In situ microscopic observation of chitin and fungal cells with chitinous cell walls in hydrothermal conditions.

Recent findings of intact chitin in fossil records suggest surprisingly high recalcitrance of this biopolymer during hydrothermal treatments. We also know in the experience of everyday life that mushroom, cells of which have chitinous cell walls, do not fall apart however long they are simmered. We used in situ optical microscopy to examine chitin and fungal cells with chitinous cell walls during hydrothermal treatments, and obtained direct evidence that they remained undegraded at temperatures well over 200 °C. The results show very hot and compressed water is needed to make mushrooms mushy.

Anomalous long-range repulsion between silica surfaces induced by density inhomogeneities in supercritical ethanol.

Anomalous long-range repulsion, extending over several micrometres, emerged between silica surfaces around the ridge of density fluctuations in supercritical ethanol at temperatures and pressures near the gas/liquid critical point (T(c) = 241 °C, P(c) = 6.14 MPa). Analysis shows that augmentation of ethanol density around silica surfaces in the presence of density fluctuations facilitates dissociation of silanol groups, leading to long-range electrostatic repulsion in the nonpolar medium.

Water transport mechanism through open capillaries analyzed by direct surface modifications on biological surfaces.

Some small animals only use water transport mechanisms passively driven by surface energies. However, little is known about passive water transport mechanisms because it is difficult to measure the wettability of microstructures in small areas and determine the chemistry of biological surfaces. Herein, we developed to directly analyse the structural effects of wettability of chemically modified biological surfaces by using a nanoliter volume water droplet and a hi-speed video system. The wharf roach Ligia exotica transports water only by using open capillaries in its legs containing hair- and paddle-like microstructures. The structural effects of legs chemically modified with a self-assembled monolayer were analysed, so that the wharf roach has a smart water transport system passively driven by differences of wettability between the microstructures. We anticipate that this passive water transport mechanism may inspire novel biomimetic fluid manipulations with or without a gravitational field.

Photoinduced reversible topographical changes on diarylethene microcrystalline surfaces with biomimetic wetting properties.

Reversible topographical changes were observed on a photochromic diarylethene microcrystalline film surface by alternate irradiation with UV and visible light. Two types of surfaces were prepared from this film: 1) Storage of the film at 30 °C for 24 hours in the dark after UV irradiation afforded a surface that was covered with needle-shaped crystals, whose diameter and length were approximately 1 µm and 10 µm, respectively, and showed a superhydrophobic lotus effect. 2) Storage of the film at 70 °C for 3 hours in the dark caused the needle-shaped crystals to be converted into larger rod-like crystals (5~8 µm wide and 20~30 µm long) by Ostwald ripening and a disappearance of the lotus effect. The obtained activation energy of the formation of the needle- and rod-shaped crystals was 143 and 162 kJ mol(-1), respectively. Subsequent UV irradiation to the surface, which was followed by storage at 50 °C for 1 hour in the dark, gave a doubly rough structure; small needle-shaped crystals were formed between the larger rod-shaped crystals. The surface showed both superhydrophobic properties and the pinned effect of the water droplet: the petal effect. Fractal analysis of both surfaces were carried out using a box-counting method, and the lotus effect was observed in the presence of smaller-sized crystals, whilst the petal effect was observed with larger sized crystals (ca. 100 µm). We demonstrated that the hydrophobic property was controlled by the distribution in crystal size of the closed-ring isomer of the diarylethene. Visible-light irradiation of both rough surfaces afforded surfaces with cubic-shaped micro-crystals of the open-ring isomer.

Unique diffusion behavior observed in supercritical ethanol.

