Vol. 21, Supplement A (2005)

Proceedings of the 39th Chemical Sensor Symposium
April 1-3, 2005

Abstracts


1.

各種金属箔を使用したガルバニ電池式酸素センサの検討

新コスモス電機

○今林秀和

Study of Galvanic Oxygen Sensor using Various Metal Leafs

H. Imabayashi

New Cosmos Electric Co., Ltd.
2-5-4, Mitsuya-naka, Yodogawa-ku, Osaka, 532-0036, Japan

A galvanic oxygen sensor has been developed using metal leaf as cathode and electrolytic solution. Various metal leafs (Cu, Ag, Au, Pt) as cathode, 3M-KOH basic solution and buffer solution consisting 4M AcOH-4MAcOK(Ac:CH3CO) acid solution as electrolytic solutions were used in the experiment to obtain optimum combination of cathode and electrolytic solution for the sensor. The Au leaf used as cathode had a lot of cracks and pinhole with size of 0.1μm-1.0μm, and this led to the sensor having fast and linear response to oxygen in a concentration range of 0% - 21%.

 

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2.

ポルフィリン分散高分子およびゾルゲル酸化ケイ素膜を用いたHCl、NO2、SO2の検出

(愛媛大工)

○中島俊一、出来克之、板垣吉晃、青野宏通、定岡芳彦

HCl , NO2 AND SO2 GASES DETECTION USING PORPHYRIN DISPERSED POLYMER AND SOL-GEL SILICON OXIDE FILMS.

Shunichi NAKASHIMA, Katsuyuki DEKI, Yoshiteru ITAGAKI, Hiromichi AONO and Yoshihiko SADAOKA

Department of Materials Science and Engineering, Faculty of
Engineering,Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan


The optochemical sensing performances of the porphyrin dyes dispersed in ethylcellulose (EC) and sol-gel SiO2 films to toxic gases such as HCl, NO2 and SO2 were examined using a photo-reflection spectrum technique. Sensing property was strongly influenced by matrices. In particular, sensitivity and response was variable with the composition of the sol-gel films.

 

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3.

モルホリン基を有する架橋高分子を塗布した水晶振動子によるHClガス検知

愛媛大工*、産総研**

○門脇良人*、松口正信*、野田和俊**、長縄竜一**

A QCM-BASED HCL GAS DETECTION USING MORPHOLINE-FUNCTIONAL CROSS-LINKED STYRENE-CO-CHLOROMETHYLSTYLENE COPOLYMER COATINGS

Yoshito KADOWAKI*, Masanobu MATSUGUCHI*, Kazutoshi NODA**, Ryuichi NAGANAWA**

*Department of Applied Chemistry, Ehime University
Matsuyama 790-8577, Japan
**Institute for Environmental Management Technology, National Institute of
Advanced Industrial Science and Technology (AIST)
Tsukuba 305-8569, Japan

A quartz resonator coated with linear or cross-linked poly(styrene-co-chloromethyl styrene) reacted with morpholine were studied for simply but accurately detecting HCl gas in air. The exposure of the resonator to 100 ppm HCl gas irreversibly decreased the oscillation frequencies. The result indicated that this device can be used for one-shot detection of HCl gas. The HCl sensitivity defined as hourly changes in frequency obtained for the morpholine-functional cross-linked copolymer was larger than that for the morpholine-functional linear copolymer. The optimum sensitivity obtained in this study demonstrated a ppm level of HCl detection.

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4.

ZnO厚膜型VSCセンサの応答特性の改善

新コスモス電機

○中村 俊一, 前川 亨, 鈴木 健吾

Improvement of response characteristic of ZnO thick film type VSC sensor

S. Nakamura, T. Maekawa, K. Suzuki

New Cosmos Electric Co., Ltd.

2-5-4 Mitsuya-naka, Yodogawa-ku, Osaka, 532-0036, Japan

Carbon particles with size of 3 to 50μm were applied to ZnO thick film to improve response to VSC (Volatile Sulfur Compounds) gases before sintering the film, and the particle with size of 3μm was found to be suitable for the purpose. An excellent porous structure was obtained after the carbon particles were oxidized into carbon dioxide in sintering process at temperature of 1100℃.

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5.

Ce1-xZrxO2を使った抵抗型酸素センサのプロパン燃焼ガス中での応答評価

(産総研)  ○伊豆典哉、申ウソク、松原一郎、村山宣光、

(ヤマハ発動機) 大堀徳子、伊藤雅樹

RESPONSE OF RESISTIVE OXYGEN SNSOR USING Ce1-xZrxO2 IN PROPANE COMBUSTION GAS

Noriya IZU, Woosuck SHIN, Ichiro MATSUBARA, Norimitsu MURAYAMA, Noriko OH-HORI*, Masaki ITOU*

National Institute of Advanced Industrial Science and Technology (AIST)
2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8569
*Yamaha Motor Co., Ltd., 2500 Shingai, Iwata, Shizuoka 438-8501

Response properties of resistive oxygen sensor using Ce1-xZrxO2 thick film in model gas of automobile exhaust gas were investigated. Model gas was prepared by mixing N2, O2 and C3H8 and combustion in catalyst. λ was defined as λ={C(O2) / C(C3H8)} / {C(O2) / C(C3H8)}stoich. , where C(O2) and (C3H8) are flow rate of O2 and C3H8, respectively, and (C(O2)/C(C3H8))stoich is stoichiometric ratio. In the case of Ce1-xZrxO2 thick film, the resistance in rich region (λ>1) and in lean region (λ<1) were several 10 Ω and several 1 kΩ, respectively. So there was a 2-order magnitude difference between two regions. It was revealed that the sensor using Ce1-xZrxO2 can be used for λ sensor, which can distinguish between rich and lean regions.

 

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6.

SmFe1-xCoxO3半導体ガスセンサによるオゾンおよびNO2の検出

愛媛大工

○細谷祐樹、森雅美、板垣吉晃、青野宏通、定岡芳彦

OZONE AND NO2 DETECTION USING SmFe1-xCoxO3 GAS SENSOR

Yuki HOSOYA, Masami MORI, Yoshiteru ITAGAKI, Hiromichi AONO, and Yoshihiko SADAOKA

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

The sensor property for Ozone and NO2 detection by using SmFe1-xCoxO3(x=0〜1.0) semiconducting material evaluated with various Co contents. The conductivity of the sensor elements in air was remarkably increased by doping Co to SmFeO3 and continued to increase with increasing the Co contents. For this increment of the reference conductivity, operating temperature for the measurable maximum sensitivity could be lowered, especially for ozone gas.

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7.


酸化インジウム薄膜マイクロセンサの塩素ガス検知特性に及ぼすマイクロギャップの効果

立命館大理工

○新美 潤、小椋俊介、小西 聡、玉置 純

EFFECT OF MICRO-GAP ELECTRODE ON CHLORINE GAS SENSING PROPERTIES OF INDIUM OXIDE THIN FILM MICROSENSORS

Jun NIIMI, Shunsuke OGURA*, Satoshi KONISHI*, Jun TAMAKI

Department of Applied Chemistry, Faculty of Science and Engineering,
Ritsumeikan University, Kusatsu-shi, Shiga 525-8577, Japan
*Department of Micro System Technology, Faculty of Science and Engineering,
Ritsumeikan University, Kusatsu-shi, Shiga 525-8577, Japan

Effects of gap-size on dilute Cl2 sensing properties of In2O3 thin film microsensors have been investigated. Micro-gap electrodes with various gap sizes (0.1-2 μm) were fabricated on SiO2/Si substrate by means of MEMS techniques (photolithography and FIB). Then the In2O3 thin film was deposited on the micro-gap electrode by using suspension dropping method to be micro-gas sensor. The sensing properties to dilute Cl2 of In2O3 thin film microsensors were evaluated in the range of 0.05-3 ppm at 250 ℃. For all sensors, the sensor resistance was increased up on exposure to dilute Cl2 larger than 1 ppm (Rg/Ra>1), while the resistance was decreased to dilute Cl2 less than 0.5 ppm (Rg/Ra<1). In both cases, the sensitivity to dilute Cl2 tended to increase with decreasing gap size. However, the sensitivity increase began at different gap size, i.e., less than 0.8 μm for resistance increase, less than 0.5 μm for resistance decrease. The behavior was almost the same as dilute NO2 detection using WO3 sensor and was explained by the large contribution of electrode-grain interface in small gap and the large resistance change at interface.

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8.

