Vol. 23, Supplement B (2007)

Proceedings of the 44th Chemical Sensor Symposium
August 19-20, 2007

Abstracts


1.

水熱法による貴金属添加酸化スズゾルの合成と炭化水素検知特性

立命館大理工

○服部泰輔、玉置 純

HYDROTHERMAL SYNTHESIS OF NOBLE METAL LOADED TIN OXIDE SOL AND HYDROCARBON SENSING PROPERTIES

Taisuke HATTORI, and Jun TAMAKI

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

Pd added SnO2 sol solutions were hydrothermally synthesized with three different methods. The mixed solution of SnCl4 and PdCl2 was neutralized with NH4HCO3. The resulting precipitate was washed, filtrated, mixed with aqueous NH3 (pH10.5), and hydrothermally treated at 200 ℃ for 3h (A method). For B method, (N3H)2(NO2)2Pd was added to SnO2 precursor and hydrothermally treated. On the other hand, (NH3)2(NO2)2Pd was mixed with SnO2 sol solution for C method. The Pd-SnO2 solutions were dropped on alumina substrate equipped with Au interdigitated electrode, dried, and calcined at 900 ℃ for 3 h to be Pd-SnO2 thin film gas sensors. The sol solutions prepared by A method were color-less clear solutions when Pd content was less than 5 wt%. Thus, Pd particle was not observed in Pd-SnO2 film, suggesting the tiny Pd particles loaded on SnO2 particles (20 nm). On the other hand, the film in which the Pd content was increased to 10 wt% and the films prepared by B and C methods had large Pd particles (100-300 nm) dispersed in the SnO2 film. The sensor response to 5 ppm octane at 300 ℃ of Pd-SnO2 sensor with 1-5 wt% Pd was almost the same as that of pure SnO2 sensor. While, the Pd-SnO2 sensors with large Pd particles (prepared by A method with 10 wt% Pd, B and C methods) showed high sensor responses, suggesting the sensor response to octane was increased with increasing Pd particle size.

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2.

逆ミセル法によりPdOを微細担持したSnO2半導体ガスセンサのガス検知特性

九大院総理工

○湯浅 雅賀、眞崎 貴則、木田 徹也、島ノ江 憲剛、山添 f

SENSING PERFORMANCES OF SnO2 SEMICONDUCTOR GAS SENSOR LOADING PdO BY REVERSE MICELLE METHOD

M. Yuasa*, T. Masaki**, T Kida*, K. Shimanoe*, N. Yamazoe*

*Faculty of Engineering Sciences, Kyushu University, Kasuga, Fukuoka
816-8580, Japan
**Interdisciplinary Graduate School of Engineering Sciences, Kyushu
University, Kasuga, Fukuoka 816-8580, Japan

To investigate the effect of PdO loading on SnO2 nano-particle, a PdO-SnO2 nano-composite was prepared by reverse micelle method. At first, a revere micelle dispersion containing [Sn(OH)6]2- solution (RM-A) was prepared. At the same time, a reverse micelle dispersion containing 0.5-1.5×10-4M Pd(NO3)2 solution and 6% HNO3 solution (RM-B) was prepared. The RM-A was mixed with the RM-B and a Pd(OH)2-Sn(OH)4 was precipitated into revere micelles. The PdO-SnO2 nano-composite after calcination at 600℃ was observed by HR-TEM (PdO = 0.5, 1.0, 1.5mol%). Although the particle size of SnO2 was as same as ca.10nm in between observed sample, the particle size of PdO got larger in increase with loading amount of PdO because of agglomeration of PdO nano-particles each other. As the result of a gas sensing measurement, it was found that particle size of PdO on SnO2 nano-particle influences the gas sensing property closely. That is, the sensor response declined gradually with increasing the particle size of PdO although the maximum of sensor response was obtained in PdO = 0.1mol% (0.08wt%).  In this method, small amount of PdO loading can be achieved as compared with a PdO-loaded SnO2 sensor prepared by conventional impregnation method.

 

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3.

半導体ガスセンサにおけるPower lawsの理論的解析

九大院総理工

○島ノ江憲剛、山添 f

THEORY OF POWER LAWS FOR SEMICONDUCTOR GAS SENSORS


K.Shimanoe, N. Yamazoe

Faculty of Engineering Sciences. Kyushu University
Kasuga-shi, Fukuoka 816-8580, Japan

It has long been known empirically that the electric resistance of a semiconductor gas sensor under exposure to a target gas (partial pressure P) is proportional to Pn where n is constant fairly specific to the kind of target gas (power law). This paper aims at providing theoretical basis to such power laws. It is shown that the laws can be derived by provideing theoretical basis to such power laws. It is shown that the laws can be derived by combining a depletion theory of semiconductor, which deals with the distributionof electrons between surface state (sueface charge) and bulk, with the dynamics of adsorption and/or reactions of gases on the surface, which is responsible for accumulation or reduction of surface surface charges. The resulting laws describe well sensor response behavior to oxygen, reducting gases and oxidizing gases.

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4.

半導体ガスセンサにおける還元雰囲気中でのCO検知特性に及ぼす担持金属の影響

愛媛大

○山浦弘之,中岡茉莉,八尋秀典

EFFECT OF TRNSITION METAL TO CO SENSING PERFORMANCE IN REDUCING ATMOSPHERE FOR SEMICONDUCTOR-TYPE SENSOR

Hiroyuki YAMAURA, Mari NAKAOKA, Hidenori YAHIRO

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

Various transition metals-loaded SnO2 sensors were investigated to CO sensing properties in reducing atmosphere such as wet H2 gas. Among them, 5qt%CuO/SnO2 sensor showed sensitivity to 1% CO in wet 50% H2 at around 150 ℃, but no sensitivity in dry 50% H2. From XRD analysis, CuO was reduced to Cu in reducing atmosphere at above 150 ℃for sensor measurements. We considered that reducibility of CuO is one of the important factors of CO response.


