Vol. 16, Supplement A (2000)

Vol. 16, Supplement A (2000)

Proceedings of the 30th Chemical Sensor Symposium
April 4-6, 2000

Abstracts

1.
CO/CH₄複合ガスセンサの開発と実用化

伊藤宗廣、森本　聡、永田　敏^*、高島裕正^*、松本晋一

エフアイエス、矢崎計器^*

DEVELOPMENT OF CO AND CH₄ GAS SENSOR WITH A SINGLE ELEMENT

Munehiro Ito, Satoshi Morimoto, Satoshi Nagata^*, Hiromasa Takashima^* and Shinichi Matsumoto

FIS Inc.
3-36-3 Kitazono, Itami, Hyogo 664-0891, Japan
^*Yazaki Meter Co.,Ltd
23 Minamikajima, Futamata, Tenryu, Shizuoka 431-3393, Japan

Recent gas leak alarms have been improved in terms of multiple functions. As a result, the gas alarms to detect both the combustible gas leak and the incomplete combustion have been widely used in the market. Such conventional alarms have been equipped with two gas sensors, one for CH₄ and the other for CO. Therefore, it is inevitable that the power consumption and production cost have been increased, and new alarms with one sensor to detect both the gases have been expected. In order to introduce such new alarms in the market, however, we have had to enhance gas selectivity and stability, and to detect CH₄ with a short time. We have investigated the catalyst to be doped into SnO₂ gas sensing material and devised the sensor operation method in order to develop a new gas sensor which can detect in a short time both CO and CH₄ selectively with single mini-bead type sensing element.

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2.
In₂O₃系水素選択性センサにおけるランタノイド添加効果の検討

勝木章、福井清、石川博

新コスモス電機株式会社

EFFECTS OF LANTHANOIDS ON SENSING CHARACTERISTICS OF H₂ SELECTIVE GAS SENSOR BASED ON SINTERED In₂O₂

Akira KATSUKI, Kiyoshi FUKUI and Hiroshi ISHIKAWA

New Cosmos Electric Co., Ltd.
3-6-25, Mitsuya-Naka, Yodogawa-Ku, Osaka 532-0036, Japan

H₂ selective hot wire type semiconductor gas sensor based on SnO₂ had a serious problem that H₂ sensitivity was declined by exposure to a high gas concentration of H₂ (over 2000 ppm). It was found that a In₂O₃ based gas sensor had an excellent durability in exposure to 2 vol% H₂. But sensitivity vs gas concentration curve of this sensor had a trend that the curve had already saturated even at ca.1000 ppm of H₂. An improvement of such a trend was carried out by addition of various lanthanoids to the sintered In₂O₃ layer. As a result, cerium oxide gave a prominent linearity of the sensitivity curve. In addition, the sensor thus obtained had also a minor humidity dependence and a long term stability.

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3.
医療用N₂O検出のための半導体ガスセンサ

金沢英一、酒井　剛、上村裕一^*、寺岡靖剛^**、三浦則雄^***、山添　曻

九大院総理工、鹿大医^*、長大工^**、九大先端センター^***

METAL OXIDE SEMICONDUCTOR N₂O SENSOR FOR MEDICAL APPLICATION

Eiichi KANAZAWA, Go SAKAI, Yuichi KANMURA, Yasutake TERAOKA, Norio MIURA and Noboru YAMAZOE

Department of Molecular and Material Sciences, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan

In order to develop a semiconductor gas sensor applicable to the monitoring of N₂O in operating room, a search for the sensing materials was carried out. Among the 23 kinds of single oxides tested, SnO₂ turned out to be the most suitable sensing material. The addition of foreign oxides (e.g. SrO, CaO, BaO, Bi₂O₃, PbO, or Sm₂O₃) to SnO₂ was effective for improving the N₂O sensitivity. Especially the element using 0.5wt%SrO-SnO₂ exhibited the N₂O sensitivity about 3 times as high as that of pure SnO₂ element, and could detect N₂O in air in the concentration range 10-300 ppm at 500℃.

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4.
酸化物半導体センサのアセトアルデヒドガス検知特性

兵頭健生、幸山　勝、清水康博、江頭　誠

長崎大工

ACETALDEHYDE SENSING PROPERTIES OF OXIDE SEMICONDUCTOR GAS SENSOR

Takeo HYODO, Masaru KOHYAMA, Yasuhiro SHIMIZU and Makoto EGASHIRA

Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan

Effect of noble metal and/or metal oxide loading on the acetaldehyde sensing properties of SnO₂ has been investigated. Among the noble metals tested, 1.5 wt% Rh loading resulted in the most improved sensitivity, but its value was as low as about 7.5, the sensitivity being defined as the ratio of the sensor resistance in air and that in 40 ppm acetaldehyde (Ra/Rg), at 300℃. On the other hand, the addition of an alkaline earth metal oxide, especially SrO, much improved the sensitivity (Ra/Rg = 170～330 for SrO/SnO₂) at 200℃. The improved sensitivity was suggested to be attributable to the reaction products including C₁-C₄ chemicals of acetaldehyde over SrO/SnO₂ and/or chemisorption of acetaldehyde itself. Furthermore, it was revealed that the sensitivity was also improved by the simultaneous addition of Rh and La₂O₃, e.g. Ra/Rg = 40～56 for 1.5Rh/1.0La₂O₃/SnO₂ at 300℃.

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5.
酸素ガス中蒸着で形成したWO₃薄膜によるNO_x検知

中込真二、佐藤　毅

石巻専修大理工

NO_x SENSING BY TUNGSTEN-TRIOXIDE THIN FILM EVAPORATED UNDER OXYGEN AMBIENT

Shinji NAKAGOMI and Tsuyoshi SATO

School of Science and Engineering, Ishinomaki Senshu University
Ishinomaki 986-8580, Japan

NO_x sensing properties of tungsten-trioxide thin film evaporated under oxygen ambient were compared with the film evaporated in vacuum. Very thin WO₃ film of 20 nm in thickness was formed on alumina substrate with Pt inter digital electrode. Electrical resistance of these WO₃ films were measured in several NO and NO₂ concentration without heat treatment after evaporation. WO₃ thin film evaporated under oxygen ambient has higher NO_x sensitivity than the film evaporated in vacuum. Thin film WO₃ evaporated under oxygen ambient has high sensitivity more than 100 to 10 ppm NO₂ and has high sensitivity more than 10 to 10 ppm NO at 200℃. Moreover, the present film has quick response and recover properties.

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6.
SmFeO₃の表面状態と電気的性質

佐藤正樹、青野宏通、エンリコトラベルサ^*、坂本政臣^**、定岡芳彦

愛媛大工・ローマ大^*・山形大理^**

SURFACE STRUCTURE AND ELECTRICAL PROPERTIES FOR SmFeO₃

Masaki SATO, Hiromichi AONO, Enrico TRAVERSA, Masatomi SAKAMOTO and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University
Matsuyama 790-8577, Japan
^*Department of Chemical Science, and Technology, University of Roma “Tor Vergata”
00133 Roma, Italy
^**Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
Yamagata 990-8560, Japan

Perovskite-type SmFeO₃ powders were prepared by the thermal decomposition of a heteronuclear complex, Sm[Fe(CN)₆]・4H₂O, and by solid-state reaction between the corresponding single oxides, Sm₂O₃ and Fe₂O₃. The surface chemical analysis was performed using X-ray photoelectron spectroscopy (XPS). The amount of adsorbed oxygen decreased with an increasing in the Fe surface coverage on the surface. Larger conductances and lower activation energies in 10 ppm NO₃ gas were observed for the films with larger Sm surface coverage.

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7.
超分子テンプレートを用いたメソポーラス酸化スズの調製

西田式宏、兵頭健生、清水康博、江頭　誠

長崎大工

PREPARATION OF MESOPOROUS TIN OXIDE VIA SUPRAMOLECULAR TEMPLATING

Norihiro NISHIDA, Takeo HYODO, Yasuhiro SHIMIZU and Makoto EGASHIRA

Department of Materials Science and Engineering, Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan

Preparation of mesoporous tin oxide was attempted by using cationic surfactants (n-cetyltrimethylammonium bromide and n-cetylpyridinium chloride ) and sodium stannate. The pH values of the mixed solution were adjusted to 7 ~ 9. The surfactant concentrations were from 0.5 to 5.0 wt%. Mesostructured tin oxide was obtained with a surfactant/Sn mole ratio of 1.0 and pH=8. The XRD patterns of as-prepared tin oxide-surfactant mesostructures exhibited an intense peak at a low angle characteristic of mesoporous materials. TEM micrographs of the as-prepared samples showed the regular array of mesopores. The surfactant was removed by calcination in air at 400℃ for 5h or by solvent extraction and subsequent calcination. However, the calcination resulted in the collapse of the mesostructured tin oxide.

