Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Ultrasonic Broadband Spectrometry of Liquids A Research Tool in Pure and Applied Chemistry and Chemical Physics

This review is a survey of the many scientific applications of ultrasonic broadbandspectrometry (absorption and velocity measurements with coherent sound waves)in liquids and liquid systems, covering, at present, a frequency range from nearly10 kHz to 10 GHz. Ultrasonic spectrometry has proved to be an almost universalresearch tool in many laboratories, one that is useful for investigation of variouschemical, biochemical, and physicochemical systems. Sound waves traversingliquids induce periodic perturbations in pressure and temperature, which can shiftequilibria, resulting in characteristic sound absorption and velocity dispersionspectra. An analysis of such spectra yields valuable information about thermodynamic and kinetic parameters of the particular system that is often difficult toobtain by other methods. Since such periodic perturbations imposed on the systemare incremental in nearly all cases, the system can be studied under equilibriumconditions. All nonlinear effects (heating, nonconstant fluid compressibility, andothers) are negligible, permitting, for instance, the application of linearized rateequations. In this review, various examples of measured broadband spectra arepresented. Related elementary processes are discussed. Among these are ionicand molecular reactions, including mechanisms of association and complexation,proton transfer, solvation, isomerization, interconversion, side-group rotation,hydrogen-bonding, as well as stacking processes and micelle formation. Specialattention will be given to the extensive research on chemical relaxation.Fundamental early and recent publications are cited and discussed. Many referencesare included with particular emphasis on less well known research and publicationsfrom countries of the former USSR. This review aims at a demonstration of thewidespread applications of modern ultrasonic techniques in many fields ofliquid-state research.     

Argument for E

In high temperature superconductors (HTSC), when magnetic relaxation approaches the equilibrium state and the superconductor is applied with current, theE × j relation is calculated by considering both forward and backward hopping of thermally activated flux (where backward hopping means hopping from the barriers with low energy to the ones with high energy). It is pointed out that the InE× Inj curve shows positive curvature. And the results are compared with other models. The discussion on the topic that whether p approaches zero asj → 0 is carried out.     

Shell Analysis and Effective Disorder in a 2D Froth

The static and evolutionary properties of two-dimensional cellular structures, or froths, are discussed in the light of recent work on structuring of the froth into concentric shells. Of interest is the dual role of a topological dislocation (defect) in an otherwise uniform froth, considered both as a source of disorder and also as a source generating a shell-structured froth. We present simulations on an initially uniform hexagonal froth. A defect is introduced by forcing either a T1 or T2 process in the stable structure, after which the froth is allowed to evolve according to von Neumann's law. In the first case, topological inclusions are found in the first few layers early in the evolution. In the second case, no inclusions appear over the entire evolutionary period. The growing disorder (as measured by the second moment of the side distribution, ₂) is isotropic. For the special case of a T2-formed froth in a uniform network, the SSI structure is retained with ₂0 only for the zeroth, first, and second layers. The ratio between topological perimeter and radius of the shells is close to 6, the value for a hexagonal froth.     

On the Distribution of Long-Term Time Averages on Symbolic Space

The pressure was studied in a rather abstract theory as an important notion of the thermodynamic formalism. The present paper gives a more concrete account in the case of symbolic spaces, including subshifts of finite type. We relate the pressure of an interaction function to its long-term time averages through the Hausdorff and packing dimensions of the subsets on which has prescribed long-term time-average values. Functions with values in ^d are considered. For those depending only on finitely many symbols, we get complete results, unifying and completing many partial results.     

Molecular dynamics in solid pregnenolone studied by H spin–lattice relaxation

Spin–lattice relaxation times T₁ in solid pregnenolone have been studied over a wide range of temperatures, from 77 up to 417 K. The dynamic processes arising from C₃ motion of the three methyl substituents are separated, and their activation parameters are determined.     

1H NMR study of N(CH3)4H(ClF2CCOO)2

The proton spin–lattice relaxation times and ¹H NMR second moments were measured over a wide range of temperature. The results were compared with those of the ¹⁹F NMR relaxation that we obtained earlier. For both nuclear species, the evolution of the longitudinal magnetizations with time is observed to be strongly bi-exponential and were in good quantitative agreement with the cross-relaxation theory.     

A novel approach to separating EPR lines arising from species with different transition moments

In pulsed EPR, spectral contributions from several species in one sample can be separated based on different EPR transition probabilities. This is usually done by monitoring the Rabi nutations in a 2D experiment. By using long pulses, the FID and echo shapes of species with different transition probabilities differ significantly, including temporal shifts of the observed echo signals in a two-pulse ESE experiment. These shifts can be used to disentangle spectral components in a 1D field-swept ESE experiment by choosing an appropriate detection time. This approach is demonstrated by experiments on a sample containing Mn(2+) and Cr(3+) centers as well as on an exchange-coupled Mn(III)/Mn(IV) system with Mn(2+) contaminations.     

Bistable behaviour in squeezed vacua: II. Stability analysis and chaos

Linear stability analysis and (numerical) investigation of the periodic and chaotic self-pulsing behaviour are presented for the Maxwell-Bloch equations of a bistable model in contact with a squeezed vacuum field. Effect of the squeeze phase parameter on the period doubling bifurcation that preceeds chaos is examined for the adiabatic and non-adiabatic regimes.