Reversible Perspiring Artificial "Fingertips".

Fingertip perspiration is a vital process within human predation, to which the species owes its survival and its biological success. In this paper, the unique human ability of extensive perspiration and controlled friction in self-assembled cholesteric liquid crystals is recreated, mimicking the natural processes that occur in the dermis and epidermis of human skin. This is achieved by inducing porosity in responsive, liquid-bearing material through the controlled-polymerization phase-separation process. The unique topography of human fingerprints is further emulated in the materials by balancing the parallel chirality-induced force and the perpendicular substrate-anchoring force during synthesis. As a result, artificial fingertips are capable of secreting and re-absorbing liquid upon light illumination. By demonstrating the function of the soft material in a tribological aspect, it exhibits a controllable anti-sliding property comparable to human fingertips and subsequently attains a higher degree of biomimicry. This biomimetic fingertip is envisioned being applied in a multitude of fields, ranging from biomedical instruments to interactive, human-like soft robotic devices.

Uni- and Bidirectional Rotation and Speed Control in Chiral Photonic Micromotors Powered by Light.

Liquid crystalline polymers are attractive materials for untethered miniature soft robots. When they contain azo dyes, they acquire light-responsive actuation properties. However, the manipulation of such photoresponsive polymers at the micrometer scale remains largely unexplored. Here, uni- and bidirectional rotation and speed control of polymerized azo-containing chiral liquid crystalline photonic microparticles powered by light is reported. The rotation of these polymer particles is first studied in an optical trap experimentally and theoretically. The micro-sized polymer particles respond to the handedness of a circularly polarized trapping laser due to their chirality and exhibit uni- and bidirectional rotation depending on their alignment within the optical tweezers. The attained optical torque causes the particles to spin with a rotation rate of several hertz. The angular speed can be controlled by small structural changes, induced by ultraviolet (UV) light absorption. After switching off the UV illumination, the particle recovers its rotation speed. The results provide evidence of uni- and bidirectional motion and speed control in light-responsive polymer particles and offer a new way to devise light-controlled rotary microengines at the micrometer scale.

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

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.

Monodisperse Liquid Crystalline Polymer Shells with Programmable Alignment and Shape Prepared by Seeded Dispersion Polymerization.

Monodisperse, micrometer-sized liquid crystalline (LC) shells are prepared by seeded dispersion polymerization. After polymerizing LC monomer mixtures in the presence of non-crosslinked polymer seeds, hollow LC polymer shells with programmable alignment and shape are prepared by removing the seeds. The LC alignment in the LC polymer shells can be easily manipulated by the polymer seeds, as a radial alignment is observed with amorphous poly(phenyl methacrylate) seeds and a bipolar alignment is observed with bipolar LC polymer seeds. After removal of the seeds, the radially aligned samples give radially aligned shells with small dimples. The resulting bipolar LC polymer shells collapse into a biconcave shape. Polarized optical microscopy and transmission electron microscopy indicate that the collapse occurs at the defect points in the shell. In the case of a lower crosslink density, LC polymer hollow shells with larger dimples are obtained, resulting in cup-shaped polymer particles. Biconcave LC polymer shells based on other LC mixtures have also been prepared, showing the versatility of the seeded dispersion polymerization method.

Wavelength-Selective Photopolymerization of Hybrid Acrylate-Oxetane Liquid Crystals.

We report on the wavelength-selective photopolymerization of a hybrid acrylate-oxetane cholesteric liquid crystal monomer mixture. By controlling the sequence and rate of the orthogonal free-radical and cationic photopolymerization reactions, it is possible to control the degree of phase separation in the resulting liquid crystal interpenetrating networks. We show that this can be used to tune the reflective color of the structurally colored coatings produced. Conversely, the structural color can be used to monitor the degree of phase separation. Our new photopolymerization procedure allows for structuring liquid crystal networks in three dimensions, which has great potential for fabricating liquid crystal polymer materials with programmable functional properties.

Thermoplastic, rubber-like marine antifouling coatings with micro-structures via mechanical embossing.

New processing routes and materials for non-biocidal, antifouling (AF) coatings with an improved performance are currently much sought after for a range of marine applications. Here, the processing, physical properties and marine AF performance of a fluorinated coating based on a thermoplastic (non-crosslinked) fluorinated polymer are reported. It was found that the addition of lubricating oil and hydrodynamic drag reducing microstructures improved the AF properties substantially, i.e. the settlement of a marine biofilm, containing mixed microalgae including diatoms, was reduced to low levels. More importantly, the remaining fouling was removed from the coatings at low hydrodynamic shear rates and promising AF properties were obtained. Moreover, additional potential benefits were revealed originating from the thermoplastic nature of the coating material which might result in significant cost reductions.

Dual Light and Temperature Responsive Micrometer-Sized Structural Color Actuators.

Externally induced color- and shape-changes in micrometer-sized objects are of great interest in novel application fields such as optofluidics and microrobotics. In this work, light and temperature responsive micrometer-sized structural color actuators based on cholesteric liquid-crystalline (CLC) polymer particles are presented. The particles are synthesized by suspension polymerization using a reactive CLC monomer mixture having a light responsive azobenzene dye. The particles exhibit anisotropic spot-like and arc-like reflective colored domains ranging from red to blue. Electron microscopy reveals a multidirectional asymmetric arrangement of the cholesteric layers in the particles and numerical simulations elucidate the anisotropic optical properties. Upon light exposure, the particles show reversible asymmetric shape deformations combined with structural color changes. When the temperature is increased above the liquid crystal-isotropic phase transition temperature of the particles, the deformation is followed by a reduction or disappearance of the reflection. Such dual light and temperature responsive structural color actuators are interesting for a variety of micrometer-sized devices.

Patterned Full-Color Reflective Coatings Based on Photonic Cholesteric Liquid-Crystalline Particles.

An easy approach to pattern angular-independent, multicolor reflective coatings based on cholesteric liquid-crystalline (CLC) particles is presented. CLC particles are fabricated by emulsification, which is a scalable, cost-effective, and environmentally friendly synthesis process. The photonic particles can be easily dispersed in a binder to produce reflective coatings. Furthermore, a simple strategy to remove the photonic cross-communication between the particles has been developed. By incorporating a reactive blue/green absorbing dye into the network structure of the CLC particles the cross-communication is absorbed by the dye, leading to well-defined structural colors. Moreover, we demonstrate the possibility of producing patterned multicolor images by controlled swelling of the particles by the binder.