Vol. 14, Supplement B (1998)

Vol. 14, Supplement B (1998)

Proceedings of the 27th Chemical Sensor Symposium
October 23-24, 1998

Abstracts

1.
耐熱性酵素を用いたα-及びβ-グルコシド類のセンシング

青木一仁、石丸雄大、飯田武揚

国立リハビリ研・埼玉工大工^*

α-,β-GLUCOSIDE SENSING USING THERMOPHILIC ENZYMES

Kazuhito AOKI, Yoshihiro ISHIMARU and Takeaki IIDA

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

An ion sensitive field effect transistor (ISFET) α-D-glucoside sensor was studied using thermophilic glucokinase (GK) from Bacillus stearothermophilus and thermophilicα-D-glucosidase from Bacillus stearothermophilus with the immobilization by BSA and glutaraldehyde. An ISFET type β-glucoside sonsor was also investigated using GK and thermophilic β-D-glucosidase from Caldocellum schaccaroliticum. The β-glucoside sensor was able to determine the salicin concentration from 3.3 mM to 33 mM at 50℃. An amperometric β-glucoside sonsor was constructed by using thermophilic glucose dehydrogenase (GDH) from Thermoplasma acidophilum and the β-D-glucosidase. The characteristics of the α- and β-glucoside sensors were evaluated.

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2.
多孔性複合金属電極を用いた酵素センサ

外山滋、松本修^*、内山俊一^*、碇山義人

国立リハビリ研・埼玉工大工^*

ENZYME SENSORS BASED ON POROUS Pt-Au BLACK ELECTRODE

Shigeru TOYAMA, Osamu MATSUMOTO^*, Shunichi UCHIYAMA^* and Yoshihito IKARIYAMA

Research Institute, National Rehabilitation Center for the Disabled
4-1 Namiki, Tokorozawa 359-8555, Japan
^*Faculty of Engineering, Saitama Institute of Technology
1690 Okabe, Saitama 369-02, Japan

Enzyme sensors, such as glucose sensor and lactate sensor, based on porous multi-metal black electrode has been investigated. Porous electrodes were fabricated on a platinum electrode by coelectrodepositing gold black and platinum black in a hexachloroaurate and hexachloroplatinate mixture solution. Enzyme was immbolized on gold potion of the electrode surface using gold-mercaptide bonding. The sensor exhibited more repeatable response than platinum black electrode based sensor, whereas the sensitivity was larger than that of gold black based sensor.

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3.
厚膜過酸化水素電極を用いた使い捨て型クレアチニンセンサ

金銀柱、春山哲也、小畠英理、柳田保子、相澤益男

東工大、生命理工

DISPOSABLE CREATININE SENSOR BASED ON THICK FILM HYDROGEN PEROXIDE ELECTRODE SYSTEM

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

Department of Bioengineering,　Faculty of Bioscience and Biotechnology Tokyo Institute of Technology
4259 Nagatsuta, Midori-ku, Yokohama 226, Japan

A disposable creatinine sensor has been developed using a carbon print thick film electrode for hydrogen peroxide. Carbon black powder paste containing 10% Pt powder was screen-printed on a plastic plate, and irradiated by UV light under pure oxygen atmosphere. Thin layer of three enzymes involving creatininase, creatinase and sarcosine oxidase　was fabricated in the vicinity of the printed electrode to form a sensor for creatinine. A drop of a test solution automatically runs through a microchannel reaching the enzyme layer and the electrode of which potential is set at 500 mV vs. Ag/AgCl. The sensor responded specifically to creatinine with sufficient sensitivity. The oxygen plasma treatment was found effective on improving the voltammetric behavior of screen-print electrodes. Linearity of the sensor response was obtained in the creatinine concentration range from 200 μM to 2 mM.

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4.
電析白金／ポリイオンコンプレックス複合電極を用いたグルコースセンサの構造解析

目黒正大、藤野裕介、逢坂哲彌

早大理工・早大材料技術研

STRUCTURAL INVESTIGATION OF GLUCOSE SENSOR BASED ON THE COMPOSITE FILM OF ELECTRODEPOSITED PLATINUM WITH POLYION COMPLEX

Masahiro MEGURO, Yusuke FUJINO and 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 glucose sensor based on the composite film of electrodeposited platinum with polyion complex (PIC) was fabricated, and the morphology of electrodeposited platinum in PIC film was investigated with the scanning electron microscope and electron probe for micro-analysis for the characterization of the glucose sensor. In the optimum deposition charge which yielded the most sensitive response to glucose, platinum was widely dispersed in the PIC film.

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5.
ポリイオンコンプレックス層／酵素層のbilayer型のセンサによるトランスアミナーゼ活性の迅速測定

水谷文雄、佐藤　縁、平田芳樹、矢吹聡一

生命工研

RAPID MEASUREMENT OF TRANSAMINASE ACTIVITIES USING AN ENZYME SENSOR BASED ON A POLYION COMPLEX/ENZYME-BILAYER MEMBRANE

Fumio MIZUTANI, Yukari SATO, Yoahiki HIRATA and Soichi YABUKI

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

An amperometric L-glutamate-sensing electrode was prepared by immobilizing glutamate oxidase on a polyion complex layer-attached electrode. The use of thin bilayer system with the inner, polyion complex membrane, which showed permselectivity based on the solute size with the molecular cut-off of ca. 100, brought about high performance characteristics to the L-glutamate-sensing electrode: it showed high sensitivity (detection limit 20 nM), rapid response (100% response time, 3 s), low interference level (e.g., the ratio of response for L-ascorbic acid to that for the same concentration of the analyte, 0.08), and high stability (usable for more than a month). The bilayer-based electrode was useful for the rapid determination of glutamate-oxaloacetate transaminase (GOT) and glutamate-pyruvate transaminase (GPT) in serum samples: each transaminase (0.2 - 1000 U L-1) could be determined within 10 s.

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6.
アニオン性ポリアニリン－ポリカチオン複合体を用いた酵素電極

小川高史、立間　徹、小山　昇

東京農工大工

ENZYME ELECTRODES WITH AN ANIONIC POLYANILINE-POLYCATION COMPLEXES

Takashi OGAWA, Tetsu TATSUMA and Noboru OYAMA

Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology
Koganei, Tokyo 184-8588, Japan

An ion complex containing horseradish peroxidase (HRP) is formed on the electrode surface from a sulfonated polyaniline, poly(2- methoxyaniline-5-sulfonic acid) (PMAS), and a polycation, poly(L- lysine) (PLL). The electrode responds amperometrically to >10 nM H₂O₂, even at neutral pH (pH 4.5 to 8.4). Catalytic activity of HRP and electrochemical activity or electronic conductivity of PMAS are essential to the response. The positive potential limit for the reductive H₂O₂ sensing is varied from 0.0 V vs. Ag/AgCl (pH 8.4) to +0.5 V (pH 4.5).

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7.
マイクロペルオキシダーゼ，フェロセン固定化ポリイオン複合膜の作製とバイオセンサへの応用

矢吹聡一，水谷文雄，平田芳樹

工技院生命工研

PREPARATION OF A POLYION COMPLEX MEMBRANE CONTAINING MICROPEROXIDASE AND FERROCENE AND ITS USE AS A BIOSENSOR

Soichi YABUKI, Fumio MIZUTANI and Yoshiki HIRATA

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

Polyion complex membrane containing microperoxidase and ferrocene was prepared on a glassy carbon electrode: polystyrene sulfonate solution, microperoxidase (MP) solution, ferrocene dispersion and poly-L-lysine solution were successively placed on a surface of the electrode and dried.
The MP, ferrocene co-immobilized polyion complex membrane was immersed into a buffer solution and was applied 0 V vs. Ag/AgCl to measure the reductive current response to hydrogen peroxide: current response was linear to the H₂O₂ concentration up to 20 μM, and lower detection limit was 0.5 μM.
Glucose oxidase was immobilized on the polyion complex membrane by glutaraldehyde, and current response to glucose was measured: response was linear to the glucose concentration up to 0.2 mM, and lower detection limit was 5 μM. The polyion complex membrane could be used as a hydrogen peroxide sensor, and could be combined with oxidases to detect their substrates.

