金属合金電極を用いた環境イオンセンサ

九工大院工
　
○中村英靖，高瀬聡子，清水陽一

A High Performance Ion-Sensor Based on Metal-Alloy Thin-Film Electrode

Hideyasu Nakamura, Satoko Takase, and Youichi SHIMIZU

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

Metal-film based ion-sensors were tried to prepare by electrodepositing or plasma thermal spraying methods. The Co₅₈Fe₄₂ thin-film electrode showed the best EMF response characteristics among the metal thin-film sensors tested. The sensor exhibited a linear potentiometric response characteristics to hydrogen-phosphate ion at the concentration range between 1.0 x 10^-4 and 1.0 x 10^-2 M with a slope of -43 mV/decade at pH 5. The sensor showed relatively fast response, high selectivity, and sensitivity. The electrode was also stable for more than 7 weeks. Thus, the sensor seems to be successfully applied as an indicating sensor in potentiometric titration of hydrogen-phosphate ion. In addition, the Al-Mg/Fe electrode was found to be a new function as nitorate-ion sensor. The Al-Mg/Fe electrode exhibited a linear potentiometric response to nitrate ion at the concentration range between 1.0 x 10^-3 and 1.0 x 10^-2 M with 90％ response time of 1 min.

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インサーション物質を用いた全固体型イオン選択性電極の特性評価

東京理科大理

○金澤 信太郎、長谷川 卓、池田 昌隆、駒場 慎一

ELECTROCHEMICAL EVALUATION OF ALL-SOLID-STATE ION-SELECTIVE ELECTRODE BASED ON ELECTROACTIVE INSERTION MATERIAL

Shintaro KANAZAWA, Taku HASEGAWA, Masataka IKEDA, and Shinichi KOMABA

Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Shinjuku-ku, Tokyo 162-8601

We evaluated an all-solid-state ion-selective electrode prepared on a Pt electrode using insertion materials such as LiFePO₄ or Na0.33MnO₂ composite covered with a plasticized poly(vinyl chloride) (PVC) membrane containing the ionophore. LiFePO₄ and Na_0.33MnO₂ were prepared by hydrothermal synthesis and solid state reaction, respectively. The upper PVC layer is formed by casting. The lithium ion selective electrode made no potential response to redox species. The all-solid-state lithium-selective sensor based on lithium ion insertion material LiFePO₄showed stable response potential, however, the all-solid-state lithium ion selective electrode using Na0.33MnO₂ generated potential drift. The impedance of all-solid-state sensors using LiFePO₄ was lower than that of coated wire electrode with direct contact between PVC and Pt.

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ペロブスカイト型酸化物微粉末の低温合成とイオンセンサへの応用

九工大院工

〇高瀬聡子、松本俊和、清水陽一

SYNTHESIS OF PEROVSKITE-TYPE OXIDE FINE POWDER AT LOW TEMPERATURE AND APPLICATION FOR ION SENSOR

Satoko Takase, Matsumoto Toshikazu, and Youichi SHIMIZU

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

Perovskite-type oxide powders could be prepared by a polymer precursor method at relatively low temperature. But, the powder obtained at low temperature, these not have a large surface area. Therefore, we have examined the effects of ligand agents even, as a mix material at sintering process. As the results, the coexistent with metal salt at a sintering process was not only preventing the formation of agglomerate but also lowering the sintering temperature for obtained a perovskite-type oxide phase. In addition, SmFeO₃ thick film were prepared by screen printing method, application anion sensing device. It was showed good properties of amperometric sensing of the hydrogen-phosphate ion. At the concentration range is between 1.0×10^-4 M and 1.0×10^-2M.

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電界によるオンライン濃縮のＳＰＲセンサへの応用

（オムロン^a、九大産学連携センター^b、九大院システム情報科学研究院^c）
○大上 直人^a、岩坂 博之^a、川口 俊一^b、都甲 潔^ｃ，三浦 則雄^b

ＡPPLICATION OF THE ON-LINE CONCENTRATION TECHNIQUES USING ELECTRIC FILED FOR SURFACE PLASMON RESONANCE SENSOR

Naoto OHGAMI ^a, Hiroyuki IWASAKA ^a, Toshikazu KAWAGUCHI ^b,
Kiyoshi TOKO ^c, Norio MIURA ^b
a Omron Corporation, Core Technology Center, Kizugawa-shi, Kyoto, 619-0283
^b Art, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580
^c Graduate School of Information Science and Electrical Engineering, Kyushu University,
Fukuoka-shi, Fukuoka 819-0395

Concentration technique using electrophoresis and electro osmotic flow　was developed to concentrate the charged particles in the microfluidic channel. A sample solution containing the polystyrene beads or E.coli O-157:H7 was injected from the injection ports and the electric potential was applied between two electrodes fabricated in channel. Then, the concentration of the charged particles was observed between these electrodes. This technique can be expected to enhance the sensitivity of various sensors.

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Ag/Auの二層構造ヘテロコア光ファイバSPRセンサにおける感度特性

創価大学工

○鈴木 貴志、��木 圭樹、佐々木 博幸、関 篤志、渡辺 一弘

CHARACTERIZATION OF BIMETALLIC SILVER/GOLD LAYERS HETERO-CORE OPTICAL FIBER BASED ON SURFACE PLASMON RESONANCE

Takashi SUZUKIa, Keiju TAKAGIa, Hiroyuki SASAKI^a, Atsushi SEKIb and Kazuhiro WATANABE^a
aDepartment of Information Systems Science, ^bDepartment of Bioinformatics,
Faculty of Engineering, SOKA University
Hachioji-shi, Tokyo 192-8577

A hetero-core optical fiber for Surface Plasmon Resonance (SPR) has been developed to measure liquid density. Two metals are used for sensors based on SPR-silver and gold. Silver has high sensitivity and narrower resonance curve, but has a poor chemical stability. Gold displays lower sensitivity than silver, but it is chemically stable. A new structure of metallic film based on bimetallic silver/gold layers (gold as an outer layer) is suggested. The outer gold layer protects silver against oxidation and degradation. In this paper, we reported characterization of bimetallic silver/gold Hetero-Core optical fiber sensor produced several ratios. Bimetallic layers sensor displays higher sensitivity than gold, and have possibilities chemically stable because silver is protected oxidation.

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ヘテロコア型光ファイバＳＰＲセンサのＯＴＤＲによる多点屈折率計測

創価大工　

○白石　正彦、��木　圭樹、西山　道子、
佐々木　博幸、関　篤志、渡辺　一弘

MULTIPOINT REFRACTIVE INDEX MEASUREMENT OF SPR SENSOR BASED
ON A HETERO-CORE STRUCTURED BY OTDR

Masahiko SHIRAISHI^a, Keiju TAKAGI^a, Michiko NISHIYAMA^a,
Hiroyuki SASAKI^a, Atsushi SEKI^b, Kazuhiro WATANABE^a
a Department of Information Systems Science, ^b Department of Bioinformatics,
Faculty of Engineering, SOKA University
Hachioji-shi, Tokyo 192-8577

In this paper, multipoint refractive index measurement is described using SPR sensors based on hetero-core structured fiber optic technique. The hetero-core SPR sensing element is fabricated by covering its surface with a thickness of 5-nm chromium film and 60-nm gold film. Multipoint measurement system consists of two SPR sensors, whose hetero-core insertion length are employed as 5- and 10-mm, located in a single transmission optical fiber and an optical time-domain reflectometer (OTDR) to be used to measure refractive index. As a result, hetero-core insertion length has trade off between sensitivity for refractive index and the number of sensors in tandem. The proposed multipoint refractive index measurement has been successfully demonstrated using two hetero-core SPR sensors and OTDR.