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8.
貴金属の吸着した酸化スズ表面に関するDV-Xα計算

松嶋　茂憲

北九州高専

DV-Xα CALCULATION OF NOBLE METAL-ADSORBED SnO₂ SURFACE

Shigenori MATSUSHIMA

Department of Chemical Engineering, Kitakyushu National College of Technology
Kita-kyushu 802-0985, Japan

The electronic structures of noble metal-adsorbed SnO₂ (001) surface are calculated using a discrete variational Xα method on model clusters, which are [Sn₁₀O₃₄]₂₈^- for the SnO₂ (001) surface and [MSn₁₀O₃₄]₂₈^- (M=Rh,Pd,Ag) for the metal-adsorbed SnO₂ (001) surface. Compared with the SnO₂ bulk, new peaks appear at the top of the valence band and at the bottom of the conduction band. These energy states are assigned to the surface states arising from unsaturated Sn-O bonding. When a Rh atom bridges two oxygen atoms on the SnO₂ (001) surface, bonding and anti-bonding states arising from the admixture Rh 4d and O 2p orbitals are formed around -4.45 eV and 0.3 eV. Nonbonding states originating from Rh 4d are located around -1.3 eV. Similar results are obtained for the [PdSn₁₀O₃₄]₂₈^- and [AgSn₁₀O₃₄]₂₈^- clusters.

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9.
各種半導体薄膜における感ガス時の温度変化

高田　義

新コスモス電機

A TEMPERATURE DROP ON EXPOSURE TO REDUCING GASES FOR VARIOUS METAL-OXIDE THIN FILMS

Tadashi TAKADA

New Cosmos Electric Co., Ltd.,
3-6-25 Mitsuya-naka, Yodogawa-ku, Osaka 532-0036, Japan

The changes in semiconductor resistance and sensor temperature were measured simultaneously when the films were exposed to 10-500 ppm C₂H₅OH. The temperature drop was observed on exposure to C₂H₅OH for films of In₂O₃, SnO₂ and WO₃, of which the change in electric conductivity ΔG(Δ= 1/R) was comparatively large. On the other hand, the temperature drop was not observed clearly for films of ZnO, CeO₂(W), CeO₂ and TiO₂, of which the ΔG was small. Incase of P-type semiconductor of CuO, of which the ΔG was negative, an increase in sensor temperature was observed. The dependence of the temperature drop on sensor temperature was also measured in the range of 300-500℃ of sensor temperature and 10-500 ppm of C2H5OH for films of In₂O₃, SnO₂ and WO₃. It was found that the dependence was nearly expressed as AT⁴×ΔG, where AT⁴ denotes the contribution of radiation in heat leak. These results confirmed that the temperature drop was caused by a change in thermal conductivity of the sensors as a result of an increase in the amount of conduction electrons due to consumption of negatively charged oxygen ad-ions.

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10.
発生機用高濃度オゾンセンサの開発

岡崎慎司、中川英元、朝倉祝治、清水博則、岩本　勇

横浜国立大学工学部、^*荏原実業（株）

A NEW SENSOR FOR AN OZONE GENERATOR

Shinji OKAZAKI, Hidemoto NAKAGAWA, Shukuji ASAKURA, Hironori SHIMIZU^* and Isamu IWAMOTO^*

Dept. of Mat. Sci. and Chem. Eng., Yokohama National University, Yokohama 240-8501, Japan
^*Ebara Jitsugyo Co. Ltd., Kawasaki 213-0012, Japan

A new sensor was developed to measure relatively high concentration of ozone with low cost. Ozone generates heat upon dissociation and the sensor measures dissociation heat of ozone. A pellistor-type flammable gas sensor was utilized to detect the dissociation heat. In order to avoid the catalysis poisoning, the devices without any catalytic substances were used for both sensing and compensating devices. Operating temperatures of the sensing device was raised to more than thermal decomposition of ozone, whereas that of the compensating device was below that temperature. An electric circuit was designed to cope with this sensing method.

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特別講演
高層気象観測用湿度センサ

山本　達夫

静岡大学　名誉教授

HUMIDITY SENSOR FOR WEATHER OBSERVATIONS AT THE UPPER ATMOSPHERE

Tatsuo Yamamoto

Emeritus Professor of Shizuoka University

Radiosonde mounts three devices which measure the atmospheric pressure (1040~5hPa), temperature(-85~+40 C) and relative humidity(5~100%RH), respectively. It climbs up to the height of about 30 Km with the averaging velocity of 6 m/sec. the moisture- sensitive polyimide capacitor with a metal-insulator-semiconductor structure (MIS) is the one of the promising humidity sensors for Radiosonde becase of their small size, short response time, low cost and compatibility with IC fabrication technology. Also, this sensor improved the characteristics in the severe environments by mixing two kinds of the polyimide resins.

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11.
ニオイ識別のための新規なサンプリング方法

前川　亨、蔡　奎千、堂上長則、鈴木健吾、高田　義、^*江頭　誠

新コスモス電機、長崎大工^*

A NEW SAMPLING METHOD FOR ODOR IDENTIFICATON

Toru Maekawa, Kuiqian Cai, Naganori Dougami, Kengo Suzuki, Tadashi Takada, and Makoto Egashira^*

New Cosmos Electric Co. Ltd.
2-5-4 Mitsuya-naka, Yodogawa-ku, Osaka 532-0036, Japan
^*Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852- 8521, Japan

The headspace sampling method is commonly used to control odor concentration in the odor identification with sensor array. However, it needs strict control of the environmental temperature and the preparation of the sample. Moreover, in the case of samples with unstable volatilization, it is difficult to reach an expected goal using the headspace sampling. We have developed two kinds of compensatory methods for the odor concentration using a signal processing that calibrates the learning data set according to the output level of a reference sensor in the sensor array for a target odor, and a hardware method in which a sample odor and clean air are mixed at a certain concentration. The mixing process is controlled by using a sampling system with two gas sensors.

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12.
ガスセンサを用いた観葉植物鉢の大気・土壌の同時汚染浄化モニタリング

大薮多可志、小野寺武^*、中原　毅^**、松浦吉展^**

金沢経済大学、金沢大学^*、フィガロ技研^**

PURIFICATION CHARACTERISTICS OF HOUSE-PLANT FOR AIR POLLUTANTS IN THE ATMOSPHERE AND SOIL USING TIN OXIDE GAS SENSORS

Takashi OYABU, Takeshi ONODERA^*, Takeshi NAKAHARA^** and Yoshinobu MATSUURA^**

Kanazawa University of Economics, Kanazawa 920-8620, Japan
^*Faculty of Engineering, Kanazawa University, Kanazawa 920-8667, Japan
^**Figaro Engineering Inc., Osaka 562-8505, Japan

Due to economic growth humans have been coming in contact with various chemicals. Therefore, people who become chemical sensitive are increasing, which results in anaphylaxis for various chemicals. Recently, sick house syndrome is occurring frequently in an indoor environment. Especially, the aged and infants mainly pass their time in a house. Since they are physically weak, there is a high probability for them to fall into the syndrome. The results are asthma or allergy. In this study, the purifying rage of house-plants (Golden pothos) is examined, namely the removal rate Pa of indoor air pollutants from an experimental sealed chamber by house plants is examined. Pa is derived from tin oxide gas-sensor characteristics for a chemical. It is the value of which the peak of the characteristic is divided by the full-width at half maximum. The smaller the molecular weight of a chemical is, the larger Pa becomes. The following chemicals are examined; formaldehyde, toluen, xylene, cigarette smoke and car exhaust. Pa of pothos for formaldehyde is 25, and 80 for ammonia gas.

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13.
ニオイセンサを用いた食事グレードの同定

沢田史子、大藪多可志、南戸秀仁^*、笠原　浩^**

金沢経済大、金沢工業大^*、新コスモス電機^**

IDENTIFICATION OF MEAL-DEGREE USING ODOR SENSORS

Ayako SAWADA, Takashi OYABU, Hidehito NANTO^*, Hiroshi KASAHARA^**

Kanazawa University of Economics, Kanazawa 920-8620, Japan
^*Kanazawa Institute of Technology, Kanazawa 924-0838, Japan
^**New Cosmos Electric Co.LTD., Osaka 532-0036, Japan

Gas and odor sensors have been used in various fields, for example detection of environmental pollution, safety and quality controls in a food industry and identification of various human behaviors in a residence. Many kinds of odors occur according to the behaviors. The analysis of the odor characteristics has been carried out. Main odors, which occur in a residence, are as follows, namely odor at preparing meal, excretion, perfume and body odors. Life pattern of a solitude elderly person can be grasped roughly by analyzing the odor sensor characteristics. Taking a meal and excretion are important vital actions to a human being. The actions are known by identifying the odors.
In this study, it is tried to identify a meal-degree, which means kinds of the taken meal, that is, a light meal, fried meal or cooked meal by oneself. Various kinds of odor molecules occur at every meal and the sensor patterns vary. Meal degree can be, therefore, understood by odor sensor patterns and it is also able to give the aged some suggestions about his health care according to long-term characteristics of plural odor sensors. As for the results, the number of responded sensors are few in a light meal and sensor-grade is also small. In construct with this matter, all of the installed sensors respond to a fried or cooked meals, and the response grade is high.

