Vol. 10, Supplement B (1994)

Proceedings of the 19th Chemical Sensor Symposium
September 19-20, 1994
Keio University

Abstracts

Last updated on 01/23/2006 06:30:27.

1. 希土類酸化物薄膜の感ガス特性

朝倉利之、竹光良浩、野村良紀、東正志、川崎吉包
阪工大工

Gas Sensing Characteristics of Rare Earth Metal Oxide Thin Films

Toshiyuki ASAKURA, Yoshihiro TAKEMITSU, Ryoki NOMURA,
Masashi AZUMA, and Yoshikane KAWASAKl
Department of Applied Chemistry,
Faculty of Engineering, Osaka Institute of Technology,
Ohmiya, Asahi-ku, Osaka 535, Japan

Gas sensing characteristics of rare-earth ( Ln ) oxide thin films have been
investigated. Several rare-earth ( Ln = Y,Nd ) sesquioxides ( LN₂O₃ ) thin films were deposited on an Al₂O₃ substrate by RF sputtering technique. The electrical conductivities of these thin films at 5.0V(DC) increased with increasing temperature in N₂ atmosphere. The electrical conductivities increased when the films exposed to 10ppm of H₂ or CO gas at 300℃, whereas did not change when exposed to O₂ or CO₂.

2. パルス駆動方式SnO₂系ガスセンサ

藤森裕樹、木虎真紀、松浦吉展、梶山裕久
フィガロ技研

PULSE DRIVE SnO₂ GAS SENSOR

Yuki FUJIMORI, Maki KITORA, Yoshinobu MATSUURA
and Yoshihisa KAJIYAMA
Figaro Engineering, INC.
Minoo-shi, Osaka 562, Japan

A pulse drive gas sensor was developed to lower power consumption. The sensor element has a multilayer structure formed by a screen-stenciled process on an aluminum substrate. The gas sensing layer was pulsatively heated by the RuO₂ heater. In the case of a duty ratio of 8/1000 every 1sec, the effective power consumption was about 14mW. The sensing materials of the sensor were also studied. Pt/SnO₂ sensor showed high sensitivity, good selectivity and quick response to CO, and was hardly effected by humidity.

3. 湿度補償型SnO₂系ガスセンサ

真鍋太祐、野村徹、松浦吉展、梶山裕久
フィガロ技研

HUMIDITY COMPENSATED SnO₂ GAS SENSOR

Taisuke Manabe,Tohru Nomura,Yoshinobu Matsuura,Yoshihisa Kajiyama
Figaro Engineering Inc.
l-5-3 Senbanishi,Minoo-shi,Osaka 562, Japan

An integrated gas sensor composed of a gas sensing element and a water vapor sensing element was developed by a screen-stenciled process. The same Pd/SnO₂ layer was printed on both elements and only the water vapor sensing element had a glass layer printed on its surface. Compared to the gas sensing element, the water vapor sensing element showed almost the same sensitivity and response to water vapor, but showed very little sensitivity to reducing gases such as ethanol, hydrogen and carbon monoxide.Therefore, the water vapor sensitivity of the gas sensing element could be easily eliminated by using the water vapor sensing element.

4. チタン酸塩を用いた高温型NO_xセンサ

山浦弘之、玉置純、三浦則雄、山添曻
九大総合理工

TITANATE - BASED NO_x SENSORS OPERATIVE AT ELEVATED TEMPERATURES

Hiroyuki YAMAURA, Jun TAMAKI, Norio MlURA, and Noboru YAMAZOE
Department of Materials Science and Technology,
Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816, Japan

A series of metal titanates was examined for their NO_x sensing properties at elevated temperatures. Among them, BaTiO₃ and SrTiO₃ were found to be remarkably sensitive to NO and/or NO₂ existing in air at 500℃. BaTiO₃ was especially sensitive to NO₂ at 500℃, although its response was rather sluggish at this temperature. On the other hand, SrTiO₃ gave lower but still fairly high sensitivity to NO₂ together with practically acceptable response rates at 500℃. Notably, its sensitivities to NO and NO₂ were almost equal to each other and increased linearly with increasing NO_x concentration in the range of 5-100 ppm. The resistance of the element using SrTiO₃ was almost independent of oxygen concentration in the range of 3～15% . The NO_x sensing mechanism of this element was briefly discussed.

5. Bi₂Sr₂CaCu₂O_x薄膜を用いたNO_xセンサ

工藤周三、大西久男、高野智^*、若田光延^*、宇佐美亮^*、山内尚雄^*、坂井久^**
大阪ガス、^*超電導工学研究所、^**関西新技術研究所

NO_x SENSOR USING Bi₂Sr₂CaCu₂O_x THIN FILMS

Shuzo KUDO, Hisao OHNISHI, Satoshi TAKANO^*, Mitsunobu WAKATA^*, Ryo USAMI^*,
Hisao YAMAUCHI^*,and Hisasi SAKAI^**
Osaka Gas Co., Ltd. , Konohana-ku, Osaka, 554, Japan
^*Superconductivity Research Laboratory, ISTEC, Koto-ku, Tokyo, 135 Japan
^**Kansai Research Institute, Shimogyo-ku, Kyoto, 600, Japan

We have developed NO sensors made of Bi₂Sr₂(Ca_1-yY_y)Cu₂O_x (y=0, 0.8) thin films. Bi₂Sr₂(Ca_1-yY_y)Cu₂O_x (y=0, 0.8) thin films showed the high sensitivity at low concentrations of NO and also showed hardly any selectivity to H₂, CO and CH₄ which are present in exhaust gases . These thin films were deposited on the MgO substrate by the laser ablation method. We measured the Hall effect of Bi₂Sr₂(Ca_0.2Y_0.8)Cu₂O_x thin film to study the NO sensing mechanism. The results of the Hall effect measurements elucidated that the electrical conductivity of the sensor mainly determined by the change in the hole density which was decreased by the adsorption of NO.

6. ペロブスカイト型複合酸化物のNO_x検知特性

栗原香暁、田中伸一、杉山和夫
埼玉大工

NO_x SENSING PROPERTIES OF PEROVSKITE-TYPE OXIDES

Yoshiaki KURIHARA, Shinichi TANAKA and Kazuo SUGIYAMA
Department of Applied Chemistry, Faculty of Engineering,
Saitama University, 255, Shimo-okubo, Urawa 338, Japan

NO_x(NO,NO₂) sensing properties of various perovskite-type oxides (ABO₃:A=La³⁺, Nd³⁺, Sm³⁺; B=Cr³⁺, Mn³⁺, Fe³⁺, CO³⁺) have been investigated at 450 ℃. The thick film (ca. 20μm) of the perovskite oxide sintered on the α-alumina substrate was used for the sensor element. A NO_x sensitivity of the elements was influenced by differences of the B site metal ions. Especially, a superior sensitivity to NO_x gas molecules appeared when the B site was made up by Cr³⁺ and Fe³⁺ ion respectively. The substitution of Sr²⁺ to the A site of LaFeO₃ element led to an increase of NO_x sensitivity.

7. 炭酸塩を用いたNO_xセンサの高温での応答特性

藤森幸一、玉置純、三浦則雄、山添曻
九大総合理工

NO_x SENSING PROPERTIES OF METAL CARBONATE-BASED SENSORS AT ELEVATED TEMPERATURES

Koichi FUJIMORI, Jun TAMAKI, Norio MIURA, and Noboru YAMAZOE
Department of Materials Science and Technology,
Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816, Japan

Semiconductor-type gas sensors using alkaline earth metal carbonates were investigated for a detection of NO_x in air at elevated temperatures. Among those tested, the sensor using BaCO₃ was found to exhibit the highest sensitivity to NO and NO₂. With increasing operating temperature in the range of 600-700 ℃, the sensitivity of BaCO₃ sensor decreased, while the response and recovery characteristics were improved. This suggests that the optimum temperature of the present sensor is 650 ℃. At this temperature, the sensitivities to both NO and NO₂ were equal to each other and increased almost linearly with increasing concentration in the range of 0～400 ppm. The cross sensitivities to other several components of exhaust gas were also examined at 650 ℃.

