Polymer Globule as a Nanoreactor

Abstract

Peculiarities of chemical reactions inside polymer globules with sizes falling in the nanometric range have been theoretically studied. The simplest example of a polymer-catalyzed bimolecular reaction between two low-molecular-weight compounds has been considered to illustrate the advantages of conducting chemical transformations in globular solution of macromolecules. Under theoretical examination of polymer-analogous transformations of polymer molecules, the possibility has been shown of reaction-induced conformational transitions between their coil and globular states. Besides, a pronounced effect has been revealed of the preferential sorption of low-molecular-weight reagents on composition of copolymers formed.

Copolymerization of Partly Incompatible Monomers: An Insight from Computer Simulations

“…Unfortunately this approach has not been considered for polymer bulk, but only for dilute solutions and so-called globular nanoreactor formation. 10,11 In addition we would like to mention several relevant and "emeritus" complex kinetic models of copolymerization, where the reactivity of the growing macroradical end depends on the macroradical sequence, namely penultimate 12 and even penpenultimate models, 13 see ref. [14] for a comprehensive review.…”

“…To the best of our knowledge, we can mention only one paper by Kuchanov and Russo where a theoretical approach was proposed to describe the copolymerization of monomer units with fixed reactivity ratios and additional Flory–Huggins χ-parameter to describe the interactions between monomers and growing copolymer chains. Unfortunately, this approach has not been considered for polymer bulk, but only for dilute solutions and so-called globular nanoreactor formation. , …”

“…In the work of Genzer’s group different types of surface and bulk initiated homopolymerization are studied; the MC simulation scheme based on the bond fluctuation model where the monomers and polymers reside on a three-dimensional cubic lattice was used to model a “living”/controlled radical polymerization. , Starovoitova et al studied copolymerization of a single molecule near a selectively adsorbing surface and observed the formation of gradient copolymers . Berezkin et al simulated copolymerization of a single chain with a simultaneous globule formation, , which is in many senses similar to the analytical works of Kuchanov already mentioned above. , See refs and for some recent comprehensive reviews in these fields. However, all these studies were mainly focused only on special and unusual conditions of copolymerization, such as a close vicinity to a flat surface or a single globular conformation of the growing chain.…”

“…Unfortunately, this approach has not been considered for polymer bulk, but only for dilute solutions and so-called globular nanoreactor formation. 3,4 In this context we can mention several relevant and "emeritus" complex analytical kinetic models of copolymerization, where the reactivity of the growing macroradical end depends on the macroradical sequence, namely penultimate 5 and even penpenultimate models 6 (see ref 7 for a comprehensive review). However, these models are mainly focused on the sequence statistics and averaged properties rather than the description of the reaction kinetics coupled with the local surroundings.…”

“…24 Berezkin et al simulated copolymerization of a single chain with a simultaneous globule formation, 25,26 which is in many senses similar to the analytical works of Kuchanov already mentioned above. 10,11 See refs. [27,28] for some recent comprehensive reviews in these fields.…”