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Masayoshi Watanabe

Publications and source records attributed to Masayoshi Watanabe.

At least 19 recordsLinked to original sources
PubMed2006

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide).

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE(n)-b-EO(m)) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO(m) without the thermo-responsive EGE(n) segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE(n) segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.

Diffusion↗
PubMed2006

How ionic are room-temperature ionic liquids? An indicator of the physicochemical properties.

Room-temperature ionic liquids (RTILs) are liquids consisting entirely of ions, and their important properties, e.g., negligible vapor pressure, are considered to result from the ionic nature. However, we do not know how ionic the RTILs are. The ionic nature of the RTILs is defined in this study as the molar conductivity ratio (Lambda(imp)/Lambda(NMR)), calculated from the molar conductivity measured by the electrochemical impedance method (Lambda(imp)) and that estimated by use of pulse-field-gradient spin-echo NMR ionic self-diffusion coefficients and the Nernst-Einstein relation (Lambda(NMR)). This ratio is compared with solvatochromic polarity scales: anionic donor ability (Lewis basicity), E(T)(30), hydrogen bond donor acidity (alpha), and dipolarity/polarizability (pi), as well as NMR chemical shifts. The Lambda(imp)/Lambda(NMR) well illustrates the degree of cation-anion aggregation in the RTILs at equilibrium, which can be explained by the effects of anionic donor and cationic acceptor abilities for the RTILs having different anionic and cationic backbone structures with fixed counterparts, and by the inductive and dispersive forces for the various alkyl chain lengths in the cations. As a measure of the electrostatic interaction of the RTILs, the effective ionic concentration (C(eff)), which is a dominant parameter for the electrostatic forces of the RTILs, was introduced as the product of Lambda(imp)/Lambda(NMR) and the molar concentration and was compared with some physical properties, such as reported normal boiling points and distillation rates, glass transition temperature, and viscosity. A decrease in C(eff) of the RTILs is well correlated with the normal boiling point and distillation rate, whereas the liquid-state dynamics is controlled by a subtle balance between the electrostatic and other intermolecular forces.

Journal Article↗
PubMed2006

Lithium secondary batteries using modified-imidazolium room-temperature ionic liquid.

Highly reversible, safe lithium secondary batteries that use imidazolium-cation-based room-temperature ionic liquid as an electrolyte and lithium metal as an anode material were realized by the molecular design. To achieve higher reduction stability, an electron-donating substituent was introduced to promote charge delocalization in the imidazolium cation of room-temperature ionic liquids.

Letter↗
PubMed2006

Mirror magneto-optical trap using circularly polarized light-emitting optical fibers.

A fiber-optic mirror magneto-optical trap (mirror-MOT) that uses a pair of circularly polarized light-emitting optical fibers as an optical access is demonstrated. The fiber is fabricated so that a length of birefringence fiber, designed to be a quarter wave retarder at both wavelengths of 780 and 852 nm, is attached directly onto a polarization-maintaining normal fiber. The polarization states of light emitted from the fibers are sufficiently circular for the operation of a mirror-MOT with 87Rb atoms. The mirror-MOT is able to capture approximately the same number of atoms obtainable with a conventional mirror-MOT. The technique makes it possible to fabricate a compact MOT apparatus by introducing the optical fibers directly into an ultrahigh-vacuum chamber.

Journal Article↗
PubMed2006

Preparations and optical properties of ordered arrays of submicron gel particles: interconnected state and trapped state.

Two types of thermosensitive opal-structured hydrogel systems, "interconnected" and "trapped" gel particle arrays, were newly developed by extremely simple methods using silica colloidal crystal as a template. Although both systems diffract visible light following Bragg's law combined with Snell's law, the temperature dependences of their optical properties were quite different. The "interconnected" array exhibited a reversible change in the peak values of the reflection spectra, mainly determined by the swelling ratio of the hydrogel, as a function of the water temperature. Since the swelling ratio is dominant over the peak value, we can observe water temperature through the color of the interconnected type of gel membrane. The "trapped" array revealed a reversible change in the peak intensity of the reflection spectra with the change in temperature, whereas no change in the peak position was observed. We can interpret this phenomenon in the following ways. As the rise in temperature causes a decrease in the water content of the NIPA gel particles, the gel particles becomes stickier on the cavity wall of polystyrene PPM. This may induce a disturbance in the ordered array of the gel particles and form many layers of rough surfaces in the inverse opal structure of the PPM. This situation may lead to the stronger diffused reflection of light from the gel particles, resulting in the decrease in peak intensity at higher temperatures.

