Remco Tuinier - 

Laboratory of Physical Chemistry / Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, the Netherlands

In this lecture I give an introduction on self-consistent field (SCF) lattice computations. After a qualitative explanation of the method used I demonstrate results for various types of applications. As a simple example, it is demonstrated that SCF enables to reasonably predict the partitioning of caprolactam over a benzene + water interface and can also quantify the interfacial tension.

Next, the strength of SCF theory is illustrated by focusing on self-assembly and the interactions between micelles. The self- and co-assembly of block copolymers in selective solvents is a well-known approach for generating a wide range of submicron scale morphologies, including spherical micelles, wormlike micelles, or vesicles. These can be exploited in for instance drug delivery, encapsulation, and cosmetics. It is shown that SCF can be employed to accurately predict the size and preferred morphology of self-assembled block copolymer micelles.^1-5

Controlling solubilization of lyophobic compounds in block copolymer micelles is a key aspect in the design of drug delivery systems with tailored release properties. Using SCF we show that solubilization is regulated by a complex interplay between enthalpic and entropic contributions, and that the spatial distribution can be controlled by the concentration and the solubility of the guest compound in the dispersion medium. A characteristic change in size and mass of the micelles upon solubilization is predicted. It is shown⁶ how this can be used experimentally as a fingerprint to assess spatial distribution indirectly. Using SCF we also study how micelles respond to other components in solution is scarce. Results will be reported on the colloidal stability of micelle suspensions in presence of (homo)polymers.

Schematic picture of block copolymers in a spherical lattice.

1. J.G.J.L. Lebouille, L.F.W. Vleugels, A.A. Dias, F.A.M. Leermakers, M.A. Cohen Stuart, R. Tuinier, Controlled block copolymer micelle formation for hydrophobic ingredient encapsulation, Eur. Phys. J. E 36 (2013) 107.
2. J.G.J.L. Lebouille, R. Tuinier, L.F.W. Vleugels, M.A. Cohen Stuart, F.A.M. Leermakers, Self-consistent field predictions for spherical biocompatible triblock copolymer micelles, Soft Matter 9 (2013) 7515-7525.
3. C. Gonzato, M. Semsarilar, E. R. Jones, F. Li, G.J.P. Krooshof, P. Wyman, O.O. Mykhaylyk, R. Tuinier, S. P. Armes, Rational synthesis of low polydispersity block copolymer vesicles in concentrated solution via polymerization-induced self-assembly. J. Am. Chem. Soc. 136 (2014) 11100–11106.
4. F. Li, M. Schellekens, J. de Bont, R. Peters, A. Overbeek, F.A.M. Leermakers, R. Tuinier, Self-assembled structures of PMAA-PMMA block copolymers; synthesis, characterization and self-consistent field computations, Macromolecules 48 (2015) 1194−1203.
5. A. Ianiro, J.P. Patterson, A. Gonzalez Garcia, M.M.J. van Rijt, M.M.R.M. Hendrix, N.A.J.M. Sommerdijk, I.K. Voets, A.C.C. Esteves, R., Tuinier, A roadmap for PEO-PCL self-assembly in water : prediction, synthesis, and characterization and characterization, J. Pol. Sci. B: Pol. Phys. 56 (2018) 330-339.
6. A. Ianiro, A. Gonzalez Garcia, S. Wijker, J.P. Patterson, A.C.C. Esteves, R., Tuinier, accepted for publication in Langmuir (2019).