Proceedings of the 24th Chemical Sensor Symposium
March 26-28, 1997

感光性ポリイミドシリコーン膜を用いた容量型湿度センサ

松口正信, 藤井清治, 酒井義郎

愛媛大工

A CAPACITIVE TYPE HUMIDITY SENSOR USING PHOTOSENSITIVE POLYIMIDE PRECURSOR

Masanobu MATSUGUCHI, Seiji FUJII and Yoshiro SAKAI

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

A capacitive type humidity sensor was prepared using photosensitive polyimide precursor (KIS). Characteristics of this sensor were influenced by the preparation conditions of the film. The optimum sensor showed a good initial performance on the following points; (1) linear change of the electrical capacitance with relative humidity, (2) small hysteresis, (3) little temperature coefficient. Also, because of the inherent chemical resistance of the present polyimide film, good sensor stability when subjected to acetone vapor was demonstrated. The sensing film was formed on the substrate according to the common lithography technique in semiconductor industries. The method may therefore allow the fabrication of sensors using IC technology.

種々の高分子複合膜を用いる湿度センサ

椎木　弘, 藤井明博, 中山雅晴, 小倉興太郎

山口大工

HUMIDITY SENSOR USING VARIOUS POLYMER COMPOSITES

Hiroshi SHIIGI, Akihiro FUJII, Masaharu NAKAYAMA and Kotaro OGURA

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

Composite films consisting of poly(o-phenylenediamine) (PoPD), poly(o-aminophenol) (PoAP), poly(m-phenylenediamine) (PmPD) or poly(o-toluidine) (PoTd), and poly(vinylalcohol) (PVA) were prepared by the chemical polymerization method. The electrical conductivities of the PoPD/PVA and PoAP/PVA composite films were linearly related to the atmospheric humidity, but the linearity did not hold for the PmPD/PVA and PoTd/PVA. A change in conductivity of the composite film upon the humidity variation was closely related to the transformation between salt and base structures of the conducting polymer.

プロトン酸をドープしたポリアニリンの伝導度に及ぼすアンモニアの影響

松村浩二, 松口正信, 酒井義郎

愛媛大工

EFFECT OF AMMONIA ON THE CONDUCTIVITY OF POLYANILINE DOPED WITH PROTON ACIDS

Koji MATSUMURA, Masanobu MATSUGUCHI and Yoshiro SAKAI

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

A resistive type ammonia gas sensor was fabricated using soluble polyaniline prepared by　chemical oxidation at low temperature. The conductivity of polyaniline reversibly decreased by exposing the air containing dilute ammonia. The conductivity and the sensitivity depend on the species of proton acid which was doped in polyaniline, Among the proton acids, sulfuric acid is the most effective dopant but poly(2-acrylamide-2-methylpropane sulfonic acid) is the most preferable because of its long term stability. When the ammonia concentration is high, a part of the change in conductivity is irreversible. It was found that this irreversible change is due to the formation of a salt between the dopant acid and ammonia. A QCM type sensor was also prepared with the same polyaniline.

TPPH₂誘導体の光学的性質とHClガスセンサへの応用

北川貴啓, 田中一成^*, 青野宏通, 定岡芳彦

愛媛大工, （株）荏原総合研究所^*

OPTICAL PROPERTIES OF TPPH₂ DERIVATIVES AND ITS APPLICATION TO HCl GAS SENSOR

Takahiro KITAGAWA, Kazunari TANAKA^*, Hiromichi AONO and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University
Bunkyo-cho-3, Matuyama, 790-77
^*Center for Advanced Technology, Ebara Research Co.,Ltd.
2-1, Honfujisawa 4-chome, Fujisawa, 251, Japan

Optochemical-type HCl gas sensor using thin film of polymerized tetraphenylporphin derivatives was investigated. The polymerization was effective to prevent the agglomeration by interaction between the molecules. This polymer having high free volume of had high sensitivity even for sub-ppm HCl and a fast response, because of easy for HCl gas diffusion into the film. The response time was improved by addition of dioctylphthalate as a plasticizer.

高分子膜を塗布した水晶振動子式ガスセンサによる酒の種類判別

近藤浩一, 山本　創, 堂上長則, 羽原正秋, 森田　崇, 筒口善央, 南戸秀仁

金沢工業大学材料科学研究センター・石川県工試^*

DISCRIMINATION OF AROMAS FROM SEVERAL KINDS OF ALCOHOL USING POLYMER-RESIN-FILM-COATED QUARTZ RESONATOR SMELL SENSOR

Kouichi KONDOU, Hajime YAMAMOTO, Naganori DOUGAMI, Masaaki HABARA, Takashi MORITA, Yoshiteru DOUGUCHI^* and Hidehito NANTO

A.M.S.R&D.Center,Kanazawa Institute of Tech.
7-1 Oogigaoka, Nonoichi-machi, Ishikawa 921, Japan
Indust.Res.Institute of Ishikawa^*
1 Tomizu-machi, Kanazawa, 920-02, Japan

Transient response curves for aromas from several kinds of alcohol such as Fruit Liquor(8[%]), Wine(14[%]), Japanese Sake(15[%]) and Whisky(43[%]) are observed using quartz-crystal-resonator gas sensor coated with synthetic-resin-film(acrylic resin, alkyd resin or urethane resin). The pattern recognition analysis using principal component analysis or neural network analysis is carried out using four parameters which characterize the transient response curves. The recognition probability of neural network for four kinds of alcohol is 100[%] for 20 trials.

