Yukikazu Takeoka

Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers.

Production of Colored Pigments with Amorphous Arrays of Black and White Colloidal Particles

There are many technical and industrial applications for colored pigments with nonfading properties. The development of a low-cost, high-volume production method for nonfading pigments with low toxicity and minimal environmental impact may promote their widespread use. To accomplish this goal, pigments need to be prepared using abundant and environmentally friendly compounds. Here, we report on the variously colored aggregates formed by spraying fine, submicrometer-sized spherical silica particles. The microstructure of the aggregate is isotropic with a shortrange order on a length scale comparable to optical wavelengths, and exhibits an angle-independent structural color as a result of wavelength-specific constructive interference. Interestingly, the color saturation of these aggregates can be controlled by the incorporation of a small amount of conventional black particles, such as carbon black (CB). We demonstrate that a Japanese-style painting can be successfully drawn with this method. Silicon dioxide, which is a major component of silica particles, is chemically stable and used in scientific glassware suitable for chemical experiments. It is also a primary component of soil and found in abundant supply in nature. Furthermore, in vivo toxicity of silica particles that are greater than 300 nm in diameter has not been detected. Therefore, submicrometer-sized silica particles are one of the best candidates for fabricating environmentally friendly materials. Fine submicrometer-sized spherical silica particles usually appear white to the human eye when they are in powdered form. However, assemblies of these particles can appear colored because of wavelength-specific optical interference, 5, 7] despite the absence of light-absorbing pigments and dyes. Such color is generally referred to as structural color, because it is essentially caused by the microstructure through optical phenomena, such as interference, diffraction, and scattering. 9] Crystalline arrays of fine submicrometersized spherical silica particles (colloidal crystals) are well known examples of assembled particles that have structural colors as a result of a very high reflectance at a certain wavelength of light. However, the structural colors produced by colloidal crystals show distinct variations, which depend on viewing and light illumination angles. Such iridescence makes the use of colloidal crystals as pigments difficult, because typical pigments generally require a constant color at different viewing angles. The iridescences of the colloidal crystals originate from Bragg reflection, which is the reflection mechanism that occurs as a result of the long-range order in the particle arrangement. Thus, if the arrangement is changed from the crystalline structure to the amorphous state, which has only a short-range order, iridescence is expected to be suppressed. In fact, amorphous aggregates of colloidal particles have been reported to exhibit angle-independent structural colors. 4, 5,12] However, amorphous colloidal arrays are difficult to fabricate because submicrometer-sized particles have a strong tendency to crystallize. Previously, amorphous colloidal arrays have been prepared by mixing two different kinds of submicrometer-sized silica particles. 4, 5, 13] These mixtures exhibit structural colors, but the colors are very pale. 4,5] Therefore, such amorphous colloidal arrays are unsuitable for use as brightly colored pigments. A simple synthetic method for the preparation of assemblies of submicrometer-sized particles with angle-independent brilliant structural colors for use as pigments has not yet been reported. Herein, we report a simple and reproducible synthetic procedure for the preparation of pigments that exhibit angleindependent, bright structural colors from amorphous colloidal arrays by spraying fine submicrometer-sized spherical silica particles of uniform size. We added a small amount of black particles to the colloidal amorphous array to enhance the saturation of the structural color by reducing incoherentlight scattering across the entire visible spectrum. Variously [*] Prof. Y. Takeoka, Prof. A. Takano, M. Teshima, Y. Ohtsuka, Prof. T. Seki Graduate School of Engineering, Nagoya University Furo-cho, Chikusa-ku, Nagoya, 464-8603 (Japan) E-mail: ytakeoka@apchem.nagoya-u.ac.jp