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Au/Ag薄膜によるヘテロコア光ファイバSPRセンサの曲率方向特性

創価大工　

○��木　圭樹、佐々木　博幸、関　篤志、渡辺　一弘

CHARACTERIZATION OF BENDING DIRECTION ON SPR SENSOR BASED ON HETERO-CORE STRUCTURED OPTICAL FIBER WITH Ag/Au FILMS

Keiju TAKAGI^a, Hiroyuki SASAKI^a, Atsushi SEKI^b and Kazuhiro WATANABE^a
aDepartment of Information Systems Science, ^bDepartment of Bioinformatics,
Faculty of Engineering, Soka University
1-236 Tangimachi, Hachioji, Tokyo 192-8577

The strength of the hetero-core structured optical fiber sensor is approximately the same as that of normal optical fiber, and its shape can be changed flexibly. Accordingly, the sensor can arbitrarily vary the SPR condition by changing shape at the sensor portion. The present study reveals SPR spectra in differential direction of changing shape at the sensor portion which was deposited in half-faced gold or silver film. In addition, SPR spectra were revealed in differential direction of changing shape at the sensor portion which was coated with symmetric Au and Ag for sensor portion. It was shown that, as result, this SPR sensor could detect the direction and the degree of the bending.

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セリア厚膜を有するCOセンサの粒径と応答特性の関係およびCO選択性

産総研

○伊豆典哉、伊藤敏雄、西堀麻衣子、申ウソク、松原一郎

RELATIONSHIP BETWEEN PARTICLE SIZE AND RESPONSE PROPERTIES OF CO SENSOR USING CERIA THICK FILM AND ITS CO SELECTIVITY

Noriya IZU, Toshio ITOH, Maiko NISHIBORI, Woosuck SHIN, Ichiro MATSUBARA

National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8560

CO sensors using two cerium oxide thick films with various particle sizes and a Pt/alumina catalyst were fabricated, and the resistance of the thick film and the output of the sensor were investigated. The sensor using the thick film fired at 950℃ showed better sensitivity than that using thick film fired at 800℃ or 1000℃. The resistance of the thick film fired at 950℃ changed more quickly than that that fired at 800℃ or 1000℃, when air including CO was introduced. The sensor using the thick film fired at 950℃ and the Pt/alumina catalyst showed small response for combustible gases excluding CO. So it is found that the sensor has CO selectivity.

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ペロブスカイト型酸化物薄膜を用いたエチレン・アセチレンガスセンサ

(九工大院工)

○田崎智久、高瀬聡子、清水陽一

IMPEDANCE METRIC ETHYLENE AND ACETYLENE GAS SENSORS BASED ON PEROVSKITE-TYPE OXIDE THIN-FILM

Tomohisa TASAKI, Satoko TAKASE and Youichi SHIMIZU

Department of Applied Chemistry, Graduate School of Engineering,
Kyushu Institute of Technology,
1-1 Sensui-cho, Tobata, City of Kitakyushu,
Fukuoka 804-8550

The thin-film devices based on the perovskite-type oxide could be prepared by a polymer precursor method. Metal nitrates were dissolved in ethylene glycol (EG) solvent with polyvinylpyrrolidone (PVP) and acetylacetone (Acac), as a polymer additive and a coordination agent, respectively, was spin coated on an alumina substrate with Au interdigitated electrode, and finally sintered at 600〜750℃. Properties of the oxide thin-films were characterized by means of XRD, SEM and so on. The oxide thin-films thus prepared showed well crystallized and almost single phase. Thickness of the film was as thin as ca. 100〜150 nm. The sensors showed good frequency characteristics at 20 kHz for acetylene gas at 400 ℃. The SmFeO3-based device seems to be a promising sensor which has low concentration detection of acetylene gas.

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ラメラ状WO₃を用いたNO₂センサの微細構造とガス応答特性

（九大院総理工）○西山 綾、湯浅雅賀、木田徹也、島ノ江憲剛、山添 �f

Influence of microstructure on NO₂ sensing properties for lamellar-structured WO₃ sensor

Aya NISHIYAMA ^a, Masayoshi YUASA ^b, Tetsuya KIDA ^b, Kengo SHIMANOE ^b and Noboru YAMAZOE <sup>b

a</sup>Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Kasuga-shi, Fukuoka 816-8580
^bDepartment of Energy and Material Sciences, Faculty of Engineering Sciences, Kyushu University, Kasuga-shi, Fukuoka 816-8580

It is well accepted that the morphology and size of particles composing sensing layers play an important role in determining the sensing properties. It has been reported that NO₂ sensors using micro-sized WO₃ lamellas shows high NO2 sensitivity. In this study, to prepare smaller WO₃ lamellas, WO₃ was prepared by an acidification method starting from an aqueous WO₄^2- solution. By using a high acidic solution, nano-sized WO₃ lamellas particles of 100-300 and 30-50 nm in basal plane and thickness, respectively, were obtained. The as-prepared WO₃ was calcinated at various temperatures to control the particle size and microstructure of the sensing layer. It was found that the sensing film composed of smaller WO₃ lamellas showed better NO₂ sensing properties in terms of sensor response, response speed, and low electric resistance. The obtained results demonstrate the importance of the microstructure control of the NO₂ sensing layer composed of thin lamellar-structured WO₃ for efficient NO₂ detection.

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酸化セリウムを用いた抵抗変化型VSCセンサ

新コスモス電機^a、産総研^b　　

○中村俊一^a、 鈴木健吾^a、　伊豆典哉^b、 松原一郎^b

THE RESISTIVE-TYPE VSC SENSOR BASED ON CERIUM OXIDE THICK FILM

Shunichi NAKAMURA^a, Kengo SUZUKI^a, Noriya IZU^b, Ichiro MATSUBARA^b
aNew Cosmos Electric Co., Ltd.
2-5-4 Mitsuya-naka, Yodogawa-ku, Osaka, 532-0036, Japan
^b National Institute of Advanced Industrial Science and Technology(AIST),
2266-98 Anagahora, Shimo-Shidami Moriyama-ku, Nagoya, 463-8560, Japan

The resistive type VSC sensor has been developed by using cerium oxide. The sensor consists of a cerium oxide thick film on an alumina substrate with Pt electrodes and a Pt thin film heater for heating a cerium oxide thick film. The sensor had the high sensitivities to H₂S, CH₃SH, C₂H₅OH, (CH₃)₂CO, CH₃CHO, CH₃COOH, while sensitivity to H₂ was much lower. Furthermore, the sensor showed quick response to VSC such as a H2S. From these results, the cerium oxide sensor is expected for the application to advanced VSC detector.

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SnO₂ナノ粒子へのFe³⁺ドーピングとセンサ特性

(九大院総理工)　

○末松　昂一、湯浅　雅賀、木田　徹也、島ノ江　憲剛、山添　�f

Effects of Fe³⁺ doping in SnO₂ nanoparticles on the gas sensing properties

K. Suematsu^a, M. Yuasa^b, T. Kida^b, K. Shimanoe^b, N. Yamazoe^b

^a Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
^b Department of Energy and Material Sciences, Faculty of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan

Recently, we have proposed theoretical models, power laws and effects of particle shape and size on sensor response, for semiconductor gas sensors. The models are based on a combination of the depletion theory of semiconductor and the dynamics of adsorption and/or reaction of gases on the semiconductor surface. The models show that the response of semiconductor gas sensors is dependent on the crystalline size and donor density of particles, which influence the depth of a depletion layer formed inside the particles. In this study, to experimentally reveal such effects, we tried to control the crystalline size and donor density in SnO₂ by Fe³⁺ doping. The effects of doping concentration, crystalline size, and partial pressure of oxygen and hydrogen on the electric resistance and sensor response are discussed to propose a new design approach for semiconductor gas sensors.