複合酸化物を用いた高温作動型NO_xセンサ

藤田弘輝, 石原達己, 西口宏泰, 滝田祐作

大分大工

CAPACITIVE TYPE NO_x SENSOR OPERABLE AT HIGH TEMPERATURE

Hiroki FUJITA, Tatumi ISHIHARA, Hiroyasu NISHIGUCHI and Yusaku TAKITA

Department of Applied Chemistry, Facutly of Engineering, Oita University
Dannoharu 700, Oita 870-11, Japan

Capacitive type NO sensor which is operable at high temperature was investigated in this study for monitoring NO in flue gases from gasoline engine vehicle. Although the high sensitivity is obtained at temperature lower than 400℃, it is negligibly small on the large part of mixed oxide examined. On the other hand, BaSnO₃ or SrSnO₃ mixed with WO₃ exhibits the high sensitivity at the temperature higher than 500℃. In particular, mixed oxide capacitor of SrSnO₃-WO₃ exhibited the high sensitivity to NO at 550℃. Since the capacitance of this oxide increased with increasing NO concentration, in the range from 10 to few 1000 ppm. NO concentration can be evaluated with the capacitance of the element. Furthermore, the capacitance of SrSnO₃-WO₃ is less sensitive to CO₂, H₂O and CO comparing that to NO. Consequently, mixed oxide of SrSnO₃-WO₃ is promising for the capacitive NO sensor operable at high temperature.

SmFeO₃膜の電導性とNO₂ガスセンサへの利用


ステファノ・ビランチ, 青野宏通, 定岡芳彦, 坂本政臣^*

愛媛大工・山形大理^*

ELECTRICAL CONDUCTIVITY AND APPLICATION TO NO₂ GAS SENSOR FOR SmFeO₃ THICK FILM

Stefano VILLANTI, Hiromichi AONO, Yoshihiko SADAOKA and Masatomi SAKAMOTO^*

Department of Materials Science and Engineering, Faculty of Engineering, Ehime University
Matsuyama, 790-77, Japan
^* Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
Yamagata 990, Japan

The thick films of SmFeO₃ were prepared from a mixture of fine particles of SmFeO₃ and α-terpineol as an additive. The sinterability, the electrical conductivity, and the sensing characteristics for NO₂ gas were examined. Mechanical strength of the sintered film is enhanced by using α-terpineol. Electrical conductivity and its activation energy in nitrogen, air and NO₂ are influenced by an addition of α-terpineol. It seems that a stoichiometry of the surface of SmFeO₃ particles is influenced by its content.

大気動態計測における化学センサー

内山政弘, 福山　力

国立環境研究所

CHEMICAL SENSOR AND ATMOSPHERIC MEASUREMENT

Masahiro UTIYAMA and Tsutom FUKUYAMA

Atmospheric Environmental Division, National Institute for Environmental Studies
Tukuba-shi, Ibaraki 305, Japan

The sources of the air pollution materials are spreading out globally. And, the air pollution materials come to extend over the border. To understand the realities of such air pollution, a construction of global and high density measurement network is demanded. However, current atmospheric chemical measurement equipments cannot appropriately deal with this external demand. The appearance of battery driven gas sensor with lightness and robustness is very significant for future atmospheric chemistry, although at present the sensitivity does not reach the lower bound of atmospheric environmental density. The development of chemical sensor for SO₂, NO_x, O₃, and for non-methane hydrocarbon with sensitivity higher than 100 ppb is hoped for. It is also desirable for the sensor to have 10 Hz or more response.

低消費電力型メタンセンサ

井澤邦之, 西村美紀, 大戸亀久美, 井上智弘, 中原毅, 松浦吉展, 麻生功

フィガロ技研(株)

LOW POWER CONSUMPTION METHANE SENSOR

Kuniyuki IZAWA, Miki NISHIMURA, Kikumi OTO, Tomohiro INOUE, Takeshi NAKAHARA, Yoshinobu MATSUURA and Isao ASO

Figaro Engineering Inc.,
1-5-11 Senbanishi, Minoo-shi, Osaka 562, Japan

For natural gas leak detectors for residential use, a sensor with low power consumption and high selectivity to methane is desirable. In order to reduce the power consumption, sensing material and RuO₂ heater were formed on an alumina substrate(1.5×1.5mm) by thick film printing process. The power consumption of 270 mW was achieved for working temperature at 440℃, which is one third of the power requirement for conventional sensors. To obtain high selectivity to methane, four kinds of sensing materials were evaluated; Material A: 1.5wt%Pd-SnO₂, Material B: 1.5wt%Pt-SnO₂, Material C: Mixture of materials A and B, Material D: Double layer with material B formed on the A layer. As a result, the material D showed the most excellent selectivity and sensitivity to methane.

