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Tetsuo Okada

Publications and source records attributed to Tetsuo Okada.

15 recordsLinked to original sources
PubMed2006

Analysis of structurally heterogeneous Langmuir-Blodgett films of folded/unfolded long-chain molecules by infrared multiple-angle incidence resolution spectroscopy.

Infrared multiple-angle incidence resolution spectroscopy (IR MAIRS) has been employed for the structural analysis of a heterogeneous multilayer Langmuir-Blodgett (LB) film of ketomycolic acid (keto-MA). Keto-MA was chosen for the study because the molecule changes its conformation largely, which depends on the layer structure of the LB film: the long alkyl chain with a keto group remains folded when it has no counter layer for interdigitation. IR MAIRS is a surface analytical technique that was originally developed to analyze anisotropic structure in a thin film prepared on an IR transparent material. In the present study, however, a newly found characteristic of MAIRS has been used to discuss the molecular conformation and the interdigitation architecture between two adjacent monolayers. As expected theoretically, the molecular folding was clearly detected as "IR MAIRS shift". Subtraction of the IR MAIRS spectra of single- and triple-monolayer LB film of keto-MA yielded unambiguous results for the interdigitated double layer in the triple-monolayer LB film, and the layer sequence was also revealed.

Journal Article↗
PubMed2006

Solvation of ions in hydrophilic layer of polyoxyethylated nonionic micelle. Cooperative approach by electrophoresis and ion-transfer voltammetry.

Electrophoretic measurements of micellar mobility have revealed that polyoxyethylated nonionic surfactant micelles have negative zeta potential in various electrolytes, indicating that the partition of anions into the micelle dominates the entire electrolyte partition and the induced surface potential of the micelle. Although an excess of a negative charge is thus revealed in the micelle, it is uncertain whether anions are preferably solvated in the micelles or cations are expelled from the micelles. To determine the solvation energies of single ions in the hydrophilic layer of the micelle, we have performed ion transfer voltammetric measurements at microinterfaces between nitrobenzene and aqueous tetraethyleneglycol solution, which acts as a model for the palisade layer of the micelles. The cooperative utilization of these different methods has allowed us to determine the Gibbs free energy of transfer of a single ion without an extrathermodynamic assumption. On the basis of the resulting values, the partition of ions and the zeta potential induced by the imbalance of anionic and cationic partition have been quantitatively explained.

Journal Article↗
PubMed2006

Kinetic monitoring of electrophoretically induced solute reaction by axial absorption detection with liquid-core waveguide.

Teflon AF-2400 capillary has been used for capillary electrophoretic separation as well as for liquid-core waveguide for axial absorption detection. This separation/detection scheme has allowed continuous monitoring of electrophoretically induced reactions. In this paper, the decomposition of Cd2+ complex with 4-(2-pyridylazo)resorcinol has been tested, and its decomposition kinetics has been studied. A simple modeling has predicted the single-exponential decay of the absorbance detected by the present axial absorption detector and has allowed the estimation of the decomposition rate constant for this reaction.

Journal Article↗
PubMed2006

Ice chromatography. Characterization of water-ice as a chromatographic stationary phase.

Water-ice has been characterized as a stationary phase for liquid chromatography. Solutes having two or more polar groups are retained on this stationary phase with THF/hexane as the mobile phase, suggesting that multipoint interactions are required for measurable solute retention. Chromatographic separation of phenols or crown ethers on water-ice is possible. The ice surface is expected to provide two different adsorption sites coming from the OH and O dangling bonds. Although the solute partition into the quasiliquid layer is also considered, the dependence of the retention times on the THF concentration implies that the interaction of solutes with the water-ice surface rather than the partition into the quasiliquid layer is responsible for solute retention. A retention model suggests that the number of adsorption sites for a crown ether depends on its ring size, whereas two sites are involved for the retention of phenols having two hydroxyl groups. Although hydroxyl groups can act as both a hydrogen bond donor and an acceptor, the interaction with the ice OH sites, which are exposed to the surroundings in comparison with the ice O sites, is more important. However, when an acyclic polyether is added to the mobile phase, its adsorption onto the water ice surface allows the creation of the O sites that phenols can approach without steric hindrance. In the presence of the polyethers adsorbed on the ice surface, the retention of phenols is enhanced, whereas crown ethers become less retained due to the competitive adsorption of the polyethers.

