Vol. 6, Supplement A (1990)

Digest of the 10th Chemical Sensor Symposium
April 5-7, 1990
Kyoto University

Abstracts

1
電析法による焼結酸化錫半導体表層への金属又は金属酸化物の担持

 福井　清

新コスモス電機

APPLICATIONS OF ELECTRODEPOSITION METHOD TO SEMICONDUCTOR GAS SENSOR

 Kiyoshi FUKUI

New Cosmos Electric Co., LTD,
2-5-4 Mitsuya-Naka Yodogawa-ku, Osaka-shi 532, Japan

The present study intended to apply electrodeposition method to loading active metals (Pd, Rh, Pt, Cu, Mn) or metal oxides on the surface layer of sintered tin oxide semiconductor. The loading state of Pd, for example was observed by SEM and EPMA. The crystallite form was needles or spheres depending on ion concentration. The tin oxide grains present in the surface were densely covered with the crystallites. The depth distribution exponentially decayed from ca. 2μm, and extended to ca.12μm. The half-width was ca. 4μm. The effects of the metals and metal oxides on the relative sensitivity to CnH2n+2 (n=1-4), C2H5OH, H2, CO, etc., were examined. The sensitivity order among the gases was likely to relate to their oxidation activities to each metal and metal oxide.　The electrodeposition method made it possible to change the surface layer with a depth less than ca.12μm of the sensing layer to an active layer, thereby the sensitivity characteristics of the gas sensor was controlled. The electrodeposition loading was found to be available for a fine processing of semiconductor gas sensors.


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2
酸化スズ系ガスセンサにおけるパラジウム担持方法の検討

 松嶋茂憲・前川知輝・玉置　純・三浦則雄・山添　f

九大総合理工

INVESTIGATION OF Pd-LOADING METHODS FOR Pd-SnO2 GAS SENSORS

 Shigenori MATSUSHIMA, Tomoki MAEKAWA, Jun TAMAKI, Norio MIURA and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

Three Pd-loading methods, i.e., impregnation, colloid adsorption, and chemical fixation, were examined to investigate the dispersion state of Pd particles on SnO2. TEM observation showed that Pd dispersion increased in the order, chemical fixation > colloid adsorption>impregnation. This order was in agreement with the order of the gas sensitivity to air-diluted H2. The promoting effect of Pd on SnO2 sensor thus increased with an increase in the degree of Pd dispersion, particularly the population density of Pd particles on the SnO2 surface.


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3
SnO2薄膜上のSiO2積層膜のガス選択性に与える影響

 松本　毅・守家浩二・中村裕司

大阪ガス基盤研

EFFECT OF SiO2 ON SnO2 THIN FILM FOR BETTER GAS SENSITIVITY

 Takeshi MATSUMOTO, Kouji MORIYA and Yuji NAKAMURA

Fundamental Research Laboratories, Osaka Gas Co., LTD
19-9, 6-chome, Torishima Konohana-ku, Osaka 554, Japan

In this paper, a study was made on an influence on gas selectability made by laminating layer, by means of laminating structure -controlled SiO2 films by the Reactive Sputtering Method. By laminating SiO2 thin film it was able to confirm the following.
Obstructing components like H2 and ethanol against CH4 were combusted within SiO2 film by laminating films, and thus, lowered a relative sensitivity on the surface of film. Next, CH4 only was permeated on selective basis to make it react on the surface of SnO2 thin film and finally the CH4 / H2 sensitivity ratio was able to be adjusted.


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4
酸化スズ系ガスセンサを用いた簡易型防災システムの検討

 大藪多可志・京念和美

金沢女子短大

Takashi OYABU and Kazumi KYONEN

Department of Information Engineering, Kanazawa Women's College
Kanazawa-shi, Ishikawa 920-13, Japan

Four kinds of sensors, carbon monoxide gas, LPG, Temperature and humidity, are used to prevent disasters in domestic circumstances. Output-signals from these sensors are processed by a Z-80 microprocessor in a pocket computer and the system makes diagnosis of gas leaks, fire, etc. The output patterns are an important factor to signal a would be disaster.


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5
ヘテロ接合をもったLnMO3/MO2素子（Ln: 希土類元素、M: 遷移金属元素）のガスセンサ特性

 荒川　剛・乙藤　晃

近畿大九州工

SENSING PROPERTIES OF LnMO3/MO2 (Ln=RARE EARTH, M=TRANSITION METAL) HAVING THE HETEROJUNCTION

 Tsuyoshi ARAKAWA and Akira OTOFUJI

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

I-V characteristics and sensing properties of LnMO3/MO2(Ln=rare earth, M=transition metal), which was prepared by mechanically contacting both sintered pellets, were investigated. For LnMnO3/SnO2 and LnFeO3/SnO2 the linear relationship between the current and the voltage was seen, but for LnCrO3/SnO2 and LnCoO3/SnO2 non-ohmic curves were obtained. When Ln ions were partly replaced by alkaline earth ions in LnCrO3 and LnCoO3, there was the difference in the sensing for alcohol and hydrogen or the non-ohmic behavior between these samples. For example, the non-ohmic behavior revealed the decrease on going LaCrO3 to La0.8Sr0.2CrO3. The non-ohmic behavior for La0.8Sr0.2CoO3 developed more clearly than that for LaCoO3. On the contrary, when the sensitivity for alcohol compared with that for hydrogen, no difference in LnCrO3/SnO2 and LnCoO3/SnO2 can be detected in the sensitivity. But the sensitivity of La0.8Sr0.2CrO3/SnO2 to hydrogen extremely reduced and the decrease of the sensitivity for alcohol observed in Sm0.8Sr0.2CoO3/SnO2.


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6
p-CaFe2O4/Pt-Pdダイオードにおけるガス応答性について

 新田文彦・松本泰道・本坊壽吉

熊大工

GAS SENSITIVITY OF p-CaFe2O4/Pt-Pd DIODE

 Fumihiko NITTA, Yasumichi MATSUMOTO and Jukichi HOMBO

Department of Applied Chemistry, Faculty of Engineering, Kumamoto University
2-39-1 Kurokami, Kumamoto 860, Japan

Oxygen and ozone sensitivities of the current at p-CaFe2O4/Pt-Pd diode were studied. Oxygen sensitivity of the current increased by substitution of alkaline metal cation for calsium cation in the CaFe2O4, and the response time was improved by Ir plating onto the surface of CaFe2O4. The former phenomenon is based on the decrease of the bulk sensitivity of CaFe2O4, while the latter phenomenon was based on the catalytic effect of Ir on the reaction of oxygen with the surface redox couple in the surface state. The experimental values of dφ/dlogPo2 were almost 0.02eV/decade, and were almost same as value, 0.018eV/decade, supporting surface redox reaction mechanism in the surface state. Ozone response was also absorbed for the same type diode, and was improved by substitution of Mg for Fe. The current increased with the concentration of ozone. and the value of dφ/dlogPo3 was 0.04eV/decade. This value is close to the theoretical value of 0.03eV/decade calculated by using the above surface redox mechanism.


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特別講演１
ガス事業におけるセンサ技術

石丸公生

大阪ガス

SENSOR TECHNOLOGY IN THE TOWN GAS INDUSTRY

 Kimio ISHIMARU

Research and Development Center, Osaka Gas Co., Ltd.

