Solvation dynamics in nonassociated polar solvents

Ultrafast solvation dynamics in three nonassociated polar solvents, namely, acetonitrile, dimethyl sulfoxide, and acetone, have been studied by using the molecular hydrodynamic theory. For solvation in acetonitrile, the solvent memory function required for this study has been obtained from recent dielectric relaxation measurements of Venabales and Schuttenmaer; earlier theoretical studies used only the Kerr relaxation data. As the latter provides only an indirect information regarding the polar dynamical response of the dipolar liquid, it fails to provide a fully quantitative description of the solvation time correlation function, S(t). The present study with full dielectric data, on the other hand, gives excellent agreement with the experimental results. The theory shows that the ultrafast part of the solvation dynamics originates almost entirely from the high-frequency component of dielectric relaxation (with time constant 0.177 ps), although the latter represents only a small part of the latter. For DMSO and acetone, however, the present theory predicts a decay slower than the experimental observation. It is proposed that for these two solvents specific chromophore-solvent interactions might be responsible for the-large discrepancy. On the basis of the theory, two experimental studies have also been proposed.

Biological water: Femtosecond dynamics of macromolecular hydration

The unique features of a macromolecule and water as a solvent make the issue of solvation unconventional, with questions about the static versus dynamic nature of hydration and the, physics of orientational and translational diffusion at the boundary. For proteins, the hydration shell that covers the surface is critical to the stability of its structure and function. Dynamically speaking, the residence time of water at the surface is a signature of its mobility and binding. With femtosecond time resolution it is possible to unravel the shortest residence times which are key for the description of the hydration layer, static or dynamic. In this article we review these issues guided by experimental studies, from this laboratory, of polar hydration dynamics at the surfaces of two proteins (Subtilisin Carlsberg (SC) and Monellin). The natural probe tryptophan amino acid was used for the interrogation of the dynamics, and for direct comparison we also studied the behavior in bulk water - a complete hydration in 1 ps. We develop a theoretical description of solvation and relate the theory to the experimental observations. In this - theoretical approach, we consider the dynamical equilibrium in the hydration shell, defining the rate processes for breaking and making the transient hydrogen bonds, and the effective friction in the layer which is defined by the translational and orientational motions of water molecules. The relationship between the residence time of water molecules and the observed slow component in solvation dynamics is a direct one. For the two proteins studied, we observed a "bimodal decay" for the hydration correlation function, with two primary relaxation times: ultrafast, typically 1 ps or less, and longer, typically 15-40 ps, and both are related to the residence time at the protein surface, depending on the binding energies. We end by making extensions to studies of the denatured state of the protein, random coils, and the biomimetic micelles, and conclude with our thoughts on the relevance of the dynamics of native structures to their functions.

Constraint loss under dynamic loading in rate independent plastic solids

The objectives of this paper are to examine the loss of crack tip constraint in dynamically loaded fracture specimens and to assess whether it can lead to enhancement in the fracture toughness at high loading rates which has been observed in several experimental studies. To this end, 2-D plane strain finite element analyses of single edge notched (tension) specimen and three point bend specimen subjected to time varying loads are performed. The material is assumed to obey the small strain J(2) flow theory of plasticity with rate independent behaviour. The results demonstrate that a valid J-Q field exists under dynamic loading irrespective of the crack length and specimen geometry. Further, the constraint parameter Q becomes strongly negative at high loading rates, particularly in deeply cracked specimens. The variation of dynamic fracture toughness K-dc with stress intensity rate K for cleavage cracking is predicted using a simple critical stress criterion. It is found that inertia-driven constraint loss can substantially enhance K-dc for (K) over dot > 10(5) MPa rootm/s.

The Mathematical modeling of inhomogeneites in ventricular tissue

Cardiac arrhythmias such as ventricular tachycardia (VT) or ventricular fibrillation (VF) are the leading cause of death in the industrialised world. There is a growing consensus that these arrhythmias arise because of the formation of spiral waves of electrical activation in cardiac tissue; unbroken spiral waves are associated with VT and broken ones with VF. Several experimental studies have been carried out to determine the effects of inhomogeneities in cardiac tissue on such arrhythmias. We give a brief overview of such experiments, and then an introduction to partial-differential-equation models for ventricular tissue. We show how different types of inhomogeneities can be included in such models, and then discuss various numerical studies, including our own, of the effects of these inhomogeneities on spiral-wave dynamics. The most remarkable qualitative conclusion of our studies is that the spiral-wave dynamics in such systems depends very sensitively on the positions of these inhomogeneities.