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メソ・マクロポーラス酸化物センサの作製とガス検知特性

（長崎大 院生産科学^a、工^b）

○原　陸洋^a、兵頭健生^a、清水康博^b、江頭　誠^b

Preparation of Meso- and Macro-porous SnO₂ for Gas Sensor Application

〇Luyang YUAN^a, Takeo HYODO^a, Yasuhiro SHIMUZU^b and Makoto EGASHIRA^b

^aGraduate School of Science and Technology, ^bFaculty of Engineering,
Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521

Two series of meso-macro porous SnO₂ (m･mp-SnO₂) powders were prepared by employing Na₂SnO₃?3H2O (C series) and SnCl₄･5H₂O (A series) as a Sn source. Mesoporous structure was controlled by n-cetylpyridinium chloride in the C series and by C₂₀H₃₇O₇SNa in the A series, while macroporous structure was controlled by polymetylmethacrylate microspheres in both series. The m･mp-SnO₂ powders with and without SiO₂ and Sb₂O₅ additives were also prepared. The resultant m･mp-SnO₂ powders were characterized by XRD, BET and SEM. The gas sensing properties of the m･mp-SnO₂ pellet-type sensors to 1000 ppm H₂ were measured in a temperature range of 300-500℃. In the case of A-series powders, the addition of 9 wt% SiO₂ was effective for enhancing the specific surface area (SSA), but the simultaneous addition of Sb₂O₅ resulted in a decrease in SSA. The addition of Sb₂O₅ up to 10 wt% was found to reduce the sensor resistance in air, but beyond that it led to an increase in resistance. Among the sensors tested, A-series m･mp-SnO₂ added with 9% SiO₂ and 5 wt% Sb₂O₅ showed the highest H₂ response at 400℃.

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高信頼・低電力Ｓｉ-ＭＯＳＦＥＴ型水素センサ

（日立基礎研^a、日立中研^b、日立日研^ｃ）

○宇佐川 利幸^a、　菊池 洋太^a、　中野 定樹^b、　嘉本 大五郎^b

ＲＥＬＩＡＢＬＥ ＬＯＷ　ＰＯＷＥＲ　Ｓｉ-ＭＯＳＦＥＴ　ＨＹＤＲＯＧＥＮ　ＳＥＮＳＯＲＳ

Toshiyuki USAGAWA^a , Youta Kikuchi^a , Sadaki Nakano^b and Daigoro KAMOTO^c

^aAdvanced Research Laboratory, Hitachi, Ltd., Kokubunnji-shi, Tokyo 185-8601
^bCentral Research Laboratory, Hitachi, Ltd., Kokubunnji-shi, Tokyo 185-8601
^cHitachi Reseach Laboratory, Hitachi, Ltd., Hitachi-shi, Ibaraki 319-1292

Si-MOSFET (Metal-Oxide-Semiconductor Field-Effect-Transistor) hydrogen-gas sensors would be suitable for hydrogen gas detection systems, because they are compact, low price, low power consumption, and easy to integrate with other semiconductor elements. However, as the catalytic gate metal thickness of FET sensors is so thin compared with commercially available sensor devices, the reliability and life times of Si-MOSFET sensors were suspected to be insufficient and short, we have devoted to research and test the reliability problems and the accelerated aging experiments, and evaluated several fundamental characteristics as sensor devices. Device targets are mainly Pt-gate Si-MOSFET hydrogen-gas sensors, which were fabricated in CMOS compatible 5φlines. Hydrogen responding amplitude is as high as Pd gate metals for wide range of hydrogen concentration from 100ppm to 10%.Very high uniformity is shown in threshold voltage Vth (3σ＝178ｍV　for 5inch Si-wafer) and hydrogen responding amplitude ΔVg, which enables easy designs of interface circuits. Little interference with hydrogen gas was observed for 0.1-1.0% methane, 0.1% ethane, 817ppm isooctane and 0.1% CO gas at 100℃ operations. The device life time is at least more than half year and more than three years from the field tests and aging experiments. Packaged sensor chips show low power consumption around 100mW.

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アンモニア・トリメチルアミン計測用高感度センサガスクロの開発

（エフアイエス）

○翁長一夫、花田真理子、上坂亜紀、田中克之、香田弘史

DEVELOPMENT OF A HIGHLY SENSITIVE SENSOR GASCHROMATOGRAPH
FOR AMMONIA AND TRIMETHYLAMINE DETECTION

Kazuo ONAGA, Mariko HANADA, Aki UESAKA,
Katsuyuki TANAKA and Hiroshi KODA

FiS Inc. 3-36-3 Kitazono, Itami, Hyogo 664-0891


To quantify very low concentrations of ammonia and trimethylamine, we have developed a chromatographic gas analyzer using a metal oxide gas sensor as a detector. Using a highly sensitive tungsten oxide gas sensor and a very short column was effective in obtaining the high sensitivity of the analyzer. This analyzer can quantify oncentration of 10ppb of ammonia or more and 1ppb of trimethylamine or more.

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木炭種によるVOC吸着能

金沢星稜大学経済学部^a、大土炭工房^b

○康　宝昇^a、大薮多可志^a、二枚田昇^b

ADSORPTION CAPABILITY FOR VOCs DUE TO WOOD CHARCOALS

BaoSheng Kang^a Takashi Oyabu^a and Noboru Nimaida<sup>b

a</sup>Kanazawa Seiryo University, Faculty of Economics, ^bOtsuchi Charcoal Workshop</p>

Charcoal has gotten a lot of attention recently according to the various kinds of functions to humans. Especially, it has been set in an indoor space and the deodorizing capability has been applied. However, the evaluation method is not established. It is necessary to construct the method and introduce the capability to general public using an index value. General public can understand the capability easily due to the value and use it positively. In this study, an evaluation method was proposed, namely the capability was evaluated in an experimental chamber using a tin oxide gas sensor, which could output the signal according to the concentration of air polluting chemical. The sensor output increases as the chemical concentration increases. The index value (Pa)indicating the capability can be represent using the sensor output characteristic to the chemical, namely peak value (h) and half-value width(tw). Pa = h / tw. The peak value means the voltage from base level to the peak value of the sensor. Four kinds of charcoals were examined. Especially the ones for Japanese cedar and Japanese oak were investigated. As the results, the both ones indicated almost same value (about Pa = 10). The cedar charcoal is cheaper and the heat is lower than the one for the oak. It is good factor for the cedar charcoal. It is considered that the installing charcoal in indoor environment to purify air quality will penetrate masses and humans can have a safe and comfortable life. Charcoal has the function to remediate the indoor environment.