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8.
導電性高分子・酵素修飾電極のグルコース応答特性

筒井典一、大島賢治、山内健、下村雅人、宮内信之助

長岡技科大工

GLUCOSE-SENSING CHARACTERISTICS OF CONDUCTIVE POLYMER BINDING WITH GLUCOSE OXIDASE

Norikazu TSUTSUI, Kenji OSHIMA, Takeshi YAMAUCHI, Masato SHIMOMURA and Sinnosuke MIYAUCHI

Department of Bioengineering, Nagaoka University of Technology
1603-1, Kamitomioka, Nagaoka 940-2188, Japan

Glucose-sensing characteristics of poly [1-(2-carboxyethyl)pyrrole] (PPy-COOH) film binding with glucose oxidase (PPy-GOD) have been studied and compared with enzyme activity. The PPy-COOH film was prepared by electrochemical polymerization on an Au electrode. GOD was immobilized on the PPy-COOH film by use of a carbodiimide regent, and apparent activity of the immobilized GOD on was measured. Amperimetric response of the PPy-GOD film to glucose was measured by applying a constant potential of +0.35 V vs S.C.E under various pH and temperature conditions. The pH and temperature profiles of amperometric response of PPy-GOD film were similar to those of the activity of glucose oxidase. The influence of film thickness on glucose-sensing was also discussed.

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9.
コレステロールセンサの開発（II）

山本智浩、池田信、吉岡俊彦、南海史朗

松下電器産業(株)研究本部

DEVELOPMENT OF CHOLESTEROL SENSOR (REPORT II)

Tomohiro YAMAMOTO, Shin IKEDA, Toshihiko YOSHIOKA and Shiro NANKAI

Matsushita Electric Industrial Co.,Ltd.
3-1-1 Yagumo-nakamachi,Moriguchi,Osaka 570-8501, Japan

In this report, we preliminarily studied on the properties of disposable cholesterol sensor on the basis of cholesterol dehydrogenase (CDH) system coupled with screen-printed electrodes. The potential-step chronoamperometric responses at screen-printed electrode increased linearly with cholesterol concentration and showed independence of more than 600 mV vs.Ag/AgCl of stepped-potential, in three electrodes system. While in also two electrodes system, a linear relationship between current response and cholesterol concentration was obtained up to 250 mg/dl of cholesterol, as same as that in three electrodes system. As a result, it could be found that the CDH system was so useful as a probe in the disposable cholesterol sensor.

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10.
ポリウレタンを包括材料に用いた酵素センサの開発（２）

安澤幹人、平野智之、橋本　優、椚　章、仲矢忠雄^*

徳島大工・阪市大工^*

GLUCOSE SENSORS BASED ON GLUCOSE OXIDASE IMMOBILIZED IN POLYURETHANE FILMS (2)

Mikito YASUZAWA, Tomoyuki HIRANO, Masaru HASHIMOTO, Akira KUNUGI and Tadao NAKAYA

Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima
2-1 Minamijosanjima, Tokushima 770-8506, Japan
Department of Bioapplied Chemistry, Faculty of Engineering, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan

New glucose sensors based on glucose oxidase (GOD) immobilized in hemocompatible polyurethane film was prepared and the glucose sensor properties were investigated. Two types of segmented polyurethane (GPU and PPU) with both good mechanical properties and excellent blood compatibility were employed, which the former contain glucose group while the latter contain the polar group of phosphatidylcholine. The sensitivity of the electrodes prepared from both GPU and PPU were similar and the relationship between the glucose concentration and the response current were found to be linear up to 7.0 mM for both. The storage stability of the electrode prepared from GPU was somewhat higher than that from PPU.

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j1.
生物機能の未利用機能に着目したバイオセンサーに関する研究

碇山義人

国立身体障害者リハビリテーションセンター

A STUDY ON THE BIOSENSORS FOCUSED ON THE NONUTILIZED BIOFUNCTIONAL MOLECULES

Yoshihito IKARIYAMA

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

I feel highly honored to have received the Seiyama Prize for my works on the new sensing approaches using biomolecules such as enzymes, antibodies, and nucleic acids, whose biofunctional properties had not been utilized yet. I am convinced that most of those works has been leading many contemporary workers. Among these works, (1) A new biosensing based on chemiluminescence and bioluminescence, (2) A design of new receptor utilizing subtle difference in bioaffinity between analytes and their analog compounds and its application to the biosensing of vitamins and hormones, (3) New developments of transducers and their application to highly sensitive biosensors, (4) Genetic breeding of fused production of marker proteins for the element of biosensor and biomonitor, and (5) Audiovisualized blood glucose sensor for the patients with diabetic retinopathy, are the examples which have been achieved by the above approaches.
These works are accelerating the fabrication of biomolecule-based sensors, and are opening new fields in bioelectronics as well as biosensing.

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j2.
ISFETによるpHセンサの開発と実用化

伊藤善孝

新電元工業・研究開発センター

DEVELOPMENT OF ISFET AND pH SENSORS

Yoshitaka Ito

Shindengen Kogyo, R & D Center
Hanno-Shi, Saitama-Ken 357, Japan

The ion sensitive FETs (ISFET), without a reference electrode, proposed by P. Bergveld in 1970 and with the reference electrode by T. Matsuo in 1971 after the T. Seiyama's works in 1962. The 1970s marked important findings and proposals. The planar ISFET, mass production and non drift Ta₂O₅ film for pH sensor were developed by Y. Ito at Shindengen. Using the device, the compact ISFET- pH meters had much commercial success in the world. In the field of chemical sensors, it was found that silicon-based chemical sensors were not as easy as anticipated. In addition to the advances by the silicon IC technology, reliability, stability and low-cost devices are also holding the important key at commercialization of silicon chemical sensors.

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11.
アンペロメトリック尿素センサの作製と評価（III）

武居　修、外山　滋、宇佐美論^*、掘越弘毅^*、碇山義人

国立リハビリ研、東洋大工^*

FABRICATION AND EVALUATION OF AMPEROMETRIC UREA SENSOR (III)

Osamu TAKEI, Shigeru TOYAMA, Ron USAMI^*, Koki HORIKOSI^* and Yoshihito IKARIYAMA

Research Institute, National Rehabilitation Center for the Disabled
4-1 Namiki, Tokorozawa 359-8555, Japan
^*Faculty of Engineering, Toyo University
2100 Nakanodai, Kujirai, Kawagoe 350, Japan

We have been developing an enzyme embodied electrode (EEE) fabricated by direct immobilization of urease, glutamate dehydrogenase and glutamate oxidase in microporous platinized electrode. However, the sensor sensitivity was not necessarily high at this stage of study. Therefore, we scrutinized the fabrication condition of platinum black and ratio of three enzymes which are to be immobilized on the electrode. The evaluation of immobilization rate was carried out by measuring the absorption of decreaseing substrate and of increasing production through optimum bienzyme reaction by spectrophotometer.

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12.
フッ素樹脂膜によるアンペロメトリック型グルコースセンサの長寿命化

松本　達，大橋昭王，伊藤成史，斉藤　敦，斉藤総一

ＮＥＣ

DEVELOPMENT OF LONG LIFE AMPEROMETRIC GLUCOSE SENSOR WITH FLUOROCARBON POLYMER FILM

Toru MATSUMOTO, Akio OHASHI, Narushi ITO, Atsushi SAITO and Souichi SAITO

NEC Corporation
4-1-1 Miyazaki, Miyamae-ku, Kawasaki-shi, Kanagawa 216-8555, Japan

Reported here is a newly developed amperometric glucose sensor capable of measuring glucose concentrations in body fluids without diluting themselves. Tests of the sensor demonstrate its capability of accurately and successively determining glucose concentrations ranging from 2.8 to 167 mM over 66 days, its capacity to reach steady-state response within 10 seconds, as well as its imperviousness to the effect of a quantitative urine control.
Test results indicated the glucose sensor could measure the urine glucose concentrations of diabetes at least for 66 days.