Adaptive control of vibration transmission in a strut system

In this article, theoretical and the experimental studies are reported on the adaptive control of vibration transmission in a strut system subjected to a longitudinal pulse train excitation. In the control scheme, a magneto-strictive actuator is employed at the downstream transmission point in the secondary path. The actuator dynamics is taken into account. The system boundary parameters are first estimated off-line, and later employed to simulate the system dynamics. A Delayed-X Filtered-E spectral algorithm is proposed and implemented in real time. The underlying mechanics based filter construction allows for the time varying system dynamics to be taken into account. This work should be of interest for active control of vibration and noise transmission in helicopter gearbox support struts and other systems.

Influence of working fluid on the performance of a standing-wave thermoacoustic prime mover

The thermoacoustic prime mover (TAPM) is an attractive alternative as a pressure wave generator to drive Pulse Tube Cryocoolers (PTCs), by the absence of moving parts, construction simplicity, reasonable efficiency, and environmental friendly. Decreasing the resonance frequency and improving the efficiency of the TAPM are important to drive the PTCs. These are controlled by the working gas parameters other than the dimensions of TAPM. In this technical note, the experimental studies carried out to evaluate the influence of different working fluids on the performances of a twin standing wave TAPM at various operating pressures have been compared with the simulation studies of the same system using DeltaEc wherever possible. The reasonably good agreement between them indicates the utility of DeltaEc for the optimal design of TAPM with the right working fluids for practical applications. (C) 2011 Elsevier Ltd. All rights reserved.

A hybrid pre-whitening technique for detection of additive spread spectrum watermarks in audio signals

Pre-whitening techniques are employed in blind correlation detection of additive spread spectrum watermarks in audio signals to reduce the host signal interference. A direct deterministic whitening (DDW) scheme is derived in this paper from the frequency domain analysis of the time domain correlation process. Our experimental studies reveal that, the Savitzky-Golay Whitening (SGW), which is otherwise inferior to DDW technique, performs better when the audio signal is predominantly lowpass. The novelty of this paper lies in exploiting the complementary nature to the two whitening techniques to obtain a hybrid whitening (HbW) scheme. In the hybrid scheme the DDW and SGW techniques are selectively applied, based on short time spectral characteristics of the audio signal. The hybrid scheme extends the reliability of watermark detection to a wider range of audio signals.

Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme

Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3694268]

Distribution of transverse chain fluctuations in harmonically confined semiflexible polymers

Two different experimental studies of polymer dynamics based on single-molecule fluorescence imaging have recently found evidence of heterogeneities in the widths of the putative tubes that surround filaments of F-actin during their motion in concentrated solution. In one J. Glaser, D. Chakraborty, K. Kroy, I. Lauter, M. Degawa, N. Kirchesner, B. Hoffmann, R. Merkel, and M. Giesen, Phys. Rev. Lett. 105, 037801 (2010)], the observations were explained in terms of the statistics of a worm-like chain confined to a potential determined self-consistently by a binary collision approximation, and in the other B. Wang, J. Guan, S. M. Anthony, S. C. Bae, K. S. Schweizer, and S. Granick, Phys. Rev. Lett. 104, 118301 (2010)], they were explained in terms of the scaling properties of a random fluid of thin rods. In this paper, we show, using an exact path integral calculation, that the distribution of the length-averaged transverse fluctuations of a harmonically confined weakly bendable rod (one possible realization of a semiflexible chain in a tube), is in good qualitative agreement with the experimental data, although it is qualitatively different in analytic structure from the earlier theoretical predictions. We also show that similar path integral techniques can be used to obtain an exact expression for the time correlation function of fluctuations in the tube cross section. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4712306]

Modeling of Ascending/Descending Velocity of Metal Droplet Emulsified in Pb-Salt System

Metal-slag emulsion is an important process to enhance the reaction rate between the two phases; thus, it improves the heat and mass transfer of the process significantly. Various experimental studies have been carried out, and some system specific relations have been proposed by various investigators. A unified, theoretical study is lacking to model this complex phenomenon. Therefore, two simple models based on fundamental laws for metal droplet velocity (both ascending and descending) and bubble velocity, as well as its position at any instant of time, have been proposed. Analytical solutions have been obtained for the developed equations. Analytical solutions have been verified for the droplet velocity, traveling time, and size distribution in slag phase by performing high-temperature experiments in a Pb-salt system and comparing the obtained data with theory. The proposed model has also been verified with published experimental data for various liquid systems with a wide range of physical properties. A good agreement has been found between the analytical solution and the experimental and published data in all cases.

