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. In this study, simultaneous measurements of the interfacial tension and surface flow speed of the unidirectional self-propelled motion of a butyl salicylate (BS) droplet in a circular channel on a sodium dodecyl sulfate (SDS) aqueous solution were achieved by the quasi-elastic laser scattering method. The droplet position was also recorded by observing its fluorescence excited by a UV light. The BS droplet speed dependence of the interfacial tension and surface flow speed were measured by varying the initial BS concentration codissolved in the SDS aqueous solution. As a result, a periodic decrease of the interfacial tension and a periodic increase of the speed of both forward and backward flows were observed when the droplet passed the sampling position of the time-resolved measurements. When they were converted to the distribution in space of the droplet position, no droplet speed dependence of the interfacial tension difference between the front and rear of the droplet was observed. On the other hand, the speed of both forward and backward flows increased as the droplet speed increased. By analysis of the above results with a simplified model, it was clarified that the forward flow driven by the interfacial tension gradient at the droplet front is actually important in the mechanism of the unidirectional self-propelled motion of a droplet.

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. This is an upgrade of the quasi-elastic laser scattering method with a closed-loop control system that introduces the dynamically tracked scattered and referential light into the detector. For the evaluation of the tilt compensation by dynamic tracking, the relationship between the apparent interfacial tension and surface inclination was examined for a water meniscus at 0-5° inclinations. It was also demonstrated that simultaneous measurements of the interfacial tension and surface flow speed around a self-propelled camphor boat on a pure water surface inclined by >3° at the back end of the boat are difficult to conduct accurately without dynamic tracking. Both the interfacial tension difference and the backward flow speed increased as the boat speed increased to 0.1 m/s; that had not been evaluated to date because of the high velocity of the boat and the surface inclination of the water around it. The direct experimental evaluation of the interfacial tension and the flow speed supported the model that the driving force of the camphor boat is the interfacial tension difference and the resistance force proportional to the boat velocity reduces its acceleration.

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. On the other hand, when the cholesterol concentration was raised, the membrane tension increased whereas the diffusion coefficient decreased. The importance of the present results goes beyond this quantitative evaluation of the relation between the membrane tension and the fluidity, as it clarifies the changes in the fundamental properties of lipid bilayers upon natural fluctuations and perturbative deformation that were hitherto unknown.

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. The sodium oleate tablet was self-propelled due to an imbalance in the interfacial tension induced by the inhomogeneous adsorption of oleate/oleic acid molecules. The kinetics of the self-propelled motion of a boat-shaped plastic sheet bearing sodium oleate tablets at a sodium oleate aqueous solution-nitrobenzene interface was also studied. The interfacial tension difference between the front and rear of the boat was quantitatively identified as the force pushing the boat forward, although the Marangoni flow due to the uneven distribution of the interfacial tension behind the boat tended to decelerate the motion.

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. EXPERIMENTS: The behavior of one fixed boat and one movable boat on a sodium dodecylsulfate aqueous solution in an oval track has been studied as a model system of two-body interactions. The surface tension around the movable boat was measured using the non-invasive, double-beam quasi-elastic laser scattering method. The Marangoni surface flow was quantitatively estimated using a mock boat in order to evaluate the net repulsive interaction between the two boats. FINDINGS: We succeeded in controlling the motion of the two camphor boats by varying the boat characteristics and the surfactant concentration. The balance/unbalance between the surface tension distribution and the surface flow around the boats was found to drive two different behavior modes: stationary and oscillatory. These results allow us to gain further insight into the dynamics of the interactions in the collective behavior of autonomous inanimate objects.

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. On the contrary, iodide ions, which are more hydrophobic than chloride ions, demonstrated opposite results. This mechanism was proposed based on the simultaneous time-resolved measurements of the interfacial tensions at both the donor/membrane and membrane/acceptor interfaces and observation of the convective flow due to Marangoni instability.

