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Solvent-free chemical oxidative polymerizations of pyrrole and its derivatives, namely

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.

This paper presents a facile method for fabricating a thin-film sample with a high asymmetry value of induced circularly polarized luminescence (iCPL) (|g

The long-term morphological and chemical stabilities of polypyrrole grains in aqueous media (1-year duration) are investigated. Polypyrrole grains doped with chloride ions or heptadecafluorooctane sulfonic acid were extensively characterized using a wide range of analytical techniques. The average sizes of the grains were 13–15 μm and consisted of submicrometer-sized atypical primary particles. The grain size increased in the case of polypyrrole doped with chloride ions, whereas no apparent changes were observed in the case of polypyrrole doped with heptadecafluorooctane sulfonic acid after storage at pH 3 and 10. The size and morphology of the primary particles did not change for each grain system. Appreciable changes in chemical structure and surface chemistry were observed. At pH 10, dedoping occurred easily, and chloride ions and heptadecafluorooctane sulfonic acid were released from the grains in a short time (within one week). On the other hand, the dopants were released slowly at pH 3, which is likely caused by nucleophilic attack by water molecules to the polypyrrole. The release rate of the dopant was slower for polypyrrole doped with heptadecafluorooctane sulfonic acid than for polypyrrole doped with chloride ions. This finding is attributed due to the stronger hydrophobic interaction between polypyrrole and heptadecafluorooctane sulfonic acid. Long-term morphological and chemical stabilities of polypyrrole grains doped with chloride ion or heptadecafluorooctane sulfonic acid in aqueous media (1-year duration) are studied. There were appreciable changes in chemical structure and surface chemistry, although the size and morphology of the polypyrrole primary particles did not change for each grain system. The dopants were released with time, and its rate was slower for the polypyrrole doped with heptadecafluorooctane sulfonic acid, compared to that doped with chloride ion. This should be due to the stronger hydrophobic interaction between polypyrrole and heptadecafluorooctane sulfonic acid.

Polystyrene particle-stabilized Pickering-type paraffin droplets were successfully coated by polypyrrole overlayers by aqueous chemical oxidative polymerization of pyrrole, and the thickness of polypyrrole overlayer could be controlled simply by changing pyrrole concentration in the polymerization media. Remote motion control of the droplets was realized on a planar air–water surface by site-selective near-infrared light irradiation, due to light-to-heat photothermal property of the polypyrrole. Furthermore, motion control of the paraffin droplet was also possible using sunlight focused using a magnifying glass. A Marangoni flow induced by site-selective light irradiation of the droplet could work as a driving force to move the droplet on the air–water surface, and the direction and timing of irradiation could control those of the motion on demand. Path length, velocity, and decay time of the droplet motions became longer and larger with an increase of thickness of polypyrrole overlayer, which was confirmed by numerical analyses.

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.

Hairy particles consisting of polyisoprene-b-polystyrene (PI-b-PS) were synthesized by polymerization-induced self-assembly (PISA) based on a living anionic polymerization method. The molecular agg...

High-density syndiotactic poly(methyl methacrylate) (st-PMMA) brushes form a helical structure and encapsulate fullerene molecules in their helical cavities, leading to a PMMA brush/fullerene inclusion complex. The brushes recognize the size of guest molecules and spontaneously adapt their helical diameter to the guest molecules. Both polymer brush/C60 and polymer brush/C70 inclusion complex on the flat substrate were characterized on the basis of grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements, and it is revealed that the main chains oriented perpendicular to the substrate. Moreover, high-density st-PMMA brushes grafted onto nanoparticles efficiently separate C70 molecules from the mixture of C60 and C70 solution. Even after 5× repeating process, the selectivity for C70 molecules remains at 99%.

A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.

Millimeter-sized polystyrene particles coated with a hydrophobic polypyrrole overlayer were successfully synthesized by aqueous chemical oxidative seeded polymerization. The dried particles could e...

The strength of silica-based mechanochromic nanocomposites was improved by a novel nanocomposite synthesized by grafting poly(butyl acrylate) (PBA)-b-poly(methyl methacrylate) (PMMA) from silica na...