液相析出法(LPD法)による SnO2薄膜センサ特性の評価

新コスモス電機,日本板硝子*,神戸大学**

○伊藤達也,神田奎千,鈴木健吾,関口幸成*,斉藤靖弘*,水畑 穣**,出来成人**

Characterization of SnO2 thin film sensor by Liquid Phase Deposition (LPD) method

Tatsuya ITO, Keisen KANDA, Kengo SUZUKI, *Yukinari SEKIGUCHI, *Yasuhiro SAITO, **Minoru MIZUHATA, **Shigehito DEKI

New Cosmos Electric Co., Ltd., Osaka, 532-0036, Japan
*Nippon Sheet Glass Co., Ltd., Kansai Research Center, Itami, 664-8520, Japan
**Department of Chemical Science & Engineering, Faculty of Engineering, Kobe University, Kobe, 657-8501 Japan

The Liquid Phase Deposition (LPD) method was applied to fabricate SnO2 sensing films. The sensing films were sintered at temperature of 600-1200℃ to control mean grain size of the films in the range of 10-60nm. The fine structure was easily controlled by LPD method. Sensing properties of the films at different operating temperatures were also investigated. Optimum condition of the sensor was observed at mean grain size of 20nm and 400&ordm;C. The sensor in this condition had much higher sensitivity and gas selectivity to aromatic hydrocarbons as compared to conventional SnO2 gas sensor.

 

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9.

MEMSによるマイクロガスセンサの開発

(矢崎総業)

○植松彰一

A MICRO-GAS SENSOR BASED ON MEMS TECHNOLOGY

Shoichi UEMATSU

Technology Center, Yazaki Co. Ltd., Susono-shi, Shizuoka 410-1194

A catalytic combustion type gas sensor with low heat capacity employing Pd/Al2O3 was fabricated by MEMS Technology. The sensor showed a large response peak before reaching a steady-state value upon pulse-driven heating for 0.4 s with a cycle of 1-30 s when volatile organic compounds were contained in the environment. The unique peak response has likely arisen from the combustion of the volatile organic molecules adsorbed on the catalytic sensor material during the non-heating period. The peak height or area increased with the concentration of target gases. The response shapes and more notably their differential profiles were dependent on the molecular structure and the chain length. From such different response profiles, it would be possible to discriminate and quantify the VOC gases.

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10.

酸化物半導体粉末表面へのメソポーラスSnO2の修飾と貴金属担持によるガスセンサ特性の改良

○伊丹誠一郎,兵頭健生,清水康博,江頭 誠

長大工

Synergistic Effect of Noble Metal-loading and Surface Modification with Mesoporous SnO2 on the Gas-sensing Properties of SNO2

S. Itami,T. Hyodo,Y. Shimizu and M. Egashira

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

Simultaneous surface modification of SnO2 powder with a mesoporous SnO2 (m-SnO2) layer and noble metal-loading has been conducted. The sensors fabricated with the powders prepared with Pt-loading and subsequent modification with the m-SnO2 layer showed higher H2 response than the sensors fabricated with the reverse procedure sequence. Similar synergistic effects in sensing properties to CH4 and C2H5OH were also observed at higher operating temperatures. However, such a synergy effect was not observed when CO was employed as a sample gas, irrespective of modification sequence, and the CO response decreased markedly probably due to a filtering effect by the m-SnO2 layer. Thus, strict control of mesoporous structure and loading state of catalyst microparticles on the surface of SnO2 was found to be important to improve gas-response properties of SnO2-based sensors.

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11.

陽極酸化膜とPd電極を組み合わせたダイオード型ガスセンサ

○兵頭健生1,大岡淳二2,清水康博2,江頭 誠1

1長大工,2長大生産科学

AN ANODIC OXIDE FILM COUPLED WITH A Pd ELECTRODE AS A DIODE-TYPE GAS SENSOR

Takeo HYODO1, Junji OHOKA2, YasuhiroSHIMIZU2 and Makoto EGASHIRA1

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

H2 sensing properties of an anodically oxidized Nb2O5 film coupled with a Pd electrode (Pd/Nb2O5) have been investigated under various operating conditions. Current-voltage characteristics of the Pd/Nb2O5 sensor at 100°C apparently showed a typical rectifying function of a metal- semiconductor junction, which was formed between the Pd electrode and the Nb2O5 thin film, especially in H2 balanced with dry air. Predictably, it exhibited high response to H2 at 100°C under a forward bias voltage of +0.5 V, while its response and recovery speed were relatively slow, because of the low operating temperature. On the other hand, it showed no response to H2 under a reverse bias voltage of -0.5 V. The H2 response was drastically improved when it was operated under a forward bias above 150°C, while the recovery speed at 150°C was almost comparable with that observed at 100°C. Furthermore, it was confirmed that the Pd/Nb2O5 could response to H2 in dry air, even at R.T.

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12.

La2O3で増感したSnO2系ガスセンサのC2H4O検知特性

九大院総理工

○釘島裕洋、島ノ江憲剛*、山添 f*

C2H4O SENSING PROPERTIES FOR THICK FILM SENSOR USING La2O3-MODIFIED SnO2

Masahiro KUGISHIMA, Kengo SHIMANOE* and Noboru YAMAZOE*

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

*Department of Material Sciences, Faculty of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580

A series of devices with various La2O3 loadings up to 7 wt.% was subjected to measurements of the electrical resistances in air and the sensor response to C2H4O. The addition of La2O3 brings about an extensive increase in Ra even at 0.5wt.% loading, further loadings giving rise to increments in Ra. The electrical resistance in air of the La2O3(5wt.%) loading device increased by about five orders of magnitude as compared that of the device without loading. The highest sensor response to C2H4O at 250 and 300℃ was attained at a loading of 5wt.%, while the sensor response at 350℃ showed no great difference in between 1-7wt.% loading. The sensor response to 20 ppm C2H4O at 250℃ for the device loading 5wt.%La2O3 was higher than that of the 0.5wt.%La2O3-loaded device reported previously.

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13.

R. F. プラズマ溶射による好感度ホルムアルデヒドセンサの開発

埼玉大学理工学研究科,ウチヤ・サーモスタット(株)

 麗琴,長谷川有貴,勝部昭明,中野 守,中村清純

HIGHLY SENSITIVE FORMALDEHYDE SENSOR FABRICATED WITH R.F. INDUCTION PLASMA DEPOSITION METHOD

Liqin Shi, Y. Hasegawa, T. Katsube, M. Nakano, K. nakamura

Faculty of Engineering, Saitama University
255 Shimo-okubo, Sakura, Saitama 338-8570, Japan
Uchiya Thermostat Co., Ltd.
2-176-1 Takasu Misato, Saitama 341-0037, Japan

The present work is concerned on developing high performance and reliable SnO2-Based gas sensor for detecting indoor air pollutant formaldehyde (HCHO) gas. The sensors were deposited on an alumina substrate using R.F. Induction Plasma Deposition (IPD) technique. The obtained sensors showed high sensitivity to typical indoor air pollutant HCHO gas at an extremely low concentration 20 parts-per-billion (ppb) with quick response and recovery time less than several minutes. The effects of the addition of various metallic addives on the gas-sensing properties were also investigated in the work.

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14.

YSZ平板と種々の温度で焼成したNiO検知極を組み合わせた混成電位型NO2センサ

九大産学連携センター1、リケン (株) 2

○ペルマル エルマレイ1,寺田 大将 1,長谷井 政治2,三浦 則雄1

YSZ-BASED MIXED-POTENTIAL-TYPE PLANAR NO2 SENSORS USING NiO SENSING ELECTRODES SINTERED AT DIFFERENT TEMPERATURES

Perumal ELUMALAI 1, Daisuke TERADA 1, Masaharu HASEI 2, Norio MIURA 1

1 Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580, Japan
2 R&D Division, Riken Corporation, Kumagaya-shi, Saitama 360-8522, Japan

A planar NO2 sensor was fabricated by using an yttria-stabilized zirconia (YSZ) plate and NiO sensing-electrode (SE). The NO2 sensing characteristics of the sensor were examined at elevated temperature. It was found that the emf output of the sensor varied linearly with NO2 concentration on a logarithmic scale. In addition, the sensor employing the 1300℃-sintered NiO-SE could detect NO2 selectively even at 900℃ under wet condition, with acceptable NO2 sensitivity as well as response/recovery rates. It was shown that the sensing mechanism of the present sensor could be explained by the mixed-potential model, based on the results of the measurements for complex impedance, polarization curve and gas-phase catalysis.

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15.

ロジウムを添加した酸化ニッケルを検知極とした混成電位型ジルコニアNOxセンサの高温作動特性

九大産学連携センター1、リケン(株)2

○王 健1,エルマレイ ペルマル1,寺田 大将1, 長谷井 政治2, 三浦 則雄1

MIXED-POTENTIAL-TYPE ZIRCONIA-BASED NOx SENSOR USING Rh-LOADED NiO SENSING ELECTRODE OPERATING AT HIGH TEMPERATURES

Jian WANG 1, Perumal ELUMALAI 1, Daisuke TERADA 1, Masaharu HASEI 2, Norio MIURA 1

1 Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580, Japan
2 R&D Division, Riken Corporation, Kumagaya-shi, Saitama 360-8522, Japan

Recently, we found that the YSZ-based sensor using NiO sensing-electrode (SE) showed good response characteristics to NO2 even at high temperatures above 800°C in the presence of water vapor. We report here the improvement of sensing characteristics by the addition of noble metal to NiO-SE. A planar sensor was fabricated by using an YSZ plate and NiO-SE loaded with various noble metals, such as Pt, Rh, Ir, Pd and Ru. Among the various noble metals examined, Rh was found to give a significant enhancement in NO2 sensitivity. In addition, this enhancement was maximum when the Rh content in NiO-SE was 3 wt.%. The emf output was as high as about 77 mV to 50 ppm NO2 for the sensor using the Rh(3 wt.%)-loaded NiO-SE even at 800°C in the presence of 5 vol.% H2O. The NO2 sensitivity was hardly affected by the change in H2O concentration in the examined range of 5-15 vol.%.