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. However, such rapid decreases were not observed for DOPE or DOPC. A decrease in the interfacial tension was exhibited by DOPE after 1000 s from the addition of DNA, which may be due to an overall structural change in the DOPE membrane. A DOTAP/DOPE complex system showed behaviors attributable to both DOTAP and DOPE, whereas the behavior of the DOTAP/DOPC system resembled that of DOPC alone. The current results provide a model for the so-called lipoplex carriers used in gene therapy.

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. The dependence of membrane tension on the cholesterol concentration of BLMs composed of phosphatidylcholine and phosphatidylethanolamine was investigated, with the membrane tension increasing from 1.3 µN m(-1) to 68.1 µN m(-1) when the cholesterol concentration increased from zero to 33%. These tension values are much smaller than some of those previously reported, because this method does not suppress membrane fluctuation unlike other conventional methods. Our LISD system can be a promising tool for the measurement of membrane tension in BLMs.

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. METHODS: Liposomes, comprised phospholipids and an NIR fluorescent dye (an indocyanine green derivative), and emulsions, consisting of phospholipids and oily radiographic contrast medium, were combined with polyglycerol-polyricinoleate to form giant cluster-like vesicles. This vesicular dispersion (300 µl) was administered into the porcine gastric submucosa using a gastroendoscope, and the detectability of the marker was examined using X-ray CT and NIR fluorescence laparoscopy. RESULTS: One hour after the administration of the vesicular dispersion, X-ray CT identified four individual injection sites, each at a 1-cm radius of a metal hemostasis clip. NIR fluorescence laparoscopy detected individual fluorescent spots 18 hours after the administration of the vesicular dispersion. CONCLUSION: We anticipate that this newly developed tissue marker will contribute to the preoperative simulation of laparoscopic gastrointestinal cancer surgery and its intraoperative navigation.

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.

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. In a water/nitrobenzene oscillatory system with continuous surfactant addition to the interface, the local adsorption of surfactants at the interface has been demonstrated and shown to be strongly related to the presence of electrolytes. In a donor/membrane/acceptor system, the dual-beam QELS method shows that surfactant adsorption at the membrane/acceptor interface is responsible for oscillations in the electric potential. The differences in the adsorption/desorption behavior of metal complex catalysts between air/liquid and liquid/liquid interfaces were considered in the propagating chemical waves of the Belousov-Zhabotinsky reaction. We successfully measured the distribution of interfacial tension around a self-propelled camphor boat and an alcohol droplet floating on an aqueous phase, and compared the mechanisms of their motion.

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.

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. The dependence of the interfacial tension on a co-surfactant, 1-butanol, and the electrolyte, NaCl, was also examined in order to clarify the relationship among the interval and the amplitude in the oscillatory electric potential behavior.

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. The diameter of the spot blur was approximately 2 cm over a 5-h period, demonstrating the utility of this procedure as a tissue marker for tumor marking, and suggesting its potential for assisting navigation during surgical procedures.

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. The delay time and the increase in interfacial tension were also reproduced by a model considering the rate constants of equilibrium adsorption.

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. There was a large time-dependence in the TERS spectra for the DOPC bilayers, whereas no such time-dependence was observed in the DPPC bilayer spectra under the probe tip. The spectral changes of DOPC bilayers are discussed in terms of the fluidity of the liquid crystalline phase. Time-resolved TERS thus has the potential to characterize inhomogeneity and diffusion in fluidic phospholipid bilayer membranes.

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. In contrast, the presence of an electrolyte induced adsorption of the surfactant ions by screening their charged polar heads. Zwitterionic and nonionic surfactants were also examined and we deduced that the salting out effect of the surfactant produced by the presence of an electrolyte results in strongly attractive interactions between the surfactant molecules and the water/nitrobenzene interface.

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. Adsorption of N3 dye on TiO2 contributed to the enhancement of 100 and 146 cm(-1) mode. The results not only reported interfacial low-frequency vibrations of TiO2 (110) with N3 dye adsorption but also suggested the coupling between the surface vibrations of TiO2 and charge transfer between N3 dye and TiO2 on the surface.

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. Vibrational assignments and possible mechanisms to excite the vibrations were discussed.