Dynamic and thermodynamic anomalies of water at low temperatures: from bulk water to reverse micelles and DNA hydration layer

Liquid water is known to exhibit remarkable thermodynamic and dynamic anomalies, ranging from solvation properties in supercritical state to an apparent divergence of the linear response functions at a low temperature. Anomalies in various dynamic properties of water have also been observed in the hydration layer of proteins, DNA grooves and inside the nanocavity, such as reverse micelles and nanotubes. Here we report studies on the molecular origin of these anomalies in supercooled water, in the grooves of DNA double helix and reverse micelles. The anomalies have been discussed in terms of growing correlation length and intermittent population fluctuation of 4- and 5-coordinated species. We establish correlation between thermodynamic response functions and mean squared species number fluctuation. Lifetime analysis of 4- and 5-coordinated species reveals interesting differences between the role of the two species in supercooled and constrained water. The nature and manifestations of the apparent and much discussed liquid-liquid transition under confinement are found to be markedly different from that in the bulk. We find an interesting `faster than bulk' relaxation in reverse micelles which we attribute to frustration effects created by competition between the correlations imposed by surface interactions and that imposed by hydrogen bond network of water.

Precipitation In Small Systems--II. Mean Field Equations More Effective Than Population Balance

Part I (Manjunath et al., 1994, Chem. Engng Sci. 49, 1451-1463) of this paper showed that the random particle numbers and size distributions in precipitation processes in very small drops obtained by stochastic simulation techniques deviate substantially from the predictions of conventional population balance. The foregoing problem is considered in this paper in terms of a mean field approximation obtained by applying a first-order closure to an unclosed set of mean field equations presented in Part I. The mean field approximation consists of two mutually coupled partial differential equations featuring (i) the probability distribution for residual supersaturation and (ii) the mean number density of particles for each size and supersaturation from which all average properties and fluctuations can be calculated. The mean field equations have been solved by finite difference methods for (i) crystallization and (ii) precipitation of a metal hydroxide both occurring in a single drop of specified initial supersaturation. The results for the average number of particles, average residual supersaturation, the average size distribution, and fluctuations about the average values have been compared with those obtained by stochastic simulation techniques and by population balance. This comparison shows that the mean field predictions are substantially superior to those of population balance as judged by the close proximity of results from the former to those from stochastic simulations. The agreement is excellent for broad initial supersaturations at short times but deteriorates progressively at larger times. For steep initial supersaturation distributions, predictions of the mean field theory are not satisfactory thus calling for higher-order approximations. The merit of the mean field approximation over stochastic simulation lies in its potential to reduce expensive computation times involved in simulation. More effective computational techniques could not only enhance this advantage of the mean field approximation but also make it possible to use higher-order approximations eliminating the constraints under which the stochastic dynamics of the process can be predicted accurately.

On the moulding of population viscosity by natural selection

In this paper, we explore the conjoint evolution of dispersal and social behaviour. The model investigated is of a population distributed over a number of sites each with a carrying capacity of two adults and an episode of dispersal in the juvenile stage. The fertilities are governed by whether an individual and its neighbour are selfish or co-operative. It is shown that the best dispersal strategy for the co-operative genotype always involves lower levels of dispersal; and further that ecological conditions favouring low levels of dispersal increase the selective advantage of a co-operative genotype. Given this positive feedback, we suggest that in any taxon viscosity and co-operativity will tend to be correlated and bimodally distributed. Hence we predict the existence of two kinds of animal societies; viscous and co-operative (e.g. quasi-social wasps such as Mischocyttarus), and non-viscous and selfish (e.g. communal sphecid wasps such as Cerceris), and relatively few social groups with intermediate levels of co-operativity and viscosity. We also suggest that when one of the two sexes disperses, it will be the sex with lower potential for co-operative behaviour.