The Japanese gas industry has a long history, initiated in 1827 by Mr. Kaemon Takashima at Yokohama.
The gas industry deal with gas production, distribution and appliances sales but its paramount duty lies in the stable supply and safety assurance of town gas. Especially, the safety with gas facilities and appliances is much related with the sensor technology. Consequently, the industry has been engaged with the development of sensor in order to diagnose not only the health of gas pipes but also gas leakage and combustion condition. This paper introduce the principle and characteristics of these sensors.


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7
Pd-La2O3-In2O3系厚膜型素子のエタノール検知特性

 前川知輝・松嶋茂憲・玉置　純・三浦則雄・山添　f

九大総合理工

ETHANOL GAS SENSING PROPERTIES OF Pd-La2O3-In2O3 THICK FILM ELEMENT

 Tomoki MAEKAWA, Shigenori MATSUSHIMA, Jun TAMAKI, Norio MIURA and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

The doubly doped In2O3 thick film element, Pd-La2O3- In2O3, was found to show excellent ethanol gas sensing properties in sensitivity, selectivity and response rate, in addition to having an electric resistance low enough to be compatible with a conventional circuitry. Such properties resulted from the modifications of In2O3-based element with the dopants and the thick film structure applied.


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8
Pt/TiO2粒状金属膜の酸素応答特性（V）

 小野　洋・堀池彰夫・森崎　弘・矢澤一彦

電通大

Pt/TiO2 GRANULAR METAL FILMS AS AN OXYGEN SENSOR (V)

Hiroshi ONO, Akio HORIIKE, Hiroshi MORISAKI and Kazuhiko YAZAWA

The University of Electro-Communications
Chofu-shi, Tokyo 182, Japan

Effect of hydrogen-pretreatment on the oxygen sensitive resistance of Pt/TiO2 composite films has been investigated. Significant effects have been found in samples treated by pure hydrogen (1.1 atm) at 200℃ for 10 min. The sample resistance decreases to about 70 percent of the original value semi-permanently. After this treatment, the oxygen sensitivity improves several times of the magnitude from that of non-treated samples. Furthermore, the recovery time decreases from about 5 minutes to less than several seconds after this hydrogen treatment.

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9
Pd/TiO2ショットキー型水素センサの動作機構の解明

 小林　光・岸本和之・坪村　宏

阪大基礎工

MECHANISM OF HYDROGEN SENSING OF Pd/TiO2 DIODES

 Hikaru KOBAYASHI, Kazuyuki KISHIMOTO and Hiroshi TSUBOMURA

Laboratory for Chemical Energy Conversion of Solar Energy and Department of Chemistry, Faculty of Engineering Science, Osaka University
Toyonaka, Osaka 560, Japan


The mechanism of hydrogen sensing of the palladium deposited TiO2 Schottky-type diodes has been investigated by measuring the current-voltage, capacitance-voltage characteristics, work function changes, and Auger electron spectra. The barrier height in TiO2 is decreased and the work function of palladium is reduced in the presence of hydrogen. The reduction of the work function is, however, less than that of the barrier height, and thus, another cause to lower the barrier height exists. The C-V measurements show that the donor density is increased by exposing to hydrogen, indicating the formation of oxygen vacancy in the TiO2 bulk. It is concluded that the barrier height is determined by the energy difference between the palladium work function and the TiO2 conduction band edge in the absence of hydrogen, while it is determined by the surface state level and the conduction band edge in the presence of hydrogen.


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10
匂いセンサ特性試験用匂い成分供給装置

 松岡英明・銅崎慎二・瀬良和司・篠原麻尾*・石井　潯*

東農工大・高砂香料総研*

ODOUR COMPOUND SUPPLIER FOR CHARACTERIZATION OF ODOUR SENSING

 Hideaki MATSUOKA , Shinji DOUSAKI, Kazushi SERA, Asao SHINOHARA* and Hiroshi ISHII*

Department of Biotechnology, Tokyo University of Agriculture and Technology
2-24-16 Nakamachi Koganei, Tokyo 184, Japan

* Central Research Laboratory, Takasago International Corporation
5-36-31 Kamata Ota-ku, Tokyo 144, Japan

For the development of a sensor system for odour compounds, whose concentrations are extremely low ( ppb or less ), it is necessary to develop a quantitative supplying system for respective odour compounds. Previously, we demonstrated a promising property of the diffusion tube type flow system. Based on the results, a desk-top type equipment has newly been constructed in this study. The present system has shown the following performance: (1) maintenance, washing and assembling are possible ;(2) whole system can be controlled at the same temperature ; (3) a bypass line is attached for the continuous idling supply. Helium gas was passed through the system and then an adsorbent column (Tenax TA) . After flushing for 1 hr, sufficiently clean carrier gas was obtained as determined by gas chromatography. It was demonstrated that supply of benzyl acetate at ppb level was possible by the present system.


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11
薄膜熱線型ガスセンサ

 国元　晃・高橋一洋・中野内幸雄

リケン

HOT WIRE TYPE GAS SENSOR OF THIN FILM TIN OXIDE

 Akira KUNIMOTO, Kazuhiro TAKAHASHI and Yukio NAKANOUCHI

Dept. of R＆D for Advanced Materials, RIKEN Corporation
810 Kumagaya, Saitama 360, Japan

Hot wire type gas sensor of SnO2 thin film has been investigated. RF sputtering was employed for the film deposition onto heater plate under Ar/O2 gas plasma. Simultaneously, donor element (Sb) and catalyst (Pt, Pd) were deposited within SnO2 films. From the results of dependence of film thickness and annealing temperature on the sensitivity, it was realized the lower the resistance of the film, the higher the output voltage. It was also found the gas selectivity was dependent on the amount of Pt in the film. In case of Pd, however, no effects on the selectivity was found. This may be caused by Pd oxidation during sputtering and annealing.


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12
フタロシアニンの酸化性ガス雰囲気中での電気的性質

 森　義幸・松口正信・定岡芳彦・酒井義郎

愛媛大工

ELECTRICAL PROPERTIES OF PHTHALOCYANINES UNDER OXYDATIVE GAS ATMOSPHERE

 Yoshiyuki MORI, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan

Phthalocyanine (Pc) whiskers and films with various central metals were prepared. Electrical properties of several phthalocyanines were investigated under oxidative atmosphere. For these samples, temperature dependence of conductivity was examined, and linear relationships were obtained between logarithm of conductivity at 150℃ and activation energy. These results were expressed byσ=σ0*･exp(E/kTo)exp(-E/kT), where T0 and σ0* were influenced by the crystal form and the central metal species.