Photoregulated Wormlike Motion of a Gel

Many approaches to the development of artificial muscle actuators are currently being investigated. To address the demand for these applications, many research groups have focused on soft materials capable of deforming their shapes by means of external stimuli such as electric fields and light irradiation. The deformation behavior of established systems, however, was mainly based on isotropic volume change or a bending motion; the movements of existing soft actuators are less complex than those of living organisms. New soft actuators that demonstrate unprecedented lithe motions are being developed so that the technology of biomimetic sensing and robotics can evolve to a high degree at a rapid pace. Herein we show that a self-sustaining peristaltic motion, completely synchronized with a nonlinear oscillatory reaction, is induced in a periodically ordered structured polymer gel with interconnecting pores and can be manipulated using visible light. The wavelike swelling–deswelling change of the porous gel is caused by the periodic redox change of a ruthenium complex, which is chemically bonded to the polymer network (Scheme 1), in the Belousov–Zhabotinsky (BZ) reaction—a well-known oscillating chemical reaction. The amplitude and the period of the peristaltic motion can be controlled by visible light because of the additional production of a BZ reaction inhibitor upon visible light irradiation. The BZ reaction is a nonlinear oscillatory reaction that serves as a classical example of non-equilibrium thermodynamics. This reaction is far from equilibrium and continues to oscillate over hours or days. As such, it provides an interesting chemical model of non-equilibrium biological phenomena. Indeed, the chemical traveling waves observed in the BZ reaction are very similar to the electromagnetic traveling waves in muscle tissue. In addition, analogues of this periodic behavior such as heartbeats and circadian rhythms exist in natural systems. Heart rate can be controlled by the concentrations of chemicals such as adrenaline and acetylcholine, which are produced in the bloodstream upon external stimuli. Similarly, in the BZ reaction, the concentrations of chemicals that play key roles in the reaction are also controlled by external stimuli. Although the shape variation of gels composed of Nisopropylacrylamide (NIPA), a Ru complex derivative monomer, and a cross-linker (namely poly(NIPA–Ru complex) gels) can be caused by the BZ reaction, the motion of the gel must show striking similarities to the characteristic motion of living organisms. As the Ru complex acts as a catalyst for the BZ reaction, and changes its redox state periodically during the BZ reaction, the polymer network of the gel, in which the Ru complex is embedded, exhibits cyclic expansion–contraction changes because of the change in the osmotic pressure inside the gel. As the BZ reaction proceeds, the overall length of a rectangular poly(NIPA–Ru complex) gel (1 mm width, 20 mm length and 0.5 mm thickness) undergoes a cyclic expansion–contraction change. However, an “antiphase mode” between the chemical and mechanical oscillations was observed in this system. The phase difference was due to the slow swelling–deswelling response of the gel compared to the cyclic redox changes. As the swelling–deswelling processes of gels are determined by the collective diffusion of the polymer networks in a fluid, which is associated with the bulk counterflow of the fluid through the polymer networks, the relaxation time of the volume change of gels (t) can be expressed as the decay time in the single-exponential region [Eq. (1)],

Confined stimuli-responsive polymer gel in inverse opal polymer membrane for colorimetric glucose sensor

We developed a totally synthetic colorimetric glucose-sensing system that is composed of glucose-responsive hydrogel particles confined in an inverse opal polymer membrane. This system exhibits structural color on the basis of Bragg diffraction arising from the 3-D ordered structure with periodicity on the order of the wavelength of visible light. The volume of the hydrogel particles reversibly changes as the glucose concentration varies in the separated pores of the inverse opal polymer membrane; this system reveals a reversible change in the color appearance and the peak intensity of the reflection spectra with the variation in the glucose concentration. By careful design of the system, we can detect the important range of glucose concentration around the threshold value for diagnosing diabetes mellitus by using the colorimetric glucose-sensing system.

Angle-independent structural coloured amorphous arrays

We are able to observe a colour due to the interference of light from microstructures composed of different refractive index materials that is comparable to the visible wavelength of light; such a colour is called a structural colour. Because structural colour is fadeless and no energy is lost from the colour mechanism, structurally coloured materials are expected to be used for energy-saving reflective displays and sensors. Previously, however, the word “iridescence” rather than “structural colour” was used to describe the property of a surface that appears to change colour as the viewing angle or the angle of light illumination changes. Thus, people who are aware of the concept of interference colour have a strong impression that all structurally coloured materials change hue when viewed from different angles, as indicated by the term “iridescence.” In fact, most artificial structurally coloured materials that we and other groups have studied so far change their hue depending on the viewing and light illumination angles because these structural colours are derived from Bragg reflection. Such angle dependence presents a barrier for developing displays and sensors using structurally coloured materials. Therefore, my group has been working to develop angle-independent structural coloured materials. The latest most notable ones are amorphous array systems. In this review, I first introduce the microstructures and optical properties of low-angle-dependent structurally coloured amorphous arrays in biological systems, then describe the fabrication and the optical nature of the artificially prepared imitations of such biological systems, and finally, present the related theoretical studies.

