研究者詳細 - 矢嶋　摂子

論文 - 矢嶋　摂子

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ニュートラルキャリヤ型イオンセンサー

矢嶋摂子, 木村恵一

ぶんせき ( 6 ) 308 - 313 2005年

Properties of dendritic and cyclic thiourea derivatives as neutral carriers for anion sensors

Sachie Uchida, Yuichiro Komatsu, Hitomi Satoh, Setsuko Yajima, Keiichi Kimura, Yoshito Tobe, Shin-Ichi Sasaki, Masaaki Mizuno, Yohei Watanabe, Keiji Hirose

Bunseki Kagaku 53 ( 9 ) 943 - 952 2004年09月 [査読有り]

We desinged seven neutral carriers for hydrophilic anion sensors: four compounds containing one thiourea group and dendritic benzyl ether derivatives, two compounds containing three or four thiourea groups, and a cyclic compound containing three thiourea groups. The association constants with dihydrogen phosphate ion for these thiourea derivatives were determined in organic solvents. The compounds exhibited high association constants with dihydrogen phosphate ion. When these compounds were used as neutral carriers of ion-selective electrodes (ISEs) for phosphate ion, the slopes of the EMF responses were very small in all cases. The ISEs showed better EMF responses for sulfate ion than for phosphate ion. Especially in the case that dendritic and cyclic derivatives containing three thiourea groups were used as neutral carriers, the ISEs exhibited excellent EMF responses for sulfate ion and anion selectivities.

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Neutral-carrier-type potassium ion-selective electrodes based on polymer-supported liquid-crystal membranes for practical use

S Oosaki, Y Kawai, S Yajima, K Kimura

ANALYTICAL SCIENCES ( JAPAN SOC ANALYTICAL CHEMISTRY ) 20 ( 8 ) 1165 - 1169 2004年08月 [査読有り]

Polymer-supported liquid-crystal membranes have been designed for neutral-carrier-type potassium ion-selective electrodes, aiming for practical applications of high-performance liquid-crystalline membrane ion sensors. Two types of polymer-supported liquid-crystal membranes were tested for their usefulness; one is microporous poly(tetra fluoroethylene) (PTFE) membranes impregnated by thermotropic liquid-crystalline compounds, and another is poly(methyl methacrylate) (PMMA) membrane dispersing the same liquid-crystalline compounds. Both of the polymer-supported liquid-crystal membranes containing a liquid-crystalline benzo-15-crown-5 neutral carrier as well as a lipophilic anion excluder work well as ion-sensing membranes for potassium ion-selective electrodes, the ion selectivities of which can be switched by the measurement temperatures. Specifically, PTFE-impregnated liquid-crystal membranes are better than the PMMA-dispersed ones in the sensitivity and selectivity of the resulting ion electrodes. A potassium ion assay in blood sera has proved that neutral-carrier-type ion-selective electrodes based on the polymer-supported liquid-crystal membranes are reliable for practical uses.

ソフトな金属イオンのためのπ－配位性芳香族ニュートラルキャリヤ－を用いる銀イオンセンシング

吉岡令雄, 矢嶋摂子, 木村恵一

分析化学 52 ( 9 ) 689 - 694 2003年09月

We have been studying neutral carriers of ion-selective electrodes (ISEs) for soft metal ions, and have reported that π-coordinate calixarene derivatives are useful for detecting soft metal ions selectively. In this study, in order to investigate what structures are essentially needed for detecting soft metal ions, several π-coordinate aromatic compounds were chosen as neutral carriers of ISEs, and the ion sensor properties were examined. An 1H-NMR study showed that t-butylcalix[4]arene tetra(allyl ether) and [2.2.2]-paracyclophane interact with silver ions power-fully, and that only t-butylcalix[4]arene interacts with thallium ions. Therefore, ISEs based on [2.2.2]-paracyclophane exhibited excellent silver ion sensor properties.