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 5.

MEMS技術を応用した省電力型マイクロCOセンサ

北陸電気工業,九大産学連携センター

○竹林 優,今村 徹治,山本 肇,三浦 則雄

POWER‐SAVING TYPE MICRO CO SENSOR FABRICATED BY MEMS TECHNOLOGY

Masaru TAKEBAYASHI, Tetsuji IMAMURA, Hajime YAMAMOTO, Norio MIURA

Hokuriku Electric Industry Co.,LTD
Toyama-shi, Toyama 939-2292
Art, Science and Technology Center for Cooperative Research, Kyushu
University,
Kasuga-shi, Fukuoka 816-8580

We have developed a power-saving type CO sensor by combining a micro heater and oxide sensing material. The Pt micro heater (0.5×0.5 mm) was fabricated on a silicon wafer by MEMS technology. The sensing material was prepared by using indium oxide and a small amount of Pt additive. The obtained micro sensor was operated by means of a pulsed-drive method in 60 s periods. The sensor was heated at 350℃ for a period of 15 ms for surface cleaning of sensing material and then the detection of gas was done at the point of 800 ms after the cleaning. The average power consumption of the sensor was as low as ca. 20μW, suggesting that the sensor could be dry-cell driven. The sensor was found to show both high sensitivity and high selectivity to CO. In addition, the heating speed and the long-term stability of the micro heater was confirmed to be high enough for practical use.

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6.

超小型半導体式ガスセンサの開発

フィガロ技研

○吉岡 健一、谷平 龍也、新西 一哉、兼安 一成

DEVELOPMENT OF EXTREMELY SMALL SEMICONDUCTOR GAS SENSOR

Ken-ichi YOSHIOKA,Tatsuya TANIHIRA, Kazuya SHINNISHI and Kazunari KANEYASU

In the field of gas sensor, a low power consumption and miniaturized sensor is strongly requested. In order to realize the request, Micro electro mechanical systems (MEMS) technology is very effective. So, we started to develop a MEMS sensor. When the sensor element was heated at 450℃, power consumption was 26mW. And temperature of the sensor element
became stable in only 0.030 second after switch on. It was also clarified that battery operation was possible by utilizing on-off drive  technique. For example, when the sensor was driven by 0.2 second on - 29.8 second off, the average power consumption of the sensor was only 170μW.

 

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7.

修飾酸化バナジウムを感応層とする高温作動抵抗型アンモニアセンサ

名大院工a、日本特殊陶業b

○鎮西勇夫a, 清水研一a, 西山寛幸b, 柿元志郎b, 菅谷聡b,薩摩篤a

HIGH TEMPERATURE OPERATED RESISTIVE AMMONIA SENSOR BASED ON MODIFIED VANADIUM OXIDES

Isao CHINZEIa, Kenichi SHIMIZUa, Hiroyuki NISHIYAMAb, Shirou
KAKIMOTOb, Satoshi SUGAYAb, Atushi SATSUMAa

a Department of Applied Chemistry, Nagoya University,Nagoya-shi, Aichi 464-0814
b R&D Center, NGK Spark Plug Co.Ltd, Komaki, Aichi 485-8510

Metal oxide-added V2O5 (supported or mixed oxides) were tested as NH3 sensing materials at 773 K. All the materials show higher sensitivity for NH3 than C3H6. Supported materials show better responses to NH3 than pure V2O5. The NH3 sensitivity increased with electronegativity of the added metal and was highest for the V-Co sample.

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8.

ITO(スズ添加酸化インジウム)薄膜を用いた高感度オゾンセンサの実用化

エフアイエス株式会社 

○柳谷 順子、松本 晋一、 翁長 一夫

DEVELOPMENT OF APPLICATION TECHNOLOGY FOR USING A THIN FILM ITO (INDIUM TIN OXIDE) BASED OZONE SENSOR IN PRACTICAL USE

Junko YANAGITANI, Shinichi MATSUMOTO, Kazuo ONAGA

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

In 2001, we have reported the development of an ITO based ozone sensor with excellent sensitivity and selectivity. Since then, we have studied the application of this ozone sensor for commercial use and developed ozone modules. Through various tests and evaluation process both in laboratory and commercial fields, we have succeeded to develop a low cost commercial ozone module with high reliability, small effect of wind velocity with long life. In this report, practical studies for most important factors such as corrosion resistance features, method of reducing the effect of wind velocity are explained.

 

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9.

安定化ジルコニアを温度補償材として用いた抵抗型酸素センサの模擬排ガス中での出力

産総研

○伊豆典哉、西ア涼香、伊藤敏雄、申ウソク、松原一郎、村山宣光

EVALUATION FOR OUTPUT OF RESISTIVE OXYGEN SENSOR HAVING STABILIZED ZIRCONIA AS TEMPERATURE COMPENSATING MATERIAL IN MODEL EXHAUST GAS

Noriya IZU, Sayaka NISHIZAKI, Toshio ITOH, Woosuck SHIN, Ichiro MATSUBARA, Norimitsu MURAYAMA

National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8569

We fabricated resistive oxygen sensors having a Ce0.9Zr0.1O2 thick film as a sensing material and a Zr0.8Y0.2O2-δ thick film as a temperature compensating material, and measured the resistance of the two thick films and the output of the sensors in model exhaust gas. The results show that the combination of these films is better. The difference in output of the resistive oxygen sensor having the optimized electrode between rich and lean regions was more than 0.7 V. From above-mentioned results, we conclude that the resistive oxygen sensors fabricated in this study are able to be used as “lambda sensors”.

