Kinetics of macromolecules

The verification of theoretical data obtained by simulation of peroxide oxidation kinetics of macromolecules with experimental data, obtained from chemiluminescent analysis of blood using automated complex ChLC-1. This automated complex was developed by the authors and laboratory colleagues. 

Traditionally, polymer research was concerned with the kinetics of macromolecule formation. A considerable simplification was achieved by Flory [1] when introducing the extent of reaction of a functional group that may belong to a monomer or a long chain. This extent of reaction a of a functional group is defined as the ratio of the number of reacted functionalities [AJ to the total number of reacted and non-reacted functionalities [A,] ... 

Gotlib YuYa, Darinskii AA, Svetlov YuE (1986) Fizicheskaya kinetika makromolekul (Physical kinetics of macromolecules, in Russian). Khimiya, Leningrad Graessley WW (1974) The entanglement concept in polymer rheology. Adv Polym Sci 16 1— 179... 

Aoqing Tang, Statistic Kinetics of Macromolecule Reaction. Science Press. Beijing, China, 366 (1985). 

In summary, the studies reported In this review provide 2 Important demonstrations (1) that In vitro release kinetics of macromolecules such as inulln from ethylene-vinyl acetate copolymer matrices are Identical to their In vivo release kinetics, and (2) that zero-order release for macromolecules can be achieved for over 60 days using a hemisphere design. Further experimentation in these areas should provide Information that will be useful In the eventual design of controlled release systems for Insulin and other important bloactlve macromolecules. 

Thus, these experiments show that in vitro and in vivo release kinetics of macromolecules from ethylene-vinyl acetater copolymer matrices are essentially identical, and they establish a methodology which can be applied to other in vitro-in vivo release comparisons. 

Gotlib YY, Darinsky AA, Svetlov YE (1986) Physical kinetics of macromolecules. Khimiya, Leningrad... 

Hence, Flory s theory offers an objective criterion for chain flexibility and makes possible to divide all the variety of macromolecules into flexible-chain (f > 0.63) and rigid-chain (f < 0.63) ones. In the absence of kinetic hindrance, all rigid-chain polymers must form a thermodynamically stable organized nematic phase at some polymer concentration in solution which increases with f. At f > 0.63, the macromolecules cannot spontaneously adopt a state of parallel order under any conditions. 

Dole, M., The Radiation Chemistry of Macromolecules, Vol. 1, Academic Press, New York, 1975. David, D., Comprehensive Chemical Kinetics, Bamford, C.H. and Tiffer, C.E.H., Eds., Elsevier, Amsterdam, 1975. 

Slomkowski, S., and Penczek, S., Influence of dibenzo-18-crown-6 ether on the kinetics of anionic polymerization of p-propiolactone, Macromolecules, 9, 367-369, 1976. 

Levy (Chapter 6) has also explored the use of supercomputers to study detailed properties of biological macromolecule that are only Indirectly accessible to experiment, with particular emphasis on solvent effects and on the Interplay between computer simulations and experimental techniques such as NMR, X-ray structures, and vltratlonal spectra. The chapter by Jorgensen (Chapter 12) summarizes recent work on the kinetics of simple reactions In solutions. This kind of calculation provides examples of how simulations can address questions that are hard to address experimentally. For example Jorgensen s simulations predicted the existence of an Intermediate for the reaction of chloride Ion with methyl chloride In DMF which had not been anticipated experimentally, and they Indicate that the weaker solvation of the transition state as compared to reactants for this reaction In aqueous solution Is not due to a decrease In the number of hydrogen bonds, but rather due to a weakening of the hydrogen bonds. 

A simple algorithm [17] makes it possible to find the probability of any fragment of macromolecules of Gordonian polymers. Comparison of these probabilities with the data obtained by NMR spectroscopy provides the possibility to evaluate the adequacy of a chosen kinetic model of a synthesis process of a particular polymer specimen. The above-mentioned probabilities are also involved in the expressions for the glass transition temperature and some structure-additive properties of branched polymers [18,19]. 

For a number of copolymers, whose kinetics of formation is described by nonideal models, the statistics of alternation of monomeric units in macromolecules cannot be characterized by a Markov chain however, it may be reduced to the extended Markov chain provided that units apart from their chemical nature... 

At the initial stage of bulk copolymerization the reaction system represents the diluted solution of macromolecules in monomers. Every radical here is an individual microreactor with boundaries permeable to monomer molecules, whose concentrations in this microreactor are governed by the thermodynamic equilibrium whereas the polymer chain propagation is kinetically controlled. The evolution of the composition of a macroradical X under the increase of its length Z is described by the set of equations ... 

An exhaustive statistical description of living copolymers is provided in the literature [25]. There, proceeding from kinetic equations of the ideal model, the type of stochastic process which describes the probability measure on the set of macromolecules has been rigorously established. To the state Sa(x) of this process monomeric unit Ma corresponds formed at the instant r by addition of monomer Ma to the macroradical. To the statistical ensemble of macromolecules marked by the label x there corresponds a Markovian stochastic process with discrete time but with the set of transient states Sa(x) constituting continuum. Here the fundamental distinction from the Markov chain (where the number of states is discrete) is quite evident. The role of the probability transition matrix in characterizing this chain is now played by the integral operator kernel ... 

Le Bon, C., Nicolai, T., and Durand, D., Kinetics of Aggregation and gelation of globular proteins after heat-induced denaturation, Macromolecules, 32,6120, 1999. 

A Peters, SJ Candau. Kinetics of swelling of polyacrylamide gels. Macromolecules 19 1952-1960, 1986. 

KA Mazich, G Rossi, CA Smith. Kinetics of solvent diffusion and swelling in a model elastomeric system. Macromolecules 25 6929-6933, 1992. 

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