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14.
植物および土壌の室内空気汚染物に対する浄化特性

小野寺武、木村春彦、大薮多可志、松浦吉展

金沢大工、金沢経済大経済、フィガロ技研

PURIFICATION CHARACTERISTICS OF FOLIAGE PLANT AND POTTED SOIL FOR INDOOR AIR-POLLUTANTS

Takeshi ONODERA, Haruhiko KIMURA, Takeshi OYABU^* and Yoshinobu MATSUURA^**

Faculty of Engineering, Kanazawa Univerisity, Kanazawa 920-8667,Japan
^*Kanazawa University of Economics, Kanazawa 920-8620, Japan
^**Figaro Engineering Inc., Osaka 562-8505, Japan

Many kinds of indoor air pollutants come from building materials, furniture, paints and many other products in indoor environment. In this study, purification ability of plant for mixed gas of indoor air pollutants is examined. Firstly, purification characteristics of a Golden pothos (Epipremnum aureum) and potted soil without plant for toluene and xylene are examined under lightness and darkness. Then, characteristics for mixed gas of toluene or xylene and formaldehyde are also examined. A combustible gas sensor and ammonia sensors are used in thesis experiments. As results, toluene and xylene are purified more effective in a light than under darkness by the Golden pothos, and they are purified more effective potted soil with plant than without plant. In the experimental of mixed gas, purification effects are not significantly reduced for toluene, xylene and formaldehyde.

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15.
高分子複合膜を用いる室温作動型炭酸ガスセンサ

椎木　弘、大穂隆博、外崎　剛、中山雅晴、小倉興太郎

山口大工

CO₂ GAS SENSOR WITH POLYMER COMPOSITE OPERATING AT ROOM TEMPERATURE

Hiroshi SHIIGI, Takahiro OHO, Tsuyoshi TONOSAKI, Masaharu NAKAYAMA and Kotaro OGURA

Faculty of Engineering, Department of Applied Chemistry, Yamaguchi University
Tokiwadai, Uve 755-8611, Japan

It has been demonstrated that the electrical conductivity of a composite film consisting of base type polyaniline(PAn) and poly(vinyl alcohol)(PVA) is linearly related to the CO₂ concentration. The base-type PAn was prepared by treating poly(anthranilic acid) (PANA) at 280℃ for 8h, and by treating acid doped PAn in 3% NH₃ solution for 6h and subsequently heating at 380℃ for 1h. The composite film consisting of the base-type PAn and PVA was coated on a Pt comb-shaped microelectrode. The composite electrode responds to CO₂ at room temperature, and the electrical conductivity shows a linearly relationship with CO₂ concentration in a wide range from 50 ppm to 100%. The increase in conductivity of the composite film in proportion to the CO₂ concentration is attributed to the transformation of the base0type PAn to the salt-type which are caused by the incorporation of carbonate ions formed by the hydrolysis of CO₂ into the base type-PAn.

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16.
合成２分子膜を用いた低温作動容量型CO₂センサ

石原達己、高木俊昭、西口宏泰、滝田祐作

大分大学工学部

LOW TEMPERATURE OPERATING CAPACITIVE TYPE CO₂ SENSOR BASED ON MULTIBILAYER FILM

Tatsumi Ishihara, Toshiki Takagi, Hiroyasu Nishiguchi and Yusaku Takita

Department of Applied Chemistry, Faculty of Engineering Oita University
Dannoharu 700, Oita 870-1192, Japan

Changes in capacitance and resistance of the self-assembled multibilayer film containing metal acetylacetonate (AcAc) upon exposure to CO₂ were investigated for a new CO₂ sensor operable at low temperature. It was found that multibilayer film consisting of dimethyldidodecylammonium bromide (DC1-16) and metal acetylacetonate exhibits a large capacitance change upon exposure to CO₂ at 373 K. Among the examined metal acetyleacetonate, mixing NiAcAc exhibits a largest change in capacitance. Capacitance of DC1-16 mixed with NiAcAc increased with increasing CO₂ concentration and hardly respond to H₂O and CH₄. This study reveals that self assembled multibilayer film can be used as a capacitive type CO₂ sensor at low temperature.

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17.
テトラフェニルポルフィリン-アクリル酸エステルポリマー複合膜を用いた光学的HClガスセンサ

山下雅弘、ヘルスプリヤトノ、中川克彦^*、定岡芳彦

愛媛大工、新居浜高専^*

OPTICAL HCl DETECTION USING COMPOSITE FILMS OF TETRAPHENYLPORPHINE-POLYACRYLATE

Masahiro YAMASHITA, Heru SUPRIYATNO, Katsuhiko NAKAGAWA^* and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Ehime University
Bunkyo-cho 3, Matsuyama-shi, Ehime 790-8577, Japan
^*Department of Applied Chemistry and Biotechnology, Niihama National College of Technology
7-1, Yagumo-cho, Niihama-shi Ehime, 792-8580, Japan

　HCl sensors using Tetraphenylporhine-polymer composite films were prepared and the effects of the glass transition temperature (Tg) of the polymer in the films were examined. A higher sensitivity was obtained when Tg of the polymer is lower (290～310K) than operating temperature (318K) of the sensors. This improvement is ascribed to an increase in free volume. However, the sensitivity were reduced when Tg value of the polymer is lower than 290K.

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18.
ポリアニリン複合膜の電気伝導性へのNH₃ガスの影響

松口正信、猪尾淳一、杉山　剛、酒井義郎

愛媛大工

EFFECT OF NH₃ GAS ON THE ELECTRICAL PROPERTIES OF POLYANILINE BLENDS

Masanobu MATSUGUCHI, Junichi IO, Go SUGIYAMA and Yoshiro SAKAI

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime, 790-8577, Japan

Effect of NH₃ gas on the electrical conductivity of polyaniline blend films were examined for the purpose of preparing NH₃ gas sensor. The DC current of both composite films in N₂ was enhanced above 2 wt% of concentration of polyaniline in the film. Above the concentration, the DC current was decreased by exposing the film to NH₃ gas. The sensitivity, the response time, and the recovery of the sensor were affected by the kind of host polymers, doped acid, and the measuring temperature. With poly(methylmethacrylate) blend, the characteristics were also affected by the used solvent for the film preparation. Toluene was effective for preparing the sensor having the fast response and the good recovery, because the porous film was formed.

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19.
電界効果トランジスタ(FET)型NO₂センサに関する研究

中田聖士、島ノ江憲剛、三浦則雄^*、山添　曻

九大院総理工・九大先端センター^*

FIELD EFFECT TRANSISTOR (FET) TYPE NO₂ GAS SENSOR

Seiji NAKATA, Kengo SHIMANOE, Norio MIURA^*, Noboru YAMAZOE

Department of Molecular and Materials Sciences, Graduate School of Engineering Sciences, Kyushu University
^*Advanced Science and Technology Center for Cooperative Research, Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan

An NaNO₂-attached FET device, NaNO₂ / Ta₂O₅ / N-type MIS-FET, was designed for the detection of NO₂. The drain current (ID) vs. gate voltage (VGS) correlation under a fixed source-drain voltage (VDS=3.0V) at 180℃ revealed that the threshold gate voltage shifted with a change in NO₂ concentration almost in accordance with the Nernst equation for one-electron reduction of NO₂. With VGS fixed at 0.5V, ID was logarithmically proportional to the NO₂ concentration in the range of 0.3 ppm to 10 ppm. The times of 90% response and recovery to switching -on and -off 1 ppm NO₂ were c.a. 2 min and 3 min, respectively.

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20.
パイロクロア型酸化物デバイスのNO_x検知特性

中野裕弘、今坂隆之^*、平山義広^*、清水陽一

九工大工、セントラルユニ^*

SENSING PROPERTIES OF PYROCHLORE-TYPE OXIDE BASED THICK-FILM NO_x SENSOR

Yasuhiro NAKANO, Takayuki IMASAKA^*, Yoshihiro HIRAYAMA^* and Youichi SHIMIZU

Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology
1-1 Sensui-cho, Tobata, Kitakyushu 804-8550, Japan
^*Planning and Development Division, Central Uni Co.,Ltd.
1144 Kawarada, Onoj o, Fukuoka 816-0932, Japan

Thick-film sensor devices fabricated with pyrochlore-type oxides prepared by a coprecipitation method have been investigated for the detection of NO and NO₂ in the range 10-1000 ppm. Among the oxides tested, Bi₂Ru₂O₇ based device was found to show highly selective sensing properties to NO at 300℃. The 90% response time to 253 ppm NO was ca. 5 min at 300℃. On the other hand, Pb₂Ru_1.7Sb_0.3O_7-y device showed highly selective NO₂ sensing properties at 200℃.