Transient state work fluctuation theorem for a classical harmonic oscillator linearly coupled to a harmonic bath

Based on a Hamiltonian description we present a rigorous derivation of the transient state work fluctuation theorem and the Jarzynski equality for a classical harmonic oscillator linearly coupled to a harmonic heat bath, which is dragged by an external agent. Coupling with the bath makes the dynamics dissipative. Since we do not assume anything about the spectral nature of the harmonic bath the derivation is not restricted only to the Ohmic bath, rather it is more general, for a non-Ohmic bath. We also derive expressions of the average work done and the variance of the work done in terms of the two-time correlation function of the fluctuations of the position of the harmonic oscillator. In the case of an Ohmic bath, we use these relations to evaluate the average work done and the variance of the work done analytically and verify the transient state work fluctuation theorem quantitatively. Actually these relations have far-reaching consequences. They can be used to numerically evaluate the average work done and the variance of the work done in the case of a non-Ohmic bath when analytical evaluation is not possible.

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.

Quantum-Ohmic Resistance Fluctuation In Disordered Conductors - An Invariant Imbedding Approach

It is now well known that in extreme quantum limit, dominated by the elastic impurity scattering and the concomitant quantum interference, the zero-temperature d.c. resistance of a strictly one-dimensional disordered system is non-additive and non-self-averaging. While these statistical fluctuations may persist in the case of a physically thin wire, they are implicitly and questionably ignored in higher dimensions. In this work, we have re-examined this question. Following an invariant imbedding formulation, we first derive a stochastic differential equation for the complex amplitude reflection coefficient and hence obtain a Fokker-Planck equation for the full probability distribution of resistance for a one-dimensional continuum with a Gaussian white-noise random potential. We then employ the Migdal-Kadanoff type bond moving procedure and derive the d-dimensional generalization of the above probability distribution, or rather the associated cumulant function –‘the free energy’. For d=3, our analysis shows that the dispersion dominates the mobilitly edge phenomena in that (i) a one-parameter B-function depending on the mean conductance only does not exist, (ii) an approximate treatment gives a diffusion-correction involving the second cumulant. It is, however, not clear whether the fluctuations can render the transition at the mobility edge ‘first-order’. We also report some analytical results for the case of the one dimensional system in the presence of a finite electric fiekl. We find a cross-over from the exponential to the power-low length dependence of resistance as the field increases from zero. Also, the distribution of resistance saturates asymptotically to a poissonian form. Most of our analytical results are supported by the recent numerical simulation work reported by some authors.

Fluctuation phenomena in electrochemistry part I. The formalism

A unified approach to the problem of electrochemical fluctuations is presented. On the basis of the Langevin procedure, primary noise sources are introduced in the basic phenomenological equations and a discussion of the secondary noise sources arising in the expressions for the power spectra of currents is given.

Fluctuation phenomena in electrochemistry part II. Modelling the noise sources

A discussion of the modelling of the primary and secondary noise sources introduced in the formalism of fluctuation phenomena in a previous report is presented. It is illustrated that the generalisation of the modelling of noise sources in mass transport as given by Tyagai is limited in its applicability. A general procedure for the same is discussed in detail.

A fluctuation-based probe to athermal phase transitions

We focus on athermal phase transitions where in discrete and dissipative avalanches are observed in physical observables as the system jumps from one metastable state to another, when driven by an external field. Using higher order statistics of time dependent avalanches, or noise, in electrical resistivity during temperature-driven martensite transformation in thin nickel-titanium films, we demonstrate evidence suggesting the existence of a singular `global instability' or divergence of the correlation length as a function of temperature at the transition. These results not only establish a mapping of non-equilibrium first order phase transition and equilibrium critical phenomena, but perhaps also call for a re-evaluation of many existing experimental claims of self-organized criticality.