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Silver ion sensing using pi-coordinate aromatic neutral carriers for soft metal ions

N Yoshioka, S Yajima, K Kimura

BUNSEKI KAGAKU ( JAPAN SOC ANALYTICAL CHEMISTRY ) 52 ( 9 ) 689 - 694 2003年09月 [査読有り]

We have been studying neutral carriers of ion-selective electrodes (ISEs) for soft metal ions, and have reported that pi-coordinate calixarene derivatives are useful for detecting soft metal ions selectively. In this study, in order to investigate what structures are essentially needed for detecting soft metal ions, several pi-coordinate aromatic compounds were chosen as neutral carriers of ISEs, and the ion sensor properties were examined. An H-1-NMR study showed that t-butylcalix[4]arene tetra(allyl ether) and [2.2.2]-paracyclophane interact with silver ions powerfully, and that only t-butylcalix[4]arene interacts with thallium ions. Therefore, ISEs based on [2.2.2]-paracyclophane exhibited excellent silver ion sensor properties.

Soft Metal Ion-Selectine Electorodes Based on π-Coordinate Calixarene Derivatives

YAJIMA S, YOSHIOKA N, TANAKA M, KIMURA K

Electroanalysis ( WILEY-V C H VERLAG GMBH ) 15 ( 15-16 ) 1319 - 1326 2003年09月

Calix[4]arene derivatives incorporating omega-unsaturated alkenyl groups or saturated alkyl groups and their monomeric analogues were used as a-coordinate neutral carriers for ion-selective electrodes (ISEs) of soft metals [silver and thallium(I)] ions. The EMF responses were excellent for most of the ISEs, among which there was no significant difference in the response. The ion selectivities of the ISEs depend on the structure of neutral carriers employed. H-1 NMR study explains the difference in the ion selectivity. In the metal-ion complexation by the pi-coordinate calixarene derivatives, thallium ion is likely to interact with the calixarene skeleton, while silver ion tends to interact with both of the calixarene skeleton and the omega-unsaturated alkenyl groups.

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Dependence of ion selectivity on ordered orientation of neutral carriers in ion-sensing membranes based on thermotropic liquid crystals

K Kimura, Y Kawai, S Oosaki, S Yajima, Y Yoshioka, Y Sakurai

ANALYTICAL CHEMISTRY ( AMER CHEMICAL SOC ) 74 ( 21 ) 5544 - 5549 2002年11月 [査読有り]

Thermotropic liquid-crystalline compounds were applied as membrane materials (membrane solvent and neutral carrier) for neutral carrier-type ion sensors to investigate how the ordered arrangement of neutral carriers affects the property of the resulting ion sensors. Nematic, smectic, and cholesteric liquid-crystalline compounds were used as the membrane solvents and crown ether derivatives with a molecular structure similar to the liquid-crystalline solvent as the K+ neutral carriers. Polarized IR spectroscopy and X-ray diffraction experiments confirmed that the highly ordered arrangement of membrane components was retained in the liquid-crystal-based ion-sensing membranes containing a neutral carrier and a lipophilic salt. The ordered arrangement of neutral carriers in the liquid-crystalline membranes enhanced the ion selectivity significantly, probably due to the efficient cooperation of two adjacent crown ether moieties in the highly ordered and aggregated state.

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Ion-sensor property and blood compatibility of neutral-carrier-type poly(vinyl chloride) membranes coated by phosphorylcholine polymers

S Yajima, Y Sonoyama, K Suzuki, K Kimura

ANALYTICA CHIMICA ACTA ( ELSEVIER SCIENCE BV ) 463 ( 1 ) 31 - 37 2002年07月

Ion-selective membranes (ion-selective electrodes) were coated by biocompatible polymers, which are copolymers of methacryloyloxyethyl phosphorylcholine and an alkyl methacrylate, in order to develop blood compatible ion-selective electrodes. The sensor properties and biocompatibility of the ion-sensors were investigated using two types of alkyl methacrylates with different molecular weights. When the concentration of polymer solution for coating was relatively low, the ISEs showed good sensor properties, which lasted for at least 6 months. When the concentration of polymer solution for coating was relatively high, the coated ion-sensing membranes also showed good biocompatibility, which lasted for about a month. (C) 2002 Elsevier Science B.V. All rights reserved.

