Recently, photo-controlled reversible addition-fragmentation chain transfer (RAFT) polymerization has been successfully applied in digital light processing 3D printing. It provides a convenient way to tune the surface properties of the 3D printed object. However, so far, 3D micro-and nanostructures and reconfigurations based on photo-induced RAFT polymerization have not been presented. In this work, one macro-photoiniferter, synthesized by photocontrolled RAFT polymerization is applied, to 3D direct laser writing. Thanks to the exquisite spatial control of the photoreaction, 3D microstructures with feature sizes of around 500 nm are successfully obtained. Taking advantage of the presence of dormant polymeric RAFT agents, photo-induced postmodification of the printed microstructures is highlighted via the elaboration of multi-chemistry patterns including thermo-responsive ones. These results open new perspectives in multi-material and 4D micro-printing.
Most current methods for the preparation of tissue spheroids require complex materials, involve tedious physical steps and are generally not scalable. We report a novel alternative, which is both inexpensive and up-scalable, to produce large quantities of viable human keratinocyte cell clusters (clusteroids). The method is based on a two-phase aqueous system of incompatible polymers forming a stable water-in-water (w/w) emulsion, which enabled us to rapidly fabricate cell clusteroids from HaCaT cells. We used w/w Pickering emulsion from aqueous solutions of the polymers dextran (DEX) and polyethylene oxide (PEO) and a particle stabilizer based on whey protein (WP). The HaCaT cells clearly preferred to distribute into the DEX-rich phase and this property was utilized to encapsulate them in the water-in-water (DEX-in-PEO) emulsion drops then osmotically shrank to compress them into clusters. Prepared formulations of HaCaT keratinocyte clusteroids in alginate hydrogel were grown where the cells percolated to mimic 3D tissue. The HaCaT cell clusteroids grew faster in the alginate film compared to the individual cells formulated in the same matrix. This methodology could potentially be utilised in biomedical applications.
The miniaturization of tools is an important step in human evolution to create faster devices as well as precise micromachines. Studies around this topic have allowed the creation of small-scale objects capable of a wide range of deformation to achieve complex tasks. Molecular arrangements have been investigated through liquid crystal polymer (LCP) to program such a movement. Smart polymers and hereby liquid crystal matrices are materials of interest for their easy structuration properties and their response to external stimuli. However, up until very recently, their employment at the microscale was mainly limited to 2D structuration. Among the numerous issues, one concerns the ability to 3D structure the material while controlling the molecular orientation during the polymerization process. This review aims to report recent efforts focused on the microstructuration of LCP, in particular those dealing with 3D microfabrication via two-photon polymerization (TPP). Indeed, the latter has revolutionized the production of 3D complex micro-objects and is nowadays recognized as the gold standard for 3D micro-printing. After a short introduction highlighting the interest in micromachines, some basic principles of liquid crystals are recalled from the molecular aspect to their implementation. Finally, the possibilities offered by TPP as well as the way to monitor the motion into the fabricated microrobots are highlighted.
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