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1. Permanent and reversibly programmable shapes in liquid crystal elastomer microparticles capable of shape switching

   https://doi.org/10.1039/d0sm01836h  

   Martinez, Alina M.; Cox, Lewis M.; Killgore, Jason P.; Bongiardina, Nicholas J.; Riley, Russell D.; Bowman, Christopher N. (January 2021, Soft Matter)

   null (Ed.)

   Reversibly programmable liquid crystal elastomer microparticles (LCEMPs), formed as a covalent adaptable network (CAN), with an average diameter of 7 μm ± 2 μm, were synthesized via a thiol-Michael dispersion polymerization. The particles were programmed to a prolate shape via a photoinitiated addition–fragmentation chain-transfer (AFT) exchange reaction by activating the AFT after undergoing compression. Due to the thermotropic nature of the AFT-LCEMPs, shape switching was driven by heating the particles above their nematic–isotropic phase transition temperature ( T NI ). The programmed particles subsequently displayed cyclable two-way shape switching from prolate to spherical when at low or high temperatures, respectively. Furthermore, the shape programming is reversible, and a second programming step was done to erase the prolate shape by initiating AFT at high temperature while the particles were in their spherical shape. Upon cooling, the particles remained spherical until additional programming steps were taken. Particles were also programmed to maintain a permanent oblate shape. Additionally, the particle surface was programmed with a diffraction grating, demonstrating programmable complex surface topography via AFT activation. 

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2. Multilayer Hydrogel Microcubes: Effects of Templating Particle Morphology on Cubic Hydrogel Properties

   https://doi.org/10.1002/mame.202300284  

   Inman, Daniel; Kozlovskaya, Veronika; Nikishau, Pavel; Nealy, Sarah; Dolmat, Maksim; Oh, Jonghwa; Lungu, Claudiu_T; Hunter, Lynzi; Kharlampieva, Eugenia (October 2023, Macromolecular Materials and Engineering)

   Abstract Non‐spherical stimuli‐responsive polymeric particles have shown critical importance in therapeutic delivery. Herein, pH‐responsive poly(methacrylic acid) (PMAA) cubic hydrogel microparticles are synthesized by crosslinking PMAA layers within PMAA/poly(N‐vinylpyrrolidone) hydrogen‐bonded multilayers templated on porous inorganic microparticles. This study investigates the effects of template porosity and surface morphology on the PMAA multilayer hydrogel microcube properties. It is found that the hydrogel structure depends on the template's calcination time and temperature. The pH‐triggered PMAA hydrogel cube swelling depends on the hydrogel's internal architecture, either hollow capsule‐like or non‐hollow continuous hydrogels. The loading efficiency of the doxorubicin (DOX) drug inside the microcubes is analyzed by high‐performance liquid chromatography (HPLC), and shows the dependenceof the drug uptake on the network structure and morphology controlled by the template porosity. Varying the template calcination from low (300 °C) to high (1000 °C) temperature results in a 2.5‐fold greater DOX encapsulation by the hydrogel cubes. The effects of hydrogel surface charge on the DOX loading and release are also studied using zeta‐potential measurements. This work provides insight into the effect of structural composition, network morphology, and pH‐induced swelling of the cubical hydrogels and may advance the development of stimuli‐responsive vehicles for targeted anticancer drug delivery. 

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3. Programmable Crowding and Tunable Phases in a Binary Mixture of Colloidal Particles under Light-Driven Thermal Convection

   https://doi.org/10.1021/acs.jpcb.4c02301  

   Lopez-Ceja, Jose; Flores, Vanessa; Juliano, Shirlaine; Machler, Sean; Smith, Stephen; Mansingh, Gargi; Shen, Meng; Tanjeem, Nabila (September 2024, The Journal of Physical Chemistry B)

