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.

Significant suppression of Rayleigh scattering loss in silica glass formed by the compression of its melted phase.

We propose the formation of silica glass with improved optical transport properties by compressing its melted phase with a hot isostatic pressure machine at high pressure and temperature. The lowest Rayleigh scattering loss was obtained for the glass held at 200 MPa and 2073 K for 4 h. The observed loss corresponds to 0.07 dB/Km at 1.55 µm, which is about half of the loss in conventional silica glass fiber. The decrease in the loss was well explained in terms of the decrease in the size of the sub-nanometer-sized structural voids observed by positron annihilation lifetime spectroscopy in silica glass. The achievement of high transparency and strong confinement of light represents a promising result for the development of future fiber-core media.

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.

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.

Near-infrared-fluorescence imaging of lymph nodes by using liposomally formulated indocyanine green derivatives.

Liposomally formulated indocyanine green (LP-ICG) has drawn much attention as a highly sensitive near-infrared (NIR)-fluorescence probe for tumors or lymph nodes in vivo. We synthesized ICG derivatives tagged with alkyl chains (ICG-Cn), and we examined NIR-fluorescence imaging for lymph nodes in the lower extremities of mice by using liposomally formulated ICG-Cn (LP-ICG-Cn) as well as conventional liposomally formulated ICG (LP-ICG) and ICG. Analysis with a noninvasive preclinical NIR-fluorescence imaging system revealed that LP-ICG-Cn accumulates in only the popliteal lymph node 1h after injection into the footpad, whereas LP-ICG and ICG accumulate in the popliteal lymph node and other organs like the liver. This result indicates that LP-ICG-Cn is a useful NIR-fluorescence probe for noninvasive in vivo bioimaging, especially for the sentinel lymph node.

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.

Giant vesicles containing superparamagnetic iron oxide as biodegradable cell-tracking MRI probes.

A major breakthrough in in vivo cellular imaging has been the clinical/preclinical use of magnetic resonance imaging (MRI) with contrast agent. Superparamagnetic iron oxide (SPIO) is a promising candidate for the development of smart MRI probes for cell-tracking. In the present study, we describe biodegradable probes made of giant vesicles (GVs; closed lipid membranes with diameters >1 µm) that encapsulate SPIO for use as an MRI contrast agent. These SPIO-containing GVs (SPIO-GVs) exhibited excellent contrast enhancement in the single cell of medaka fish (Oryzias latipes) embryos immediately after their microinjection, and this enhancement disappeared when the GV membranes were destroyed. Our results demonstrate that SPIO-GVs are useful MRI probes for single cell-tracking that have minimum cytotoxicity and will greatly improve clinical/preclinical in vivo cellular imaging techniques.

Analysis of the Chemical State in Y-zeolite Pores by Positron Annihilation Lifetime Spectroscopy.

The chemical state of the active sites in the pores of zeolites is known to greatly affect their chemical and catalytic properties, e.g. the presence of Brønsted acid sites enhances their action as polar adsorbents. Ortho-positronium diffusion in the pore network has been widely used to clarify the zeolite structure, but its interaction with acid centers under different environments remains unclear. Here, a systematic study on Y-zeolites over a wide range of Si/Al ratios in the absence and presence of water in the framework was carried out using positron annihilation lifetime spectroscopy. The acidity of the pores was found to significantly inhibit positronium formation and annihilation within the crystalline micropore network in the dehydrated condition, highlighting a strong positronium oxidizing action of the acid centers. Upon water adsorption, the interaction of the acid sites with the water molecules enabled the recovery of positronium formation in the hydrophilic low-silica samples.

Oxygen-flask combustion with light beam ignition.

A robust oxygen-flask combustion system was developed using light beam ignition. An appropriate amount of environmental sample was wrapped with a small piece of filter paper and held in a basket made of platinum-zirconium spiral. After the sample was inserted into an oxygen-filled flask containing an acid mixture, the light beam from an overhead projector lamp was focused to ignite the sample. The combusted products were absorbed into the acid mixture by shaking the flask and then used for the ICP-AES measurement of metals. The proposed method was successfully applied to the determination of metals in Environmental Standard Reference Materials and Artemia salina. The present method is also applicable to ion chromatographic measurements of chlorine in polyvinyl chloride wall paper by using hydrogen peroxide as absorbent.

Production of a positron microprobe using a transmission remoderator.

A production method for a positron microprobe using a beta+-decay radioisotope (22Na) source has been investigated. When a magnetically guided positron beam was extracted from the magnetic field, the combination of an extraction coil and a magnetic lens enabled us to focus the positron beam by a factor of 10 and to achieve a high transport efficiency (71%). A 150-nm-thick Ni(100) thin film was mounted at the focal point of the magnetic lens and was used as a remoderator for brightness enhancement in a transmission geometry. The remoderated positrons were accelerated by an electrostatic lens and focused on the target by an objective magnetic lens. As a result, a 4-mm-diameter positron beam could be transformed into a microprobe of 60 microm or less with 4.2% total efficiency. The S parameter profile obtained by a single-line scan of a test specimen coincided well with the defect distribution. This technique for a positron microprobe is available to an accelerator-based high-intensity positron source and allows 3-dimensional vacancy-type defect analysis and a positron source for a transmission positron microscope.