 

 

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10.

吸着燃焼式ガスセンサを用いた室内VOC濃度モニタの開発

矢崎総業株式会社

荘田隆博, ○高橋信之, 笹原隆彦 

A CONCENTRATION MONITOR USING AN ADSORPTION/CONBUTION-TYPE GAS SENSOR FOR TOTAL VOLATILE ORGANIC COMPOUNDS IN INDOOR AIR

Takahiro SHODA, Nobuyuki TAKAHASHI and Takahiko SASAHARA

Research and Technology Center, Yazaki Corp., Susono-shi,
Shizuoka 410-1194

We developed a concentration monitor using an adsorption/ combustion-type gas sensor for total volatile organic compounds (TVOCs) in indoor air. The TVOCs concentration was obtained from detector output based on the different responses of two different adsorption periods of the sensor. The output increased with increasing the concentration of toluene as a typical VOC. The long term stability of the output was checked by a continuous driving for 200 days. On an indoor field test, the ventilation responses of the detector to indoor TVOCs were confirmed to be highly capable.

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11.

酸化スズ系厚膜センサのVOCガスに対する感度特性

(富山県工業技術センターa、産総研b

〇角崎雅博a、坂井雄一a、田村幾夫a、松原一郎b、伊藤敏雄b

SENSING PROPERTIES OF TIN OXIDE-BASES THICK FILM SENSOR FOR DETECTING VOCS

Masahiro KADOSAKIa, Yuichi SAKAIa, Ikuo TAMURAa, Ichiro MATUBARAb, Toshio ITOHb

aTayama Industrial Technology Center
Takeda, Toyama 930-0866
bNational Institute of Advanced Industrial Science and Technology(AIST)
Anagahora Sidanmi Moriyama Nagoya 463-8560

At present, a lot of persons still suffer from indoor-air pollutants, especially in the new residential building. It is mostly caused by volatile organic compounds(VOCs) emission such as toluene (C6H5CH3) and xylene (C6H4(CH3)2) included in adhesives or paints used for residential buildings. In order to develop the sensor which detects total VOC, the sensitivities of 4 oxide semiconductor materials to 37kinds of VOC gases were studied. Those materials showed low sensitivities to halogenated hydrocarbons gases and aliphatic hydrocarbons gase. As a result of improving the sensitivity to these gases, among 4 metal oxides examined, SnO2 and WO3 showed high sensitivities by the addition of Pd and Pt. The sensing properties of SnO2 for halogenated hydrocarbons gases were extremely improved by addition of 0.5wt% Pd. Also. the sensing properties of SnO2 for aliphatic hydrocarbons gases were improved by addition of 0.7wt% Pt. In addition, the doubly promoted element, Pt(0.5wt%)-Pd(0.5wt%)-SnO2, Showed a high sensitivity in a lot of kinds of examined VOC gases.

 

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12.

芳香族系VOC検知用酸化タングステン薄膜センサにおける貴金属添加効果

立命館大理工、松下電工*

○金松健児、玉置 純、梶田 進*

EFFECT OF NOBLE METAL ON AROMATIC VOCs SENSING PROPERTIES OF WO3 THIN FILM SENSORS

Kenji KANEMATSU, Jun TAMAKI, and Susumu KAJITA*

Department of Applied Chemistry, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu-shi, Shiga 525-8577, Japan
*Advanced Technologies Fusion Laboratory, Matsushita Electric Works, Ltd., Kadoma, Osaka 571-8686, Japan

The sensing properties of WO3 thin film sensors to aromatic VOCs (toluene, xylene, ethylbenzene and styrene) have been modified with noble metal loading to WO3 in order to improve gas sensitivity as well as selectivity. When (NH3 )2(NO2)2Pd was mixed with the H2WO4 suspension with content of 1.0 wt% (Pd-H2WO4 suspension) and the Pd-WO3 film was fabricated with this suspension, the Pd (1.0 wt%)-WO3 thin film sensor showed the high sensor response to all of aromatic VOCs at 300-350 ℃. By loading with Pd, the lower operating temperature was realized and the high sensitivity, but non-selective, aromatic VOCs sensor was obtained. On the other hand, Pt loading with 1.0 wt% from (NH3 )2(NO2)2Pt decreased the sensor response to aromatic VOCs. However, when the Pt loading was decreased to 0.2 wt%, only the sensor response to styrene was enhanced at 350 ℃ for 0.2 wt% Pt-WO3 thin film sensor.

 

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(清山賞受賞講演1)

半導体式VOCセンサの開発とポータブル VOC分析計への応用

新コスモス電機株式会社

○神田奎千

DEVELOPMENT OF A SEMICONDUCTOR TYPE VOC SENSOR AND ITS APPLICATION TO A PORTABLE VOC ANALYZER

Keisen Kanda

Cosmos Laboratory. R&D Center, Cosmos Laboratory
New Cosmos Electric Co., LTD
3-6-25 Mitsuya-naka, Yodogawa-ku, Osaka 532-0036, Japan

A highly sensitive VOC gas sensor has been developed by the authors for the detection of VOCs, especially for the aromatic hydrocarbons, toluene, etylebenzene, xylene and styrene, using a WO3 thick film in which Pd and Pt were applied to a limited area of the film to effectively promote sensitivity and improve gas selectivity. The sensor showed extremely high sensitivity to the aromatic hydrocarbon gases and good gas selectivity. A portable VOC analyzer has also been developed by applying the sensor to the analyzer in conjunction with gas chromatography. Target VOCs at concentration level of ppb could be simply measured with the analyzer by directly injecting only 10mL sample into the system without using any sampler to concentrate sample gas, and the concentrations of the target gases were correctly determined by an original quantitative analysis method incorporated in the VOC analyzer system.

