Magnetophoretic detection of photo-induced spin transition.
Magnetophoretic velocimetry detected the spin transition of a single Co-Fe Prussian Blue analogous micro-crystal in water induced by a single-shot pulse laser.
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Biomedical subjects
Hitoshi Watarai
Publications and source records attributed to Hitoshi Watarai.
High-magnetic-field electromagnetophoresis of micro-particles in a capillary flow system.
The electromagnetophoretic migration of micro-particles in a capillary flow system was demonstrated using a homogeneous magnetic field applied at right angles to an electric current. We utilized a high-magnetic-field of 10 T for observing this phenomenon. When the direction of the electric current was alternatively changed, polystyrene latex particles in a flowing aqueous medium migrated zigzag affected by a Lorentz force exerted on the medium. Carbon particles also migrated in the same manner with polystyrene particles. Further, we tried the electromagnetophoretic migration of biological particles, such as yeasts and human red blood cells. The migration velocity component perpendicular to the flow was proportional to both the electric current and the magnetic flux density. These results proved that the dominant force of the zigzag migration was an electromagnetophoretic buoyancy generated in the flowing medium. Moreover, it was found that the force exerted on the particles in the magnetic field of 10 T was sufficient for the desorption of particles adsorbed on the capillary wall.
Carbon↗
Surface-enhanced Raman scattering from oleate-stabilized silver colloids at a liquid/liquid interface.
Oleate-stabilized silver colloids of 5-nm-diameter were adsorbed to a toluene/water interface, and surface enhanced Raman scattering (SERS) spectra from these colloids were measured under the total internal reflection (TIR) condition. From the observed spectra, we examined the states of oleate ions and toluene molecules on silver colloids at the liquid/liquid interfacial region. The TIR-SERS spectra of oleate ions showed stronger peaks of the carboxylate group and the ethylene group than those of alkyl chains. From these results, it was found that the oleate ions were adsorbed on the silver surface in two different ways at the liquid/liquid interface; the carboxylate group adsorbed in the organic phase side, while the ethylene group adsorbed in the aqueous phase side. The shifts of the toluene in the interfacial SERS spectra were identical to those of bulk toluene, though the relative intensities among the peaks were not same. This result suggested that the toluene was adsorbed with a weak interaction, but was significantly enhanced by the local electromagnetic field at the colloid surface.
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New principle of magnetophoretic velocity mass analysis.
We propose a novel principle of velocity mass analysis of a micro-particle using magnetophoretic force. The new method can determine the mass of a particle from its magnetophoretic velocity change in a high magnetic field gradient in a low viscous medium such as air. In the present study, the new principle was demonstrated by the magnetophoretic acceleration of an aqueous manganese(II) chloride micro-droplet and the deceleration of a water micro-droplet in the atmosphere. The observed velocity change was analyzed taking into account the mass of the droplet through the acceleration term of the equation of motion. The experimental results proved that the inertia force in the magnetophoretic velocity of a micro-particle could be detected in air. The present method provided an innovative mass analysis method without any ionization of the sample.
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Measurement of circular dichroism spectra of liquid/liquid interface by centrifugal liquid membrane method.
The direct measurement of the circular dichroism (CD) spectra of liquid/liquid interface has been achieved for the first time by the centrifugal liquid membrane (CLM) method combined with a conventional CD spectropolarimetry. In the sample chamber of the CD spectropolarimeter, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at ca. 7000 rpm to generate a two-phase liquid membrane with a high specific interfacial area. The CD spectra of the J-aggregate of protonated 5,10,15,20-tetraphenylporphyrin formed at the toluene/sulfuric acid interface in the rotating cell have been measured. The results demonstrated the novelty and advantages of this method.
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Magnetic field enhanced microextraction rate of europium(III) with 2-thenoyltrifluoroacetone and oxalate at dodecane-water interface.
A microscopic system for the observation of reactions at a liquid-liquid interface was established, to which strong magnetic fields (0-0.4 T) could be applied with permanent magnets. In situ observation for the interfacial extraction of fluorescent and paramagnetic Eu(III) ion with 2-thenoyltrifluoroacetone (Htta) in dodecane was carried out. In the presence of oxalate (ox2-), micro-aggregates of Eu(III)-tta-ox complexes were generated in the aqueous phase before its extraction. When the micro-aggregates diffused to the dodecane-water interface, Eu(tta)3 was extracted with excess Htta in the dodecane phase. The microextraction process of the aggregates was observed as random flashes of Eu(tta)3 fluorescence at the dodecane-water interface. The single flash contained about 10(-16)-10(-14) mol of Eu(III). An application of magnetic fields made the flash frequency increase, which corresponded to an enhancement of interfacial Eu(III) extraction rate. The enhancement effect was attributable to the magnetophoresis of the paramagnetic microaggregates to the dodecane-water interface.
