Deformation dynamics of an oil droplet into a crescent shape during intermittent motion.

A paraffin droplet containing camphor and oil red O (dye) floating on the water surface shows spontaneous motion and deformation generated by the surface tension gradient around the droplet. We focused on the intermittent motion with a pronounced deformation into a crescent shape observed at specific concentrations of camphor and oil red O. We quantitatively analyzed the time changes in the droplet deformation and investigated the role of the oil red O by measuring the time-dependent paraffin-water interfacial tension with the pendant drop method.

Flow-Driven Self-Propulsion of Oil Droplet on a Surfactant Solution Surface, as Observed by Time-Resolved Interfacial Tension and Surface Flow Speed Measurements.

The imbalanced force of the interfacial tension applied to an object has often been taken into account in the analysis of the motion mechanism of self-propelled systems. However, heterogeneous distributions of the interfacial tension also cause Marangoni flows, and these flows also contribute to the self-propulsion through the viscous force. The contribution of such flows has not been observed directly, while the interfacial tension difference has been measured in some systems.

Time-Resolved Measurements of Interfacial Tension and Flow Speed of the Inclined Water Surface around a Self-propelled Camphor Boat by the Quasi-elastic Laser Scattering Method.

An inclined liquid surface, such as a meniscus, plays an important role in advection and transport phenomena at a liquid's surface. However, there is no time-resolved measurement method for the interfacial tension of an inclined liquid-air interface. Here, a noninvasive method for simultaneous measurements of the interfacial tension and surface flow speed for an inclined water surface is described.

Effects of Cholesterol Concentration and Osmolarity on the Fluidity and Membrane Tension of Free-standing Black Lipid Membranes.

Although the mechanical properties and compositions of lipid bilayer membranes can change upon deformation, the fundamental relations between the composition, membrane tension and fluidity of membranes with little curvature have not yet been studied. In the current study, the membrane tension and the diffusion coefficients of free-standing black lipid membranes (BLMs), based on 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), were observed by systematic control of the cholesterol concentration and the osmotic pressure with the laser-induced surface deformation (LISD) and fluorescence recovery after photobleaching (FRAP) techniques. When the osmotic pressure was raised and, therefore, the curvature became larger, both the membrane tension and the diffusion coefficients increased as well.

Experimental Investigation of the Self-Propelled Motion of a Sodium Oleate Tablet and Boat at an Oil-Water Interface.

The self-propelled behaviors of macroscopic inanimate objects at surfaces and interfaces are ubiquitous phenomena of fundamental interest in interface science. However, given the existence of a large variety of systems with their own inherent chemical properties, the kinematics of the self-propelled motion and the dynamics of the forces driving these systems often remain largely unknown. Here, we experimentally investigate the spontaneous motion of a sodium oleate tablet at a water-nitrobenzene interface, under nonequilibrium and global isothermal conditions, through measurements of the interfacial tension with the noninvasive, quasi-elastic laser scattering method.

Motion modes of two self-propelled camphor boats on the surface of a surfactant-containing solution.

Hypothesis: The existence of a surface tension difference and a surface flow around self-propelled objects, such as camphor boats, has been confirmed by many studies. However, the interactions in the collective motion of several camphor boats have not been explicitly discussed. Here, a model system of two camphor boats was investigated for the first time from the viewpoint of surface tension and surface flow.

Effects of halide ions on the acceptor phase in spontaneous chemical oscillations in donor/membrane/acceptor systems.

The effects of halide ions on the acceptor phase in the chemical oscillation in donor/membrane/acceptor systems were examined. The transfer of cetyltrimethylammonium (CTA(+)) ions from the donor phase and their adsorption and desorption at the membrane/acceptor interface led to spontaneous, nonlinear oscillations of the electric potential. Chloride ions stabilized the adsorption of CTA(+) ions and gave rise to a large-amplitude, long-interval, and a long relaxation-time constant.

Changes in Interfacial Tension of a Lipid Membrane Formed at the Water/Chloroform Interface upon DNA Complex Formation.

Changes in the interfacial tension of a lipid monolayer membrane formed at the water/chloroform interface upon DNA addition were measured using the quasi-elastic laser scattering (QELS) method. A cationic lipid, N-[1-(2,3-dioleoyloxy)propyl]-N,N,N-trimethylammonium chloride (DOTAP), as well as zwitterionic lipids, 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), were used to form lipid monolayer membranes at different calcium ion concentrations. A rapid decrease of the interfacial tension resulting from electrostatic interactions between DOTAP and DNA was observed within 10 s.

Measurement of membrane tension of free standing lipid bilayers via laser-induced surface deformation spectroscopy.