 

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13.

固体電解質型CO2センサの電極構造が センサ特性に与える影響

長崎大1院生産科学、2

○森尾昌隆1、兵頭健生2、清水康博2、江頭 誠2

STRUCTURAL EFFECTS OF AN AUXILIARY ELECTRODE ON CO2 SENSING PROPERTIES OF SOLID-ELECTROLYTE GAS SENSORS

Masataka MORIO1, Takeo HYODO2, Yasuhiro SHIMIZU2 and Makoto EGASHIRA2

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

Structural effects of an auxiliary electrode on CO2 gas sensing properties of NASICON (Na3Zr2Si2PO12) solid electrolyte sensors were investigated. The sensor with a porous Li2CO3-BaCO3-based auxiliary electrode, which was prepared by utilizing constituent metal acetates and polymethlmethacrylate microspheres, showed faster response and recovery for CO2 and smaller EMF drift against humidity changes than that with dense auxiliary layer without pores. Their magnitude of CO2 response was larger than theoretical one, while a sensor with a conventional auxiliary electrode prepared from commercial constituent carbonates showed theoretical response. This may be due to the effect of other species, which react with CO2, existing in the porous auxiliary electrode prepared in the present study.

 

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14.

NASICONとアルカリ炭酸塩を用いた炭酸ガスセンサの安定性

愛媛大院

○西村 健吾、青野 宏通、定岡 芳彦

STABILITY OF CO2 GAS SENSOR USING NASICON AND ALKALI CARBONATE

Kengo NISHIMURA, Hiromichi AONO, and Yoshihiko SADAOKA

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

High dense samples with composition in NASICON(Na1+xZr2SixP3-xO12, x=2.0 and 3.0) were synthesized using a sol-gel method. The conductivity was decreased by the increase in x value from 2.0 and 3.0. The x=2.0 sample is reactive to alkali carbonate (M2CO3, M=Li and Na) at 600℃ and higher to form alkali rich NASICON. In the case of x=3.0, the NASICON phase in the mixture with Li carbonate and Na carbonate was stable even at 700℃, since all the alkali ion sites in the NASICON is filled by Na+ ions for x=3.0. We confirmed that the EMF drift for the CO2 gas sensor using x=3.0 electrolyte is smaller compared with that using x=2.0 electrolyte.

 

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15.

アパタイト構造を有するリチウムアルミノシリケートの伝導性と電位応答型ガスセンサへの可能性

愛媛大院

○竹田 尚貴、定岡 芳彦

IONIC CONDUCTIVITY OF LITHIUM ALUMINOSILICATES AND ITS APPLICATION TO GAS SENSORS

Naoki Takeda and Yoshihiko Sadaoka

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

Mixtures of Li2CO3, La2O3 and SiO2 in the prescribed ratios for LixLa10-x(SiO4)6O3-x were sintered. The sinters consisted of several components in a viewpoint of chemical and crystal structure. The major product was the material with an apatite-like crystal structure. The lattice parameters decreased with an increase in the Li-content, x, to x=2.0 and remained the constant above x ≥ 2. With an increase in x-value to 1.5, the conductivity increased due to the decrease in the content of sub-products, La2SiO5. In the range of x ≥ 2.0, the increase in x resulted an increase in the conductivity and was related to an increase in the content of Li2SiO3 acting as a high Li-ionic conductor. Nernst response to oxygen concentration suggested that the main ionic carrier is oxygen for x<2.0 and Li-ion is also mobile for x ≥ 2.

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16.

大気環境中炭化水素の高感度検出を目指した 混成電位型ジルコニアセンサ

九大院総理工a、国立環境研b、九大産学連携センターc

○森 峻司a、和間 良太郎a、内山 政弘b、三浦 則雄c

MIXED-POTENTIAL-TYPE ZIRCONIA SENSOR FOR HIGHLY-SENSITIVE DETECTION OF HYDROCARBON IN ATMOSPHERIC AIR

○Shunji Mori a, 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

The sensing characteristics to low concentration of C3H6 were examined at temperatures of 450 - 600℃ for the mixed-potential-type yttria-stabilized zirconia (YSZ) sensor attached with each of several oxide sensing-electrodes (SEs). Among five oxide-SEs tested, In2O3-SE was found to give the highest sensitivity to 50 ppb C3H6 at 450℃ under the wet condition (1.35 vol. % H2O). The emf response of the sensor varied almost linearly with the logarithm of C3H6 concentration in the range of 10 - 200 ppb at 450℃. In addition, the present sensor showed relatively low cross-sensitivities to other gases (NO2, CO, H2, CH4; each maximum permissible level in atmospheric air) and its sensitivity to C3H6 was hardly affected by the change in water vapor concentration examined. On the basis of the results obtained here, it appears that the present sensor has a potential to use for monitoring of environmental HCs.

 

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17.

