Self-consistent microscopic treatment of the effects of self-motion of the probe on ionic and dipolar solvation dynamics

A simple but self-consistent microscopic theory for the time dependent solvation energy of both ions and dipoles is presented which includes, for the first time, the details of the self-motion of the probe on its own solvation dynamics. The theory leads to several interesting predictions. The most important of them is that, for dipolar solvation, both the rotational and the translational motions of the dipolar solute probe can significantly accelerate the rate of solvation. In addition, the rotational self-motion of the solute can also give rise to an additional mechanism of nonexponentiality in solvation time correlation functions in otherwise slow liquids. A comparison between the present theoretical predictions and the recent experimental studies of Maroncelli et al. on solvation dynamics of aniline in l-propanol seems to indicate that the said experiments have missed the initial solvent response up to about 45 ps. After mapping the experimental results on the redefined time scale, the theoretical results can explain the experimental results for solvation of aniline in 1-propanol very well. For ionic solvation, the translational motion is significant for light solutes only. For example, for Li+ in water, translational motion speeds up the solvation by about 20%. The present theory demonstrates that in dipolar solvation the partial quenching of the self-motion due to the presence of specific solute-solvent interactions (such as H-bonding) may lead to a much slower solvation than that when the self-motion is present. This point has been discussed. In addition, we present the theoretical results for solvation of aniline in propylene carbonate, Here, the solvation is predicted to be complete within 15-20 ps.

The Metal-Nonmetal Transition: A Global Perspective

A wide range of condensed matter systems traverse the metal-nonmetal transition. These include doped semiconductors, metal-ammonia solutions, metal clusters, metal alloys, transition metal oxides, and superconducting cuprates. Certain simple criteria, such as those due to Herzfeld and Mott, have been highly successful in explaining the metallicity of materials. In this article, we demonstrate the amazing effectiveness of these criteria and examine them in the light of recent experimental findings. We then discuss the Limitations in our understanding of the phenomenon of the metal-nonmetal transition.

Signal compression through spatial frequency-based motion estimation

The interest in low bit rate video coding has increased considerably. Despite rapid progress in storage density and digital communication system performance, demand for data-transmission bandwidth and storage capacity continue to exceed the capabilities of available technologies. The growth of data-intensive digital audio, video applications and the increased use of bandwidth-limited media such as video conferencing and full motion video have not only sustained the need for efficient ways to encode analog signals, but made signal compression central to digital communication and data-storage technology. In this paper we explore techniques for compression of image sequences in a manner that optimizes the results for the human receiver. We propose a new motion estimator using two novel block match algorithms which are based on human perception. Simulations with image sequences have shown an improved bit rate while maintaining ''image quality'' when compared to conventional motion estimation techniques using the MAD block match criteria.

Translational and rotational motion in molecular liquids: A computer simulation study of Lennard-Jones ellipsoids

In order to understand the translational and rotational motion in dense molecular liquids, detailed molecular dynamics simulations of Lennard-Jones ellipsoids have been carried out for three different values of the aspect ratio kappa. For ellipsoids with an aspect ratio equal to 2, the product of the translational diffusion coefficient (D-T) and the average orientational correlation time of the l-th rank harmonics (tau(lR)), converges to a nearly constant value at high density. Surprisingly, this density independent value of D-T tau(lR) is within 5% of the hydrodynamic prediction with the slip boundary condition. This is despite the fact that both D-T and tau(lR) themselves change nearly by an order of magnitude in the density range considered, and the rotational correlation function itself is strongly nonexponential. For small aspect ratios (kappa less than or equal to 1.5), the rotational correlation function remains largely Gaussian even at a very large density, while for a large aspect ratio (kappa greater than or equal to 3), the transition to the nematic liquid-crystalline phase precludes the hydrodynamic regime. Thus, the rotational dynamics of ellipsoids show great sensitivity to the aspect ratio. At low density, tau(lR) goes through a minimum value, indicating the role of interactions in enhancing the rate of orientational relaxation. (C) 1997 American Institute of Physics. [S0021-9606(97)50142-5].

