分子理论：预测聚合物、纳米粒子、双亲分子和其他软材料自组装结果的工具《ACS Omega》

Molecular Theory: A Tool for Predicting the Outcome of Self-Assembly of Polymers, Nanoparticles, Amphiphiles, and Other Soft Materials

Gervasio Zaldivar, Yamila A. Perez Sirkin, Gabriel Debais, Maria Fiora, Leandro L. Missoni, Estefania Gonzalez Solveyra, and Mario Tagliazucchi*

Departamento de Química Inorgánica Analítica y Química Física, Ciudad Universitaria, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2 C1428EGA, Buenos Aires, Argentina

Instituto de Química de los Materiales, Ambiente y Energía (INQUIMAE). Ciudad Universitaria, CONICET, Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Pabellón 2 C1428EGA, Buenos Aires, Argentina

ACS Omega 2022, XXXX, XXX, XXX-XXX

Publication Date: October 19, 2022

https://doi.org/10.1021/acsomega.2c04785

Abstract

The supramolecular organization of soft materials, such as colloids, polymers, and amphiphiles, results from a subtle balance of weak intermolecular interactions and entropic forces. This competition can drive the self-organization of soft materials at the nano-/mesoscale. Modeling soft-matter self-assembly requires, therefore, considering a complex interplay of forces at the relevant length scales without sacrificing the molecular details that define the chemical identity of the system. This mini-review focuses on the application of a tool known as molecular theory to study self-assembly in different types of soft materials. This tool is based on extremizing an approximate free energy functional of the system, and, therefore, it provides a direct, computationally affordable estimation of the stability of different self-assembled morphologies. Moreover, the molecular theory explicitly incorporates structural details of the chemical species in the system, accounts for their conformational degrees of freedom, and explicitly includes their chemical equilibria. This mini-review introduces the general ideas behind the theoretical formalism and discusses its advantages and limitations compared with other theoretical tools commonly used to study self-assembled soft materials. Recent application examples are discussed: the self-patterning of polyelectrolyte brushes on planar and curved surfaces, the formation of nanoparticle (NP) superlattices, and the self-organization of amphiphiles into micelles of different shapes. Finally, prospective methodological improvements and extensions (also relevant for related theoretical tools) are analyzed.

SUBJECTS:

• Micelles,

• Monomers,

• Peptides and proteins,

• Polymers,

• Self organization