Non-invasive measurement of the membrane tension of free-standing black lipid membranes (BLMs), with sensitivity on the order of μN m(-1), was achieved using laser-induced surface deformation (LISD) spectroscopy. A BLM was vertically formed via the folding method and aqueous phases with different refractive indices were added on each side in order to induce radiation pressure by a laser beam. The dynamic response of the deformed BLMs was measured under periodic intensity modulation and their tensions could be estimated.

Molecular building blocks and their architecture in biologically/environmentally compatible soft matter chemical machinery.

This review briefly summarizes recent developments in the construction of biologically/environmentally compatible chemical machinery composed of soft matter. Since environmental and living systems are open systems, chemical machinery must continuously fulfill its functions not only through the influx and generation of molecules but also via the degradation and dissipation of molecules. If the degradation or dissipation of soft matter molecular building blocks and biomaterial molecules/polymers can be achieved, soft matter particles composed of them can be used to realize chemical machinery such as selfpropelled droplets, drug delivery carriers, tissue regeneration scaffolds, protocell models, cell-/tissuemarkers, and molecular computing systems.

Development of a non-blurring, dual-imaging tissue marker for gastrointestinal tumor localization.

Background: Knowing the exact location of gastrointestinal tumors both preoperatively and intraoperatively is essential for planning and performing laparoscopic surgery. Different techniques have been introduced to ascertain tumor locations during surgery, but none of these are fully satisfactory at establishing the minimum margins for organ resection while retaining curability. A new, non-blurring tissue marker, detectable by both X-ray computed tomography (CT) and near-infrared (NIR) fluorescence laparoscopy, has been developed, and we here examine its utility using an animal model.

Quasi-elastic laser scattering for measuring inhomogeneous interfacial tension in non-equilibrium phenomena with convective flows.

An inhomogeneous distribution of interfacial tension can induce different types of non-equilibrium spontaneous motion at the interface by convective flow, or by the solutal Marangoni effect. Several applications of the quasi-elastic laser scattering (QELS) method used to study these effects are presented here. The relationship between the interfacial tension and the non-equilibrium phenomena has been verified experimentally for each application.

Spontaneous oscillation mechanism by simultaneous time-resolved measurements of interfacial tensions of both the donor/membrane and membrane/acceptor phases.

The time courses of the interfacial tension of two interfaces and the electric potential between the donor/membrane/acceptor phases were simultaneously examined using a quasi-elastic laser scattering method, which monitors capillary wave frequencies. An aqueous solution of cetyltrimethylammonium bromide (CTAB), a nitrobenzene solution of tetrabutylammonium tetraphenylborate (TPATPB), and an aqueous solution of sodium chloride (NaCl) were used as the surfactant in the aqueous donor phase, the hydrophobic electrolyte in the organic membrane phase, and the electrolyte in the aqueous acceptor phase, respectively. It has been found that the oscillatory behavior of the potential is synchronized with that of the interface tension at the membrane/acceptor interface, which is caused by the feeding and the following rapid adsorption of CTA(+) surfactants to it due to the Marangoni effect.

Surface tension gradient around an alcohol droplet moving spontaneously on a water surface.

The surface tension gradients in the front and rear sides of a 1-hexanol droplet exhibiting self-propelled motion were compared by a time-resolved quasi-elastic laser scattering method. The velocity of the alcohol droplet strongly correlated to the difference of the inverse of the recovery distances of the surface tensions between the front and rear sides. This result indicates that the spontaneous alcohol droplet motion is governed by an imbalance in the Marangoni convection flow, induced by an asymmetric surface tension distribution.

Application of a novel near infrared-fluorescence giant vesicle- and polymerasome-based tissue marker for endoscopic and laparoscopic navigation.

In this study, we describe the development of a novel tissue marker that can be injected from within the digestive tract by using an endoscopic instrument, and visualized using near-infrared (NIR) fluorescence imaging. The marker was prepared in three steps, (i) mixing NIR-fluorescent indocyanine green (ICG) with giant vesicles (GVs) of lecithin, (ii) suspending the ICG-containing giant vesicles (ICG-GV) in an oil phase dissolving polyglycerol-polyricinoleate (PGPR), and (iii) centrifugation of the suspension layered on a buffered solution to obtain a giant polymer vesicle (polymerasome) containing ICG-GV. We injected the tissue marker into the inner gastric surface of an anesthetized pig using an endoscopic syringe, and observed the injection site using a fluorescence laparoscopic camera.

Giant vesicles functionally expressing membrane receptors for an insect pheromone.