8. 希土類、銅の複合酸化物のNO_x検出特性

廣田洋平、今中信人、足立吟也
阪大工

NO_x SENSING PROPERTIES OF RARE EARTH COPPER OXIDES

Yohei HIROTA, Nobuhito IMANAKA, and Gin-ya ADACHI
Department of Applied Chemistry,
Faculty of Engineering,Osaka University
2-1 Yamadaoka,Suita,Osaka 565, Japan

The NO_x (NO, NO₂) sensing characteristics of semiconducting Ln₂Cu₂O₅(Ln=Tb,Tm,Yb etc.) compounds were investigated. The electrical resistivity of the Yb₂Cu₂O₅ oxide bulk decreased with the increase of the NO₂ concentration at the temperatures below 550℃. The oxide was insensitive to the NO content change in the temperature region above 500℃. This clearly indicates that the Yb₂Cu₂O₅ semiconducting material responds only to NO₂ among NO_x gases at the operating temperatures around 550℃.

9. スカンジウムを添加したニッケル－銅系酸化物簿膜のNO_x検知能

坂野晋、今中信人、足立吟也
阪大工

THE NO_x SENSING PERFORMANCE OF SCANDIUM-DOPED NICKEL COPPER OXIDE THIN FILM

Susumu BANNO, Nobuhito IMANAKA and Gin-ya ADACHI
Department of Applied Chemistry, Faculty of Engineering,
Osaka University
2-1 Yamadaoka, Suita, Osaka 565, Japan

Scandium-doped nickel copper oxide bulk, which consists of Ni_0.8Cu_0.2O, CuO, Sc₂O₃, and Sc₂Cu₂O₅, responded only to NO₂ (50-500 ppm) among NO_x gases. Thin films of the oxide were prepared by a RF magnetron sputtering method, and their NO_x sensing performances were investigated. The electrical resistivity of the film decreased with the increase in the NO₂ concentration, while it increased with the NO content. As was expected, the film responded to NO₂ more sensitively than the bulk shape did. However, the film responded to both NO₂ and NO. The disappearance of crystalline Sc₂Cu₂O₅ in the film might affect the sensing behavior for NO_x.

10. La₂CuO₄における導電率のNO_x濃度依存性

長谷井政治^*、米村友紀、水崎純一郎^**、田川博章
リケン^*、横浜国大環科研セ、東北大科研^**

DEPENDENCE OF La₂CuO₄ CONDUCTIVITY ON NO_x CONCENTRATION

Masaharu HASEI^* , Yuki YONEMURA,
Junichiro MIZUSAKI^** and Hiroaki TAGAWA
^*Riken Co.,4-14-1 Suehiro, Kumagaya-shi, Saitama 360, Japan
Institute of Environmental Science and Technology Yokohama
National Univ.,156 Tokiwadai, Hodogaya-ku, Yokohama 240, Japan
^**RISM, Tohoku Univ., 2-1-1 Katahira, Aoba-ku, Sendai 980-77, Japan

The conductivity of La₂CuO₄ was measured in O₂-N₂, and NO_x- O₂-N₂ atmospheres at temperatures 500-750℃. The conductivity in O₂-N₂ atmospheres increased with the oxygen concentration, but was independent of temperature. In NO₂-O₂-N₂ atmospheres, the conductivity increased with the NO₂ concentration. The variations in the conductivity with NO₂ concentration were greater than those with the same concentration of O₂, moreover the conductivity decreased with temperature. In NO-O₂-N₂ atmospheres, the conductivity did not change with NO concentration and temperature. Because NO₂ continuously decomposed on the surface of La₂CuO₄, the oxygen activity on the surface became extraordinary high, resulting in the large oxygen excess nonstoichiometry and the increase of p-type conductivity.

11. 白金／シリコン酸化膜／シリコンＭＩＳ型トンネルダイオードの電流－電圧曲線の水素によるシフトのメカニズム

岩館秀典、小林光、中戸義禮
阪大基礎工、有機光センター

MECHANISM OF HYDROGEN - INDUCED VOLTAGE SHIFTS OF THE CURRENT-VOLTAGE CURVES FOR PLATINUM / SILICON OXIDE / SILICON MIS TUNNELING DIODES

Hidenori Iwadate, Hikaru Kobayashi, and Yoshihiro Nakato
Research Center for Photoenergetics of Organic Materials,
and Department of Chemistry, Faculty of Engineering Science,
Osaka University, Toyonaka, Osaka 560, Japan

We have attributed the shifts of Ⅰ-V curves for the MIS tunneling diodes caused by hydrogen to the following three factors: i) the decrease in the effective Pt work- function, ii) the movement of protons in the silicon oxide layer, and iii) the formation of interface states through the reaction between protons and Si / silicon oxide interface. The time constant for the formation of the interface states increases with the hydrogen concentration, which is explained by the formation of two-dimensional aggregations of the interface states.

12. CuO-BaTiO₃系複合酸化物における接合界面の電子状態とCO₂検知特性

西雄一郎、石原達己、滝田祐作
大分大工

Adsorption State of CO₂ on CuO-BaTiO₃ and the Characterization of Energy Barrier at Grain Junction between CuO and BaTiO₃.

Yuichirou Nishi, Tatsumi Ishihara, Yusaku Takita,
Department of Applied Chemistry, Faculty of Engineering,
Oita University, Dannoharu 700, Oita 870-11, Japan

Capacitance of CuO-BaTiO₃ is highly sensitive to CO₂ detection. In this study, detection mechanisms of CuO-BaTiO₃ capacitor were investigated. Since the adsorption of CO₂ is stronger than that of O₂ upon CuO-BaTiO₃, adsorption of CO₂ make the trapped electron free resulting in the increased electron density in CuO-BaTiO₃. It is expected that increased electron density decreased the height of energy barrier and narrowed the width of the depletion layer at the junction of p-type CuO and n-type BaTiO₃. From this point, adsorption of CO₂ on CuO-BaTiO₃ is similar with the application of forward bias potentials to p-n junction. It became clear that capacitance of the element increased upon exprodure to CO₂ as a result of decreased width of depletion layer at the junction between CuO and BaTiO₃.

13. 薄膜ジルコニア空燃比センサ

鈴木隆之、木野修、嘉山春夫^*、二田穂積
矢崎計器、矢崎部品^*

THIN-FILM ZIRCONIA AIR TO FUEL RATIO SENSOR

Takayuki SUZUKI, Osamu KINO, Haruo KAYAMA^* and Hozumi FUTATA
Yazaki Meter Co.,Ltd. Gas Equipment Development Department
23 Minamikashima, Futamata-cho, Tenryu-shi, Shizuoka 431-33, Japan
^*Yazaki Parts Co.,Ltd.
Conpornent manufacturing engineering Department
206-1 Nunohikihara, Haibara-cho, Haibara-gun, Shizuoka 42l-04, Japan

Thin film limiting current-type oxygen sensor based upon a porous alumina substrate has interresteing characteristics in the case of the voltage applied to the electrolytic cell
changes from usual direct current to alternating current. It appear to be able to measure not only oxygen concentration in oxidation combustion exhaust but also hydrogen concentration in reduction combustion exhaust. The sensor output has a good linearity to oxygen and hydrogen concentration and its polarity is changed by which is the atmosphere around the sensor oxidation or reduction.

14. 天然ガス機関三元触媒システム用酸素センサの検討（１）

守家浩二、佐古孝弘
大阪ガス

DEVELOPMENT OF OXYGEN SENSOR FOR 3-WAY CATALYST SYSTEM ON NATURAL GAS ENGINE (1)

Koji MORIYA and Takahiro SAKO
Research and Development Center, Osaka Gas Co.,Ltd.
6-19-9 Torishima, Konohana-ku, Osaka-shi, Osaka 554, Japan

A window tracking sensor, which can detect the window of the deteriorated catalyst, was required for precise A/F control. Owing to the analysis of the catalyst deterioration mechanism, an oxygen sensor with low methane oxidation activity was supposed to show a good performance. Methane oxidation activities and sensor characteristics of 2 sensors on the market and a sample prepared according to the patent was measured. Strong correlation was found between them.