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16.

複素インピーダンス応答型ジルコニアセンサの炭化水素に対する検知特性

九大院総理工a、九大産学連携センターb

○中藤 充伸a、三浦 則雄b

SENSING PERFORMANCES OF IMPEDANCEMETRIC ZIRCONIA-BASED SENSOR FOR DETECTING HYDROCARBONS

Mitsunobu NAKATOU a, Norio MIURA b

a Interdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580, Japan
b Art, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580, Japan

We have recently proposed and examined new-type impedancemetric sensors using yttria-stabilized zirconia (YSZ) and oxide sensing-electrode (SE) for detection of total NOx, H2O and hydrogen-containing gases at high temperatures. Here, we report that this type impedancemetric sensor based on YSZ can detect some hydrocarbons (HCs) sensitively and selectively under wet condition, if the selection of SE material and operating condition could be made properly. Among the various single-oxide SEs examined, SNO2 gave the highest sensitivity to C3H6 at 600°C. However, this oxide has also given relatively high sensitivity to CH4 which is not regulated as an air pollutant. Thus, we have chosen ZnO as an SE material which gives rather high sensitivity to C3H6 as well as negligible sensitivity to CH4. In addition, when 1.5 wt.% Pt was added to ZnO-SE and +50 mV vs. Pt counter electrode (CE) / reference electrode (RE) was applied to this SE, the present sensor was found to detect C3H6 rather sensitively having little interference with other gases, such as CO, NO, NO2, H2 and CH4, at 600°C even in the presence of 1 vol.% H2O.

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17.

固体電解質インピーダンストランスデューサと酸化物レセプタを用いたNOxセンサ

九工大工

○木庭大輔、高瀬聡子、清水陽一

NOx SENSOR USING SOLID ELECTROLYTE IMPEDANCE TRANSDUCER AND OXIDE RECEPTOR

Daisuke KOBA, Satoko TAKASE and Youichi SHIMIZU

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

Impedance metric new all-solid-state ceramic NOx sensor has been developed using solid-electrolyte and oxide receptor. The electrochemical device composed of Li1.5Al0.5Ti1.5(PO4)3 (LATP) and perovskite-type oxide LaBO3 (B= Co, Cr, Ni, Mn, Fe) as the transducer and the receptor, respectively, have been systematically investigated for the detection of NOx (NO, NO2 and N2O) in the range 10-2000ppm at 400-500℃. Responses of these sensors were able to divide component between resistance and capacitance, and it was found that the device is applicable to the selective detection of NO and NO2 concentration in each ingredient, while
no response was observed to N2O with them. Among the sensor devices tested, those using LaCoO3-, and LaCrO3 based receptor gave good selectivity to NO. The LaNiO3/LATP based sensor element showed excellent NOx sensing properties.

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18.

LaGaO3系酸化物を電解質とする電流検出型NOxセンサにおける応答特性向上

九大院工

○石原達己*,Atanu Dutta,松本広重

IMPROVEMENT OF RESPONSE CHARACTERISTICS OF AMPEROMETRIC NOX SENSOR USING LaGaO3 BASED OXIDE ELECTROLYTE

Tatsumi Ishihara, Atanu Dutta, Hiroshige Matsumoto

Department of Applied Chemustry, Faculty of Engineering, Kyushu University
Hakozaki 6-10-1, Higashiku, Fukuoka 814-8581

In order to detect NOx selectively in exhaust gas from internal combustion engines, amperometric NOx sensor using LaGaO3 based oxide electrolyte was studied. It was found that the oxygen pumping current is highly selective to NO when La0.5Sr0.5MnO3 (LSM) and La0.4Sr0.6Mn0.8Ni0.2O3(LSMN) are used for inactive and active electrode respectively. However, 90 % response requires a little longer time and so, improvement for response characteristics is required. Potential response to NO suggests that slow response is result from slow response on LSM electrode. It was found that addition of small amount of Fe is effective for increasing the response time to NO and 90% response can be achieved within 10 s at all temperature range examined.

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19.

EPD法およびスクリーンプリント法によるLa0.8Sr0.2MnO3薄膜の調製と限界電流式酸素センサへの応用

(愛媛大工)

○甲木純、Sophii Elfi Reza、板垣吉晃、定岡芳彦

PREPARATION OF La0.8Sr0.2MnO3 FILMS BY EPD METHOD AND SCREEN PRINT AND APPLICATION FOR LIMITING CURRENT OXYGEN SENSOR

Jun KATSUKI, Sophii Elfi REZA, Yoshiteru ITAGAKI, and Yoshihiko SADAOKA

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

 Limiting current oxygen sensor with LSM/YSZ binary layer was fabricated. The LSM layer as an oxygen diffusion barrier was found by EPD and screen print methods. Up to 14% good linearity was observed between the limiting current and O2 concentration. The sensor property was fairly dependent on the film thickness and structure.

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20.

BiCuVOx固体電解質にペロブスカイト型酸化物電極を組み合わせた酸素センサの低温作動特性

九大院総理工

趙漢尚、○島ノ江憲剛*、山添 f*

OXYGEN SENSOR COMBINING BiCuVOx SOLID ELECTROLYTE WITH PEROVSKITE TYPE OXIDE ELECTRODE

H.-S. Cho, K. SHIMANOE* and N. YAMAZOE*

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


Oxygen concentration cells were investigated by using a disk of BiCuVOx attached with the composite electrode of BiCuVOx and perovskite-type oxide in the oxygen concentration of 10% to 100% at various temperatures. Among the composite electrodes tested, La0.6Sr0.4Co0.78Ni0.02Fe0.2O3 composite electrode-attached cell showed good EMF response, which included Nernst correlation to oxygen concentration with reaction electron number of 4, in the temperature range of 350 to 700℃.

 

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21.

YSZを用いた水素センサの開発

新コスモス電機

○中里嘉浩, 川端有香, 前川亨

A SOLID ELECTROLYTE TYPE HYDROGEN GAS SENSOR USING YTTRIA STABILIZED ZIRCONIA

Yoshihiro NAKAZATO, Yuka KAWABATA, Toru MAEKAWA

New Cosmos Electric Co., Ltd.
2-5-4 Mitsuya-naka, Yodogawa-ku, Osaka 532-0036, Japan

A solid electrolyte type hydrogen(H2)gas sensor has been developed using yttria stabilized zirconia(YSZ). The sensor was fabricated on an alumina substrate with a Pt thin film heater on one side by fixing a rectangular YSZ sensing element on the other side of the substrate. The dependency of the sensor on operating temperature was investigated at a temperature range of 400-700℃, and the sensing characteristics of the sensor were investigated with four kinds of gases. The optimum operating temperature of the sensor was found at 600℃. The sensor showed high sensitivity and good gas selectivity to H2 in a concentration range of 10-10000ppm with fast response, though the sensor output does not obey the Nernst equation.

 

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22.

アパタイト型希土類シリケート系酸化物イオン伝導体の調整と応用

愛媛大工

○竹田尚貴、中村悠一、板垣吉晃、青野宏通、定岡芳彦

PREPARATION AND APPLICATION OF APATITE-TYPE RARE-EARTH SILICATE OXIDE IONIC CONDUCTORS

Naoki TAKEDA, Yuuichi NAKAMURA, Yoshiteru ITAGAKI, Hiromichi AONO and Yoshihiko SADAOKA

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

The Ln9.33+x/3Si6-xAlxO26.(Ln=La,Nd,Sm, 0≦x≦2) were prepared by the sintering at 1600 ℃ for 5h. The single phase and the highest conductivity were obtained for x=1.5. The conductivity for the x=1.5 depended on the ionic radius of Ln3+ ion and the maximum value was obtained for La9.83Si4.5Al1.5O26 (6.98×10-5 S・cm-1 at 500 ℃). The electron number for O2 gas concentration cell was almost agreed with theoretical value even at 400 ℃.

 

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23.

NASICONを用いた炭酸ガスセンサにおける検知電極の安定化

愛媛大工

○津村直樹、島本洋一、板垣吉晃、青野宏通、定岡芳彦

STABILIZATION OF SESNSING ELECTRODE FOR CARBON DIOXODE SENSOR USING NASICON

Naoki TSUMURA, Youichi SHIMAMOTO, Yoshiteru ITAGAKI, Hiromichi AONO,and Yoshihiko SADAOKA

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

Stabilization of EMF response was studied for the CO2 gas sensor using NASICON electrolyte with mixture of oxide material and Li2CO3 as an auxiliary phase. The long-term stability was improved for the sensor using Li2CO3-Nd2O3 mixture (Nd2O2CO3 was formed by pre-heating at 800℃ in 100% CO2 gas) as the auxiliary phase.