酸化スズガスセンサの焼結時間の電気的特性に及ぼす影響

中川英元, 土屋雅裕, 朝倉祝治, 福田健三, 高橋祥夫^*, 重盛徹志^*

横浜国大・工学部, 新コスモス電機^*

EFFECTS OF CALCINATION TIME ON ELECTRICAL CHARACTERISTICS OF SnO₂ GAS SENSING MATERIAL

H. NAKAGAWA, M. TSUCHIYA, S. ASAKURA, K. FUKUDA,　S. TAKAHASHI^* and T. SHIGEMORI^*

Dept. of Mater. Sci. & Chem. Eng., Yokohama Nat'l Univ., New Cosmos Electric Co. Ltd.^*

Electrical characteristics of SnO₂ sintered gas sensors with different calcination times of a same calcination temperature were investigated. The crystal growth is a rather rapid process, the primary crystal size of over 80 % of its final size was attained in first 15 minutes. However TEM observation indicated several hours are necessary for the crystal facets to dominate. The electrical resistivity increased with the prolonged calcination times, and their operation temperature dependence varied. The results could be interpreted by the slow relaxation process of lattice oxygen vacancies which act as donors. Despite large variations in conductivities, the gas sensing characteristics are rather similar, suggesting the similar nature of adsorbed oxygen reactions on surfaces of different morphologies with ethanol gas.

Pd-adsorbed SnO₂表面に関する半経験的バンド計算(I)


松嶋茂憲, 原口俊秀, 小林健吉郎^*, 白方　祥^*, 香山正憲^**

北九州高専・愛媛大工^*・大工研^**

SEMI-EMPIRICAL BAND CALCULATION OF Pd-ADSORBED SnO₂ SURFACE (I)

Shigenori MATSUSHIMA, Toshihide HARAGUCHI, Kenkichiro KOBAYASHI, Sho SHIRAKATA and Masanori KOHYAMA

Department of Chemical Engineering, Kitakyushu National College of Technology
Kitakyushu-city, 803, Japan

The electronic structure of Pd-adsorbed SnO₂ surface is calculated by using a semi-empirical tight binding method. Some peaks appear newly near the bottom of the conduction band. The peak at -8.35 eV is attributable to anti-bonding states arising from the admixture of 4d (Pd) and 2p (O) orbitals. In addition, non-bonding d states of Pd are located at -9.2 eV. The Fermi level is calculated to be -8.37 eV. This means that electrons are present in not only non-bonding d-states but also anti-bonding states arising from p-d hybridization.

接触燃焼式ガスセンサのPt-Pd担持触媒の構造

河田泰之, 市村剛重, 津田孝一

富士電機総合研究所　機能デバイス研究所

Pt-Pd CATALYST STRUCTURE OF CATALYTIC-COMBUSTION TYPE GAS SENSOR.

Yasuyuki KAWADA, Takeshige ICHIMURA and Koichi TSUDA

Functional Device Lab. Fuji Electric Corporate R&D Ltd.
2-2-1 Nagasaka, Yokosuka-shi, Kanagawa, Japan

Catalytic-combustion type gas sensors for gas leak alarms have been prepared using Pt-Pd catalytic beads. Pt-Pd catalytic structure on active aluminium oxide was investigated by XRD,XPS,FE-TEM and EDX. Both Pt and PdO peaks were observed in XRD patterns, whereas Pt peak was not detected by XPS. We prepared Pt-Pd catalysts with various compositions supported on active aluminium oxide beads, and measured XPS Pt spectra. Pt peak intensity determined by XPS decreased with the increase of PdO. Surface sensitive EDX spectrum showed Pd segregation at the catalyst particle surface. By these experimental results, the Pt catalyst particles are assumed to be covered by PdO.

Nb₂O₅系バリスタ型ガスセンサのH₂ガス検出特性

金沢英一, 高尾雄二^*, 清水康博, 江頭　誠

長崎大・工, ・海洋^*

H₂ SENSING PROPERTIES OF Nb₂O₅-BASED VARISTOR GAS SENSORS

Eiichi KANAZAWA, Yuji TAKAO^*, Yasuhiro SHIMIZU and Makoto EGASHIRA

Department of Materials Science and Engineering, Faculty of Engineering, ^*Graduate School of Marine Science and Engineering,
Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan

Effects of Bi₂O₃ addition on the H₂-sensitive breakdown voltage of Nb₂O₅ have been investigated in the H₂ concentration range of 0.2-2.0% H₂ at 400℃-700℃. Nb₂O₅ itself exhibited nonlinear I-V characteristics both in air and in H₂ in the temperatures range studied. It also exhibited a shift in breakdown voltage to a lower electric field upon exposure to H₂, but its sensitivity decreased with a rise in temperature. Addition of 1.0 mol% Bi₂O₃ to Nb₂O₅ resulted in an increase in breakdown voltage in air and led to an increase in H₂ sensitivity. The breakdown voltage in air increased with increasing Bi₂O₃ contents, but H₂ sensitivity exhibited its maximum at 1.0 mol% and then decreased with increasing Bi₂O₃ contents. No visible change in grain size was induced by the addition of Bi₂O₃. However, Bi₂Nb₁₀O₂₈ phase was newly formed and its content increased with increasing the additive amounts of Bi₂O₃. From these results, Bi₂Nb₁₀O₂₈ is suggested to be responsible for the increase in the height of double Schottky barrier and to be less effective for promoting the reaction of H₂ with chemisorbed oxygen near grain boundaries. Anyway, it was revealed that the highest H₂ sensitivity was achieved at 400C with the Nb₂O₅ doped with 1.0 mol% Bi₂O₃ among the specimens tested.