15. Na₂O・Al₂O₃・4SiO₂/ZrO₂複合膜を用いたCO₂センサ

ヘルー・スプリアトノ、定岡芳彦、アンドレアス・デュベ, 酒井義郎
愛媛大工

CO₂ SENSOR USING Na2O ･ Al₂O₃ ･ 4SiO₂ / ZrO₂ COMPOSITES

Heru SUPRIYATNO, Yoshihiko SADAOKA, Andreas DUBBE and Yoshiro SAKAI
Department of Applied Chemistry Faculty of Engineering
Ehime University, Matsuyama-shi, Ehime 790, Japan

ABSTRACTS
The sensing characteristic of CO₂ gas sensor using the combination of Na₂O･Al₂O₃･4SiO₂ glass and Yttria-stabilized Zirconia was examined. The sensor exhibited a good sensitivity and fast response but a little effect of water vapor still appeared. At temperature higher than 400℃, the sensor makes a good agreement with Nernst's equation based on 2 electrons.

16. 安定化ジルコニアをべース材科とした小型CO₂センサ

野中誠二郎、巌永鉄、三浦則雄、山添曻
九大総合理工

CHIP-TYPE CO₂ SENSOR BASED ON STABILIZED ZIRCONIA

Seijiro NONAKA, Yongtie YAN, Norio MIURA, and Noboru YAMAZOE
Department of Materials Science and Technology,
Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816, Japan

A planar-type solid electrolyte CO₂ sensor was fabricated by using a chip of MgO-stabilized zirconia (MSZ) and an auxiliary phase of a metal carbonate (Li₂CO₃). The EMF response of the sensor was found to vary logarithmically with CO₂ concentration, following the Nernst's equation for the 2-electron reaction of CO₂ in the range of 100-2000 ppm at 500-650 ℃. The CO₂ sensitivity of this sensor was hardly affected by coexistent O₂, H₂, NO, NO₂, or H₂O. The CO₂ sensing mechanisms of the MSZ-based sensor was discussed on the basis of the concept of an intermediate layer at the interface of heterojunction.

17. 多価陽イオン固体電解質を用いた炭酸ガスセンサの開発

池田章一郎、近藤達也、加藤貞夫、伊藤要、野村勝裕^*、藤田雄耕^**
名工大、大工研^*、日本電池^**）

DEVELOPMENT OF CO₂ GAS SENSOR USING MULTI-CATIONIC CONDUCTING SOLID ELECTROLYTES

Shoichiro IKEDA, Tatsuya KONDO, Sadao KATO, Kaname ITO, Katsuhiro NOMURA^*
and Yuko FUJITA^**
Department of Applied Chemistry, Nagoya Institute of Technology
Gokiso-cho, Showa-ku, Nagoya 466, Japan
^* Inorganic Material Dept., Government Industrial Research Institute Osaka
Midorigaoka 1, Ikeda, Osaka 563, Japan
^** Development Dept., Corporate R & D Center, Japan Storage battery Co., Ltd.
Nishinosho, Kisshoin, Minami-ku, Kyoto 601, Japan

We have systematically investigated on a series of the multi-valent cationic conducting solid electrolytes having zirconium phosphate frameworks. Among them, MgZr₄(PO₄)₆ (MgZP) shows a relatively high divalent cationic conductivity promising an application for electrochemical devices such as a solid state gas sensors. EMF type CO₂ gas sensors, having following cell construction; Pt | CO₂, O₂ | alkaline carbonate || solid electrolyte | O₂, Pt. In the case of Na₂CO₃, the sensor showed the Nernstian response to CO₂ in the pressure range between 1 and 100 kPa at temperatures from 400 to 500 ℃ within a few minutes. Using partially Si-substituted MgZP (MgZrPSiO), the Nernstian response temperature range has been expanded to 300 ℃ although it takes a longer response time.

18. プラズマ重合固体電解質膜を用いたプレーナ型COセンサ

山鹿範行、藤岡透、渡辺祥文、土井謙之、幡井崇、草薙繁量
松下電工

PLANER TYPE CO SENSOR USING PLASMA-POLYMERIZED SOLID ELECTROLYTE

Noriyuki Yamaga, Toru Fujioka, Yoshihumi Watabe
Kenji Doi, Takashi Hatai, Shigekazu Kusanagi
Central Research Laboratory, Matsushita Electric Works, Ltd.
1048, Kadoma. Osaka, Japan

A planer type electrochemical CO sensor was developed using a new solid electrolyte prepared by plasma-polymerization of trifluorochloroethylene (TFCE) and trifluoromethanesulfonic acid (TMSA) and the performance of the sensor were investigated. A linear calibration curve was obtained in the range from 25ppm to 500ppm with the 90% response time of about 20sec and the detection limit (S/N=2) was 0.5ppm.

19. 銀化合物のNO₂検知特性

片所功、上林孝哲、佐藤秀樹、橋本喜裕、田原修
島津製作所

NO₂ SENSING CHARACTERISTICS OF Ag IONIC CONDUCTORS

Isao KATASHO, Takanori KAMIBAYASHI, Hideki SATO,
Yoshihiro HASHIMOTO ,and Shu TAHARA

Shimadzu Corporation,l Nishinokyo-kuwabaracho,
nakagyo-ku ,Kyoto, 604, Japan

NO₂ Sensing characteristics of several silver ionic conductors were investigated by potentiometry and Ag₂S was found to give good response to NO₂ from room temperature to 200℃ . The sensor showed stable EMF and linear relationship to logarithms of NO₂ concentration. As low as 8ppb of NO₂ colud be detected at 27℃. CO₂,O₂,NO,H₂O and SO₂ have little interference to the NO₂ response of the sensor.

20. 高温型プロトン導電体を用いた水同位体センサ

日比野高士、岩原弘育
名大工

AMPEROMETRIC SENSOR FOR MEASUREMENT OF D₂O CONCENTRATION IN WATER ISOTOPES USING HIGH TEMPERATURE TYPE PROTONIC CONDUCTOR

Takashi HIBINO and Hiroyasu IWAHARA
Synthetic Crystal Research Laboratory, School of Engineering,
Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-01, Japan

Amperometric sensor for the measurement of D₂O concentration in a mixture of H₂O and D₂O has been studied using CaZr_0.9In_0.1O₃-α as a high temperature type protonic conductor. When the sensor heated at 900 ℃ was exposed to air passed through the H₂O + D₂O mixture at 20 ℃, it could respond to D₂O in the concentration range of 5 to 100% with a 90% response time of about 15 min.

21. ZnO系バリスタガスセンサの水素ガス感度に及ぼすY₂O₃の添加効果

林豊倉、高尾雄二、清水康持、江頭誠
長崎大工

EFFECT OF Y₂O₃ CONTENT ON HYDROGEN SENSING PROPERTIES OF ZINC OXIDE VARISTOR GAS SENSORS

Feng-Cang LIN, Yuji TAKAO, Yasuhiro SHIMIZU, and Makoto EGASHIRA
Department of Materials Science and Engineering
Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan

Current-voltage characteristics of two series of ZnO varistors with and without 5.0 mol% Cr₂O₃ have been investigated as a function of Y₂O₃ content in air as well as in 1.0 % H₂ in the temperature range 400℃ - 600℃. Every varistor exhibited a shift of breakdown voltage to a lower electric field in the presence of 1.0% H₂. For both series of varistors, the magnitude of the breakdown voltage shift (H₂ sensitivity) increased with increasing Y₂O₃ content, then reached a maximum value at 0.25 mol% Y₂O₃. From the standpoints of the H₂ sensitivity and the nonlinearity, the varistor containing 5.0 mol% Cr₂O₃ and 0.25 mol% Y₂O₃ was found to be the most promising candidate as a H₂ sensor among the varistors tested.

