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Flower-Like Colloidal Particles through Precipitation Polymerization of Redox-Responsive Liquid Crystals.

ABSTRACT: We report on the synthesis of monodisperse, flower-like, liquid crystalline (LC) polymer particles by precipitation polymerization of a LC mixture consisting of benzoic acid-functionalized acrylates and disulfide-functionalized diacrylates. Introduction of a minor amount of redox-responsive disulfide-functionalized diacrylates (≤10 wt %) induced the formation of flower-like shapes. The shape of the particles can be tuned from flower- to disk-like to spherical by elevating the polymerization temperature. The solvent environment also has a pronounced effect on the particle size. Time-resolved TEM reveals that the final particle morphology was formed in the early stages of the polymerization and that subsequent polymerization resulted in continued particle growth without affecting the morphology. Finally, the degradation of the particles under reducing conditions was much faster for flower-like particles than for spherical particles, likely a result of their higher surface-to-volume ratio.

SUBMITTER: Liu X

PROVIDER: S-EPMC9298913 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Flower-Like Colloidal Particles through Precipitation Polymerization of Redox-Responsive Liquid Crystals.

Liu Xiaohong X Moradi Mohammad-Amin MA Bus Tom T Debije Michael G MG Bon Stefan A F SAF Heuts Johan P A JPA Schenning Albert P H J APHJ

Angewandte Chemie (International ed. in English) 20211117 52

We report on the synthesis of monodisperse, flower-like, liquid crystalline (LC) polymer particles by precipitation polymerization of a LC mixture consisting of benzoic acid-functionalized acrylates and disulfide-functionalized diacrylates. Introduction of a minor amount of redox-responsive disulfide-functionalized diacrylates (≤10 wt %) induced the formation of flower-like shapes. The shape of the particles can be tuned from flower- to disk-like to spherical by elevating the polymerization temp ...[more]

PMID: 34672077

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Project description:This feature article describes recent advances in several areas of research involving the interfacial ordering of liquid crystals (LCs). The first advance revolves around the ordering of LCs at bio/chemically functionalized surfaces. Whereas the majority of past studies of surface-induced ordering of LCs have involved surfaces of solids that present a limited diversity of chemical functional groups (surfaces at which van der Waals forces dominate surface-induced ordering), recent studies have moved to investigate the ordering of LCs on chemically complex surfaces. For example, surfaces decorated with biomolecules (e.g., oligopeptides and proteins) and transition-metal ions have been investigated, leading to an understanding of the roles that metal-ligand coordination interactions, electrical double layers, acid-base interactions, and hydrogen bonding can play in the interfacial ordering of LCs. The opportunity to create chemically responsive LCs capable of undergoing ordering transitions in the presence of targeted molecular events (e.g., ligand exchange around a metal center) has emerged from these fundamental studies. A second advance has focused on investigations of the ordering of LCs at interfaces with immiscible isotropic fluids, particularly water. In contrast to prior studies of surface-induced ordering of LCs on solid surfaces, LC-aqueous interfaces are deformable and molecules at these interfaces exhibit high levels of mobility and thus can reorganize in response to changes in the interfacial environment. A range of fundamental investigations involving these LC-aqueous interfaces have revealed that (i) the spatial and temporal characteristics of assemblies formed from biomolecular interactions can be reported by surface-driven ordering transitions in the LCs, (ii) the interfacial phase behavior of molecules and colloids can be coupled to (and manipulated via) the ordering (and nematic elasticity) of LCs, and (iii) the confinement of LCs leads to unanticipated size-dependent ordering (particularly in the context of LC emulsion droplets). The third and final advance addressed in this article involves interactions between colloids mediated by LCs. Recent experiments involving microparticles deposited at the LC-aqueous interface have revealed that LC-mediated interactions can drive interfacial assemblies of particles through reversible ordering transitions (e.g., from 1D chains to 2D arrays with local hexagonal symmetry). In addition, recent single-nanoparticle measurements suggest that the ordering of LCs about nanoparticles differs substantially from micrometer-sized particles and that the interactions between nanoparticles mediated by the LCs are far weaker than predicted by theory (sufficiently weak that the interactions are reversible and thus enable self-assembly). Finally, LC-mediated interactions between colloidal particles have also been shown to lead to the formation of colloid-in-LC gels that possess mechanical properties relevant to the design of materials that interface with living biological systems. Overall, these three topics serve to illustrate the broad opportunities that exist to do fundamental interfacial science and discovery-oriented research involving LCs.

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Flower-Like Colloidal Particles through Precipitation Polymerization of Redox-Responsive Liquid Crystals.

Publications

Flower-Like Colloidal Particles through Precipitation Polymerization of Redox-Responsive Liquid Crystals.

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