Modeling RAFT Gelation and Grafting of Polymer Brushes for the Production of Molecularly Imprinted Functional Particles

Abstract

Summary RAFT precipitation polymerization was here used for the molecular imprinting of 5‐fluorouracil (a drug used in cancer treatment) followed by grafting of polymer functional brushes in the particles surface. Materials combining high molecular recognition capabilities and stimulation triggered by changes in the surrounding environment (e.g. pH/temperature) have thus been sought. Mathematical modeling of the RAFT copolymerization of vinyl/divinyl monomers was used to describe the crosslinking process involved in the molecular imprinting step. The size of the grafted polymer functional brushes was estimated using models for the calculation of molecular weight distribution in RAFT homopolymerization. One of the goals of this study consists in the development of polymer reaction engineering tools for the design of synthesis conditions leading to tailored molecularly imprinted particles with responsive features. A first sketch of the two steps involved in the production of the MIP responsive particles is here presented. However, the need for new kinetic studies accounting for specificities of the molecular imprinting and surface extension processes (e.g. presence of template during molecular imprinting and solvent effects) is here identified. Measurements of the dynamics of gelation and brushes growth are also needed to perform model validation. Improvement on the modeling of RAFT gelation with heterogeneous conditions avoiding some simplifications and the amelioration of the numerical efficiency in the calculation of the MWD of RAFT polymers are other issues to be addressed in future works.

Molecular Imprinting Technology for Biomimetic Assemblies

“…Mathematical modeling of the RAFT copolymerization of vinyl/divinyl monomers was used to describe the crosslinking process involved in the molecular imprinting step. The assessment of polymer reaction engineering tools to aid the design of synthesis conditions leading to tailored MIPs with responsive features was a critical goal of this research [106]. Along with the modeling study, the group synthesized and evaluated molecularly imprinted particles with surface grafted functional polymer brushes aiming to choose either methacrylic acid (MAA) or 2-hydroxyethyl methacrylate (HEMA) as functional monomers.…”

Model Discrimination between RAFT Polymerization Models Using Sequential Bayesian Methodology

“…A large number of literature references have used, for instance, the method of moments, kinetic Monte Carlo simulations, and the software Predici . Application of these numerical techniques to RAFT polymerization includes mainly: i) synthesis of homopolymers with narrow molar mass distributions (MMD or MWD), ii) synthesis of polymer networks by crosslinking/branching reactions of vinyl/divinyl monomers, iii) microwave‐assisted radical polymerization, iv) copolymers with controlled chain composition distribution via semibatch reactors, v) dispersion polymerization in supercritical CO 2 , vi) continuous stirred tank reactors, and vi) miniemulsion polymerization …”