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Synthesis and photochromism of spirobenzopyrans and spirobenzothiapyran derivatives bearing monoazathiacrown ethers and noncyclic analogues in the presence of metal ions

M Tanaka, T Ikeda, Q Xu, H Ando, Y Shibutani, M Nakamura, H Sakamoto, S Yajima, K Kimura

JOURNAL OF ORGANIC CHEMISTRY ( AMER CHEMICAL SOC ) 67 ( 7 ) 2223 - 2227 2002年04月 [査読有り]

Spirobenzopyrans bearing monoazathiacrown ethers and noncyclic analogues were synthesized, and their ion-responsive photochromism depending on the dual metal ion interaction with the crown ether and the phenolate anion moieties was examined using alkali and alkaline-earth metal ions, Ag+, Tl+, Pb2+, Hg2+, and Zn2+. The prepared spirobenzopyrans showed a selective binding ability to Mg2+ and Ag+ with negative and positive photochromism, respectively. Among the metal ions, only Ag+ facilitated photoisomerization to the corresponding merocyanine form. Depending on the ring size of the monoazathiacrown ether moieties, soft metal ions such as Hg2+ and Ag+ showed significant shifts in the UV-vis absorption spectra, while hard metal ions such as Mg2+, Zn2+, and Pb2+ did not afford any meaningful shift. This result reflects that the monoazathiacrown ether and phenolate anion moieties prefer soft and hard metal ions, respectively. Therefore, the Mg2+ and Ag+ selectivities are mainly derived from the phenolate anion and monoazathiacrown ether moieties, respectively. On the other hand, a spirobenzothiapyran bearing 3,9-dithia-6-monoazaundecane showed a remarkable selectivity to Ag+.

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Decisive factors in the photoisomerization behavior of crowned spirobenzopyrans: Metal ion interaction with crown ether and phenolate anion moieties

Abdussalam M. A. Salhin, Mutsuo Tanaka, Kenji Kamada, Hisanori Ando, Tomokazu Ikeda, Yasuhiko Shibutani, Setsuko Yajima, Makoto Nakamura, Keiichi Kimura

European Journal of Organic Chemistry ( Wiley-VCH Verlag ) ( 4 ) 655 - 662 2002年 [査読有り]

The influence of metal ion interaction with crowned spirobenzopyrans on the photoisomerization behavior was investigated through the use of various solvents, crowned spirobenzopyrans, and metal ions. Studies on the photoisomerization behavior of crowned spirobenzopyrans in various solvents revealed that solvation of the phenolate anion moiety in the merocyanine form induced photoisomerization back to the spiropyran form, giving rise to negative photochromism. Metal ion interaction with the phenolate anion moiety similarly caused photoisomerization back to the spiropyran form, while that with the crown ether moiety just produced a polar environment and its influence on photoisomerization behavior was dependent on the affinity of the metal ion captured by the crown ether moiety for the phenolate anion. Therefore, photochromic switching of crowned spirobenzopyrans between positive and negative to control the metal ion interaction with the phenolate anion moiety through the crown ether moiety is possible. This finding suggests a molecular design method for crowned spirobenzopyrans showing desired ion-responsive photochromism.