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13.
酵素を用いた有機リン系化合物センサのPAMによる再活性化に関する検討(II)

岡崎慎司、中川英元、福田健三、朝倉祝治、木内宏美^*、重盛徹志^*、高橋祥夫^*

横浜国大工・新コスモス電機^*

REACTIVATION OF AN AMPEROMETRIC ORGANOPHOSPHATE PESTICIDE BIOSENSOR BY PAM (2-PYRIDINEALDOXIME METHOCHLORIDE)

Shinji OKAZAKI, Hidemoto NAKAGAWA, Kenzo FUKUDA, Shukuji ASAKURA, Hiromi KIUCHI, Tessi SHIGEMORI and Sachio TAKAHASHI

Department of Materials Science and Chemical Engineering, Yokohama National University
Hodogaya-ku, Yokohama,240-8501, Japan

Inhibitions and re-activation characteristics of a biosensor by the organophosphate and carbamate pesticides were investigated. The amperometric enzyme sensor co-immobilized on a platinum electrode by crosslinking was fabricated. Inhibition of the biosensor by Dichlorvos (DDVP, dimethyl 2,2-dichlorovynyl phosphate) as a model organophosphate pesticide was tested. The relative inhibition parameter (RI) was proportional to the concentration over wide range. It was found that nearly reversible inhibition process was observed if the inhibition is weak. However, irreversibility was observed when the inhibition was strong. In this case, PAM(2-pyridinealdoxime methochloride) successfully regenerated the enzyme activity. PAM treatment ascertained stable recovery rate in enzyme activity and sensitivity.

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14.
分子インプリントを利用したアンペロメトリーセンサーの開発

吉見靖男、大平亮、飯山千秋

芝浦工大

AN AMPEROMETRIC SENSOR USING MOLECULARLY IMPRINTED POLYMER

Yasuo YOSHIMI, Ryo OHDAIRA and Chiaki IIYAMA

Department of Industrial Chemistry, Shibaura Institute of Technology
Minato-ku, Tokyo 108-8548, Japan

The authors studied the effect of guest molecule on cyclic voltammogram by indium-tin oxide (ITO) electrode on which molecularly imprinted polymer was grafted. Methacrylic acid and ethylene glycol dimethacrylate was copolymerized in the presence of theophylline as a guest and of methacryloxytrimethoxysilane-treated ITO. The copolymer was grafted on the ITO. A traditional cyclic voltammetry of ferrocyanide was performed using the copolymer grafted ITO as electrode in the presence / absence of theophylline. The presence of theophylline enhanced anodic current. While the presence of caffeine hardly changed the anodic current. Theses results suggested that an electrode grafted molecularly imprinted polymer is functional as selective chemical sensor.

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15.
ＩｇＧクラスの特異抗体を用いたトランスフェリン免疫センサ（２）

安澤幹人、松木　崇、佐古洋文、椚　章

徳島大工

DEVELOPMENT OF TRANSFERRIN IMMUNOSENSOR USING FERROCENE-LABELED IgG CLASS ANTIBODIES (2)

Mikito YASUZAWA, Takashi MATSUKI, Hirofumi SAKO and Akira KUNUGI

Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima
2-1 Minamijosanjima, Tokushima 770-8506, Japan

An amperometric immunosensor for the quantification of transferrin was investigated using two monoclonal IgG class anti-rat transferrin antibodies,15C2H3 and 22A06D2. The former was immobilized on a gold electrode (gold=antibody) while the latter was conjugated with eletrochemically redox active “ferrocene” (antibody= ferrocene). The quantitative analysis of transferrin was investigated by measuring the electrooxidation current of ferrocene, which is proportional to the transferrin concentration for the equivalently observed sandwich formation (gold=antibody-antigen-antibody=ferrocene). BSA coating on the antibody immobilized electrode was performed to eliminate nonspecific binding. The deposition of electroconductive polymer, poly[ferrocenylmethyl-3-(pyrrol-1-yl)propyl-dimethylammonium bromide] (poly-PF), on the surface of gold=antibody before the sandwich formation increased the sensor response. This result is probably indicating that poly-PF facilitated the charge transfer from the ferrocene-modified antibody to the electrode.

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16.
チロシナーゼを用いたシアン及びシアン配糖体のオプティカルセンシング

立間　徹、小森喜久夫、小山　昇

東京農工大工

OPTICAL SENSING OF CYANIDE AND CYANOGENIC GLUCOSIDES USING TYROSINASE

Tetsu TATSUMA, Kikuo KOMORI and Noboru OYAMA

Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology
Koganei, Tokyo 184-8588, Japan

A colorimetric method for the determination of cyanide and cyanogenic glucosides is developed. In the presence of dissolved oxygen, tyrosinase catalyzes oxidation of L-tyrosine to dark melanin via red dopachrome. This coloring reaction is inhibited by cyanide, which is added or liberated from a cyanogenic glucoside as a result of hydrolysis catalyzed by a β-glucosidase. This inhibition is utilized to determine cyanide and cyanogenic glucosides. Dynamic range of this sensing system can be controlled by changing enzyme concentrations. This system will be applied to an optical sensor and test plates for cyanide and cyanogenic glucosides.

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17.
メタンフェタミン（覚醒剤）検出用高感度 SPR免疫センサ

中田聖士、酒井　剛、宇田泰三^*、三浦則雄、山添　曻

九大院総理工、広島県立大^*

HIGHLY SENSITIVE DETECTION OF METHAMPHETAMINE (STIMULANT DRUG) BY USING SPR IMMUNOSENSOR

Seiji NAKATA, Go SAKAI, Taizo UDA*, Norio MIURA and Noboru YAMAZOE

Department of Molecular and Material Sciences, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan
^*School of Biosciences, Hiroshima Prefectual University
Shoubaru-shi, Hiroshima 727-0023, Japan

Highly sensitive and selective detection of methamphetamine (MA, stimulant drug) was achieved by using surface-plasmon-resonance (SPR) immunosensor. The incident angle of the MA-BSA immobilized sensor chip increased with increasing concentration of anti-MA-BSA antibody up to about 20 ppm. The sensor chip could be used repeatedly at least 50 times, if the chip was washed with acidic solution (pH2.3) after each response. The addition of MA into the antibody solution (20 ppm) was found to decrease the incident angle shift because of the inhibition effect of MA. The present sensor could detect MA very sensitively in the concentration range 100 ppt - 10 ppm not only in PBS solution but also in 1% urine-containing PBS solution.

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18.
フローイムノアッセイシステムを用いた抗dsDNA抗体の測定

林　泰圭、菰田由美子、中村徳幸、松永　是

東京農工大工

MEASUREMENT OF ANTI DOUBLE STRANDED DNA ANTIBODY USING FLOW IMMUNOASSAY SYSTEM

Tae-kyu LIM, Yumiko KOMODA, Noriyuki NAKAMURA and Tadashi MATSUNAGA

Department of Biotechnology, Tokyo University of Agriculture and Technology
Koganei, Tokyo 184-8588, Japan

Automated flow immunoassay system for quantification of anti double stranded (ds) DNA autoimmune in serum of patients suffering from systemic lupus erythematosus (SLE) was performed. dsDNA (360 bp) was covalently coupled with alkaline phosphatase (ALP) to form a novel analytical reagent (ALP-DNA). After immunoreaction, antibody-antigen complexes between ALP-DNA and anti dsDNA antibody were separated from unreacted ALP-DNA by an ion exchange column on the basis of the difference in isoelectric points. The output signal correlated linearly with a concentration of the standard anti dsDNA antibody in the range of 0 - 400 IU/ml. This simple, rapid, and convenient immunoassay method can detect anti dsDNA antibody continuously.

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19.
LaF₃を用いた溶存CO₂センサ

大城　誠博、上門　直子、三浦　則雄^*、山添　曻^*

琉球大理・九大院総理工^*

DISSOLVED CO₂ SENSOR USING LaF₃ SOLID ELECTROLYTE

Seihiro OSHIRO, Naoko UEJOH, Norio MIURA^* and Noboru YAMAZOE^*

Department of Chemistry, Biology and Marine science, Faculty of Science, University of the Ryukyus
1 Senbaru, Nishihara-Cho, Okinawa 903-0213, Japan
^*Department of Molecular and Material Sciences, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

The sensing properties of a dissolved CO₂ sensor combing LaF₃ （ fluoride ion conductive solid electrolyte ) with an auxiliary phase of BaCO₃ were investigated. The sensor element was composed of the following electrochemical cell : ( reference electrode ) Au ｜ LaF₃ ｜Pt-BaCO₃ ( sensing electrode ) . When measured in a phosphate buffer solution of pH 7.0 at 30℃, the sensor EMF changed logarithmically with a change in dissolved CO₂ concentration in the range from 300 to 1300 ppm, following a Nernst's equation. The Nernst's slope was ca. 25 mV/decade. The 90% response time was from 5 to 7 minutes.

