Non-isothermal unfolding/denaturing kinetics of egg white protein

Egg protein is an important part of our food to get protein in our daily diet, and makes this protein more important to researchers to understand its kinetic behavior to understand the energy involved in the digestion of the egg protein. Hence, the present study explores the denaturing kinetics of the protein obtained from the hen??s egg white (EW) using high resolution calorimetric technique. Fresh EW was scanned for heating and cooling to see the thermodynamics from 10 to 100?°C at different heating ramp rates varying from 1 to 20?°C?min^?1. An endothermic peak was found on heating scan showing denaturing of protein which was found absent at the cooling indicating the absence of any residue after heating. The denature peak shifted towards higher temperature as ramp rate increases following Arrhenius behavior and shows an activated denaturing kinetics of the egg protein. This peak was also compared with the water to avoid water effects. Behavior of denaturing peak can be explained in terms of Arrhenius theory and further discussed to get the energy involved in digestion.     

A simulation model for long-chain branching in vinyl acetate polymerization: 1. Batch polymerization

A new simulation model for the kinetics of long-chain branching formed via chain transfer to polymer and terminal double-bond polymerization is proposed. This model is based on the branching density distribution of the primary polymer molecules. The theory of branching density distribution is that each primary polymer molecule experiences a different history of branching and provides information on how each primary polymer molecule is connected with other chains that are formed at different conversions, therefore making possible a detailed analysis on the kinetics of the branched structure formation. This model is solved by applying the Monte Carlo method and a computer-generated simulated algorithm is proposed. The present model is applied to a batch polymerization of vinyl acetate, and various interesting structural changes occurring during polymerization (i.e., molecular weight distribution, distribution of branch points, and branching density of the largest polymer molecule) are calculated. The present method gives a direct solution for the Bethe lattice formed under nonequilibrium conditions; therefore, it can be used to examine earlier theories of the branched structure formation. It was found that the method of moments that has been applied successfully to predict various average properties would be considered a good approximation at least for the calculation of not greater than the second-order moment in a batch polymerization. © 1994 John Wiley & Sons, Inc.     

On the kinetics of styrene emulsion polymerization above CMC. I. A mathematical model

A detailed mathematical model of the kinetics of styrene emulsion polymerization has been proposed. Its main features/assumptions are compartmentalization, micellar and homogeneous nucleation, particle formation by both initiator‐derived and desorbed radicals, dependence on the particle size of the rate coefficients, thermodynamic considerations, and aqueous phase kinetics. The model predicts that micellar nucleation dominates over homogeneous nucleation and that the evolution of the nucleation rate reaches a maximum, where desorbed radicals have an important contribution. Initiator‐derived radicals with only one monomeric unit have also a significant contribution on the rate of capture in particles. The results suggest that the correctness of the instantaneous termination approach depends not only on the size of the particle, but also on the type of entering radical (initiator‐derived or monomeric). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2201–2218, 2000     

The polymerization rate of freshly nucleated particles during emulsion polymerization with micellar nucleation

A simple procedure was developed to account for the contribution of freshly nucleated particles to the total polymerization rate during micellar nucleation. It has been shown that the polymerization rate of the freshly nucleated particles cannot be described by a steady-state solution for a radical population balance over the particle size distribution, i.e., the classical Smith-Ewart recursion relation. Once nucleated, the particles grow for a significant period of time with one radical before either radical desorption or radical absorption, followed by instantaneous bimolecular termination, occur. For most emulsion polymerizations, radical desorption is the dominant process for radical loss of the freshly nucleated particles. A relation for the mean time that the freshly nucleated particles grow with one radical was derived. © 1996 John Wiley & Sons, Inc.     

Stability of nanodispersions: a model for kinetics of aggregation of nanoparticles

In the course of aggregation of very small colloid particles (nanoparticles) the overlap of the diffuse layers is practically complete, so that one cannot apply the common DLVO theory. Since nanopoarticles are small compared to the extent of the diffuse layer, the process is considered in the same way as for two interacting ions. Therefore, the Br?nsted concept based on the Transition State Theory was applied. The charge of interacting nanoparticles was calculated by means of the Surface Complexation Model and decrease of effective charge of particles was also taken into account. Numerical simulations were performed using the parameters for hematite and rutile colloid systems. The effect of pH and electrolyte concentration on the stability coefficient of nanosystems was found to be more pronounced but similar to that for regular colloidal systems. The effect markedly depends on the nature of the solid which is characterized by equilibrium constants of surface reactions responsible for surface charge, i.e., by the point of zero charge, while the specificity of counterions is described by their association affinity, i.e., by surface association equilibrium constants. The most pronounced is the particle size effect. It was shown that extremely small particles cannot be stabilized by an electrostatic repulsion barrier. Additionally, at the same mass concentration, nanoparticles aggregate more rapidly than ordinary colloidal particles due to thier higher number concentration.     