NH₄⁺-Ga₂O₃を用いたアンモニアセンサへの水蒸気の影響

今中信人, 田村真治, 足立吟也

阪大工

The Water Vapor Influence to the Sensitivity of Ammonia Sensor Based on NH₄⁺-Ga₂O₃ Solid Electrolyte

Nobuhito IMANAKA , Shinji TAMURA and Gin-ya ADACHI

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

An ammonia sensor was fabricated with the combination of NH₄⁺-Ga₂O₃ and Pr₂(SO₄)₃・(NH₄)₂SO₄ applied as a solid electrolyte and a reference electrode, respectively. The sensor output was consistent with the relation derived from Nernst equation. The sensor response was accurate and reversible with the NH₃ variation. From the investigation of water vapor influence to the sensitivity of ammonia sensor, no interference with the sensitivity of the sensor based on NH₄⁺-Ga₂O₃ solid electrolyte was observed.

小型限界電流式酸素センサによる水蒸気分圧計測

鈴木隆之, 奥野辰行, 飯尾元昭, 二田穂積^*

矢崎計器株式会社, 矢崎総業株式会社^*

MEASUREMENT OF THE PARTIAL PRESSURE OF WATER VAPOR BY MEANS OF A COMPACT LIMITING CURRENT-TYPE OXYGEN SENSOR

Takayuki SUZUKI, Tatsuyuki OKUNO, Motoaki IIO and Hozumi FUTATA^*

YAZAKI METER CO., LTD. ,Gas equipment development division
23 minamikajima futamata-cho tenryu-shi SHIZUOKA 431-33, Japan
^*YAZAKI CORPORATION,Gas equipment division
1370 koyasu-cho hamamatsu-shi SHIZUOKA 431

Experimental automatic control over the desiccating processes of industrial plants is being conducted by means of measuring the partial pressure of water vapor in the high temperature atmosphere. Ceramic-type sensors are now being in use, however, they are not sufficient in terms of their response time, accuracy, and cost. Meanwhile, our laboratory, engaged in broad, practical applications of the thin film limiting current-type oxygen sensors, is also in charge of studying the feasibility of measurement of water vapor because of sensors dependence upon the partial pressure of water vapor. They prove themselves to have a fast response time which is within one second to rise up to 90% of their full responsiveness, and good linearity of their output characteristics under the high partial pressures of water vapor.

安定化ジルコニアとCdCr₂O₄を用いた高温作動型NO_xセンサ

盧　革宇, 三浦則雄, 山添　�f

九大総合理工

A HIGH-TEMPERATURE NO_x SENSOR BASED ON STABILIZED ZIRCONIA AND CdCr₂O₄

Geyu LU, Norio MIURA and Noboru YAMAZOE

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

A high-temperature NO_x sensor coupled with stabilized zirconia and a mixed-metal oxide electrode was investigated. Among twelve kinds of spinel-type oxides tested, CdCr₂O₄ was found to be the best NO_x sensing electrode material. The CdCr₂O₄-attached device showed an excellent response and recovery characteristics to both NO and NO₂ at 500-600 ℃. The EMF value of the device was almost linear to the logarithm of NO_x concentrations with a plus (for NO₂) or minus (for NO) slope. It was also observed that the device gave a good NO_x selectivity with respect to the other gases, such as H₂, CO, CH₄, CO₂ and H₂O. A sensing mechanism involving mixed potential was confirmed based on the measurements of polarization curves.

Na⁺導電体を用いた電流検出式高感度NO₂センサ

小野正樹, 盧　革宇, 島ノ江憲剛, 三浦則雄, 山添　�f

九大総合理工

A HIGHLY SENSITIVE AMPEROMETRIC NO₂ SENSOR USING Na⁺ CONDUCTOR

Masaki ONO, Geyu LU, Kengo SHIMANOE, Norio MIURA and Noboru YAMAZOE

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

A solid-state amperometric sensor for NO₂ was designed by attaching a Na⁺ conductor (NASICON) based device with an NaNO₂ layer deposited on the counter electrode. With the sensing electrode being polarized at a constant potential relative to the reference Au electrode, electric current flowing through the device under exposure to NO₂ was measured as the sensing signal. The current response was almost linear to the NO₂ concentration in the range from 10 ppb to 1 ppm at 150 ℃. The 90% response time to even 20 ppb NO₂ was ca. 60 s. The NO₂ sensitivity was hardly affected by the coexistence of CO₂ , H₂O and O₂. A sensing mechanism was proposed from the sensing characteristics obtained.

パイロクロア型酸化物電極を用いたNASICON系NO_xセンサ

清水陽一, 前田浩二

九工大工

NASICON-BASED NOX SENSOR ATTACHED WITH PYROCHLORE-TYPE OXIDE ELECTRODE

Youichi SHIMIZU and Koji MAEDA

Department of Chemistry, Kyushu Institute of Technology
1-1 Sensui-cho, Tobata, Kitakyushu 804, Japan

Solid electrolyte-based electrochemical devices fabricated with NASICON and pyrochlore-type oxide electrodes have been investigated for the detection of NO and NO₂ in the range 10-1000ppm. The elements attached with Pb₂M₂O_7-y (M=Ir, Ru) electrodes exhibited rather good performance for the potentiometric sensing of NO as well as NO₂ at 400C. The EMF responses were almost linear to the logarithm of NO or NO₂ concentration. The use of Pb₂Ru_2-xPb_xO_7-y (x=0-0.75) system as the electrode was found to show rather high sensitivity to NO and/or NO₂. Among them, the device attached with Pb₂Ru_1.5Pb_0.5O7-y electrode gave excellent NO sensing properties. The EMF changed drastically with changing the gas concentration of NO diluted in N₂ or NO diluted in O₂ and N₂ mixture with negative or positive slope, respectively , while it kept almost constant to the concentration change of NO₂, O₂ and CO₂ diluted in air.