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20.
マイクロマシーニング技術によるSeveringhaus型二酸化炭素電極の微小化

荒川浩亮、鈴木博章、佐々木聰*、軽部征夫*

琉球大理・九大院総理工^*

MINIATURIZATION OF THE SEVERINGHAUS-TYPE CARBON DIOXIDE ELECTRODE USING MICROMACHINIG TECHNIQUES

Hiroaki ARAKAWA, Hiroaki SUZUKI, Satoshi SASAKI and Isao KARUBE

Institute of Materials Science, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
^*RCAST, The University of Tokyo
4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan

A miniature Severinghaus-type carbon dioxide electrode was fabricated using micromachining techniques. An anodic iridium oxide film (AIROF), which was formed by repetitive potential cycling in 0.1 M H₂SO₄, was used as the pH-sensing element. A thin-film Ag/AgCl reference electrode was formed by covering the surface of a silver pattern with a hydrophobic negative photoresist layer and growing AgCl from the edges. The container with a liquid junction was formed on a silicon substrate using anisotropic etching. The gas-permeable membrane was formed on the silicon substrate. The AIROF showed a super-Nernstian response with a slope of approximately -80 mV/pH. The miniature carbon dioxide electrode showed a distinct response. Its characteristics including the response time and calibration curve were those expected for the Severinghaus-type electrode.

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21.
鉄ポルフィリンをドープしたナフィオン膜被覆ＧＣ電極によるNOの定量

池田　修、小山博行、来嶋邦久^*、小村照寿^*、北嶋　彰^**、三宅幹夫^**、山本浩一^***、大和谷　厚^***

金沢大理・工^*・北陸先端大^**・阪大医^***

DETECTION OF NITRIC OXIDE WITH THE IRON-PORPHYRIN DOPED　NAFION|GLASSY CARBON ELECTRODE

Osamu IKEDA, Hiroyuki KOYAMA, Kunihisa KIJIMA, Teruhisa KOMURA, Akira ITAJIMA, Mikio MIYAKE, Kouichi YAMAMOTO and Atsushi YAMATODANI

Department of Chemistry, Faculty of Science, Kanazawa University
Kakuma, Kanazawa, Ishikawa 920-1192, Japan

Nitric oxide dissolved in buffer solutions has been detected by the electrochemical oxidation reaction at the glassy carbon (GC) electrode coated with Nafion film doped with various iron(III) porphyrins. The electrochemical detection was carried out by using different methods, such as normal pulse voltammetry (NPV), differential pulse voltammetry (DPV) and amperometry. All iron(III) porphyrins examined showed a catalytic activity for the electrolytic oxidation of nitric oxide. The best electrocatalyst was tetrakis-(pentafluorophenyl)porphyrin iron(III) chloride (Fe(TPFPP)Cl). The limit of the detection of nitric oxide was about 10 nM at the GC electrode coated with Nafion film doped with Fe(TPFPP)Cl. At this electrode, a stable calibration curve was obtained by using amperometry.

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22.
ペロブスカイト型酸化物系電極によるリン酸イオンのアンペロメトリックセンシング

石川文俊、高瀬聡子、清水陽一

九工大工

AMPEROMETRIC SENSING PROPERTIES TO PHOSPHATE-ION OF PEROVSKITE-TYPE OXIDE-BASED ELECTRODE

Ayatoshi ISHIKAWA, Satoko TAKASE and Youichi SHIMIZU

Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology
1-1 Sensui-cho, Tobata, Kitakyushu 804-8550, Japan

PTFE-bonded carbon electrodes loaded with perovskite-type oxide (Ln-Co-O system: Ln=La, Nd, Pr, Sm) were found to show good amperometric sensing to hydrogen-phosphate ion at the concentration range of as low as 1.0 x 10^-5 M. The anodic current at +0.85 V vs. SCE was increased with increasing the concentration of hydrogen-phosphate ion between 1.0 x 10^-5 M and 1.0 x 10^-3 M, with 90% response time of 35-100 min at 30℃. The device showed high selectivity to HPO₄^2- among the examined anions of F^-, Cl^-, Br^-, SCN^-, NO₃^-, SO₄^2-, CO₃^2-, and ClO₄^-, while it got serious interference from I^- . The use of thin-film electrode of perovskite-type oxide gave drastical improvement of amperometric sensing to phosphate-ion. The 90% response time of the LaCoO₃-thin-film device was as short as ca. 5 min or ca. 10 s for the change at low- or high- concentration range of hydrogen-phosphate ion, respectively.

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23.
メチルアンモニウム電極の開発と細胞内外ｐＨ差測定への応用

勝　孝、赤木正章、平松寿章、土屋友房

岡山大薬

DEVELOPMENT OF A METHYLAMMONIUM-SELECTIVE MEMBRANE ELECTRODE AND ITS APPLICATION TO THE DETERMINATION OF THE pH DIFFERENCE ACROSS A CELL MEMBRANE

Takashi KATSU, Masaaki AKAGI, Toshiaki HIRAMATSU, and Tomofusa TSUCHIYA

Faculty of Pharmaceutical Sciences, Okayama University
Tsushima, Okayama 700-8530, Japan

We developed a method for determining pH differences across cell membranes, using a methylammonium-selective membrane electrode, based on monitoring of the pH gradient-induced uptake of methylammonium in situ. The methylammonium electrode was constructed using calix[6]arene-hexaacetic acid hexaethyl ester as a neutral carrier and bis(2-ethylhexyl) sebacate as a membrane solvent in a poly(vinyl chloride) membrane matrix This electrode exhibited a near-Nernstian response to methylammonium in the concentration range 2 x 10^-5 - 1 x 10^-2 M with a slope of 58 mV per concentration decade in buffer solution of 150 mM choline chloride/10 mM Tris-HCl (pH 7.5). The limit of detection was 5 x 10^-6 M. In experiments using liposomes, the uptake of methylammonium into liposomes occurred effectively when the pH of the outside suspension medium was alkaline, and the determination of changes in methylammonium concentrations in the outer medium was quantitatively related to changes in the pH differences across the liposomal membrane. The transmembrane pH differences in Escherichia coli cells were also determined by this method.

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24.
ELECTROCHEMICAL RECOGNITION OF AMINO ACIDS WITH CHIRAL SELECTIVE MOLECULAR SENSORS

周　延秀、陳　智棟、長岡　勉

山口大工

Yanxiu Zhou and Tsutomu Nagaoka^*

Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University

2557 Tokiwadai, Ube 755-8611, Japan

The authors constructed a simple monitoring device for distinguishing between the left- and right-handed forms of an amino acid derivative, N-carbobenzoxy-aspartic acid (CBZ-Asp), based on a molecularly imprinted ODS/ITO monolayer (ODS, octadecyltrichlorosilane; ITO, indium-tin-oxide). The sensor exhibited recognition properties only to the L-isomer of CBZ-Asp without any preseparation process. This supramolecular sensor translated an enantioselective molecular recognition event into a potential change to detect CBZ-L-aspartic acid in a concentration range of 6.4×10^-4 -7.8×10^-3 M. Mechanistic investigation of the sensor responses revealed that protons are emitted from the cationic form of the L-amino acid taken up in the template, producing positive responses on the ITO surface. This sensor, based on an artificial recognition system, demonstrated long-time stability in harsh chemical environments.