   We employ photothermally driven self-assembly of colloidal particles to design microscopic structures with programmable size and tunable order. The experimental system is based on a binary mixture of “plasmonic heater” gold nanoparticles and “assembly building block” microparticles. Photothermal heating of the gold nanoparticles under visible light causes a natural convection flow that efficiently assembles the microscale building block particles (diameter 1–10 μm) into a monolayer. We identify the onset of active Brownian motion of colloidal particles under this convective flow by varying the conditions of light intensity, gold nanoparticle concentration, and sample height. We realize a crowded assembly of microparticles around the center of illumination and show that the size of the particle crowd can be programmed using patterned light illumination. In a binary mixture of gold nanoparticles and polystyrene microparticles, we demonstrate the formation of rapid and large-scale crystalline monolayers, covering an area of 0.88 mm2 within 10 min. We find that the structural order of the assembly can be tuned by varying the surface charge of the nanoparticles and the size of the microparticles, giving rise to the formation of different phases–colloidal crystals, crowds, and gels. Using Monte Carlo simulations, we explain how the phases emerge from the interplay between hydrodynamic and electrostatic interactions, as well as the assembly kinetics. Our study demonstrates the promise of self-assembly with programmable shapes and structural order under nonequilibrium conditions using an accessible setup comprising only binary mixtures and LED light. 

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4. Diffusion of Anisotropic Colloidal Microparticles Fabricated Using Two‐Photon Lithography

   https://doi.org/10.1002/ppsc.202100033  

   Doan, David; Kulikowski, John; Gu, X. Wendy (July 2021, Particle & Particle Systems Characterization)

   Abstract Polymeric particles with complex shapes are required for biomedical therapies, colloidal self‐assembly, and micro‐robotics. It has been challenging to synthesize particles beyond simple shapes (e.g., spheres, cubes) with high structural accuracy using existing methods. Here, a method for fabricating polymeric microparticles of complex 3D shapes is reported using two‐photon lithography, and dispersing the particles in an aqueous solution on a glass substrate. The fabrication of polyhedrons (e.g., tetrahedron, pyramid), polypods (e.g., tetrapod, hexapod), and other shapes of 5–10 µm in size is demonstrated. Confocal microscopy is used to track the motion of the sphere, tetrahedron, tetrapod, and screw‐shaped particles near the substrate, and determine their translational diffusion coefficients. HYDRO++ is used to simulate the motion of the particles far from the substrate. The influence of particle size and substrate effects on diffusion in the spherical particles is determined and finds that the non‐spherical particles have increased hindrance at the substrate compared to the spherical particles. 

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5. Viscosity of Mono‐ and Polydisperse Mixtures of Photopolymer and Rigid Spheres for Manufacturing of Engineered Composite Materials Using Vat Photopolymerization

   https://doi.org/10.1002/adem.202301630  

   Reynolds, John; Unterhalter, John; Francoeur, Mathieu; Bortner, Michael; Raeymaekers, Bart (May 2024, Advanced Engineering Materials)

   Vat photopolymerization (VP) additive manufacturing involves selectively curing low‐viscosity photopolymers via exposure to ultraviolet light in a layer‐wise fashion. Dispersing filler materials in the photopolymer enables tailored end‐use properties, but also increases the viscosity and the timescale associated with interparticle network structural recovery postshear. These rheological properties influence self‐leveling and recoating of the liquid photopolymer mixture during VP. Herein, viscosity of photopolymer and rigid spherical glass microparticles (filler) is experimentally determined as a function of filler fraction, filler size distribution (mono‐ and polydisperse), shear rate, and temperature, which are important VP process parameters. Employing existing viscosity models for mono‐ and polydisperse polymer mixtures demonstrates that particle–particle interactions and the formation of nonspherical clusters of particles strongly affect the viscosity of both monodisperse and polydisperse mixtures with particle volume fractions > 0.05 due to agglomeration/deagglomeration of clusters at elevated shear rates. Consequently, unmodified viscosity models, which assume uniformly dispersed, rigid, spherical particles, are applicable only for mixtures with particle volume fractions < 0.05. It is shown that modifying model parameters such as the fluidity limit and intrinsic viscosity, which explicitly account for nonspherical clusters of particles, improves agreement between viscosity models and experiments, in particular when using a fractal approach. 

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