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.

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.

Digestion of plastic materials for the determination of toxic metals with a microwave oven for household use.

A rapid sample-digestion method for the determination of toxic metals, cadmium, chromium, and lead, in polyethylene and polyvinyl chloride has been developed by using a microwave oven for household use. An appropriate amount of the sample taken in a PTFE decomposition vessel was mixed with nitric acid or nitric and sulfuric acids. The vessel was heated in a microwave oven by a predetermined operating program. The digested sample was diluted to a definite volume with water after evaporating most of the nitric acid. The precipitate, if formed, was filtered off by a membrane filter. The metals were determined by ICP-AES. The sample digestion required 5 min (for 20-mg sample) to 25 min (for 60-mg sample). The analytical results obtained for cadmium, chromium, and lead in a polyethylene certified reference material, BCR-680, digested with nitric acid, were in good agreement with the certified values.

Adsorption characteristics of a nanodiamond for oxoacid anions and their application to the selective preconcentration of tungstate in water samples.

A nanodiamond with a mean particle size of 4 nm, which was prepared by the detonation of a nanodiamond, has been characterized and used as a collector for tungstate in water samples. An aqueous solution of nanodiamond was found to be stable over the pH range from 3 to 10. Coagulation of the nanodiamond could be brought about by adding an electrolyte solution. The adsorption characteristics of nanodiamond have been elucidated to be attributable to amino groups on its surface by the elemental-analysis data and the zeta potential measured in weak acid media. The unique adsorption properties of the nanodiamond for oxoacid anions were applied to a selective preconcentration method for tungstate in water samples. An appropriate amount of nanodiamond was added to a sample solution at pH 5 and a calcium chloride solution was added to aggregate nanodiamond. The sample solution was then allowed to stand for 2 h and centrifuged. The nanodiamond was transferred onto a membrane filter, washed with a diluted calcium chloride solution and treated in advance of an ICP-AES measurement by either of the following procedures: (a) redispersion of the nanodiamond into dilute nitric acid with an ultrasonic washer and (b) ashing of the membrane filter and the coagulated nanodiamond at 700 degrees C, followed by a treatment of the ash with hydrochloric and tartaric acids. The average recovery of tungstate from 100-ml artificial river-water was found to be 99% at the 0.25 ppm level with an RSD of 2.2% (n = 3). The concentration factor at present is 10.

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.

Hydrodynamically induced chemical oscillation at a water/nitrobenzene interface.

By measuring a time course of interfacial tension and interfacial electrical potential, we successfully observed oscillatory phenomena that were based on alternatively appearing adsorption and desorption processes of anionic surfactant molecules (sodium dodecyl sulfate (SDS)) at the water/nitrobenzene interface. These oscillation patterns were drastically modified by slightly changing the rate of SDS aqueous solution injection into the water phase. When 10 mM of SDS aqueous solution was injected at a low rate, for example, at less than 1 microl/min, abrupt adsorption was repeatedly followed by slow desorption of DS- ions; in other words, the sequence of the oscillation and relaxation processes was repeated. However, when it was injected at a higher rate, no remarkable periodic phenomenon occurred after the first oscillation. In addition, the rapid adsorption process was observed to be accompanied by a flip motion of the liquid/liquid interface and a flow along the interface. This is caused by a Marangoni convection that is brought about by the generation of heterogeneity of interfacial tension. Furthermore, by estimating the flow speed, it was determined that the faster flow tends to quench the periodic oscillation patterns.

A novel separation and preconcentration method for traces of manganese, cobalt, zinc and cadmium using coagulation of colloidal silica.

A separation and preconcentration method has been developed for traces of heavy metals using coagulation of colloidal silica. An appropriate amount of colloidal silica was added to a sample solution, the pH was adjusted to 11 with tetramethylammonium hydroxide solution and calcium chloride solution was then added to coagulate the silica. The coagulated silica and solution were separated by centrifugation, and the silica was then treated with hydrofluoric and perchloric acids. The residue was taken up in dilute nitric acid and subjected to ICP-AES to determine manganese, cobalt, zinc and cadmium. The proposed method was successfully applied to analysis of river-water.

Chemical oscillation with periodic adsorption and desorption of surfactant ions at a water/nitrobenzene interface.

Chemical oscillations with periodic adsorption and desorption of surfactant ions, alkyl sulfate ions, at a water/nitrobenzene interface have been investigated. The interfacial tension was measured with a quasi elastic laser scattering (QELS) method and the interfacial electrical potential was obtained. We found that this oscillation consists of a series of abrupt adsorptions of ions, followed by a gradual desorption. In addition, we observed that each abrupt adsorption was always accompanied by a small waving motion of the liquid interface. From the analysis of the video images of the liquid interface or bulk phase, we could conclude that each abrupt adsorption is caused by nonlinear amplification of mass transfer of ions from the bulk phase to the liquid interface by a Marangoni convection, which was generated due to local adsorption of the surfactant ions at the liquid interface that resulted in the heterogeneity of the interfacial tension. In the present paper, we describe the mechanism of the chemical oscillation in terms of the hydrodynamic effect on the ion adsorption processes, and we also show the interfacial chemical reaction with ion exchange during the ion desorption process.