Journal Article↗
PubMed2005

Low-capacity channel designed for particle separation with controlled electric fields and evaluation of involved forces.

Electric field is one of the suitable physical fields applicable to particle separations. Although long rectangular channel is used for particle separation in usual electrical field flow fractionation (FFF), a short low-capacity channel can replace it if the field is precisely controlled. Several separation principles are proposed with this channel. The elution behavior of particles has revealed that the gravitational, diffusion, and hydrodynamic lift force (HLF) play important roles in the determination of the elution behavior of particles. The elution threshold voltage (V(th)) was defined and experimentally determined for various system configurations and particles. The electric force no longer overcomes the other forces, and particles are taken off the wall, when the applied voltage becomes lower than V(th). V(th) values have allowed us not only to estimate surface charge density of a particle but also to evaluate the hydrodynamic lift force against particle.

Electricity↗
PubMed2005

Resolution of small molecules by passage through an open capillary.

When a solute passes through an open capillary, in which a laminar flow is established, different peak profiles can be obtained according to its diffusion property under a working condition, i.e., the radius and length of the capillary and the flow rate of the carrier solution. If a solute diffuses over the entire cross section of the capillary before it is eluted, a Gaussian-shaped diffusion peak appears, which has an apex at the travel time of the average flow. Insufficient solute diffusion, which is realized, e.g., by increasing flow rates or capillary radius, produces a new peak having an apex at the travel time of the maximum flow. This implies that two solutes can be resolved simply by passing through a capillary. However, our previous study indicated that the diffusion coefficients of two solutes should be at least one order different for their resolution based on this principle, suggesting that its applicability is highly restricted. In the present paper, this concept has been extended to the resolution between dissolved solutes that have similar intrinsic diffusion properties. The incorporation of molecular aggregates in the carrier makes a solute less diffusive according to the extent of their interaction and allows the resolution of a dissolved molecule from other ones differing in the affinity to the molecular aggregates. Several examples of peak resolution for phenols, aromatic hydrocarbons, and inorganic anions are shown and discussed on the basis of the modification of the diffusion natures due to their interactions with micelles or vesicles.

Journal Article↗
PubMed2005

Local structures of ions at ion-exchange resin/solution interface.

The local structures of Cl- and Br- in anion-exchange resins have been studied by X-ray absorption fine structure (XAFS), and separation selectivity is discussed on the basis of results. When two different anion-exchange resins having trimethylammonium and dimethylammonium groups as anion-exchange groups are employed for ion-exchange experiments, slightly higher Br- selectivity has been obtained with the former. XAFS has indicated that the average hydration numbers for a given anion is not affected by the structure of the ion-exchange group, but that the extent of ion-association between the anion and the ion-exchange groups depends on the type of the ion-exchange group. Shorter interaction distance (and in turn stronger ion-association) has been confirmed for the dimethylammonium-type resin, and is consistent with lower Br- selectivity of this resin.

Anion Exchange Resins↗
PubMed2005

Solute distribution coupled with laminar flow in wide-bore capillaries: what can be separated without chemical or physical fields?

Solute diffusion coupled with an orthogonal laminar flow has been systematically studied with wide-bore capillaries to establish its limitations and reveal its potentials as separation methodology requiring neither chemical nor physical interactions. Simulations based on the advection-diffusion equation in a cylindrical coordinate system indicate several important features of this potentially useful method: (1) if a solute diffuses over the entire cross-section of the capillary before it is eluted from the capillary, it behaves as a diffusive solute and gives a Gaussian-shaped peak (diffusion peak) having an apex at the traveling time of the average flow; (2) when a solute is poorly (or not) diffusive, a new peak appears with an apex at the elution time of the maximum flow (non-diffusion peak); (3) these two peaks are simultaneously detected for intermediately diffusive solutes; (4) the transformation from the diffusion to non-diffusion peak occurs when the solute diffuses over the distance 0.86 times as large as the capillary radius before it leaves the capillary. These results of simulations are consistent with experimental results for selected solutes having various diffusivities. This method has proved useful particularly for the evaluation of diffusion coefficients of poorly diffusive solutes. Separation of PS particles having different sizes is also attempted.