22. CO₃O₄膜の湿分応答吸光度変化特性

安藤昌儀、小林哲彦^*、春田正毅，
新技団さきがけ研究２１・大工研、^*地環研

OPTICAL HUMIDITY SENSITIVITY OF CO₃O₄ FILMS

Masanori ANDO, Tetsuhiko KOBAYASHI and Masatake HARUTA
Light and Material Group, PRESTO, JRDC
and Osaka National Research Institute, AIST
l-8-31 Midorigaoka, Ikeda. Osaka 563, Japan

Cobalt oxide (CO₃O₄) films prepared by organometallic decomposition have been found to show reversible absorbance change in the UV-visible-near IR wavelength region as a function of humidity at room temperature. The humidity-sensitive increase in absorbance of CO₃O₄ film was most pronounced at wavelengths around 350-400 nm. The reversible absorbance change and the response time within several minutes suggest that the CO₃O₄ film is potentially applicable to optical humidity detection.

23. テトラフェニルポルフィリン類の感湿特性

惠原貴志、黒沢誠、中込真二、山本達夫
石巻専修大理工

HUMIDITY SENSING CHARACTERISTICS OF TETRAPHENYLPORPHYRIN DERIVATIVES

Takashi Ehara, Makoto Kurosawa, Shinji Nakagomi
and Tatsuo Yamamoto
School of Science and Engineering,
Ishinomaki Senshu University
Ishinomaki, Miyagi, 986-80, Japan

Humidity sensing characteristics of some tetraphenylporphyrin (TPP) metal complexes have been studied. Simple capacitance type elements that use interdigital electrode were fabricated and measured. All elements showed significant sensitivity in high humid air with more than 80 % of relative humidity (RH), by increasing of capacitance. On the contrary, they did not display strong sensitivity in low humidity from 20 %RH to 60 %RH. However, sensing characteristics of the materials in low humidity were different from each other. The element that uses Zn-TPP as sensing material showed better sensitivity than the other element in 60 or 70 %RH. Although the tendency is not remarkable, these materials indicated dependency of sensing characteristics on properties of the central metals in low humidity.

24. 水晶振動子マイクロバランス法による高分子金属錯体膜への酸素の収脱着の研究

山地豪、定岡芳彦、松口正信、酒井義郎
愛緩大工

STUDY ON THE OXYGEN SORPTION INTO THE POLYMER COORDINATED METAL COMPLEX FILMS WITH A QUARTZ CRYSTAL MICROBALANCE TECHNIQUE

Tsuyoshi YAMAJl, Yoshihiko SADAOKA Masanobu MATSUGUCHI and Yoshiro SAKAI
Department of Applied Chemistry, Faculty of Engineering
Ehine Univertity, Matsuyama, Ehime 790, Japan

Polymer coordinated (N',N'-Disalicylidene ethylene diamine)cobalt(II) (Co(salen)) complex binds molecular oxygen rapidly and reversibly even in the solid state. In this study, oxygen sorption behavior of poly(4-vinylpyridine) (P4VPy) - Co(salen) complex and poly(octyl methacrylate)-co-(4-vinylpyridine)] (POMPy) - Co(salen) complex was investigated by using a Quartz Crystal Microbalence method. The amount of sorbed oxygen, depends on the concentration of Co(salen) in the film as well as the composition of copolymer as a ligand. The mole ratio of reversibly sorbed oxygen to Co(salen) is high at low concentration of Co(salen) in the film.

25. 水晶振動子式ガスセンサによるアルコールの判別

南戸秀仁、椿野史朗、北川成樹、羽原正秋、ルース・ウエイト^*、筒口善央^**
金沢工大デバイス研、ローズハルマン大^*、石川県工業試験場^**

DISCRIMINATION OF ALCOHOL BY PATTERN RECOGNITION ANALYSIS OF TRANSIENT RESPONSES MEASURED USING A QUARTZ RESONATOR GAS SENSOR

Hidehito NANTO, Shiro TSUBAKINO, Shigeki KITAGAWA, Masaaki HABARA.
Ruth I. WAITE 1 and Yoshiteru DOUGUCHI 2
EDS Research Laboratory, Kanazawa Institute of Tech.,
7-1 Oogigaoka, Nonoich-machi, P.O.Kanazawa-South, Ishikawa 921, Japan
^*Rose-Hulman Institute of Tech., 5500 Wabash Avenue,Terre Haute, IN 47803
^**lndust. Res. Institute of Ishikawa, 1 Tomizu-machi, Kanazawa, 920-2, Japan

Transient response curves for exposure to aromas which are generated by vaporizing each mixture with different ratio of ethylalcohol to distilled water are observed using an epoxy-coated quartz-resonator gas sensor. The pattern recognition using principal component analysis is carried out using parameters which characterize the transient response curves. The responses for individual aroma tend to cluster in discrete sections of space with well-defined boundaries .

26. メチルカルセイン色素一高分子複合膜を用いた光学的ガスセンサの研究

山田昌弘、定岡芳彦、酒井義郎
愛緩大工

OPTICAL GAS SENSOR BY USING METHYLCALCEIN-POLYMER COMPOSITES

Masahiro YAMADA, Yoshihiko SADAOKA, and Yoshiro SAKAI
Department of Applied Chemistry, Faculty of Engineering,
Ehime University, Matsuyama, Ehime 790, Japan

For 4-vinylpyridine-styrene-co-polymer composite thin film, fluorescence intensity at λmax=540nm was enhanced by sorption of water and hardly influenced by ammonia vapor. For poly (acrylic acid) composite thin film in humidity ambient, fluorescence intensity at λmax=530nm decreased with increasing ammonia concentrations. For methylcalcein-polymer composite thin films, sensitivity and selectivity for ammonia and humidity depend on acidity/basicity of polymer matrix, and therefore sensitivity and selectivity can be controlled.

27. CuO/Au膜のプラズモン吸収変化によるCO検知

安藤昌儀、小林哲彦^*、春田正毅
新技団さきがけ研究21・大工研、^*地環所）

OPTICAL CO SENSITIVITY OF CuO/Au FILMS IN THE PLASMON ABSORPTION BAND

Masanori ANDO, Tetsuhiko KOBAYASHI and Masatake HARUTA
Light and Material Group, PRESTO, JRDC
and Osaka National Research Institute, AIST
1-8-31 Midorigaoka, Ikeda, Osaka 563, Japan

Composite films consisting of ultrafine Au particles covered with thin CuO layers have been found to show the optical CO sensitivity. The optical absorption of CuO/Au composite films increases with an increase in CO concentration in air and reversibly recovers in fresh air free of CO. The absorbance change due to CO reached to a maximum in the plasmon band of Au (λ=700-800 nm) and it was enhanced with an increase in temperature. Such an absorbance change may be ascribed to a change in the structure and electronic state of ultrafine Au particles at the contact interface with CuO.

28. センサ用の高感度な光導波路の開発

陳暁民、伊藤公紀、村林眞行
横浜国大環境研

A high sensitive and low loss optical waveguide for sensor use

Xiao-Min CHEN, Kiminori ITOH and Masayuki MURABAYASHl
Institute of Environmental Science and Technology, Yokohama National University,
Tokiwadai, Hodogaya-ku, Yokohama 240, Japan

A composite OWG combining a TiO₂ film with a K+-doped glass optical waveguide was prepared on one substrate using sputtering in order to realize very sensitive and low loss OWG system for sensors. This OWG system worked as an efficient tapered velocity coupler, and showed relative sensitivity of more than 2000 times per centimeter optical path. Moreover it was stable against UV-irradiation.

29. 固定化pH指示薬による各種アミンガスの検知

高尾雄二、笹原隆彦、清水康博、江頭誠
長崎大工

DETECTION OF AMINE GASES BY COLOR CHANGES OF ACID-BASE INDICATORS SUPPORTED ON INORGANIC FILMS

Yuji TAKAO, Takahiko SASAHARA, Yasuhiro SHIMIZU and Makoto EGASHIRA
Department of Materials Science and Engineering, Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan, Japan

Sensing properties of inorganic films to amine gases have been investigated based on the color changes of acid-base indicators loaded on the films. Among several kinds of silica gel, the best sensing property was obtained by employing spherical silica gel powders with 120 nm in diameter. It has been revealed that the sensitivity depends on the amount of adsorbed water in the film, the pKb value of objective gases and the pH range for the color change observed for acid-base indicators used.

