Non-Aqueous Polyhedral Liquid Marbles Stabilized with Polymer Plates Having Surface Roughness.

Hydrophobic polymer plates with smooth and rough surfaces are used as a stabilizer for cubic liquid marbles (LMs) to study the effect of surface roughness on their formation. The smooth and rough polymer plates can stabilize LMs using liquids with surface tensions of 72.8-26.6 and 72.8-22.9 mN m-1, respectively. It is clarified that the higher the surface roughness, the lower the surface tension of the liquids are stabilized to form the LMs. These results indicated that the introduction of surface roughness improves the hydrophobicity of the polymer plates and the rough polymer plates can stabilize LMs using liquids with a wider surface tension range. Electron microscopy studies and numerical analyses confirmed that the LMs can be formed, when the Cassie-Baxter wetting state, where θY>90° (θY: the contact angle on smooth surfaces) and θR>90° (θR: the contact angle on rough surfaces), and the metastable Cassie-Baxter wetting state, where θY<90° and θR>90°, are realized. Finally, the synthesis of cubic polymer particles are succeeded by free radical polymerization of the cubic LMs containing a hydrophobic vinyl monomer (dodecyl acrylate) in a solvent-free manner.

Nitrogen-Containing Carbon Tubes Fabricated by Light Irradiation.

Cotton-core/polypyrrole (PPy)-sheath fibers (cotton/PPy fibers) were synthesized by aqueous chemical oxidative seeded polymerization and were utilized as precursors for nitrogen-containing carbon (NCC) tubes. Irradiation of the cotton/PPy fibers with a near-infrared (NIR) laser heated them to approximately 300 °C due to light-to-heat photothermal conversion by the PPy, and the cotton core was thermally decomposed and vaporized. Scanning electron microscopy studies revealed the formation of tubes with monodispersed diameters, and elemental microanalysis, Fourier transform infrared spectroscopy, and Raman spectroscopy confirmed that the PPy sheath was converted into NCC. Furthermore, sunlight also worked as the light source in fabricating the NCC tubes. The thicknesses of the tubes were controlled between 410 nm and 2.30 µm by tuning the PPy sheath thickness. The method developed in this study can be extended to other polymeric fibers, including acrylic and wool fibers. The shapes of the cross sections and surface nanomorphologies of the NCC tubes can be reflected in those of the polymer/PPy fibers.

Dynamics of Nanocomposite Hydrogel Alignment during 3D Printing to Develop Tissue Engineering Technology.

Taking inspiration from spider silk protein spinning, we developed a method to produce tough filaments using extrusion-based 3D bioprinting and salting-out of the protein. To enhance both stiffness and ductility, we have designed a blend of partially crystalline, thermally sensitive natural polymer gelatin and viscoelastic G-polymer networks, mimicking the components of spider silk. Additionally, we have incorporated inorganic nanoparticles as a rheological modifier to fine-tune the 3D printing properties. This self-healing nanocomposite hydrogel exhibits exceptional mechanical properties, biocompatibility, shear thinning behavior, and a well-controlled gelation mechanism for 3D printing.

Polyhedral Vinyl Polymer Particles Synthesized Via Solvent-Free Radical Polymerization.

Liquid marbles (LMs) with a cubic shape are created by using various vinyl monomers as an inner liquid and polymer plates with mm size as a stabilizer. The relationship between the surface tension of the vinyl monomers and formability of the LMs is investigated. LMs can be fabricated using vinyl monomers with surface tensions of 42.7-40.3 mN m-1. The cubic polymer particles are successively synthesized via free-radical polymerizations by irradiation of the cubic LMs with UV light in a solvent-free manner. In addition, controlling the number of polymer plates per one LM, the shape of the plate or the coalescence of the LMs can lead to production of polymer particles with desired forms (e.g., Platonic and rectangular solids) that correspond to the shapes of the original LMs.

Aqueous Bubbles Stabilized with Millimeter-Sized Polymer Plates.

(Sub)millimeter-sized hexagonal polymer plates that were monodisperse in shape and size were utilized as stabilizers for aqueous bubbles, and the effects of the hydrophilic-hydrophobic property, size, and solid concentration of the plates on the formability, stability, and shape and structure of aqueous bubbles were investigated. The formability and stability of the bubbles were improved by increasing the hydrophobicity of the plate surface, decreasing the plate size, and increasing the solid concentration of the plates. For plates with suitable water wettability, three-dimensional bubbles with nearly spherical and polyhedral shapes were formed by the adsorption of plates to the bare air bubbles introduced into the continuous water phase by air-water mixing. On the contrary, two-dimensional bubbles with accordion-type structures consisting of alternating layers of plates and entrapped air bubbles were formed by the transfer of multiple plates with poor wettability from the air phase to the water phase by air-water mixing. Furthermore, a correlation was found between the bubble/stabilizer size ratio and bubble shape for plates with the suitable wettability: bubbles with nearly spherical shapes were formed when the bubble/plate size ratios were >2, bubbles with hexahedral, pentahedral, and tetrahedral shapes were formed when the size ratios were approximately 1, and bubbles with triangular and sandwich shapes were formed when the size ratios were <0.8. Additionally, bubbles with similar shapes were formed when the bubble/plate size ratios were close, even when the sizes of the plates and bubbles were different.