Li-Co系複合酸化物を固体基準極として用いたCO₂センサー

張　益燦, 田川博章, 水崎純一郎^*

横浜国大環境研, 東北大科研^*

CO₂ SENSOR USING Li-Co COMPLEX OXIDE AS SOLID REFERENCE ELECTRODE

Yi Can ZHANG, HIroaki TAGAWA and Junichiro MIZUSAKI^*

Institute of Environmental Science and Technology, Yokohama National University
Yokohama 240, Japan
^*Research Institute for Scientific Measurements, Tohoku University
Sendai 980-77, Japan

A solid-state electrochemical cell of the type Pt/LiCoO₂−5 mol%Co₃O₄/Li₂CO₃(−5mol%Li₃PO₄+9wt%LiAlO₂)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, is an electrolyte, and LiCoO₂-Co₃O₄ is used as the solid reference electrode. The electromotive force (EMF) of the cell depended logarithmically on the CO₂ partial pressure in CO₂/O₂ gas mixtures at temperatures between 350 and 400℃. At 400℃, EMF reached a constant value within 1 min after the change of CO₂ partial pressure. The sensor worked stably during a test of 30days. The sensing mechanism of CO₂ was discussed together with an explanation to the stability of this sensor.

耐熱酵素グルコキナーゼを用いたISFET型グルコースセンサ及びスクロースセンサ(1)

青木一仁, 石丸雄大, 飯田武揚

埼玉大工

ISFET-TYPE GLUCOSE SENSOR AND SUCROSE SENSOR USING THERMOPHILIC GULCOKINASE (1)

Kazuhito AOKI, Yoshihiro ISHIMARU and Takeaki IIDA

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

An ion sensitive field effect transistor (ISFET) glucose sensor was constructed using an immobilized thermophilic glucokinase from a moderate thermophilic bacterium Bacillus stearothermophilus. The ISFET gulcose sensor, on which thermophilic glucokinase, hen egg white lysozyme and bovine serum albumin (BSA) were immobilized by glutaraldehyde, was able to determine the D-glucose concentration , and the glucose sensor was applied to the sucrose sensor using thermostable invertase from Candida utilis .

シリコーン制限透過膜を用いたグルコースセンサの特性改善

古澤真抄子, 松本　達, 伊藤成史

NEC資源環境技術研究所

IMPROVED CHARACTERISTICS OF AN AMPEROMETRIC GLUCOSE SENSOR WITH A SILICONE MEMBRANE

Masako FURUSAWA, Toru MATSUMOTO and Narushi ITO

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

This report describes the development of an amperometric glucose sensor coated with a silicone membrane comprising primarily polyalkylsiloxane. A sensor whose membrane contained 16 % polyalkylsiloxane was found to be capable of determining glucose concentrations ranging from 10to 1000 mg/dl. Furthermore, the membrane stabilized sensor output against changes in pH, ionic strength, and the buffer capacity of samples, making sensor capable of measuring glucose concentrations in undiluted urine samples.

グルコースセンサ／インベルターゼ固定化セル系を用いたグルコース, スクロースの同時, 迅速測定

水谷文雄, 矢吹聡一

生命工研

RAPID ASSAYS OF GLUCOSE AND SUCROSE USING A GLUCOSE-SENSING ELECTRODE COMBINED WITH AN INVERTASE-ATTACHED MEASURING CELL

Fumio MIZUTANI and Soichi YABUKI

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

Glucose and sucrose are simultaneously determined by the use of an enzyme sensor system consisting of a glucose-sensing electrode based on a lipid-modified glucose oxidase and a measuring cell that contains an invertase/mutarotase-coimmobilized layer. From the current response of the enzyme electrode after the addition of a glucose/sucrose mixture, the concentrations of the two sugars can separately be determined: the concentration of glucose (0.2μM-2.5 mM) is determined from the steady-state current increase obtained from 2-6 s after the addition of the mixture, and that of sucrose (10μM-6 mM), from the rate of current increase from 8 to 30 s after the addition. The system can be applied to the rapid determination of glucose and sucrose in food samples.

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

木内宏美, 岡崎慎司, 中川英元, 福田健三, 朝倉祝治, 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)

H. Kiuchi, S. Okazaki, H. Nakagawa, K. Fukuda, S. Asakura, T. Shigemori^* and S. Takahashi^*

Department of Material Science and Chemical Engineering, Yokohama National University,
Hodogaya-ku, Yokohama 240, Japan
^* New Cosmos Electric Co., Ltd.
Osaka, Japan

Reactivation of an amperometric organophosphate biosensor using bi-enzymatic system by PAM (2-pyridinealdoxime methochloride) was investigated. An irreversible inhibition of the sensor was observed in a presence of DDVP, and characteristics of the sensor were confirmed quantitatively. The enzyme inhibited with 4.5ppm DDVP were reactivated easily by using the low concentration of PAM. Furthermore, the sensitivity was almost stable after reactivation operation was repeated several times. However, both reactivation efficiency and sensitivity decreased with the use of high concentration of PAM. Some irreversible change in one of enzymes due to the PAM exposure of high concentration is suspected.