Polypyrrole, poly(N-methyl pyrrole) and poly(N-ethyl pyrrole) grains were synthesized by aqueous chemical oxidative polymerization in the presence of sodium dodecyl sulfate as both a dopant and a hydrophobizing agent. The resulting grain products were characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilic–hydrophobic balance, (photo)thermal property, and conductivity. Scanning electron microscopy studies indicated that the grains were aggregates of atypical particles with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirmed the production of dodecyl sulfate-doped polypyrrole, poly(N-methyl pyrrole) and poly(N-ethyl pyrrole) materials, and they showed near-infrared light-to-heat photothermal properties, which was confirmed by thermography. The data obtained through X-ray photoelectron spectroscopy indicated the presence of dodecyl sulfate dopants on the surface of the grains. The dried polypyrrole and poly(N-ethyl pyrrole) grains showed hydrophobic character, and therefore, they can adsorb to the air–water interface and act as a light-responsive liquid marble stabilizer. Locomotion of the liquid marble can be driven by near-infrared laser irradiation-induced Marangoni flow on a planar air–water surface. The release of internal liquid can be achieved by controlled disruption of liquid marbles via external stimulus application. Polypyrrole and poly(N-alkyl pyrrole) grains were synthesized by aqueous chemical oxidative polymerization in the presence of sodium dodecyl sulfate as both a dopant and a hydrophobizing agent. The dried polypyrrole and poly(N-ethyl pyrrole) grains showed hydrophobic character and can act as a light-responsive liquid marble stabilizer. Locomotion of the liquid marble can be driven by near-infrared laser irradiation-induced Marangoni flow on a planar air–water surface. Furthermore, the release of internal liquid can be achieved by controlled disruption of liquid marbles via external stimulus application.

An efficient solution-based process for the fabrication of air-stable n-type thermoelectric films is reported. A nickel-ethenetetrathiolate complex was synthesized in dimethyl formamide and used to produce a dispersion in an aqueous medium. The film, fabricated via a simple drop-casting method with ethylene glycol, exhibited a remarkably high thermoelectric n-type power factor of 33 μW m−1 K−2.

Anionic polymerization of methacrylate-functionalized ionic monomers, 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTAC) and 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate...

Nafion is widely utilized as key polymer for proton electrolyte fuel cells owing to their high chemical, mechanical, and proton-conducting properties. The molecular aggregation state in Nafion films strongly affects the performance in the fuel cells. During operation process in fuel cells, peroxide derivatives such as H2O2 is generated and the chemical species deteriorates Nafion membrane, leading to a decreasing of performance of the fuel cells. The detail deterioration process including local structure, however, does not well-understand. In this work, we evaluate the local molecular aggregation state in deteriorated Nafion using microbeam wide X-ray diffraction (WAXD) measurements. Figure 1a shows WAXD line profile of before and after deterioration of Nafion membranes. The diffraction peaks were observed in ranging from 11 to 12 nm-1, which could be assigned to crystalline and amorphous structure in Nafion. The ratio of crystalline peak in deteriorated Nafion was more striking than that of initial Nafion membrane. This phenomenon might be explained following two mechanism. ① Polymer chains in amorphous domain were disconnected and were removed from the membrane. ② Polymer chains were disconnected and molecular motion of lower molecular weight is activated, leading to a formation of new crystalline domain caused by aggregation of lower molecular weight polymer chains. It is anticipated that above mechanisms occurs individually or at the same time. Though the dominant mechanism is still not clear, we can conclude that deterioration in Nafion starts from amorphous domain. To evaluate local molecular aggregation state in deteriorated Nafion, microbeams with size of 50 μm and 7 μm were utilized for WAXD measurements. Figure 1b and c show variation of ratio in crystalline domain as function of strain. The ratio of the crystalline domain in deteriorated Nafion was more striking than that of untreated Nafion. The ratio was constant when 50 μm beam was used, but not the case in 7 μm beam. This indicates that deterioration of Nafion membrane occurs 7 to 50 μm scale. The detail will be discussed in my presentation. Figure 1

