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Wettability Engendered Templated Self-Assembly (WETS) for the Fabrication of Biocompatible, Polymer-Polyelectrolyte Janus Particles.

ABSTRACT: Fabrication of charged, multiphasic, polymeric micro- and nanoparticles with precise control over their composition, size, and shape is critical for developing the next generation of drug carriers for combinatorial therapies and theranostics. The addition of charged polyelectrolyte multilayers on the surface of polymeric particles can significantly improve their stability, targeting efficacy, drug-release kinetics, and their ability to encapsulate different drugs within a single particle. Many of the traditional methods for multilayer functionalization of multiphasic polymeric particles are time and energy intensive which significantly limits their scalability, and therefore therapeutic potential. In this work, we combine the bulk layer-by-layer polyelectrolyte application methodology with our previously developed technique of fabricating multiphasic polymeric particles on substrates with patterned wettability to synthesize biocompatible, monodisperse, Janus polymer-polyelectrolyte particles.

SUBMITTER: Kobaku SPR

PROVIDER: S-EPMC9178926 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Wettability Engendered Templated Self-Assembly (WETS) for the Fabrication of Biocompatible, Polymer-Polyelectrolyte Janus Particles.

Kobaku Sai P R SPR Snyder Catherine S CS Karunakaran Raghuraman G RG Kwon Gibum G Wong Philip P Tuteja Anish A Mehta Geeta G

ACS macro letters 20191025 11

Fabrication of charged, multiphasic, polymeric micro- and nanoparticles with precise control over their composition, size, and shape is critical for developing the next generation of drug carriers for combinatorial therapies and theranostics. The addition of charged polyelectrolyte multilayers on the surface of polymeric particles can significantly improve their stability, targeting efficacy, drug-release kinetics, and their ability to encapsulate different drugs within a single particle. Many o ...[more]

PMID: 35651187

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Project description:Janus particles exhibit a strong tendency to directionally assemble and segregate to interfaces and thus offer advantages as colloidal analogues of molecular surfactants to improve the stability of multiphasic mixtures. Investigation and application of the unique adsorption properties require synthetic procedures that enable careful design and reliable control over the particles' asymmetric chemistry and wettability profiles with high morphological uniformity across a sample. Herein, we report on a novel one-step synthetic approach for the generation of amphiphilic polymer Janus particles with highly uniform and tunable wettability contrasts, which is based on using reconfigurable bi-phasic Janus emulsions as versatile particle scaffolds. Two phase-separated acrylate oils were used as the constituent droplet phases and transformed into their solidified Janus particle replicas via UV-induced radical polymerization. Using Janus emulsions as particle precursors offers the advantage that their internal droplet geometry can be fine-tuned by changing the force balance of surface tensions acting at the individual interfaces via surfactants or the volume ratio of the constituent phases. In addition, preassembled functional surfactants at the droplet interfaces can be locked in position upon polymerization, which enables both access toward postfunctionalization reaction schemes and the generation of highly uniform Janus particles with adjustable wettability profiles. Depending on the particle morphology and wettability, their interfacial position can be adjusted, which allows us to stabilize either air bubbles-in-water or water droplets-in-air (liquid marbles). Motivated by the interfacial activity of the particles and particularly the longevity of the resulting particle-stabilized air-in-water bubbles, we explored their ability to promote the delivery of oxygen inside a liquid-phase reaction medium, namely, for the heterogeneous Au-NP-mediated catalytic oxidation of d-glucose. We observed a 2.2-fold increase in the reaction rate attributed to the increase of the local concentration of oxygen around catalysts, thus showcasing a new strategy to overcome the limited solubility of gases in aqueous reaction media.

Project description:Immobilizing particles on beads, fibers, or filaments, when only one side is exposed to the reaction medium and therefore can be selectively functionalized, is a scalable and easy to control strategy for the fabrication of amphiphilic Janus particles. Here we describe a new, robust method for the fabrication of amphiphilic Janus particles based on immobilization of polymethylsilsesquioxane (PMSQ) particles on polycarbonate (PC), a high impact-resistance polymer with superior mechanical properties. The immobilization of the particles on the PC microspores is performed via inverse solvent displacement method. PMSQ particles are added to a PC solution in tetrahydrofuran (THF), a good solvent for PC. The solution is then precipitated by the introduction of aqueous surfactant solution (antisolvent for PC) under an ultrasonic field. It is important to note that THF and water are miscible and do not form emulsion. During precipitation, PMSQ particles are assembled onto the surface of the PC spherical precipitates/microspheres. The exposed hemispheres of the PMSQ particles are then selectively silanized by (3-Aminopropyl)triethoxysilane (APTES) to introduce amine groups on their surface. To increase the polarity of the functionalized hemispheres, the amine groups are further modified to introduce carboxyl groups. SEM characterization confirms the fine embedment of PMSQ particles onto the PC microspheres. Covalent attachment of silica nanoparticles (NPs) to the functionalized hemispheres of the resulting particles along with fluorescent confocal microscopy conclusively prove the successful fabrication of amphiphilic Janus particles. The immobilization of particles onto highly rigid polymeric microspheres such as PC may pave the way for the development of a robust fabrication procedure with high resistance to temperature fluctuations and harsh mixing conditions that can arise during preparation. This method can be implemented toward a large variety of other synthetic commercial polymers such as polyamide, polyether sulfones, Polyether, ether ketone, or similar.

Dataset Information

Wettability Engendered Templated Self-Assembly (WETS) for the Fabrication of Biocompatible, Polymer-Polyelectrolyte Janus Particles.

Publications

Wettability Engendered Templated Self-Assembly (WETS) for the Fabrication of Biocompatible, Polymer-Polyelectrolyte Janus Particles.

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