Slow orientational dynamics of water molecules at a micellar surface

The dynamics of water molecules near an aqueous micellar interface is studied in an atomistic molecular dynamics simulation of cesium pentadecafluorooctanoate (CsPFO) in water. The dipolar orientational time correlation function (tcf) and the translational diffusion of the water molecules are investigated. Results show that both the reorientational and the translational motion of water molecules near the micelle are restricted. In particular, the orientational tcf exhibits a very slow component in the long time which is slower than its bulk value by 2 orders of magnitude. This slow decay seems to be related to the slow decay often observed in experiments. The origin of the slow decay is analyzed.

Main chain and segmental dynamics of semi interpenetrating based on polyisoprene and poly(methyl methacrylate)

Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate)(PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below T-g of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K.complex spectra were obtained with the slow component mostly arisingout of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into thehighly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentionedsemi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in a-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the T-g regions were also calculated. T-50G was found to correlate with the T-g of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm(3).C-13 T-1 rho measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer sized morphology in the case of highly crosslinked semi IPN. (C) 2010 Elsevier Ltd. All rights reserved.

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.

Two-dimensional moist stratified turbulence and the emergence of vertically sheared horizontal flows

Moist stratified turbulence is studied in a two-dimensional Boussinesq system influenced by condensation and evaporation. The problem is set in a periodic domain and employs simple evaporation and condensation schemes, wherein both the processes push parcels towards saturation. Numerical simulations demonstrate the emergence of a moist turbulent state consisting of ordered structures with a clear power-law type spectral scaling from initially spatially uncorrelated conditions. An asymptotic analysis in the limit of rapid condensation and strong stratification shows that, for initial conditions with enough water substance to saturate the domain, the equations support a straightforward state of moist balance characterized by a hydrostatic, saturated, vertically sheared horizontal flow (VSHF). For such initial conditions, by means of long time numerical simulations, the emergence of moist balance is verified. Specifically, starting from uncorrelated data, subsequent to the development of a moist turbulent state, the system experiences a rather abrupt transition to a regime which is close to saturation and dominated by a strong VSHF. On the other hand, initial conditions which do not have enough water substance to saturate the domain, do not attain moist balance. Rather, the system is observed to remain in a turbulent state and oscillates about moist balance. Even though balance is not achieved with these general initial conditions, the time scale of oscillation about moist balance is much larger than the imposed time scale of condensation and evaporation, thus indicating a distinct dominant slow component in the moist stratified two-dimensional turbulent system. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3694805]

Hydration dynamics of protein molecules in aqueous solution: Unity among diversity

Dielectric dispersion and NMRD experiments have revealed that a significant fraction of water molecules in the hydration shell of various proteins do not exhibit any slowing down of dynamics. This is usually attributed to the presence of the hydrophobic residues (HBR) on the surface, although HBRs alone cannot account for the large amplitude of the fast component. Solvation dynamics experiments and also computer simulation studies, on the other hand, repeatedly observed the presence of a non-negligible slow component. Here we show, by considering three well-known proteins (lysozyme, myoglobin and adelynate kinase), that the fast component arises partly from the response of those water molecules that are hydrogen bonded with the backbone oxygen (BBO) atoms. These are structurally and energetically less stable than those with the side chain oxygen (SCO) atoms. In addition, the electrostatic interaction energy distribution (EIED) of individual water molecules (hydrogen bonded to SCO) with side chain oxygen atoms shows a surprising two peak character with the lower energy peak almost coincident with the energy distribution of water hydrogen bonded to backbone oxygen atoms (BBO). This two peak contribution appears to be quite general as we find it for lysozyme, myoglobin and adenylate kinase (ADK). The sharp peak of EIED at small energy (at less than 2 k(B)T) for the BBO atoms, together with the first peak of EIED of SCO and the HBRs on the protein surface, explain why a large fraction (similar to 80%) of water in the protein hydration layer remains almost as mobile as bulk water Significant slowness arises only from the hydrogen bonds that populate the second peak of EIED at larger energy (at about 4 k(B)T). Thus, if we consider hydrogen bond interaction alone, only 15-20% of water molecules in the protein hydration layer can exhibit slow dynamics, resulting in an average relaxation time of about 5-10 ps. The latter estimate assumes a time constant of 20-100 ps for the slow component. Interestingly, relaxation of water molecules hydrogen bonded to back bone oxygen exhibit an initial component faster than the bulk, suggesting that hydrogen bonding of these water molecules remains frustrated. This explanation of the heterogeneous and non-exponential dynamics of water in the hydration layer is quantitatively consistent with all the available experimental results, and provides unification among diverse features.