混成電位型安定化ジルコニアセンサによる 高温でのメタンの選択的検知

九大院総理工a、九大産学連携センターb、リケン(株)c

○ 上田 太郎a、エルマレイ ペルマルb、ブラディミル プラシニツァb
長谷井 政治c、三浦 則雄b

SELECTIVE DETECTION OF METHANE AT HIGH TEMPERATURE BY USING MIXED-POTENTIAL-TYPE ZIRCONIA SENSOR

○ Taro UEDAa, Perumal ELUMALAIb,Vladimir V. PLASHNITSAb,
Masaharu HASEIc, Norio MIURAb

aInterdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580
bArt, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580
c R&D Division, Riken Corporation, Kumagaya-shi, Saitama 360-8522

Since hydrocarbons have strong photo-chemical reactivity in the environmental eco-system, there is a strong demand for their emission control and detection. We have recently examined and reported the impedancemetric and amperometric sensors using yttria-stabilized zirconia (YSZ) and oxide sensing electrode (SE) for detection of propene (C3H6). Here, we proposed mixed-potential-type YSZ-based methane sensor and examined its sensing characteristics at high temperature. Among various metal-oxide SEs examined, In2O3 was found to give the highest sensitivity as well as good selectivity to CH4 at 790℃. The sensitivity to 400 ppm CH4 for the sensor attached with In2O3-SE was as high as 90 mV. The sensitivity of the present sensor varied logarithmically with the CH4 concentration in the examined range of 50-800 ppm. To improve the response/recovery rate, the sintering temperature was changed from 1400℃ to 1300℃. As a result, the sensor attached with the 1300℃-sintered In2O3- SE exhibited enhanced response/recovery rates which were three times higher than those of the sensor attached with the 1400℃-sintered SE.

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18.

3価のアルミニウムイオン伝導体を用いた亜硫酸ガスセンサ

阪大院工

○稲葉祐一、田村真治、今中信人

SULFUR DIOXIDE GAS SENSOR BASED ON THE TRIVALENT AL3+ ION CONDUCTING SOLID ELECTROLYTE

Yuuichi INABA, 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 gas sensor was fabricated by the combination of trivalent aluminum cation conducting (Al0.2Zr0.8)20/19Nb(PO4)3 and divalent oxide anion conducting yttria stabilized zirconia (YSZ) with NaAl(SO4)2 as an auxiliary detecting electrode. Since the present sensor shows such a superior sensing performance of stable, continuous, and reproducible response over a month and also shows a linear relationship between the sensor EMF output and the logarithm of the SO2 gas concentration with obeying the theoretical Nernst relationship, it is greatly expected to be a practical SO2 gas sensing device.

 

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19.

電子ビーム蒸着法を用いた光ファイバ
水素センサの開発−検知特性の膜厚依存性−

横国大a、東大b、エネ総研c

○渡邉太一a、伊藤大輔a、岡崎慎司a、中川英元b、斉藤逸郎b、鎮西恒雄b、阿部祐輔b、福田健三c、曽根英文c

SENSING CHARACTERISTIC OF A FIBER OPTIC HYDROGEN SENSOR FABRICATED BY ELECTRON BEAM DEPOSITION

Taichi WATANABEa, Daisuke Itoua, Sinji OKAZAKIa, Hidemoto NAKAGAWAb, Itsuro SAITOUb, Tuneo CHINZEIb, Yusuke ABEb, Kenzo FUKUDAc and Hidefumi SONEc

aGraduate School of Engineering, Yokohama National University
Tokiwadai 79-5, Hodogayaku, Yokohama 240-8501, Japan
bResearch Center for Advanced Science and Technology, The University of Tokyo
4-6-1 Komaba, Meguro-ku, Tokyo 153-8904 JAPAN
c The Institute of Applied Energy
Shimbashi SY Bldg., 1-14-2 Nishi-Shimbashi, Minato-ku, Tokyo 105-0003, Japan

An evanescent-type fiber optic hydrogen sensor has advantages of a long sensing length and a capability of leak position specification with optical time domain reflectometry. A sol-gel method was used for the sensing film formation [1]. The fabricated sensors exhibited good sensitivity, but strong optical absorption hampered the realization of long detection length. To overcome this difficulty, the electron beam (EB) deposition method was applied in the present investigation to form a thin sensing film. Tungsten trioxide and platinum powder were deposited by EB method with a base pressure of 2 x 10-4 Pa. The source-to-substrate distance was about 20cm. The sensing optical fibers were connected with dummy cables and the propagation loss increase due to hydrogen gas were measured at 1310 nm. Optical absorption depended on film thickness and sensor length. A 15 cm detection sensor can detect 1 % H2 (N2 Balance), but the detection limit is increased to 3 % when the balance gas was oxygen. SEM observation revealed that the sensing film often has cracks, suggesting poor adhesion to fiber core.

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20.

放射性廃棄物処分容器の長期腐食モニタリング用光ファイバ酸素センサの開発

横浜国大工a、東京大学先端科学技術研究センターb、電源開発株式会社c

○中村 祐樹a、伊藤 大輔a、横山隆a、岡崎 慎司a、中川 英元b、新井 隆c

DEVELOPMENT OF A FIBER-OPTIC OXYGEN SENSOR FOR LONG-TERM CORROSION MONITORING OF RADIOACTIVE-WASTE REPOSITORY

Yuki NAKAMURAa , Daisuke ITOa ,Takashi YOKOYAMAa , Shinji OKAZAKIa , Hidemoto NAKAGAWAb and Takashi ARAIc

aFaculty of Engineering, Yokohama National University, Tokiwadai 79-5, Hodogaya-ku, Yokohama 240-8501, Japan, bResearch Center for Advanced Science and Technology, Tokyo University, Komaba 4-6-1, Meguro-ku, Tokyo 153-8904,Japan, cElectric Power Development Co.,Ltd. Ginza 6-15-1, Chuo-ku, Tokyo 104-8165, Japan

A fiber-optic oxygen sensor for long-term use was developed and its durability was studied. The ensing mechanism is based on quenching of luminescence by oxygen. Ruthenium complex whose counter-anion is dodecyl sulfate was utilized as fluorescence dye and dispersed into silicone resin. This sensing material was immobilized on quartz substrate by curing at ambient temperature. Thermal degradation tests were conducted at 150℃ in various atmospheric conditions. The sensitivity showed strong temperature dependence. Furthermore, irreversible change in sensitivity due to degradation were observed in both air and nitrogen atmosphere. The degradation in air was severer than that in nitrogen. In order to investigate the degradation mechanism, thermal behavior of sensing materials were measured by DSC(Differential Scanning Calorimetry) It is found that thermal decomposition of Ru complex started at 410℃ in nitrogen atmosphere. Oxidation peak was not appeared in the therm al analysis curve from 50℃ to 300℃. It is suggested that sensing material was not chemically oxidized and almost stable in the practical condition. Therefore, the degradation of sensitivity would be mainly attributed to physicochemical change of sensing film such as coagulation of Ru complex.