Journal Article↗
PubMed2004

Hydration of halide anions in ion-exchange resin and their dissociation from cationic groups.

The local structures of Cl- and Br- in an anion-exchange resin have been investigated by X-ray absorption fine structure (XAFS). The resins, which have been equilibrated under various partial water vapor pressures to allow the anions to have various hydration numbers, are provided for XAFS measurements. The XAFS spectra indicate that two scattering groups around the counteranion are present, that is, water molecules and an ion-exchange group. Regression analyses allow the separation of the contributions from these two scattering groups; thus, the average hydration number (N) is determined. The hydration number linearly increases with increasing the number of water molecules (n) adsorbed by an ion-exchange pair (an ion-exchange group and a counteranion) until the ion-exchange pair adsorbs ca. 3 water molecules, indicating that all of the adsorbed water molecules coordinate the counteranion. However, an increase in N with increasing n becomes small as n exceeds 3; N finally reaches 3.9 (+/-0.4) for Cl- and ca. 3.4 (+/-0.5) for Br-. Detailed studies of the water adsorption isotherms imply that the maximum hydration number of these anions is three when they are bound by the ion-exchange groups, and as more water molecules are supplied, they are dissociated from the ion-exchange groups; ca. 40% of total counteranions are dissociated from the ion-exchange groups.

Journal Article↗
PubMed2004

Ion exchange at a surface monolayer.

Total reflection total conversion electron yield X-ray absorption fine structure is applied to the evaluation of ion exchange occurring at the surface monolayer of two-tailed ammonium ions. X-ray absorption measurements at a Br K-edge allow us to detect ion-exchange equilibria between Br- and Cl- added in a subphase. The ion-exchange selectivity of Br- over Cl- basically increases as the monolayer is compressed, indicating that Cl- is selectively squeezed out by compression because of its larger hydrated ionic radius.

Absorption↗
PubMed2003

Complexation of a hydrophobic thiazorylazophenol with Ni2+ at sodium dodecylsulfate micellar surface.

Complexation of thiazorylazododecylphenol (TADP) with Ni2+ at the surface of sodium dodecylsulfate (SDS) micelles has been spectrophotometrically studied. Complicated spectral changes are analyzed by a factor and multivariate analysis, which implies the formation of [TDAP(OH-)Ni]0 as well as a simple 1:1 complex of Ni2+ with TDAP at the micellar interface. All of the equilibrium constants required to describe this system are substantially affected by electrolyte concentrations. Coexistent electrolytes vary the surface potential of the micelle, and in turn influence the equilibria taking place on the micellar surface. The electrostatic potential estimated based on the equilibrium shifts is more negative than that calculated according to Poisson-Boltzmann theory, which simply involves electrostatic effects. This disagreement is possibly caused by different aqueous environments around the micelle from bulk solution, which also facilitate the formation of unusual complex such as [TDAP(OH-)Ni]0.

Journal Article↗
PubMed2003

Capillary electrophoresis as a nanoreactor of separation capability: on-capillary reaction catalyzed by transition metal ions.

The catalytic oxidation of 1,2-dihydroxy-benzene-3,6-disulfonate (tiron) by metal ions has been studied for detection of the metal ions in capillary electrophoresis (CE). Although Co(2+) shows the strongest catalytic capability, some other metal ions also catalyze this reaction. If metal ions encounter a H(2)O(2 )zone after electrophoretic separation in the running buffer containing tiron, tiron is catalytically oxidized while the metal ion passes through the H(2)O(2) zone. Anionic tiron radicals produced by the reaction are finally measured by the detector; in this scheme, the capillary acts as a nano- or microreactor as well as a microseparator. The effective capillary length can be controlled by changing the interval between metal ion and H(2)O(2) injections. This scheme has been successfully applied to the detection of Co(2+), Cu(2+), Mn(2+), and VO(2+). The detectability is discussed from several viewpoints, such as the intrinsic catalyst ability of metal ions, the kinetics of the catalytic reaction, and reaction times determined by the mobility of the zone of the metal ion. Some strange behaviors, which cannot be predicted by batch experiments, are also reported.

Catalysis↗