30. 定電位電解式センサを用いたCO₂ガスの検出

石地徹、飯島鉄也、高橋勝緒
理研計器、理化学研究所^*

Detection for Carbon Dioxide by Electrochemical Gas Sensor

Toru ISHIJI, Tetsuya IIJIMA and Katsuo TAKAHASHI^*

Riken Keiki Co.Ltd., 2-7-6 Azusawa, Itabashi-ku, Tokyo 174, Japan
^*The Institute of Physical and Chemical Research(RIKEN), 2-1 Hirosawa,
Wako-shi, Saitama 351-01, Japan

An amperometric sensor based on the pH-dependent reduction of platinum oxide electrode was developed for the detection of carbon dioxide(CO₂). The reduction current of the sensor was proportional to the square root of the CO₂ gas concentration. The effect of the components of the electrolytic solution was studied to improve the characteristics of the sensor. A linear relationship between the reduction current and the CO₂ gas concentration was obtained by addition of hydrogencarbonate to the electrolytic solution. The linear relation can be explained by hydrogen ion generation with dissociation of CO₂ in a solution.

31. 高分子アニオン複合ポリピロール膜を用いた全固体型カリウムイオン選択性電極の特性評価

山本真由美、駒場慎一、門間聰之、逢坂哲彌
早大理工・早大材料技術研

EVALUATION OF ELECTRODE CHARACTERISTICS OF ALL SOLID STATE POTASSIUM-SELECTIVE ELECTRODE USING POLYPYRROLE/POLYANION COMPOSITE FILM

Mayumi YAMAMOTO, Shin-ichi KOMABA, Toshiyuki MOMMA and Tetsuya OSAKA
Department of Applied Chemistry, School of Science and Engineering ^*;
Kagami Memorial Laboratory for Materials Science and Technology, Waseda University.
13-4-1 Okubo, Shinjuku-ku, Tokyo 169, Japan

All solid state potassium-selective electrode was constructed by covering with a plasticized poly(vinyl chloride) (PVC) membrane containing valinomycin over to polypyrrole/poly(4-styrensulfonate) (PPy/PSS) composite film. It shows good Nernstian slope of potential response. The potential stability is controlled by selecting the preparation conditions of PPy/PSS composite film. Moreover, the immersion of the under composite film in a KCl solution before forming the upper layer makes the electrode impedance lower.

32. DRIFT MECHANISM OF SOLID-STATE ION SENSORS WITH ION-SELECTIVE LIQUID MEMBRANE

Yujj Miyahara, Koutarou Yamashita, Satoshi Ozawa and Yoshio Watanabe

Central Research Laboratory, Hitachi Ltd.,
1-280, Higashikoigakubo, Kokubunji, Tokyo 185, Japan

ABSTRUCT
The interface between an ion-selective membrane and a silver-silver chloride electrode was modified with various electrolyte salts to elucidate the drift mechanism of the solid-state ion sensors.The drift characteristics and the EMF shifts were strongly dependent on the concentration of the salt at the interface. This indicates that the shift and the drift of the EMF are completely governed by the electrochemical process at the interface between the ion-selective membrane and the silver- silver chloride electrode. Active ion exchange, and as a result the thermodynamically defined interface are essential for the stable EMF response of the solid-state ion sensor.

33. 脂溶性四級アンモニウム塩を感応物質としたＰＶＣ液膜のフェノール類に対する電位応答

伊藤貴志、遠田浩司、ハンナ　ラデッカ^*、長縄竜一^*、小田嶋和徳^**、梅沢喜夫
東大理、北大理^*、東大薬^**

POTENTIOMETRIC RESPONSES TO PHENOL DERIVATIVES AS NEUTRAL SPECIES BY PVC MATRIX LIQUID MEMBRANES BASED ON LIPOPHILIC QUATERNARY AMMONIUM CATIONS AND RELATED SENSORY ELEMENTS

Takashi ITO, Koji TOHDA, Hanna RADECKA^*, Ryuichi NAGANAWA^*,
Kazunori ODASHIMA^**, and Yoshio UMEZAWA
Department of Chemistry, School of Science, The University of Tokyo,
Bunkyo-Ku, Tokyo 113.
^* Department of Chemistry, Faculty of Science, Hokkaido University,
Kita-Ku, Sapporo, Hokkaido 060, Japan
^** Faculty of Pharmaceutical Sciences, The University of Tokyo,
Bunkyo-Ku, Tokyo 113, Japan

Anionic potentiometric responses to phenol derivatives were observed by membranes based on lipophilic quaternary ammonium salts at pH 6.0, at which these guests exist almost exclusively in their uncharged forms. The response slope in a concentration range between 10-3 and 10-2 M of phenol was ca.-70 mV, which was greater than the theoretical value for a monovalent anion according to the Nernst equation (-58.2 mV/decade at 20 ℃). The potentiometric selectivity seems to reflect both logPoct and pK1 value of each phenol derivative, whereas potentiometric responses toward compounds having no phenolic OH group such as cyclohexanol and veratrole were negligible.

34. フッ化ランタンの非化学量論的溶出と固／液界面におけるイオン選択的電荷分離の基礎研究

谷　幸則、梅沢喜夫、近間克己^*、辺見彰秀^*、相馬光之^**
東大埋、北大理^*、国立環境研^**

NON-STOICHIOMETRIC DISSOLUTION OF LANTHANUM FLUORIDE (LaF₃) AND ITS RELEVANCE TO A PROCESS OF ION-SELECTIVE CHARGE SEPARATION AT THE SOLID/SOLUTION INTERFACE1)

Yukinori TANI^*, Yoshio UMEZAWA^*, Katsumi CHIKAMA^**
Akihide HEMMI^** and Mitsuyuki SOMA^***
^* Department of Chemistry, School of Science, The University of
Tokyo, Hongo, Tokyo 113, Japan, ^** Department of Chemistry, Faculty of
Science, Hokkaido University, Sapporo 060, Japan, ^*** National Institute
for Environmental Studies, Tsukuba, Ibaragi 305, Japan

The solubilities of lanthanum fluoride (LaF₃) powder and single-crystals were measured in various aqueous electrolyte solutions. In contrast to the classical assumption of the stoichiometric dissolution of LaF₃, it was found that the dissolution of the component cation, La³⁺, was undetectable and the fluoride ion dissolved preferentially: CF > 3 x CLa³⁺ where C is the ion concentration. X-ray photoelectron spectroscopy (XPS) of the LaF₃ surface treated with electrolyte solutions corroborated this observation. As a result of the preferential fluoride dissolution, charge separation was expected to occur in such a way that the LaF₃ surface would have positively charged "fluoride vacancies". This was confirmed by changes in membrane potential as a function of the fluoride dissolution and the adsorption of an anionic adsorption marker, Eosin-Y, on the solid surface. It was also found that the preferential dissolution of fluoride ions was accompanied by simultaneous adsorption of almost the same amount of electrolyte anions (e.g. NO₃-) onto the LaF₃ surface. This was confirmed by both solution measurements and surface analysis by diffuse reflectance IR Fourier transform (DRIFT) spectrometry. The result of this anion adsorption was explained in terms of ion-exchange to ensure electroneutrality in the bulk of the adjacent electrolyte solution, which would otherwise be violated by the preferential fluoride dissolution. The anionic adsorption marker and DRIFT measurements were used to characterize further the above-mentioned ion-exchange and selective uptake of fluoride ions into the "fluoride-vacancies". Release of the adsorbed Eosin-Y or electrolyte anions, such as NO₃-, from the LaF₃ surface was found to be induced only by F^- or OH^- ions only. On the basis of the this observation, the response mechanism of the fluoride ion-selective electrodes will be discussed.