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21.
NASICONを基本とする固体電解質を用いた塩素ガスセンサ

青野宏通、定岡芳彦

愛媛大工

Cl₂ GAS SENSOR USING SOLID ELECTROLYTES BASED ON NASICON

Hiromichi AONO and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University, Matsuyama-shi, Ehime, 790-8577, Japan

The EMF (electromotive force) responses were investigated for a Cl₂ gas sensor using Na_1.3Y_0.3Zr_1.7(PO₄)₃ solid electrolyte and RuO₂+NaCl (1:1) measuring electrode. This sensor gave rapid EMF changes even for sub-ppm level of Cl₂ gas concentration (below 10 ppm). The minimum response time was obtained when operating temperature is 450~500 ℃. The side-reaction between Na₂O and Cl₂ gas at the measuring electrode was suggested from the results of gas flow rate dependence of the response time.

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22.
Ｆ化合物を検出する固体電解質ガスセンサ（Ⅰ）－ＨＦに対する検出効果－

山内四郎　　木村秀　　皆川忠郎　　永尾栄一　西田智恵子　　亀井光仁

三菱電機

SOLID STATE IONIC GAS SENSOR FOR DETECTING FULUORIDE COMPOUNDS. (Ⅰ) DTECTING HF GAS

Shiro. YAMAUCHI, Minoru. KIMURA, Tadao. MINAGAWA, Eiichi. NAGAO, Chieko. NISHIDA, Mitsuhito. KAMEI

Mitsubishi Electric Corporation
1-1,Tsukaguchi-Honmachi, Amagasaki-city, Hyogo 66--8661, Japan

Gas sensors for detecting SF6 decomposition products are being pursued as low cost instrumentation for detecting and locating faults in Gas Insulated Switchgear (GIS). We developed an amperometric solid state ionic sensor using fluorine ion conductive solid electrolyte. It has been confirmed that the sensor responds promptly from 1 ppm to 50 ppm HF gas at room temperature, and returns to its original level once the HF gas is removed. Further this paper reports the evaluation and separation of the anode and cathode potentials by setting Ag/AgF reference electrode. The polarization curves show that the anode potential changed small, while the cathode potentials changed large.

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23.
Na⁺導電体を用いた低温作動型CO₂センサ

小畑賢次、熊澤志津子^*、島ノ江憲剛、三浦則雄^**、山添　曻

九大総合理工・ＴＤＫ^*・九大先端センター^**

POTENTIOMETRIC SENSOR BASED ON NASICON FOR DETECTION OF CO₂ AT LOW TEMPERATURE

Kenji OBATA, Sizuko KUMAZAWA^*, Kengo SHIMANOE, Norio MIURA^** and Noboru YAMAZOE

Department of Molecular and Material Sciences, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan
^*R & D Center, TDK Corporation
Ichikawa-shi, Chiba 272-8558, Japan
^**Advanced Science and Technology Center for Cooperative Research, Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan

Material search was carried out for those metal oxides which could promote the CO₂ sensing capability of a NASICON(Na⁺ conductor)-based potentiometric device at room temperature. Among the 8 kinds of single-metal oxides tested, SnO₂ and In₂O₃, when deposited over the sensing electrode (Au), were most effective for producing fairly high sensitivity to CO₂ in air under a constant humidity. However, these devices suffered humidity-dependent variations in EMF response (DE) or absolute EMF to a fixed concentrations of CO₂. It was found that for the In₂O₃-attached device, the addition of Na₃PO₄ and NaHCO₃ to the interface between In₂O₃ and NASICON could eliminate the disturbance by humidity. The EMF values of the modified device followed well the Nernst equation for 1.2 electron-reduction of CO₂.

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24.
Sc₂(WO₄)₃固体電解質を用いた炭酸ガスセンサ

上川将行、今中信人、田村真治、足立吟也

阪大院工

CO₂ GAS SENSOR WITH TRIVALENT Sc³⁺ ION CONDUCTING Sc₂(WO₄)₃ SOLID ELECTROLYTES

Masayuki KAMIKAWA , Nobuhito IMANAKA , Shinji TAMURA and Gin-ya ADACHI

Department of Applied Chemistry, Faculty of Engineering, Osaka University
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

A compact carbon dioxide gas sensor was constructed by using the combination of trivalent Sc³⁺ ion-conducting Sc₂(WO₄)₃ solid electrolyte and an oxide anion conducting stabilized zirconia. The time necessary to obtain a 90% response for the CO₂ detection was less than 1 min. The sensor output was exactly equal to the Nernst relation and the 1:1 linear relationship was obtained between the sensor output and the logarithm of the CO₂ gas concentration. A quantitative CO₂ gas detection was successfully achieved with a rapid, continuous, and reproducible response.

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25.
チロシナーゼを用いたプロテアーゼ活性測定バイオセンサ

成田公義、矢吹聡一、水谷文雄

生命工研

DEVELOPMENT OF PROTEASE ACTIVITY BIOSENSOR USED TYROSINASE

Kimiyoshi NARITA, Soichi YABUKI, Fumio MIZUTANI

National Institute of Bioscience and Human-Technology
Higashi 1-1, Tsukuba, Ibaraki 305-8566, Japan

An electrochemical biosensor for L-tyrosine was prepared by using an immobilized tyrosinase layer and a Clark-type oxygen electrode and was applied to the assay of protease: L-tyrosine produced through the protease reaction was oxidized in the tyrosinase layer, which followed a decrease in the current of the oxygen probe. The steady-state current decrease of the enzyme electrode was proportional to the L-tyrosine concentration up to 0.4 mM, and the lower detection limit was 0.04 mM (S/N=5). The addition of casein, the substrate of protease, caused the fluctuation of the electrode current, owing to the adsorption of casein on the tyrosinase layer. The casein adsorption could be avoided by covering the tyrosinase layer with a hydrophobic PTFE membrane filter. The protease activity was determined by the biosensor method correlate well with that obtained by a conventional spectrophotometric method.

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26.
糖鎖を有するピロールの電解重合により作製した酵素固定電極のセンサ特性

安澤幹人・藤井慎二・高岡宏樹・椚　章・今井信治^*

徳島大工・東洋精密工業^*

PROPERTIES OF ENZYME-IMMOBILIZED ELECTRODES PREPARED BY THE ELECTROPOLYMERIZATION OF PYRROLE CONTAINING A SACCHARIDE UNIT

Mikito YASUZAWA, Shinji FUJII, Hiroki TAKAOKA, Akira KUNUGI and Shinji IMAI^*

Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima
2-1 Minamijosanjima, Tokushima 770-8506, Japan
^*Toyo Precision Parts MFG. Co., Ltd.
97-1 Higashinaka, Yamatotakada, Nara 635-0066, Japan

An amperometric glucose sensor prepared by the electropolymerization of pyrrole derivatives having saccharide units, 1-(6-D-gluconamidohexyl)pyrrole (GHP), in the presence of glucose oxidase (GOD) was measured based on the cathodic detection of oxygen consumption during the enzyme reaction. The linear relationships between the glucose concentration and the response current was up to 5 mmol dm-3. However, more than 10 min was required to obtain a steady state current. The long-term stability of the obtained electrode was examined over 40 days and showed relatively constant response current for 30 days, after an inital loss of signals. The response current of the electrode was approximately not influenced by the addition of ascorbic acid, uric acid, acetaminophen, urea, or D-(-)-fructose.

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27.
GOx/HRP複合累積膜によるグルコースセンサの作製

小林由佳、安斉順一

東北大院薬

GLUCOSE SENSORS BASED ON COIMMOBILIZATION OF GOx AND HRP IN MULTILAYER FILMS

Yuka KOBAYASHI and Jun-ichi ANZAI

Graduate School of Pharmaceutical Sciences, Tohoku University
Aramaki, Aoba-ku, Sendai 980-8578, Japan

Bienzyme multilayer films composed of GOx and HRP were prerared on a glassy carbon electrode, through specific binding of Con A and hydrocarbon chains on the surface of the GOx or HRP. The amperometric response is based on the detection of hydrogen peroxide produced by GOx in the presence of methylene blue as a mediator to transfer electron between the electrode and HRP. Both enzymes built into the multilayer thin films were catalytically active and the response time to substrate was fast. The response current to glucose depended on the number of enzyme layers deposited.

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28.
耐熱性酵素グルタミンシンテターゼを用いるISFET型GPT活性測定用センサの特性

的場孝盛、石丸雄大、飯田武揚

埼玉大工

CHARACTERISTICS OF AN ISFET SENSOR FOR MONITORING GPT ACTIVITY USING THERMOPHILIC GLUTAMINE SYNTHETASE

Takamori MATOBA, Yoshihiro ISHIMARU, and Takeaki IIDA

Department of Functional Materials Science, Faculty of Engineering, Saitama University Shimo-okubo, Urawa-shi, Saitama-ken 338-8570, Japan

An ion sensitive field effect transistor (ISFET) type GPT (Glutamic-Pyruvic Transaminase) sensor using a thermophilic enzyme glutamine synthetase (GS) was studied. At first the GPT sensor was constructed by the bienzyme system using GPT and thermophilic glutamine synthetase. However, the bienzyme sensor was not able to monitor the GPT activity over 40℃. Therefore, the GPT sensor using thermophilic GS was studied to determine the GPT activity at various temperatures. The characteristics of the GPT sensor were described.

