Slowdown Of Kinetics Research Articles

Salt induced slowdown of kinetics and dynamics during thermal gelation of egg-yolk.

We investigated the effect of the NaCl concentration (0.3-2M) on the structure and dynamics of hen egg yolk at room temperature and during thermal gelation at temperatures in the range of 66-90 °C utilizing low-dose x-ray photon correlation spectroscopy in ultra-small angle x-ray scattering geometry. With an increase in the salt concentration, we observe progressive structural and dynamic changes at room temperature, indicating the disruption of yolk components such as yolk-granules and yolk-plasma proteins. Temperature- and salt-dependent structural and dynamic investigations suggest a delay in the gel formation and aggregation of yolk low-density lipoproteins with increasing ionic strength. However, the time-temperature superposition relationship observed in all samples suggests an identical mechanism underlying protein aggregation-gelation with a temperature-dependent reaction rate. The sol-gel transition time extracted from kinetic and dynamic information follows Arrhenius's behavior, and the activation energy (460kJ/mol) is found to be independent of the salt concentration.

How Far Is "Bulk Water" from Interfaces? Depends on the Nature of the Surface and What We Measure.

Using systematic molecular dynamics (MD) simulations, we revisit the question: At what distance from an interface do the properties of "bulk water" get recovered? We have considered three different kinds of interfaces: nonpolar (hydrophobic; isooctane-water interface), charged (negative; AOT bilayer), and polar (zwitterionic; POPC bilayer). In order to interrogate the extent of perturbation of the interfacial water molecules as a function of the distance from the interface, we utilize a diverse range of structural and dynamical parameters. To capture the structural perturbations, we look into local density (translational order), local tetrahedral order parameter, and dipolar orientation of the water molecules. We also explore the anisotropic diffusion of the water molecules in the direction perpendicular to the interface as well as the planar diffusion parallel to the interface in a distance dependent manner. In addition, the orientational time correlation functions have been computed to understand the extent of slowdown in the rotational dynamics. As expected, the electrostatic field emanating from the charged AOT interface seems to have the highest long-range effect on the orientational order and dynamics of the water molecules, whereas specific interactions like hydrogen bonding and electrostatic interaction lead to significant trapping and kinetic slowdown for both AOT and POPC (zwitterionic) very close to the interface. Our analysis highlights that not only the length-scale of perturbation depends on the nature of the interfaces and specific interactions but also the type of water property that we measure/calculate. Different water properties seem to have widely different length-scale of perturbation. Orientational order parameters seem to be perturbed to a much longer length-scale as compared to translational order parameters. The global orientational order of water can be perturbed even up to ∼4-5 nm near the negatively charged AOT surface in the absence of any extra electrolyte. This observation has significant implication toward the interpretation of experimental measurements as well since different spectroscopic techniques would probe different parameters or water properties with possible mutual disagreement and inconsistency between different types of measurements. Thus, our study provides a broader and unifying perspective toward the aspect of "context dependent" structural and dynamical perturbation of "interfacial water".

Breakdown of diffusivity\u2013entropy scaling in colloidal glass-forming liquids

Glass is a liquid that has lost its ability to flow. Why this particular substance undergoes such a dramatic kinetic slowdown yet remains barely distinguishable in structure from its fluid state upon cooling constitutes the central question of glass transition physics. Here, we investigate the pathway of kinetic slowdown in glass-forming liquids that consist of monolayers of ellipsoidal or binary spherical colloids. In contrast to rotational motion, the dynamics of the translational motion begin to violently slow down at considerably low area fractions (ϕT). At ϕT, anomalous translation–rotation coupling is enhanced and the topography of the free energy landscape become rugged. Based on the positive correlation between ϕT and fragility, the measurement of ϕT offers a novel method for predicting glassy dynamics, circumventing the prohibitive increase in equilibrium times required in high-density regions. Our results highlight the role that thermodynamical entropy plays in glass transitions.