Journal Article↗
PubMed2006

Physicochemical properties and structures of room-temperature ionic liquids. 3. Variation of cationic structures.

A series of room-temperature ionic liquids (RTILs) were prepared with different cationic structures, 1-butyl-3-methylimidazolium ([bmim]), 1-butylpyridinium ([bpy]), N-butyl-N-methylpyrrolidinium, ([bmpro]), and N-butyl-N,N,N-trimethylammonium ([(n-C(4)H(9))(CH(3))(3)N]) combined with an anion, bis(trifluoromethane sulfonyl)imide ([(CF(3)SO(2))(2)N]), and the thermal property, density, self-diffusion coefficients of the cation and anion, viscosity, and ionic conductivity were measured over a wide temperature range. The self-diffusion coefficient, viscosity, ionic conductivity, and molar conductivity follow the Vogel-Fulcher-Tamman equation for temperature dependencies, and the best-fit parameters have been estimated, together with the linear fitting parameters for the density. The relative cationic and anionic self-diffusion coefficients for the RTILs, independently determined by the pulsed-field-gradient spin-echo NMR method, appear to be influenced by the shape of the cationic structure. A definite order of the summation of the cationic and anionic diffusion coefficients for the RTILs: [bmim][(CF(3)SO(2))(2)N] > [bpy][(CF(3)SO(2))(2)N] > [bmpro][(CF(3)SO(2))(2)N] > [(n-C(4)H(9))(CH(3))(3)N][(CF(3)SO(2))(2)N], has been observed, which coincides with the reverse order to the viscosity data. The ratio of molar conductivity obtained from the impedance measurements to that calculated by the ionic diffusivity using the Nernst-Einstein equation quantifies the active ions contributing to ionic conduction in the diffusion components and follows the order: [bmpro][(CF(3)SO(2))(2)N] > [(n-C(4)H(9))(CH(3))(3)N][(CF(3)SO(2))(2)N] > [bpy][(CF(3)SO(2))(2)N] > [bmim][(CF(3)SO(2))(2)N] at 30 degrees C.

Journal Article↗
PubMed2005

Magnitude and directionality of interaction in ion pairs of ionic liquids: relationship with ionic conductivity.

The intermolecular interaction energies of nine ion pairs of room temperature ionic liquids were studied by MP2/6-311G level ab initio calculations. The magnitude of the interaction energies of 1-ethyl-3-methylimidazolium (emim) complexes follows the trend CF(3)CO(2)(-) > BF(4)(-) > CF(3)SO(3)(-) > (CF(3)SO(2))(2)N(-) approximately PF(6)(-) (-89.8, -85.2, -82.6, -78.8, and -78.4 kcal/mol, respectively). The interaction energies of BF(4)(-) complexes with emim, ethylpyridinium (epy), N-ethyl-N,N,N-trimethylammonium ((C(2)H(5))(CH(3))(3)N), and N-ethyl-N-methylpyrrolidinium (empro) are not very different (-85.2, -82.8, -84.6, and -84.4 kcal/mol, respectively), while the size of the orientation dependence of the interaction energies follows the trend emim > epy approximately (C(2)H(5))(CH(3))(3)N > empro. Comparison with the experimental ionic conductivities shows that the magnitude and directionality of the interaction energy of the ion pairs play a crucial role in determining the ionic dissociation/association dynamics in the ionic liquids. The electrostatic interaction is the major source of attraction between ions. The induction contribution is small but not negligible. The hydrogen bonding with the C(2)-H of imidazolium is not essential for the attraction in the ion pair. The interaction energy of the BF(4)(-) complex with 1-ethyl-2,3-dimethylimidazolium (em2im) (-81.8 kcal/mol) is only 4% smaller than that of the emim complex.