We have systematically investigated the diffusion behavior of silica nanoparticles within supercritical ethanol, in terms of solvent properties by varying temperature (T) and pressure (P), to elucidate how the inhomogeneous solvent structures and density fluctuations in the solvent affect the diffusion behavior of solute particles. Results show that at a constant pressure, the diffusion coefficient (D) of the particles increases with increasing temperature, reaches the maximum (D(max)) within the gaslike supercritical fluid (slightly below the ridge), and finally decreases abruptly at very low fluid density when temperature is increased further. Results reveal that D is appreciably larger than the theoretical prediction (Einstein-Stokes relationship) in the vicinity of the critical density (rho(c)) of the solvent. We interestingly observed that D becomes maximum (D(max)) at a particular thermodynamic condition (T(i),P(i)), which is expressed by the empirical formula T(ri)=P(ri) (0.16) (for T(ri)>1, P(ri)>1). Here, T(ri)=T(i)/T(c) and P(ri)=P(i)/P(c); T(c) and P(c) are the temperature and the pressure at critical point, respectively. Results further reveal that D(max) increases significantly with decreasing solvent density within the gaslike supercritical fluid where the changes in viscosities are negligible. These findings are unique, novel, and intriguing. We suggest that the enhancement of the diffusion coefficient in the vicinity of the critical density and the abrupt decrease in the diffusion coefficient in very low density gaslike fluid are associated with the change in the solvent-solvent and solute-solvent direct correlation function (related to the effective interaction potential) upon density change when the fluid crosses the ridge of density fluctuations and within the gaslike fluid.

Versatile solidified nanofibrous cellulose-containing media for growth of extremophiles.

Solidified media that employ a porous matrix of nanofibrous cellulose are described. The physicochemical stability of the porous structure allows the development of solidified media that can support the growth of extremophiles, such as acidophilic Acidiphilium, alkaliphilic Bacillus, thermophilic Geobacillus and Thermus, alkalithermophilic Bacillus, and acidothermophilic Sulfolobus microbes. The cellulose-supported media have several advantages over agar- and gellan gum-derived media, including versatility and stability.

Characterization and structural investigation of fractal porous-silica over an extremely wide scale range of pore size.

We have succeeded in creating Menger sponge-like fractal body, i.e., porous-silica samples with Menger sponge-like fractal geometries, by a novel template method utilizing template particles of alkylketene dimer (AKD) and a sol-gel synthesis of tetramethyl orthosilicate (TMOS). We report here the first experimental results on characterization and structural investigations of the fractal porous-silica samples prepared with various conditions such as calcination temperature and packing condition of the template particles. In order to characterize the fractal porous-silica samples, pore volume distribution, porosity and specific surface area were measured over an extremely wide scale from 1 nm to 100 microm by means of mercury porosimetry, (1)H NMR cryoporometry, nitrogen gas adsorption experiments together with direct evaluations of cross-sectional fractal dimension D(cs), and size limits of D(cs). We have found that the pore volume distribution and specific surface area of the fractal porous-silica samples can be discussed in terms of different fractal porous structures at different scale regions.

Characterization of curved hair of Japanese women with reference to internal structures and amino acid composition.

The variation of hair curvature in Japanese women was quantitatively investigated and the structure of curved hair was characterized with transmission electron microscopy (TEM) and amino acid analysis. Two hundred and thirty Japanese women volunteers, aged from 10 to 70 years, were randomly selected. The evaluation of the volunteers' natural hair shape showed that 53% of Japanese women have straight hair, while the remaining 47% have curved hair (varying from a slightly wavy shape to a frizzy style). The average curl radius of the volunteers' hair was determined to be 4.4 +/- 2.3 cm, and ranged widely from 0.6 to 16 cm. The TEM observation of curved hair fiber revealed an inhomogenous internal structure between the outer and inner regions of the curved shape. In relation to the inhomogeneous structure of the curved hair, different amino acid composition of the hair keratin was observed between the outer and inner regions. Interestingly, these results of the TEM observation and the amino acid analysis are analogous to the difference between the ortho- and paracortical cells in wool fibers, suggesting the universal structure of curved mammalian hair.

Spontaneous formation of super water-repellent fractal surfaces in mixed wax systems.

Alkylketene dimers (AKDs) and triglyceride waxes form fractal surfaces spontaneously and show super water-repellent property. Spontaneous formation of fractal structures on their surfaces takes place when the meta-stable crystalline phase of the waxes transforms to the thermodynamically stable form of crystal. The triglyceride waxes form the meta-stable alpha-phase in whole specimen when solidified from their melt. In the case of AKD, on the other hand, only a small portion of the specimen solidifies in the meta-stable form of crystal. The surface of the AKD, however, becomes fractal in the whole part. We have, thus, examined the fractal structure formation in the mixed wax systems in which one wax forms fractal surfaces and the other one does not. In the stearic acid/tristearin mixed system as a typical one, the super water-repellent fractal surfaces form in the higher composition region of tristearin than that of the eutectic point in their mixture.

