Terahertz response of dipolar impurities in polar liquids: On anomalous dielectric absorption of protein solutions

A theory of radiation absorption by dielectric mixtures is presented. The coarse-grained formulation is based on the wavevector-dependent correlation functions of molecular dipoles of the host polar liquid and a density-density structure factor of the positions of the solutes. A nonlinear dependence of the absorption coefficient on the solute concentration is predicted and originates from the mutual polarization of the liquid surrounding the solutes by the collective field of the solute dipoles aligned along the radiation field. The theory is applied to terahertz absorption of hydrated saccharides and proteins. While the theory gives an excellent account of the observations for saccharides without additional assumptions and fitting parameters, experimental absorption coefficient of protein solutions significantly exceeds theoretical calculations within standard dielectric models and shows a peak against the protein concentration. A substantial polarization of protein's hydration shell is required to explain the differences between standard theories and experiment. When the correlation function of the total dipole moment of the protein with its hydration shell from numerical simulations is used in the present analytical model an absorption peak similar to that seen is experiment is obtained. The result is sensitive to the specifics of protein-protein interactions in solution. Numerical testing of the theory requires the combination of terahertz dielectric and small-angle scattering measurements.Comment: 11 p

Anomalous temperature dependence of surface tension and capillary waves at liquid gallium

The temperature dependence of surface tension \gamma(T) at liquid gallium is studied theoretically and experimentally using light scattering from capillary waves. The theoretical model based on the Gibbs thermodynamics relates the temperature derivative of \gamma to the surface excess entropy -\Delta S. Although capillary waves contribute to the surface entropy with a positive sign the effect of dipole layer on \Delta S is negative. Experimental data collected at a free Ga surface in the temperature range from 30 to 160 C show that the temperature derivative of the tension changes sign near 100 C.Comment: 11 pages, 1 Postscript figure, submitted to J. Phys.

Why Are Alkali Halide Solid Surfaces Not Wetted By Their Own Melt?

Alkali halide (100) crystal surfaces are anomalous, being very poorly wetted by their own melt at the triple point. We present extensive simulations for NaCl, followed by calculations of the solid-vapor, solid-liquid, and liquid-vapor free energies showing that solid NaCl(100) is a nonmelting surface, and that its full behavior can quantitatively be accounted for within a simple Born-Meyer-Huggins-Fumi-Tosi model potential. The incomplete wetting is traced to the conspiracy of three factors: surface anharmonicities stabilizing the solid surface; a large density jump causing bad liquid-solid adhesion; incipient NaCl molecular correlations destabilizing the liquid surface. The latter is pursued in detail, and it is shown that surface short-range charge order acts to raise the surface tension because incipient NaCl molecular formation anomalously reduces the surface entropy of liquid NaCl much below that of solid NaCl(100).Comment: 4 pages, 3 figure

Ageing and Relaxation in Glass Forming Systems

We propose that there exists a generic class of glass forming systems that have competing states (of crystalline order or not) which are locally close in energy to the ground state (which is typically unique). Upon cooling, such systems exhibit patches (or clusters) of these competing states which become locally stable in the sense of having a relatively high local shear modulus. It is in between these clusters where ageing, relaxation and plasticity under strain can take place. We demonstrate explicitly that relaxation events that lead to ageing occur where the local shear modulus is low (even negative), and result in an increase in the size of local patches of relative order. We examine the ageing events closely from two points of view. On the one hand we show that they are very localized in real space, taking place outside the patches of relative order, and from the other point of view we show that they represent transitions from one local minimum in the potential surface to another. This picture offers a direct relation between structure and dynamics, ascribing the slowing down in glass forming systems to the reduction in relative volume of the amorphous material which is liquid-like. While we agree with the well known Adam-Gibbs proposition that the slowing down is due to an entropic squeeze (a dramatic decrease in the number of available configurations), we do not agree with the Adam-Gibbs (or the Volger-Fulcher) formulae that predict an infinite relaxation time at a finite temperature. Rather, we propose that generically there should be no singular crisis at any finite temperature: the relaxation time and the associated correlation length (average cluster size) increase at most super-exponentially when the temperature is lowered

Melting of Hard Cubes

The melting transition of a system of hard cubes is studied numerically both in the case of freely rotating cubes and when there is a fixed orientation of the particles (parallel cubes). It is shown that freelly rotating cubes melt through a first-order transition, whereas parallel cubes have a continuous transition in which positional order is lost but bond-orientational order remains finite. This is interpreted in terms of a defect-mediated theory of meltingComment: 5 pages, 3 figures included. To appear in Phys. Rev.