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吸着燃焼式ガスセンサに用いる触媒材料の設計

（¹長崎大院生産科学，²矢崎総業，³長崎大工）

○兵頭健生¹，稗田耕士¹，笹原隆彦²，清水康博³，江頭　誠³

DESIGN OF CATALYST MATERIALS
FOR ADSORPTION/COMBUSTION-TYPE GAS SENSORS

Takeo HYODO¹, Koji HIEDA¹, Takahiko SASAHARA², Yasuhiro SHIMIZU³
and Makoto EGASHIRA<sup>3

1</sup>Graduate School of Science and Technology, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521
²Research and Technology Center, Yazaki Corporation, 1500 Mishuku, Susono, Shizuoka 410-1194
³Faculty of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521

Mesoporous γ-alumina (mp-Al₂O₃) with high specific surface area was prepared by a solvothermal method employing an appropriate amount of aluminum sec-butoxide and behenic acid in propan-1-ol, and the mp-Al₂O₃ loaded with noble metal were used as a gas sensing material for adsorption/combustion-type gas sensors. As for Pd-loaded mp-Al₂O₃ sensors, the response to 1000 ppm ethanol increased with an increase in the amount of loaded Pd, due to increased activity for ethanol oxidation. The gas response decreased obviously by the replacement of a half part of Pd with Cu. On the other hand, the gas response remained almost unchanged by the replacement of a half part of Pd with Au, probably due to compensation of the decreased catalytic activity with the increased thermal conductivity of the catalyst material. Thus, besides the catalytic activity, the thermal conductivity of the catalyst material was suggested to be another important factor in determining the gas response.

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指紋認証デバイスを利用したバイオセンサの開発

東京農工大学

○田中 剛、　畠山　慶一、松永　是

DEVEROPMENT OF BIOSENSOR USING FINGERPRINT PHOTOSENSOR

Tsuyoshi TANAKA, Keiichi HATAKEYAMA and Tadashi MATSUNAGA
Department of Biotechnology, Tokyo University of Agriculture and Technology, 2-24-16, Naka-cho, Koganei, 184-8588, Tokyo, Japan

This work describes a disposable DNA-arrayed fingerprint photosensor integrating a miniaturized reaction unit and a photoelectronic effect-based internal detection sensor. Single stranded DNA was chemically conjugated and arrayed on the fingerprint photosensor, which was fabricated by the semiconductor integrated circuit (IC) technology, for the detection of specific target DNA by DNA-DNA hybridization. The DNA-arrayed fingerprint photosensor can directly detect signals onto the sensor surface such as excited fluorescence and generated chemiluminescence signals. Miniaturized genetic diagnostic chip with microfluidic channel onto the oligonucleotide-arrayed photosensor was constructed. SNP detection by the genetic diagnostic chip was successfully achieved using PCR products amplified from whole blood sample. The developed fingerprint photosensor will further promote the development of disposable photodetecting devices applicable in genetic diagnosis.

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電荷蓄積型過酸化水素センサをプラットフォームとした尿中腫瘍マーカーの高感度検出

兵庫県立大院物質理学^a、株式会社トランスジェニック^b

○安川 智之^a、稲積 伸吾^a、品川 真吾^b、能勢　博^b、水谷 文雄^a

HIGHLY SENSITIVE DETECTION OF MARKERS IN URINE SAMPLES BY USING COULOMETRIC HYDROGEN PEROXIDE SENSORS

Tomoyuki YASUKAWA ^a, Shingo INADUMI ^a, Shingo SHINAGAWA ^b,
Hiroshi NOSE ^b and Fumio MIZUTANI ^a
a Graduate School of Material Science, University of Hyogo, 3-2-1 Kouto, Kamigori, Ako, Hyogo 678-1297
^b TransGenic, Inc., 7-1-14 Minatojimaminami-machi, Chuo-ku, Kobe, 650-0047

A novel electrochemical enzyme immunoassay system was developed for the determination of diacetyl-polyamine, N1,N12-diacetylspermine, an important urinary marker of malignancy. N1-acetylspermine was immobilized on the polymer layers prepared on the Indium-tin-oxide (ITO) substrates. The different concentrations of solution containing N1,N12-diacetylspermine were added to an anti-N1,N12-diacetylspermine antibody solution to undergo an immunological reaction. Then, unreacted anti-N1,N12-diacetylspermine antibody and anti-mouse IgG antibody conjugated with glucose oxidase (GOx) were successively trapped on the acetylspermine-immobilized polymer. Then, hydrogen peroxide generated by the enzyme reaction with the trapped conjugate (GOx) was coulometrically determined. The enhanced sensitivity for hydrogen peroxide enabled the determination of a trace concentration of N1,N12-diacetylspermine with the immunoassay using the antibody modified with a hydrogen peroxide-producing enzyme. The results suggested the possible application of the proposed method to an on-site diabetic sensing system.

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負の誘電泳動によるマイクロ微粒子集積-再分散を応用したイムノセンシング

（東北大学環境科学研究科^a、兵庫県立大学大学院物質理学研究科^b）　

○LEE HYUN JUNG^a、安川智之^ｂ、珠玖仁^a、末永智一^a

ONE-STEP SANDWICH IMMUNOSENSING BY NEGATIVE DIELECTROPHORESIS

Hyun Jung LEE^a, Tomoyuki YASUKAWA^b, Hitoshi SHIKU^a, and Tomokazu MATSUE^a
a Graduate School of Environmental Studies, Tohoku University,
Aramaki-Aoba, Aoba, Sendai 980-8579
^b Graduate School of Material Science, University of Hyogo,
3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo 678-1297

Here, we propose a one-step sandwich immunosensing system combined with negative dielectrophoresis (n-DEP), which is fast and the secondary antibody-free. The same antibody was pre-coated both microbeads and poly-(dimethylsiloxane) (PDMS) substrate. In the presence of analyte, n-DEP for several tens of seconds at room temperature allows the antibody-coated microbeads to be immobilized on PDMS surface on the designated region via immunoreaction after turning the applied voltage off. Line patterns with microbeads were also created on PDMS surface in the absence of mouse IgG; however, the aligned microbeads were resuspended in the solution when the electric field was switched off. These results clearly verified that the sandwich structure by antigen-antibody immunoreaction was accelerated by n-DEP to be formed between the anti-mouse IgG immobilized on PDMS surface and microbeads via mouse IgG.

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ナノ周期構造への固定化膜作製と局在表面プラズモン共鳴センサによるα-fetoproteinの検出

オムロン株式会社、技術本部　コアテクノロジーセンター

○藤田悟史、 西川武男、 蓮井亮介、 増田梨恵、 奥野雄太郎

IMMOBILIZATION OF ANTIBODIES ON A NANOGROOVE STRUCTURE AND SENSITIVE DETECTION OF ALPHA-FETOPROTEIN USING THE LOCALIZED SURFACE PLASMON RESONANCE SENSOR

Satoshi FUJITA, Takeo NISHIKAWA, Ryosuke HASUI, Rie MASUDA and Yutaro OKUNO

OMRON Corporation, Core Technology Center, Kizugawa-shi, Kyoto 619-0283

The localized surface plasmon resonance (LSPR) which occurs on the gold nanogroove structure has gotten attention as a sensing technology to detect the protein-protein interactions at the nanoscale. Since the sensor can localize the sensing depth closer to the interface, the noise factors such as temperature fluctuation can be eliminated. To obtain the high-performance of immunosensing, we evaluated a novel immobilization surface called as ORLA18. In this paper, we made an attempt to form the ORLA18 surface on our gold nanogroove structure. As a result, we confirmed the certain immobilization of ORLA18 on its structure and could achieve the rapid and high sensitivity detection of alpha-fetoprotein (AFP) using our LSPR sensor.