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13
BaTiO3系複合酸化物による容量型 CO2センサ

 石原達己・米谷和浩・滝田祐作

大分大工

BaTiO3 MIXED OXIDE CAPACITOR AS A CARBON DIOXIDE SENSOR

 Tatsumi ISHIHARA, Kazuhiro KOMETANT, Yusaku TAKITA

Department of Environmetal Chemistry and Engineering, Faculty of Engineering, Oita University
Oita 870-11, Japan

Mixed oxide capacitor containing BaTiO3 are studied as the sensor for CO2 detection. Mixture of BaTiO3 and PbO gave the large capacitance change on exposure to CO2. Sensitivity to CO2 and the optimum operation temperature were strongly dependent on the oxide combined with BaTiO3. The elements containing basic oxides such as MgO and CaO were very sensitive to CO2, but required the operation temperature higher than 1073 K. Among the elements investigated in this study, CuO-BaTiO3 exhibited the highest sensitivity to CO2. Capacitance of the CuO-BaTiO3 element is insensitive to CH4 and H2, but sensitive to CO2 and CO. Eighty percent of the steady response on CuO-BaTiO3 was attained within 25 S after exposure to the air containing 2％ CO2. Capacitance of the element was restored to the original level within 80 S after the introduction of the pure air. Mixed oxide capacitor consisted of BaTiO3 and metal oxide is one of the prominent materials for CO2 sensor based on the capacitance change.


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14
シリコン樹脂を用いた容量型湿度センサ

 岡本利治・松口正信・定岡芳彦・酒井義郎

愛媛大工

CAPACITIVE-TYPE HUMIDITY SENSOR USING SILICON RESIN

 Toshiharu OKAMOTO, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Indusutrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan

Capacitive-type humidity sensor using ladder type polysiloxane having phenyl and methyl groups was examined. The replacement of methyl group by phenyl group induce the decrement of the sensitivity. The sensitivity defined as the ratio of capacitance at 90％RH to that at 0％RH for the ladder type polysiloxane film is greater than 1.05, which is greater than that of the linear type film. The capacitance decreases with temperature and its temperature coefficient of the ladder type films much smaller than that of the linear type.


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15
PEG-K2CO3複合膜の電気特性に対する炭酸ガス及び水蒸気の影響

 玉井和彦・松口正信・定岡芳彦・酒井義郎

愛媛大工

THE EFFECT OF CARBON DIOXIDE AND WATER VAPOR ON THE ELECTRICAL PROPERTIES OF PEG-K2CO3 COMPLEX FILMS

 Kazuhiko TAMAI, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama 790, Japan

the effect of CO2 gas on the electrical conductivity of polyethylene glycol (PEG)-K2CO3 complex films was investigated as a function of molecular weight of PEG. The electrical conductivity of these complex films was decreased by exposing to CO2 gas. The sensitivity to CO2 gas increased with a decrease in molecular weight of PEG. The triethylene glycol (TEG)-K2CO3 complex film exhibited the largest sensitivity and reversible response at 0％RH at ambient temperature. In addition, the stability of the hybrid films was improved by incorporating the TEG-K2CO3 solution in PEG6000 film.


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16
相互侵入網目構造を有するポリマーアロイを用いた耐水性湿度センサ（II）

 平山和子・松口正信・定岡芳彦・酒井義郎

愛媛大工

WATER RESISTIVE HUMIDITY SENSOR COMPOSED OF INTERPENETRATING POLYMER NETWORKS. (II)

Kazuko HIRAYAMA, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime 790, Japan

A humidity sensor using the film of a interpenetrating polymer networks (IPNs) was prepared. The IPNs film was composed of crosslinked HMPTAC and crosslinked HEMA. The sensitivity of this humidity sensor was comparable to that of HMPTAC homopolymer film. The deterioration by immersion in water was dramatically improved by application of the IPNs technique. It seems that this is due to the high compatibility of the HMPTAC and HEMA.


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17
アンペロメトリー型膜被覆イオン選択性電極 ―分極性ニトロフェニル誘導体/水界面 ISEの特性

 澤田恵夫・大西伊郎・小川康明・大堺利行*・千田　貢**

近畿大工、神戸大教養*、京大農**

AMPEROMETRIC MEMBRANE-COVERED ION SELECTIVE ELECTRODES
―POLARIZABILITY OFο-NITROPHENYL ETHER/WATER INTERFACES

 Shigeo SAWADA, Ichiro OONISHI, Yasuaki OGAWA, Toshiyuki OSAKAI* and Mitsugi SENDA**

Faculty of Science and Technology, Kinki University Higashiosaka-shi, Osaka 577, Japan

*College of Liberal Arts, Kobe University
Nada-ku, Kobe 657, Japan

**Faculty of Agriculture, Kyoto University
Sakyo-ku, Kyoto 606, Japan

Amperometric membrane-covered ion selective electrodes (ISE's) with the polarizable oil/water interface have been prepared by the use of o-nitrophenyloctylether (NPOE), o-nitrophenylphenylether (NPPE) and 2-fluoro-2'-nitrodiphenylether (FNDPE) as the solvent of oil phase. The voltammetric behavior of the ISE's has been investigated in detail. The results have shown that the polarizable potential ranges for the o-nitrophenyl ethers are equal to or wider than those for nitrobenzene (NB) and 1,2-dichloroethane (DCE) which have been so far used in measurements of this kind. The ISE's prepared with the o-nitrophenyl ethers, NB, and DCE show somewhat different ion selectivities from each other. A pulse amperometric technique is also applicable to the ISE's using the o-nitrophenyl ethers. In conclusion, the new solvents examined here appear to be promising for the development of amperometric ISE's.


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18
電極不活性アニリン誘導体重合膜のヨウ素イオンに対する選択的応答

 矢野　潤

山梨大教育

SELECTIVE RESPONSE OF AN ELECTROINACTIVE POLY (ANILINE DERIVATIVE) TO DISSOLVED IODIDE ION

 Jun YANO

Faculty of Education, Yamanashi University
Kofu, Yamanashi 400, Japan

Poly(N.N-di-n-butylaniline) (PBA) was easily obtained by the electroxidation of N.N-di-n-butylaniline in acidic media. Only the redox wave of I- was observed on the PBA coated electrode, though those of Fe(edta)-, Fe2+ [Fe(CN)6]4-, Mn2+, hydroquinone, Tl+, and Br- were not observed on it. PBA itself was almost an insulator but it became conducting only when it underwent the special treatment with I-. PBA had an anion exchange ability, due to its structure with positively charged sites as quaternary ammonium groups in the polymeric backbone. The PBA coated electrode which incorporated the oxidized products of I- electrostatically showed selective potential response to dissolved I-.


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19
ポリアニリン膜の水素イオン感応性の評価（I）

 竹中　豊・春山隆之・境　浩司

オムロン

pH SENSOR USING POLYANILINE FILM (I)

Yutaka TAKENAKA, Takayuki HARUYAMA and Koji SAKAI

Tsukuba Laboratory, Omron Corporation
45 Wadai Tsukuba, Ibaraki 300-42, Japan

The dependence of a potential and/or absorbance with a polyaniline (PAn) film electrode on the value of pH of the solution was investigated. Measurements of potential vs SCE and absorbance vs air were made on a system of PAn/NESA/ITO/glass in standard buffer solutions such as pH 1.68, 4.01, 6.86, 9.18, and 10.02 at room temperature. The obtained results were as follows: mV=-75.1pH +560 (the correlation coefficient -0.999), Abs (800 nm) =-0.21 pH +2.47 (-0.996), Abs (420 nm)=-0.10 pH +1.42 (-0.999). These results indicated that a PAn film could be used as a Potentiometric pH sensor and a Optical pH sensor. A PAn film could be repeatedly used by acid rinse and water rinse as a pH sensor.