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25.
ヘテロ積層型半導体ガスセンサの n-C₄H₁₀に対する応答・回復特性

川原昭彦、勝木宏昭、江頭　誠^*

佐賀県窯業技術センター・長崎大工^*

RESPONSE AND RECOVERY CHARACTERISTICS OF HETEROLAYERED SEMICONDUCTOR GAS SENSORS IN THE DETECTION OF n-C₄H₁₀

Akihiko KAWAHARA, Hiroaki KATSUKI and Makoto EGASHIRA^*

Fine Ceramic Division, Saga Ceramics Research Laboratory
Arita-machi, Nishimatsuura-gun, Saga 844-0024, Japan
^*Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan

Semiconductor gas sensors of heterolayered thick films were prepared by a slide-off printing method. Gas-sensing characteristics to n-C₄H₁₀ of the heterolayer sensors with the sequence of stacking of SnO₂, In₂O₃ and TiO₂-based layers were investigated. Among the sensors examined, a heterolayer sensor in which a TiO₂ layer was covered with a SnO₂ layer showed the maximum sensitivity of S=34.2 to 425 ppm n-C₄H₁₀ at 410℃; particularly, it was found that the recovery characteristics were much better than those of a sensor with the reverse sequence of stacking. Namely, a heterolayer structure, in which a less conductive layer was covered with a more conductive layer, showed excellent gas sensing properties. The variations in the gas-sensing properties have been discussed in terms of the conduction pass of the heterolayered thick films and the permeation properties of the related gases.

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26.
イオン注入法で作製した薄膜型半導体ガスセンサの水素検出特性

狩野伸自、馬場恒明^**、兵頭健生、高尾雄二^*、清水康博、江頭　誠

長崎大学工学部材料工学科，環境科学部^*・長崎県工業技術センター^**

HYDROGEN-SENSING PROPERTIES OF THIN FILM SEMICONDUCTOR GAS SENSORS FABRICATED BY ION BEAM-ASSISTED DEPOSITION

Shinji KARINO, Koumei BABA, Takeo HYODO, Yuji TAKAO, Yasuhiro SHIMIZU and Makoto EGASHIRA

Department of Materials Science and Engineering, Faculty of Engineering
^*Faculty of Environmental Studies, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan
^**Technology Center of Nagasaki
2-1303-8 Ikeda, Omura, Nagasaki 856-0026, Japan

Gas-sensing properties of WO₃ and Nb₂O₅ thin films fabricated on a Si substrate by Ar⁺ and O₂⁺ ion beam-assisted deposition (IBAD) have been investigated with respect to the magnitude of sensitivity and long-term stability. Although as-deposited films were amorphous, they were crystallized to WO₃ and Nb₂O₅, respectively, by the heat treatment at 700℃ for 48 h in air. Both the WO₃ and Nb₂O₅ films exhibited extremely high sensitivity to H₂. The WO₃ film also exhibited relatively high sensitivity to NO₂, but the Nb₂O₅ film was less sensitive. As-deposited films were peeled off from the substrate, irrespective of the simultaneous bombardment of Ar⁺ and O₂⁺ ions during the deposition. After the heat treatment, however, the films subjected to the ion bombardment exhibited excellent adhesive property against the substrate. These results suggest the occurrence of the mixing at an atomic level between the sensor material and the substrate during the ion bombardment and the formation of solidified interface during the subsequent heat treatment. Although the WO₃ film fabricated without the ion beam exhibited poor stability, the IBAD method improved the long-term stability of the film at elevated temperature with maintaining extremely high H₂ sensitivity owing to the solidified interface between the sensor material and the substrate.

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27.
低湿度依存性の酸化インジウムガスセンサ

福井清、西田幸子

新コスモス電機(株)

In₂O₃-BASED GAS SENSOR WITH LOW HUMIDITY DEPENDENCE

K. Fukui and S. Nishida

New Cosmos Electric Co., Ltd.

2-5-4, Mitsuya-Naka, Yodogawa-Ku, Osaka 532-0036, Japan

The powder of the indium oxide semiconductor was prepared by calcination (600 degree C for 4 h) of In(OH)₃ (the purity of 99.99%). The conductivity of the In₂O₃ semiconductor was controlled by doping Sn⁴⁺ or Ge⁴⁺. The indium oxide was distributed in sphere(0.50 mm in diameter) to cover a platinum wire(0.020 mm in diameter) coil, following by being sintered (600 degree C for 12 h) by the coil heating. The gas sensor was operated by a bridge circuit. An optimum sensor temperature was ca. 480 degree C(ca.160 mW). An extremely low humidity dependence was obtained as compared to a conventional SnO₂-based sensor. Further, a prominent long term stability was also ascertained, and a possibility of reliable detection at a low gas concentration was obtained in the present study.

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28.
In₂O₃系酸化物のNO_x応答特性

田中伸一郎，江坂享男

鳥取大学工学部

NO_x SENSING CHARACTERISTICS OF In₂O₃-BASED OXIDES

Shinichiro TANAKA and Takao ESAKA

Department of Materials Science, Faculty of Engineering, Tottori University

Minami 4-101, Koyamacho, Tottori 680, Japan

To develop a high sensitive gas sensor monitoring NO_x，various kinds of n-type semiconductors made of In₂O₃ were prepared and relation between the doped impurities and the gas sensitivity (or response time) were studied. As a result, it was found that the samples doped with alkaline earth metal elements have highly sensitivities and responsiveness. This phenomenon was investigated using high sensitive thermal analysis.

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29.
各種金属酸化物を積層した酸化スズセンサアレイによるニオイの識別

前川　亨、鈴木　健吾、高田　義、小林　哲彦^*

新コスモス電機、大工研^*

ODOUR IDENTIFICATION USING A SnO₂-BASED SENSOR ARRAY COVERED WITH METAL OXIDE

Toru MAEKAWA, Kengo SUZUKI, Tadashi TAKADA and Tetsuhiko KOBAYASHI^*

New Cosmos Electric Co., Ltd.
2-5-4 Mitsuya-Naka, Yodogawa-ku, Osaka 532-0036, Japan
^*Osaka National Research Institute
Midorigaoka 1, Ikeda, Osaka 563-8577, Japan

We have developed an odour identification system using a SnO₂-based sensor array, which had 8 sensing elements with different odour-selectivities. We have attempted to identify various kinds of odour gases and essential oils using this system. For example, citrus fruit oils such as lemon, sweet orange, grapefruit, bergamot and petitgrain oils, which contain a large amount of limonene as the major component, were discriminated from each other by analyzing with principal component. This result denotes that the present system has capability to identify each of citrus fruit oils with a trace amount of minor components. It seems that the method for preparation of sample, the reproducibility and selectivity of the sensing elements are the keys for identification of odours of the same group.

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30.
酸化スズ系COガスセンサの経時安定性

尾崎康隆、鈴木祥代、盛満正嗣^*、松永守央^*

フィガロ技研・九工大工^*

LONG-TERM STABILITY OF SnO2-BASED CO SENSOR

Yasutaka OZAKI, Sachiyo SUZUKI, Masatsugu MORIMITSU^* and Morio MATSUNAGA^*

Figaro Engineering Inc.
1-5-11, Senba-nishi, Mino, Osaka 562-0036, Japan
^*Department of Applied Chemistry, Kyushu Institute of Technology
Tobata, Kitakyushu 804-8550, Japan

The resistance of SnO₂-based CO sensor varies with time, which makes it difficult to calibrate the sensitivity and loses the reliability during long operation. In this study, new treatment of the SnO₂-based sensor is investigated to reduce the resistance variation. The impregnation of SnO₂-based element in dilute sulfuric acid improves the long-term stability of the sensor resistance. The resistance of the sensor treated in 0.04 mol/dm3 sulfuric acid has been unchanged for more than 8 months. The immersion of SnO₂-based element in dilute thiourea solution also induces the high stability of the sensor resistance with the improved sensitivity for CO gas.

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31.
酸化スズ系COガスセンサ素子に及ぼす浸漬処理の影響

格内裕紀、盛満正嗣、松永守央、尾崎康隆^*、鈴木祥代^*

九工大工・フィガロ技研^*

EFFECTS OF DIPPING TREATMENT ON SnO₂-BASED CO GAS SENSOR ELEMENTS

Hironori KAKU-UCHI, Masatsugu MORIMITSU, Morio MATSUNAGA, Yasutaka OZAKI and Sachiyo SUZUKI

Department of Applied Chemistry,Kyushu Institute of Technology
1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan
^*Figaro Engineering Inc.
1-5-11 Senba-nishi,Mino,Osaka 562-8505,Japan

The effects of dipping treatment on SnO₂-based CO gas sensor elements were studied. The surface morphology,elemental distribution, crystal structure of the sensor element were analyzed using FE-SEM,EPMA,and XRD.NO remarkable change in the surface morphology and crystal structures was observed before and after the dipping treatment in sulfuric acid or thiourea solution.However,the surface analysis of the sensor element by EPMA revealed that sulfur is present on the surface of the element after the dipping treatment and the distribution of sulfur corresponds to that of Sn.