Does Young's equation hold on the nanoscale? A Monte Carlo test for the binary Lennard-Jones fluid

When a phase-separated binary ($A+B$) mixture is exposed to a wall, that preferentially attracts one of the components, interfaces between A-rich and B-rich domains in general meet the wall making a contact angle $\theta$. Young's equation describes this angle in terms of a balance between the $A-B$ interfacial tension $\gamma_{AB}$ and the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ between, respectively, the $A$- and $B$-rich phases and the wall, $\gamma _{AB} \cos \theta =\gamma_{wA}-\gamma_{wB}$. By Monte Carlo simulations of bridges, formed by one of the components in a binary Lennard-Jones liquid, connecting the two walls of a nanoscopic slit pore, $\theta$ is estimated from the inclination of the interfaces, as a function of the wall-fluid interaction strength. The information on the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ are obtained independently from a new thermodynamic integration method, while $\gamma_{AB}$ is found from the finite-size scaling analysis of the concentration distribution function. We show that Young's equation describes the contact angles of the actual nanoscale interfaces for this model rather accurately and location of the (first order) wetting transition is estimated.Comment: 6 pages, 6 figure

Dynamics of viscous amphiphilic films supported by elastic solid substrates

The dynamics of amphiphilic films deposited on a solid surface is analyzed for the case when shear oscillations of the solid surface are excited. The two cases of surface- and bulk shear waves are studied with film exposed to gas or to a liquid. By solving the corresponding dispersion equation and the wave equation while maintaining the energy balance we are able to connect the surface density and the shear viscocity of a fluid amphiphilic overlayer with experimentally accessible damping coefficients, phase velocity, dissipation factor and resonant frequency shifts of shear waves.Comment: 19 pages, latex, 3 figures in eps-forma

Corrections to scaling in 2--dimensional polymer statistics

Writing $= AN^{2\nu}(1+BN^{-\Delta_1}+CN^{-1}+ ...)$ for the mean square end--to--end length $$ of a self--avoiding polymer chain of $N$ links, we have calculated $\Delta_1$ for the two--dimensional {\em continuum} case from a new {\em finite} perturbation method based on the ground state of Edwards self consistent solution which predicts the (exact) $\nu=3/4$ exponent. This calculation yields $\Delta_1=1/2$. A finite size scaling analysis of data generated for the continuum using a biased sampling Monte Carlo algorithm supports this value, as does a re--analysis of exact data for two--dimensional lattices.Comment: 10 pages of RevTex, 5 Postscript figures. Accepted for publication in Phys. Rev. B. Brief Reports. Also submitted to J. Phys.

Spooked

There’s always something a bit scary about a ghost story. Somehow, though, when you read a collection of them you’re expecting to meet a spook or two. It takes a little more effort to frighten the reader. We hope we’ve managed to do just that with this bunch of tales and our striking cover. We hope as well you’ll find the stories as different from each other as they are from the normal ghost story. You’ll come across some old friends amongst the authors in this volume. Bridge House is beginning to es-tablish a brand and we have several writers now who have the measure of what we’re looking for. You’ll also meet some new names and writing styles. We’re sure both will please. And now to the ghosts…. They too have a life of their own … precisely drawn by our authors. It’s that time of year isn’t it? When the nights are getting longer, the days are getting shorter, when strange shadows lurk and you begin to hear noises you don’t understand. We have traditional ghosts, more subtle ghosts, naughty ghosts, nice ghost, nasty ghost and in one or two of our stories it’s a little difficult to work out who is haunting whom. Stoke up the fire, sit back, enjoy and prepare to be: Spooked

Increased Matrix Metalloproteinase (MMPs) Levels Do Not Predict Disease Severity or Progression in Emphysema

Rationale: Though matrix metalloproteinases (MMPs) are critical in the pathogenesis of COPD, their utility as a disease biomarker remains uncertain. This study aimed to determine whether bronchoalveolar lavage (BALF) or plasma MMP measurements correlated with disease severity or functional decline in emphysema. Methods: Enzyme-linked immunosorbent assay and luminex assays measured MMP-1, -9, -12 and tissue inhibitor of matrix metalloproteinase-1 in the BALF and plasma of non-smokers, smokers with normal lung function and moderate-to-severe emphysema subjects. In the cohort of 101 emphysema subjects correlative analyses were done to determine if MMP or TIMP-1 levels were associated with key disease parameters or change in lung function over an 18-month time period. Main Results: Compared to non-smoking controls, MMP and TIMP-1 BALF levels were significantly elevated in the emphysema cohort. Though MMP-1 was elevated in both the normal smoker and emphysema groups, collagenase activity was only increased in the emphysema subjects. In contrast to BALF, plasma MMP-9 and TIMP-1 levels were actually decreased in the emphysema cohort compared to the control groups. Both in the BALF and plasma, MMP and TIMP-1 measurements in the emphysema subjects did not correlate with important disease parameters and were not predictive of subsequent functional decline. Conclusions: MMPs are altered in the BALF and plasma of emphysema; however, the changes in MMPs correlate poorly with parameters of disease intensity or progression. Though MMPs are pivotal in the pathogenesis of COPD, these findings suggest that measuring MMPs will have limited utility as a prognostic marker in this disease. © 2013 D'Armiento et al