Aya Fujimoto

Robust Liquid Marbles Stabilized with Surface-Modified Halloysite Nanotubes

We have demonstrated the fabrication of fluorine-free liquid marbles from halloysite nanotube. Halloysite is a naturally occurring inorganic nanotube that has a high aspect ratio, and the surface was modified with octadecyltrimethoxysilane. The surface-modified halloysite formed pincushion agglomerates on the surface of the liquid droplets, which create superhydrophobic surface similar to that of the plant gall surface prepared by aphids. As a result, the liquid marbles showed high mechanical strength upon impact without the use of low surface energy fluoroalkyl or fluorine-modified materials. Our results suggest a new strategy for designing novel materials for liquid marbles inspired by nature.

Preparation of poly(lactic-acid)-particle stabilized liquid marble and the improvement of its stability by uniform shell formation through solvent vapor exposure

A liquid marble was prepared from bio-based poly(lactic acid) [PLA] microparticles and water droplets. Solvent vapor exposure to the liquid marble changed the morphology of the granular PLA microparticle shell layer to a film-like shell layer even though the spherical shape of the liquid marble is retained. The morphological changes suppressed the evaporation of the water within the liquid marble by a factor of six compared with a liquid marble without the solvent vapor treatment. The compression test revealed that the mechanical stability of the solvent-treated liquid marble was changed due to the increased rigidity of the shell structure. Solvent vapor exposure is a simple but effective way to fabricate a robust liquid marble with long-term stability.

Scaffold for Growing Dense Polymer Brushes from a Versatile Substrate

We have demonstrated a universal approach to growing polymer brushes from various substrates. Urushiol was mixed with initiator-containing catechol, and it was spin-coated or cast on various substrates. Because urushiol is strongly adhered to various substrates, the thin film can serve as a general scaffold for grafting polymer brushes from various substrates. Note that the film was formed even onto the surface of polyolefins and thermosetting resins that are known as chemically inert materials to functionalize the surface. Moreover, the initiator-immobilized scaffold showed mechanical robustness and chemical inertness because of the flexible long unsaturated hydrocarbon side chain of urushiol. After the grafting of polyelectrolyte PMTAC polymer brushes, the material obtained exhibited hydrophilicity, typical of PMTAC. The concept shown here could provide a general approach for grafting practical polymer brushes from various substrates.

Manipulation of surface properties: the use of nanomembrane as a nanometre-thick decal

Precise control of surfaces and interfaces is essential for the fabrication of various functional materials. Although various methods have been applied to the functionalization of surfaces, these methods are specialized for the fabrication of specific surfaces for specific purpose. In this context, a versatile, yet efficient tool for the surface manipulation is strongly desired. Here, we demonstrate a simple method of functionalizing various surfaces through a decal-like transfer of a giant nanomembrane. Control of wettability was chosen as an example, and a hydrophobic nanomembrane was transferred to various other substrates, including Si, polymer film, and metal. A drastic change in contact angle clearly indicated that the wettability of the processed material was identical to that of the surface-functionalized nanomembrane. In contrast, other physical properties such as the mechanical properties of the processed material remain unchanged. The decal-like transfer of nanomembrane will become a powerful means for the fabrication of unique functional surfaces.

Surface Functionalization by Decal-like Transfer of Thermally Cross-Linked Urushiol Thin Films

We have demonstrated surface functionalization through the decal-like transfer of thermally cross-linked urushiol thin films onto various substrates. Tensile adhesive strength measurements showed that the film adheres strongly to the surface of various substrates including chemically inert materials, such as polyolefins and thermosetting resins, because of the properties of urushiol. Furthermore, the highly cross-linked structure of urushiol made the films mechanically robust. These two properties allowed the fabrication of practicable thin films for indirect surface modification. Actually, the robust thin film served as a scaffold for an Au thin film, which was then bound to various substrates. Surface-texturing of nanodecal was also demonstrated as an application aspects.

Biobased Polymer Coating Using Catechol Derivative Urushiol

We have investigated the mechanism of the superior mechanical robustness of coated thin films of the catechol derivative urushiol. We synthesized hydrogenated urushiol (h-urushiol) by hydrogenating the double bonds in the long alkyl side chain of urushiol, and the physical properties of thin films of mixtures of urushiol and h-urushiol were evaluated. Atomic force microscopy observations revealed that these coated thin films have a homogeneous surface with no phase separation, regardless of the h-urushiol content, arising from the similarity of the chemical structures. The films showed good adhesive properties because the adhesion originates from the catechol structure. In contrast, curing time depended strongly upon the h-urushiol content. The curing of the h-urushiol thin film took 12 h, whereas the urushiol thin film was cured within 10 min. Moreover, the strain-induced elastic buckling instability for mechanical measurements test and the bulge test confirmed that the increase in the h-urushiol content decreased the mechanical strength. Because the double bonds in the urushiol side chain contribute to forming the highly cross-linked structure, the lack of double bonds in h-urushiol resulted in the slow curing and low mechanical strength. Interestingly, the mechanical robustness started to increase over 80 mol % h-urushiol. The saturated long alkyl side chain of h-urushiol faced the surface, and the regular structure of the uniform side chain may improve the mechanical properties of the coated film. Our results will help to develop biomimetic catechol-based coatings.

Spray-Assisted Nanocoating of the Biobased Material Urushiol

We have demonstrated the spray-assisted coating of the catechol derivative, urushiol. Spraying a mixture of urushiol and iron(II) acetate formed a uniform coating about 10 nm thick, as confirmed by AFM observations. XPS measurements revealed that various substrates, including polyolefins and thermosetting resins, were successfully coated with urushiol. The coating showed good solvent tolerance and coating adhesion after baking at 100 °C for 10 min or after aerobic oxidation for several days. Interestingly, quartz crystal microbalance (QCM) measurements and strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) revealed that density and Youngs modulus of the spray-assisted nanocoatings were higher than those of spray-coated samples. Moreover, the coating was uninvolved in physical properties except surface properties, as demonstrated by several experiments. Because urushiol is a promising biobased material, our unique spray-assisted coating technique could provide a general approach for material-independent surface modification techniques that are environmentally sustainable.

Concealing surface topography by attachment of nanometer-thick film.

Concealing of surface topology of substrates by decal-like attachment of nanomembrane is demonstrated. The nanomembrane attachment provides a flat surface on various substrates, including porous substrates, and the surface property such as wettability was changed to that of the nanomembrane. The monitoring of drying process revealed that a nanomembrane with certain thickness tolerates their flexural deflection during the procedure. Moreover, the supporting position of nanomembranes as well as the physical properties of nanomembranes strongly affected the degree of deflection. The decal-like attachment of nanomembranes shown here is potentially a powerful method for creating a new functional surface that is independent of the topological and chemical properties of the original substrate.

The Hippo Signaling Pathway: A Candidate New Drug Target for Malignant Tumors

The Hippo pathway has the unique capacity to sense tissue architecture and the external forces that shape it, and dysregulation of this pathway leads to tumorigenesis. The study of mice bearing systemic or tissue-specific mutations of Hippo elements has driven huge progress in understanding this pathway’s role in normal physiology and disease. Here, we summarize how disruption of Hippo signaling relates to cancer, and we highlight the importance of this pathway as a new drug target for malignant tumors.

In situ synchrotron radiation X-ray diffraction studies on molecular aggregation structure of nylon 12 films during bulge testing

It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films.