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32.
電子ビーム蒸着法により調製したWO₃薄膜のトリメチルアミン検知特性(1)
－膜厚の影響－

大谷岳史^*、玉置　純^*、山本善史^*、松岡政夫^*、喜多純一^**

立命館大理工^*・島津製作所^**

SENSING PROPERTIES TO TRIMETHYLAMINE OF WO₃ THIN FILM PREPARED BY ELECTRON BEAM EVAPORATION (1) -EFFECTS OF FILM THICKNESS-

Takeshi OHTANI^*, Jun TAMAKI^*, Yoshifumi YAMAMOTO^*, Masao MATSUOKA^* and Jun-ichi KITA^**

^*Department of Chemistry, Faculty of Science and Engineering, Ritsumeikan University
Kusatsu-shi, Shiga 525-8577, Japan
^**Analytical Instruments Div., Shimadzu Corporation
Kyoto 604-8511, Japan

WO₃ thin films were prepared by means of an electron beam evaporation and the effects of film thickness on the film microstructure as well as the sensing property to dilute TMA were investigated. The 270 nm film calcined at 500 ℃ showed the orientation along (200) and (001) planes of triclinic WO₃ phase and no XRD peak of (020) plane was observed. The WO₃ thin film sensors exhibited the highest sensitivity to 10 ppm TMA at 450 ℃. At this temperature, the resistance in air as well as TMA sensitivity were low for the films thinner than 300 nm, while they suddenly increased when the film thickness exceeded 350 nm. These behaviors were explained in relation to the film microstructure.

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33.
電子ビーム蒸着法により調製したWO₃薄膜のトリメチルアミン検知特性(2)
－添加物の効果－

玉置　純^*、大谷岳史^*、山本善史^*、松岡政夫^*、喜多純一^**

立命館大理工^*・島津製作所^**

SENSING PROPERTIES TO TRIMETHYLAMINE OF WO₃ THIN FILM PREPARED BY ELECTRON BEAM EVAPORATION (2) -EFFECTS OF ADDITIVES-

Jun TAMAKI^*, Takeshi OHTANI^*, Yoshifumi YAMAMOTO^*, Masao MATSUOKA^* and Jun-ichi KITA^**

^*Department of Chemistry, Faculty of Science and Engineering, Ritsumeikan University
Kusatsu-shi, Shiga 525-8577, Japan
^**Analytical Instruments Div., Shimadzu Corporation
Kyoto 604-8511, Japan

WO₃ based thin films added with various foreign oxides (loading of oxide : 1 wt%) were prepared by means of an electron beam evaporation and the effects of additives on the film microstructure as well as the TMA sensing properties were investigated. The modified WO₃ thin films calcined at 450 ℃ (thickness : 200 nm) had the highly oriented crystal structure along (200 ) plane of triclinic WO₃ phase. On the other hand, the resistance in air was increased when In₂O₃, SnO₂, or Sb₂O₅ was added to WO₃ thin film and the TMA sensitivity was also enhanced for these films. Particularly, the In₂O₃-WO₃ thin film exhibited the highest sensitivity of 340 to 5 ppm TMA at 350 ℃. However, the addition of La₂O₃ or Bi₂O₃ was hardly successful in increasing the TMA sensitivity of WO₃ thin film. For the detection of dilute TMA, the SnO₂-WO₃ thin film had the highest sensitivity, i.e., the film showed the sensitivity as high as 2.5 to 0.01 ppm TMA at 350 ℃.

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34.
多核錯体を前駆体とする熱分解による銅-希土類複合酸化物の調製とH₂Sガスセンサへの利用

青野宏通、岡田夕紀、坂本政臣^*、定岡芳彦

愛媛大工・山形大理^*

PEPEARATION OF THE Cu-RE SYSTEM OXIDES BY THERMAL DECOMPOSITION OF HETERONUCLEAR COMPLEXES AND APPLICATION TO H₂S GAS SENSITIVE FILMS

Hiromichi AONO, Yuuki OKADA, Masatomi SAKAMOTO^* and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University
Matsuyama 790-8577, Japan
Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
Yamagata 990-8560, Japan

Heteronuclear CuRE(dhbaen)(NO₃)(H₂O)n (RE=Rare Earth) complexes were synthesized and their thermal decomposition products were investigated for the application to sensor materials. The structure of the decomposition products is controlled by the coordination number and ionic size of RE³⁺ ion. In the case of the RE=La system, mixed phase of CuLa₂O₄ and CuO was obtained by the thermal decomposition. The conductivity for the La system was decreased by 7.8 ppm H₂S gas. After the H₂S measurement, S atom map on the surface of the sensor was agreed with Cu-map which was determined by Auger electron spectroscopy (AES). The H₂S gas adsorbs on and/or reacts to CuO. The formation of CuS or Cu₂S might be reason for the conductivity change.

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35.
SiC-MIS型センサにおけるCO , O₂ 相互作用の温度依存性

中込真二、野本宗輝

石巻専修大理工

TEMPERATURE DEPENDENCE OF INTERACTION BETWEEN CARBON-MONOXIDE AND OXYGEN ON SiC-MIS TYPE SENSOR

Shinji NAKAGOMI and Muneteru NOMOTO

School of Science and Engineering, Ishinomaki Senshu University

Ishinomaki 986-8580, Japan

Schottky diode based on catalytic metal-oxide-silicon carbide devices are investigated. The sensitivity of the devices to mixtures of carbon monoxide and oxygen is studied in region from 400 to 600℃. A large binary response o f the sensor to carbon monoxide is observed close to the stoichiometric ratio of carbon monoxide and oxygen at the temperature region. The response-slope changes from abrupt to gentle at lower operating temperature and under higher concentration. Carbon monoxide and oxygen are effective to the sensor at lower and higher temperature, respectively. Carbon monoxide affects to the sensor even under excess oxygen condition at 400℃.

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t1.
センサとマイクロシステム( MEMS )

安原　光

株式会社　フジクラ

SENSORS AND MICROSYSTEMS ( MEMS )

Hikaru YASUHARA

Electron Device Laboratory　Fujikura Ltd.
1-5-1 Kiba Koto-ku, Tokyo 135, Japan

In order to reduce the sensor size physically, thus cause the production cost down, the so-called micromachining technology is necessary to be introduced. Furthermore, the technology makes it possible to integrate a sensor with electronics of a signal conditioning and other functions as system, and the system works effectively to expand the industry. This paper reviews the recent researches as microelectromechanical systems imply not only electromechanical components and micromachines, but advance the possible fabrication development of the chemical or electrical factory on a silicon chip.

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36.
酸化物薄膜表面の気体吸着作用に及ぼす弾性表面波の効果

ニパットポーカイ　ラッタナー、西山　洋、斉藤信雄、佐藤一則、井上泰宣

長岡技大工

EFFECTS OF SURFACE ACOUSTIC WAVE ON GAS ADSORPTION ON METAL OXIDE THIN FILMS

Rattana NIPATPOKAI, Hiroshi NISHIYAMA, Nobuo SAITO, Kazunori SATO and Yasunobu INOUE

Department of Chemistry, Nagaoka University of Technology
Nagaoka 940-2188, Japan

Thin film oxides of NiO and SnO₂ were deposited on a 128°rotated Y-cut LiNbO₃ substrate which generates surface acoustic wave (SAW) by Rf power, and the effects of SAW on the adsorptive and desorptive properties of the thin film oxides were investigated with surface conductivity measurements. In the propagation of a 10 MHz Rayleigh SAW, conductivity increase in NiO due to O₂ adsorption was considerably enhanced, and the conductivity decrease by O₂ desorption was also remarkably promoted. Similar SAW effects were observed for H₂ adsorption on SnO₂. From correlation between the resistivity of the thin film oxides and the propagation loss of SAW, it has been demonstrated that the SAW has remarkable interactions with the carriers in the metal film oxides which affect the adsorption (desorption)-induced conductivity changes.