SPRセンサへの酵素センサの集積化

鈴木正康, 中島祐一, 森　悠丞

九工大情報工

INTEGRATION OF ENZYME SENSORS INTO THE SPR IMMUNOSENSOR

Masayasu SUZUKI, Yuichi NAKASHIMA and Yusuke MORI

Department of Biochemical Engineering and Science, Faculty of Computer, Science and Systems Engineering, Kyushu Institute of Technology,
Iizuka-shi, Fukuoka 820, Japan

The surface plasmon resonance (SPR) sensor is expected as a real-time immunosensor, and its sensing chip is a thin gold layer, which is the same as amperometric micro enzyme sensors. In this study, amperometric micro glucose and lactate sensors were integrated into the SPR sensor chip, and the integrated sensor for simultaneous measurement of human immunoglobulin G, glucose and lactate were developed. The following problems caused by the integration of immuno- and enzyme sensors were discussed: 1) Enlargement of calibration range of enzyme sensors, 2)Shortening the measurement time of the immunosensor, 3)Effect of dissociation buffer on the enzyme sensor activities. Finally the integrated sensor was applied to the model experiment of on-line monitoring of animal cell culture bioreactor.

SPRセンサを用いたモルヒネの高感度検出

緒方京子, 酒井　剛, 宇田泰三^*, 三浦則雄, 山添　�f

九大総合理工, 広島県立大^*

HIGHLY SENSITIVE DETECTION OF MORPHINE BY USING SPR IMMUNOSENSOR

Kyoko OGATA, Go SAKAI, Taizo UDA^*, Norio MIURA and Noboru YAMAOZE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
^* School of Bioresources, Hiroshima Prefectural University,
Shoubara-shi, Hiroshima 727


Highly sensitive and selective detection of morphine (MO) was realized by using an immunosensor based on surface-plasmon-resonance (SPR) phenomena. A normorphine-bovine serum albumin (NM-BSA) conjugate was prepared as an antigen. It was immobilized on the Au thin film of sensor chip by physical adsorption. The incident angle of the NM-BSA immobilized sensor increased with increasing concentration of anti-NM-BSA antibody up to ca. 5μg/ml (ppm) and then almost saturated above this concentration. The addition of MO into the antibody solution (5 ppm) was found to decrease the incident angle shift sharply because of the inhibition effect of MO. The present sensor was confirmed to detect MO very sensitively in the concentration range of 0.1-10 ng/ml (ppb).

電解重合ポリピロール/ポリイオンコンプレックス複合膜を用いた尿素センサの
フローインジェクション分析への適用

逢坂哲彌, 駒場慎一, 瀬山倫子, 藤野裕介, 佐藤生男^*

早大理工, 早大材料技術研, 神奈川工大^*

APPLICATION OF UREA SENSOR BASED ON COMPOSITE FILM OF ELECTROPOLYMERIZED POLYPYRROLE AND POLYION COMPLEX TO FLOW INJECTION ANALYSIS

Tetsuya OSAKA, Shinichi KOMABA, Michiko SEYAMA, Yusuke FUJINO and Ikuo SATOH^*

Department of Applied Chemistry, School of Science and Engineering; Kagami Memorial Laboratory for Materials Science and Technology, Waseda University
Shinjuku-ku, Tokyo 169, Japan
^* Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino, Atugi-shi, Kanagawa 243-02, Japan

We previously reported a series of potentiometric biosensors for urea based on a electropolymerized insulating polypyrrole (PPy). Among them, composite PPy with polyion complex (PIC) showed a high sensitivity for urea determination. In order to enable the fast and continuous analysis, the PPy/PIC urea sensor was applied to a flow injection analysis (FIA) system. This sensor demonstrated 85 mV decade-1 of sensitivity, and 12 samples h-1 could be assayed. Furthermore, the effect of carrier buffer concentration and pH were investigated.

ポリイオンコンプレックスを利用したpH検出型クレアチニンセンサ

駒場慎一, 天野昌朗, 逢坂哲彌, 佐藤生男^*

早大理工, 早大材料技術研, 神奈川工大工^*

POTENTIOMETRIC CREATININE SENSOR BASED ON POLYION COMPLEXES

S. Komaba, A. Amano, T. Osaka and I. Satoh^*

Department of Applied Chemistry, School of Science and Engineering; Kagami Memorial Laboratory for Materials Science and Technology, Waseda University
Shinjuku-ku, Tokyo 169, Japan
^*Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino, Atsugi-shi, Kanagawa 243-02, Japan

Potentiometric creatinine sensors were fabricated with use of the composite film consisted of the polyion complex (PIC) containing the creatinine iminohydrolase (CIH, EC 3.5.4.21) and the electroinactive polypyrrole (PPy) by electropolymerization. The PPy/PIC composite film electrode demonstrated potential response to creatinine owing to pH changes resulting from NH₃ generation of the enzymatic reaction. The sensitivities of creatinine response depended on the kinds of polyions of the PIC used for the immobilization of CIH. The lower detection limit was a few mmol dm^-3. This means that the sensor can be applied to monitor creatinine levels in the physiological range.

ラッカーゼを用いたフローインジェクションカロリメトリー

佐藤生男, 櫻井郁子

神奈川工科大学・応用化学科

FLOW-INJECTION CALORIMETRY USING A LACCASE-COLUMN

Ikuo SATOH and Ikuko SAKURAI

Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute of Technology
Atsugi-shi, Kanagawa-Ken, 243-02, Japan

Flow-injection calorimetry for L-ascorbate was investigated using laccase purified from Trametes sp.. The enzymes immobilized onto porous glass beads with controlled pore size were packed into a small polymer column. The column was attached to a temperature probe and then, housed in a flow-calorimeter. Change in temperature response attributable to injections of samples was successively monitored and displayed on a pen recorder. The exothermic responses to the injections of L-ascorbate were obtained and related to increase in its concentrations. The calibration graph was linear from 0.05 mM (M=mol/dm³ )to 5.0 mM for 0.1-mL L-ascorbate. The assaytook within 6 min or shorter. The relative standard deviation for 5.0 mM L-ascorbate was found to be 0.8%(n=10).