35. 蛍光性イオノフォアを用いる液液界面促進イオン移動の電位規制フルオロメトリー

小野和人、高須陽子、垣内　隆、仁木克己
横浜国大工

VOLTAGE-SCAN FLUOROMETRY OF THE FACILITATED ION TRANSFER ACROSS THE OIL / WATER INTERFACE USING FLUOROIONOPHORES

Kazuto ONO, Yoko TAKASU, Takashi KAKIUCHI, Katsumi Niki
Department of physical chemistry, Yokohama National University
Yokohama-shi, Hodogaya-ku, Tokiwadai 156, Japan

Ion-transfer voltfluorometry, which detects the transfer of fluorescent ions in nM level across the liquid-liquid interface, has been extended to the study of non-fluorescent ion transfer by making use of the facilitated transfer of these ions with a fluorescent ionophore, coumarin 153 linked to monoaza-15-crown-5 (C153-crown(O₄)). When the concentration of C153-crown(O₄) in DCE was 2 μM and the aqueous phase contained excess amount of alkali-and alkaline earth metal ions, the increase in fluorescence accompanied by the linear scan of the voltage was observed. In alkali ion transfers, the differential voltfluorograms were isomorphic to cyclic voltammograms.

36. イオン選択性電極液膜界面におけるカチオンパームセレクティビィティーのFTIR-ATRによる直接観測

梅澤香代子、林　暁明、西澤精一、管原正雄、梅澤喜夫
東大教養、北大理、東大埋

CATION PERMSELECTIVITY IN THE PHASE BOUNDARY OF IONOPHORE-INCORPORATED SOLVENT POLYMERIC MEMBRANES AS STUDIED BY FT-IR ATR SPECTROSCOPY

Kayoko UMEZAWA^*, Xiao Ming LIN^**, Seiichi NISHIZAWA^***,
Masao SUGAWARA^*** and Yoshio UMEZAWA^***
^* Department of Chemistry, College of Art and Science, The University of Tokyo, Komaba, Tokyo 153, Japan, ^** Division of Environmental Conservation, Graduate School of Environmental Science, Hokkaido University, Sapporo 060, Japan; ^*** Department of Chemistry, School of Science, The University of Tokyo, Hongo, Tokyo 113, Japan

Behaviors of permselective membrane transports were studied by FT-IR ATR spectroscopy and potential measurements for the solvent polymeric membranes incorporated respectively with several different ionophores. The stoichiometric ratios between the complexed cations and their corresponding counter anions in the phase boundary, 0.31 - 1.8μm in depth, of the membrane were determined for each membrane made, beforehand, in contact with various primary ion solutions. When hydrophilic counter anions were used for the primary ion solutions, the IR spectra for the membrane were exclusively from the complexed cations, and no IR-active anionic peak appeared. On the contrary, when a hydrophobic counter anion, SCN-, was used for the primary ion solutions, the spectra from both the complexed cation and corresponding counter anion showed up, of which stoichiometric ratios changed depending on the concentrations of primary ion salts, and on the coexistence of a derivative of tetraphenyl borate in the membrane. The obtained results were discussed in terms of the extent of cation permselectivity and its relevance to the potential response of ionophore-incorporated liquid membrane ion-selective electrodes.

37. 光第二高調波発生(SHG)によるイオン選択性液膜／試科溶液界面の直接観察

遠田浩司、吉谷川真司^*、梅澤喜夫、橋本訓^**、川崎昌博^**
東大埋、北大理^*、北大電子研^**

CATION PERMSELECTIVITY AT THE PHASE BOUNDARY OF IONOPHORE INCORPORATED SOLVENT POLYMERIC MEMBRANES AS STUDIED BY OPTICAL SECOND HARMONIC GENERATION (SHG)

Koji TOHDA, Yoshio UMEZAWA, Shinji YOSHIYAGAWA^*, Satoshi HASHIMOTO^**
and Masahiro KAWASAKI^**
Department of Chemistry, School of Science, The university of Tokyo, Tokyo 113, Japan
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060, Japan
^** Research Institute of Electronic Science, Hokkaido university, Sapporo 060, Japan

The optical second harmonic generation (SHG) was observed at the surface of various ionophore-incorporated poly(vinyl chloride) (PVC) liquid membranes. The SHG signal of the membrane in contact with the aqueous solution generally increased with increasing primary cation activities in the solution, and then leveled off at higher cation concentrations. The concentration dependence of primary cations as well as the ionophore on the SHG intensities was analyzed based on the Langmuir type adsorption model. When a lipophilic counter anion, SCN-, was used for the primary ion solution, the decreases in the potentiometric and SHG responses were observed in the same concentration region. The improvement in the SHG as well as potentiometric responses was observed with the addition of a lipophilic anionic site into the membrane. These parallel changes in membrane potentials and SHG signals demonstrated allowed us to conclude that the observed membrane potentials are primarily governed by the SHG active oriented species at the membrane surface. However, another important feature of the SHG response is that the saturation occurs with higher cation concentrations where Nernstian potentiometric responses were still observed. The latter results suggest that the SHG inactive complex due to insufficient molecular orientation, locating somewhat membrane interior, also contributes to the membrane potential. To evaluate the contribution of the SHG active oriented complexes to the generation of the ISE potentials, the SHG responses were analyzed on the basis of a space-charge model.

38. SOS型SPVセンサ

伊藤善幸、石川孝明
新電元工業

SPV SENSOR with SOS WAFER

Yoshitaka Ito, Takaaki Ishikawa
Research & Development Center, Shindengen
Hanno-shi, Saitama 357, Japan

A novel integrated surface photovoltage (SPV) sensor system has been investigated by joining a Silicon on Sapphire (SOS) wafer to a visible laser light. The 5 sensors are made on SOS wafer with the thickness of 0.6 μm and located with 1×1mm² in area at a 2 mm pitch each to each, covered of Si3N4 layer for pH sensor. The back-side of the sensor is illuminated with the He-Ne laser beams of red and green. The present study indicates that the sensor illuminated by green laser having the wavelength 543.5 nm is superior to achieve a satisfactory position and sensitivity precision without cross-talk between sensing bits to conventional SPV sensors made of Si wafer.

39. SPV法を用いた甘味料センサの試作

佐々木豊、内田秀和、勝部昭明
埼玉大工

FABRICATION OF SWEET DETECTABLE SENSOR WITH SPV METHOD

Yutaka SASAKI, Hidekazu UCHIDA and Teruaki KATSUBE
Faculty of Engineering, Saitama University
255 Shimo-Okubo, Urawa-shi, Saitama 338, Japan

A sweet taste sensor was developed using SPV (surface photo-voltage) technique with polyvinylbutyral resin for the immobilization of ion sensitive material (artificial lipid membrane). A differential SPV method based on a time sharing process, which has been developed in our laboratory[l] , was successfully used to discriminate four kinds of commercially available sugars. It was also shown that the polyvinylbutyral resin has strong adhesion to Si3N4 film leading to the stabilization of sensor response.

40. アビジン・ビオチンシステムによる酵素固定化量の制御とセンサヘの応用

星　友典、安斎順一、長　哲郎
東北大薬

PREPARATION OF ENZYME MULTILAYERS BASED ON AN AVIDIN/BIOTIN SYSTEM FOR THE REGULATION OF THE PERFORMANCE OF ENZYME SENSORS

Tomonori HOSHI, Jun-ichi ANZAI and Tetsuo Osa
Pharmaceutical Institute, Tohoku University,
Aobayama, Sendai 980-77, Japan

The multilayer of glucose oxidase (GOx) on platinum (Pt) electrode was prepared by use of avidin and biotinylated GOx and its performance as an amperometric glucose sensor was characterized. An alternate and repeated deposition of avidin and biotinylated GOx gave protein multilayers composed of avidin monolayers and biotinylated-GOx monolayers which are connected with each other through strong affinity between avidin and biotin moieties of the enzyme (binding constant: 1015 M-1). Amperometric response of the glucose sensors constructed by using these enzyme multilayers was controlled stepwise and rather precisely by regulating the number of GOx layers.