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29.
脂質修飾酵素をポリジメチルシロキサン膜中に固定化したグルコースセンサ

水谷文雄、矢吹聡一、平田芳樹、飯島誠一郎

生命工研

AMPEROMETRIC GLUCOSE SENSOR USING A POLYDIMETHYLSILOXANE LAYER CONTAINING LIPID-MODIFIED GLUCOSE OXIDASE

Fumio MIZUTANI, Soichi YABUKI, Yoshiki HIRATA, and Seiichiro IIJIMA

National Institute of Bioscience and Human-Technology
1-1 Higashi, Tsukuba, Ibaraki 305-8566, Japan

An amperometric glucose-sensing electrode was prepared by coating a platinum electrode surface with an aqueous dispersion containing polydimethylsiloxane (PDMS) and lipid-modified glucose oxidase: the water-insoluble, lipid-modified enzyme was immobilized on the electrode surface with a PDMS layer. The permselectivity of PDMS for oxygen made it possible to monitor the oxygen consumption rate without interference hydrogen peroxide, a product of the enzymatic reaction. The concentration of glucose (0.02 - 5 mM) could be determined from the decrease in the cathodic current at -0.3 V vs. Ag/AgCl, whithout any interference from uric acid, acetaminophen and L-cysteine.

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30.
耐熱性酵素を用いた表面光電圧法によるグルコース、スクロース及びマルトースセンサの集積化特性

青木一仁、内田秀和^*、勝部昭明^*、石丸雄大、飯田武揚

埼玉大学　工学部

CHARACTERIZATION OF INTEGRATED SURFACE PHOTOVOLTAGE SENSOR FOR GLUCOSE, SUCROSE AND MALTOSE USING THERMOSTABLE ENZYMES

Kazuhito AOKI, Hideaki UCHIDA^*, Teruaki KATSUBE^*, Yoshihiro ISHIMARU and Takeaki IIDA

Department of Functional Materials Science, ^*Department of Information and Computer Sciences, Faculty of Engineering, Saitama University, 255 Shimo-okubo, Urawa-shi, Saitama-ken 338-8570, Japan

Surface photovoltage (SPV)　technique was applied to the integrated saccharide sensor which was able to differentiate glucose, sucrose and maltose using thermostable enzymes such as glucokinase, invertase and α-glucosidase immobilized with BSA and glutaraldehyde. In our previous studies, the ISFET maltose sensor using thermostable enzymes responded to maltose, glucose and sucrose. However, the integrated SPV sensor was able to distinguish between those 3 saccharides. Time response curves of each saccharide reached stable values in 5-10 min after the sample was added. The calibration curves were obtained by noise filtering of time response curves. The detection limits were found to be 0.03 mM for glucose, 0.1 mM for sucrose and 0.03 mM for maltose.

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31.
グルコースオキシダーゼ含有ポリアクリルアミド膜修飾白金電極の非水系ボルタンメトリー

中村俊夫，田中愛子，宮坂貴広，梅本喜三郎

信州大理

ELECTROCHEMICAL BEHAVIORS OF THE PLATINUM DISK ELECTRODE MODIFIED WITH A GLUCOSE OXIDASE CONTAINING POLYACRYLAMIDE IN A NONAQUEOUS SOLUTION

Toshio NAKAMURA，Aiko TANAKA，Takahiro MIYASAKA，and Kisaburo UMEMOTO

Department of Chemistry，Faculty of Science，Shinshu University
Asahi， Matsumoto，390-8621, Japan

Electrochemical behaviors of the modified platinum disk electrode coated with non-plasticized polyacrylamide containing such enzymes as glucose oxidase and/or catalase for some substances in acetonitrile are reported．The redox current peaks were observed by cyclic voltammetry (CV) and the enzymatic activity of the electrodes to such substances as glucose，oxygen，hydrogen peroxide，and ethanol were confirmed by CV and amperometry．The correlation between the peak height of the current and the concentration of respective substances was investigated．

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32.
同一基質に対する酵素の拮抗反応を利用する溶存酸素検出型過酸化水素センサ

内山俊一、長谷部靖、沼尻和也

埼玉工大工

HYDROGEN PEROXIDE SENSOR BASED ON AN OXYGEN ELECTRODE, USING AN ANTAGONISM OF ENZYMATIC REACTIONS TO THE SAME SUBSTRATE

Shunichi UCHIYAMA, Yasushi HASEBE, Kazuya NUMAJIRI

Deaprtment of Applied Chemistry, Faculty of Engineering, Saitama Institute of Technology
1690 Okabe, Saitama 369-0293, Japan

The oxidations of L-ascorbic acid (catechol) to dehydroascorbic acid (1,2-benzoquinone) by oxygen and hydrogen peroxide are catalyzed by ascorbate oxidase (ASOD) or tyrosinase and peroxidase (POD), respectively. The both oxidase reactions consume oxygen but POD reaction does not consume oxygen. Then, when hydrogen peroxide is added to the POD containing solution in which oxidase reaction of L-ascorbic acid (or catechol) had taken place, the consumption rate of oxygen in oxidase reaction should be decreased by commencing POD reaction, because L-ascorbic acid or catechol works as a common substrate of both enzymatic reactions. In this work, hydrogen peroxide sensors were fabricated by combining two kinds of bienzyme membranes with an oxygen electrode. These sensor responses were increased in proportional to the added H₂O₂ (linear concentration range is from 1 x 10^-6M to 8 x 10^-5M (ASOD) and 5 x 10^-6 M to 2 x 10^-4 M (tyrosinase)with detection limits of 5 x 10^-7M and 2 x 10^-6 M, respectively). The use of oxygen electrode with gas permeable membrane should increase the selectivity of H₂O₂ because non-volatile electroactive species in the sample solution are not detected.

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33.
電析白金層上にPICバイエンザイム固定化層を用いたアンペロメトリックアセチルコリンセンサ

桑原貴之、目黒正大、逢坂哲彌

早大理工、早大材料技術研

AMPEROMETRIC ACETYLCHOLINE SENSOR BASED ON BIENZYME IMMOBILIZED BY POLYION COMPLEX ON THE ELECTRODEPOSITED PLATINUM

Takayuki KUWAHARA, Masahiro MEGURO, Tetsuya OSAKA

Department of Applied Chemistry, School of Science and Engineering; Kagami Memorial Laboratory for Materials Science and Technology, Waseda University
Shinjuku-ku, Tokyo 169-8555, Japan

Highly sensitive acetylcholine sensor was fabricated by use of polyion complex (PIC) layer containing acetylcholine esterase and choline oxidase on the electrodeposited platinum. The resulting sensor demonstrated higher current response to acetylcholine and the lower detection limit was around 4×10^-8 M. And the influences of the conditions of electrodeposition on response characteristics were investigated.

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34.
ガラクトースオキシダーゼを感応素子とするヒスタミンセンサ

長谷部靖、馬藤克成、内山俊一

埼玉工大・工

HISTAMINE SENSOR USING GALACTOSE OXIDASE AS A SENSING ELEMENT

Yasushi HASEBE, Katsunari BATO and Shunichi UCHIYAMA

Department of Applied Chemistry, Faculty of Engineering, Saitama Institute of Technology
1690, Fusaiji, Okabe, Saitama 369-0293, Japan

Catalytic activity of galactose oxidase (GAO) was reversibly changed by exogenous histamine possessing imidazole residue which binds at copper-active center of GAO. ESR study suggests that an equatorial H₂O ligand at Cu(II) site in GAO is replaces by an exogenous histamine which leads to a change in the structure of the active center and the catalytic activity. Kinetic experiments indicate that the histamine competitively inhibits the catalytic activity for dihydroxyaceton and activates that for L-ascorbic acid (AsA). These phenomena were applied for flow injection analysis (FIA) system consisted of immobilized GAO reactor and oxygen electrode detector that monitors a change in a concentration of dissolved oxygen in AsA-containing carrier due to the GAO-histamine complex-catalyzed oxidation of AsA.