 

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21.

酸化物蛍光体のマクロポーラス化とガス感応膜としての可能性

長崎大 1院生産科学,2

○倉由香里1,兵頭健生2,清水康博2,江頭 誠 2

PREPARATION OF MACROPOROUS OXIDE PHOSPHOR THICK FILMS AND THEIR APPLICATION TO GAS SENSORS

Yukari TAKAKURA 1, Takeo HYODO2, Yasuhiro SHIMIZU2 and Makoto EGASHIRA2

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

Acetone sensing properties of macroporous (mp-)SnO2 thick films doped with 5 mol% Eu and 0~10 mol% Mg (Lmp-SnO2(mMg):Eu, L: the size of PMMA microsphere used: 400 or 800 (nm), m: Mg content), which were fabricated by a modified sol-gel method employing PMMA microspheres as a template and constituent metal chlorides as an oxide source, were investigated by
monitoring their photoluminescence (PL) properties at 588 nm in air at 25℃(excitation wavelength = 260 nm). The PL intensity increased with increasing the Mg content in the thick films, and decreased clearly upon exposure to acetone balanced with air. Among the films tested, Lmp-SnO2 (1Mg):Eu showed the highest ratio R (= I0/I) of PL intensity in air (I0) to that (I) in acetone, irrespective of the size of macropores, while the signal/noise (S/N) ratio was extremely low. On the other hand, ΔI (= I0-I) of Lmp-SnO2(mMg):Eu was the highest at m = 10 with a high S/N ratio.

 

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22.

酸化コバルトナノ粒子堆積膜の光応答型COガスセンサ特性

産総研

Hyun-Jeong Nam, 佐々木 毅, ○越崎直人

OPTICAL CO GAS SENSING PROPERTY OF COBALT OXIDE NANOPARTICLE AGGREGATED FILMS

Hyun-Jeong Nam, Takeshi Sasaki, Naoto Koshizaki

Nanoarchitectonics Research Center (NARC)
National Institute of Advanced Industrial Science and Technology (AIST)
Central 5, 1-1-1 Tsukuba, Ibaraki, 305-8565

We investigated the effect of Ar pressure during deposition on the morphology and CO gas sensing properties of cobalt oxide films deposited by pulsed laser deposition (PLD). The Ar pressure influenced the morphology of the films, and hence remarkably affected the sensor properties. The films deposited at 13.3 and 133 Pa of Ar exhibited high sensitivity. However, the sensitivities of films prepared at 133 Pa mostly derived from nanoparticle aggregates that attached weakly to underlying films. The amount of nanoparticle aggregates increased with deposition time, resulted in the large light scattering effect and sensitivity degradation. Films prepared at 13.3 Pa were smooth and adhered firmly to the substrate. The sensitivity of films deposited at 13.3 Pa increased with the thickness and saturated at 160 nm.


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23.

複数ゲートをもつ電界効果型ガスセンサ

石巻専修大理工

○中込真二、星飛雄馬、伊澤修平、國分義弘

FIELD EFFECT GAS SENSOR DEVICE WITH MULTI GATE

Shinji NAKAGOMI, Hyuma HOSHI, Shuhei ISAWA and Yoshihiro KOKUBUN

Faculty of Sciences and Engineering, Ishinomaki Senshu University, Ishinomaki-shi, Miyagi 986-8580

The hydrogen-sensing property of a new type field-effect gas sensor device based on silicon was studied. The device has an FET structure with plural Schottky gates between source and drain electrodes. We suggest and demonstrate hydrogen sensing using variation in electric potential of the gate electrode itself. The sensor device has a simple planar structure and was fabricated by applying a lift-off technique of a metal film. The device can detect hydrogen in an oxygen atmosphere at room temperature. In the measurement of response curves, a constant current was supplied from the drain to the source, and electric potentials of each four gate were recorded for changing hydrogen concentrations for a constant O2 concentration in Ar. The behavior of electric potential of each four gates depending on a condition of coexisting oxygen concentration is reported. The device has a potential to give us several information from each gate.

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24.

ダイオード型センサの構造制御と水素検知特性

長崎大1工,2院生産科学

○兵頭健生1,柴田浩希2,清水康博1,江頭 誠1

STRUCTURAL CONTROLS AND HYDROGEN SENSING PROPERTIES OF DIODE-TYPE GAS SENSORS

Takeo HYODO1, Hiroki SHIBATA2, Yasuhiro SHIMIZU1 and Makoto EGASHIRA1

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

A thermally oxidized TiO2 or Nb2O5 film equipped with a top Pd film electrode and a bottom Ti or Nb plate electrode (Pd/MO/M, MO: oxide film, M: metal plate) has been investigated as a diode-type H2 sensor. H2 responses of Pd/TiO2/Ti sensors fabricated by thermal oxidation were not better than those of Pd/TiO2/Ti sensors fabricated by anodic oxidation reported in our previous studies. On the other hand, Pd/Nb2O5/Nb sensors showed relatively better responses than Pd/TiO2/Ti sensors, by applying higher voltage. Pd/Nb2O5/Ti sensors, which were fabricated by rf magnetron sputtering of Nb metal on Ti substrates, followed by thermal oxidation at 450℃, showed the largest H2 response among the sensors tested.