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20
ポリアニリン膜の水素イオン感応性の評価（II）

 竹中　豊・春山隆之・境　浩司

オムロン

pH SENSOR USING POLYANILINE FILM (II)

Yutaka TAKENAKA, Takayuki HARUYAMA and Koji SAKAI

Tsukuba Laboratory, Omron Corporation
45 Wadai Tsukuba, Ibaraki 300-42, Japan

The effect of the addition of Cl- or NO3- on the potential with a polyaniline (PAn) film was investigated. Measurement of potential vs SCE with a PAn film was made on a system of PAn/NESA/ITO/glass in a standard buffer solution of pH 6.86 in addition to KCl, NaCl, KNO3, and NaNO3 at room temperature. The deviation of the value of pH due to the change of the total ionic strength of the solution was corrected. The potential with a PAn film was in proportion to the concentrations of added electrolytes. The potential measured in a solution of 0.5M-KCl was higher by 3.5 mV than that of 0.5M-NaCl and 0.5M-NaNO3 was 2.1 mV. It may be noticed that a PAn film has a sensitivity for anions, e.g. OH-. These characteristics of a PAn film electrode, i.e. sensitive for H+ and OH-, should bring the high sensitivity such as -75 mV/pH.


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21
ポリアニリン薄膜を利用するオプティカルpHセンサ

 篠原寛明・相澤益男・碇山義人

東工大工

OPTICAL pH SENSOR USING A POLYANILINE THIN FILM

 Hiroaki SHINOHARA, Masuo AIZAWA and Yoshihito IKARIYAMA

Department of Bioengineering, Faculty of Engineering, Tokyo Institute of Technology
Ookayama Meguro-ku, Tokyo 152, Japan

pH dependent changes of optical properties of a polyaniline film have been investigated to develop a new optical pH sensor. The sensor element was prepared by chemical synthesis of a polyaniline thin film onto the top of a optical fiber. The element was attached to the top of a Y-shaped optical fiber connected to both a light source and a spectrometer to measure the fluorescence of the polyaniline thin film in real time. It was demonstrated that the fluorescence intensity depended on solution pH in the range from 1 to 7. The time-response of fluorescence intensity upon pH control corresponded to that of pH measured by a glass pH electrode.

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22
透過膜、電極、電解質を一体化させた構造の酸素センサの対極

 片倉勝己・小久見善八*・竹原善一郎*

奈良高専・京大工*

COUNTER ELECTRODES OF THE SENSOR COMPOSED OF TIGHTLY STACKED MEMBRANE/ELECTRODE/ELECTROLYTE

 Katsumi KATAKURA, Zempachi OGUMI*, Zen-ichirou TAKEHARA*

Department of Chemical Engineering, Nara National College of Technology
Yata-chyo Yamatokoriyama Nara 639-11, Japan

*Department of Industrial Chemistry, Kyoto University
Sakyou-ku, Kyoto 606, Japan

Anode reactions of the oxygen sensor composed of tightly stacked membrane/Pt-electrode/Nafion have been discussed in the two-electrode arrangement. Ag-HCl, Pb-H2SO4, and Pt-H2SO4 and Pt deposited directly on the Nafion are examined as an anode. The Ag-HCl system behaves as a counter electrode of a galvanic sensor. Pt and Pb require the external applied voltage of 1.2 V to work under mass-transfer-limiting conditions. In all systems, response time is longer than that in the three-electrode system under potentiostatic operation. H2O supply and properties of coating layers formed on the counter electrode are important for stable operation of two-electrode systems.


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23
ガス透過性機能性膜電極のアルシンに対する応答特性

 船崎菜穂美・浅野泰一

電気化学計器

BASIC PROPERTIES OF CATALYTIC ELECTROCHEMICAL SENSOR TO ARSINE

Naomi FUNAZAKI and Yasukazu ASANO

DKK CORPORATION
Musashino-shi, Tokyo 180, Japan

A catalytic electrochemical gas sensor to arsine was developed and its performances were investigated. The sensor consisted of a working and a counter electrodes and an inner solution was filled between the two electrodes. The working electrode was a gas permeable catalytic membrane. The catalytic membrane was prepared by baking a PTFE membrane impregnated with a Nafion solution suspended the novel metal catalyst. The kinds of the catalyst and its particle size affected the sensitivity and the selectivity of the sensor. The sensor showed high selectivity to arsine against carbon monoxide, hydrogen and nitrogen monoxide. The selectivity coefficients relative to other gases were 10-6 for hydrogen, 10-6 for acetone, 10-6for toluene, 10-5 for carbon monoxide, 10-4 for ethanol, 0.27 for sulfur dioxide, and 0.25 for nitrogen oxide. The lower limit of detection was 0.01 ppm. The 90％ response time was about 30 s for 0.05 ppm arsine. The coefficient of variation for detection of 0.05 ppm arsine was less than 6.0％. The sensor was applied to monitoring in a room where arsine gas will be able to leak out, and it has been stable for 6 months. The sensor developed proved to be practical in use for arsine detection.


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24
プロトン導電性セラミックスを用いた高温水素センサ

 小出邦博・山本君二・矢嶋　保*・岩原弘育*

TYK研・名大工*

HIGH TEMPERATURE TYPE HYDROGEN SENSOR USING PROTON CONDUCTING CERAMICS

 Kunihiro KOIDE, Kunji YAMAMOTO, Tamotsu YAJIMA and Hiroyasu IWAHARA

Research and Development Center, TYK Corporation
3-1 Ohbata-cho, Tajimi 507

*Synthetic Crystal Research Laboratory, Faculty of Engineering, Nagoya University
Furo-cho Chikusa-ku, Nagoya 464-01, Japan

A galvanic cell type high temperature hydrogen sensor was constructed using SrCe0.95Yb0.05O3-α ceramic as a solid electrolyte and AIPO4-LaCoO3 mixture as a solid state standard material. This sensor showed stable emf in correspondence to partial pressure of hydrogen. The relation between emf and logarithms of hydrogen partial pressure was linear. Emfs were independent of steam partial pressure in the test gas below 700℃.

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給湯器の排ガス中におけるジルコニア酸素センサの出力挙動

 末益龍夫・山本秀男・石橋功成

藤倉電線

OUTPUT CHARACTERISTICS OF ZIRCONIA OXYGEN SENSOR IN EXHAUST GAS OF DOMESTIC WATER HEATER

 Tatsuo SUEMASU, Hideo YAMAMOTO and Kohsei ISHIBASHI

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

The combustion control using the limiting current type of the zirconia oxygen sensor has been examined for the purposes of improving the combustion efficiency and reducing CO and NOx concentration in the exhaust gas of the domestic water heater. In this paper, the structure of the direct insertion type of the oxygen sensor and the output characteristics in the exhaust gas of the fully pre-mixed combustion type of the domestic water heater are reported. As a result, the ambient temperature dependence of the output is very small which is 0.23％ O2 from 200℃ to 300℃ and this sensor shows high response and stable output in the exhaust gas of the domestic water heater during the experiment.