酵素累積膜バイオセンサー：レクチン-糖鎖結合の利用

安斉順一, 小林由佳

東北大薬

ENZYME MULTILAYER-MODIFIED BIOSENSORS BASED ON LECTHIN-SACCHARIDE INTERACTIONS

Jun-ichi ANZAI and Yuka KOBAYASHI

Faculty of Pharmaceutical Sciences, Tohoku University
Aobayama, Sendai 980-77, Japan

Enzyme multilayer-modified biosensors were prepared using a layer-by-layer deposition technique based on the specific interaction between concanavalin A (Con A) and mannose-modified lactate oxidase (LOD). The deposition behavior of the ConA/LOD multilayer was studied by quartz-crystal microbalance and UV absorption techniques. Both techniques revealed that ConA forms monomolecular layers. The output current of the lactate sensors thus prepared depended linearly on the number of the LOD layers. The lactate sensors showed a linear calibration graph to 10^-6 - 2x10^-3 ML-lactate. This sensor showed a moderate stability in the repeated use for the measurement of 1 mM L-lactate. The output current of the sensor decreased gradually after 10 days.

SPV法を用いた微小BODセンサー

菊池貴幸, 村上裕二, 阪口利文, 横山憲二, 滝上昌孝^*, 伊藤善孝^**、内田秀和^***, 勝部昭明^***, 民谷栄一

北陸先端科技大, テクノローグ^*, 新電元^**, 埼玉大工^***

A NOVEL TYPE BOD SENSOR USING SPV DEVICE

T. Kikuchi, Y. Murakami, T. Sakaguchi, K. Yokoyama, M. Takiue^*, Y. Ito^**, H. Uchida^***, T. Katsube^*** and E. Tamiya

Department of Materials Science, Japan Advanced Institute of Science and Technology Hokuriku
1-1 Asahidai, Tatsunokuchi, Ishikawa 921-12, Japan
^* Teknologue Corporation
1-26-3 Tamagawa, Chofu, Tokyo 182, Japan
^** Shindengen Corporation
10-13 Minami, Hannou, Saitama, Japan
^*** Department of Information and Computer Sciences, Faculty of Engineering, Saitama University
255 Shimo-okubo, Urawa 388, Japan

The silicon based device, Surface Photo Voltage (SPV) was applied to the fabrication of a novel BOD sensor. The SPV device is a transducer that transduces the surface potential of the device, especially pH of the solution near the surface. Trichosporon cutaneum, designated to used for BOD sensor in Japan Industrial Standard (JIS), was used as immobilized microbial. The system showed linear response to pH in the range of 2-12. The sensitivity was 9.9 nA/pH and the response time was 25 min. The calculated value of the surface potential change was 46 mV/pH, though it is calculated to be 58 mV/pH from Nernst equation. The SPV-based BOD of some waste water samples were determined. The good agreement between the SPV-base sensor and BOD5 methods were obtained for the test sample.

電気化学/圧電応答バイオセンサーの原理と応用

立間　徹, 小山　昇, D. A. Buttry^*

東京農工大工, ワイオミング大^*

ELECTROCHEMICAL/PIEZOELECTRIC DUAL-RESPONSE BIOSENSOR

Tetsu TATSUMA, Noboru OYAMA and Daniel A. BUTTRY^*

Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology
Naka-cho, Koganei, Tokyo 184, Japan
^* Department of Chemistry, University of Wyoming
Laramie, Wyoming 82071, U.S.A.

A heme peptide-modified quartz crystal oscillator is fabricated as an electrochemical/piezoelectric dual response biosensor. Binding of a ligand, such as imidazole, histidine, or histamine, to heme peptide causes inhibition of its catalytic activity, which is observed as the electrochemical response, and a mass increase monitored as the piezoelectric response. The dual response sensor can give two independent pieces of information at the same time. That is, qualitative (identification of the species) and quantitative (determination of its concentration) analyses can be made simultaneously. Simultaneous quantitative analysis for two components is also possible.

グルタミン酸イオンチャンネルセンサー：アゴニスト化学選択性の評価法

平野愛弓, Marian Rehak, 中西　淳, 河合勲二^*, 佐藤　準^**, 菅原正雄, 梅澤喜夫

東大院理, 三菱化学^*, 北大理^**

ELECTROCHEMICAL EVALUATION OF CHEMICAL SELECTIVITY OF GLUTAMATE RECEPTOR ION CHANNEL PROTEINS WITH A MULTI-CHANNEL SENSOR

Ayumi HIRANO, Marian REHAK, Jun NAKANISHI, Kunji KAWAI^*, Hitoshi SATO^**, Masao SUGAWARA and Yoshio UMEZAWA

Department of Chemistry, School of Science, The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113, Japan
^* Yokohama Research Center, Mitsubishi Chemical Co.
Aoba-ku, Yokohama 227, Japan
^** Department of Chemistry, Faculty of Science, Hokkaido University
Sapporo 060, Japan

A new method for evaluating chemical selectivity of agonists toward receptor ion channel proteins is proposed by using glutamate receptors (GluRs) ion channel proteins and their agonists N-methyl-D-aspartic acid (NMDA), L-glutamate, and (2S, 3R, 4S) isomer of 2-(carboxycyclopropyl)glycine (L-CCG-IV). Integrated multi-channel currents, corresponding to the sum of total amount of ions passed through the multiple open channels, were used as a measure of agonists' selectivity to recognize ion channel proteins and induce channel currents. GluRs isolated from rat synaptic plasma membranes were incorporated into planar bilayer lipid membranes (BLMs) formed by the folding method. The order of selectivity among the agonists for the NMDA receptor subtype was found to be L-CCG-IV L-glutamate NMDA, which is consistent with the order of binding affinity of these agonists toward the same NMDA subtypes.