A perspective of biological supramolecular electron transfer

Electron transfer is an essential activity in biological systems. The migrating electron originates from water-oxygen in photosynthesis and reverts to dioxygen in respiration. In this cycle two metal porphyrin complexes possessing circular conjugated system and macrocyclic pi-clouds, chlorophyll and hems, play a decisive role in mobilising electrons for travel over biological structures as extraneous electrons. Transport of electrons within proteins (as in cytochromes) and within DNA (during oxidative damage and repair) is known to occur. Initial evaluations did not favour formation of semiconducting pathways of delocalized electrons of the peptide bonds in proteins and of the bases in nucleic acids. Direct measurement of conductivity of bulk material and quantum chemical calculations of their polymeric structures also did not support electron transfer in both proteins and nucleic acids. New experimental approaches have revived interest in the process of charge transfer through DNA duplex. The fluorescence on photoexcitation of Ru-complex was found to be quenched by Rh-complex, when both were tethered to DNA and intercalated in the base stack. Similar experiments showed that damage to G-bases and repair of T-T dimers in DNA can occur by possible long range electron transfer through the base stack. The novelty of this phenomenon prompted the apt name, chemistry at a distance. Based on experiments with ruthenium modified proteins, intramolecular electron transfer in proteins is now proposed to use pathways that include C-C sigma-bonds and surprisingly hydrogen bonds which remained out of favour for a long time. In support of this, some experimental evidence is now available showing that hydrogen bond-bridges facilitate transfer of electrons between metal-porphyrin complexes. By molecular orbital calculations over 20 years ago. we found that "delocalization of an extraneous electron is pronounced when it enters low-lying virtual orbitals of the electronic structures of peptide units linked by hydrogen bonds". This review focuses on supramolecular electron transfer pathways that can emerge on interlinking by hydrogen bonds and metal coordination of some unnoticed structures with pi-clouds in proteins and nucleic acids, potentially useful in catalysis and energy missions.

Counselling and predictive testing for familial adenomatous polyposis in a rural South Indian community

Background—Mutations of the APC gene cause familial adenomatous polyposis (FAP), a hereditary colorectal cancer predisposition syndrome.Aims—To conduct a cost comparison analysis of predictive genetic testing versus conventional clinical screening for individuals at risk of inheriting FAP, using the perspective of a third party payer. Methods—All direct health care costs for both screening strategies were measured according to time and motion, and the expected costs evaluated using a decision analysis model.Results—The baseline analysis predicted that screening a prototype FAP family would cost $4975/£3109 by molecular testingand $8031/£5019 by clinical screening strategy, when family members were monitored with the same frequency of clinical surveillance (every two to three years). Sensitivity analyses revealed that the genetic testing approach is cost saving for key variables including the kindred size, the age of screening onset, and the cost of mutation identification in a proband. However, if the APC mutation carriers were monitored at an increased (annual) frequency, the cost of the genetic screening strategy increased to $7483/ £4677 and was especially sensitive to variability in age of onset of screening, family size, and cost of genetic testing of at risk relatives. Conclusions—In FAP kindreds, a predictive genetic testing strategy costs less than conventional clinical screening, provided that the frequency of surveillance is identical using either strategy. An additional significant benefit is the elimination of unnecessary colonic examinations for those family members found to be noncarriers.

Mode shapes during asynchronous motion and non-proportionality indices

When synchronous motion does not exist, it is not possible to draw the classical mode shapes. In this paper, a representative shape of motion during free vibration of a non-classically damped system is sought. It is noted that this shape provides an optimal representation of free motion. Interpretations of the optimality thus introduced are presented. Their connection with non-proportionality of damping and of gyroscopy is brought out. In the spirit of the optimality presented in this paper, two indices of non-proportionality are defined. Properties of these indices are discussed. Comparison with other indices of non-proportionality available in the literature is presented. Illustrative examples are given. (C) 1999 Academic Press.

Strong ground motion at Bhuj city during the Kutch earthquake

In the absence of near field strong motion records, the level of ground motion during the devastating 26 January 2001 earthquake has to be found by indirect means. For the city of Bhuj, three broad band velocity time histories have been recorded by India Meteorological Department. In this paper these data are processed to obtain an estimate of strong ground motion at Bhuj. It is estimated that the peak ground acceleration at Bhuj was of the order of 0.38 g. Ground motion in the surrounding region is indirectly found using available spectral response recorder (SRR) data. These instrument-based results are compared with analytical results obtained from a half-space regional model.

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).

Motion of a charged particle in superposed Heliotron and biconical cusp fields

We have studied the behaviour of a charged particle in an axially symmetric magnetic field having a neutral point, so as to find a possibility of confining a charged particle in a thermonuclear device. In order to study the motion we have reduced a three-dimensional motion to a two-dimensional one by introducing a fictitious potential. Following Schmidt we have classified the motion, as an ‘off-axis motion’ and ‘encircling motion’ depending on the behaviour of this potential. We see that the particle performs a hybrid type of motion in the negative z-axis, i.e. at some instant it is in ‘off-axis motion’ while at another instant it is in ‘encircling motion’. We have also solved the equation of motion numerically and the graphs of the particle trajectory verify our analysis. We find that in most of the cases the particle is contained. The magnetic moment is found to be moderately adiabatic.

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.

An Adaptive Feature Based Low Power Motion Estimation Algorithm

Motion Estimation is one of the most power hungry operations in video coding. While optimal search (eg. full search)methods give best quality, non optimal methods are often used in order to reduce cost and power. Various algorithms have been used in practice that trade off quality vs. complexity. Global elimination is an algorithm based on pixel averaging to reduce complexity of motion search while keeping performance close to that of full search. We propose an adaptive version of the global elimination algorithm that extracts individual macro-block features using Hadamard transform to optimize the search. Performance achieved is close to the full search method and global elimination. Operational complexity and hence power is reduced by 30% to 45% compared to global elimination method.