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Na+導電体を用いた NO2センサ

 岡本保朗・姚　　勝・清水陽一・三浦則雄・山添　f

九大総合理工

NO2 SENSOR USING SODIUM ION CONDUCTOR

 Yasuo OKAMOTO, Sheng YAO, Youichi SHIMIZU, Norio MIURA and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

Possibilities of NO2 sensors using Na+ conductor were investigated for detecting a small amount of NO2 in air at 200-460℃. With a sensor element of the galvanic cell; sample gas, (NaNO3+Pt) |Na+-β/β“alumina (or NASICON)|Pt (or Pt+NaNO3), air, e.m.f. responses were linear to the logarithm of the NO2 concentration in the range 13-130 ppm at 250℃. The Nernst's slope indicated a one-electron reaction of NO2 at the sensing electrode. The 90％ response time to 42 ppm NO2 was ca. 60 s. When the reference electrode was provided with NaNO3, the short-circuit current between the two electrodes was found to be directly proportional to the NO2 concentration, with a 90％ response time of ca. 60 s to 20 ppm NO2 at 250℃. It was further found that, although the operation temperature of the above element was limited up to the melting point of NaNO3 (307℃), the use of other electrode materials such as Ba(NO3)2 made it possible to stand operation at higher temperatures 400-500℃.


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プロトン導電体を用いたFET型マイクロガスセンサ

 三浦則雄・吉田宣昭・原田達朗・清水陽一・山添　f

九大総合理工

FET-TYPE MICRO GAS SENSOR USING PROTON CONDUCTOR

 Norio MIURA, Nobuaki YOSHIDA, Tatsuro HARADA, Youichi SHIMIZU, and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

An FET-type micro gas sensor using proton conductor was developed for detecting small amount of H2 in air at room temperature. The sensor element was fabricated as follows : the proton conductor paste, e.g., antimonic acid powder mixed with polyvinyl alcohol and water, was applied on the surface of an ISFET element (chip size: 0.38 x 5.8 mm, gate length: 320μｍ、channel width: 15μｍ) to form an antimonicacid thick-film (ca. 10-20μｍ), on which a suputtered Pt film was deposited as a sensing electrode. The output voltage between the Pt electrode and the source (VGS) was measured as a sensor signal under a constant drain current (ID) at 30℃.
An almost linear correlation was obtained between VGS and the logarithm of H2 concentration in the range 4-5060 ppm. The slope of the correlation, 100-150 mV/decade, was comparable to that for the non FET-type H2 sensor we previously reported. The 90％ response time to 5060 ppm H2 was as short as ca. 5 s.

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LaF3単結晶を用いた平面型酸素センサ

 桑田茂樹・三浦則雄*・山添　f*

新居浜高専・九大総合理工*

A PLANAR-TYPE OXYGEN SENSOR USING LaF3 SINGLE CRYSTAL

 Shigeki KUWATA, Norio MIURA *and Noboru YAMAZOE*

Department of Industrial Chemistry, Niihama National College of Technology
Niihama-shi, Ehime 792, Japan

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

A planar-type oxygen sensor using LaF3 single crystal (fluoride ion conductor) was developed for monitoring oxygen partial pressure at lower temperatures. The sensing electrode (Pt) and the counter electrode (Au, Ag, or Sn) were deposited on the surface of the LaF3 single crystal disc, leaving a space (0.5mm) in between. The electromotive force (EMF) of the sensor was found to vary logarithmically with oxygen partial pressure at 25℃, in accordance with the Nernst's equation, while little dependence was observed above 100℃. With no reference gas flow being necessary, this sensor element would be compatible to miniaturization as well as simplification.


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プロトン導電体/リチウムイオン導電体混合膜を用いた水素センサ

 中原　毅・佐竹和子・武内　隆

徳山曹達

HYDROGEN GAS SENSOR WITH MIXED LAYER CONSISTING OF A PROTONIC CONDUCTOR AND A LITHIUM IONIC CONDUCTOR

 Takeshi NAKAHARA, Kazuko SATAKE and Takashi TAKEUCHI

Fujisawa Research Labs., Tokuyama Soda Co.Ltd.,
2051 Endo Fujisawa-city, Kanagawa 252, Japan

A hydrogen gas sensor oparative at room temperature has been developed using a mixed layer composed of antimonic acid and lithium polymer electrolyte. The mixed layer was fabricated onto an alumina substrate by screen printing. Platinum was used as a sensing electrode and gold was adopted as a counter electrode. The gas sensing characteristics of the sensor were examined by measuring the electromotive force between the two electrodes. The gas sensitivity of the sensor was higher in the order, H2 > C2H5OH > CO > CH4 = i-C4H10. The 90% response time from air to air containing 3000ppm of H2 was less than 10 sec. Compensating elements were also developed to reduce the temperature and humidity dependence of the sensor.


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特別講演２
システム展開を指向したセンサ開発 (特別講演)

 小山内　裕

藤倉電線

SENSOR DEVELOPMENT FOR SYSTEM APPLICATIONS

 Hiroshi OSANAI

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

Sensor development in Fujikura Ltd. is briefly reported from viewpoint of system applications. The semiconductor pressure sensor and ceramic oxygen sensor have been developed by using technology derived from development of the optical fiber cable. The limiting current type of ceramic oxygen sensor is suitable for system applications thanks to its high reliability and long-term stability. The structure, characteristics and example of system application for concentrated monitoring system are introduced.


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酵素固定化電極を用いたNADHおよび L-アミノ酸のセンシング

 張　憲彰・上野明則・山田　弘・末永智一・内田　勇

東北大工

NADH AND L-AMINO ACID SENSORS USING ENZYME-IMMOBILIZED ELECTRODE

 Hsien-Chang CHANG. Akinori UENO, Hiroshi YAMADA, Tomokazu MATSUE and Isamu UCHIDA

Department of Molecular Chemistry and Engineering, Faculty of Engineering, Tohoku University
Sendai 980, Japan

NADH- and L-amino acid-sensing electrodes based on immobilized enzyme reaction have been studied. Diaphorase [Dp: EC 1.6.99.-] and/ or leucine dehydrogenase [LeuDH: EC 1.4.1.9] were immobilized on electrode surfaces by closs-linking using glutaraldehyde. In the presence of an appropriate mediator such as ferrocenyl methyl alcohol (FMA) , the regeneration of NAD+ from NADH was achieved smoothly by using Dp immobilized electrode at a mild potential. This system was applied for the amperometric detection of NADH. The current response upon addition of NADH increased linearly with NADH in the concentration range, (1×10-6 - 1×10-4M). The Dp/LeuDH coimmobilized electrode was also used for the determination of L-Leucine in the presence of FMA and NADH. The response was linear in the range of (2×10-6 - 5×10-5 M). We are now investigating the quantitative analysis of L-leucine in urine.