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37.
高分子膜を塗布した水晶振動子式においセンサの機能設計

南戸秀仁、堂上長則、向井達哉、羽原正秋、草野英二、小川俊夫、金原　粲

金沢工大　高材センター

FUNCTIONAL DESIGN OF POLYMER-FILM-COATED QUARTZ RESONATOR SMELL SENSOR

Hidehito NANTO, Naganori DOUGAMI, Tatsuya MUKAI, Masaaki HABARA, Eiji KUSANO, Toshio OGAWA and Akira KINBARA

Advanced Materials Science R&D Center, Kanzawa Institute of Technology
3-1 Yatsukaho, Mattou, Ishikawa 924-0838, Japan

The copolymerized propylene-butyl of which solubility parameter almostly coincides with that of harmful gases such as toluene, xylene, octane, diethyether, chloroform and acetone, is chosed as a material of sensing membrane coated on the qyartz resonator. It is found that copolymerized propylene-butyl-film coated quartz resonator gas sensor exhibites high sensitivity and excellent selectivity for these harmful gases, especially for toluene and xylene gas.

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38.
側鎖にアミノ基をもつコポリマーを用いたQCM法CO₂ガスセンサの開発

高島洋介、松口正信、酒井義郎

愛媛大工

QCM CO₂ GAS SENSOR USING A COPOLYMER WITH AMINO GROUP

Yousuke TAKASHIMA, Masanobu MATSUGUCHI and Yoshiro SAKAI

Department of Applied Chemistry, Faculty of Engineering, Ehime University
3 Bunkyo-cho, Matsuyama 790-5877, Japan

Sorption Behavior of CO₂ in poly(styrene-co-chloromethylstyrene) derivative was investigated using QCM method. The amount of CO₂ sorbed in the copolymer derivatives with amino group was more than that of the original copolymer.
Using the dual-mode sorption model, it was confirmed that the introduced amino group acted as the CO₂ sorption site. CO₂ sorption ability was also affected by the structure of amino groups.

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39.
Poly-2-acrylamido-2-methyl propane sulfonic acid (PAMS)を用いた抵抗型湿度センサ

影山　啓、松口正信、酒井義郎

愛媛大工

A HUMIDITY SENSOR USING POLYELECTROLYTES WITH SULFONATE GROUP

Kei KAGEYAMA, Masanobu MATSUGUCHI and Yoshiro SAKAI

Department of Applied Chemistry, Faculty of Engineering, Ehime University
3 Bunkyo-cho, Matsuyama 790-5877, Japan

In order to prepare a resistive-type humidity sensor that is durable at high humidities, poly(2-acryamide-2-methylpropane sulfonic acid-co-propylene glycol monomethacrylate) (PAMPS-co-PGM) was crosslinked with various crosslinking agents on an alumina substrate with a pair of gold electrodes. In most cases, the impedance increased after the sensor soaked in water due to the dissolution of the insufficiently crosslinked polymer. However, sufficient sensitivity was still maintained for PAMPS-co-PGM crosslinked with melamine above 40 %RH after soaking in water for 120 min.

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40.
導電性/絶縁性高分子複合膜の湿度応答におよぼす絶縁性高分子の吸湿特性

椎木　弘、藤井明博、中山雅晴、小倉興太郎

山口大工

EFFECT OF HYGROSCOPIC CHARACTERISTICS OF INSULATING POLYMER EXERTING ON THE HUMIDITY-DEPENDENCE OF CONDUCTING / INSULATING POLYMER COMPOSITES

Hiroshi SHIIGI, Akihiro FUJII, Masaharu NAKAYAMA and Kotaro OGURA

Department of Applied Chemistry, Yamaguchi University
Tokiwadai, Ube 755-8611, Japan

The electrical conductivity of composites consisting of polyaniline derivatives and hygroscopic insulating polymers is linearly related with the relative humidity. The effect of hygroscopic characteristics of the insulating polymer on the humidity-dependence of the composite was here investigated. Poly(vinyl alcohol)(PVA) and poly(ethyleneoxide)(PEO) were used as insulating polymers. The electrical conductivity of the poly(o-aminophenol)(PoAP)/PVA composite was proportinal to the relative humidity without accompanying any hysteresis. For the PoAP/PEO composite, however, a hysteresis was observed in the measurements at the moistening and desiccating stages. The linear dependence of electrical conductivity on the relative humidity is attributed to the existence of "strongly bound water molecules", but as show below, the hysteresis observed for the PoAP/PEO composite is caused by the smaller amount of "strongly bound water molecules" in the composite.

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41.
テトラフェニルポルフィリン－ポリマー複合膜を用いた光学的HClガスセンサにおけるガラス転移温度の影響

ヘルスプリヤトノ、北川貴啓、中川克彦^*、青野宏通、定岡芳彦

愛媛大工・新居浜高専^*

EFFECT OF GLASS TRANSITION TEMPERATURE ON OPTOCHEMICAL HCl GAS SENSOR USING TRAPHENYLPORPHINE-POLYMER COMPOSITES

Heru SUPRIYATNO, Takahiro KITAGAWA, Katsuhiko NAKAGAWA^*, Hiromichi AONO and Yoshihiko SADAOKA

Department of Material 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, 792-8580, Japan

The composite films of　Tetraphenylporphine(TPPH₂)-polymer were examined for detection of ppm levels of HCl gas. Their response behaviours were affected by glass transition temperature (Tg) of polymer matrixes. When the glass transition temperature is lower than working temperature (318 K), the sensitivity increases with increasing the glass transition temperature, and achieve the maximum for Tg=269K, and then decrease at higher Tg. These results can be explained by free volume for HCl diffusion and molecular vibration.

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42.
Pd薄膜を用いた光検知式水素ガスセンサーの回復特性

奥原芳樹、今井裕司、高田雅介

長岡技術科学大学

RECOVERY CHARACTERISTICS OF OPTICAL HYDROGEN SENSOR USING Pd THIN FILM

Yoshiki Okuhara, Yuji Imai, and Masasuke Takata

Department of Electrical Engineering, Nagaoka University of Technology
1603-1 Kamitomioka, Nagaoka, Niigata 940-2188, Japan

Recovery characteristics of optical hydrogen sensor using palladium (Pd) thin film have been investigated to achieve the faster recovery. The recovery speed related to dehydrogenation for the Pd hydride thin film increases with ambient oxygen partial pressure. The dependence of oxygen partial pressure on recovery speed indicates that the rate-determining step for the dehydrogenation reaction is hydrogen desorption with water forming on the Pd surface. Moreover, the recovery characteristics remarkably improved by supported platinum (Pt) on the Pd surface, which exhibits that the hydrogen desorption is accelerated by the support of Pt.

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43.
分子鋳型法で作製したCuO-BaTiO₃薄膜のCO₂センサ特性(2)

高木俊昭、石原達己、伊藤正実^*、西口宏泰、滝田祐作

大分大工・大分大地域共同研究センター^*

CAPASITIVE TYPE CO₂ SENSOR OF CuO-BaTiO₃ PREPARED BY SELF-ASSEMBLED MULTIBILAYER FILM (2)

Toshiaki TAKAGI, Tatsumi ISHIHARA, Masami ITO^*, Hiroyasu NISHIGUCHI and Yusaku TAKITA

Department of Applied Chemistry, Faculty of Engineering, Oita University
Dannoharu 700, Oita 870-1192, Japan
^*Research and Development Center, Oita University
Dannoharu 700, Oita 870-1192

Mixed oxide of CuO and BaTiO₃ fine powder was prepared by the thermal decomposition of self-assembled organic film, in which Cu existed in organic phase and BaTiO₃ existed in hydrophobic phase. Since the capacitance of the obtained CuO-BaTiO₃ film was increased upon exposure to CO₂. CO₂ concentration can be estimated with capacitance of CuO-BaTiO₃ mixed oxide film obtained by the decomposition of self-assembled organic film. The CO₂ sensing characteristics was strongly affected by the decomposition condition of organic film and it was found that the optimized decomposition temperature was 900℃ when calcination period was 3h.