Reversible adsorption of calcium ions by imprinted temperature sensitive gels

With the aim of developing polymeric gels sensitive to external stimuli and able to reversibly adsorb and release divalent ions, copolymer gels of N-isopropylacrylamide (NIPA) and methacrylic (MAA) monomers were prepared. We chose calcium as a target divalent ion. Two MAAs form a complex with a calcium ion, and the NIPA component allows the polymers to swell and shrink reversibly in response to temperature. The adsorbing site develops an affinity to target ions when the adsorbing molecules come into proximity, but when they are separated, the affinity diminishes. To enhance the affinity to calcium, an imprinting technique was applied using Ca2+ and Pb2+ ions as templates in methylsulfoxide and dioxane media, respectively. The adsorption capacity of the imprinted gels was compared with that of the nonimprinted gels, and the effects of the templates, the solvents, and the amount of methacrylic monomers used in the synthesis and the medium temperature over the Ca2+ adsorption capacity of the gels from aqueou...

Stimuli-responsive opals: colloidal crystals and colloidal amorphous arrays for use in functional structurally colored materials

Two distinct types of colloidal particle aggregated states exist in opal, namely, the colloidal crystal and the colloidal amorphous array. Today, these aggregates can be artificially prepared and are now studied as non-fading structurally colored materials as a result of our better understanding of their optical properties. Additionally, by applying the aggregates as stimuli-responsive materials, we can fabricate stimuli-responsive structurally colored systems that change their hue and saturation in response to external stimuli. In this review, the conditions necessary for fabricating stimuli-responsive structurally colored systems using the two types of aggregates present in opal are explained.

Structural colored gels for tunable soft photonic crystals.

A periodically ordered interconnecting porous structure can be embodied in chemical gels by using closest-packed colloidal crystals as templates. The interconnecting porosity not only provides a quick response but also endows the porous gels with structural color arising from coherent Bragg optical diffraction. The structural colors revealed by porous gels can be regulated by several techniques, and thus, it is feasible to obtain desirable, smart, soft materials. A well-known thermosensitive monomer, N-isopropylacrylamide (NIPA), and other minor monomers were used to fabricate various structural colored gels. The selection of minor monomers depended on the targeted properties. This review focuses on the synthesis of templates, structural colored porous gels, and the applications of structural colored gel as smart soft materials for tunable photonic crystals.

Electrochromism based on structural colour changes in a polyelectrolyte gel

Electrochromism based on structural colours was demonstrated by employing a simple system composed of a two-electrode cell, a salt-free organic solvent, and a nanostructured electroactive soft material. A polyelectrolyte gel, poly(HEMA-co-MAPTA-PF6), with an inverse-opal structure was prepared by using a polystyrene close-packed colloidal crystal as a template. The resulting gel swollen in binary organic solvents exhibited monochromatic structural colours. The structural colour of the gel was altered over the entire visible light region by changing the solvent polarity. Moreover, the structural colour could be tuned by applying a relatively low voltage, where the change in the lattice constant of the inverse-opal along the gel thickness direction, triggered by an electrodragging force on the polyelectrolyte gel under the electric field, was responsible for the colour change. The present system offers a novel concept for full-colour electrochromic materials, and the system can be tuned to exhibit the full range of colours by using single materials.

Structurally Coloured Secondary Particles Composed of Black and White Colloidal Particles

This study investigated the colourful secondary particles formed by controlling the aggregation states of colloidal silica particles and the enhancement of the structural colouration of the secondary particles caused by adding black particles. We obtained glossy, partially structurally coloured secondary particles in the absence of NaCl, but matte, whitish secondary particles were obtained in the presence of NaCl. When a small amount of carbon black was incorporated into both types of secondary particles, the incoherent multiple scattering of light from the amorphous region was considerably reduced. However, the peak intensities in the reflection spectra, caused by Bragg reflection and by coherent single wavelength scattering, were only slightly decreased. Consequently, a brighter structural colour of these secondary particles was observed with the naked eye. Furthermore, when magnetite was added as a black particle, the coloured secondary particles could be moved and collected by applying an external magnetic field.