3D Printing of Aqueous Two-Phase Systems with Linear and Bottlebrush Polyelectrolytes.

We formed core-shell-like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes could be tuned by the conformation of the BBs. By combining the linear/bottlebrush polyelectrolyte complexation with all-liquid 3D printing, flow-through tubular constructs were produced that showed selective transport across the PEC membrane comprising the walls of the tubules. These tubular constructs afford a new platform for flow-through delivery systems.

Mixed Nanosphere Assemblies at a Liquid-Liquid Interface.

The in-plane packing of gold (Au), polystyrene (PS), and silica (SiO2) spherical nanoparticle (NP) mixtures at a water-oil interface is investigated in situ by UV-vis reflection spectroscopy. All NPs are functionalized with carboxylic acid such that they strongly interact with amine-functionalized ligands dissolved in an immiscible oil phase at the fluid interface. This interaction markedly increases the binding energy of these nanoparticle surfactants (NPSs). The separation distance between the Au NPSs and Au surface coverage are measured by the maximum plasmonic wavelength (λmax) and integrated intensities as the assemblies saturate for different concentrations of non-plasmonic (PS/SiO2) NPs. As the PS/SiO2 content increases, the time to reach intimate Au NP contact also increases, resulting from their hindered mobility. λmax changes within the first few minutes of adsorption due to weak attractive inter-NP forces. Additionally, a sharper peak in the reflection spectrum at NP saturation reveals tighter Au NP packing for assemblies with intermediate non-plasmonic NP content. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) measurements confirm a decrease in Au NP domain size for mixtures with larger non-plasmonic NP content. The results demonstrate a simple means to probe interfacial phase separation behavior using in situ spectroscopy as interfacial structures densify into jammed, phase-separated NP films.

Investigating Time-Dependent Active Motion of Janus Micromotors using Dynamic Light Scattering.

Advances in fabrication methods have positioned Janus micromotors (JMs) as candidates for use as autonomous devices in applications across diverse fields, spanning drug delivery to environmental remediation. While the design of most micromotors is straightforward, the non-steady state active motion exhibited by these systems is complex and difficult to characterize. Traditionally, JM active motion is characterized using optical microscopy single particle tracking for systems confined in 2D. Dynamic light scattering (DLS) offers an alternative high-throughput method for characterizing the 3D active motion in bulk JM dispersions with additional capabilities to quantify time-dependent behavior for a broader range of JM sizes. Here, the active motion of spherical JMs is examined by DLS and it is demonstrated that the method enables decoupling of the translational and rotational diffusion. Systematic studies quantifying the time-dependent diffusive properties as a function of fuel concentration, JM concentration, and time after fuel addition are presented. The analyses presented in this work position DLS to facilitate future advances of JM systems by serving as a fast-screening characterization method for active motion.