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35.
酵母固定化ＳＰＶデバイスを用いた酒造用米麹の評価

千代智之，松井圭三，村上裕二^*，横山憲二^*，民谷栄一^**

福光屋，^*北陸先端科技大

YEAST-IMMOBILIZED SPV DEVICE FOR THE ESTIMATION OF QUALITY OF RICE KOJI

T. Chiyo, K. Matsui, Y. Murakami^*, K. Yokoyama^*, and E. Tamiya^*

Fukumitsuya Sake Breweries
Kanazawa-shi, Ishikawa 920-8638, Japan
^*Advanced Institute of Science and Technology
Hokuriku, Nomi-gun, Ishikawa 923-1292, Japan

We employed the SPV method for measurement of yeast metabolic activity, and combined it with a microbial membrane to construct a sensor system that estimates the quality of a koji. This system responds the production of acidic substances due to the metabolism of the sake yeast. The sample solution is pumped into the flow cell for 5 minutes in order to get stable response. As the result, the response becomes stable, and the system indicates the linear relationship between the response and the glucose concentration from 10 to 60 mM. And then we measured the response of the koji, which was sampled from sake breweries, extract solution with the sensor. The system indicate the metabolism of the yeast against not only glucose and but other substances. And the response of Saccharomyces cerevisiae K701 against substances except for glucose was more than the one of K9 relatively. It is consistent with their capacity for the producing acidic substances. Therefore, the system was expected to estimate not only the quality of the koji and but the process for fermenting foods with the microorganism.

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36.
アンぺロメトリー型果汁用酸度センサー

楠　文代、大槻さなえ、荒井健介、西田　毅*、日下部　毅*

東薬大薬・九州松下電器（株）^*

AMPEROMETRIC ACID SENSOR FOR JUICE

Fumiyo KUSU, Sanae OHTSUKI, Kensuke ARAI, Takeshi NISHIDA^* and Tsuyoshi KUSAKABE^*

School of Pharmacy, Tokyo University of Pharmacy and Life Science
1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
^*Kyushu Matsushita Electric Co.
1-62 4-Chome, Minoshima, Hakata-Ku, Fukuoka 812-8531, Japan

We developed a new sensor for determining total acid concentration in juice. The sensing was based on voltammetric reduction current of 3,5-di-t-butyl-1,2-benzoquinone (DBBQ) in the presence of acid in an unbuffered solution, ethanol-2-propanol-water (5:1:4) containing 100 mM NaCl. The sensor could be applied to measuring total acid concentration in the range of 0.2-0.6 mM (0.1-3.0％) citric acid. The relative standard deviation of the response for 1％ total acid concentration was 0.86％ (n=10). The sensor was used for the determination of total acid concentration in orange juice. The obtained results were in good agreement with those obtained by titration method (r=0.997).

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37.
針型グルコースセンサによる生体組織中連続測定の試み

矢尾板仁(1),(2)、藤波寛子(1)

帝京科学大バイオサイエンス(1)、帝京科学大バイオテク研究センター(2)

CONTINUOUS in vivo MEASUREMENT WITH A NEEDLE TYPE GLUCOSE SENSOR

Masashi YAOITA, Hiroko FUJINAMI

Teikyo University of Science and Technology, (1)Department of Biosciences, and (2)Biotechnology Research Center, 2525 Yatsusawa, Uenohara, Yamanashi 409-0193, Japan

A micro glucose sensor system of needle type was fabricated and the response current of the sensor was continuously measured in tissue of a goldfish. After about 5 min from the sensor system insertion, the current almost became constant for 180 min before an abnormal rise of the current was observed. When the sensor response was measured outside the living body after the in vivo measurement, the sensor had no response for glucose. From the calibration curve of this sensor, we conjectured the in vivo glucose concentration. The current value of about 5 nA was measured for 180 min, and was correspond the response current to 2 mM glucose. From the results, we concluded that the needle type glucose sensor system was able to measure about 3 hours in the goldfish tissue, continuously.

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38.
マイクロプレーナ型バイオセンサに用いる参照電極の性能解析

松本　達，大橋昭王，伊藤成史

ＮＥＣ資源環境技術研究所

EVALUATION FOR A MICRO-PLANER REFERENCE ELECTRODE FOR AN AMPEROMETRIC BIOSENSOR

Toru MATSUMOTO, Akio OHASHI, and Narushi ITO

NEC Resources and Environment Protection Research Laboratories
4-1-1 Miyazaki Miyamae-ku Kawasaki-shi Kanagawa 216-8555, Japan

A micro-planar reference electrode for a quantitative biosensor has been evaluated. As a reference electrode, we tested a silver/silver chloride electrode coated with 3-aminopropyltriethoxysilane and newly developed perfluorocarbon polymer in this order to fabricate a multilayered (two-layered) membrane. Tests demonstrate the electrode's imperviousness to the effect of interference species (1 mM potassium bromide, 1 mM potassium iodide, and 1 mM potassium sulfide), and its ability to successively be stabilized over a 100-hour period in saturated potassium chloride solution and a 82-day perio d in 150 mM of this solution.

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39.
マイクロ電極を用いた単一細胞計測用マイクロバイアルの作製と評価

安川智之，池谷俊通，末永智一

東北大院工

FABRICATION AND CHARACTERIZATION OF A MICROVIAL WITH A MICRODISK ELECTRODE FOR CELLULAR MEASUREMENTS

Tomoyuki YASUKAWA, Toshimichi IKEYA and Tomokazu MATSUE

Department of Biomoleculer Engineering, Graduate School of Engineering, Tohoku University
Aramaki, Aoba 07, Sendai 980-8579, Japan

We fabricated and characterized microvial electrodes with a Pt disk for electrochemical measurements in picoliter level vials for single cells. The photosynthetic activity of a single protoplast was investigated in the microvial electrode. The microvial electrode (radius, 25 μm; depth, 50 μm ) was fabricated utilizing an electrochemical etching (300 Hz, ac voltage with 5-10 Vp-p) for 10 min in a NaNO₃ aqueous solution. The topographic image of the microvial electrodes was obtained with scanning electrochemical microscopy (SECM). The imaging based on oxygen reduction current clearly demonstrated the photosynthetic activity of a single protoplast in the microvial. Cyclic voltammetry was used for electrochemical characterization of microvials.

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40.
血液電解質測定用微小センシングモジュールの試作

城石久徳、鈴木博章

筑波大物質工

FABRICATION OF A MINIATURIZED SENSING MODULE FOR BLOOD ELECTROLYTES

Hisanori SHIROISHI and Hiroaki SUZUKI

Institute of Materials Science, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan

An integrated sensing module for K⁺, Na⁺, and Cl^- was fabricated and its performance examined. Thin-film Ag/AgCl elements and an auxiliary electrode were patterned on a glass substrate by photolithography. Micro containers for electrolyte solutions and a flow channel were formed on a silicon substrate by anisotropic etching. The module features an integrated on-chip liquid-junction reference electrode. Although the lifetime of the thin-film Ag/AgCl element in saturated KCl-AgCl solution could be elongated by forming a hydrophilic polymer layer and/or to apply a small constant current, the lifetime of the completed on-chip liquid-junction reference electrode remained around 60 h due to the effusion of internal KCl. The ion-selective membranes were prepared with ionophores for respective target ions and were formed over the through-holes in the silicon containers. No substantial deviation was observed between the indicator electrode potentials measured with the on-chip reference electrode and a macroscopic reference electrode.

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41.
環境モニタリング用マイクロ電気泳動チップ（I）：ハイブリッド型CEによる予備的検討

脇田慎一、千葉篤志^*、竹田さほり、福士惠一^**、松田十四夫^*

大工研・立命館大理工^*・神戸商船大^**

MICRO CHIP BASED CAPILLARY ELECTROPHORESIS FOR ENVIRONMENTAL MONITORING (I): STUDY ON PINCHED TYPE SAMPLE INJECTION OF CAPILLARY ELECTROPHORESIS USING BRANCHED CAPILLARYR

Shin-ichi WAKIDA, Atsushi CHIBA^*, Sahori TAKEDA, Keiichi FUKUSHI^** and Toshio MATSUDA^*

Department of Energy and the Environment, Osaka National Research Institute, AIST
Ikeda, Osaka 563-8577, Japan
^*Department of Chemistry, Faculty of Science and Technology, Ritsumeikan University
Kusatsu, Shiga 525-8577, Japan
^**Research Institute for Marine Cargo Transportation, Kobe Univ. of Mercantile Marine, Higashinada, Kobe 658-0022, Japan

We preliminarily studied pinched type injection of hybrid type capillary-electrophoresis, which was self-made using PC controlled voltage-supply, cross type capillary and fluorometric on-line detection, to design micro channel in micro chip based capillary electrophoresis. Using fluorescein and calcein as model samples, we investigated the condition of applied voltage to each reservoir to control the pinched type sample-injection. Under the optimal condition, the model samples were completely separated in 10 min.