A generic approach to decipher the mechanistic pathway of heterogeneous protein aggregation kinetics

Amyloid formation is a generic property of many protein/polypeptide chains. A broad spectrum of proteins, despite having diversity in the inherent precursor sequence and heterogeneity present in the mechanism of aggregation produces a common cross β-spine structure that is often associated with several human diseases. However, a general modeling framework to interpret amyloid formation remains elusive. Herein, we propose a data-driven mathematical modeling approach that elucidates the most probable interaction network for the aggregation of a group of proteins (α-synuclein, Aβ42, Myb, and TTR proteins) by considering an ensemble set of network models, which include most of the mechanistic complexities and heterogeneities related to amyloidogenesis. The best-fitting model efficiently quantifies various timescales involved in the process of amyloidogenesis and explains the mechanistic basis of the monomer concentration dependency of amyloid-forming kinetics. Moreover, the present model reconciles several mutant studies and inhibitor experiments for the respective proteins, making experimentally feasible non-intuitive predictions, and provides further insights about how to fine-tune the various microscopic events related to amyloid formation kinetics. This might have an application to formulate better therapeutic measures in the future to counter unwanted amyloidogenesis. Importantly, the theoretical method used here is quite general and can be extended for any amyloid-forming protein.

Amyloid formation is a generic property of many protein/polypeptide chains.     

Protein mechanical unfolding: a model with binary variables

A simple model, recently introduced as a generalization of the Wako-Saito; model of protein folding, is used to investigate the properties of widely studied molecules under external forces. The equilibrium properties of the model proteins, together with their energy landscape, are studied on the basis of the exact solution of the model. Afterwards, the kinetic response of the molecules to a force is considered, discussing both force clamp and dynamic loading protocols and showing that theoretical expectations are verified. The kinetic parameters characterizing the protein unfolding are evaluated by using computer simulations and agree nicely with experimental results, when these are available. Finally, the extended Jarzynski equality is exploited to investigate the possibility of reconstructing the free energy landscape of proteins with pulling experiments.     

Matrix polymerization on polycationic backbones: A continuous method for following the polymerization kinetics

A novel method of following polymerization kinetics in dilute solutions of ionic monomers is described. The method, based on conductimetry, is very well adapted to follow polymerization of ionic species in very dilute solutions, in micellar solutions, or at interfaces, i.e., in all systems in which the polymerization process involves a shift in ionic equilibria. The method is applied to matrix polymerization of p-styrene sulfonate–(2,2,2)4-ionene complex and yields results in full agreement with the standard spectroscopic method frequently used in such systems. The conversion curves obtained by conductimetry are satisfactorily explained by Manning's ion condensation model and are in agreement with a previously proposed mechanism, based on ion condensation theory, for matrix polymerization of ionized monomers on polyelectrolytes.     

Ring-opening polymerization. V. Hydroxyl-initiated polymerization of phenyl-substituted 1,3-dioxolan -2,4-diones: A model study

The reaction of C(5) phenyl-substituted 1,3-dioxolan-2,4-diones with a series of alcohols has been studied in order to obtain quantitative information relating to the role of hydroxyl initiation in the polymerization of these compounds. Results relating to both the effect of C(5) substitution and the structure of the attacking alcohol are presented. The reactions are secondorder (first-order with respect to each component) and show some of the kinetic features associated with monosubstituted 1,3,2-dioxathiolan-4-one-2-oxides. Structural effects are adequately represented in terms of Taft σ^* and E_s substituent constants. Of the parameters describing the properties of the reaction medium, the donicity concept was found to give the best correlation with rate data. It is considered that hydroxyl initiation will contribute to a relatively small extent in the polymerization of 5,5-diphenyl-1,3-dioxolan-2,4-dione and 5-methyl, 5-phenyl-1,3-dioxolan-2,4-dione but will form the basis for the major chain-growth process in 5-phenyl-1,3-dioxolan-2,4-dione.     

Influence of catalyst depletion or deactivation on polymerization kinetics. II. Nonsteady-state polymerization

The number-average and weight-average degrees of polymerization at the end of the polymerization process have been calculated in terms of the initial monomer concentration, initial catalyst concentration, and rate constants for various polymerization processes, all of which assume instantaneous initiation. The mechanisms differ among themselves in that there is either first-order catalyst deactivation, or transfer to monomer, or both. The calculation is greatly simplified if only the molecular weights at the end of polymerization are considered. The method given is particularly useful for systems where the calculation of the distribution function as a function of time is complicated. The fact that the monomer concentration and catalyst concentration have a marked effect on the molecular weight provides a good test of the validity of the mechanism under consideration. A comparison of the calculated and observed molecular weights obtained for the homogeneous polymerization of acrylonitrile with an organometallic catalyst will be given in a later communication.     