Clusters of lysozyme in aqueous solutions

Equilibrium clusters of protein lysozyme are at the center of an ongoing scientific debate. Previous attempts to provide a microscopic description of the clusters that is consistent with all experimental evidence have not been fully successful. The primary reason is the use of model potentials that have a predefined shape. In this paper we derive a model-free interprotein potential directly from experimental structure factor. The derived potential is globally repulsive but has a local minimum at short distances. The minimum is essential for the correct behavior of the structure factor with protein concentration, in particular the shifting pattern of the signature maximum at short wave vectors. Equilibrium clusters are observed throughout the entire range of concentrations, but their nature differs in the low and high concentration limits. At low concentrations, the clusters are extended in shape. As the concentration is increased, small clusters collapse while large clusters are assembled from the small ones. Hydrodynamic interactions drive a kinetic slowdown at high concentrations, where a transition into a fluid of permanent clusters of specific size is observed. In good agreement with the available experimental data, our simulations shed light on the microscopic nature of protein clusters.

Adsorption Thermodynamics and Kinetics of Light Hydrocarbons on Microporous Activated Carbon at Low Temperatures

The removal of light hydrocarbons from exhaust air and process gas is important for a variety of applications, e.g., in natural-gas treatment. However, particularly at lower concentrations, the removal of C1 and C2 hydrocarbons is either very expensive or unfeasible with standard technology. Adsorption processes at temperatures below 0 °C may provide a technical solution, but until today, no systematic study on the dynamics of trace adsorption at low temperatures is available. Therefore, in this work, we present breakthrough curve experiments of ethane, propane, and n-butane over a temperature range from +20 to −80 °C and a concentration range from 5 to 1000 Pa on microporous activated carbon. Equilibrium loadings are calculated and modeled with the temperature-dependent Toth equation. From dynamic simulations of the experimental breakthrough curves, kinetic parameters are determined. The lowering of temperature results in the slowdown of kinetics, which, however, is overcompensated by a simultaneous capa...

Reactive diffusion in the presence of a diffusion barrier: Experiment and model

Reactions in thin films and diffusion barriers are important for applications such as protective coatings, electrical contact, and interconnections. In this work, the effect of a barrier on the kinetics of the formation for a single phase by reactive diffusion is investigated from both experimental and modeling point of views. Two types of diffusion barriers are studied: (i) a thin layer of W deposited between a Ni film and Si substrate and (ii) Ni alloy films, Ni(1%W) and Ni(5%Pt), that form a diffusion barrier during the reaction with the Si substrate. The effect of the barriers on the kinetics of δ-Ni2Si formation is determined by in situ X ray diffraction and compared to models that explain the kinetic slowdown induced by both types of barrier. A linear parabolic growth is found for the deposited barrier with an increasing linear contribution for increasing barrier thickness. On the contrary, the growth is mainly parabolic for the barrier formed by the reaction between an alloy film and the substrate. The permeability of the two types of barrier is determined and discussed. The developed models fit well with the dedicated model experiments, leading to a better understanding of the barrier effect on the reactive diffusion and allowing us to predict the barrier behaviour in various applications.

Generalized thermodynamics of phase equilibria in scalar active matter.

Motility-induced phase separation (MIPS) arises generically in fluids of self-propelled particles when interactions lead to a kinetic slowdown at high densities. Starting from a continuum description of scalar active matter akin to a generalized Cahn-Hilliard equation, we give a general prescription for the mean densities of coexisting phases in flux-free steady states that amounts, at a hydrodynamics scale, to extremizing an effective free energy. We illustrate our approach on two well-known models: self-propelled particles interacting either through a density-dependent propulsion speed or via direct pairwise forces. Our theory accounts quantitatively for their phase diagrams, providing a unified description of MIPS.

Role of Casting Solvent on Nanoparticle Dispersion in Polymer Nanocomposites

We investigate the influence of casting solvent on the final spatial dispersion of nanoparticles (NPs) in polymer nanocomposites (PNCs). We prepared nanocomposites of bare silica NPs and poly(2-vinylpyridine) (P2VP) by casting from two different solvents—methyl ethyl ketone (MEK) and pyridine—which are theta/good solvents, respectively, for both the polymer and the NPs. In MEK, we show that P2VP strongly adsorbs onto the silica surface to create a temporally stable bound polymer layer. The resulting “hairy” particles are sterically stabilized against agglomeration, and thus good NP dispersion in PNCs is always achieved, independent of P2VP molecular weight, concentration, or NP loading. On the contrary, in pyridine, P2VP does not adsorb on the silica NPs. The phase behavior in this case is thus governed by a subtle balance among electrostatic repulsion, polymer-induced depletion attraction, and the kinetic slowdown of diffusion-limited NP aggregation. While there is little remnant solvent in the dry PNC, ...