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42.
新型分子素子としての期待～「スーパー抗体酵素」の特徴と性質

宇田泰三、一二三恵美、小原京子、清水浩輔

広島県立大生物資源

POSSIBILITY AS A NEW MOLECULAR DEVISE~CHARACTERISTIC FEATURES OF "SUPER CATALYTIC ANTIBODY"

Taizo UDA, Emi HIFUMI, Kyoko OHARA, and Kosuke SHIMIZU

School of Biosciences, Hiroshima Prefectural University
562 Shoubara-shi, Hiroshima 727-0023, Japan

Immunosensor for the practical application has not been fabricated at present time in contrast that the practical enzyme sensors have been supplied for many years. Authors have proposed a concept that the practical immunosensor must be assembled by generating new epoch-making antibody. We have succeeded to obtain such antibody which exhibited to enzymatically decompose the antigen, besides it specifically recognized and bound to the antigen. The antibody was raised against the conserved region of gp41 of HIV-1 envelope. Its light chain could not only decompose the conserved region peptide of HIV-1 gp41 but also destroy the intact gp41 molecule within 14 hr. Thus, the light chain was referred as "super catalytic antibody". This super catalytic antibody can be applicable for developing an epoch-making immunosensor being detectable the antigen by the same way as enzyme sensors. Certainly, it should give a breakthrough to fabricate the practical immunosensor in very near future.

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43.
使い捨て厚膜型過酸化水素電極を用いた免疫センシングシステム

金　銀柱、О春山哲也、柳田保子、小畠英理、相澤益男

東工大生命理工

IMMUNOSENSING SYSTEM BASED ON A DISPOSABLE THICK-FILM HYDROGEN PEROXIDE ELECTRODE

Eunju KIM, Tetsuya HARUYAMA, Yasuko YANAGITA, Eiry KOBATAKE and Masuo AIZAWA

Department of Biological Information, Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology

The immunosensing system coupled with a disposable amperometric GOD sensor was developed for the determination of AFP. The combination of the simple, portable, and low cost electrochemical measurement with the specific and sensitive enzyme-linked immunosorbent assay (ELISA) procedure represents a promising means to establish an immunosensing system. The results proved that the established immunosensing system was capable of detecting AFP in the low concentration value of ng mL-1. The assay took 20 min to be completed using electrode and pre-coated microtiter plate with anti-AFP. The assay showed linearity for AFP in the response range from 10-8 to 10-5 g mL-1. On the basis of these results, the immunosensing system could offer excellent performance within a short time (20 min) compared with typical ELISA, which took several hours.

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44.
電気化学NO検出を基盤とした細胞バイオセンシングシステム

亀井謙一郎、春山哲也、小畠英理、相澤益男

東工大　院　生命理工

CELLULAR BIOSENSING SYSTEM BASED ON ELECTROCHEMICAL MONITORING OF NITRIC OXIDE

Ken-ichiro KAMEI, Tetsuya HARUYAMA, Eiry KOBATAKE and Masuo AIZAWA

Department of Biological Information, Graduate School of Bioscince and Biotechnology, Tokyo Institute of Technology,Nagatsuta, Midori-ku, Yokohama 226-8501, Japan

To develop a cellular biosensing system for assessment of endocrine disruptive chemicals, electrochemical NO sensing devices, which is coupled with cultured cells, have been investigated. Two types of cultured cells, RAW264.7 cells and HUVEC which produce NO with chemical stimulation, are employed for the system. A NO sensing system was constructed by a layer of living cells adhered on a polyion complex layer and an electrochemical NO sensor which has high sensitivity and selectivity for NO. The cellular biosensing system may assess safety of chemicals by sensing NO released from the cells on a polyion complex layer which is a response signal to chemicals stimulations.

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特別講演
芳香族炭化水素色素分子間相互作用を用いた遺伝子センシング

増子正行

浜松ホトニクス

GENE SENSING BASED ON MOLECULAR INTERACTIONS BETWEEN AROMATIC HYDROCARBON DYES

Masayuki MASUKO

Tsukuba Research Laboratory, Hamamatsu Photonics K. K.
Tsukuba, Ibaraki 300-0032, Japan

Aromatic hydrocarbon molecules are suitable for nucleic acid hybridization assays as fluorescent labels because of their unique interactions with each other. To demonstrate such potential, we used the hybridization between a target and its complementary two sequential deoxyribonucleotide probes whose neighboring terminals were each respectively labeled with an aromatic hydrocarbon. The pair of pyrenes as labels, for example, can specifically form excimer upon hydbridization. Using the pair of pyrene and perylene, we can observe the fluorescence resonance energy transfer from pyrene to perylene upon hybridization. Both pairs can be characterized by large Stokes shift emission, indicating that they enable homogeneous solution assays without removing the probes added in excess.

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受賞講演
マイクロ電極系における材料機能評価と応用展開

西澤松彦

東北大院工

MICROELECTRODE-BASED CHARACTERIZATION SYSTEMS FOR ADVANCED MATERIALS IN SENSOR AND BATTERY APPLICATIONS

Matsuhiko MISHIZAWA

Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aramaki Aoba, Aoba-Ku, Sendai 980-8579, Japan

Microelectrodes were used for characterization of advanced materials in sensor and battery applications. The present talk will be focused on the potentiality of interdigitated-array-type microelectrodes (IDA electrodes) in the design of micro-sensors. A hydrophobic pretreatment of the gap part of IDA was effective to bridge the array with an electropolymerized ultrathin conducting polymer films. The prepared device (ultrathin conducting polymer-coated IDA) performed as a conductometric chemical sensor. Attempts to fabricate a conductometric enzyme-sensor were also presented.

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45.
複合光導波路のTEモードとTMモードの干渉を利用した化学センサの構築 Ⅱ

祁志美，西広一義，伊藤公紀，村林真行，柳裕之^*

横国大環境研、トクヤマ^*

A Composite Optical Waveguides-Based Interferometer for Chemical Sensing Ⅱ

Zhimei Qi, Kazuyoshi Nishihiro, Kiminori Itoh, Masayuki Murabayashi, and Hiroyuki Yanagi^*

Institute of Environmental Science and Technology, Yokohama National University
Yokohama 240-8501, Japan
^*Tokuyama Co., Ltd.
Fujisawa, Kanagawa 252-0816, Japan

The novel interferometer is based on the TE₀-TM₀ mode segregation and recombination inside a composite optical waveguide (COWG) consisting of a potassium ion-exchanged glass overlaid with a high-index thin film. Using a TiO₂/K⁺ COWG, the interferometer can respond to a superstrate-index change of DnC = 3.8x10^-6 that results in a phase-difference shift of Df = 1o between the TE₀ and TM₀ modes. The TiO₂/K⁺ COWG-based interferometer was also used as a formaldehyde gas sensor by covering TiO₂ thin film with a polymer containing S₂O₄ group, and a reversible change of Df " 32p for 150ppm formaldehyde was observed. The extinction ratio of COWG-based interferometers, which corresponds to the resolution in Df, was improved by suppressing the birefringence of potassium ion-exchanged OWGs.

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46.
温度補正機構を用いた表面プラズモン共鳴免疫（SPR）センサの改良

大出　明、森原智和^*、外山　滋、山内　繁、碇山義人

国立リハ研、東洋大工^*

IMPROVEMENT OF SMALL-SIZED SPR SENSOR HAVING THERMAL COMPENSATING MECHANISM

Akira OHIDE, Tomokazu MORIHARA, Shigeru TOYAMA, Shigeru YAMAUCHI, and Yoshihito IKARIYAMA

Research Institute, National Rehabilitation Center for the Disabled
4-1 Namiki, Tokorozawa, Saitama 359-8555, Japan

tabilization method of SPR signal fluctuation due to thermal change has been examined. Here, an experimental SPR setup, where a thermistor was embedded in the stainless holder of the flow through cell attached to the sensor, was newly fabricated. The temperature was artificially changed during continuous measurements. This sensor exhibits good sensing properties in the conditions of fluctuated temperature.

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47.
表面プラズモン共鳴化学センサを利用した日本酒の種類判別

南戸　秀仁、藤岡　淳、浜口　佑樹、向井　達哉、草野　英二、大藪　多可志^*、黒澤　茂^**、金原　粲

金工大　高度材料研究科学開発センター、^*金沢経大、^*物質工学工業技術研究所

Identification of Japanese Sake Using an SPR Chemical Sensor

H.Nanto, J.Fujioka, Y.Hamaguchi, T.Mukai, E.Kusano, T.Ooyabu＊, S.Kurosawa＊＊, A.Kinbara

Adv.Mat.Sci.R&D Center Kanazawa Inst.of Tech
^*KanazawaUniversity of Economics
^**Ultrathin Film Group,Department of Polymer Physics

A chemical sensor based on the surface plasmon resonance (SPR), which has four channels of SPR signals, is studied for identification of Japanese Sake. It was found that the SPR sensor responds to the different kinds of Japanese Sake, where distilled water is used as the reference liquid and responses of the SPR sensor are different from sample to sample, indicating that the identification of kinds of Japanese Sake can be possible.