Photo- and Thermoresponsive Liquid Marbles Based on Fatty Acid as Phase Change Material Coated by Polypyrrole: From Design to Applications.

Responsive liquid marbles (LMs), which can change their shape, stability, and motion by the application of stimuli, attract a growing interest due to their wide range of applications. Our approach to design photo- and thermoresponsive LMs is based on the use of micrometer-sized fatty acid (FA) particles as phase change material covered with polypyrrole (PPy) overlayers with photothermal property. The core-shell particles were synthesized by aqueous chemical oxidative seeded dispersion polymerization. First, we investigated the effect of the alkyl chain length of FA on the resulting FA/PPy core-shell particles by characterizing their size and its distribution, shape, morphology, chemical composition, and photothermal behavior. Then LMs were fabricated by rolling water droplets on the dried FA/PPy particle powder bed and their light and temperature dual stimuli-responsive nature was studied as a function of the FA alkyl chain length. For all FAs studied, LMs disrupted in a domino manner by light irradiation as the first trigger: the temperature of the FA/PPy particles on the LM surface increased by light irradiation, followed by phase change of FA core of the particles from solid to liquid, resulting in disruption of the LM and release of the encapsulated water. The disruption time was closely correlated to the melting point of FA linked to the alkyl chain length and light irradiation power, and it could be controlled and tuned easily between quasi instantaneous and approximately 10 s. Finally, we showed potential applications of the LMs as a carrier for controlled delivery and release of substances and a sensor.

Nonspherical Epoxy Resin Polymer Particles Synthesized via Solvent-Free Polyaddition Reactions.

Cubic liquid marbles (LMs) were fabricated by using various epoxy monomers as internal liquids and millimeter-sized polymer plates as stabilizers. Successively, cubic polymer particles were synthesized via solvent-free polyaddition reactions by exposing the cubic LMs to NH3 vapor used as a curing agent. The effect of the solubility parameters (SPs) for the epoxy monomers on the formation of the cubic polymer particles was investigated. As a result, we succeeded in fabricating cubic polymer particles reflecting the shapes of the original LMs by using epoxy monomers with SP values of 23.70-21.66 (MPa)1/2. Furthermore, the shapes of the LMs could be controlled on demand (e.g., pentahedral and rectangular) by control of the number of polymer plates per LM and/or coalescence of the LMs, resulting in fabrication of polymer particles with shapes reflecting those of the LMs.

Colloidally Stable Polypyrrole Nanoparticles Synthesized by Surfactant-Free Coupling Polymerization.

Surfactant-free polypyrrole (PPy) nanoparticles, which were colloidally stable in aqueous medium, were successfully synthesized by coupling polymerization of pyrrole using Fe(NO3)3 solids in the absence of any colloidal stabilizer. The pyrrole monomers were gradually supplied from the vapor phase, and the coupling reaction of the monomers could proceed to generate PPy in a water medium. The resulting PPy nanoparticles were extensively characterized in terms of diameter, bulk chemical composition, surface chemistry, and colloidal stability by dynamic light scattering, electron microscopy, elemental microanalysis, Fourier transform infrared spectroscopy, Raman spectroscopy, electrophoresis, and X-ray photoelectron spectroscopy. The characterization results indicated that the PPy nanoparticles can be colloidally stable based on the electrostatic stabilization mechanism due to cationic charges generated on the PPy molecules by doping during the polymerization. General chemical oxidative polymerization in aqueous medium using the Fe(NO3)3 oxidant without a colloidal stabilizer as a control experiment resulted in generation of atypical PPy aggregates with over a micrometer size, indicating that the polymerization at low ionic strength is essential for colloidal particle formation. Finally, it was demonstrated that the PPy nanoparticles worked as a surfactant-free black-colored particulate emulsifier by adsorption at the oil-water interface to stabilize Pickering-type oil-in-water emulsions.

A Highly Conductive n-Type Coordination Complex with Thieno[3,2-b]thiophene Units: Facile Synthesis, Orientation, and Thermoelectric Properties.