Evolution of quantum discord and its stability in two-qubit NMR systems

We investigate evolution of quantum correlations in ensembles of two-qubit nuclear spin systems via nuclear magnetic resonance techniques. We use discord as a measure of quantum correlations and the Werner state as an explicit example. We, first, introduce different ways of measuring discord and geometric discord in two-qubit systems and then describe the following experimental studies: (a) We quantitatively measure discord for Werner-like states prepared using an entangling pulse sequence. An initial thermal state with zero discord is gradually and periodically transformed into a mixed state with maximum discord. The experimental and simulated behavior of rise and fall of discord agree fairly well. (b) We examine the efficiency of dynamical decoupling sequences in preserving quantum correlations. In our experimental setup, the dynamical decoupling sequences preserved the traceless parts of the density matrices at high fidelity. But they could not maintain the purity of the quantum states and so were unable to keep the discord from decaying. (c) We observe the evolution of discord for a singlet-triplet mixed state during a radio-frequency spin-lock. A simple relaxation model describes the evolution of discord, and the accompanying evolution of fidelity of the long-lived singlet state, reasonably well.

Catalysis of tRNA Aminoacylation: Single Turnover to Steady-State Kinetics of tRNA Synthetases

Aminoacyl-tRNA synthetases (aaRS) catalyze the bimolecular association reaction between amino acid and tRNA by specifically and unerringly choosing the cognate amino acid and tRNA. There are two classes of such synthetases that perform tRNA-aminoacylation reaction. Interestingly, these two classes of aminoacyl-tRNA synthetases differ not only in their structures but they also exhibit remarkably distinct kinetics under pre-steady-state condition. The class I synthetases show initial burst of product formation followed by a slower steady-state rate. This has been argued to represent the influence of slow product release. In contrast, there is no burst in the case of class H enzymes. The tight binding of product with enzyme for class I enzymes is correlated with the enhancement of rate in presence of elongation factor. EF-TU. In spite of extensive experimental studies, there is no detailed theoretical analysis that can provide a quantitative understanding of this important problem. In this article, we present a theoretical investigation of enzyme kinetics for both classes of aminoacyl-tRNA synthetases. We present an augmented kinetic scheme and then employ the methods of time-dependent probability statistics to obtain expressions for the first passage time distribution that gives both the time-dependent and the steady-state rates. The present study quantitatively explains all the above experimental observations. We propose an alternative path way in the case of class II enzymes showing the tRNA-dependent amino acid activation and the discrepancy between the single-turnover and steady-state rate.

Performances of single and two-stage pulse tube cryocoolers under different vacuum levels with and without thermal radiation shields

Single and two-stage Pulse Tube Cryocoolers (PTC) have been designed, fabricated and experimentally studied. The single stage PTC reaches a no-load temperature of similar to 29 K at its cold end, the two-stage PTC reaches similar to 2.9 K in its second stage cold end and similar to 60 K in its first stage cold end. The two-stage Pulse Tube Cryocooler provides a cooling power of similar to 250 mW at 4.2 K. The single stage system uses stainless steel meshes along with Pb granules as its regenerator materials, while the two-stage PTC uses combinations of Pb along with Er3Ni/HoCu2 as the second stage regenerator materials. Normally, the above systems are insulated by thermal radiation shields and mounted inside a vacuum chamber which is maintained at high vacuum. To evaluate the performance of these systems in the possible conditions of loss of vacuum with and without radiation shields, experimental studies have been performed. The heat-in-leak under such severe conditions has been estimated from the heat load characteristics of the respective stages. The experimental results are analyzed to obtain surface emissivities and effective thermal conductivities as a function of interspace pressure.

Multi-port network modeling for fractal shape microstrip antenna

In this paper we demonstrate the use of multi-port network modeling to analyze one such antenna with fractal shaped parts. Based on simulation and experimental studies, it has been demonstrated that model can accurately predict the input characteristics of antennas with Minkowski geometry replacing a side micro strip square ring.

Shear bands mediate cavitation in brittle metallic glasses

Recent experimental studies have revealed nanoscale cavities and periodic corrugations on the fracture surfaces of brittle metallic glasses. How such cavitation in these materials leads to brittle failure remains unclear. Here we show, using atomistic and continuum finite element simulations, that a shear band can mediate cavity nucleation and coalescence owing to plastic flow confinement caused by material softening. This leads to brittle fracture as cavities nucleate and coalesce within a shear band, causing the crack to extend along it. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.