Journal Article↗
PubMed2005

Electron transfer reactions of glucose oxidase at Au111 electrodes modified with phenothiazine derivatives.

The catalytic reaction of glucose oxidase (GOx) mediated by 3-(10-phenothiazyl)propionic acid (PT-PA) and phenothiazine-labeled poly(ethylene oxide) (PT-PEO1000) that are covalently bonded to Au(111) electrodes has been investigated. The PT-PA and PT-PEO1000 are reacted with 2-aminoethanethiol (AET), followed by the formation of a self-assembled monolayer (SAM) onto the Au surface. The PT group immobilized on the SAM of AET acts as an effective mediator for the electron transfer (ET) between the electrode and the FAD center of freely diffusing GOx in solution. The ET rate constant estimated from the catalytic current using a newly derived equation is larger by 1 order of magnitude for the PT-PA-modified system (1.1 x 10(5) dm(3) mol(-1) s(-1)) than for the PT-PEO1000 system (1.4 x 10(4) dm(3) mol(-1) s(-1)). The order of the magnitude of the ET rate constant clearly contrasts with the GOx hybrid systems that we previously investigated (Anal. Chem. 2003, 75, 910-917), in which the presence of the PEO spacer enhances the ET reaction rate. The reduction in the apparent PT concentration at the electrode interface due to the high mobility of the PEO chain, leading to low efficiency in the formation of an enzyme-mediator complex, is a possible reason for the lower mediation ability of PT-PEO1000 than that of PT-PA for the ET between the FAD group and PT(+) immobilized on the electrode. Inhibition of the penetration of GOx molecules into the monolayer and of the accessibility of some part of PT groups to GOx molecules could also be reasons for the lower mediation ability of PT-PEO1000 thickly modified on the electrode.

Aspergillus niger↗
PubMed2005

Physicochemical properties and structures of room temperature ionic liquids. 2. Variation of alkyl chain length in imidazolium cation.

The alkyl chain length of 1-alkyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([Rmim][(CF(3)SO(2))(2)N], R = methyl (m), ethyl (e), butyl (b), hexyl (C(6)), and octyl (C(8))) was varied to prepare a series of room-temperature ionic liquids (RTILs), and the thermal behavior, density, viscosity, self-diffusion coefficients of the cation and anion, and ionic conductivity were measured over a wide temperature range. The self-diffusion coefficient, viscosity, ionic conductivity, and molar conductivity change with temperature following the Vogel-Fulcher-Tamman equation, and the density shows a linear decrease. The pulsed-field-gradient spin-echo NMR method reveals a higher self-diffusion coefficient for the cation compared to that for the anion over a wide temperature range, even if the cationic radius is larger than that of the anion. The summation of the cationic and anionic diffusion coefficients for the RTILs follows the order [emim][(CF(3)SO(2))(2)N] > [mmim][(CF(3)SO(2))(2)N] > [bmim][(CF(3)SO(2))(2)N] > [C(6)mim][(CF(3)SO(2))(2)N] > [C(8)mim][(CF(3)SO(2))(2)N], which greatly contrasts to the viscosity data. The ratio of molar conductivity obtained from impedance measurements to that calculated by the ionic diffusivity using the Nernst-Einstein equation quantifies the active ions contributing to ionic conduction in the diffusion components, in other words, ionicity of the ionic liquids. The ratio decreases with increasing number of carbon atoms in the alkyl chain. Finally, a balance between the electrostatic and induction forces has been discussed in terms of the main contribution factor in determining the physicochemical properties.

Journal Article↗
PubMed2005

Ion gels prepared by in situ radical polymerization of vinyl monomers in an ionic liquid and their characterization as polymer electrolytes.

To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named "ion gels", decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10(-2) S cm(-1). Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI(-) anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself.

Journal Article↗
PubMed2005

Distinct difference in ionic transport behavior in polymer electrolytes depending on the matrix polymers and incorporated salts.