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EEE型グルコースセンサの応答特性の検討

 山内　繁・長井律子*・矢尾板仁・吉田泰彦*・碇山義人**

国立リハ研・東洋大工*・東工大工**

THE RESPONSE CHARACTERISTICS OF EEE

 Shigeru YAMAUCHI, Ritsuko NAGAI*, Masashi YAOITA, Yasuhiko YOSHIDA* and Yoshihito IKARIYAMA**

Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan

* Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan

** Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan

The wide dynamic range of EEE glucose sensor partly results from anomolously large apparent value of Km. The Km calculated from the calibration curve measured in a phosphate buffer solution of pH 6.8 was 49.7±1.7 mM, whereas colorimetric measurement gave the Km as 17.3 mM in a phosphate buffer solution. A reaction model is proposed taking the diffusion of glucose to be reacted in albumin and/or porosity of platinum black into account. Km value of 32.0±1.9 mM was obtained, suggesting the decrease in pH at the surface of the electrode by the dissociation of the produced gluconate.


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EEEセンサの非定常応答測定法の検討

 山内　繁・矢尾板仁・片山明秀・吉田泰彦*・碇山義人**

国立リハ研・東洋大工*・東工大工**

PULSE VOLTAMMETRIC TECHNIQUE WITH PREOXIDATION PULSE BY ENZYME EMBODIED ELECTRODE Shigeru YAMAUCHI, Masashi YAOITA, Akihide KATAYAMA*, Yasuhiko YOSHIDA* and Yoshihito IKARIYAMA**

Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan

* Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan

** Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan

Pulse voltammetric technique with enzyme-embodied electrode for glucose determination is a direct measurement method which requires no dilution of sample. Transient response by this technique, however, contains slight oxidation-current of concomitant substances other than hydrogen peroxide produced by the glucose oxidase reaction. Therefore, it has been necessary to subtract response current for blank sample.
In this paper, we have applied preoxidation pulse before measurement pulse to reduce blank response current. With the preoxidation pulse of +0.6V (vs. Ag/AgCl) for 60 s, transient current at 10 ms was observed 27μA for 5 mM glucose sample. Whereas we obtained 0.04μA for blank sample. By the preoxidation pulse, calibration with a blank sample is not necessary, and more reproducible data were obtained for glucose determination.


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コレステロールオキシダーゼと電子メディエータのポリピロール膜中への同時固定化とそのコレステロールセンサへの応用

 津田　量・梶谷芳男・米山　宏

阪大工

SIMULTANEOUS IMMOBILIZATION OF CHOLESTEROL OXIDASE AND AN ELECTRON MEDIATOR IN POLYPYRROLE FILMS AND ITS APPLICATION TO CHOLESTEROL SENSOR

 Ryo TSUDA, Yoshio KAJIYA and Hiroshi YONEYAMA

Department of Applied Chemistry, faculty of Engineering, Osaka University
Suita, Osaka 565, Japan

Simultaneous immobilization of cholesterol oxidase and ferrocenecarboxylate ions has successfully been accomplished by electropolymerization of pyrrole from aqueous solution containing both cholesterol oxidase and ferrocenecarboxylate. The resulting polypyrrole films exhibited enzymatic activity giving current response to cholesterol. Current response properties of polypyrrole films were influenced by current density and quantity of electricity during electropolymerization of pyrrole. The cholesterol sensitivity was stable for more than one week.


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補酵素と同時固定化した酵素、ポリピロール修飾電極のグルコースセンサとしての特性

 加洲教雄・木谷　晧・佐々木和夫

広島大工

SENSOR CHARACTERISTICS OF ENZYME/COENZYME/POLYPYRROLE MODIFIED ELECTRODES

 Norio KASYU, Akira KITANI and Kazuo SASAKI

Department of Applied chemistry, Faculty of Engineering, Hiroshima University
Higashi-Hiroshima 724, Japan

The effect of simultaneous immobilization of flavin coenzyme (Flavin) on sensor characteristics of Glucose oxidase (GOD)/Polyprrole (PPy) modified electrode was investigated. The GOD/Flavin/PPy electrode was prepared by electrodeposition of composite PPy film onto platinum from the solution containing pyrrole, GOD and flavin coenzyme. The sensitivity of GOD/Flavin/PPy electrode was increased about one order of magnitude over that of GOD/PPy electrode. After aging this electrode for about 5 days, its sensitivity was stable on storage of 100 days. The sensitivity of aged GOD/Flavin/PPy electrode was also stable on repetitive use. The improvement of sensitivity was mainly due to the increase of GOD activity caused by simultaneously immobilized flavin coenzyme.


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デヒドロゲナーゼ/ジアホラーゼ二分子層修飾電極

 立間　徹・味村秀士・渡辺　正

東大生研

DEHYDROGENASE/DIAPHORASE HETEROBILAYER-MODIFIED ELECTRODES

 T. TATSUMA, H. AJIMURA AND T. WATANABE

Institute of Industrial Science, University of Tokyo
Roppongi Minato-ku, Tokyo 106, Japan

Dehydrogenase/diaphorase heterobilayer-modified electrodes were fabricated by covalently derivatizing the surface of a tin oxide coated glass plate successively with diaphorase then with a dehydrogenase (glucose dehydrogenase, lactate dehydrogenase, or alcohol dehydrogenase), which reduces NAD to NADH under the presence of a substrate. These electrodes functioned at a potential of +350mV vs. Ag/AgCl and with NAD as electron mediator between dehydrogenase and diaphorase, and ferricyanide as mediator between diaphorase and the electrode. Each dehydrogenase/diaphorase electrode responded to the substrate only in the presence of NAD added; this evidences the essential contribution of diaphorase to the sensor performance.


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小型酸素電極特性への電極構成・材料の影響

 鈴木博章・菅間明夫・小嶋尚美

富士通研

EFFECT OF ELECTRODE CONFIGURATION AND MATERIALS ON THE CHARACTERISTICS OF THE MINIATURE OXYGEN ELECTRODE

 Hiroaki SUZUKI, Akio SUGAMA and Naomi KOJIMA

FUJITSU LABORATORIES LTD.,
Atsugi, Kanagawa 243-01, Japan

A miniature Clark-type oxygen electrode with a 3-electrode configuration was fabricated and its characteristics were compared with those of 2-electrode configuration oxygen electrodes whose sensitized area was similar to the 3-electrode one. 90% response time was from 20 s to 50 s. A good linearity was obtained in the oxygen concentration below 7.9 ppm at 27℃.
By using the 3-electrode configuration, the response became faster, the residual current became smaller, and linearity of the calibration curve was improved. The stability of the oxygen electrode was better than the 2-electrode configuration electrode with a Ag/AgCl anode.


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37
電子メディエータを用いるヒポキサンチンセンサ

 大熊廣一・川原浩司・赤星亮一・高橋仁志・関向修一

新日本無線・東洋大工*

MEDIATED AMPEROMETRIC BIOSENSOR FOR HYPOXANTHINE

 Hirokazu OKUMA, Kouji KAWAHARA*, Ryoichi AKAHOSHI*, Hitoshi TAKAHASHI and Shuichi SEKIMUKAI

Research and Development Laboratory, New Japan Radio co. Ltd.,
Kamifukuoka-shi, Saitama 356, Japan

*The Faculty of Engineering, Toyo University
Kawagoe-shi, Saitama 360, Japan

A hypoxanthine sensor was prepared from a xanthine oxidase immobilized by covalent binding to cellulose triacetate and a carbon paste electrode containing hydroxymethyl ferrocene as an electron transfer mediator. The xanthine oxidase membrane was fixed on the carbon paste electrode and covered with dialysis membrane. Hypoxanthine was determined amperometrically at an applied potential of +0.29 V vs Af/AgCl. The limit of detection is 6×10-7M, the relative standard deviation is 2.8% (n=28), and the response is linear up to 7×10-4M.