Slow m=1 instabilities of softened gravity Keplerian discs

We present the simplest model that permits a largely analytical exploration of the m =1 counter-rotating instability in a `hot' nearly Keplerian disc of collisionless self-gravitating matter. The model consists of a two-component softened gravity disc, whose linear modes are analysed using the Wentzel-Kramers-Brillouin approximation. The modes are slow in the sense that their (complex) frequency is smaller than the Keplerian orbital frequency by a factor which is of order the ratio of the disc mass to the mass of the central object. Very simple analytical expressions are derived for the precession frequencies and growth rates of local modes; it is shown that a nearly Keplerian discm must be unrealistically hot to avoid an overstability. Global modes are constructed for the case of zero net rotation.

Comparison of the ultrafast to slow time scale dynamics of three liquid crystals in the isotropic phase

The dynamics of three liquid crystals, 4'(pentyloxy)-4-biphenylcarbonitrile (5-OCB), 4'-pentyl-4-biphenylcarbonitrile (5-CB), and 1-isothiocyanato-(4-propylcyclohexyl)benzene (3-CHBT), are investigated from very short time (similar to1 ps) to very long time (>100 ns) as a function of temperature using optical heterodyne detected optical Kerr effect experiments. For all three liquid crystals, the data decay exponentially only on the longest time scale (> several ns). The temperature dependence of the long time scale exponential decays is described well by the Landau-de Gennes theory of the randomization of pseudonematic domains that exist in the isotropic phase of liquid crystals near the isotropic to nematic phase transition. At short time, all three liquid crystals display power law decays. Over the full range of times, the data for all three liquid crystals are fit with a model function that contains a short time power law. The power law exponents for the three liquid crystals range between 0.63 and 0.76, and the power law exponents are temperature independent over a wide range of temperatures. Integration of the fitting function gives the empirical polarizability-polarizability (orientational) correlation function. A preliminary theoretical treatment of collective motions yields a correlation function that indicates that the data can decay as a power law at short times. The power law component of the decay reflects intradomain dynamics. (C) 2002 American Institute of Physics.

Infinite Dimensional Slow Modulations In A Delayed Model For Orthogonal Cutting Vibrations

We apply the method of multiple scales (MMS) to a well known model of regenerative cutting vibrations in the large delay regime. By ``large'' we mean the delay is much larger than the time scale of typical cutting tool oscillations. The MMS upto second order for such systems has been developed recently, and is applied here to study tool dynamics in the large delay regime. The second order analysis is found to be much more accurate than first order analysis. Numerical integration of the MMS slow flow is much faster than for the original equation, yet shows excellent accuracy. The main advantage of the present analysis is that infinite dimensional dynamics is retained in the slow flow, while the more usual center manifold reduction gives a planar phase space. Lower-dimensional dynamical features, such as Hopf bifurcations and families of periodic solutions, are also captured by the MMS. Finally, the strong sensitivity of the dynamics to small changes in parameter values is seen clearly.

CCD: Connected Component Descriptor for Robust Mosaicing of Camera-Captured Document Images

We propose a robust method for mosaicing of document images using features derived from connected components. Each connected component is described using the Angular Radial Tran. form (ART). To ensure geometric consistency during feature matching, the ART coefficients of a connected component are augmented with those of its two nearest neighbors. The proposed method addresses two critical issues often encountered in correspondence matching: (i) The stability of features and (ii) Robustness against false matches due to the multiple instances of characters in a document image. The use of connected components guarantees a stable localization across images. The augmented features ensure a successful correspondence matching even in the presence of multiple similar regions within the page. We illustrate the effectiveness of the proposed method on camera captured document images exhibiting large variations in viewpoint, illumination and scale.