The aqueous oxidative coupling polymerization of 3,4-ethylenedioxythiophene was conducted in the presence of heptadecafluorooctane sulfonic acid, which was used as a perfluoroalkyl dopant to synthesize hydrophobic poly(3,4-ethylenedioxythiophene) particles. The poly(3,4-ethylenedioxythiophene) particles were characterized in terms of their size, morphology, surface and bulk chemical compositions, conductivity, hydrophilic–hydrophobic balance and (photo)thermal properties. The electron microscopy studies confirmed that poly(3,4-ethylenedioxythiophene) consisted of aggregates of primary atypical particles of a submicrometer size. X-ray photoelectron spectroscopy and the contact angle measurement indicated that the perfluoroalkyl dopants were present on the surface of the poly(3,4-ethylenedioxythiophene) particles, which caused them to have a hydrophobic character. The electrical conductivity of the pressed pellet was 15.5 S cm−1, which was one order of magnitude higher than that of the poly(3,4-ethylenedioxythiophene) that was synthesized in the absence of the perfluoroalkyl dopant. The dried poly(3,4-ethylenedioxythiophene) particles could be used as a near-infrared-responsive liquid marble stabilizer exhibiting light-to-heat conversion properties. The movement of the poly(3,4-ethylenedioxythiophene) particle-coated liquid marbles on a planar water surface was driven by near-infrared laser-induced Marangoni propulsion. The inner liquid could be released by the disruption of the liquid marbles via an application of an external stimulus. The aqueous oxidative coupling polymerization of 3,4-ethylenedioxythiophene was conducted in the presence of heptadecafluorooctane sulfonic acid, which was used as a perfluoroalkyl dopant to synthesize hydrophobic poly(3,4-ethylenedioxythiophene) particles. The dried poly(3,4-ethylenedioxythiophene) particles could be used as a near-infrared-responsive liquid marble stabilizer exhibiting light-to-heat conversion properties. The movement of the poly(3,4-ethylenedioxythiophene) particle-coated liquid marbles on a planar water surface was driven by near-infrared laser-induced Marangoni propulsion.

Solvent-free oxidative coupling polymerization of 3-hexylthiophene using FeCl3 oxidant was conducted to synthesize poly(3-hexylthiophene) grains. Optical and scanning electron microscopy studies confirmed production of submillimeter-sized atypical grains with rough surfaces. Solubility test, Fourier transform infrared spectroscopy, and 1H nuclear magnetic resonance studies indicated the branching and cross-linking of the poly(3-hexylthiophene). Elemental microanalysis and X-ray photoelectron spectroscopy studies confirmed that the poly(3-hexylthiophene) grains were doped with chloride ions. The poly(3-hexylthiophene) grains showed hydrophobic character due to hexyl side chains, and the critical surface tension was determined to be 25.9 mN m–1. The poly(3-hexylthiophene) showed a light-to-heat photothermal property, and near-infrared laser irradiation to the poly(3-hexylthiophene) grains induced a rapid temperature increase up to 664 °C. The poly(3-hexylthiophene) grains can work as an effective liquid mar...

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.

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.

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor that controls the performance of catalyst layers in membrane electrode assemblies of polymer electrolyte fuel cells. Herein, the effects of water/alcohol compositions on the morphological properties and proton transport are examined by grazing incidence small-angle X-ray scattering, grazing incidence wide-angle X-ray scattering, and electrochemical impedance spectroscopy. The thin films cast by a high water/alcohol ratio Nafion dispersion have high proton conductivity and well-defined hydrophilic/hydrophobic phase separation, which indicates that the proton conductivity and morphology of the Nafion thin films are strongly influenced by the state of dispersion. This finding is expected to further understand the morphology and proton transport properties of Nafion thin films with different water/alcohol ratios, which has implications for the performance of the Pt/Nafion interface.

Polyhedral liquid marbles were fabricated using hydrophobic polymer plates in the shape of a circle, a heart and a star as a stabilizer and water as an inner liquid phase. Boxes could be fabricated by the evaporation of the inner water from the liquid marbles. The fabrication efficiency and stability of these boxes as a function of the plate shape were investigated. Functional materials such as polymers and colloidal particles were successfully introduced into the boxes., Boxes containing functional materials are fabricated from plate-stabilized liquid marbles via the evaporation of the inner liquid.

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.

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.