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38
導電性酵素膜を用いる酵素センサの作製

 石塚俊博・篠原寛明*・碇山義人*・相澤益男*

オリエンタル電気・東工大工*

FABRICATION OF A NEW ENZYME SENSOR USING ELECTROCONDUCTIVE ENZYME MEMBRANE

 Toshihiro ISHIZUKA, Hiroaki SHINOHARA*, Yoshihito IKARIYAMA* and Masuo AIZAWA*

Department of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan

* Oriental Electric Co., Ltd.
3-9-7 Nobidome Niiza-shi, Saitama 352, Japan

An effective transducer electrode for a dehydrogenase was fabricated by coating a platinum electrode with an electroconductive enzyme membrane, in which a dehydrogenase, NAD, and a mediator were co-immobilized. Reversible electron transfer between NAD and an electrode was hardly performed due mainly to the irreversible electrochemistry of NAD (P), but we solved the electrochemical problem by employing an electron mediator and immobilizing the electron transferring system with a dehydrogenase in conductive polymer membrane. In this research, we show the fabrication method of a biosensing electrode by employing alcohol dehydrogenase (ADH) or lactate dehydrogenase (LDH) with the electron transferring system of Meldola blue-NAD prepared in polypyrrole.


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39
ウルトラマイクロ電極を用いたプロトプラスト内のケミカルセンシング

 阿部孝之・松本伯夫・板橋武之・末永智一・内田　勇

東北大工

CHEMICAL SENSING AT THE ULTRAMICROELECTRODE IN A SINGLE PROTOPLAST

 Takayuki ABE, Norio MATSUMOTO, Takeyuki ITABASHI, Tomokazu MATSUE and Isamu UCHIDA

Department of Molcular Chemistry and Engineering, Faculty of Engineering, Tohoku University
Aramaki-Aoba, Sendai 980, Japan

The permeability of the cell membrane of a living cell, protoplast of Bryopsis, were determined from in-vivo amperometric measurement using an Ag ring ultramicroelectrode. The permeability coefficient of oxygen was obtained to be ca. 1.3×10-4 cm/s. The permeability coefficients of Fe(CN)63- and DCBQ determined by the same measurements were 2.5×10-7, 1.1×10-5cm/s. Respectively. The above results demonstrated that the cell membrane possesses highly selectivity of permeability to chemicals.


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40
ポテンシオメトリックタイプのプレーナ型酵素電極

 荒井真人・遠藤英樹・中嶋　聡・滝沢耕一

オムロンライフサイエンス研

DEVELOPMENT OF A PLANER-TYPE ENZYME ELECTRODE USING TiN

 Masato ARAI, Hideki ENDO, Satoshi NAKAJIMA and Koichi TAKIZAWA

17 Chudoji Minami-machi Shimogyo-ku, Kyoto 600, Japan

A planer-type enzyme electrode based on TiN was developed. Urease and Creatinine deiminase were immobilized using Glutaraldehyde and BSA on planer-type TiN electrodes and obtained linear calibration curve of Urea from 0.5 mM to 5 mM and Creatinine from 2 mM to 20 mM.


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41
パルス溶解析出法による白金黒マトリクスを利用したミクロバイオセンサ
 青柿良一・片山明秀*・吉田泰彦*・矢尾板仁**・碇山義人***・山内　繁**
職業訓練大・東洋大工*・国立リハ研**・東工大工***
MICRO BIOSENSOR UTILIZING PLATINIZED PLATINUM MATRIX BY PULSE DISSOLUTION DEPOSITION TECHNIQUE

 Ryoichi AOGAKI, Akihide KATAYAMA*,Yasuhiko YOSHIDA*,Masashi YAOITA**, Yoshihito IKARIYAMA*** and Shigeru YAMAGUCHI**

Dept. of Engineering Design, The Institute of Vocational Training
1960 Aihara Sagamihara-city, Kanagawa 229, Japan

*Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan

**Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan

***Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan

In order to prepare platinum black suitable for EEE sensors, pulse dissolution-deposition technique has been employed for making a micro platinum electrode of 20μm in diameter. With this technique platinum black of 0.11μm in diameter was easily prepared, which had no edge effect. EEE glucose sensor using this electrode demonstrated a linear response to glucose samples from 100μm to 10 mM.


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42
鮮度計測用微少バイオセンサの開発

 鈴木正康・磯部公泰**・木村　純*・軽部征夫・R.D. Schmid**

東大先端研・日本電気*・GBF**

DEVELOPMENT OF MICRO ENZYME SENSORS FOR ESTIMATION OF FRESHNESS

 Masayasu SUZUKI, Kimiyasu ISOBE**, Jun KIMURA*, Isao KARUBE and Rolf D. SCHMID**

Research Center for Advanced Science and Technology, University of Tokyo
Meguro-ku, Tokyo 153, Japan

*Environmental Protection Engineering Research Laboratory, NEC Corporation
Miyamae-ku, Kawasaki 213, Japan

**Department of Enzyme Engineering, Gesellschaft tuer Biotechnologische Forschung mbH, Braunschweig
D-3300, F.R.Germany

A micro amine- and putrescine-sensor were developed based on the immobilized enzymes (amine oxidase (EC 1.4.3.6) and putrescine oxidase (EC 1.4.3.10)) on micro planar hydrogen peroxide electrode.
The amine sensor showed rapid responses to histamine (90% response: 80s) and relationship between histamine concentration and output current increase was linear between 0.07-2.3μM, under optimal reaction conditions (pH 7.8, 37℃).
The putrescine sensor also showed rapid responses to putrescine (90% response: 40s) and could determine putrescine in the concentration range between 0.03-30μM, under optimal conditions (pH 8.0, 37℃).
Both sensors showed very high sensitivity which was adequate for freshness estimation.


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43
水晶振動子免疫センサによる尿中微量アルブミンの測定

 太田文彦・宮　好宏

日立化成茨城研

MEASUREMENT OF URINARY ALBUMIN BY ANTIBODY-COATED PIEZOELECTRIC QUARTZ CRYSTAL

 Fumihiko OHTA and Yoshihiro MIYA

Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.
Hitachi-shi, Ibaraki 317, Japan

Measurement of Urinary Albumin by antibody-coated piezoelectric quartz crystal was investigated. At-cut crystals, with a fundamental resonant frequency of 9 MHz, were mounted in a flow type cell, and the surface was directly coated with aHSA . Upon exposure to solution containing HSA, the resonant frequency decrease due to the selective binding of HSA to aHSA was observed.
By using the RI labeling method, we also investigated the relationship between the frequency change and the amount of HSA adsorbed on the surface of quartz crystal. Then, a frequency change of approximately 0.64 Hz for each 1 ng/cm2 of HSA was observed.


