of sorbate diameter in order to verify the existence of anomalous diffusion. Results suggest persistence of anomalous diffusion or ring effect. This suggests that the anomalous behavior is a general effect characteristic of zeolites Y and A. The barrier for diffusion across the eight-ring window is seen to be negative and is found to decrease with sorbate size. The effect of sorbate on the cage motion has also been investigated. Results suggest that the window expands during intercage migration only if the sorbate size is comparable to the window diameter. Flexible cage simulations yield a higher value for the diffusion coefficient and also the rate of intercage diffusion. This increase has been shown to be due to an increase in the intercage diffusions via the centralized diffusion mode rather than the surface-mediated mode. It is shown that this increase arises from an increase in the single particle density distribution in the region near the cage center.

Effect of the valine-threonine constraint on the dynamics of the proline helix — A molecular dynamics study

Proline residues in helices play an important role in the structure of proteins. The proline residue introduces a kink in the helix which varies from about 5-degrees to 50-degrees. The presence of other residues such as threonine or valine near the proline region can influence the flexibility exhibited by the kinked helix, which can have an important biological role. In the present paper, the constraint introduced by threonine and valine on a proline helix is investigated by molecular dynamics studies. The systems considered am (1) a poly-alanine helix with threonine-proline residues (TP) and (2) a poly-alanine helix with valine-threonine-proline residues (VTP), in the middle. Molecular dynamics simulations are carried out on these two systems for 500 ps. The results are analyzed in terms of structural transitions, bend-related parameters and sidechain orientations.

Effect of orientational motion of mobile chromophores on the dynamics of Forster energy transfer in polymers

Brownian dynamics (BD) simulations have been carried out to explore the effects of the orientational motion of the donor-acceptor (D-A) chromophore pair on the Forster energy transfer between the D-A pair embedded in a polymer chain in solution. It is found that the usually employed orientational averaging (that is, replacing the orientational factor, kappa, by kappa (2) = 2/3) may lead to an error in the estimation of the rate of the reaction by about 20%. In the limit of slow orientational relaxation, the preaveraging of the orientational factor leads to an overestimation of the rate, while in the opposite limit of very fast orientational relaxation, the usual scheme underestimates the rate. The latter results from an interesting interplay between reaction and diffusion. On the other hand, when one of the chromophores is fixed, the preaveraged rate is found to be fairly reliable if the rotational relaxation of the chromophore is sufficiently fast. The present study also reveals a power law dependence of the FRET rate on the chain length (rate proportional to N- alpha, with alpha approximate to 2.6).

Process induced electroactive beta-polymorph in PVDF: effect on dielectric and ferroelectric properties

The effects of various processing conditions, like annealing, poling, mechanical rolling and their combinations, on the dielectric and ferroelectric properties of PVDF poly(vinylidene fluoride)] were systematically studied in this work. Further, the effect of processing sequence on the structure and properties was investigated. While all the processing conditions adopted here resulted in phase transformation of the alpha- to electroactive beta-polymorph in PVDF, the fraction of beta-phase developed was observed to be strongly contingent on the adopted process. The transformation of alpha- to electroactive beta-polymorph was determined by X-ray diffraction and FTIR. The neat PVDF showed only beta-phase, whereas mechanically rolled samples exhibited the highest ca. 85% beta-phase in PVDF. Both the permittivity and the loss tangent decreased in the samples which had undergone different processing conditions. The polarization-electric field (P-E) loops for all the samples were evaluated. Interestingly, the energy density, estimated from the electrical displacement-electric field (D-E) loops, was observed to be highest for the poled samples which were initially rolled. The results indicate that various processing conditions can influence the dielectric and the ferroelectric properties differently.

Mapping Post-translational Modifications of Mammalian Testicular Specific Histone Variant TH2B in Tetraploid and Haploid Germ Cells and Their Implications on the Dynamics of Nucleosome Structure

Histones regulate a variety of chromatin templated events by their post-translational modifications (PTMs). Although there are extensive reports on the PTMs of canonical histones, the information on the histone variants remains very scanty. Here, we report the identification of different PTMs, such as acetylation, methylation, and phosphorylation of a major mammalian histone variant TH2B. Our mass spectrometric analysis has led to the identification of both conserved and unique modifications across tetraploid spermatocytes and haploid spermatids. We have also computationally derived the 3-dimensional model of a TH2B containing nucleosome in order to study the spatial orientation of the PTMs identified and their effect on nucleosome stability and DNA binding potential. From our nucleosome model, it is evident that substititution of specific amino acid residues in TH2B results in both differential histone-DNA and histone-histone contacts. Furthermore, we have also observed that acetylation on the N-terminal tail of TH2B weakens the interactions with the DNA. These results provide direct evidence that, similar to somatic H2B, the testis specific histone TH2B also undergoes multiple PTMs, suggesting the possibility of chromatin regulation by such covalent modifications in mammalian male germ cells.

Study of texture evolution in metastable beta-Ti alloy as a function of strain path and its effect on alpha transformation texture

Texture evolution in a low cost beta titanium alloy was studied for different modes of rolling and heat treatments. The alloy was cold rolled by unidirectional and multi-step cross rolling. The cold rolled material was either aged directly or recrystallized and then aged. The evolution of texture in alpha and beta phases were studied. The rolling texture of beta phase that is characterized by the gamma fiber is stronger for MSCR than UDR; while the trend is reversed on recrystallization. The mode of rolling affects alpha transformation texture on aging with smaller alpha lath size and stronger alpha texture in UDR than in MSCR. The defect structure in beta phase influences the evolution of a texture on aging. A stronger defect structure in beta phase leads to variant selection with the rolled samples showing fewer variants than the recrystallized samples.