Equivalent Circuit Analysis of Serpentine Folded-waveguide Slow-wave Structures for Millimeter-wave Traveling-wave Tubes

A simple equivalent circuit model for the analysis of dispersion and interaction impedance characteristics of serpentine folded-waveguide slow-wave structure was developed by considering the straight and curved portions of structure supporting the dominant TE10-mode of the rectangular waveguide. Expressions for the lumped capacitance and inductance per period of the slow-wave structure were derived in terms of the physical dimensions of the structure, incorporating the effects of the beam-hole in the lumped parameters. The lumped parameters were subsequently interpreted for obtaining the dispersion and interaction impedance characteristics of the structure. The analysis was simple yet accurate in predicting the dispersion and interaction impedance behaviour at millimeter-wave frequencies. The analysis was benchmarked against measurement as well as with 3D electromagnetic modeling using MAFIA for two typical slow-wave structures (one at the Ka-band and the other at the W-band) and close agreement observed.

Analysis of Rectangular Folded-Waveguide Millimeter-Wave Slow-wave Structures using Conformal Transformations

An analysis of rectangular folded-waveguide slow-wave structure was developed using conformal mapping technique through Schwarz's polygon transformation and closed form expressions for the lumped capacitance and inductance per period of the slow-wave structure were derived in terms of the physical dimensions of the structure, incorporating the effects of the beam hole in the lumped parameters. The lumped parameters were subsequently interpreted for obtaining the dispersion and interaction impedance characteristics of the structure. The analysis was benchmarked for two typical millimeter-wave structures, one operating in Ka-band and the other operating in Q-band, against measurement and 3D electromagnetic modeling using MAFIA.

Classical and Cosserat plasticity and viscoplasticity models for slow granular flow

We consider models for the rheology of dense, slowly deforming granular materials based of classical and Cosserat plasticity, and their viscoplastic extensions that account for small but finite particle inertia. We determine the scale for the viscosity by expanding the stress in a dimensionless parameter that is a measure of the particle inertia. We write the constitutive relations for classical and Cosserat plasticity in stress-explicit form. The viscoplastic extensions are made by adding a rate-dependent viscous stress to the plasticity stress. We apply the models to plane Couette flow, and show that the classical plasticity and viscoplasticity models have features that depart from experimental observations; the prediction of the Cosserat viscoplasticity model is qualitatively similar to that of Cosserat plasticity, but the viscosities modulate the thickness of the shear layer.

Structure and properties of two component hydrogels comprising lithocholic acid and organic amines

We demonstrate the aptitude of supramolecular hydrogel formation using simple bile acid such as lithocholic acid in aqueous solution in the presence of various dimeric or oligomeric amines. By variation of the choice of the amines in such mixtures the gelation properties could be modulated. However, the replacement of lithocholic acid (LCA) by cholic acid or deoxycholic acid resulted in no hydrogel formation. FT-IR studies confirm that the carboxylate and ammonium residues of the two components are involved in the salt (ion-pair) formation. This promotes further assembly of the components reinforced by a continuous hydrogen bonded network leading to gelation. Electron microscopy shows the morphology of the internal organization of gels of two component systems which also depends significantly on the amine part. Variation of the amine component from the simple 1,2-ethanediamine (EDA) to oligomeric amines in such gels of lithocholic acid changes the morphology of the assembly from long one-dimensional nanotubes to three-dimensional complex structures. Single crystal X-ray diffraction analysis with one of the amine-LCA complexes suggested the motif of fiber formation where the amines interact with the carboxylate and hydroxyl moieties through electrostatic forces and hydrogen bonding. From small angle neutron scattering study, it becomes clear that the weak gel from LCA-EDA shows scattering oscillation due to the presence of non-interacting nanotubules while for gels of LCA with oligomeric amines the individual fibers come together to form complex three-dimensional organizations of higher length scale. The rheological properties of this class of two component system provide clear evidence that the flow behavior can be modulated varying the acid-amine ratio.