An organometallic nickel complex containing thieno[3,2-b]thiophene units was designed and synthesized. Composite films of the resulting nickel complex and polyvinylidene difluoride, which can be fabricated via a simple solution process under atmospheric conditions, exhibit remarkably high n-type conductivity (>200 S cm-1). Moreover, the thermoelectric power factor of the n-type composite film was proven to be air stable. A grazing-incidence wide-angle X-ray diffraction analysis indicated a significant impact of introducing the thieno[3,2-b]thiophene core into the backbone of the nickel complex on the orientation within the composite films.

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.

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.

Monodispersed Nitrogen-Containing Carbon Capsules Fabricated from Conjugated Polymer-Coated Particles via Light Irradiation.

Near-infrared (NIR) light irradiation induced the transformation of polypyrrole (PPy) to nitrogen-containing carbon (NCC) material due to its light-to-heat photothermal property. The temperature of the PPy increased over 700 °C within a few seconds by the NIR laser irradiation, and elemental microanalysis confirmed the decreases of hydrogen and chloride contents and increases of carbon and nitrogen contents. Monodispersed polystyrene (PS)-core/PPy shell particles (PS/PPy particles) synthesized by aqueous chemical oxidative seeded polymerization were utilized as a precursor toward monodispersed NCC capsules. When the NIR laser was irradiated to the PS/PPy particles, the temperature rose to approximately 300 °C and smoke was generated, indicating that the PS component forming the core was thermally decomposed and vaporized. Scanning electron microscopy studies revealed the successful formation of spherical and highly monodispersed capsules, and Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy studies confirmed the capsules consisted of NCC materials. Furthermore, sunlight was also demonstrated to work as a light source to fabricate NCC capsules. The size and thickness of the capsules can be controlled between 1 and 80 µm and 146 and 231 nm, respectively, by tuning the size of the original PS/PPy particles and PPy shell thickness.

Effect of Stabilizing Particle Size on the Structure and Properties of Liquid Marbles.

A liquid marble (LM) describes a liquid droplet that is wrapped by nonwetting micro- or nanoparticles and therefore obtains characteristics of a solid powder particle. Here, we investigate the effect of the stabilizing particle size on the resulting structure and properties of the LM. We synthesize a series of polystyrene particles with ultrathin coatings of heptadecafluorooctanesulfonic acid-doped polypyrrole with diameters ranging between 1 and 1000 µm by an aqueous chemical oxidative seeded polymerization of pyrrole. The methodology produced a set of hydrophobic particles with similar surface characteristics to allow the formation of LMs and to probe size effects in the LM formation and stabilization efficiency. We found that particles with a size above 20 µm adsorb as a particle monolayer to the surface of the LM, while smaller particles are adsorbed as ill-defined, multilayered aggregates. These results indicate that the balance between particle-particle interaction and gravity is an important parameter to control the surface structure of the LMs. The assembly behavior and size of the particles also correlated with the mechanical integrity of the LM against fall impact. The mechanical resistance was affected by the gap distance between the inner liquid of the LM and supporting substrate, the capillary forces acting between the particles at the LM surface, and the potential energy that depended on the particle size. Last, we demonstrate that the broadband light-absorbing properties of the polypyrrole shell also allow manipulating the evaporation rate of the inner liquid.

Morphology Changes in Perfluorosulfonated Ionomer from Thickness and Thermal Treatment Conditions.

The morphological changes of Nafion thin films with thicknesses from 10 to 200 nm on Pt substrate with various annealing histories (unannealed to 240 °C) were systematically investigated using grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS). The results revealed that the hydrophilic ionic domain and hydrophobic backbone in Nafion thin films changed significantly when the annealing treatment exceeded the cluster transition temperature, which decreased proton conductivity, due to the constrained hydrophilic/hydrophobic phase separation, and increased the crystalline-rich domain. This research contributed to the understanding of ionomer thermal stability in the catalyst layer, which is subjected to thermal annealing during the hot-pressing process.

Liquid Marbles in Nature: Craft of Aphids for Survival.

Some aphids that live in the leaf galls of the host plant are known to fabricate liquid marbles consisting of honeydew and wax particles as an inner liquid and a stabilizer, respectively. In this study, the liquid marbles fabricated by the galling aphids, Eriosoma moriokense, were extensively characterized with respect to size and size distribution, shape, nanomorphology, liquid/solid weight ratio, and chemical compositions. The stereo microscopy studies confirmed that the liquid marbles have a near-spherical morphology and that the number-average diameter was 368 ± 152 µm, which is 1 order of magnitude smaller than the capillary length of the honeydew. The field emission scanning electron microscopy studies indicated that micrometer-sized wax particles with fiber- and dumpling-like shapes coated the honeydew droplets, which rendered the liquid marbles hydrophobic and nonwetting. Furthermore, the highly magnified scanning electron microscopy images confirmed that the wax particles were formed with assemblage of submicrometer-sized daughter fibers. The contact angle measurements indicated that the wax was intrinsically hydrophobic and that the liquid marbles were stabilized by the wax particles in the Cassie-Baxter model. The weight ratio of the honeydew and the wax particles was determined to be 96/4, and the honeydew consisted of 19 wt % nonvolatile components and 81 wt % water. The 1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, and mass spectroscopy studies confirmed that the wax mainly consisted of triglycerides and that the honeydew mainly consisted of saccharides (glucose and fructose) and ribitol. The atomic force microscopy studies confirmed that honeydew is sticky in nature.

Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity.

Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.

Depth-Resolved Characterization of Perylenediimide Side-Chain Polymer Thin Film Structure Using Grazing-Incidence Wide-Angle X-ray Diffraction with Tender X-rays.

Polymers with a perylenediimide (PDI) side chain (PAc12PDI) consist of two kinds of crystalline structures with various types of orientations in a thin film. Understanding the population of the microcrystalline structure and its orientation along the thickness is strongly desired. Grazing-incidence wide-angle X-ray diffraction (GIWAXD) measurements with hard X-rays, which are generally chosen as λ = 0.1 nm, are a powerful tool to evaluate the molecular aggregation structure in thin films. A depth-resolved analysis for the outermost surface of the polymeric materials using conventional GIWAXD measurements, however, has limitations on depth resolution because the X-ray penetration depth dramatically increases above the critical angle. Meanwhile, tender X-rays (λ = 0.5 nm) have the potential advantage that the penetration depth gradually increases above the critical angle, leading to precise characterization for the population of crystallite distribution along the thickness. The population of the microcrystalline states in the PAc12PDI thin film was precisely characterized utilizing GIWAXD measurements using tender X-rays. The outermost surface of the PAc12PDI thin film is occupied by a monoclinic lattice with a = 2.38 nm, b = 0.74 nm, c = 5.98 nm, and ß = 108.13°, while maintaining the c-axis perpendicular to the substrate surface. Additionally, the presence of solid substrate controls the formation of the crystallite with unidirectional orientation.

Preparation of High-Density Polymer Brushes with a Multihelical Structure.

It is well-known that a mixture of isotactic and syndiotactic polymethyl methacrylate (PMMA) forms a stereocomplex consisting of a multihelical structure in which an isotactic chain is surrounded by a syndiotactic chain. Here, we report the basic structure of the stereocomplex formed when the syndiotactic PMMA chains are tethered to a silicon substrate and form a high-density polymer brush. The influence of geometric confinement was investigated by preparing the high-density polymer brushes on a flat and spherical substrate. In both cases, mixing the untethered isotactic PMMA with the grafted syndiotactic PMMA led to the formation of a stereocomplex with a multihelical structure. Static contact angle measurements showed a hindered surface mobility at the outermost surface of the polymer brush, indicating that the stereocomplex forms a crystalline structure. A syndiotactic polymer brush with substituted fluoroalkyl groups was prepared to increase the contrast for grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements. The GIWAXD results verified that the stereocomplex forms a crystalline structure oriented perpendicular to the substrate with a relatively low degree of orientation.

Bis-Copper(II)/π-Radical Multi-Heterospin System with Non-innocent Doubly N-Confused Dioxohexaphyrin(1.1.1.1.1.0) Ligand.

A contracted doubly N-confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open-shell π-radical ligand was synthesized as a new multi-heterospin motif. X-ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the presence of unpaired d electrons strongly antiferromagnetically coupled with π-radicals delocalized on the macrocycle. The 25 π non-innocent dioxohexaphyrin ligand allowed the facile interconversion between antiaromatic 24 π and aromatic 26 π species, respectively, upon redox reactions.

Dynamics of a bioinert polymer in hydrated states by dielectric relaxation spectroscopy.

The chain dynamics of well-defined poly(2-methoxyethyl acrylate) (PMEA), which has been used in practice as a bioinert coating for heart-lung machines, was examined as a function of water content by dielectric relaxation spectroscopy (DRS). Two relaxation processes observed in both dried and hydrated films were assigned to the segmental motion (α-process) and the relatively smaller scale motion such as the hindered rotation of side chains (ß-process). Water molecules adsorbed on PMEA made the α-process faster, meaning that water molecules in PMEA played the role of a plasticizer. Combining the above knowledge with the depth dependence of water content in the PMEA film previously obtained by neutron reflectivity, the segmental dynamics of PMEA at the water interface, which should be crucial to bio-inertness, is discussed. We found that the segmental motion was markedly faster than that in the bulk and almost comparable to the side chain motion.