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Complex formation of copper(II) and iron(II) with octadecyloxythiazolylazophenol at the heptane-water interface.
The complex formation of Cu(II) and Fe(II) with a hydrophobic ligand, 5-(octadecyloxy)-2-(2-thiazolylazo)phenol (TARC18), was investigated in the heptane/water system by the high-speed stirring spectrometry and the micro-two phase flow ESI/MS method. At first, the dissociation constant of TARC18 at the heptane/water interface was determined as pKa = 7.11. The interfacial complexation of the ligand with Cu(II) and Fe(II) under stirred conditions progressed with an increase of the pH. The experimental results showed that a 1:1 complex of Cu(II) and TARC18 was formed at the interface, but was hardly extracted into the heptane phase. On the other hand, the 1:2 complex of Fe(II) with TARC18 formed at the interface was significantly extracted into the heptane phase. The extraction constants and interfacial complex formation constants were estimated for the two systems from the experimental results, and all of the reaction schemes, including the interfacial reactions, were elucidated.
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Interfacial hydrolysis in the mu-oxo dimer formation of tetraphenylporphinatomanganese(III) in the toluene/water system.
The interfacial adsorption and dimerization behavior of tetraphenylporphinatomanganese(III)chroride (Mn(TPP)Cl) in the toluene/water two phase system was studied. The absorption spectra of the porphyrin complex in the organic phase were blue shifted with increasing of pH in the aqueous phase, suggesting the formation of the mu-oxo dimer. The interfacial species in these systems were examined by means of UV/vis external reflection (ER) spectrophotometry. ER spectral maxima were also blue shifted with the increase in pH, whereas the shape of the ER spectra in the basic conditions was different from that of the mu-oxo dimer. The observed results suggest that the hydroxide-coordinated monomer, Mn(TPP)OH, was generated from the Mn(TPP)(H2O)+ at the interface under the basic conditions and that was further converted to the mu-oxo dimer, which was soluble into the toluene phase.
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Migration analysis of micro-particles in liquids using microscopically designed external fields.
The recent development of new migration methods of micro-particles in liquids using various external fields is reviewed. The combination of a laser scattering force and a photothermal effect produced photothermal-conversion laser-photophoresis. A dielectric field generated in a planer or a capillary quadrupole electrode realized dielectrophoresis. Using a micrometer-scaled magnetic field gradient, the "Magnetophoretic velocimetry" of micro-particles was invented. Furthermore, the Lorentz force generated by combining an electric field and a magnetic field was utilized for electromagnetophoresis. These new methods were overlooked and the advantages in analytical use were discussed.
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Magnetophoresis and electromagnetophoresis of microparticles in liquids.
The magnetic field-induced migration of particles in liquids is a highly-promising technique for the micro-separation analysis of bioparticles, such as cells and large DNA. Here, new methods that make use of magnetophoresis and electromagnetophoresis to induce the migration of microparticles in liquids are briefly reviewed. Magnetic force and Lorentz force are utilized in the new methods. Some typical examples of the use of these methods are described, and the advantages of using a superconducting magnet for them are demonstrated.
Cell Separation↗
Magnetophoretic velocity of microorganic droplets adsorbed by dysprosium(III) laurate in water.
By using an improved apparatus for the observation of magnetophoresis, the magnetophoretic velocity of 2-fluorotoluene droplets including lauric acid was measured in aqueous dysprosium(III) solution. The magnetophoretic velocity of pure 2-fluorotoluene droplets was proportional to the square of the radius. On the other hand, the velocity of the organic droplets including lauric acid in the dysprosium(III) solution showed a deviation from the square radius relationship, more remarkably in smaller droplets than 2 microm in radius. These results indicated that the dysprosium(III)-laurate complex was formed at the liquid-liquid interface. This study is the first report on the detection of the interfacial complex by the magnetophoresis of the microdroplet.
Adsorption↗
Structural isomers in a 2-(5-bromo-2-pyridylazo)-5diethylaminophenolatochloropalladium(II) crystal.