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48.
ピラノースオキシダーゼカラムの長期間使用における計測特性

佐藤　生男、上田晋太郎

神奈川工科大学

PERFORMANCE CHARACTERISTICS OF A PYRANOSE OXIDASE COLUMN FOR LONG-TERM USE

Ikuo SATOH and Shintaro UEDA

Department of Applied Chemistry, Kanagawa Institute of Technology
1030 Shimo-Ogino, Atsugi-shi, Kanagawa 243-0292, Japan

Pyranose oxidase from Coriolus versicolor immobilized on porous glass beads was examined as a recognition element for microdetermination of D-glucose. The flow-amperometric sensing system was assembled with a small column containing the immobilized enzymes mounted in a water-jacketed holder and a polarographic oxygen electrode in a flow-through cell. Variations in oxygen levels at the outlet of the column were successively monitored and used as the measure of the catalytic activity. The responses attributable to dissolved oxygen consumed were observed by injecting the substrate solutions with various concentrations. A calibration graph was obtained up to 10 mM substrate solution as a function of decrease in dissolved oxygen. Although the column was used at room temperature for about 6500 assays during three years, it exhibited significantly well operational-stability.

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49.
アポ酵素活性化法によるピコモーラーレベルの亜鉛(Ⅱ)イオンの計測

佐藤　生男、有賀　貴子

神奈川工科大学

DETERMINATION OF ZINC(II) IONS IN PICOMOLAR LEVELS BASED ON THE APOENZYME REACTIVATION METHOD

Ikuo SATOH and Takako ARIGA

Department of Applied Chemistry, Kanagawa Institute of Technology
1030 Shimo-Ogino, Atsugi-shi, Kanagawa 243-0292, Japan

Alkaline phosphatase covalently fixed onto porous glass beads was packed into a small polymer column and then used as a recognition element for zinc(II) ions in flow streams. The flow-injection analytical system was assembled with the column housed in a water-jacketed holder and a quartz flow-through cell attached to a UV/VIS monitor. The enzymatic activity was assessed by injecting 0.1 ml of 2 mM p-nitrophenyl phosphate(pH 8.0). Regeneration of the column could be made by introducing 100 mM 2,6-pyridine dicarboxylate solution to remove zinc(II) ions coordinated in the active site of the enzyme molecules. Zinc(II) ions in picomolar levels were photometrically determined through its reactivation of the apoenzyme, i.e., metal-free enzyme. Performance characteristics of the system were examined.

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50.
ゲルの相転移を利用したサンプリング機構とその血糖値測定システムへの適用

小林邦幸、鈴木博章

筑波大物質工

A SAMPLING MECHANISM EMPLOYING THE PHASE TRANSITION OF A GEL AND ITS APPLICATION TO A MICRO ANALYSIS SYSTEM FOR BLOOD GLUCOSE

Kuniyuki KOBAYASHI and Hiroaki SUZUKI

Institute of Materials Science, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan

Poly(n-isopropylacrylamide) gel swells and shrinks in response to a variation in temperature. This phenomenon was utilized to construct a micro sampling mechanism. The gel changed its volume immediately in response to a step change in temperature and stabilized within 1 min. Also, the gel could change its volume reproducibly in response to repeated thermal cycles. The sampling mechanism was incorporated in a micro analysis system which had a micro glucose sensor based on the detection of hydrogen peroxide. After the gel was shrunk at 40℃ making contact with a buffer solution, the inlet of the sampling mechanism was made in contact with a sample solution at 30℃. It was observed that the sample solution was introduced and moved to the interior of the system following the swelling of the gel. The microglucose sensor showed a distinct response accompanying a peak. A linear calibration curve was obtained for glucose concentrations less than 2.5 mM.

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51.
相転移材料による酵素活性阻害作用の制御

森　博、高橋宏行、立間　徹、藤嶋　昭

東大院工

CONTROL OF AN INHIBITION EFFECT ON ENZYMAYIC ACTIVITY BY USING PHASE TRANSITION POLYMER

Hiroshi MORI, Hiroyuki TAKAHASHI, Tetsu TATSUMA, and Akira FUJISHIMA

Department of Applied Chemistry, Faculty of Engineering, University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

Enzymatic activity of heme peptide (HP), a peroxidase model compound, is controlled by using a phase transition polymer, which is prepared from N-isopropylacylamide (NIPA) and　 1-vinylimidazole (VI). Lower critical solution temperature (LCST) of NIPA-VI copolymer is about 36℃, so that it is soluble at 25℃ and insoluble at 45℃ in aqueous solutions. Currents for H₂O₂ reduction obtained at the HP electrode is inhibited by the polymer at 25℃, which it is not inhibited at 45℃. From visible spectroscopy, it is suggested that the inhibition effect is caused by coordination of the imidazole group of NIPA-VI copolymer to the active site of HP.

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52.
水晶振動子を用いた陰イオン界面活性剤センサー開発のための表面修飾と吸着挙動に関する研究

藤田昌司，尾関　徹，冨士元英二^*，小林幸太^*

兵庫教育大学，北斗電工^*

STUDY OF EFFECT OF CHEMICAL MODIFICATION OF GOLD SURFACE ON ADSORPTION OF AN IONIC SURFACTANT IN AIM FOR DEVELOPMENT OF CHEMICAL SENSOR USING QUARTZ CRYS TAL MICROBALANCE

asashi FUJITA, Toru OZEKI, Eiji FUJIMOTO^* and Kohta KOBAYASHI^*

Hyogo University of Teacher Education
Shimokume 942-1, Yashiro-cho, Kato-gu n, Hyogo 673-1494, JAPAN
^*Hokuto Denko Corporation
Himonya 4-22-13, Meguro-ku, Tokyo 152-0003, JAPAN

In recent years, a large amount of surfactant has been used in daily life. The major surfactant is an anionic surfactant. As some surfactants act as d isinfectant, the expose of the human body to the surfactant for long period is considered to be harmful. Thus the monitoring of the surfactant in envir onment is important. The official analytical method of anionic surfactant, however, uses pretty large amount of chloroform as an extractant solvent. S ince the chloroform also has a harmful effect on human body, the development of a new analytical method without using chloroform is required. For this purpose, we have started the study of the use of quartz crystal microbalance (QCM), which has been developed for liquid systems. In this paper, the inf luence of the chemical modifications of gold surface of the quartz crystal o n the adsorption of anionic surfactant is reported.

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53.
水晶振動子を用いたクリプトスポリジウムセンサの開発

大八木　茂樹、長塩　尚之、井関　基弘^*

日新電機、大阪市立大医^*

EVALUATION OF CRYPTOSPORIDIUM SENSOR USING A QUARTZ-CRYSTAL　MICROBALANCE

S. Ohyagi, N. Nagashio, M. Iseki^*

Advanced Materials Research Department , R&D Div. , Nissin Electric Co. Ltd.
47, Umezu-Takase-cho, Ukyo-ku, Kyoto-shi, Kyoto 615-8686, Japan
^*Dept. of Medical Zoology, Osaka City University Medical School
1-4-3, Asahimachi, Abeno-ku, Osaka-shi, Osaka 545-8585, Japan

In recent years, numerouse outbreaks of waterborne cryptosporidiosis have been reported even in developed countries. Cryptosporidium parvum, a pathogenic protozoan parasite, has become the most important contaminant in drinking water. Current methods for detection of C. parvum oocysts from water samples are much complicated and required. Therefore we think that a sensor which can detect Cryptosporidium easily and monitor its concentration continuously is necessary, and we have developed a basic flow-cell system equipped with an immuno-sensor using a quartz-crystal microbalance coated by its antibody.

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54.
内分泌撹乱物質のメダカを用いたバイオアッセイの開発

西　和人、近江　みゆき^*、水上　春樹、森田　資隆^*、村上　裕二^*、横山　憲二^*、民谷　栄一^*

(株)エンバイオテック・ラボラトリーズ
^*北陸先端科学技術大学院大学

DEVELOPMENT OF THE BIOASSAY USING MEDAKA(Oryzias latipes) FOR ENDOCRINE DISRUPTERS

Kazuto NISHI，Miyuki CHIKAE^*, Haruki MIZUKAMI, Yasutaka MORITA^*, Yuzi MURAKAMI^*, Kenzi YOKOYAMA^*, Eiichi TAMIYA^*

EnBioTec Laboratories
^*School of Materials Science，Japan Advanced Institute of Science and Technology
1-1 Asahidai，Tatsunokuchi，Ishikawa 923-12, Japan

Recently, EDCs-Endcrine Disrupting Chemicals have become a social issue in the world. However little is known about details of the EDCs effect against wildlife and humans because of the lack of simple and reliable assay system. On the other hand, fish vetellogenin assay has been proven to be useful for the detection of the estrogenic effect of EDCs. In these circumstances, we have developed Medaka (Oryzias latipes) Bioassay system using vitellogenin ELISA assay with 2 different monoclonal antibodies. In order to assess the sensitivity of this assay, the vitellogenin concentration of male plasma samples, which was exposed to estradiol for 1 week, was measured. The results showed the sensitivity of this bioassay was 0.01 ppb estradiol exposure.

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