To date, biochemical approaches to membrane receptors have been limited to the following methods: knockout or overexpression of membrane receptors by gene introduction and genome engineering or extraction of membrane receptor-surfactant complexes from innate cells and their introduction into model biomembranes. Here, we describe the development of a third method involving gene expression using cell-free in situ protein synthesis inside model biomembrane capsules. We verified this method by synthesizing olfactory receptors from the silkmoth Bombyx mori inside giant vesicles and found that they were excited in the presence of their ligand the Bombyx mori sex pheromone.

Delayed response of interfacial tension in propagating chemical waves of the Belousov-Zhabotinsky reaction without stirring.

Time-resolved measurements of the interfacial tension of propagating chemical waves of the Belousov-Zhabotinsky reaction based on the iron complex catalysts were carried out without stirring by monitoring the frequency of capillary waves with the quasi-elastic laser scattering method. A delayed response of the interfacial tension with respect to absorption was found with the delay being ligand-dependent when the reaction was conducted at a liquid/liquid interface. This behavior is attributed to differences in adsorption activity of the hydrophobic metal catalyst.

Effects of surfactants and electrolytes on chemical oscillation at a water/nitrobenzene interface investigated by quasi-elastic laser scattering method.

We used a time-resolved interfacial tension measurement method with quasi-elastic laser scattering to investigate the effects of electrolytes and various surfactants on the nonlinear dynamics of the chemical oscillation that occurred at a water/nitrobenzene interface when a surfactant was added to the interface through a capillary. For both cationic and anionic surfactants, an electrolyte in the water phase was required for slow desorption of the surfactant from the interface. In the absence of an electrolyte, repulsion between the polar head groups of the ionic surfactants hindered adsorption of the surfactant molecules at the interface, resulting in their rapid desorption.

Tip-enhanced Raman spectroscopy of lipid bilayers in water with an alumina- and silver-coated tungsten tip.

Tip-enhanced Raman spectroscopy (TERS) of supported phospholipid bilayers in an aqueous environment is discussed in this paper. Two bilayer membranes were examined: 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). We fabricated alumina- and silver-coated tungsten tips that are very robust in water.

Phonon mode of TiO2 coupled with the electron transfer from N3 dye.

Low frequency vibrational spectra of submonolayer N3 dye (Ru(4,4(')-dicarboxy-2,2(')-bipyridine)2(NCS)2) adsorbed on TiO2 (110) were reported by using fourth-order coherent Raman spectroscopy, which is interface-sensitive vibrational spectroscopy. Most of the peaks observed in the experiment were at the same frequency as that of Raman and infrared spectra of the dye and TiO2. Two interfacial modes at 640 and 100 cm(-1) and one resonantly enhanced phonon at 146 cm(-1) appeared in addition to the pure TiO2 and N3 spectra.

Optically excited near-surface phonons of TiO(2) (110) observed by fourth-order coherent Raman spectroscopy.

We observed the fourth-order and third-order optical responses in the time domain on a TiO(2) (110) surface covered with trimethyl acetates. Coherent vibrations assignable to near-surface phonon modes were present at 179, 191, 359, 440, 507, 609, and 823 cm(-1) in the fourth-order responses. The amplitude and phase of each mode were determined with different azimuths and polarizations of pump and probe light pulses.

Fourth-order coherent Raman spectroscopy of liquid-solid interfaces: near-surface phonons of TiO2 (110) in liquids.

The fourth-order coherent Raman response of a TiO2 (110) surface covered by HCl aqueous solution, neat octanol, acetic acid, or carbon tetrachloride layers is acquired. Four fourth-order optical responses were identified at 837-826, 452-448, 371-362, and 184-183 cm(-1) and assigned to near-surface phonons of TiO2. A third-order response produced in the bulk liquid layer was superimposed on the fourth-order response, when coherent vibrations are efficiently excited in the layer.

Fourth-order coherent Raman spectroscopy in a time domain: applications to buried interfaces.

A Raman-based, nonlinear optical spectroscopy is a promising method for observing vibrational modes localized at buried interfaces. The principles of Raman excitation and interface-selective detection of coherent vibrations are described. Applications to air-liquid, liquid-liquid, air-solid, liquid-solid, and solid-solid interfaces are reviewed.

Excited-state structure and dynamics of 1,3,5-tris(phenylethynyl)benzene as studied by Raman and time-resolved fluorescence spectroscopy.

Excited-state structure and dynamics of 1,3,5-tris(phenylethynyl)benzene (TPB) have been studied in n-hexane and n-heptane solutions. Time-resolved fluorescence spectra, fluorescence anisotropy, and lifetime of TPB were recorded with femtosecond to nanosecond time resolution. Raman depolarization ratio was also measured to elucidate a nonplanar structure of the ground state.