41. 基質透過性疎水化隔膜におけるメディエータ反応とセンサヘの応用

三和幸晴、未永智一、内田　勇
東北大工

Permeation and Electrocatalysis at hydrophobically prepared diaphragm electrode and its application to a sensor

Y. Miwa, T. Matsue, and I. Uchida
Department of Molecular Chemistry and Engineering,
Faculty of Engineering, Tohoku University,
Aramaki-Aoba, Aoba-ku, Sendai 980-77, Japan

We here report a new type of a mediated enzyme sensor, where cofactors of enzymes and analytes are separated by a hydrophobically prepared Au or Pt diaphragm electrode. Ethanol in an analyte phase permeated through the diaphragm, and was catalytically oxidized at the electrode coated with diaphorase and alcohol dehydrogenase in a cofactor / mediator phase. No permeation of the cofactor and mediator through the diaphragm was observed.

42. 電解重合絶縁性ポリピロール膜を用いた尿素センサの作製

駒場慎一、瀬山倫子、門間聰之、逢坂哲彌
早大埋工・早大材料技術研

POTENTIOMETRIC BIOSENSOR FOR UREA USING INSULATING POLYPYRROLE FILM

Shin-ichi KOMABA, Michiko SEYAMA, Toshiyuki MOMMA and Tetsuya OSAKA
Department of Applied Chemistry, School of Science and Engineering ^*;
Kagami Memorial Laboratory for Materials Science and Technology, Waseda Universisity,
^*3-4-1 Okubo, Shinjuku-ku, Tokyo 169, Japan

Potentiometric biosensor for urea was prepared by electropolymerization process of pyrrole in an NaHCO₃ aqueous solution containing urease (Urs). Urs was entrapped into insulating and electroinactive polypyrrole (PPy) film during electropolymerization, and the selection of the polymerization conditions makes the urea response possible. This PPy(Urs) electrode shows the Nernstian response to urea in Tris buffer solution at 35 ℃. The urea response of the PPy(Urs) electrode is suggested to be due to good pH response of the insulating PPy electrode.

43. ファジイエキスパートによる酸素センサのキャリブレーション

山田裕之、清水和幸、鈴木正康
九工大情報工

CALIBRATION OF ENZYME SENSORS BASED ON FUZZY EXPERT SYSTEM

Hiroyuki YAMADA, Kazuyuki SHIMIZU, and Masayasu SUZUKI
Faculty of Computer Science and Systems Engineering, Kyushu Institute of
Technology, 680-4 Kawazu, Iizuka, Fukuoka 820, Japan

Integrated micro enzyme sensors are required in bioprocess monitoring. The auto-calibration is necessary for the on-line monitoring but it is not easy for micro enzyme sensors because of their frequent abnormal data, narrow linear range, cross-talking and so on. In this study, an intelligent calibration method was developed by using a fuzzy expert system. Based on "expert information" obtained from the data of preliminary experiments, the membership functions were determined. The relationship between sensor outputs and concentrations was described by these membership functions. The present method could eliminate abnormal data and required only a short time for the calculation.

44. 表面プラズモン現象を利用した光センサによるタンパク質の検出

林田匡史、岡本大介、荒川剛
近大九州工

SURFACE PLASMON RESONANCE STUDY FOR THE DETECTION OF SOME PROTEIN

Tadashi HAYASHIDA, Daisuke OKAMOTO
and Tsuyoshi ARAKAWA

Department of Industrial Chemistry, Faculty of Engineering Kinki University in Kyushu,
Iizuka-shi, Fukuoka 820, Japan

The detection of cytochrome C has been investigated by an optical chemical sensor based on laser-excited surface plasmon resonance. When the medium outside was changed from air to the cytochrome C solution (cytochrome C (100μM) + 0.1M PBS (KH₂PO₄:Na₂HPO₄=l:2, pH7.06) , the resonance angle first varied from 23.08° to 52.01°, followed by increasing to a constant value (52.51°) . In the use of the sensor head of which a silver thin film was coated by a Nafion thin film , the shift of incident angle was also observed by the incorporation of cytochrome C into Nafion thin film .

45. 差動型表面光電圧測定法による免疫センサの高感度化

楽　海芳、佐々木豊、内田秀和、勝部昭明．
埼王大工

HIGH SENSITIVE IMMUNO-SENSOR USING A DIFFERENTIAL SURFACE PHOTOVOLTAGE MEASUREMENT TECHNIQUE

Yueh Hai Feng, Yutaka SASAKI, Hidekazu UCHIDA
and Teruaki Katsube
Department of Information and Computer Sciences,
Faculty of Engineering, Saitama University
255 Shimo-okubo, Urawa, 338, Japan

New measurement methods of surface photo-voltage (SPV) technique - phase shift method and differential SPV - were developed to fabricate a high sensitive immuno-sensor. It was first shown that the phase shift method, which is based on the detection of phase shift of the surface photo-current, made it possible to detect neutral charge material as well as charge density of the electrode surface.
It was also shown that the differential SPV method increases the signal to noise ratio of the system both of phase shift method and surface potential measurement method leading to the fabrication of a high sensitive immuno-sensor.

46. イムノアフィニティーを利用したエイズセンサの構築 (1)エンベロープタンパクgp41抗原および抗体の検出

宇田泰三、小林利章、一二三恵美、清水浩輔
広島県立大生物資源

DEVELOPMENT OF IMMUNOAFFINITY AIDS SENSOR(Ⅰ) DETECTION OF ENVELOPE PROTEIN gp41 ANTIGEN AND ANTIBODY

Taizo UDA, Toshiaki KOBAYASHI, Emi HIFUMI, and Kousuke SHIMIZU
School of Bioresources, Hiroshima Prefectual University,
Shoubara-shi, Hiroshima 727, Japan

A monoclonal antibody for the conservative region of gp41 was produced and then the antigen determining site was analyzed by means of epitope mapping in order to obtain the suitable affinity peptide for construction of an immunoaffinity AIDS sensor. The peptide having slightly less immunoaffinity, EGIEE, was the most preferable. EGIEE was labeled with catalase and used as a mimic antigen which had been bound to the fixed antibody on immuno-membrane prior to the sensing by an oxygen electrode. The mimic antigen was replaced by gp41, generating some oxygens in proportion to the concentration of gp41. On the other hand, anti gp41 antibody was also detected using a mimic antibody chemically modified with polyethylene glycol.

47. カーボンフェルト電極／GOD含有溶液系によるカテコール類の高感度測定

水谷文雄、矢吹聡一
生命工研

HIGHLY-SENSITIVE MEASUREMENT OF CATECHOLS USING CARBON FELT ELECTRODE IMPREGNATED WITH GLUCOSE OXIDES-CONTAINING SOLUTION

Fumio MIZUTANI and Soichi YABUKI

A carbon felt electrode impregnated with a glucose oxidase / glucose-solution was used for measuring dihydroxyphnols (e.g., catechol and dopamine). Dihydroxyphenol molecules are oxidized but regenerated by the enzymatic reaction. The consumption/ regeneration cycle for dihydroxyphenols resulted in an amplified electrode response. Further, the measuring method could be free from the electrochemical interference by oxidizable species such as L-ascorbic acid.

48. アデノシン－５'－トリホスフェート(ATP)に応答するバイオセンサの開発

勝　孝、山中弘司、Xiurong Yang^*、Garry A. Rechnitz^*
岡山大薬、ハワイ大バイオセンサ研^*

DEVELOPMENT OF BIOSENSORS RESPONDING TO ADENOSINE-5'-TRIPHOSPHATE (ATP)

Takashi KATSU, Koji YAMANAKA, Xiurong YANG^* and
Garry A. RECHNITZ^*
Faculty of Pharmaceutical Sciences, Okayama University,
Tsushima, Okayama 700, Japan and ^*Hawaii Biosensor
Laboratory, Department of Chemistry, University of Hawaii,
Honolulu, HI 96822, U.S.A.