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24.

固体電解質を用いたCO2ガスセンサの開発

新コスモス電機、阪大院工*、日本分析化学専門学校**

○川端有香、中里嘉浩、前川 亨、鈴木健吾、石川 博、田村真治*、今中信人*、足立吟也**

DEVELOPMENT OF SOLID ELECTROLYTE TYPE CARBON DIOXIDE GAS SENSOR

Yuka KAWABATA, Yoshihiro NAKAZATO, Toru MAEKAWA, Kengo SUZUKI, Hiroshi ISHIKAWA, Shinji TAMURA*, Nobuhito IMANAKA*, and Gin-ya ADACHI**

New Cosmos Electric Co., Ltd.,
2-5-4 Mitsuya-naka, Yodogawa-ku, Osaka 532-0036, Japan
*Department of Applied Chemistry, Faculty of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
**Juri Institute for Environmental Science and Chemistry, College of Analytical Chemistry,
2-1-8 Tenma, Kita-ku, Osaka 565-0043, Japan

A compact solid electrolyte type carbon dioxide (CO2) gas sensor was fabricated by applying Al3+ cation and O2- anion conducting solid electrolytes with the refractory Li2CO3-doped La2O2SO4 solid as the detecting auxiliary electrode. An excellent contact between the two solid electrolytes was successfully realized by sintering the Al3+ cation conductor and the O2- anion conductor simultaneously, promising the stable CO2 sensing performance. The sensor output of the present compact CO2 sensor obeys Nernstian theoretical relationship with the response time less than 10 s and with holding the long-term stability at the operating temperature of 500°C. Since the electric consumption of the sensor is ca. 0.5 W which allows the sensor operation by batteries, the present sensor is greatly expected to be a commercial CO2 gas sensing tool.

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25.

多価イオンを伝導種とする固体電解質を用いた新規なSO2ガスセンサ

阪大院工

○長谷川功、田村真治、今中信人

SULFUR DIOXIDE GAS SENSOR BASED ON MULTIVALENT ION CONDUCTING SOLID ELECTROLYTES

Isao HASEGAWA, Shinji TAMURA, Nobuhito IMANAKA

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

A new solid electrolyte type sulfur dioxide (SO2) gas sensor was fabricated by using trivalent Al3+ cation and divalent O2- anion conducting solid electrolytes with the rare earth oxysulfate based auxiliary electrode. The present SO2 gas sensor showed such good sensing performances of rapid, stable, continuous, and reproducible response and the linear relationship between the sensor output and the logarithm of the SO2 concentration was obtained in the SO2 gas concentration range from 200 to 2000 ppm at 500℃. The n value (2.04) calculated from the EMF - log(P so2) relationship was in an excellent agreement with the theoretical one (n=2.00) for the sensor with 0.7La2O2SO4-0.3Li2SO4 as the auxiliary electrode.

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26.

金属酸化物相を接合した固体電解質NO2センサの室温における検知特性評価

北九州高専

小畑賢次, 末吉 聡, 松嶋茂憲

SENSING PROPERTIES OF NASICON-BASED NO2 SENSOR ATTACHED WITH METAL OXIDE OPERATIVE AT ROOM TEMPERATURE

Kenji OBATA, Satoshi SUEYOSHI and Shigenori MATSUSHIMA

Department of Materials Science and Chemical Engineering, Kitakyushu
National College of Technology, 5-20-1 Shii, Kokuraminami-ku,
Kitakyushu-shi, Fukuoka 802-0985

NASICON (Na3Zr2Si2PO12)?based potentiometric NO2 devices, such as an Au-attached and an (ITO, NaNO2)-attached types, were prepared and their NO2 sensing properties investigated in the range of 1.9 to 6.7 ppm NO2 diluted with air at 30 °C. The Au-attached device was found to have a NO2 sensing capability under a humidity condition (30 %RH) without any auxiliary phase, although it showed no EMF response under a dry condition (below 1 %RH). This experimental result suggests that NO2 sensing reaction of the device is closely related with water vapor. To enhance the NO2 sensitivity of the NASICON-based device, the (ITO, NaNO2)-attached device was therefore fabricated. As the result, the EMF of the (ITO, NaNO2)-attached device was estimated to be 43.6 mV under a humidity condition and improved more remarkably, in comparison with 17.7mV of the Au-attached one.

 

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27.

ペロブスカイト型酸化物とBiCuVOxを複合参照極とした電位検出型CO2センサ

九大院総理工

○宮地 祐治、岸 章太郎、島ノ江憲剛*、山添 f*

POTENTIOMETRIC TYPE CO2 SENSOR USING A MIXTURE OF A PEROVSKITE TYPE OXIDE AND A BiCuVOx AS A COMPOUND REFERENCE ELECTRODE

Yuji MIYACHI, Shotaro KISHI, Kengo SHIMANOE* and Noboru YAMAZOE*

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

A composite of perovskite type oxide (La0.6Sr0.4Co0.78Ni0.02Fe0.2O3) and BiCuVOx (Bi2Cu0.1V0.9O5.35) was investigated as a reference electrode for a potentiometric detection type CO2 sensor using NASICON (Na+ conductor, Na3Zr2Si2PO12). It was found that the potential of the composite electrode was very stable to exposure of CO2 gas at 400-450 oC under humid as well as dry conditions. The CO2 sensor using the compound reference electrode showed good CO2 sensing properties. In addition, although the measurement time was very short, thermal cycling between the operating temperature (450 oC) and room temperature under 80% relative humidity condition indicated that the compound reference electrode exhibited showed the properties of a reliable counter electrode, i.e., rapid warm-up characteristics and reproducible stationary potential at 450 oC.

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28.

LiXLn10-XSi6O27‐X(Ln=La,Nd)の固体電解質CO2ガスセンサへの応用

愛媛大工

○藤嶋 学、宮広 匠、板垣吉晃、青野宏通、定岡芳彦

PREPARATION OF LiXLn10-XSi6O27‐X(Ln=La,Nd) AND ITS APPLICATION FOR POTENTIOMETRIC CO2 GAS SENSOR

Manabu FUJISHIMA, Takumi MIYAHIRO, Yoshiteru ITAGAKI, Hiromichi AONO,and Yoshihiko SADAOKA

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

To develop a stable solid-state lithium ionic conductor for potentiometric CO2 gas sensor, LiXLn10-XSi6O27‐X(Ln=La,Nd)(x=1~3) sinters were prepared. The dense electrolyte was formed for Li2Ln8Si6O25 by sintering at 1300oC while for other examined materials were porous. Li2CO3 mixed with the Li2Ln8Si6O25 was remarkably stable and not decomposed until ca. 800oC in air. For comparison single decomposition of the Li2CO3 was observed at 700oC. It is expected that the Li2CO3 auxiliary phase with Li2Ln8Si6O25 electrolyte is stable at the working temperature of the potentimetric CO2 sensor with the structure of CO2,Li2CO3,Pt/Li+-conductor/Pt.

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29.

K-Ln-Si-O系固体電解質(Ln=Nd,Sm)のイオン伝導と炭酸ガスセンサへの応用

愛媛大工

○伊東祐介、横井厚平、板垣吉晃、青野宏通、定岡芳彦

IONIC CONDUCTIVITY FOR SOLID ELECTROLYTE OF K-Ln-Si-O SYSTEM (Ln=Nd,Sm) AND ITS APPLICATION OF CO2 GAS SENSOR

Yusuke ITOH, Kohei YOKOI, Yoshiteru ITAGAKI, Hiromichi AONO, and Yoshihiko SADAOKA

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

The K-Ln-Si-O (Ln=Nd,Sm) system electrolyte was prepared and it applied for an EMF type CO2 gas sensor. The maximum conductivity was obtained for K2O-Sm2O3-4SiO2.The drifts of EMF response were confirmed for CO2 gas sensor using the K2O-Sm2O3-4SiO2 with A2CO3 (A=Li,Nd,Sm) auxiliary phase. The formation of some alkali silicates was confirmed by the reaction of A2CO3 (A=Li,Na,K) and the solid electrolyte.

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32.

SIMULTANEOUS ELECTROANALYSIS OF PEROXONE

Mohamed Ismail Awad and Takeo Ohsaka

Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan

Peroxone, a mixture of ozone (O3) and hydrogen peroxide (H2O2), has been analysed potentiometrically using Pt indicator electrode and I-/I3- redox couple as a probing potential buffer. The analysis is based on the measurement of the change of the open circuit potential of the indicator electrode as a result of the reaction of the oxidant mixture and I-. The large difference in the reaction rates of the oxidation of I- by the two oxidants enabled a selective and simultaneous analysis of both oxidants: a transient potential response corresponding to the reactions of the two species with I- was observed, typically a few seconds and several minutes for PAA and H2O2, respectively. The selectivity was optimized by controlling the experimental factors expected to affect the oxidation rates of I- by the two oxidants. Further, the equation describing the time dependency of the potential change was derived by considering the rate constants of the reactions of I- and the oxidants, and it was found to fit into the experimental results.