Crystal structure of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenolatochloropalladium(II) (PdLCl) has been determined by X-ray diffraction. A crystal of PdLCl was constructed by two structural isomers of PdLCl molecules, which were particularly different in the positions of the carbon atoms at the diethylamino group, having cis-like or trans-like conformation for the carbon atoms. The molecules of PdLCl in the crystal were warped by a steric hindrance of the diethylamino group.
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Effects of viability and lectin protein binding on dielectrophoretic behavior of single yeast cells.
The dielectrophoretic (DEP) behavior of individual yeast cells (5-7 microm in diameter) in aqueous media was observed in a fabricated planar quadrupole microelectrode with a working area of 100 microm in diameter by an optical microscope. The yeast cells migrated in the radial direction in the working area. The DEP velocity of the cells increased as they approached the electrode. The DEP trajectory of the cells was analyzed with a theoretical equation derived previously, and the dielectrophoretic mobility was determined. The dielectrophoretic mobility was found to be affected by the viability of cells, the conductivity of the medium, and the binding of lectin protein (concanavalin A) to the cell surface. These DEP behaviors were analyzed based on the permittivities and conductivities of the cell interior and wall, and those of the medium.
Concanavalin A↗
Simultaneous measurement of the migration velocity and adsorption force of micro-particles using an electromagnetophoretic force under a high magnetic field.
A simultaneous measurement technique for determining the migration velocity of a micrometer-sized particle in a capillary and the adsorption force to the inner surface of the capillary has been proposed. This technique is based on an electromagnetophoretic force being exerted on a micro-particle in an electrolyte solution, which is governed mainly by the electromagnetic buoyancy, when a homogeneous magnetic field is applied at a right angle to the electric current through the medium. By the electromagnetic buoyancy, micro-particles such as polystyrene, carbon and yeast were migrated perpendicular to the direction of the electric current and reached a fused-silica wall. A switching of the current direction could desorb the particle from the wall, and allowed to calculate the detaching force from the desorbing current. The migration velocity normalized to the size in the magnetic field of 10 T was increased in the order of yeast, carbon and polystyrene, while reflecting the decreasing order of the apparent conductivity of the particles. The desorption force could be measured up to 1 nN with a sensitivity of pN. The observed interaction forces of polystyrene and carbon were in the range of 250-600 pN with large deviations.
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Magnetophoretic velocimetry of manganese(II) in a single microdroplet in a flow system under a high gradient magnetic field generated with a superconducting magnet.
An experimental system for magnetophoretic velocimetry, which could determine the volume magnetic susceptibility of a single particle dispersed in a liquid phase from a magnetophoretic velocity, has been developed. A micrometer-sized high-gradient magnetic field could be generated in a capillary by a pair of iron pole pieces in a superconducting magnet (10 T). The magnetophoretic behavior of a single particle in a capillary flow system was investigated under the inhomogeneous magnetic field. From the magnetophoretic velocity of a polystyrene latex particle dispersed in a MnCl2 aqueous solution, the product of the magnetic flux density and the gradient, B(dB/dx), was determined as a function of the position along the capillary. The maximum value of B(dB/dx) was 4.7 x 10(4) T2 m(-1), which was approximately 100 times higher than that obtained by two Nd-Fe-B permanent magnets (0.4 T). Organic droplets extracting manganese(II) with 2-thenoyltrifluoroacetone and tri-n-octylphosphine oxide from MnCl2 solution were used as test samples. The difference of the volume magnetic susceptibility between the droplet and the medium could be determined from the magnetophoretic velocity. This method allowed us to continuously measure a volume magnetic susceptibility of 10-6 level for a picoliter droplet and to determine manganese(II) in the single droplet at the attomole level.
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Capillary magnetophoresis of human blood cells and their magnetophoretic trapping in a flow system.
The performance of a capillary magnetophoretic device was improved by enhancing the magnetic field gradient using a pair of small iron tips attached to the Nd-Fe-B magnets. The magnetophoretic intensity, B(dB/dx), was determined as a function of distance along the gap between the tips from the magnetophoretic velocity of a 3 microm polystyrene microparticle in 0.6 M manganese(II) chloride solution. The maximum intensity was increased 4.5 times by the attached iron pieces. The magnetophoresis of a single human blood cell in 0.1 M manganese(II) solution was studied by this method and its magnetic susceptibility was estimated. Magnetophoretic trapping of red blood cells was demonstrated under counter-current flow conditions in the capillary.
Cell Separation↗
Direct electrospray ionization mass spectroscopic measurement of micro-flow oil/water system.
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