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Equilibrium Model for Supramolecular Copolymerizations.

ABSTRACT: The coassembly of different building blocks into supramolecular copolymers provides a promising avenue to control their properties and to thereby expand the potential of supramolecular polymers in applications. However, contrary to covalent copolymerization which nowadays can be well controlled, the control over sequence, polymer length, and morphology in supramolecular copolymers is to date less developed, and their structures are more determined by the delicate balance in binding free energies between the distinct building blocks than by kinetics. Consequently, to rationalize the structures of supramolecular copolymers, a thorough understanding of their thermodynamic behavior is needed. Though this is well established for single-component assemblies and over the past years several models have been proposed for specific copolymerization cases, a generally applicable model for supramolecular cooperative copolymers is still lacking. Here, we provide a generalization of our earlier mass-balance models for supramolecular copolymerizations that encompasses all our earlier models. In this model, the binding free energies of each pair of monomer types in each aggregate type can be set independently. We provide scripts to solve the model numerically for any (co)polymerization of one or two types of monomer into an arbitrary number of distinct aggregate types. We illustrate the applicability of the model on data from literature as well as on new experimental data of triarylamine triamide-based copolymers in three distinct solvents. We show that apart from common properties such as the degree of polymerization and length distributions, our approach also allows us to investigate properties such as the copolymer microstructure, that is, the internal ordering of monomers within the copolymers. Moreover, we show that in some cases, also intriguing analytical approximations can be derived from the mass balances.

SUBMITTER: Ten Eikelder HMM

PROVIDER: S-EPMC6681264 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Equilibrium Model for Supramolecular Copolymerizations.

Ten Eikelder Huub M M HMM Adelizzi Beatrice B Palmans Anja R A ARA Markvoort Albert J AJ

The journal of physical chemistry. B 20190709 30

The coassembly of different building blocks into supramolecular copolymers provides a promising avenue to control their properties and to thereby expand the potential of supramolecular polymers in applications. However, contrary to covalent copolymerization which nowadays can be well controlled, the control over sequence, polymer length, and morphology in supramolecular copolymers is to date less developed, and their structures are more determined by the delicate balance in binding free energies ...[more]

PMID: 31287320

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Project description:Elucidating the microstructure of supramolecular copolymers remains challenging, despite the progress in the field of supramolecular polymers. In this work, we present a detailed approach to investigate supramolecular copolymerizations under thermodynamic control. Our approach provides insight into the interactions of different types of monomers and hereby allows elucidating the microstructure of copolymers. We select two monomers that undergo cooperative supramolecular polymerization by way of threefold intermolecular hydrogen bonding in a helical manner, namely, benzene-1,3,5-tricarboxamide (BTA) and benzene-1,3,5-tris(carbothioamide) (thioBTA). Two enantiomeric forms and an achiral analogue of BTA and thioBTA are synthesized and their homo- and copolymerizations are studied using light scattering techniques, infrared, ultraviolet, and circular dichroism spectroscopy. After quantifying the thermodynamic parameters describing the homopolymerizations, we outline a method to follow the self-assembly of thioBTA derivatives in the copolymerization with BTA, which involves monitoring a characteristic spectroscopic signature as a function of temperature and relative concentration. Using modified types of sergeants-and-soldiers and majority-rules experiments, we obtain insights into the degree of aggregation and the net helicity. In addition, we apply a theoretical model of supramolecular copolymerization to substantiate the experimental results. We find that the model describes the two-component system well and allows deriving the hetero-interaction energies. The interactions between the same kinds of monomers (BTA-BTA and thioBTA-thioBTA) are slightly more favorable than those between different monomers (BTA-thioBTA), corresponding to a nearly random copolymerization. Finally, to study the interactions of the monomers at the molecular level, we perform density functional theory-based computations. The results corroborate that the two-component system exhibits a random distribution of the two monomer units along the copolymer chain.

Dataset Information

Equilibrium Model for Supramolecular Copolymerizations.

Publications

Equilibrium Model for Supramolecular Copolymerizations.

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