Two different electrolyte salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and a room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), were incorporated into network polymers to obtain ion-conductive polymer electrolytes. Network polymers of poly(ethylene oxide-co-propylene oxide) (P(EO/PO)) and poly(methyl methacrylate) (PMMA) were chosen as matrixes for LiTFSI and EMITFSI, respectively. Both of the polymer electrolytes were single-phase materials and were completely amorphous. Ionic conductivity of the polymer electrolytes was measured over a wide temperature range, with the lowest temperatures close to or below the glass transition temperatures (Tg). The Arrhenius plots of the conductivity for both of the systems exhibited positively curved profiles and could be well fit to the Vogel-Tamman-Fulcher (VTF) equation. The conductivity of the PMMA/EMITFSI electrolytes was higher at most by 3 orders of magnitude than that of the LiTFSI/P(EO/ PO) electrolytes at ambient temperature. When the ideal glass transition temperature, T0 (one of the VTF fitting parameters), was compared with the Tg, a difference in the ionic conduction was apparent in these systems. In the P(EO/PO)/LiTFSI electrolytes, the T0 and Tg increased in parallel with salt concentration and the T0 was lower than the Tg by ca. 50 degrees C. On the contrary, the difference between the T0 and the Tg increased with increasing content of PMMA in the PMMA/EMITFSI electrolytes, with the observed difference in the concentration range studied reaching up to ca. 100 degrees C. The conductivity at the Tg, sigma(Tg), for the LiTFSI/P(EO/PO) electrolytes was on the order of 10(-14-)10(-13) S cm(-1) and increased with increasing salt concentration, whereas that for the PMMA/EMITFSI polymer electrolytes reached 10(-7) S cm(-1) when the concentration of PMMA was high. The ion transport mechanism was discussed in terms of the concepts of coupling/decoupling and strong/fragile for the two different polymer electrolytes.

Journal Article↗
PubMed2005

Ionic liquid crystal as a hole transport layer of dye-sensitized solar cells.

Use of a new ionic liquid crystal, 1-dodecyl-3-methylimidazolium iodide, and iodine as an electrolyte of dye-sensitized solar cells leads to a high short circuit photocurrent density and a high light-to-electricity conversion efficiency, due to a self-assembled structure of the imidazolium cations, resulting in high conductivity of the electrolyte.

Journal Article↗
PubMed2004

Surface activity and redox behavior of a non-ionic surfactant containing a phenothiazine group.

A novel non-ionic surfactant, alpha-(phenothiazinylhexyl)-omega-hydroxy-oligo(ethylene oxide) (PCPEG) containing phenothiazine as an electro-active group has been synthesized. Fundamental interfacial behavior of the surfactant at the air/water interface has been investigated by means of surface tensiometry to provide an insight into the relationship between the structure of the hydrophobic moiety and the surfactant properties. A comparison of diffusivity of PCPEG in the aqueous phase with that in the acetonitrile solution at high PCPEG concentrations shows that micellization has a pronounced effect on the redox behavior of PCPEG. The electrochemical responses for PCPEG aqueous solutions at the interface of a glassy carbon electrode are fairly dependent on the concentration of PCPEG. Above CMC, PCPEG molecules self-associate to form micellar aggregates and the formation and disruption of micelles can be reversibly controlled by change in the redox state of the phenothiazine group. The cyclic voltammetric responses for PCPEG aqueous solutions have been correlated with the dissolved states to explain the distinctive feature of the surfactant.

Adsorption↗
PubMed2004

Effect of a modification site on the electron-transfer reaction of glucose oxidase hybrids modified with phenothiazine via a poly(ethylene oxide) spacer.