DOI

Sol-gel modification of pH electrode glass membranes for sensing anions and metal ions

K Kimura, S Yajima, H Takase, M Yokoyama, Y Sakurai

ANALYTICAL CHEMISTRY ( AMER CHEMICAL SOC ) 73 ( 7 ) 1605 - 1609 2001年04月 [査読有り]

To obtain glass membrane electrodes selective for anions and metal ions, pH electrode glass membranes were modified by a sol-gel method using a quaternary ammonium salt and a bis(crown ether). A chloride ionsensing glass membrane was designed, in which a pH electrode glass membrane was modified chemically by an alkoxysilyl quaternary ammonium chloride. X-ray photoelectron spectroscopy confirmed the chemical bonding of the quaternary ammonium moiety to the starting glass surface, which afforded the first example of glass-based "anion"-sensing membranes. A neutral carrier-type sodium ion-selective glass membrane was also fabricated which encapsulates a bis(12-crown-4) derivative in its sol-gel-derived surface. Both sol-gel-modified anion and metal ion-selective glass electrodes exhibited high sensitivity to their ion activity changes. The present sol-gel modification paves the way for designing glass-based ion sensors with tailor-made ion selectivities toward anions as well as cations.

Liquid crystal effect on neutral-carrier-type ion-sensing membranes

K Kimura, Y Kawai, S Yajima, Y Sakurai

CHEMICAL COMMUNICATIONS ( ROYAL SOC CHEMISTRY ) ( 14 ) 1302 - 1303 2001年 [査読有り]

Silver ion-selective electrodes using pi-coordinate calix[4]arene derivatives as soft neutral carriers

K Kimura, S Yajima, K Tatsumi, M Yokoyama, M Oue

ANALYTICAL CHEMISTRY ( AMER CHEMICAL SOC ) 72 ( 21 ) 5290 - 5294 2000年11月

Calix[4]arene derivatives incorporating pi -coordinate substituents such as allyl, benzyl, and propargyl groups were designed as soft neutral carriers for silver ion sensors. Most of all, tert-butylcalix[4]arene tetra(allyl ether) is an excellent neutral carrier for plasticized poly(vinyl chloride)membrane sih er ion-selective electrodes. The ion sensors showed high silver ion selectivity over alkali metal ions and also good selectivity against other soft metal ions such as lead and mercury(II) ions. The electrode potential response was as rapid as that for neutral-carrier-type alkali metal ion electrodes due to the soft interaction between pi -coordinate substituents and silver ion, which was elucidated by H-1 NMR spectroscopy.

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Potentiometric ion sensors with neutral-carrier-type ion-sensing membranes coated by biocompatible phosphorylcholine polymers

S Yajima, K Suzuki, K Kimura

ANALYTICAL SCIENCES ( JAPAN SOC ANALYTICAL CHEMISTRY ) 16 ( 9 ) 899 - 900 2000年09月

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イオンセンシングの最近の動向

矢嶋摂子, 木村恵一

分析化学 ( Japan Society for Analytical Chemistry ) 49 ( 5 ) 279 - 296 2000年

Ion sensors include electrochemical sensors to detect analyte ions electrochemically, i.e., mem- brane-potential sensors, such as ion-selective electrodes
voltammetric sensors, such as chemically-modified electrodes
and optical sensors to detect them spectrophotometrically, i.e., optodes or optrodes. There has been much information reported so far on ion sensors from two types of research, viz., the development of new sensors and basic studies about the response mechanism of ion sensors. The present review is concernd mainly with research topics of our intered, which include potentiometric anion sensors based on new neutral carriers and metal complexes. biocompatible ion sensors for the continuous detection of analyte ions in biological samples, and optodes for detecting electrically neutral molecules.

