Time-Resolved Resonance Raman Studies on Proton-Induced Electron-Transfer Reaction from Triplet Excited State of 2-Methoxynaphthalene to Decafluorobenzophenone

In this paper time-resolved resonance Raman (TR3) spectra of intermediates generated by proton induced electron-transfer reaction between triplet 2-methoxynaphthalene ((ROMe)-R-3) and decafluorobenzophenone (DFBP) are presented The TR3 vibrational spectra and structure of 2-methoxynaphthalene cation radical (ROMe+) have been analyzed by density functional theory (DFT) calculation It is observed that the structure of naphthalene ring of ROMe+ deviates from the structure of cation radical of naphthalene

Intraspecific variation in brain size and architecture : population divergence and phenotypic plasticity

Brain size and architecture exhibit great evolutionary and ontogenetic variation. Yet, studies on population variation (within a single species) in brain size and architecture, or in brain plasticity induced by ecologically relevant biotic factors have been largely overlooked. Here, I address the following questions: (i) do locally adapted populations differ in brain size and architecture, (ii) can the biotic environment induce brain plasticity, and (iii) do locally adapted populations differ in levels of brain plasticity? In the first two chapters I report large variation in both absolute and relative brain size, as well as in the relative sizes of brain parts, among divergent nine-spined stickleback (Pungitius pungitius) populations. Some traits show habitat-dependent divergence, implying natural selection being responsible for the observed patterns. Namely, marine sticklebacks have relatively larger bulbi olfactorii (chemosensory centre) and telencephala (involved in learning) than pond sticklebacks. Further, I demonstrate the importance of common garden studies in drawing firm evolutionary conclusions. In the following three chapters I show how the social environment and perceived predation risk shapes brain development. In common frog (Rana temporaria) tadpoles, I demonstrate that under the highest per capita predation risk, tadpoles develop smaller brains than in less risky situations, while high tadpole density results in enlarged tectum opticum (visual brain centre). Visual contact with conspecifics induces enlarged tecta optica in nine-spined sticklebacks, whereas when only olfactory cues from conspecifics are available, bulbus olfactorius become enlarged.Perceived predation risk results in smaller hypothalami (complex function) in sticklebacks. Further, group-living has a negative effect on relative brain size in the competition-adapted pond sticklebacks, but not in the predation-adapted marine sticklebacks. Perceived predation risk induces enlargement of bulbus olfactorius in pond sticklebacks, but not in marine sticklebacks who have larger bulbi olfactorii than pond fish regardless of predation. In sum, my studies demonstrate how applying a microevolutionary approach can help us to understand the enormous variation observed in the brains of wild animals a point-of-view which I high-light in the closing review chapter of my thesis.

Charge Transfer Complexes of Crown Ethers with 2, 3, 5, 6 - Tetracyano Pyrazine

The interaction of five crown ethers, 15-crown-5, 18-crown-6, benzo-15-crown-5, dibenzo-l8-crown-6, and dibenzo-24-crown-8 with 2, 3, 5, 6 - tetracyano pyrazine has been studied by spectroscopic methods. The association constants and thermodynamic parameters of the 1:1 complexes formed by donor ethers with the acceptor have been evaluated. There is an indication that oxygens of the ethers and aryl part of the ether act cooperatively in binding of the acceptor.

Fatigue crack propagation model for plain concrete - An analogy with population growth

In this work, an analytical model is proposed for fatigue crack propagation in plain concrete based on population growth exponential law and in conjunction with principles of dimensional analysis and self-similarity. This model takes into account parameters such as loading history, fracture toughness, crack length, loading ratio and structural size. The predicted results are compared with experimental crack growth data for constant and variable amplitude loading and are found to capture the size effect apart from showing a good agreement. Using this model, a sensitivity analysis is carried out to study the effect of various parameters that influence fatigue failure. (C) 2010 Elsevier Ltd. All rights reserved.

Transposable element-medicated evolution of sex: A population genetic model

For a population made up of individuals capable of sexual as well as asexual modes of reproduction, conditions for the spread of a transposable element are explored using a one-locus, two-haplotype model. The analysis is then extended to include the possibility that the transposable element can modulate the probability of sexual reproduction, thus casting Hickey’s (1982,Genetics 101: 519–531) suggestion in a population genetics framework. The model explicitly includes the cost of sexual reproduction, fitness disadvantage to the transposable element, probability of transposition, and the predisposition for sexual reproduction in the presence and absence of the transposable element. The model predicts several kinds of outcome, including initial frequency dependence and stable polymorphism. More importantly, it is seen that for a wide range of parameter values, the transposable element can go to fixation. Therefore it is able to convert the population from a predominantly asexual to a predominantly sexual mode of reproduction. Viewed in conjunction with recent results implicating short stretches of apparently non-coding DNA in sex determination (McCoubreyet al. 1988,Science 242: 1146–1151), the model hints at the important role this mechanism could have played in the evolution of sexuality.