Glucose oxidase [GOx-(PT-PEONH2)] hybrids are synthesized by attaching phenothiazine (PT) groups to aspartic and glutamic acid residues on the enzyme surface via poly(ethylene oxide) (PEO) spacers of different molecular weights. A fast oxidation of FADH2/FADH by PT+ with the aid of the local motion of a hydrophilic, long, flexible PEO spacer is achieved for the GOx-(PT-PEONH2) hybrids and yields greater electron-transfer (ET) rates than that for GOx-(PTNH2) hybrids, in which the PT groups are directly bonded to the GOx surface. The ET rate of GOx-(PT-PEONH2) hybrids depends on the molecular weight of PT-PEONH2, and the maximum is obtained at a molecular weight of 3000. The ET rates of GOx hybrids are compared in terms of the location of the PT modification and the length and structure of the spacer chain connection of the PT mediator to a surface amino acid residue. Greater ET rates are obtained for the modification at aspartic and glutamic acid residues than for the lysine modification when the PT groups are bonded directly or via a short PEO spacer chain. In contrast, no advantage of aspartic and glutamic acid residues over lysine residues in generating a fast oxidation of FADH2/FADH by PT+ is observed for GOx hybrids in which the PT groups are attached via longer PEO spacers. The long PEO spacer is able to compensate the disadvantage of lysine residues locating far from the FAD center in GOx hybrids whose mediation reactions are based on the so-called wipe mechanism.

Electron Transport↗
PubMed2004

Temperature-induced reversible change in the redox response in phenothiazine-labeled poly(ethoxyethyl glycidyl ether) and its application to the thermal control of the catalytic reaction of glucose oxidase.

Novel redox-active thermosensitive polymers (phenothiazine-labeled poly(ethoxyethyl glycidyl ether), PT-PEEGE), composed of a polyoxyalkylene backbone, ethoxyethoxymethyl side chains, and an electroactive phenothiazine end group, were prepared by base-catalyzed anionic ring-opening polymerization of ethoxyethyl glycidyl ether monomer in the presence of 10-(2-hydroxyethyl)phenothiazine. Phase separation of a 1.0 mmol dm(-3) (0.33 wt %) PT-PEEGE aqueous solution occurs at 28 degrees C. While the phase separation temperature (Tc) is almost constant in the concentration range above 1.0 mmol dm(-3), it increases at below 1.0 mmol dm(-3). A 10-fold decrease in the oxidation current of PT-PEEGE is observed above Tc and reflects the decrease in the apparent concentration of electroactive PT-PEEGE due to the phase separation. The redox response mainly comes from PT-PEEGE molecules in the dilute phase, resulting from the phase separation, and the half-wave potential and peak separation are independent of the phase separation. This thermally induced change in the redox response is reversible and is applied for the thermal control of the electrocatalytic reaction of glucose oxidase (GOx). The catalytic current in the presence of PT-PEEGE as an electron mediator decreases at temperatures higher than Tc. This originates from the phase separation of PT-PEEGE, and PT-PEEGE molecules which remained to be soluble participate in the electrocatalytic reactions of GOx as mediators.

Catalysis↗
PubMed2004

[Examination of occupational exposure to medical staff (primarily nurses) during 131I medical treatments].

Recently, a new amendment to protect against radiation damage to humans has been enacted based on a 1990 recommendation by the ICRP. Consequently, the dose limits of occupational exposure to medical staff were cut down sharply compared with conventional readjustments. This amended bill, however, may be triggering a reduction in the number of applicants, which hope to engage in radiotherapy. This being the case, we measured the dose levels of the occupational exposure to medical staff (doctor's group, nuclear medicine technologist's group, nurse's group and pharmacist's group) from 1999 to 2002. Moreover, we investigated what the main factor is in nurse's occupational exposure to 131I. The highest doses of occupational exposure were 3.640 mSv to doctors, 7.060 mSv to nuclear medicine technologists, 1.486 mSv to nurses and 0.552 mSv to pharmacists. According to our results, it was clear that the highest doses in each group were far below the legally mandated upper limits of exposure doses. Although we investigated the correlations between the factors of nurse's occupational exposure to 131I with the number of inpatients, the amount of 131I and the number of servicing times for patients, there were no correlations found. Furthermore, to analyzing the factors in detail, it became clear that the main factor in the nurse's occupational exposure was due to the existence of patients who needed many more servicing times for their care than ordinary patients.

Humans↗