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　　　　遺伝子レベルでの配向性酵素分子の創成と高機能性デバイスの構築

（福井大学大学院工学研究科^a、香川大学農学部^b、九州大学大学院農学研究院^c）

○末　信一朗^a、白石智美^a、櫻庭春彦^b、大島敏久^c

ORIENTED IMMOBILIATION OF HYPERTHERMOSTABLE L-PROLINE DHYDROGENASE ON THE MODIFIED ELECTRODE

Shin-ichiro SUYE ^a, Satomi SHIRAISHI, Haruhiko SAKURABA, and Toshihisa OHSHIMA ^b

^aGraduate School of Engineering, University of Fukui,Bunkyo, Fukui 910-8507　
^bFaculty of Agriculture, Kagawa University, Ikenobe, Miki-cho, Kita-gun, Kagawa 761-0795
cGraduate School of Agriculture, Kyushu University,Hakozaki, Fukuoka 812-8581

Recently, protein orientation control technique shows much more applications on biosensor area. Design and preparation procedures for oriented immobilization of enzyme are key technique of construction of biosensors, because stability of enzyme and efficient electron transfer between enzyme and electrode could be improved by oriented immobilization of enzyme.　Hiperthermostable L-proline dehydrogenase (L-ProDH) from hyperthermophilic Achaean (Therococcus profundus) catalyzes the oxidation of L-proline in the presence of artificial electron acceptors. L-ProDH consists of a heterotetrameric a/b/g/d structure. The b subunit catalyzed the dye-linked L-proline dehydrogenase reaction by itself and that, unexpectedly, the a subunit exhibited dye-linked NADH dehydrogenase activity. Both a and b subunits have FAD, and g subunit contains ferredoxine. For oriented immobilization of L-ProDH, His-tag was introduced on the C-terminal site of each subunit and oriented enzyme was found to Ni complex on the electrode.　We cloned the gene cording for the L-ProDH foreign DNA into pET15b plasmid vector that provides the enzyme with a C-terminal His-tag. His-tagged pdhα and His-tagged pdhβ and His-tagged pdhγ were expressed in E. coli. L-ProDH was purified using heat treatment and immobilized metal-ion affinity chromatography from cell free extract. His-tagged enzymes were immobilized on the gold electrode via NTA-Ni. His tagged a subunit L-ProDH immobilized electrode showed higher electrochemical response compared with other His-tagged subunits enzyme immobilized electrodes. Efficient electron transfer between substrate and electrode thorough the enzyme molecule was found between b and a subunits. The results in this study show that an enzyme immobilization system has the potential to be applied in a sensitive biosensing system.

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γーポリグルタミン酸を用いた微細針状グルコースセンサの作製

徳島大院ソシオテクノサイエンス

○安澤幹人、枝川和明、高岡宏樹

PREPARATION OF NEEDLE TYPE GLUCOSE SENSORS USING γ-POLYGLUTAMIC ACID

Mikito YASUZAWA, Kazuaki EDAGAWA and Hiroki TAKAOKA

Department of Chemical Science and Technology, The University of Tokushima, 2-1 Minamijosanjima, Tokusima 770-850

Long-term stability of glucose oxidase (GOx) immobilized electrode was improved by the introduction of dietary fiber, gamma-polyglutamic acid (PGA) due to the formation of poly-ion complex between positively charged polypyrrole and negatively charged PGA, which stabilized the enzyme immobilized film. The electrode prepared by the electropolymerization of 1-(6-D-gluconamidohexyl)pyrrole in the presence of GOx and PGA showed best performance in both stability and sensitivity. Outer layer film coating of polyurethane provided good response in horse serum measured at 40℃. Although, the influence of electroactive compounds in biological fluid such as ascorbic acid was low, the influence of uric acid to sensor response was unneglectable.

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分子インプリント自己支持膜のゲート効果

（芝浦工大）

○吉見靖男、関根真一、吉泉玲司、新井梨佳、森　　晋、宮本純平

GATE EFFECT OF SELF-STANDING MEMBRANE IMPRINTED WITH PHENYLALANINE

Yasuo YOSHIMI, Shinichi SEKINE, Reiji YOSHIIZUMI, Rika ARAI, Susumu MORI and Junpei MIYAMOTO

Department of Applied Chemistry, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548

Solute permeability of thin layer of some kinds of molecularly imprinted polymers (MIPs) is sensitive to specific binding with their templates (gate effect). We have studied the gate effect in MIP layer grafted on the substrate (electrode or semi-permeable membrane). However, the MIP grafted on the substrate has been so thin (less then ten nanometer) that control and estimation of the quality is difficult. In this study, we developed molecularly imprinted self-standing membrane (MISSM) of L- (or D-) phenylalanine (Phe) with thickness of several dozen micrometer. The dialysis of creatinine was carried out using MISSM. In the results, the overall mass transfer coefficient of creatinine increased by the presence of the template, however almost insensitive to the enantiomer of the template. The equilibrium-adsorbed amount of Phe on the MISSM could be determined by batchwise analysis. The adsorbed amount of the template was remarkably larger than that of the enantiomer. The oxidative current of ferrocyanide at the MISSM-immobilized electrode was sensitive to the template with chiral-sensitivity. Then the MISSM is applicable for recognitive element for a biomimetic sensor.

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アメフラシ神経の蛍光膜電位イメージング

（芝浦工大）

○吉見靖男、青木一途、赤池　哲

FLUORESCENT VOLTAGE IMAGING OF CENTRAL NERVE SYSTEM IN APLYSIA

Yasuo YOSHIMI, Shinichi SEKINE, Reiji YOSHIIZUMI, Rika ARAI, Susumu MORI and Junpei MIYAMOTO

Department of Applied Chemistry, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548

Aplysia has been used as an ideal experimental model for studying neuronal networks involved in learning and memory because large and identifiable neurons present in its central nervous system (CNS). Fluorescent voltage imaging with a voltage-sensitive dye (VSD) is a potential tool for multiple-site monitoring of neuronal activity.
Fluorescent voltage imaging of Aplysia CNS would contribute greatly toward basic research on neuronal network; however, this has not yet been implemented because of the difficulty in staining of Aplysia neurons with a VSD. In the present study, we developed a variant of voltage imaging using Aplysia ganglion neurons and di-4-ANEPPS, which is a commonly used fluorescent VSD. An Aplysia abdominal ganglion was digested using protease to facilitate the removal of fibrous sheath with microscissors. This treated ganglion was soaked in di-4-ANEPPS solution containing Aplysia hemolymph. The ganglionic neurons were stained well with the VSD, which emitted a detectable
fluorescence. The change in fluorescent intensity agreed with the spontaneous firing in membrane potentials of the neurons. Results showed that fluorescent voltage imaging of Aplysia CNS neurons was possible after appropriate pretreatment of the ganglion.

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新規タンパク質検出用蛍光分子プローブの開発とSDS-PAGEへの応用

産総研バイオニクス

○鈴木　祥夫、横山　憲二

DEVELOPMENT OF FLUORESCENT MOLECULAR PROBES FOR PROTEIN DETECTION AND THEIR APPLICATION TO SDS-PAGE

Yoshio SUZUKI a and Kenji YOKOYAMA ^a,b

^a Research Center of Advanced Bionics, National Institute of Advanced Industrial Science and Technology (AIST), c/o Katayanagi Advanced Research Laboratories, Tokyo University of Technology, 1404-1 Katakura, Hachioji, Tokyo 192-0982, Japan

^b Research Center of Advanced Bionics, National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 4, 1-1-1 Higashi, Tsukuba 305-8562, Japan

Novel fluorescent and colorimetric molecular probes were designed and synthesized in order to detect proteins via non-covalent bonding. Fluorescent molecular probes based on the cyanopyranyl moiety produce no fluorescence emission in the absence of protein. On the other hand, strong fluorescence emission was observed after the addition of BSA. These fluorescence spectral changes upon binding proteins were caused by the ICT process. A good linear relationship was observed between fluorescence intensity and protein concentration. Similar results were observed for other proteins (IgG, etc.). In the case of colorimetric molecular probe based on phenol derivative, a clear color change from pink to deep purple was observed upon binding to protein, which was caused by the solvatochromic effect. To demonstrate the application of these spectrophotometric probes, proteins after the separation using SDS-PAGE were stained in a medium containing these reagents, and the imaging of the proteins in the gel was successful. Moreover, simplification of the in-gel protein staining protocol was successful using fluorescent molecular probes in order to achieve the high-throughput analysis of proteins for SDS-PAGE. These experimental results clearly showed that these probes are good protein indicators for the easy and highly-sensitive detection.