Influence of adsorption or desorption and surface diffusion on the formation kinetics of open half-monolayer coverage.

The formation kinetics of open half-monolayer films on solid substrates is studied by the deposition of particles from a gaseous (vapor) phase to a cold substrate (room temperature) provided the lateral interaction between the particles of adsorbed layer (adlayer) is attractive. A detailed analysis of two limiting cases is presented: when the half-monolayer film formation rate is limited by the adsorption of particles from the gas phase and when the formation of the half-monolayer film surface is determined by the rate of surface diffusion of the adsorbed particles. The asymptotic analysis of the coverage dispersion evolution and the characteristic spatial scale of coverage inhomogeneities at the early and late stages of relaxation of a submonolayer film after quenching under the spinodal is carried out. It is found that separation of the adlayer occurs, so inhomogeneities of submonolayer films at the later stages of the process tend to equilibrium values of coverage in any case. However, asymptotic and numerical analysis shows that in the second case for some relationship between the kinetic and thermodynamic parameters of the adlayer an intermediate asymptotic relaxation process can be observed. It testifies to a kinetic slowdown of the separation process at the spinodal values of coverages. This fact manifests as the appearance of the intermediate plateau in the evolution curves for the coverage dispersion and nonmonotonic change of the characteristic spatial scale of coverage inhomogeneities. Moreover, at the early stages of the coverage evolution, the incubation period is revealed in the development of its inhomogeneities. It is shown that at the later stages of the separation of the half-monolayer film, the characteristic spatial scale of coverage inhomogeneities increases with time according to the law τ {1/2} and the width of the transition region between enriched and depleted regions of adlayer decreases as 1/τ {1/2}.

Glass Transition Thermodynamics and Kinetics

The remarkable kinetic slowdown experienced by liquids as they are cooled toward their glass transition is not accompanied by any obvious structural change. Understanding the origin of this behavior is a major scientific challenge. At present, this area of condensed matter theory is characterized by an abundance of divergent viewpoints that attempt to describe well-defined physical phenomena. We review representative theoretical views on the unusual kinetics of liquid supercooling, which fall into two broad competing categories: thermodynamic and kinetic. In the former, an apparent “ideal,” thermodynamic, glass transition caused by rapid loss of entropy in the supercooled liquid underlies kinetic slowdown; in the latter, purely kinetic constraints are responsible for loss of ergodicity. The possible existence of an ideal thermodynamic glass transition is discussed and placed in its proper statistical mechanical context.

Theoretical Studies on Competitive Binding of Caldesmon and Myosin S1 to Actin: Prediction of Apparent Cooperativity in Equilibrium and Slow-Down in Kinetics of S1 Binding by Caldesmon

Several laboratories have reported cooperative binding of S1 to actin in the presence of caldesmon. This cooperative binding has been interpreted with a model similar to that proposed for the binding of S1 to regulated actins in which the binding affinity of S1 is controlled by the position of the tropomyosin filaments. In a recent paper [Sen, A., Chen, Y., Yan, B., and Chalovich, J. M. (2001) Biochemistry 40, 5757-64], we showed qualitatively that S1 binding resulted in rapid dissociation of caldesmon from actin or actin-tropomyosin. This suggests that the cooperativity observed in the case of caldesmon is not due to a conformational change in actin-caldesmon but to the displacement of caldesmon. We show in this paper that the pure competitive binding model, in which both S1 and caldesmon are competing for the same binding sites on actin, can simulate quantitatively the effect of caldesmon on both the equilibrium and the kinetics of S1 binding to actin. This model successfully predicts an apparent cooperativity for the binding of S1 to actin-caldesmon without the need to assume multiple actin-caldesmon structures and produces a decreased rate of S1 binding to actin in the presence of caldesmon. This suggests that the inhibitory action of caldesmon on the actin-activated ATPase activity of myosin in solution and on the generation of active force in a contracting muscle may be simply due to the blocking of myosin binding sites on actin by caldesmon.