 

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25.

シッフ試薬と多孔質ガラスを用いたホルムアルデヒドセンサの開発

NTT環境研a、国環研b、東洋大c

○丸尾容子a、中村二朗a、内山政弘b、泉克幸c、樋口正憲c

DEVELOPMENT OF FORMALDEHYDE SENSING ELEMENT USING POROUS GLASS IMPREGNATED WITH SCHIFF'S REAGENT

Yasuko Y. MARUOa, Jiro NAKAMURAa, Masahiro UCHIYAMAb, Katsuyuki, IZUMIc, and Masanori HIGUCHIc

aNTT Energy & Environmental Laboratories, Atsugi-shi, Kanagawa 243-0198
bNational Institute of Environmental Studies, Tsukuba-shi, Ibaragi 305-0053
cToyo University, Kawagoe-shi, Saitama 350-8585

We developed a sensor element for detecting formaldehyde. The sensor element was made of a porous glass impregnated with both Schiff・s reagent and an acid. The sensor element changed color from yellow to violet after exposure to formaldehyde, and absorption with a peak wavelength of 570-580 nm appeared. There was a quasi-linear relationship between the 570-580 nm absorbance of the sensor element after exposure to formaldehyde, and a logarithm of the exposed formaldehyde concentration. Also, the sensor element worked as reversible not as accumulate, and the absorbance at 570-580 nm of a once exposed sensor element decreased when it was exposed to a less concentrated formaldehyde atmosphere. These results indicate that our developed sensor element is reversible and thus suitable for the detection of a wide formaldehyde concentration range, for example from 20 ppm to 10 ppb.

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26.

アルコール類を用いた金ナノ粒子修飾くし型電極のインピーダンス応答解析

熊本大院

○山名来充恵、冨永昌人、谷口 功

Impedance Analyses of Adsorbed Alcohols on Interdigitated Microelectrode (IME) Modified with Gold Nanoparticles

Kumie YAMANA, Masato TOMINAGA, Isao TANIGUCHI

Graduate school of Science and Technology,
Kumamoto University
2-39-1, Kurokami, Kumamoto 860-8555, Japan

Au nanoparticles film can be prepared by crosslinking nanoparticle cores with organic molecules such as bifunctional alkanedithiols. These linker molecules act as insulating barriers between the metal cores, and determine the distances between the metal cores. In this study, we prepared interdigitated microelectrode (IME) and Quartz Crystal Microbalance (QCM) covered with Au nanoparticles film by crosslink process using 11-mercaptoundecanoic acid (MUA) as a linker molecule. Impedance response for Au nanoparticles film modified IME (MUA-Au/IME, QCM) was investigated, when MUA-Au/IME was exposed to alcohols vapors. It was found that the impedance response for alcohols depended on the charge transfer resistance of Au nanoparticles.

 

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27.

ポリアミドアミンデンドリマーのNO2ガス吸着特性とそのセンサへの応用の可能性

愛媛大院理工

○小谷頼利、松口正信

NO2 ADSORPTION OF POLY(AMIDOAMINE) DENDRIMER AND POSSIBILITY OF APPLICATION TO GAS SENSOR

Yorikazu KOTANI, Masanobu MATSUGUCHI

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

Various composition of copolymers composed of methyl methacrylate and chloromethyl styrene (poly(MMA-co-CMSt)) were coated on thickness shear mode (TSM) quartz crystal resonators. The mass loading response toward NO2 gas was measured after modification with poly(amidoamine) (PAMAM) dendrimers of first-, third-, fifth-generation. The effect of composition of copolymers, PAMAM dendrimer generation size, and surface functional group on the NO2 adsorption properties were examined.

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28.

黒鉛を用いた燃焼排ガス用電気化学式NO2センサの開発

光明理化学工業株式会社

中村 仁

DEVELOPMENT OF AMPEROMETRIC NO2GAS SENSOR USING GRAPHITE FOR MONITORING OF COMBUSTION GAS

Hitoshi NAKAMURA

Komyo Rikagaku Kogyo K.K. 1-8-28 Shimonoge, Takatsu-ku, Kawasaki-City
213-0006

We have developed an amperometric nitrogen dioxide(NO2) gas sensor for monitoring of combustion gas. The working electrode of the sensor consists of porous menbrane and Graphite powder. The sensor showed no signal by NO and high concentration CO in combustion gas. Moreover the NO2 signal was not influenced by SO2 and H2S substantially. We also combined NO gas sensor with NO2 gas sensor in order to monitor NOx concentration.

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29.

カーボンナノチューブとプラズマ重合を用いる酵素センサ

芝浦工大工

○松井泰憲、柴山 悠、六車仁志

ENZYME SENSOR WITH CARBON NANOTUNE AND PLASMA-POLYMERIZED FILM

Yasunori MATSUI, Yu SHIBAYAMA, and Hitoshi MUGURUMA

Department of Electronic Engineering, Shibaura Institute of
Technology, Toyosu, Koto-ku, Tokyo 135-8548