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過酸化ポリピロール分子鋳型センサによるATPの高感度定量

阪府大産学官連携機構

武田信太郎，椎木　弘，○長岡　勉

A Highly Sensitive Amperometric Adenosine Triphosphate Sensor Based on Molecularly Imprinted Overoxidized Polypyrrole

Shintaro TAKEDA, Hiroshi SHIIGI, and Tsutomu NAGAOKA

FSIC, Osaka Prefecture University, Sakai-shi, Osaka 599-8570

We have developed an amperometric sensor based on molecularly imprinted polymer, which allows the detection of trace concentrations of adenosine triphosphate (ATP), aiming at food safety applications. The sensor has a small carbon electrode covered with an overoxidized polypyrrole film imprinted with an ATP molecule. The sensor operated in the triple pulse amperometric mode and was characterized in both the batchwise and flow injection measurements. We have detected trace levels of ATP down to 5 nM without employing any separate preconcentration procedures.

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太陽光の変動によるポトス植物生体電位とその個体差

金沢星稜大学^a、金沢大学^b

○藤井正基^a　柴田慎一^a　大薮多可志^a　南保英孝^b　木村春彦^b

BIOELECTRIC POTENTIAL FOR POTHOS AND ITS INDIVIDUAL VARIABILITY UNDER SUNLIGHT VARIATION

Masaki Fujiia, Shin-ichi Shibataa, Takashi Oyabua, Hidetaka Namboband Haruhiko Kimurab

^a Kanazawa Seiryo University Kanazawa-shi, Ishikawa 920-8620
^b Kanazawa University Kanazawa-shi, Ishikawa 920-1192

Plant bioelectric potential fluctuates according to the environmental factors, such as light intensity, atmospheric temperature and pressure, fertilization, watering and touching. It is remarkably influenced by light intensity. This results from photosynthesis activity. The sunlight strength influences the potential fluctuation especially. In this study, the potential influenced by sunlight pouring through window was examined. The potential was measured every 0.1 seconds. And the data for a minute (number: 600) were summarized. It is called as the integrated potential (vm1). The histogram for the potential distribution showed normal distribution. The standard deviation (SD) and the average (Ave) were changed, namely SDs for noon (under light) became larger than the ones for midnight (in darkness). The two subjective plants were adopted in this study and the individual variability was also investigated. At that time, the standardized data were derived and used. There was not individual marked variability among the standardized potentials for the subjects. The plants also have individuality to a greater or lesser extend.
Keywords: bioelectric potential, plant, individual variability, plant sensor, environmental sensor.

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ヘテロコア光ファイバによる高速応答性湿度センサの研究・開発

創価大院工^a,b

○秋田尚平^a、佐々木博幸^a、関篤志^b、渡辺一弘^a

A RESEARCH AND DEVELOPMENT FOR A HIGH RESPONSIBLE HETERO-CORE OPTICAL FIBER RELATIVE HUMIDITY SENSOR

Shohei AKITA ^a, Hiroyuki SASAKI ^a, Atsushi SEKI ^b, Kazuhiro WATANABE ^a
a Department of Information Systems Science, ^b Department of Bioinformatics, Faculty of Engineering, Soka University
1-236 Tangi, Hachioji-shi, Tokyo 192-8577, Japan

A hetero-core optical fiber was used to fabricate a new optical fiber sensor. A new type of fiber optic sensor that has a hetero-core structure has been developed for sensing relative humidity. This relative humidity sensor was produced by using a hetero-core optical fiber that was coated with hygroscopic films by a Layer-By-Layer technique. The sensor consists of a multimode fiber coated with a [poly-Glu/poly-Lys] nanostructured overlay; this overlay ensures that the transmitted optical intensity loss is sensitive to changes in the refractive index of the polymer coating. The optical loss varied with changes in the relative humidity of the air near the sensor. In this study, response rate results showed that the response time between the commencement of blowing and the optical loss peak was approximately 500 ms. These results indicate that the sensor demonstrated in this study, which is based on a hetero-core optical fiber, should be useful for sensitively and fast responsible measuring the relative humidity in various environments.

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ヘテロコア型光ファイバ湿度センサの相対湿度特性

創価大学院

○濱田英作、 秋田尚平、佐々木博幸、 関篤志、 渡辺一弘

A RESEARCH IN A RELATIVE HUMIDITY CHARACTERISTIC
WITH A HETERO-CORE OPTICAL FIBER RELATIVE HUMIDITY SENSOR.

Eisaku HAMADA^a, Shohei AKITA^a, Hiroyuki SASAKI ^a, Atsushi SEKI ^b and Kazuhiro WATANABE ^a
a Department of Information Systems Engineering,^b Department of Bioinformatics, Faculty of Engineering, Soka University
1-236 Tangi, Hachioji, Tokyo 192-8577, Japan

A hetero-core optical fiber humidity sensor is a new optical fiber sensor coated with a hygroscopic polymer (poly glutamic acid and poly lysine). This sensor structure has simple structure and comparable strength to a common optical fiber. This sensor has high sensitivity because the transmitted light was increased of 2.0dB in the high relative humidity of above 80% RH. However, this sensor has low sensitivity in the low relative humidity of below 80%RH. And we report that optical loss decrease by increasing the number of hygroscopic polymer layers. It is considered that the result is influenced by an equivalent index refraction of a clad and a hygroscopic polymer.

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ポルフィリン-高分子複合クラッドを用いた光ファイバ式ガスセンサ

愛媛大院理工　

○板垣 吉晃、　山中 暁、　定岡　芳彦

FIBER-OPTIC GAS SENSING USING PORPHYRIN-POLYMER COMPOSITE CLAD

Yoshiteru ITAGAKI, Satoru YAMANAKA and Yoshihiko SADAOKA

Graduate School of Science and Engineering, Ehime University, Matsuyama-shi, Ehime 790-8577

Porphyrin-dispersed polymer composites were applied as clad materials for a fiber-optic gas sensor. Poly(ethylene oxide) (PEO) and ethylcellulose (EC) were chosen as polymer matrices in this study. The optical response to HCl gas was fairy dependent on the polymer matrices in the clad layer. In EC matrix, the spectral change due to the equilibrium reaction, TPPH₂ + 2H⁺ = TPPH₄²⁺, was observed at > 2 ppm. Meanwhile, PEO matrix gave a higher sensitivity in the low concentration region of HCl at 25℃, but it became saturated at > 4 ppm. By increase in operating temperature, although the sensitivity was lowered, concentration dependent response was observed at > 4 ppm. The response times of the PEO based sensor from 20 pmm to lower concentrations examined at 50℃ were within 2min.

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カーボンブラック複合コポリマー膜を用いたトルエン蒸気検知

愛媛大院理工

朝原　浩次、松口　正信

AMINO-FUNCTIONAL COPOLYMER/CARBON BLACK COMPOSITES FOR SENSING OF TOLUENE VAPOR

Kouji ASAHARA and Masanobu MATSUGUCHI

Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, 3, Bunkyo-cho, Matsuyama 790-8577

Electrically conductive polymer composites containing carbon black dispersed in an amino-functional copolymer (DMPDA-MMA-CMSt) were studied as sensing materials for toluene vapor. The copolymer newly developed in our laboratory showed large toluene sorption capacity and fast rate of sorption compared with well-known polymer coatings, such as polyisobutylene, for toluene sensing. As a result, enhanced sensitivity and fast response towards 200 ppm of toluene vapor was obtained at 30℃ when the copolymer was used as the insulating component. It was found that the sensitivity increased as the thickness and the resistance of the composite film increased.