長鎖アシル化ベンゾクラウンイオノフォアのK⁺選択特性評価

星野豊正, 為実茂人, 小山宗孝, 岡崎　敏

京大院工

EVALUATION OF K⁺ ION SELECTIVITY OF ACYLATED BENZO-15-CROWN-5 IONOPHORES

Toyomasa HOSHINO, Shigeto TAMEZANE, Munetaka OYAMA and Satoshi OKAZAKI

Department of Material Chemistry, Graduate School of Engineering, Kyoto University
Yoshida, Sakyo-ku, Kyoto 606-01, Japan

Acylated benzo-15-crown-5 ether ( B15C5 ) derivatives having long-chain alkanoyl substituents were synthesized and used as the ionophores for potassium ion-selective PVC membrane electrodes (K⁺-ISEs). From the measurements of their potentiometric response behavior and selectivity characteristics, it was clarified that the modification of B15C5 ionophores with alkanoyl substituents is very effective to improve not only the potentiometric response but also the selectivity for K⁺. Especially in the case of the K⁺-ISE with lauryl B15C5 ionophore, a Nernstian response was observed over the wide concentration range from 10^-1 M to 10^-6 M, and the selectivity constant over Na⁺ was as high as log K^pot_K⁺_/Na⁺ = -3.08. In order to discuss the K⁺ selectivity of these ionophores, the Raman spectra of ionophores and their metal complexes were observed. In addition, the interaction between these ionophores and K⁺ in methanol was analyzed by using 39K-NMR Spectroscopy.

ペロブスカイト型酸化物系電極のリン酸イオン検出特性

高瀬聡子, 小寺　修, 井関宏二, 清水陽一

九工大工

PHOSPHATE-ION SENSING PROPERTIES OF CARBON-BASED ELECTRODE LOADED WITH PEROVSKITE-TYPE OXIDE

Satoko TAKASE, Osamu KODERA, Kouji ISEKI and Youichi SHIMIZU

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

Carbon-based electrodes loaded with perovskite-type oxide were found to show rather good properties of amperometric sensing to hydrogen-phosphate ion. The electrodes loaded with La-Co-O system gave high activity to the electrochemical oxidation of HPO₄^2-, the anodic current was increased with increasing the concentration of hydrogen-phosphate ion at the anodic potential range above 0.2V vs. SCE. The use of hot-press method to prepare a carbon-based electrode gave drastical improvement of the amperometric sensing of the ion. The sensing current of the electrode using La_0.8Sr_0.2CoO₃ was found to be approximately proportional to the concentration of hydrogen-phosphate ion between 1x10^-3M and 1x10^-2M at +0.85V vs. SCE. The 90% response time was as short as ca.10s at 30C .

15-Crown-5を用いたアルカリ金属イオンの検出法

平川廣満, 上村忍文

鹿児島大・工

DETECTION OF ALKALI-METAL IONS BY MEANS OF 15-CROWN-5

Hiromitsu Hirakawa and Shinobu Kamimura
Department of Electrical and Electronics Eng., Faculty of Engineering, Kagoshima University
1-21-40 Korimoto-cho, Kagoshima-shi 890, Japan

Sedimentation potential (SP) of chlorides in water and methanol containing 15-Crown-5 (15C5) are measured with SP measuring apparatus. The significant differences between SP of chlorides in methanol containing 15C5 and those of not containing 15C5 are observed. SP of KCl in methanol containing 15C5 at a concentration of 1.0 M shows the biggest difference among SP obtained. In order to verify whether the SP depends on forming 15C5 complex with Na⁺ /K⁺ ion or doesn't , conductivity and intensity of photoelectron of the same solution used to measure SP are measured with conductivity meter and ESCA . As the result, it is clarified that 15C5 forms complex with K⁺ ion efficiently.

溶液希釈システムによる辛み電極の評価

川口明廣, 馬飼野信一, 祖父江和治, 櫻井正己

神奈川県産業技術総合研究所

EVALUATION OF PUNGENT SENSING ELECTRODE USING GRADUAL DILUTION SYSTEM IN FLOW ANALYSIS

Akihiro KAWAGUCHI, Shin'ichi MAGAINO, Kazuharu SOBUE and Masami SAKURAI

Kanagawa Industrial Technology Research Institute
705-1 Shimoimaizumi, Ebina-shi, Kanagawa 243-04, Japan

The instrumental error of a gradual dilution system was investigated for the determination of chloride ion concentration by using a chloride ion-selective electrode in flow analysis. We prepared a pungent sensing electrode that was modified allyl isothiocyanete on a wire tip of copper by an electro-migration and deposition method. The potential fluctuation of this electrode showed 6% relative standard deviation. This gradual dilution system makes for the high potential response of the pungent sensing electrode, easily.