Spool valve mechanism used in a 20 K Gifford-McMahon cycle cryorefrigerator and its effect on the P-V diagram

The design and fabrication of a spool valve for a two-stage Gifford-McMahon cycle cryorefrigerator is described. The effect of this valve on the P-V diagram and practical methods of reducing the P-V degradation are also discussed.

Pressure effect on the phase transition of trissarcosine calcium chloride

The dielectric measurement of ferroelectric trissarcosine calcium chloride (TSCC) was made under various pressures up to 6 kbar. A striking decrease in the peak value of the permittivity, epsilon r, at the transition temperature, Tc, was observed with increasing pressure. The value of Tc increases linearly with a pressure coefficient dTc/dp=11.1K kbar-1 at low pressures. This increase in Tc supports the suggestion that the ferroelectric transition is of the pure order-disorder type. It is suggested on the basis of the behaviour of epsilon r with pressure that the order of the ferroelectric transition changes from second to first order on application of pressure.

Penetration Rate Effect on Miniature Cone Tip Resistance for Different Cohesionless Materials

Cone penetrometer tests were carried out in a 140 mm diameter triaxial chamber by using a miniature cone of diameter 19.5 mm. The rate of cone penetration was varied from 0.01 mm/s to 0.1 mm/s. Tests were performed in (i) clean sand, (ii) silty sand, and (iii) sand added with fly ash. Two different effective vertical pressures (sigma(nu)), 100 kPa and 300 kPa, were employed. It was noted that for clean and silty sand, the effect of penetration rate on the ultimate tip resistance (q(cu)) of the cone was found to remain only marginal. On the other hand, for sand added with 30% fly ash, the variation in q(cu) values with penetration rate was found to become quite significant. The effect of penetratio rate on q(cu) in all the cases was found to increase with a decrease in the rate of cone penetration. It was noted that with an increase in sigma(nu), the effect of penetration rate on q(cu) was found to become smaller. The effect of the cone penetration rate on q(cu) generally reduces with an increase in the relative density of the material.

Size effect on the lattice parameter of KCl during mechanical milling

The size effect on the lattice parameter of ionic KCl nanocrystals was studied systematically during mechanical milling of Pure KCl powder under vacuum. The results suggest anomalous lattice expansion, with the lattice parameter increasing from 6.278 angstrom at d = 6 mu m to 6.30307 angstrom at d = 85 mn. The defects generated during ball milling of KCl and surface stress are deemed to be responsible for this lattice parameter expansion. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface treatments for pistons and their effect on engine performance

Surface treatment alters the frictional behaviour of pistons in I.C. engines and can be used to improve engine performance. Surface treatments applied to aluminium alloy pistons of a high speed diesel engine and their effect on the engine performance are described. Certain piston surface treatments improve engine performance and also reduce the run-in period.

Effects of solar radiation pressure and Aerodynamic forces on satelliteattitude Dynamics and their utilization for Control: a survey

The environmcnl exerts an important inJuence on the pefirmance of space systems. A brief rel'iew of mo.s/ of the studies, pre.~ented over the past eightem years, relating to the influence ar7d the possible utilization of thc solar radiation pressure &d aero&namic forces, with particular reference to attitude dynamics and control qf satellites is presented here. The semi-passive stabilizers employing rhese forces show p~qmise of long life, low power and economic sjsfems, which though slower in response, compare we1I wit11 the octiw coi~trollers. It is felt that mud more attention is necessary to the actual implema~tution of these ideas and devices: some of which me quite ingenious und unique.

Preparation temperature effect on the synthesis of various carbon nanostructures

Various carbon nanostructures (CNs) have been prepared by a simple deposition technique based on the pyrolysis of a new carbon source material tetrahydrofuran (THF) mixed with ferrocene using quartz tube reactor in the temperature range 700-1100 degrees C. A detailed study of how the synthesis parameter such as growth temperature affects the morphology of the carbon nanostructures is presented. The obtained CNs are investigated by scanning electron microscope (SEM), X-ray diffraction (XRD), electron dispersive scattering (EDS)thermogravimetry analysis (TGA), Raman and transmission electron microscope (TEM). It is observed that at 700 degrees C. normal CNTs are formed. Iron filled multi-walled carbon nanotubes (MWCNTs) and carbon nanoribbons (CNRs) are formed at 950 degrees C. Magnetic characterization of iron filled MWCNTs and CNRs studied at 300 K by superconducting quantum interference device (SQUID) reveals that these nanostructures have an enhanced coercivity (Hc = 1049 Oe) higher than that of bulk Fe. The large shape anisotropy of MWCNTs, which act on the encapsulated material (Fe), is attributed for the contribution of the higher coercivity. Coiled carbon nanotubes (CCNTs) were obtained as main products in large quantities at temperature 1100 degrees C.

Shape effect on optimal geometric conditions in surface aeration systems

The performance of surface aeration systems, among other key design variables, depends upon the geometric parameters of the aeration tank. Efficient performance and scale up or scale down of the experimental results of an aeration ystem requires optimal geometric conditions. Optimal conditions refer to the conditions of maximum oxygen transfer rate, which assists in scaling up or down the system for ommercial utilization. The present work investigates the effect of an aeration tank's shape (unbaffled circular, baffled circular and unbaffled square) on oxygen transfer. Present results demonstrate that there is no effect of shape on the optimal geometric conditions for rotor position and rotor dimensions. This experimentation shows that circular tanks (baffled or unbaffled) do not have optimal geometric conditions for liquid transfer, whereas the square cross-section tank shows a unique geometric shape to optimize oxygen transfer.