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33.

藻類の鞭毛運動を利用した環境毒性物質検出法

東大生研

○四反田功,高田主岳,酒井康行,立間 徹

DETECTION OF TOXIC COMPOUNDS IN THE ENVIRONMENT ON THE BASIS OF ALGAL FLAGELLAR MOVEMENT

Isao SHITANDA, Kazutake TAKADA, Yasuyuki SAKAI, Tetsu TATSUMA

Institute of Industrial Science, University of Tokyo,
4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan

Electrochemical biosensors for toxic substances such as toluene were developed on the basis of motility and gravitaxis of unicellular flagellate Chlamydomonas reinhardtii. Changes in the flagellar movement of the flagellates in response to the substances were monitored as changes in the redox currents for a coexisiting redox marker. The gravitaxis-based biosensor was more sensitive to toxicity than the motility-based biosensor. A dual electrode system sensitive to both gravitaxis and motility was also developed.

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34.

PMSを修飾したQCMセンサのタンパク応答に関する研究

埼玉工大院工

○関岡直行、山口忍、内山俊一

STUDY ON PROTEIN RESPONSE USING QCM SENSOR MODIFIED WITH PMS

Naoyuki.SEKIOKA, Shinobu.YAMAGUCHI, Shunichi.UCHIYAMA

Graduate School of Engineering, Saitama Institute of Technology

1690 Fusaiji Okabe Saitama 369-0293 Japan


Polymaleimidostyrene (PMS) has a plenty of maleimide groups on its polystyrene chain and is useful for immobilization of enzymes and other biopolymers. This study reports the preparation method of QCM sensor modified with PMS using dithiothreitol (DTT), and urease was measured by immobilization of urease to maleimide group of PMS. In conventional QCM measurement, the frequency continues to be changed because urease accumulates to the QCM surface although urease concentration is very low. But in this research, it was found that the stepwise frequency change was observed because PMS bonded urease was eliminated from PMS surface.The reciprocal number of steady state frequency change was proportional to that of urease concentration, and the novel analytical method using QCM was proposed.

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35.

ニュートン流体中における水晶振動子共振周波数変化の浸漬角度依存性

○丸山泰寛、黒澤 茂*、吉本 稔

鹿児島大、産総研*

IMMERSION-ANGLE DEPENDENCE OF THE RESONANT FREQUENCY OF THE QUARTZ CRYSTAL MICROBALANCE IN A NEWTONIAN LIQUID

Yasuhiro MARUYAMA, Shigeru KUROSAWA*, and Minoru YOSHIMOTO

Bioengineering, Kagoshima University, Kagoshima 890-0065, Japan
*National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan

We report the novel behavior of the immersion-angle dependence of the resonant frequency shift (僥) of the one-face sealed quartz crystal microbalance (QCM) in a Newtonian liquid. The immersion-angle dependence of 僥 appears below the sucrose concentration of 12wt%. However, the transition phenomenon of 僥 occurs between 12 and 20wt% and then the immersion-angle dependence of 僥 disappears above 20wt%. Namely, the 僥 values above 20wt% become equal to those of 90° in all immersion angles. We have also found that the same phenomenon appears in an increase with the source power of the impedance analyzer. This phenomenon has been observed in both cases of the one-face sealed QCM mounted at up and down orientations.

 

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36.

Belousov-Zhabotinsky反応における振動現象の溶液粘度依存性

○久保 臣悟,白濱 博幸,吉本 稔

鹿児島大

THE SOLUTION VISCOSITY DEPENDENT OF OSCILLATORY PHENOMENON IN BELOUSOV-ZHABOTINSKY REACTION

Shingo KUBO, Hiroyuki SHIRAHAMA, Minoru YOSHIMOTO

Department of Bioengineering, Faculty of Engineering, Kagoshima University,
1-21-40 Korimoto, Kagoshima 890-0065, Japan

We investigated the relationship between the redox potential and the periodic change of the solution viscosity and density in the Belousov-Zhabotinsky (BZ) reaction of the iron catalyst system ([Fe(Phen)3]2+ - [Fe(Phen)3]3+). Especially, we studied it by changing systematically the stir strength and the solution viscosity and density. The stir strength was controlled by the stirrer bar speed and the solution viscosity and density were varied by the non-ionic surfactant. As a result, it has become clear that the three main regions exist by the time difference between the redox potential and the solution viscosity and density. Moreover, we have found that these regions are closely related to the critical micelle concentration.

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37.

多成分系酸化物薄膜型エレクトロクロミック素子によるリン酸イオンセンサ

九工大工

○竹安智宏、宮谷 晃、大峰成人、高瀬聡子、清水陽一

ELECTROCHROMIC HYDROGEN-PHOSPHATE ION SENSOR USING MULICOMPONENT OXIDE THIN-FILM

Tomohiro TAKEYASU, Akira Miyatani, Naruhito OMINE, Satoko TAKASE and Youichi SHIMIZU

Department of Applied Chemistry, Faculty of Engineering,
Kyushu Institute of Technology, Tobata, Kitakyusyu 804-8550

Electrochromic behavior of various multicomponent metal oxide thin-film electrodes and their electrochemical characteristics have been studied for the use of hydrogen-phoshate ion sensing devices. The metal oxide thin-film electrodes were prepared by a spin-coating method at 500℃. Cyclic voltammograms of SnMn(9:1)Ox thin-film electrode showed dependence on hydrogen- phosphate ion concentration at -0.75V vs. SCE. The transmittance at 440 nm of SnMn(9:1)Ox thin-film electrode exhibits dependence on hydrogen- phosphate ion concentration at -0.75V vs. SCE, and also depended on nitrate ion concentration, while the response to nitrate ion was reverse in sign that to hydrogen-phosphate ion. So we could demonstrate hydrogen-phosphate ion sensor with high ion selectivity and sensitivity.

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38.

ALPカラムを用いた亜鉛(U)イオンの微量計測

神奈川工科大工・応用化学科

○佐藤生男・岩坪香織・飯田泰広

MICRODETERMINATION OF ZINC(II) IONS USING AN ALP COLUMN

Ikuo SATOH, Kaori IWATSUBO, and Yasuhiro IIDA

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

A flow-injection photometric sensing system armed with an alkaline phosphatase(ALP) column as a recognition element was applied to microdetermination of copper(II) ions. The enzymes covalently immobilized onto porous glass beads with controlled pore size (24.2 nm) were packed into a small polymer column. The enzyme-packed column was placed into a water-jacketed holder(303 K), which was incorporated into the sensing system equipped with a flow-through cell mounted in a UV/VIS detector. The catalytic activity was assessed by monitoring variations in absorbance at 405 nm attributable to p-nitophenol formed in the hydrolysis of p-nitophenyl phosphate as substrate solution. Exposing the column to 20 mM ethylenediaminetetraacetate solution (EDTA, pH 4.0) caused significant decrease in the catalytic activity. Then, recovery of the activity attributable to subsequent addition of 1.0 mM zinc(II) ions was observed. The activity partially reactivated was a function of zinc(II) ions injected. Thus, zinc(II) ions in a range of 1.0 uM to 1.0 mM could be photometrically determined.

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39.


アルカリホスファターゼ補因子の除去および付与の評価と計測への適用

神奈川工科大工・応用化学科

○飯田泰広・関根正史・佐藤生男

Estimation of Removal and Addition of Cofactors from Alkaline Phosphatase and Application of the Process to Determination of Zinc(II) Ions

Yasuhiro IIDA, Masashi SEKINE, and Ikuo SATOH

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

Removal and addition of a cofactor, i.e. zinc(II) ion, of alkaline phosphatase was investigated and then, the process was applied to measurement of zinc(II) ions in combination with a spectrophotometric flow-injection analysis (FIA) system. Alkaline phosphatase, a kind of typical metalloenzymes, was covalently immobilized onto porous glass beads, and packed into a small polymer column. Tris-HCl buffer as the carrier solution was continuously pumped through the system. Sample solutions were introduced into the system and the catalytic activity of the ALP column was assessed by injecting p-nitrophenyl phosphate as a substrate. The enzyme activity was not detected when chelating agents were introduced into the system or constant current was applied to the column at the isoelectric point. The recovery of the enzymatic activity could be revealed when zinc(II) ions solution was injected into the FIA system. Amounts of the cofactors removed from ALP were determined by using 5-Br-PAPS method in both of using chelating agents and applying constant current. The removal and addition processes were applied to the cofactor sensing.

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40.

基板修飾によるカーボンナノチューブセンサーの構築

北大創成

○武田晴治,服部聡史,澤村誠,石井睦,武笠幸一

IMMOBILIZATION OF CARBON NANOTUBES ON A CHWMICALLY MODIFIED SURFACES OF A SILICON OXIDE

Seiji TAKEDA, Satoshi HATTORI, Makoto SAWAMURA, Atsushi ISHII, Koichi MUKASA

Division of Project Research, Creative Research Initiative "Sousei"
Hokkaido Univversity, Sapporo 001-0021

Carbon nanotubes were immobilized on chemically modified silicone oxide surfaces and the Au electrode pad covered the surfaces to produce nanotube sensors. The property of the nanotube was investigated by measuring I-Vg curves and some of them showed FET characteristics. The yield of the producing of the sensors without chemically modification was lower than that of the sensors with chemical modification.

