Synthesis of Polypyrrole and Its Derivatives as a Liquid Marble Stabilizer via a Solvent-Free Chemical Oxidative Polymerization Protocol.

Solvent-free chemical oxidative polymerizations of pyrrole and its derivatives, namely N-methylpyrrole and N-ethylpyrrole, were conducted by mechanical mixing of monomer and solid FeCl3 oxidant under nitrogen atmosphere. Polymerizations occurred at the surface of the oxidant, and optical and scanning electron microscopy studies confirmed production of atypical grains with diameters of a few tens of micrometers. Fourier transform infrared spectroscopy studies indicated the presence of hydroxy and carbonyl groups which were introduced during the polymerization due to overoxidation. The polymer grains were doped with chloride ions, and the chloride ion dopant could be removed by dedoping using an aqueous solution of sodium hydroxide, which was confirmed by elemental microanalysis and X-ray photoelectron spectroscopy studies. Water contact angle measurements confirmed that the larger the alkyl group on the nitrogen of pyrrole ring the higher the hydrophobicity and that the contact angles increased after dedoping in all cases. The grains before and after dedoping exhibited photothermal properties: the near-infrared laser irradiation induced a rapid temperature increase to greater than 430 °C. Furthermore, dedoped poly(N-ethylpyrrole) grains adsorbed to the air-water interface and could work as an effective liquid marble stabilizer. The resulting liquid marble could move on a planar water surface due to near-infrared laser-induced Marangoni flow and could disintegrate by exposure to acid vapor via redoping of the poly(N-ethylpyrrole) grains.

Multimotion of Marangoni Propulsion Ships Controlled by Two-Wavelength Near-Infrared Light.

Multimode motion of Marangoni propulsion ships on a water surface as per a near-infrared, two-wavelength selective response is achieved for the first time. The ships are rhombus- or propeller-shaped polyacrylamide or siloxane resin-based gels in which Nd2O3 and Yb2O3 nanoparticles are incorporated separately for photothermal conversion at 808 and 980 nm, respectively. The rhombus geometry is for straight locomotion, and the propeller geometry is for rotation. On/off remote control of the forward and backward locomotion of a rhombus-shaped ship and of the clockwise and counterclockwise rotations of a propeller-shaped ship via irradiation with 808 or 980 nm near-infrared light is demonstrated. The nanoparticles are incorporated into the desired locations of the gels, enabling selective local heating of the gels without focusing the light. The temperature gradient of the ships by local heating, based on a photothermal conversion, generates a Marangoni propulsion force to move the ship in the desired direction.

Controllable Positive/Negative Phototaxis of Millimeter-Sized Objects with Sensing Function.

Phototaxis, which is the directional motion toward or away from light, is common in nature and inspires development of artificial light-steered active objects. Most of the light-steered objects developed so far exhibit either positive or negative phototaxis, and there are few examples of research on objects that exhibit both positive and negative phototaxis. Herein, small objects showing both positive and negative phototaxis on the water surface upon near-infrared (NIR) light irradiation, with the direction controlled by the position of light irradiation, are reported. The millimeter-sized tetrahedral liquid marble containing gelled water coated by one polymer plate with light-to-heat photothermal characteristic, which adsorbs onto the bottom of the liquid marble, and three polymer plates with highly transparent characteristic, which adsorb onto the upper part of the liquid marble, is utilized as a model small object. Light irradiation on the front side of the object induces negative phototaxis and that on the other side induces positive phototaxis, and the motion can be controlled to 360° arbitrary direction by precise control of the light irradiation position. Thermographic studies confirm that the motions are realized through Marangoni flow generated around the liquid marble, which is induced by position-selective NIR light irradiation. The object can move centimeter distances, and numerical analysis indicates that average velocity and acceleration are approximately 12 mm/s and 71 mm/s2, respectively, which are independent of the direction of motions. The generated force is estimated to be approximately 0.4 µN based on Newton's equation. Furthermore, functional cargo can be loaded into the inner phase of the small objects, which can be delivered and released on demand and endows them with environmental sensing ability.

Locomotion of a Nonaqueous Liquid Marble Induced by Near-Infrared-Light Irradiation.

Micrometer-sized hydrophobic polyaniline (PANI) grains were synthesized via an aqueous chemical oxidative polymerization protocol in the presence of dopant carrying perfluoroalkyl or alkyl groups. The critical surface tensions of the PANIs synthesized in the presence of heptadecafluorooctanesulfonic acid and sodium dodecyl sulfate dopants were lower than that of PANI synthesized in the absence of dopant, indicating the presence of hydrophobic dopant on the grain surfaces. The PANI grains could adsorb to air-liquid interfaces, and aqueous and nonaqueous liquid marbles (LMs) were successfully fabricated using liquids with surface tensions ranging between 72.8 and 42.9 mN/m. Thermography studies confirmed that the surface temperature of the LMs increased by near-infrared light irradiation thanks to the photothermal property of the PANI, and the maximum temperatures measured for nonaqueous LMs were higher than that measured for aqueous LM. We demonstrated that transport of the LMs on a planar water surface can be achieved via Marangoni flow generated by the near-infrared light-induced temperature gradient. Numerical analyses indicated that the LMs containing liquids with lower specific heat and thermal conductivity and higher density showed longer path length per one light irradiation shot and longer decay time. This is because generated heat could efficiently transfer from the LMs to the water surface and larger inertial force could work on the LMs. The LMs could also move over the solid substrate thanks to their near-spherical shapes. Furthermore, it was also demonstrated that the inner liquids of the LMs could be released on site by an external stimulus.