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44
抗体固定化磁気微粒子を利用した抗原のセンシング

 中村徳幸・松永　是

東農工大工

ALLERGENSENSING BY ANTIBODY IMMOBILIZED MAGNETIC PARTICLES

 Noriyuki NAKAMURA and Tadashi MATSUNAGA

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

We have developed a novel immunoassay method using bacterial magnetic particles for the sensing of allergen. Fluorescein isothiocyanate (FITC) conjugated anti immunoglobulin E (IgE)-bacterial magnetic particles were prepared. The fluorescence quenching caused by aggregation of FITC-anti IgE-bacterial magnetic particle conjugates was measured by the fluorescence spectrophotometer. The fluorescence intensity became constant after a 15 min incubation. The relative fluorescence intensity decreased with increasing allergen concentration. The use of antibody immobilized magnetic particles for fluoroimmunoassay allows easier handling of the separation and aggregation steps.


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45
化学発光を利用したフロー式バイオセンサの設計

 中田俊秀・鈴木雅博・赤池敏宏*

エクォス・リサーチ、東農工大工*

DESIGN OF FLOW-TYPE CHEMILUMINESCENCE BIOSENSOR

 Toshihide NAKATA, Masahiro SUZUKI and Toshihiro AKAIKE

EQUOS RESEARCH LTD.
2-19-12 Soto-kanda Chiyoda-ku, Tokyo 101, Japan

*Faculty of Technology, Tokyo University of Agriculture and Technology
2-24-16 Nakamachi Koganei-shi, Tokyo 184, Japan

We studied flow-type biosensor, which contained a photomultiplier as transducer. At sensing part of this sensor system, a transparent teflon tube was installed spirally on the face of photomultiplier, and a nylon string on which enzyme catalyzing luminescent reaction were immobilized, was inserted into this teflon tube. Once the injected sample solution containing luminescent reagents was flown through the sensing part, quick measurement of luminescence generated was made.
As an application of this sensor system, at first, we tried the detection of hydrogen peroxide, with horse radish peroxidase (POD) immobilized on the nylon string. And secondly, D-glucose was measured by immobilizing both POD and glucose oxidase (GOD) on the nylon string. Optimal condition of the immobilization of enzyme, the ratio of the activity of two enzyme, etc. was examined from the vies point of design of flow-type chemiluminescence glucose sensor. By using this sensor, 10-8〜10-4M H2O2 and 10-4〜10-2 M glucose were determined.


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46
固定化酸性ウレアーゼを利用する酵素サーミスタ

 佐藤生男・赤羽正志

神奈川工科大

AN ENZYME THERMISTOR USING IMMOBILIZED ACID UREASE

 Ikuo SATOH and Masashi AKAHANE

Department of Chimical Technology, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino Atsugi-shi, Kanagawa-ken 243-02, Japan

Acid urease immobilized onto porous glass beads with controlled pore size is packed into a small plastic column. The biosensing system for urea is assembled with the enzyme column and a flow-calorimetric device (so-called enzyme thermistor). The heat evolved in enzymatic hydrolysis of urea is microcalorimetrically monitored with the device. The calibration graph was linear up to 2.0 mM urea for 1.0-mL samples. The relative standard deviation for 1.0 mM urea was 1% (n=10). The assay took 6 min.


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47
グルコースFIA検出素子の作製と特性評価

 池田　信・大坂武男・小山　昇

東農工大工

FABRICATION AND CHARACTERIZATION OF GLUCOSE FIA DETECTOR

 Shin IKEDA, Takeo OHSAKA and Noboru OYAMA

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

The characterization of an immobilized enzyme chemically modified electrode(IECME) as a glucose sensor for flow injection analysis (FIA) was conducted. The electrode substrate was coated with two kinds of polymeric films, that is, firstly with a cobalt tetrakis (o-aminophenyl) porphyrin polymer (poly-CoTAPP) film with the capability of electrocatalytic reduction for O2, secondly with glucose oxidase (GOx) film. The IECME showed a reproducible response for each injection of glucose solution. The response depended on glucose concentration, amount of Gox confined in the enzyme film and carrier flow rate. The sensor characteristics of the IECME were unaffected by interference (ascorbic acid etc.) and a reproducible response was obtained for human serum samples. The IECME showed long-term stability (more than 1 month).


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48
マルチチャンネル電気化学検出器のHPLCへの応用

 青木　純・末永智一・内田　勇

東北大工

APPLICATION OF MULTICHANNEL ELECTROCHEMICAL DETECTOR TO HPLC SYSTEM

 Atsushi AOKI, Tomokazu MATSUE and Isamu UCHIDA

Department of Molecular Chemistry & Engineering, Faculty of Engineering, Tohoku University
Aramaki-Aoba Aoba-ku, Sendai 980, Japan

A multichannel electrochemical flow-through detector with a microelectrode array was fabricated and applied to high performance liquid chromatography (HPLC). The array consisted of an assembly of 16 independent microband electrodes held at different potentials by a multipotentiostat. The current flowing in each microband electrode was collected in a computer to show 16 channel three-dimensional results. The 80 channel detection was performed by applying a 5-step potential staircase to the individual electrodes in order to obtain a high potential resolution. This system was applied to detect some electro-chemical species in new born calf serum.


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49
フロー型バイオセンサにおける２成分測定ソフトウェアの開発

 橋爪義雄・刈米昭夫・林　隆造

神崎製紙研

COMPUTER-ASSISTED FIA SYSTEM WITH ENZYME ELECTRODES TO MEASURE TWO COMPONENTS SIMULTANEOUSLY

 Yoshio HASHIZUME, Akio KARIYONE and Ryuzo HAYASHI

Kanzaki Paper Mfg. Co., Ltd., R&D
4-3-1 Jokoji Amagasaki, Hyogo 660, Japan

Computer-assisted FIA system with two enzyme electrodes was studied. Strategies of Peak top detection and pump noise reduction were also discussed. In order to get high sampling frequency, peak heights were used as response of each electrodes. The sampling rate of 60 h-1 could be achieved. For example, this system was applied to determination of glucose/sucrose concentrations simultaneously. Sucrose concentration was estimated by the response which subtructed the glucose contribution to sucrose electrode in which GOD, invertase and mutarotase were co-immobilized. This method could be applied to determine each concentration of glucose and the related disaccharides in mixture.


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50
グルコース・アルコール同時計測システムの開発

 林　隆造・刈米昭夫・橋爪義雄

神崎製紙研

SIMULTANEOUS DETERMINATION OF GLUCOSE AND ETHANOL WITH ENZYME ELECTRODE AND REACTOR

 Ryuzo HAYASHI, Akio KARIYONE and Yoshio HASIZUME

Kanzaki Paper Mfg. Co., Ltd., R&D
4-3-1 Jokoji Amagasaki, Hyogo 660, Japan

FIA system for simultaneous determination of glucose and ethanol was investigated. The FIA system consisted of single-line manifold. An enzyme electrode immobilized glucose oxidase (GOD, EC: 1.1.3.4) and a column reactor immobilized alcohol oxidase (AOD, EC: 1.1.3.13) were used. Temperature and pH dependence of the immobilized AOD activity was discussed. AOD immobilized covalently on fire-brick showed excellent long-term stability. The system was optimized to use two immobilized enzymes under the same condition. The sampling rate was 60 h-1. The glucose and ethanol contents in alcoholic beverages determined by this system agreed well with the results by conventional methods.


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