Ethylene polymerization reactions with Ziegler–Natta catalysts. I. Ethylene polymerization kinetics and kinetic mechanism

Kinetics of ethylene homopolymerization reactions and ethylene/1-hexene copolymerization reactions using a supported Ziegler–Natta catalyst was carried out over a broad range of reaction conditions. The kinetic data were analyzed using a concept of multicenter catalysis with different centers that respond differently to changes in reaction parameters. The catalyst contains five types of active centers that differ in the molecular weights of material they produce and in their copolymerization ability. In ethylene homopolymerization reactions, each active center has a high reaction order with respect to ethylene concentration, close to the second order. In ethylene/α-olefin copolymerization reactions, the centers that have poor copolymerization ability retain this high reaction order, whereas the centers that have good copolymerization ability change the reaction order to the first order. Hydrogen depresses activity of each type of center in the homopolymerization reactions in a reversible manner; however, the centers that copolymerize ethylene and α-olefins well are not depressed if an α-olefin is present in the reaction medium. Introduction of an α-olefin significantly increases activity of those centers, which are effective in copolymerizing it with ethylene but does not affect the centers that copolymerize ethylene and α-olefins poorly. To explain these kinetic features, a new reaction scheme is proposed. It is based on a hypothesis that the Ti—C₂H₅ bond in active centers has low reactivity due to the equilibrium formation of a Ti—C₂H₅ species with the H atom in the methyl group β-agostically coordinated to the Ti atom in an active center. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4255–4272, 1999     

Oxidative polymerization of aromatic hydrocarbons: A study of kinetics and mechanism

Aromatic hydrocarbons were homopolymerized by means of an oxidative polymerization reaction with the use of the catalyst system anhydrous aluminum chloride–cupric chloride. The kinetics of the benzene homopolymerization carried out under different experimental conditions was followed by the determination of the amounts of cuprous ion and polymeric product formed in the reaction. Cuprous ion was spectrophotometrically titrated in the form of its complex with 2,2′-biquinolyl (cuproine). The experimental results do not agree with cationic mechanism for this reaction previously proposed in the literature. Ethylbenzene was kinetically studied under the same experimental conditions. In view of the experimental evidences obtained in this work and on some literature data, a mechanism based on formation of cation-radicals is proposed for the oxidative polymerization reaction when carried out under the studied conditions.     

Thermodynamics and kinetics of competing aggregation processes in a simple model system

A simple model system has been used to develop thermodynamics and kinetics for bulk and surface aggregation processes capable of competing with each other. The processes are the stepwise aggregation of monomers in a fluid medium and on an impenetrable solid surface bounding the fluid medium, besides the adsorption and desorption of the same species at the solid-fluid interface. Emphasis is on aggregation processes in the high friction limit. The theoretical model is used to compare the kinetics and thermodynamics of the processes and to infer the conditions in which one process dominates another, in the high friction limit, such as in a liquid. The motivation of this study is obtaining insight into competition between aggregation in solution and on an adjoining surface, such as a cell membrane.     

Crystallization kinetics of isotactic polypropylene nucleated with octamethylenedicarboxylic dibenzoylhydrazide under isothermal and non-isothermal conditions

Octamethylenedicarboxylic dibenzoylhydrazide (TMC-300) was used as a nucleating agent for isotactic polypropylene (iPP) for the first time. The Avrami method and the Caze method were used to analyze the isothermal and non-isothermal crystallization kinetics of iPP incorporated with TMC-300, respectively. During isothermal crystallization, the half crystallization time at 130 °C reduces from 130 s of virgin iPP to 44 s after addition of TMC-300, which reflects that TMC-300 increased the crystallization rate of iPP obviously. The crystallization activation energy decreases from 382.5 kJ mol^?1 of virgin iPP to 275.3 kJ mol^?1 of iPP/TMC-300. During non-isothermal crystallization, the crystallization peak temperature of iPP nucleated with TMC-300 was increased by 5.1 °C when compared to that of virgin iPP at the cooling rate of 20 °C min^?1, and both the reduction of half crystallization time and the increase in peak crystallization temperature also justified that the addition of TMC-300 accelerated the crystallization of iPP.

     

Non-isothermal kinetics of free-radical polymerization of 2,2-dinitro-1-butyl acrylate

The free-radical bulk polymerization of 2,2-dinitro-1-butyl-acrylate (DNBA) in the presence of 2,2′-azobisisobutyronitrile (AIBN) as the initiator was investigated by DSC in the non-isothermal mode. Kissinger and Ozawa methods were applied to determine the activation energy (E _a) and the reaction order of free-radical polymerization. The results showed that the temperature of exothermic polymerization peaks increased with increasing the heating rate. The reaction order of non-isothermal polymerization of DNBA in the presence of AIBN is approximately 1. The average activation energy (92.91±1.88 kJ mol ⁻¹) obtained was smaller slightly than the value of E _a=96.82 kJ mol⁻¹ found with the Barrett method.