 

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41.

微細針状デバイスを用いたインビボ測定

徳島大工,東洋精密工業*,カンザス大学**

安澤幹人, ○高岡宏樹,清水利泰*,今井信治*,George S. Wilson**

IN VIVO MEASUREMENT USING FINE NEEDLE TYPE SENSORS

Mikito YASUZAWA, Hiroki TAKAOKA, Toshiyasu SHIMIZU*, Shinji IMAI*, George S. WILSON**

Department of Chemical Science and Technology, The University of
Tokushima, 2-1 Minamijosanjima, Tokusima 770-8506, Japan
*Toyo Precision Parts MFG. Co., Ltd., 97-1 Higashinaka, Yamatotakada,
Nara 635-0066, Japan
** Department of Chemistry, University of Kansas, 1251 Wescoe Hall Dr.,
Lawrence, KS 66045, USA

This study attempts to eliminate the noise signals observed on the response of in vivo glucose measurement due more to operational problem than the sensor properties. Measurement was performed without anesthesia in order to eliminate the influence of anesthetic on blood glucose level. Catheter was inserted into femoral vein for glucose injection and blood sampling for in vitro measurement. Fine needle type sensors were placed in flank adipose tissue, intra-abdominal tissue and veins of the neck and were measured using wired and wireless potentiostat. No noise and spike signals due to the operation of glucose injection and blood sampling were observed by the use of catheter. Clear glucose sensor response with good correlation with in vitro value was able to obtain on all three regions measurement, while time differences existed. The possibilities of successful measurements were lower on intra-abdominal tissue and veins of the neck than that of
adipose tissue.

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42.

電気化学バイオリソグラフィーによる微小流路内へのタンパク質の局所固定化

東北大院工1・院環境科学2

○梶 弘和1,月舘和人1,安部 隆1,末永智一2,西澤松彦1

ELECTROCHEMICAL BIO-LITHOGRAPHIC APPROACH TO LOCALLY IMMOBILIZE PROTEINS INSIDE MICROCHANNELS

Hirokazu KAJI1, Kazuto TSUKIDATE1, Takashi ABE1, Tomokazu MATSUE2, Matsuhiko NISHIZAWA1

1Department of Bioengineering and Robotics, Graduate School of Engineering,
2Department of Environmental Studies, Graduate School of Environmental Studies,
Tohoku University, Sendai 980-8579, Japan

A microfluidic device has been developed that can locally immobilize proteins on the bottom wall of the microchannel. The present technique is based on our finding that the protein-repellent feature of heparin-coated substrate can be switched to protein-adsorptive by exposure to an oxidizing agent such as hypobromous acid, which can be produced by electrochemical oxidation of bromide ion in aqueous solution. Since the microelectrode array fabricated at the upper wall of the channel enables the local generation of such reactive species, the subsequent introduction of protein solution into the channel results in the formation of protein pattern on the bottom wall of the channel. Our method can provide an expedient platform on which a set of protocols such as immobilization and measurement can be carried out under typical physiological conditions.

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44.

LIGAプラスチックレプリカプロセスによるマルチチャネル電気泳動チップ

産総研,甲南大理工,スターライト工業,イデヤ,京大院工

○脇田慎一,石井秀幸,鳴石奈穂子,宮道 隆,黒川正也,下間 昌,出村 民,田畑 修

Multichannel Microfluidic Chip Based on Capillary Electrophoresis Using Industrial LIGA Plastic Replica Process

Shin-ichi WAKIDA, Hideyuki ISHII, Nahoko NARUSIHI, Takashi MIYADO, Masaya KUROKAWA, Sakae SHIMOTSUMA, Tami DEMURA, Osamu TABATA

Research Center for Human Stress Signal, National Institute of Advanced Industrial Science and Technology (AIST),
Ikeda, Osaka 563-8577, Japan
Faculty of Science and Technology, Konan University, Kobe, Hyogo 658-8501, Japan
Starlite Co. Ltd., Kusatsu, Shiga 520-3004, Japan
Ideya Co. Ltd., Kizu, Kyoto 619-0021, Japan
Graduate School of Engineering, Kyoto University, Kyoto, Kyoto 606-8501, Japan

We fabricated 32-channel PMMA replica chip using industrial LIGA process based on the moving mask deep X-ray lithography technology, the automated electroplating apparatus technology and the plastic injection molding technology. The compact chip designed with 50 mm length and 30 mm wide was realized with a high aspect ratio channel of 0.03 mm wide, 0.05 mm depth and 0.1 mm channel pitch. We investigated electrophoretic separation for standard DNA ladder using a floating sample injection with cellulose based sieving media containing EtBr as an in-channel labeling reagent and detected with an avalanche photodiode detection system. The DNA ladder was separated from 100 bp to 700 bp within 2 minutes. We successfully demonstrated the DNA separation with the almost the same theoretical plate as that of the available plastic chip.

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46.

イオン注入ダイヤモンド電極による電気化学分析

慶大理工・東大RIC・KAST

○栄長泰明・Ivandini T. A.・佐藤利佳・巻出義紘・藤嶋昭

ELECTROCHEMICAL ANALYSIS BY USING ION-IMPLANTED DIAMOND ELECTRODES

Yasuaki EINAGA, Tribidasari A. IVANDINI, Rika SATO, Yoshihiro MAKIDE, Akira FUJISHIMA

Department of Chemistry, Keio University, Yokohama 223-8522, Japan
Radioisotope Center, The University of Tokyo, Tokyo 113-0032, Japan
Kanagawa Academy of Science and Technology, Kawasaki 213-0012, Japan


The determination of the electrochemical properties of supported catalyst particles is of great interest for fundamental and technical applications. Metal modification of conductive diamond has attracted great interest since it is reported that dispersion of metallic particle within an organic polymer or an inert surface resulting in drastic increase of the sensitivity of the electrode. Ion implantation is important since provide excellent stability of metal position at the diamond surface. We report here on the characterization of the physical, chemical, and electrochemical properties of ion-implanted boron-doped diamond electrode. As a result, we could detect H2O2, glucose, and arsenic compounds with high sensitivity by using the composite electrodes.

 

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47.

水素終端ダイヤモンド電極の電気化学的特性

慶大理工・KAST

○Ivandini Tribidasari. A.,藤嶋昭, 栄長泰明

THE IMPORTANCE OF H-TERMINATION FOR ELECTROCHEMICAL ANALYSIS USING DIAMOND ELECTRODES

Tribidasari A. IVANDINI , Akira FUJISHIMA and Yasuaki EINAGA

Department of Chemistry, Faculty of Science and Technology, Keio University,
3-14-1 Hiyoshi, Yokohama 223-8522, Japan
Kanagawa Academy of Science and Technology, KSP,
3-3-1 Sakado, Kawasaki 213-0012, Japan


The importance of H-terminated diamond electrodes for electrochemical oxidation of oxalic acid is examined by cyclic voltammetry and flow-injection analysis. The anodic oxidation of the compound has clearly shown that the charge of both analyte and electrodes is important to optimize the electrochemical reaction. The effects of pH and scan rate have also been observed.


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48.

平面脂質二分子膜を用いた味覚センサの開発

鹿児島大工

○野元満、西上原誠、吉本稔

Development an artificial taste sensor which used the planar lipid bilayer membranes

Mitsuru NOMOTO, Makoto NISHIKANBARA, Minoru YOSHIMOTO

Department of Bioengineering,Faculty of Engineering,Kagoshima University,
1-21-40 Korimoto, Kagoshima 890-0065, Japan

The dynamical behavior of the lipid bilayer membranes was experimentally studied under superposition of random, periodic membrane-potential fluctuations or constant membrane potential. The analysis of the mutual information has revealed that, in less than 10 Hz of random fluctuations, each of the time series of the mutual information of the transmembrane current for the five chemical substances (five basic tastants) has its inherent pattern, but not in a periodic fluctuation. On the other hand, the analysis of the power spectrum of the frequency could not distinguish those five basic tastants in random membrane-potential fluctuations. In addition, the periodic membrane-potential fluctuations and constant membrane potential could not distinguish those five basic tastants. We provide the new detection idea of tastants by random fluctuations.

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49.

病床環境における排泄臭の高感度検出システムの開発

大分大工,大分看護大*,大分精神保健福祉センター**

○井上高教,安部恭子*,宇都宮仁美*,藤内美保*,伊東朋子**,倉内芳秋,大賀一也

EXCRETION SMELL SENSING AND MONITORING SYSTEM IN A SICKBED

T.Inoue*, K.Abe**, H.Utsumiya**, M.Tounai**, T.Ito**, Y.Kurauschi, K.Ohga

*Oita Univ., ** Oita university of Nursing and Health Sciences

For the monitoring in a sickbed and air condition in a room, five gas sensors combined and the each signals were took simultaneously for a long time. The analysis of air by the room in the office space and the sickbed room and monitors were done. The density of the smell and ammonia increased at the diaper exchange and the signal changed. Principal component analysis clarified the subtle change. It was able to be thought that various gases can be judged from the score map of sensor signals. For the detection of stench when urinating in diapers, a little change of some sensors was able to be detected momentarily of urination.