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物材機構センサ材料センター^a、物材機構光材料センター^b

○大垣　武^a、菱田　俊一^a、坂口　勲^b、斎藤　紀子^a、大橋　直樹^b、羽田　肇^a

MODIFICATION OF CHEMICAL SENSORS USING A COMBINATORIAL ION-IMPLANTATION METHOD

Takeshi OHGAKI ^a, Shunichi HISHITA ^a, Isao SAKAGUCHI ^b, Noriko SAITO ^a, Naoki OHASHI ^b and Hajime HANEDA ^a

^a Sensor Materials Center, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044
^b Optronic Materials Center, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044

Doping of different elements into host material is effective in improving the sensor properties such as sensitivity, stability and response time. Optimization of doping elements and their amount is one of barrier for the development of new chemical sensors. In order to realize high-throughput material search for chemical sensors, we are considering application of the combinatorial ion-implantation method, which make it possible to obtain a specimen containing doping elements from ppb to percent order. The combinatorial ion-implantation method can be used to prepare specimens in which large numbers of materials with different compositions/properties are arranged in 2-demensional micro region. We report the possibility of high-throughput searching of new chemical sensor materials with the combinatorial ion-implantation method.

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マクロポーラス化した酸化スズ系蛍光膜のガス応答特性

長崎大 ¹院生産科学，²工

○��倉由香里¹，兵頭健生¹，清水康博²，江頭　誠²

GAS-SENSITIVE PHOTOLUMINESCENCE PROPERTIES OF MACROPOROUS TIN OXIDE-BASED PHOSPHOR FILMS

Yukari TAKAKURA¹, Takeo HYODO¹, Yasuhiro SHIMIZU² and Makoto EGASHIRA²

¹Graduate School of Science and Technology, ²Faculty of Engineering Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521

Macroporous (mp-)SnO₂ thick films doped with 5 mol% Eu and 0~50 mol% Mg (Lmp-SnO₂(mMg):Eu, L: the size of PMMA microspheres used: 800 (nm), m: Mg content) were fabricated by a modified sol-gel method by employing PMMA microspheres as a template and constituent metal chlorides as oxide sources. For comparative purpose, screen-printed (s-)SnO2(mMg):Eu thick films without macropores were fabricated with fine powders prepared by thermal decomposition of precursor solutions. Sensing properties of these thick films to various gases were investigated by monitoring their photoluminescence (PL) properties at 588 nm in air at room temperature (excitation wavelength = 260 nm). The PL intensity of both Lmp-SnO₂(mMg):Eu and s-SnO₂(mMg):Eu films showed its maximum at m = 10-20. Both kinds of the films showed reversible O₂ response in N₂, along with an increase in the PL intensity upon exposure to O₂. Among the films tested, 800mp-SnO₂(30Mg):Eu showed the highest oxygen response, when the response is defined as the difference of PL intensity (D = I - I0, I: PL intensity in O2 balanced with N₂, I0: PL intensity in N₂). The PL intensity of 800mp-SnO₂(mMg):Eu also increased upon exposure to H₂O balanced with air, while it decreased upon exposure to acetone or methanol balanced with air.

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触媒化学発光式ガスセンサを用いたガスクロマトグラフによる清酒の香り成分の検出

岡山理科大学^a、日本電産コパル��^b

○林　久美子^a、松原　悠子^a、国井弘毅^b、中川　益生^a

DETECTON OF FLAVORS IN SAKE USING A GAS-CHROMATOGRAPH WITH A CATALUMINESCENCE-BASED GAS-SENSOR

Kumiko HAYASHI^a, Yuko MATSUBARA^a, Koki KUNII^b and Masuo NAKAGAWA^a

^aOkayama University of Science, 1-1 Ridai-cho, Okayama 700-0005

We have investigated a cataluminescence(CTL)-based gas-sensor as an analytical detector of gases for gas-chromatograph. As it has high sensitivity, high signal to noise ratio, fast response, linear concentration dependence and sensitivity for various combustible gases, it is suitable for the detector. For the analytical detection of gases, the temperature of the CTL-based sensor is modulated alternatively between 497 and 537℃ at an interval of 1s and CTL-intensity is measured. The amplitude and phase of CTL-intensity depend on the types of flavors in sake, e.g. ethanol, ethyl acetate and isobutyraldehyde, so that we can identify these gases. Gas chromatogram of air containing these gases was measured using a temperature-modulated CTL-based gas sensor.? ?

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ナノAu検知極を用いたジルコニアセンサのNH₃検知特性

（九大産学連携センター^a、日本学術振興会^b、九大院総理工^c）

○ブラディミル プラシニツァ^a、ペルマル エルマレイ^a,b、藤尾 侑輝^c、三浦 則雄^a

SENSING PERFORMANCES OF ZIRCONIA-BASED NH₃ SENSOR UTILIZING NANO-Au SENSING ELECTRODE

○ Vladimir V. PLASHNITSA^a, Perumal ELUMALAI^a,b, Yuki FUJIO^c, Norio MIURA^a

^aArt, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580
^bJapan Society for the Promotion of Science, Tokyo 102-8471
^cInterdisciplinary Graduate School of Engineering Sciences, Kyushu University, Kasuga-shi, Fukuoka 816-8580

The single-crystal (111) and polished-polycrystalline yttria-stabilized zirconia (YSZ) plates were used for fabrication of sensors. Both plates were treated with the colloidal gold solution having the particles size of 5 nm, followed by annealing at 1000℃ to form the sensing electrode (SE). Both sensors attached with each of Au-SEs were found to give selective and sensitive response to NH₃ in the temperature range of 675-700℃. The single-crystal YSZ-based sensor showed good sensitivity to NH₃ in the concentration range of 50-400 ppm only just after fabrication, whereas the sensor utilizing the polished YSZ gave the sensitive response to 20-200 ppm NH₃ even after 45-day operation. Such a discrepancy in NH₃ response was attributed to the difference in the state of re-arrangement of Au nano-particles on the surface of each of YSZ plate during high-temperature operation.

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限界電流式酸素センサのバランスガスによる特性への影響

矢崎計器（株）ガス機器開発センター

　　○岡本　卓、鈴木　隆之、石黒　義昭、高橋　英昭

BALANCE GASES EXERT INFLUENCE ON THE LIMITING CURRENT TYPE OXYGEN SENSOR.

Takashi Okamoto, Takayuki Suzuki, Yoshiaki Ishiguro, and Hideaki Takahashi

Gas Equipment Development Center , Yazaki Meter Co.Ltd., Hamamatsu,Shizuoka 431-3393,Japan

The limiting current type oxygen sensor formed with zirconia, is expected to use in various environments. Oxygen sensor output characteristics in inart gases of N₂, He, and Ar as balance gases, were investigated by the type of oxygen diffusion restricted with a porous substrate, a diaphragm with a pin-hole. If concentration of oxygen was constant, output current value of the porous substrate type sensor became Ar > N₂> He, because it followed Knudsen diffusion. On the other hand, the output current value of the pin-hole type sensor became He > N₂> Ar, because it followed molecular diffusion. It was understood that these phenomenon phenomena caused in the diffusion coefficient of oxygen gas affected that of balance gases.