New amperometric and potentiometric biosensors responding to adenosine-5'-triphosphate (ATP) were constructed. The amperometric biosensor was designed using a platinum-dispersed carbon paste into which glycerol kinase and glycerol-3-phosphate
oxidase were incorporated. The biosensor is based on the detection of hydrogen peroxide produced by the enzymatic reaction of ATP with glycerol and the subsequent oxidation of glycerol-3-phosphate. The use of the platinum-dispersed carbon paste electrode lowered the oxidation potential for hydrogen peroxide. The potentiometric method used a choline-sensitive membrane electrode and choline kinase enzyme. Choline reacted with ATP to produce the electrode-insensitive choline phosphate and, therefore, the concentration of ATP could be determined by the measurement of choline consumed by the enzymatic reaction.

49. 固定化サーモリシンを用いた亜鉛(II)イオンのカロリメトリックバイオセンシング

佐藤生男、木村　出、矢口秀章
神奈川工大

CALORIMETRIC BIOSENSING OF ZINC(II) IONS USING AN IMMOBILIZED THERMOLYSIN

lkuo SATOH, Izuru KIMURA, and Hideaki YAGUCHI
Department of Chemical technology, Faculty of Engineering,
Kanagawa Institute of Technology
1030 Shimo-Ogino, Atsugi-shi, Kanagawa-ken, 243-02, Japan

Calorimetric biosensing of zinc(II) ions was tested with use of thermolysin covalently immobilized on porous glass beads. The biosensing system was assembled with the beads-containing column mounted in a flow-injection calorimetric device for monitoring the enzyme activity. Change in temperature at the outlet of the column was successively detected and recorded. The metal-free enzyme (apoenzyme) was regenerated by exposing EDTA solution(pH 4.0) to the column. Zinc(II) ions in submillimolar levels were determined through the activation of the immobilized apoenzymes.

50. 分子育種大腸菌による環境汚染物質の発光モニタリング

新美智久、春山哲也、小畠英理、碇山義人、相澤益男
東工大生命理工

BIOLUMINESCENT MONITORING OF ENVIRONMENTAL POLLUTANTS BY RECOMBINANT ESCHERICHIA COLI

Tomohisa NIIMI, Tetsuya HARUYAMA, Eiry KOBATAKE. Yoshihito IKARIYAMA, aud Masuo AIZAWA
Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology

For the sensitive and rapid detection of environmental pollutants, we have made a recombinant E.coli transformed with a plasmid pTSN316 containing a gene for luciferase and the promoter region of TOL plasmid. As luciferine, the substrate of luciferase, was difficult in permeating to through E.coli membrane, it took considerably longer time to get a sufficient luminescence. In the present study, the permeability of luciferine through E.coli membrane was enhanced in acidic conditions. The optimum pH was found to be around 4.5. m-Xylene was determined in the concentration range from 5μM to 0.5μM at pH 4.8.

51. バイオセンサを用いた小麦のアミラーゼ活性の迅速測定

萩野谷隆一、酒井久仁子、安井貞夫、小松隆、佐々木聰、矢野和義、池袋一典、輕部征夫
東大先端研、日清製粉

RAPID MEASUREMENT OF AMYLASE ACTIVITY IN WHEAT FLOUR USING BIOSENSOR METHOD

Ryuichi HAGINOYA, Kuniko SAKAI, Sadao YASUI, Takashi KOMATSU, Satoshi
SASAKI, Kazuyoshi YANO, Kazunori IKEBUKURO and Isao KARUBE
Research Center for Advanced Science and Technology, University of Tokyo
4-6-1 Komaba, Meguro-ku, Tokyo 153, Japan
Technical Research Center, Nisshin Flour Milling Co., Ltd.
5-3-1 Tsurugaoka, Oi-machi, Iruma-gun, Saitama 356, Japan

Amylase activity in wheat flour is very important indicator for evaluating baking quality of wheat flour. One of the conventional method for the measurement of amylase activity in flour is an amylograph which is one of viscometers. However, the data from the amylograph are only characteristic curves of scalded flour. In this study, we have developed a quick and easy measurement method of amylase activity in wheat flour using a flow injection analysis (FIA) type biosensor system. And the amylase activity measured by the biosensor method was compared with that obtained by commercial measurement kit. Good correlation was obtained between the biosensor method and the measurement kit method.

52. 脂質修飾グルコース酸化酵素／α－グルコシダーゼを用いたアンペロメトリックなマルトース応答性電極

壇　金宗、山本信子、水谷文雄^*、矢吹聡一^*
テクノメディカ開発センター・生命工研^*

AMPEROMETRIC MALTOSE-SENSING ELECTRODE BASED ON LIPID-MODIFIED GLUCOSE OXIDASE AND α-GLUCOSIDASE

Jinzong TAN, Shinko YAMAMOTO, Fumio MIZUTANI^* and Soichi YABUKI^*
Research and Development Center, Techno Medica Co. Ltd., East Building 502 of
Kanagawa Science Park (KSP), Takatsu-ku, Kawasaki, Kanagawa 213, Japan
^* National Institute of Bioscience and Human Technology, 1-1 Higashi, Tukuba, Ibaraki 305, Japan

A maltose-sensing electrode was developed by using lipid-modified enzymes, glucose oxidase and α-glucosidase : first, a platinum base electrode was dipped into a benzene solution containing these modified enzymes and dried, and second, the electrode was dipped into Kodak AQ-29D polymer solution and dried. The electrode thus obtained had a response time of 15 seconds and a linear response from 0.01 to 2.0 mM for maltose. The electrode could be used for two weeks.

特別講演１．
材科のインテリジェント化

（東京大学・環境安全研究センター・工学部）柳田博明

INSTALLATION OF INTELLIGENT MECHANISMS INTO MATERIALS THEMSELVES

Hiroaki YANAGIDA
Faculty of Engineering
Environmental Science Center,
University of Tokyo,
Hongo, Bunkyo-ku, Tokyo 113, Japan

The essential purpose to develop intelligent materials is to aboid spaghetti syndrome of technology. Keywords are wisdom, integration of structural performance and functional behavior, tecology,etc. One of the most important cases is to assure reliability of large structures. This is only achieved to make materials strong enough and diagnose themselves. Design of self-diagnosis is explained in this paper.

特別講演２　
特定目的を付与した微生物の分子育種と難分解性物質の発光モニタリング

碇山義人^*、小島英理^**、相澤益男^**
国立身障者リハビリセンター研究所^*、東京工業大学生命理工学部^**

MOLECULAR BEADING OF LUMINOUS MICROORGANISM HAVING A SPECIFIC PURPOSE AND ITS APPLICATION TO MONITOR HARDLY DECOMPOSABLE CHEMICAL COMPOUNDS IN THE ENVIRONMENT

Yoshihito IKARIYAMA
Research Institute of National Rehabilitation Center for the Disabled
4-1 Namiki, Tokorozawa, Saitama 359, Japan
Eiry KOBATAKE, Masuo AIZAWA
Department of Bioengineering, Tokyo Institute of Technology
4259 Nagatsuda, Midori-ku, Yokohama. Kanagawa 227, Japan

A new strategy toward the detection of aromatic hydrocarbons such as benzene (B), toluene (T), and xylene (X) with a recombinant E.coli has been taken. We have constructed a new plasmid (pTSN316) for light generation. A fragment from TOL plasmid, responsible for the digestion of BTX and their derivatives, bearing the promoter (Ps) of the xyl S gene for a transcriptional activator, was fused to the luciferase gene of firefly (Photinus pyralis) . The E. coli strain containing the plasmid (HB101(pTSN316)) can emit photons in the presence of a benzene derivative. The xyl R regulatory gene of TOL plasmid plays an important role to induce luciferase. The bioluminescence of the transformed E. coli increased with the increase in BTX concentration. When compared at 0.8 or 0.9 mM concentration, the bioluminescence became smaller in order of m-xylene. p-xylene, toluene. and benzene. This indicates that specific binding the regulatory protein, Xyl R, and BTX is very important. Moreover, we made a monitoring devise by immobilizing the recombinant E. coli to the tip of a fiber optic, and tried to measure BTX concentration in a batch system. In this result, several ppm of BTX was measured.
　These findings suggest that realtime monitoring of BTX is possible. And the aromatic hydrocarbon concentration can be easily measured by using the proposed fiber optic device. We believe that substances which cause environmental deterioration can be sensitively monitored in this method.

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