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50.

プレーナ型尿糖センサの長寿命化

タニタ体重科学研究所

○池田 悟,細井秀樹,大橋昭王,宮下真理子,伊藤成史

A MICRO-PLANER AMPEROMETRIC BIOSENSOR FOR QUANTITATIVE URINARY GLUCOSE MEASUREMENT WITH IMPROVED LONGEVITY

Satoshi IKEDA, Hideki HOSOI, Akio OHASHI, Mariko MIYASHITA, Narushi ITO

TANITA Body Weight Scientific Institute
1-14-2, Maeno-cho, Itabashi-ku, Tokyo 174-8630, Japan

A quantitative urinary glucose meter developed by us contains a micro-planer amperometric biosensor for the quantitative urinary glucose measurement. The sensor has an organic thin-film layered structure consisting of a diffusion limiting layer, an enzyme layer, Nafion layer and a silane coupling layer. The structure allows accurate measurements of urinary glucose levels with removal of interferents effect. However, the reusability of the existing biosensor is 30 days when used for the actual measurements of urine samples. By investigating ways to improve the long-term stability, it has been clarified that the removal of interferents effect deteriorates with repeated measurements of actual samples. Based on this result, we have modified configuration parameters of Nafion layer and the silane coupling layer which participate in the removal of interferents effect. The improvement provides the biosensor with improved longevity of 60 days.

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51.

温度補正機能を備えたプレーナ型尿糖センサの開発

タニタ体重科学研究所

○細井秀樹,池田悟,大橋昭王,宮下真理子,伊藤成史

DEVELOPMENT OF A QUANTITATIVE URINARY GLUCOSE SENSOR CONTANING THE TEMPERATURE CORRECTION FUNCTION OF SAMPLES

Hideki HOSOI, Satoshi IKEDA, Akio OHASHI, Mariko MIYASHITA, Narushi ITO

TANITA Body Weight Scientific Institute
Maeno-cho, Itabashi-ku, Tokyo 174-8630, Japan

A quantitative urinary glucose meter containing a micro-planer amperometric biosensor has been developed. The biosensor's enzymatic reactions by glucose oxidase yield hydrogen peroxide (H2O2), which is transferred to electrochemical reactions. Since the enzymatic reactions are easily affected by the sample temperature, the urinary glucose sensor is adjacent to a thermistor. This configuration allows simultaneous measurements of glucose levels and temperature of urine samples. The temperature correction equation is derived from the relationship between the outputs of the urinary glucose sensor and the temperatures detected by the thermistor is excellent;y=0.0011x2-0.003x+ 0.4126,R=0.991. In conclusion, the temperature correction function of samples furnished to the sensor provided accurate urinary glucose levels consistent with the change of ambient temperature in the range of 5 and 40℃ that is seen at home bathrooms.

 

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52.

ケミカルCCDとそのバイオセンサとしての応用

(株)ホリバ・バイオテクノロジー

奥村弘一

CHEMICAL CCD AND IT'S APPLICATION FOR BIOSENSOR

KOICHI OKUMURA

HORIBA Biotechnology Co., Ltd.
48 Kurumamichi, Kisshoin, Minami-ku, Kyoto 601-8315, Japan

We have been investigating a novel biosensor based on the CCD(Charged Coupled Device) technology. This sensor (Chemical CCD) can monitor the direct transduction of surface density change by charged biomolecules interaction. Here we show the ability of monitoring of DNA hybridization and antigen-antibody reaction by using Chemical CCD.

 

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53.

ケミカルCCDを用いた蛋白質の吸着及び特異的結合反応のリアルタイム検出

富山大工

○ 堀井雅恵, 加藤寛隆, 篠原寛明

REAL TIME MONITORING OF ADOSORPTION REACTION AND ANTIGEN-ANTIBODY SPECIFIC BINDING REACTION WITH CHEMICAL CCD

Masae HORII, Hirotaka KATO, Hiroaki SHINOHARA

Department of System Engineering of Materials & Life Science, Faculty of Engineering, Toyama University
Gofuku 3190, Toyama, Toyama 930-8555, Japan

Chemical CCD (C-CCD) is a novel semiconductor sensor that converts the interfacial potential of the gate surface exposed to a measuring solution to the amplified electric signal with integrated charge in the device. Therefore C-CCD is expected to be very useful to detect subtle change of interfacial potential. In this study, the output change by adsorption of various proteins possessing different isoelectric point onto the Au-gate surface was measured to investigate dependence of the output on surface charge of the adsorbed molecules. The measurement results showed that the change in output could not be explained only in difference of charge of adsorbed molecules. Furthermore, detection of the binding reaction of anti-human α-fetoprotein (AFP) to AFP was attempted with the C-CCD. Output drop by the specific binding reaction of anti-AFP to AFP immobilized on the Au-gate was distinctly observed as compared with little output change by non-specific adsorption to BSA in the control channel.

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54.

光導波路法に基づいたDNAセンサの開発

横浜国大院環境情報

○小野寺賢一、許一太、藤生英子、内山兼一、雨宮隆、伊藤公紀

DEVELOPMENT OF DNA SENSOR BASED ON OPTICAL WAVEGUIDES

Kenichi ONODERA, Yitai XU, Hideko. FUJIU, Kenichi UCHIYAMA, Takashi AMEMIYA, Kiminori ITOH

Graduate school of Environment and Information Science, Yokohama National University,
Tokiwadai 79-7, Hodogaya-ku, Yokohama 240-8501, Japan

The purpose of this research is developing the DNA sensor with high sensitivity which used the method of optical waveguides (OWG). The sensing system that can measure absorption of light and fluorescence simultaneously was designed. When it measured using the constructed OWG-DNA sensor, the hybridization reaction between probes DNA fixed on the substrate and Cy5-labeled target DNA has been detected with sufficient sensitivity. It could measure in the concentration range of 100 pM from 10 nM, and the response depending on concentration was shown. Moreover, if examination is advanced using a fluorescence method, using a substrate with high sensitivity, it can measure with still more sufficient sensitivity.

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55.

還元性アニオンのルミノール電気化学発光への阻害作用

芝浦工大, 早大理工

○ 鎌田正行, 吉見靖男, 服部浩二, 酒井清孝

Mechanism of INHIBITION of Luminol electrochemiluminescence by anionic reducing agents

Masayuki KAMADA, Yasuo YOSHIMI, Koji HATTORI, Kiyotaka SAKAI

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

 A chemiluminescence of luminol with hydrogen peroxide is a very useful tool for sensitive determinations of biochemicals by conjugation with oxidase. An electrochemiluminescence (ECL) of luminol can occur in completely-mixed solutions of luminol and hydrogen peroxide, then that is promising for more stable determination. However, ECL is not of practical use due to low quantum yield at physiological pH. We have succeeded in the improvement of the ECL method in mild pH by electrode modification with cationic polymer adsorption. However, the cationic polymer also enhanced inhibition of ECL by anionic reducing reagents. In this work, we expected that the anionic polymer layer would block permeation of anionic reducing reagents by electrostatic repulsion. The anodic currents of anionic reducing reagents were decreased by anionic polymer modification. This result indicates that the anionic polymer layer on the cationic polymer modified electrode excludes anionic reducing reagents by electrostatic repulsion. However, anionic polymer layer could not prevent the inhibitions of anionic reducers from ECL of luminol.

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56.

SPR免疫センサによるTNTのppt レベル検出

九州大学a, JSTb

○D. ラビ シャンカランa,b, 松本 清a, 都甲 潔a, 三浦則雄a

DETECTION OF TNT AT PARTS-PER-TRILLION LEVEL BY USING SPR IMMUNOSENSOR

Dhesingh RAVI SHANKARANa,b, Kiyoshi MATSUMOTOc, Kiyoshi TOKOd, Norio MIURAa

aArt, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka, 816-8580, Japan
bJapan Science and Technology Agency, Japan
cGraduate School of Agriculture, Kyushu University, Fukuoka, 812-8581, Japan
dGraduate School of Information Science and Electrical Engineering,
Kyushu University, Fukuoka, 812-8581, Japan

A high-performance immunosensor was developed for rapid and highly sensitive detection of TNT (2,4,6-trinitrotoluene) using a newly prepared anti-TNPh-KLH antibody (2,4,6-trinitrophenyl-keyhole limpet hemocyanine) based on indirect inhibition method. A solid-phase immunoassay consists of physically immobilized TNPh-OVA (2,4,6-trinitrophenyl-ovalbumine) conjugate was allowed to interact with anti-TNPh-KLH antibody and the resonance angle changes due to the biomolecular interactions were monitored by means of surface plasmon resonance (SPR). The concentration of TNT was measured based on the change in the resonance angle shift for binding of the antibody with the conjugate in the presence of TNT. The immunoassay showed a detection range from 5 pg/ml (ppt) to 250 ng/ml (ppb) for TNT with a response time as short as about 5 min. The proposed immunoassay is simple and possesses highly desirable analytical characteristics for the development of new sensors for environmental monitoring and on-site detection of explosives.