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排ガス中のCO選択検知を目的とした電流検出型固体電解質センサ

九大院工

○石原達己，門脇理恵，松本広重

Amperometric Solid State CO Sensor in Exhaust Gas by Using Solid State Electrolyte

T.Ishihara, R. Kadowaki and H. Matsumoto

Kyushu Univ.

Department of Applied Chemistry, Faculty of Engineering, Kyushu University, Motooka 744, Nishi-Ku, Fukuoka, 819-0395

Amperometric CO sensor in exhaust gas was studied based on the oxygen pumping current. It was fund that the oxygen pumping current sensitively varied with CO concentration when Au and RuO₂ was used for electrode. Combination of In₂O₃-SnO₂ with Au and RuO₂ with La_0.6Sr_0.4CoO₃ is highly effective for increasing CO sensitivity. Pumping current was changed with CO concentration from few ppm to 1000ppm. On the other hand, sensitivity to CO increases with increasing operating temperature. Although the highest sensitivity is achieved at 500℃, it is seen that the optimum operating temperature for this sensor exist around 400℃ because of stability. This study reveals that oxygen pumping current is highly sensitive to CO in exhaust gas.

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活性酸素を利用したディーゼルパティキュレートセンサの開発

産総研^a、名大^b、日本自動車部品^c

冨田 衷子^a、○日比野高士^b、　寺西 真哉^c、伊藤 健一^b、柘植 昭人^b

A DEISEL PARTICULATE MATTER SENSOR USING ELECTROCHEMICALLY ACTIVATED OXYGEN

Atsuko TOMITA ^a, Takashi HIBINO ^b, Shinya TERANISHI ^c, Ken-ichi ITO ^b, and Akihito TSUGE ^b

^a Materials Research Institute for Sustainable Development, National Institute of Advanced Industrial Science and Technology, Moriyama-ku, Nagoya 463-8560　
^b Graduate School of Environmental Studies, Chikusa-ku, Nagoya University, Nagoya 464-8601　
^c Nippon Soken, Inc., Nishio-shi, Aichi-ken, 445-0012

Diesel engine cars have been rapidly widespread in the past decade because of their higher efficient fuel combustion and lower CO₂ emission, compared to gasoline engine cars. At the same time, however, hazard to human health by particulate matters (PMs) emitted from diesel engine cars has become a subject of great concern. The PMs are currently removed by trapping the particles on ceramic filters and then by burning them. The main challenge of this technology is that the filter regeneration is needed for PM combustion to inject additional diesel fuel into the exhaust, reducing the fuel efficiency of the diesel engines. Another challenge is that small PMs with particle sizes of several decade nanometers pass through the pores in the filter. Seriously, such PMs have large health implications. An approach to avoid these challenges is to develop an on-board PM monitoring technology. In this study, we report a new type of PM sensor based electrochemical oxidation of carbon by water vapor present in the exhaust. An active oxygen species is formed via water-vapor electrolysis over a Pt electrode, oxidizing carbon to carbon dioxide, with a current efficiency of approximately 100%. This reaction causes a large jump in the measured electrode potential, providing information on the carbon amount.

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希土類硫酸アンモニウム塩を検出極に用いた新規な固体電解質型アンモニアセンサ

阪大院工

○永井つかさ、田村真治、今中信人

A NOVEL SOLID ELECTROLYTE TYPE AMMONIA GAS SENSOR APPLYING RARE-EARTH AMMONIUM SULFATE BASED AUXILIARY SENSING ELECTRODE

Tsukasa NAGAI, Shinji TAMURA, Nobuhito IMANAKA

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

Ammonia gas is one of the useful gas species in the industrial field. However, ammonia gas is very toxic, and the ammonia gas sensor showing the exact gas detection with a rapid response is greatly required in order to detect the gas leakage. In this work, we fabricated a new solid electrolyte type ammonia (NH₃) gas sensor by using trivalent Al³⁺ ion conducting solid electrolyte ((Al_0.2Zr_0.8)₂₀/₁₉Nb(PO₄)₃) and the praseodymium ammonium sulfate (Pr₂(SO₄)₂･(NH₄)₂SO₄) as the auxiliary sensing electrode, and the ammonia gas sensing performance was investigated. Since the present sensor shows such a superior sensing performance of quantitative, continuous, and reproducible response with obeying the theoretical Nernst relationship between the sensor EMF output and the logarithm of the NH₃ gas concentration, it is greatly expected to be an ammonia gas detecting device.

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混成電位型高感度プロペンセンサの応答特性の改善

九大総理工^a、国立環境研^b、九大産学連携センター^c

○和間 良太郎^a、内山 政弘^b、三浦 則雄^c

IMPROVEMENT IN SENSING CHARACTERISTICS OF HIGHLY SENSITIVE MIXED-POTENTIAL TYPE PROPENE SENSOR

○ Ryotaro WAMA ^a, Masahiro UTIYAMA ^b, Norio MIURA ^c

^a Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Kasuga-shi, Fukuoka 816-8580
^b National Institute for Environmental Studies, Tsukuba-shi, Ibaraki 305-8506
^c Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580

Recently we have reported that the mixed-potential-type sensor using yttria-stabilized zirconia (YSZ) and In₂O₃ sensing-electrode (SE) can detect propene (C₃H₆) even in several tens ppb level at 450℃ under the wet condition (1.35 vol.% H₂O). However, the selectivity to C₃H₆ of the sensor was not yet satisfactory. Thus, we tried to improve the C₃H₆ selectivity by adding each of noble metals (Ir, Pd, Pt, Rh, Ru) to In₂O₃-SE. As a result, the sensor attached with Pt (0.3 wt.%)-added In₂O₃-SE gave the excellent selectivity to C₃H₆ maintaining good sensitivity. Furthermore, the long-term stability of the present sensor could be improved by adding 10 wt.% YSZ to In₂O₃-SE. The emf response of the obtained sensor attached with In₂O₃ (+ 10 wt.% YSZ + 0.3 wt.% Pt)-SE varied almost linearly with the logarithm of C3H6 concentration in the examined range of 10 - 200 ppb at 450℃. In addition, the C₃H₆ sensitivity was hardly affected by the change in relative humidity (30 ~ 95% RH, at 30℃) in the sample gas.

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YSZを用いた電位応答型VOCガスセンサ
-検知極へのSmFeO₃微粒子コートの影響-

愛媛大院理工　

○西村浩幸、安藤弘矩、森　雅美、板垣吉晃、定岡芳彦

POTENTIOMETRICAL DETECTION OF VOC WITH 8YSZ BASED OXYGEN SENSOR
-EFFECT OF WORKING ELECTRODES WITH SMFEO₃ PARTICLES-

Hiroyuki NISHIMURA, Hironori ANDO, Masami MORI, Yoshiteru ITAGAKI and Yoshihiko SADAOKA

Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577

All solid-state electrochemical sensors for volatile organic compounds (VOCs) based on commercial yttria stabilized zirconia (YSZ) sheet were fabricated using Pt or Pt covered with SmFeO₃ layer as electrodes. When the Pt electrode was exposed to several VOCs, electromotive force (EMF) decreased corresponding to the decrease in the activity of oxygen ion of the sensing electrode. For the sensor with Pt electrode as sensing side, the change of the EMF for 7ppm VOCs/air was as follows; acetic acid > ethanol > methyl ethyl ketone, benzene, p-xylene > o-xylene > toluene and for the sensor with Pt electrode covered with SmFeO₃ was as sensing side as follows; benzene > p-xylene, toluene > o-xylene ≫ acetic acid > methyl ethyl ketone, ethanol at 400℃. The sensitivity for oxygenated compounds was distinctly decreased with the over-coating of Pt electrode with SmFeO₃ layer.

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