Padé approach to potential transients: Part 1. Electron transfer without and with coupling to first-order homogeneous reactions at planar electrodes

Potential transients are obtained by using “Padé approximants” (an accurate approximation procedure valid globally — not just perturbatively) for all amplitudes of concentration polarization and current densities. This is done for several mechanistic schemes under constant current conditions. We invert the non-linear current-potential relationship in the form (using the Lagrange or the Ramanujan method) of power series appropriate to the two extremes, namely near reversible and near irreversible. Transforming both into the Pad́e expressions, we construct the potential-time profile by retaining whichever is the more accurate of the two. The effectiveness of this method is demonstrated through illustrations which include couplings of homogeneous chemical reactions to the electron-transfer step.

Analytical and numerical solutions of inward spherical solidification of a superheated melt with radiative-convective heat transfer and density jump at freezing front

Analytical and numerical solutions of a general problem related to the radially symmetric inward spherical solidification of a superheated melt have been studied in this paper. In the radiation-convection type boundary conditions, the heat transfer coefficient has been taken as time dependent which could be infinite, at time,t=0. This is necessary, for the initiation of instantaneous solidification of superheated melt, over its surface. The analytical solution consists of employing suitable fictitious initial temperatures and fictitious extensions of the original region occupied by the melt. The numerical solution consists of finite difference scheme in which the grid points move with the freezing front. The numerical scheme can handle with ease the density changes in the solid and liquid states and the shrinkage or expansions of volumes due to density changes. In the numerical results, obtained for the moving boundary and temperatures, the effects of several parameters such as latent heat, Boltzmann constant, density ratios, heat transfer coefficients, etc. have been shown. The correctness of numerical results has also been checked by satisfying the integral heat balance at every timestep.

A porphyrin bearing tetrahydrothiophene pickets; co-ordination behaviour and electron transfer

A novel ‘picket-fence’ porphyrin, 5,10,15,20-tetrakis[o-(tetrahydro-2-thenoylamino)phenyl]porphyrin (H2L) with ligating tetrahydrothiophene rings disposed perpendicular to the porphyrin plane has been synthesised. Its zinc(II) derivative, [ZnL], binds two silver(I) ions co-operatively with a dissociation constant of 4.8 × 10–8 dm3 mol–1. Time-resolved fluorescence lifetime measurements reveal the presence of intramolecular photoexcited electron transfer in this donor–acceptor system.

Benzyltriethylammon Tetrathiomolybdate: An Improved Sulfur Transfer Reagent for the Synthesis of Disulfides

Benzyltriethylammonium tetrathiomolybdate has been found to be a superior reagent for the conversion of alkyl halides to the corresponding disulfides in chloroform at room temperature.

Dynamics of charge transfer in the excited amine complexes of the fullerenes C60 and C70.: A picosecond laser flash photolysis study

In benzene solution, C60 and C70 interact weakly in the ground state with amines having favourable oxidation potentials. Picosecond time-resolved absorption measurements show that on photoexcilation, the weak complexes undergo charge separation to produce ion pairs which in turn undergo fast geminate recombination either to produce the triplet state of the fullerenes or give back the ground slate of the complex, depending on the oxidation potential of the amine. Free-ion yield is generally negligible.

Concepts of Static Var System Control For Enhancing Power Transfer in Long Transmission Lines

This paper is concerned with the influence of different levels of complexity in modelling various constituent subsystems on the dynamic stability of power systems compensated by static var systems (SVS) operating on pure voltage control. The system components investigated include thyristor controlled reactor (TCR) transients, SVS delays, network transients, the synchronous generator and automatic voltage regulator (AVR). An overall model is proposed which adequately describes the system performance for small signal perturbations. The SVS performance is validated through detailed nonlinear simulation on a physical simulator.

Analysis of heat and mass transfer during bulk hydraircooling of spherical food products

Hydraircooling is a technique used for precooling food products. In this technique chilled water is sprayed over the food products while cold unsaturated air is blown over them. Hydraircooling combines the advantages of both air- and hydrocooling. The present study is concerned with the analysis of bulk hydraircooling as it occurs in a package filled with several layers of spherical food products with chilled water sprayed from the top and cold unsaturated air blown from the bottom. A mathematical model is developed to describe the hydrodynamics and simultaneous heat and mass transfer occurring inside the package. The non-dimensional governing equations are solved using the finite difference numerical methods. The results are presented in the form of time-temperature charts. A correlation is obtained to calculate the process time in terms of the process parameters.

Excitation energy transfer in covalently linked pheophorbied—porphyrin systems

Steady-state fluorescence, lifetime measurements and time-resolved absorption spectra of the covalently linked hetero dimers consisting of pheophorbide and porphyrin revealed rapid (1011–1012s−1) and efficient singlet—singlet excitation energy transfer from porphyrin unit to pheophorbide.