Thermo-responsive poly(N-isopropylacrylamide) gel containing polymeric surfactant poly(2-(methacryloyloxyl)decylphosphate): correlation between rapid collapsing characters and micelles of polymeric surfactant.

This paper deals with a thermo-responsive poly(N-isopropylacrylamide) (NIPA) gel containing a polymeric surfactant poly(2-(methacryloyloxyl)decylphosphate) (PMDP) which shows rapid volume change above phase transition temperature at ca. 34 degrees C. Based on the measurements of dye-solubilization, it was suggested that intra-molecular micelles of the polymeric surfactant PMDP are inside NIPA gel-network. It is concluded that the intra-molecular micelles of polymeric surfactant involving NIPA chains may play crucial role in the rapid collapse of the NIPA-PMDP gel at the phase transition temperature.

Effect of pressure on colloidal behavior in hydrothermal water.

The pressure dependence of the colloidal phenomena of nanoparticles in hydrothermal water was investigated by both experiment and theory. Dynamic light scattering experiments show that diamond nanoparticles, which are highly stable in ambient water, easily aggregate in high-temperature and high-pressure water. Although the stability of nanoparticles in ambient pure water does not depend on pressure, it is interestingly found that at constant temperature particles aggregate faster in the hydrothermal regime when the pressure is higher. A theoretical interpretation is proposed to predict the stability of colloids in water as a function of temperature and pressure. Numerical analysis shows that the repulsive interparticle potential barrier, which stabilizes particles in the dispersion, decreases dramatically in high-temperature and high-pressure water. The decrease in the potential barrier arises from the temperature and the pressure dependencies of the dielectric constant (epsilon) and the ion product (p K w) of water. Numerical analysis shows that the pressure dependence of epsilon is negligible in the temperature range of 20-300 degrees C, whereas the pressure dependence of p K w is significant at temperatures of T > 150 degrees C. The theory reveals that the pressure dependence of the rate of size increment in the hydrothermal regime results from the pressure dependence of p K w. An increase in pressure in the hydrothermal water enhances the ionization of water molecules which reduces the surface potential of the particles. This effect lowers the interparticle repulsive potential barrier, which accelerates aggregation of the particles.

Super water-repellent poly(alkylpyrrole) films having environmental stability.

We present electrochemical synthesis of super water-repellent poly(alkylpyrrole) films which exhibit excellent environmental stability in terms of contact angle (>150 degrees ) for water. The poly(alkylpyrrole) films synthesized under an optimized electrochemical condition consisted of thousands of micro-scaled 'needles' which densely aligned by shoulder to shoulder. The surface of the aligned 'needles' was analyzed by a box-counting method, to be a fractal structure with a dimension of 2.18.

Supercritical ethanol--a fascinating dispersion medium for silica nanoparticles.

For the first time, the dispersion stability of silica nanoparticles has been investigated in high-temperature and high-pressure ethanol by measuring the hydrodynamic diffusion coefficient of the particles by means of dynamic light scattering. The silica nanoparticles remain stable in ethanol within a wide temperature range of 24-304 degrees C at 12.3 MPa, and they start to aggregate at T >or= 305 degrees C. Numerical analysis reveals that the net interparticle repulsive potential barrier decreases dramatically with increasing temperature due to the changes in the properties of the medium. We observed that particles remain highly stable in the nonpolar supercritical ethanol in the temperature regime 241-304 degrees C, where the DLVO potential barrier is only 5-2 k(B)T. The dispersion stability of silica nanoparticles at this low potential barrier in high-temperature and high-pressure ethanol, especially in the supercritical ethanol, is fascinating. The silica-ethanol system might be a unique and special example in the colloidal dispersions. Results suggest that silica nanoparticles may be used as a model colloid to investigate the colloidal transport phenomena in the supercritical ethanol.

Spontaneous formation of fractal structures on triglyceride surfaces with reference to their super water-repellent properties.