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Supported sol-gel-derived membranes for neutral carrier-type ion-selective electrodes

K Kimura, S Yajima, K Okamoto, M Yokoyama

JOURNAL OF MATERIALS CHEMISTRY ( ROYAL SOC CHEMISTRY ) 10 ( 8 ) 1819 - 1824 2000年 [査読有り]

For neutral carrier-type ion-selective electrodes, several sol-gel-derived membranes were designed which encapsulate valinomycin and bis(crown ether) derivatives as the neutral carriers. Relatively large size ion-sensing membranes based on sol-gel-derived glass were successfully fabricated by using membrane filters and sintered glass filters as the membrane supports. Potassium and sodium ion-selective electrodes, at the tip of which sol-gel-derived membranes containing a neutral carrier and a poly(tetrafluoroethylene) membrane filter were incorporated, exhibit high electrode performance in their sensitivity, selectivity, and response time. The supported sol-gel-derived membranes were also modified chemically by alkoxysilylated bis(crown ether) derivatives and were tested for their usefulness as sensing membranes of ion-selective electrodes.

Metal-ion stabilization of photoinduced open colored isomer in crowned spirobenzothiapyran

M Tanaka, K Kamada, H Ando, T Kitagaki, Y Shibutani, S Yajima, H Sakamoto, K Kimura

CHEMICAL COMMUNICATIONS ( ROYAL SOC CHEMISTRY ) ( 16 ) 1453 - 1454 1999年08月 [査読有り]

Anion-sensitive field-effect transistors based on sol-gel-derived membranes incorporating quaternary ammonium salts

K Kimura, H Takase, S Yajima, M Yokoyama

ANALYST ( ROYAL SOC CHEMISTRY ) 124 ( 4 ) 517 - 520 1999年04月

Quaternary alkylammonium chlorides were encapsulated or bonded covalently to sol-gel-derived membranes made of mixtures of two alkoxysilanes so as to obtain sensing membranes for anion-sensitive field-effect transistors. Both types of anion sensors responded to chloride-ion activity changes with high sensitivity. The anion-sensing membranes modified chemically by an alkoxysilyl derivative of quatenary ammonium salt are superior to those simply encapsulating an ammonium salt in their durability and protein-adsorption properties. The anion sensors are applicable to chloride-ion assay in serum samples.

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Cation complexation, isomerization, and photoresponsive ionic conduction of a crown ether derivative carrying two spirobenzopyran units

K Kimura, T Teranishi, M Yokoyama, S Yajima, S Miyake, H Sakamoto, M Tanaka

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 ( ROYAL SOC CHEMISTRY ) ( 2 ) 199 - 204 1999年02月 [査読有り]

Cation complexation and subsequent isomerization of a diaza-18-crown-6 derivative possessing two spirobenzopyran units, crowned bis(spirobenzopyran), were investigated in solution and compared with those of its corresponding derivative incorporating only one spirobenzopyran unit. Complexation of multivalent metal ions, especially Ca2+ and La3+, by crowned bis(spirobenzopyran) enhanced the isomerization of the spirobenzopyran moiety to the corresponding merocyanine form due to the effective intramolecular interaction between a crown-complexed cation and two phenolate anions in the cation complexes of the merocyanine form. Significant photoinduced switching of ionic conductivity was realized in composite films containing crowned bis(spirobenzopyran) and a calcium salt.

Variation of thermodynamic parameters in the adduct formation of beta-diketonato chelates with 1,10-phenanthroline across the lanthanoid series

S Yajima, Y Hasegawa

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN ) 71 ( 12 ) 2825 - 2829 1998年12月

The enthalpy change in the adduct formation of tris[1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato]lanthanoids (LnA(3)) with 1,10-phenanthroline (phen) as well as the formation constant of the adduct has been determined in chloroform across the lanthanoid series at 298 K by calorimetric titration and solvent-extraction techniques. The enthalpy change in the first adduct formation changes remarkably from light lanthanoids (endothermic) to heavy ones (exothermic), while the entropy change decreases largely from the middle to the heavy lanthanoids along with a small change from light to the middle of the series. Such a trend has been explained on the basis of the difference in the dehydration from lanthanoid(III) chelates and in the strength of the new bonding of chelates formed between tris(beta-diketonato) lanthanoid(III) and phen across the lanthanoid series.

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