Self-Aggregation in Aqueous Media of Amphiphilic Diblock and Random Block Copolymers Composed of Monomers with Long Side Chains

Sapir Rappoport; Varvara Chrysostomou; Martha Kafetzi; Stergios Pispas; Yeshayahu Talmon

doi:10.1021/acs.langmuir.2c03294

Self-Aggregation in Aqueous Media of Amphiphilic Diblock and Random Block Copolymers Composed of Monomers with Long Side Chains

Langmuir. 2023 Mar 7;39(9):3380-3390. doi: 10.1021/acs.langmuir.2c03294. Epub 2023 Feb 21.

Authors

Sapir Rappoport¹, Varvara Chrysostomou², Martha Kafetzi², Stergios Pispas², Yeshayahu Talmon¹

Affiliations

¹ Department of Chemical Engineering and The Russell Berrie Nanotechnology Institute (RBNI), Technion-Israel Institute of Technology, Haifa 3200003, Israel.
² Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.

PMID: 36802652
DOI: 10.1021/acs.langmuir.2c03294

Abstract

Amphiphilic diblock copolymers and hydrophobically modified random block copolymers can self-assemble into different structures in a selective solvent. The formed structures depend on the copolymer properties, such as the ratio between the hydrophilic and the hydrophobic segments and their nature. In this work, we characterize by cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) the amphiphilic copolymers poly(2-dimethylamino ethyl methacrylate)-b-poly(lauryl methacrylate) (PDMAEMA-b-PLMA) and their quaternized derivatives QPDMAEMA-b-PLMA at different ratios between the hydrophilic and the hydrophobic segments. We present the various structures formed by these copolymers, including spherical and cylindrical micelles, as well as unilamellar and multilamellar vesicles. We also examined by these methods the random diblock copolymers poly(2-(dimethylamino) ethyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate) (P(DMAEMA-co-Q_6/12DMAEMA)-b-POEGMA), which are partially hydrophobically modified by iodohexane (Q₆) or iodododecane (Q₁₂). The polymers with a small POEGMA block did not form any specific nanostructure, while a polymer with a larger POEGMA block formed spherical and cylindrical micelles. This nanostructural characterization could lead to the efficient design and use of these polymers as carriers of hydrophobic or hydrophilic compounds for biomedical applications.