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44.
基準物質を必要としない固体電解質型高温水蒸気センサ

片平幸司、小出邦博、松本広重^*、岩原弘育^*

株式会社TYK・名大理工総研^*

HIGH TEMPERATURE SOLID ELECTROLYTE STEAM SENSOR WITHOUT STANDARD MATERIAL

Koji KATAHIRA, Kunihiro KOIDE, Hiroshige MATSUMOTO^* and Hiroyasu IWAHARA^*

TYK Corporation, Advanced Materials Research & Development Center
3-1 Ohbata-cho, Tajimi 507-8607, Japan
^*Center for Integrated Research in Science and Engineering, Nagoya University
Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan

High temperature solid electrolyte steam sensor without standard material was designed and investigated.　Two discs of proton conducting oxide with porous platinum electrodes were stuck and a slight hole was made in order to leak the gas at the interface.　Constant voltage was applied to one cell to pump hydrogen from atmosphere.　EMF of another cell was measured using the pumped hydrogen as a standard material.　 On applying a certain voltage, good EMF response against vapour pressure was observed over a wide range of P_H₂O at 700℃.

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45.
ペロブスカイト型酸化物電極を用いた固体電解質CO₂センサ

山下南美、清水陽一

九工大工

SOLID-STATE CO₂ SENSOR USING NASICON AND PEROVSKITE-TYPE OXIDE ELECTRODE

Nami YAMASHITA and Youichi SHIMIZU

Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology
1-1 Sensui-cho, Tobata, Kitakyushu 804-8550, Japan

A solid-state electrochemical CO₂ sensor was obtained by using NASICON (Na₃Zr₂Si₂PO₁₂) electrolyte and metal-oxide electrode. Among the various oxide electrodes examined, Co-based perovskite-type oxides were found to show excellent sensing properties to CO₂ at 200-300℃. Especially, La_0.6Ca_0.4CoO₃-, and NdCoO₃-based elements showed best CO₂ sensing properties, i.e., the sensor response (EMF) were almost linear to the logarithm of CO₂ concentration in the range between 100 and 2000 ppm, the response time to 500 ppm CO₂ was short as 1-2 min. An open-reference electrode type NASICON-based CO₂ sensor element could be demonstrated with combining NdCoO₃ and La_0.8Pb_0.2CoO₃ for sensing and reference electrodes, respectively. The CO₂ sensor device was hardly affected by oxygen partial pressure.

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46.
COの選択的検知が可能な混成電位型安定化ジルコニアセンサ

柳橋孝明、来仙貴久、蘆　革宇、三浦則雄、山添　曻

九大院総理工

HIGHLY SELECTIVE CO SENSOR BASED ON STABILISED ZIRCONIA AND A COUPLE OF OXIDE ELECTRODES

Takaaki YANAGIHASHI, Takahisa RAISEN, Geyu LU, Norio MIURA and Noboru YAMAZOE

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

Tubular and planar electrochemical devices based on stabilized zirconia have been designed for selective detection of CO at high temperatures by using two oxide electrodes. Of the oxides tested, the combination of CdO and SnO₂ was found to be best suited for the electrode couple, giving a rapid and selective response to CO in air at 600℃. The 90% response time to 200 ppm CO of the planar device obtained was as short as ca. 10 s. The EMF value varied logarithmically with the CO concentration in the range from 40 to 1000 ppm. In addition, the EMF was not affected significantly by the other gases, such as H₂, NO, NO₂, CO₂, O₂, and H₂O. Based on the measurements of polarization curves, it was confirmed that the sensing mechanism of these devices involved a mixed potential at the oxide electrode.

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47.
混成電位を利用した固体電解質型炭化水素センサ

柿元志郎、日比野高士^*、佐野　充

名大院人情・名工研^*

SOLID STATE SENSOR FOR HYDROCARBON GASES BASED ON MIXED POTENTIAL

Shiro KAKIMOTO, Takashi HIBINO^* and Mitsuru SANO

Graduate School of Human Informatics, Nagoya University
Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan
^*National Industrial Research Institute of Nagoya
Hirate-cho, Kita-ku, Nagoya 462-8510, Japan

Non-Nernstian behaviors of a zirconia-based oxygen sensor for 0-500 ppm satu rated and unsaturated hydrocarbon gases were studied in the presence of 10% oxygen at 600℃. The sensor using a Pt sensing electrode could not respond to all the hydrocarbons, but the sensor using an Au sensing electrode exhbited large electromotive forces (emfs) for the unsaturated hydrocarbons which were alip hatic as well as aromatic. The emf values of the sensor for hydrocarbons were strong ly affected by their unsaturation fraction, carbon number, and chain structure. Then, the mechanism of the mixed potential for the hydrocarbons was also studied by the measurements of the polarization curves for the two electrodes and their cat alytic activity.

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48.
薄膜限界電流式酸素センサの安定性向上

高橋英昭、稲葉忠司、近藤春義、山下勝次

豊田中研

AN IMPROVEMENT OF THE STEADY PERFOMANCE OF THE THIN-FILM LIMITING CURRENT TYPE OXYGEN SENSOR

Hideaki TAKAHASHI, Tadashi INABA, Haruyoshi KONDO and Katuji YAMASHITA

Toyota Central Research & Development Labs., Inc.
Nagakute, Aichi 480-1192, Japan

Thin film limiting current type oxygen sensor has many good characteristics such as small size, wide measuring range for oxygen with high speed response. We found that the change in the boundary state of the electrodes and ZrO₂ electrolyte was most important for the stability in the practical use of this sensor in our former research. In this study, several 100-nm-thick Pt/ZrO₂ gradient layer electrode prepared by ion beam sputtering equipment was inserted between electrodes and ZrO₂ electrolyte to improve the bonding strength of boundary. As result, the sensor resistance was declined and the stability was improved remarkably.

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49.
酸素ポンピングによる酸化亜鉛薄膜のガス検知特性の制御

小川　亮、宮山　勝、工藤徹一

東大院工

CONTROL OF GAS SENSING CHARACTERISTICS OF A ZINC OXIDE THIN FILM BY OXYGEN PUMPING

Akira OGAWA, Masaru MIYAYAMA and Tetsuichi KUDO

Department of applied chemistry ,school of engineering ,The University of Tokyo
7-3-1 hongo, Bunkyo-ku, Tokyo 113-8656, Japan

A ZnO thin film was fabricated on 8YSZ(8mol% Y₂O₃ stabilized zirconia) plate by R.F. magnetron sputtering, and effects of oxygen pumping through 8YSZ on gas sensing characteristics of the ZnO thin film were investigated. Sensitivities of the ZnO thin film for CO and CH₄ gases were much larger under applying +0.5V to 8YSZ than those without applying voltage at 400-550℃. It was confirmed that the oxygen pumping gives an amplification effect for ZnO gas sensitivity as ; a decrease in ZnO resistance by gases makes the oxygen pumping initiate, leadingfurther decrease in ZnO resistance.

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50.
酸素ポンプを利用した固体電解質型炭化水素センサ

日比野高士、桑原好孝

名工研

SOLID STATE SENSOR FOR HYDROCARBON GASES BASED ON ELECTROCHEMICAL OXYGEN PUMP

Takashi HIBINO and Yoshitaka KUWAHARA

National Industrial Research Institute of Nagoya
Hirate-cho, Kita-ku, Nagoya 462-8510, Japan

An electrochemical device for detecting various hydrocarbons at high temperatures has been fabricated by attaching two Pd｜YSZ｜Au cells together in which the Pd electrodes are located on the inside of the assembly. The sensing properties for C₁ - C₆ alkanes, C₂ - C₄ alkenes, C₆ - C₈ aromatic hydrocarbons were investigated at 700 ℃. When the sample gases containing 200 - 1000 ppm hydrocarbon and 250 - 1000 ppm oxygen were supplied to the device at a flow rate of 100 ml min^-1, large EMF values were generated from one cell and then compensated by electrochemically pumping oxygen from the other cell.
The current applied to the latter cell linearly increased with increasing hydrocarbon concentration and was not affected by changing the oxygen concentration. In addition, the sensitivity to the hydrocarbons became more significant as the carbon number of the hydrocarbons increased.

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