Alkylketene dimer (AKD), a kind of wax, has been known to form fractal surfaces spontaneously and show super water-repellency. Such formation of water-repellent and fractal surfaces was also found in this work for triglycerides. Since the crystal phase transitions of these waxes were well studied, we studied the formation of their fractal surfaces through contact angle measurements, differential scanning calorimetry (DSC), and X-ray diffraction (XRD). From time-dependent contact angle measurements, it was found that the formation of super water-repellent surfaces with fractal structures occurred spontaneously also on the triglyceride surfaces at different temperatures. The freshly solidified triglyceride surfaces were almost transparent, and their initial contact angles of water were close to 110 degrees. The surfaces then became rough and clouded after being incubated for a certain time at a specified temperature. The super water-repellent surfaces were quite rough and showed fractal structures with the dimension of ca. 2.2 calculated from the scanning electron microscopic (SEM) images by the box-counting method. The phase transformation from a metastable state to a stable cystalline one after the solidification from the melt of triglycerides was clearly observed by DSC and XRD measurements. The fractal crystalline structures and the super water-repellency resulted from this phase transformation and the crystal growth. Ensuring the initial sample solidified into the metastable state and curing the surface at an appropriate temperature are key factors for the successful preparation of fractal triglyceride surfaces by the solidification method.

Effect of ionic surfactants on the iridescent color in lamellar liquid crystalline phase of a nonionic surfactant.

A nonionic surfactant, n-dodecyl glyceryl itaconate (DGI), self-assembles into bilayer membranes in water having a spacing distance of sub-micrometer in the presence of small amounts of ionic surfactants, and shows beautiful iridescent color. Ionic surfactants have strong effects on this iridescent system. We have interestingly found that the iridescent color changes with time after mixing DGI and ionic surfactants and the color in equilibrium state changes greatly with concentration of the ionic surfactants. The time-dependent color change results from the transformation of DGI aggregate structure after being mixed with ionic surfactant. It is first found that the iridescent color of this nonionic system can be changed from red to deep blue by altering the concentration of ionic surfactants added even though the total concentration of surfactant is almost constant. Such large blue shift of the iridescent color in equilibrium state cannot be fully explained by the ordinary undulation theory applied so far for this phenomenon. The flat lamellar sheets tend to curve by increasing the concentration of ionic surfactants to form separated onion-like and/or myelin-like structures. These separated structures of lamellar system result in the decrease of spacing distance between bilayer membranes because some vacant spaces necessarily appear among these structures.

Preparation and characterisation of nanofibrous cellulose plate as a new solid support for microbial culture.

Porous plates made of nanofibrous crystalline cellulose were prepared, and used as a solid support for microbial cultures. Representative mesophilic microorganisms (, , and ) grew on the cellulose plate, just as well as they did on the conventional agar plate. optical microscopic examination revealed that the cellulose plate remained unchanged up to 280 °C at a constant pressure of 25 MPa. Due to the structural stability at high temperatures, a representative thermophile, , was cultured successfully on the cellulose plate at 80 °C. Mouse fibroblast cells did not show significant adhesion or extension on the cellulose plate.

Supercritical water: a fascinating medium for soft matter.

Properties of water change dramatically at high temperatures and high pressures near and/or above the critical point ( = 374 °C, = 22.1 MPa). The dielectric constant, for example, decreases from 78 at 25 °C and 0.1 MPa to 6 at the critical point, the value of which is comparable to that of 1-dodecanol. As fascinating characteristics of soft matter rely on unique properties of ambient liquid water, the change should have significant impacts on soft matter. However, our knowledge of soft matter under such extreme conditions is virtually nonexistent. In this article, properties of colloidal dispersions in water at high temperatures and high pressures are described. Implications of the findings for geological processes in deep-subsurface are also discussed.

Synthetic myelin figures immobilized in polymer gels.

Myelin-like instabilities usually form from the interface of amphiphilic lamellar phases and solvent, and resemble the neuron-like structures in nerve systems. However, these myelin structures are thermodynamically unstable. We herein present our first success in synthesizing stable myelin figures separated organized-polymerization. Myelin figures formed with a polymerizable nonionic surfactant have been immobilized in polymer gels. The results obtained from confocal laser scanning microscopy (CLSM), small angle X-ray scattering (SASX) and freeze fracture transmission electron microscopy (FF-TEM) clearly prove that the myelin structures have been well immobilized without any structural change. The immobilized myelin structures in polymer gels were kept for 6 months and no obvious change was observed in their structures and/or shapes. The success in stabilizing these unstable myelin structures provides some potential for applications, such as anisotropic gels, electrophoresis mediums for the separation of hydrophobic materials and so on.