Electric-field-dependent average resistance and the resistance fluctuation in one-dimensional disordered systems

Following an invariant-imbedding approach, we obtain analytical expressions for the ensemble-averaged resistance (ρ) and its Sinai’s fluctuations for a one-dimensional disordered conductor in the presence of a finite electric field F. The mean resistance shows a crossover from the exponential to the power-law length dependence with increasing field strength in agreement with known numerical results. More importantly, unlike the zero-field case the resistance distribution saturates to a Poissonian-limiting form proportional to A‖F‖exp(-A‖F‖ρ) for large sample lengths, where A is constant.

Fluctuation Theory Of The Specific-Heat Of Normal Liquid-3He

The measured specific heat of normal liquid 3He shows a plateau for 0.15<1 K; below 0.15 K and above 1 K, it rises linearly with temperature. However, the slope on the high-temperature side is very much reduced compared with the free-Fermi-gas value. We explain these features through a microscopic, thermal spin- and density-fluctuation model. The plateau is due to spin fluctuations which have a low characteristic energy in 3He. Because of the low compressibility, the density fluctuations are highly suppressed; this leads to a reduced slope for CV(T) for high temperatures.

Valence fluctuation in some Yb intermetallics by X-ray photoemission and X-ray absorption

The valence state of Yb in some of its intermetallics, YbNi2Ge2, YbCu2Si2 and YbPd2Si2 has been investigated by LIII(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds.

Resistance fluctuation at the mobility edge

Following a Migdal-Kadanoff-type bond moving procedure, we derive the renormalisation-group equations for the characteristic function of the full probability distribution of resistance (conductance) of a three-dimensional disordered system. The resulting recursion relations for the first two cumulants, K, the mean resistance and K ~ t,he meansquare deviation of resistance exhibit a mobility edge dominated by large dispersion, i.e., K $ ’/ K=, 1, suggesting inadequacy of the one-parameter scaling ansatz.

Voltage gated Na+ channels contribute to membrane voltage fluctuation in \alpha T3-1 pituitary gonadotroph cells

\alpha T3-1 cells showed a slope resistance of 1.8 G\omega. The cell membrane surface was not smooth and a scanning electron micrograph showed a complex structure with blebs and microvilli like projections. The cells showed spontaneous fluctuations at zero current resting membrane potential and hyperpolarization increased the amplitude of membrane potential fluctuations. The amplitude of membrane potential fluctuations at hyperpolarized membrane potential was attenuated on application of TTX to the bath solution. The potential at which half steady state inactivation of isolated sodium current occurred, was at a very hyperpolarized potential (-95.4 mV). The study presented in this paper shows that the voltage gated sodium channels contribute to the increase in the amplitude of electrical noise with hyperpolarization in \alpha T3-1 cells.

Prevalence and analysis of t(14;18) and t(11;14) chromosomal translocations in healthy Indian population

Hematopoietic malignancies like leukemia and lymphoma are characteristically associated with various chromosomal translocations. Follicular lymphoma (FL) and mantle cell lymphoma (MCL) are two subtypes of non-Hodgkin's lymphoma which possess t(14;18) and t(11;14) translocations, respectively. The incidence of FL and MCL is higher in the western countries as compared to India. Interestingly, the associated translocations are also found in healthy individuals in western population, which is 50-80% for t(14;18), whereas t(11;14) occurs at a very low frequency. However, there are no studies to explore thes translocations in healthy Indian population, which could explain the lower incidence of FL and MCL. We employed Southern hybridization following nested PCR to detect above translocations in healthy individuals from India. Our results suggest that this assay can detect one t(14;18) translocation event in up to 10(7) normal cells where as one t(11;14) in 10(8) normal cells. According to our results, 87 out of 253 individuals carry t(14;18) indicating 34% prevalence in the population. The presence of this translocation was also detectable at the transcript level. Although, no gender-based difference was observed, an age-dependent increase in the prevalence of translocation was found in adults. However, even after studying 210 people, we could not detect any t(11;14) translocation, indicating that it is uncommon in Indian population. These results suggest that lower incidence of FL and MCL in India could be attributed to lower prevalence of these translocations in healthy individuals.