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57.

SPR法による脳性ナトリウム利尿ペプチド(BNP)検出の検討

産業技術総合研究所

○栗田僚二、松浦宏昭、佐藤縁、水谷文雄、丹羽修

DETERMINATION OF B-TYPE NATRIURETIC PEPTIDE (BNP) BY SURFACE PLASMON RESONANCE MEASUREMENT

R. Kurita, H. Matsuura, Y. Sato, F. Mizutani, O. Niwa

National Institute of Advanced Industrial Science and Technology, Tsukuba
Central 6, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8566, Japan, 2-17
Tsukisamu-Higashi, Toyohira, Sapporo 162-8517, Japan

We propose the novel determination of B-type Natriuretic Peptide (BNP) which is one of the most important cardiac neurohormone by combining an enzyme immunoassay and a surface plasmon resonance measurement. BNP concentration was measured by monitoring a shift in SPR degree caused by the adsorption of thiocholine produced by acetylcholine-esterase labeled anti-BNP antibody. We observed that the SPR degree gradually increased with increasing time because thicholine was accumulated on the silver electrode surface. This suggests that the possibility of a highly sensitive BNP measurement by accumulation process even if the BNP concentration is very low. We succeeded in monitoring of 5 U/L acetylcholine-esterase and 10μg/L BNP, respectively.

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58.

2次元SPRイメージング装置の高解像度化

富山大工、NTT-AT

入部康敬,大島豊弘,飛田達也,○鈴木正康

DEVELOPMENT OF A HIGH RESOLUTION TWO-DIMENSIONAL SPR IMAGER

Yasunori IRIBE , Toyohiro OHSHIMA, Tatsuya TOBITA, Masayasu SUZUKI

Faculty of Engineering, Toyama University, Toyama-shi, Toyama 930-8555, Japan
NTT Advance Technology Corp., Atsugi-shi, Kanagawa 243-0124, Japan

We are developing micro-well array chip system for parallel monitoring of single lymphocyte function. This micro-well array chip has a quarter million wells on one chip (ca. 20 mm x 20 mm), and diameter of each well is 10 micron and only one lymphocyte can be occupied for each well. We employed a two-dimensional surface plasmon resonance imaging sensor (2D-SPR) for immunochemical monitoring in micro wells. In this study, in order to realize high resolution 2D-SPR, effects of the materials and preparation methods of metal thin layer (sensor chips), and wave length of light source, on the resolution of the two dimensional SPR imager was evaluated. The 2D-SPR image showed the highest resolution when the sensor chip was the silver layer prepared with an ion-sputtering.

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59.

高選択測定目的とした電極前処理の検討とフローセルへの適用

芝浦工大1, NTT MI研2,九大3

○太田雅史1, 林 勝義2, 岩崎 弦2, 吉見靖男1, 砂川賢二3, 館 彰之2

INVESTIGATYION OF ELECTRODE PRE-TREATMENT METHOD FOR HIGHLY SELECTIVE DETECTION OF BIOMOLECULE AND APPLICATION OF THE PRE-TREATED ELECTRODE TO A MICROFABRICATED FLOW CELL

Masashi OOTA1, Katsuyoshi HAYASHI2, Yuzuru IWASAKI2, Yasuo YOSHIMI1, Kenji SUNAGAWA3, Akiyuki TATE2

1 Department of Applied Chemistry, Shibaura Institute of Technology,
Minatoku, Tokyo 108-8548,
2 Microsystem Integration Laboratories, NTT,
Atsugi, Kanagawa 243-0198
3 Department of Cardiovascular Medicine Kyushu University Graduate School of Medical Sciences,
Fukuoka, Fukuoka 812-8552

We investigated electrode pre-treatment methods for highly selective detection of dopamine (DA) against L-ascorbic acid (AA). We used argon plasma and electrolysis in sulfuric acid as the pre-treatment method. We compared responses obtained from DA and AA at the pre-treated gold film electrodes. When measuring DA, the responses obtained at the electrode treated with both methods were almost same. On the other hand, when measuring AA, the electrode treated with electrolysis in
sulfuric acid provided inhibition of AA oxidation. We applied the electrode treated with electrolysis in sulfuric acid to a microfabricated flow cell, and confirmed that the electrode was also able to control the AA oxidation in a continuous measurement.

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62.

新規蛍光性非天然アミノ酸を位置特異的に導入した人工蛍光蛋白質によるバイオセンシング

1岡山大工・2富山大工・3Univ. of Gdansk・4北陸先端大材料

○濱田 浩幸1, 篠原 寛明2, 亀島 直子1, 瀧 真澄1, Szymanska Aneta3, 芳坂 貴弘4, 宍戸 昌彦1

CREATION OF ARTIFICIAL FLUORESCENCE PROTEIN IN WHICH A NOVEL FLUORESCENT NONNATURAL AMINO ACID IS SITE-SPECIFICALLY INCORPORATED FOR NEW BIOSENSING

1Hiroyuki HAMADA, 2Hiroaki SHINOHARA, 1Naoko KAMESHIMA, 1Masumi TAKI, 3Aneta SYZMANSKA, 4Takahiro HOHSAKA, 1Masahiko SISIDO

1Department of Bioscience and Biotechnology, Faculty of Engineering, Okayama University,
Okayama, Okayama 700-8530, Japan
2Faculty of Engineering, Toyama University,
Toyama, Toyama 930-8555, Japan
3University of Gdansk, Faculty of Chemistry,
Sobieskiego 18, 80-952 Gdansk, Poland ;
4School of Materials Science and Technology, JAIST
Nomi, Ishikawa 923-1292, Japan

A new fluorescent amino acid, L-2-acridonylalanine (acdAla), was incorporated into proteins at the specific positions using 4-base codon/anticodon strategy. AcdAla was highly fluorescent when it was excited at the wavelengths of blue lasers (415 nm) and highly durable compared with conventional fluorophores often used for biological analyses. The amino acid was incorporated into various positions of camel single-chain antibody (cAb). The efficiency of the incorporation of acdAla was high enough to obtain an enough amount of mutant protein. The mutants of cAb were found to work as fluorescence probes for antigenic lysozyme binding.

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63.

アルカンチオール修飾電極でのドーパミンの選択的測定

創価大工

○久保いづみ、吉村和崇、前原信義

Selective Measurement of Dopamine With An Alkanethiol-Modified Electrode

Izumi KUBO, Kazutaka YOSHIMURA, Nobuyoshi MAEHARA

Department of Bioinformatics, Faculty of engineering, Soka University
Hachioji-shi, Tokyo, 192-8677, Japan

A surface of gold electrode was modified with a self-assembled monolayer in order to protect the oxidation of ascorbic acid, which exists in biological fluid. The electrode was prepared by the modification with 5-carboxypentanethiol(5C), 7-carboxyheptanethiol (7C) and 10-carboxy decanethiol (10C). At pH 7.0, alkanethiol modified electrodes did not show any anodic response to ascorbic acid but oxidize dopamine. Dopamine was most selectively oxidized with the 7C modified electrode prepared in 0.15mg/ml 7C. The anodic current to dopamine was 90 times more than that of ascorbic acid. The modification with alkane thiol was quite effective to selective oxidation of dopamine to ascorbic acid. The selectivity was not observed at pH 4.0.

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65.

共有結合型分子インプリント高分子薄膜のゲート効果を利用したグルコースセンサの可能性

芝浦工大、早大理工*
○吉見靖男、赤堀裕大、小川貴久*、服部浩二*、酒井清孝*

AN ENZYMELESS GLUCOSE SENSOR USING GATE EFFECT OF THIN LAYER OF COVALENTLY IMPRINTED POLYMER

Yasuo YOSHIMI , Yuhta AKABORI , Takahisa OGAWA, Koji HATTORI, Kiyotaka SAKAI

Department of Applied Chemistry, Shibaura Institute of Technology,
Minato-ku, Tokyo, 108-8548
*Department of Chemical Engineering, Waseda University,
Shinjuku-ku, Tokyo, 169-8555

The purpose of this work is development of an enzyme-free glucose sensor using molecularly imprinted polymer (MIP). Glucose and 4-vinylphenyl boronic acid (VPBA) were allowed to conjugate by azeotropic distillation of pyridine. The conjugate was purified reprecipitation. The conjugate was allowed to copolymerized with crosslinking monomer ethyleneglycol dimethacrylate and methacrylic group fixed on indium tin oxide (ITO) in order to graft glucose-imprinted polymer onto the ITO. However, the faradic current of ferricyanide at the grafted ITO electrode was insensitive glucose against our attempt. The design of the polymerization of the MIP would be needed in order to obtain the gate effect of the MIP for the development of the glucose sensor.


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