We report on an amperometric biosensor that is based on carbon nanotubes (CNT) and plasma-polymerized film (PPF). A simple and reliable dry-chemical based layer-by-layer process was employed for device fabrication according to the following procedure: (1) a 10-nm-thick acetonitrile PPF layer (first PPF layer) was formed on a sputtered gold electrode; (2) a solution cast CNT layer was formed on the first PPF layer; (3) the CNT layer was treated by nitrogen or oxygen plasma; (4) a solution cast glucose oxidase (GOx) layer was formed onto the CNT layer; (5) immobilized GOx was overcoated with a 20-nm-thick acetronitrile PPF layer (second PPF layer). The resulting device showed that the oxidizing current response due to enzymatic reaction was 4 to 16-fold larger than that with only CNT or PPF, showing that the PPF and/or plasma process is an enzyme-friendly platform for designing electrochemical communication from the reaction center of GOx to the electrode via CNTs. The optimized glucose biosensor showed high sensitivity (sensitivity of 42 μA mM-1 cm-2, correlation coefficient of 0.992, linear response range of 0.025-2.2 mM, and a detection limit of 6 μM at signal/noise ratio of 3, +0.8 V vs. Ag/AgCl), high selectivity (almost no interference by 0.5 mM ascorbic acid) for glucose quantification, and rapid response (<4 s to reach 95% of maximum response). Additionally, the devices showed a small and stable background current (0.35 ± 0.013 A) compared with the glucose response (ca. 10 μA at 10 mM glucose) and suitable reproducibility from sample-to-sample (<3%, n = 4).

 

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30.

グルコース脱水素酵素とプラズマ重合膜を用いるグルコースセンサ

芝浦工大工 

○藤沢 幸太、新開弘之、六車仁志

GLUCOSE SENSOR WITH GLUCOSE DEHDROGENASE AND PLASMA-POLYMAERIZED FILM

Kouta FUJISAWA, Hiroyuki SHINKAI, and Hitoshi MUGURUMA

Department of Electronic Engineering, Shibaura Institute of
Technology, Toyosu, Koto-ku, Tokyo 135-8548

A novel design is described for an amperometric biosensor based on NAD(P)-dependent glucose dehydrogenase combined with a plasma-polymerized thin coating film (PPF). An acetonitrile PPF is deposited directly onto the surface of a sputtered gold electrode. The resulting film coating is extremely thin (~60 nm); adheres well to the substrate (electrode); has a flat surface and a highly-crosslinked network structure; and is hydrophilic in nature. Glucose dehydrogenase is densely immobilized onto the surface of the acetonitrile PPF on the gold electrode. This PPF plays the role of interface between enzyme and electrode. The amperometric biosensor characteristics covered 2.5 - 42 mM glucose concentration at +0.6 V of applied potential. Unlike conventional wet-chemical processes incompatible with mass production techniques, this dry-chemistry procedure has great potential for enabling high-throughput production of bioelectronic devices.

 


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31.

グルコースオキシダーゼミセルとアミノ化カーボン電極を組み合わせたアンペロメトリックグルコースセンサ

埼玉工大院工

○Xiuyun WANGa, b 内山俊一

AMPEROMETRIC GLUCOSE SENSOR FABRICATED BY COMBINING GLUCOSE OXIDASE MICELLE MEMBRANE AND AMINATED GLASSY CARBON ELECTRODE

○Xiuyun WANGa, b and Shunichi UCHIYAMAa*

aDepartment of Materials & Science, Graduate School of Engineering,

Saitama Institute of Technology, Fukaya, Saitama 369-0293, Japan.

bSchool of Chemical Engineering, University of Science and Technology
Liaoning, Anshan, Liaoning, 114051, P. R. China.

An amperometric glucose biosensor has been developed by employing an aminated glassy carbon electrode (AGCE) coated with polystyrene (PS) membrane containing glucose oxidase (GOD) micelle. This study demonstrates that polymaleimidostyrene (PMS) can react with GOD, and PMS-immobilized GOD contained in PS membrane forms micelle structure that can be viewed by scanning electron microscope (SEM). GOD micelle membrane was prepared by spreading the mixture of 30 μL of 10.0 mg mL-1 PS chloroform solution and 10 μL of 5.0 mg mL-1 PMS chloroform solution mixed with 1.0 mg GOD. This glucose sensor has good sensitivity with short response time (within 2 min.). A good linear relationship was observed in the concentration range of 0.2 mM to 2.6 mM when the applied potential was-0.45 V vs. Ag/AgCl. Interferences of uric acid and L-ascorbic acid can be ignored at the proposed glucose biosensor.

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32.

酵素-有機色素同時吸着カーボンフェルトを用いるフロー型バイオセンサ

埼玉工大・工  

○長谷部 靖、廣野 眞希、小室 涼太

FLOW BIOSENSOR USING ENZYME-ORGANIC DYE CO-ADSORBED CARBON FELT

Yasushi HASEBE, Masaki HIRONO and Ryota KOMURO

Department of Life Science and Green Chemistry, Saitama Institute of Technology,1690 Fusaiji, Fukaya-shi, Saitama 369-0293

Glucose oxidase (GOx) and organic dyes (OD) [e.g., methylene blue (MB), thionine (TN) etc.,] were co-adsorbed onto the porous carbon felt (CF) from GOx-OD mixed solution to fabricate the CF-based flow biosensor. The GOx and OD co-adsorbed CF (GOx-OD/CF) was used as a bioreactor, and was connected to the CF-based H2O2 detector using horseradish peroxidase (HRP) and TN co-adsorbed CF (HRP-TN/CF). The glucose was oxidized in the GOx-OD/CF reactor, and produced H2O2 was cathodically detected on the HRP-TN/CF detector at applied potential of 0 V vs. Ag/AgCl. The adsorption conditions (i.e., kinds and concentrations of OD, solvent, and ionic strength) and operational conditions (carrier pH and flow rate) were optimized. Cationic dyes (e.g., methylene blue, thionine, toluidine blue, methylene green and meldra's blue) were effective to retain catalytic activity of adsorbed GOx. In contrast, the GOx-adsorbed CF (without OD) showed no significant response, probably because of denaturation of GOx at the CF surface. The catalytic activity of the GOx-OD/CF reactor increased with increasing OD concentration in adsorption solution. Electrostatic and/or specific interactions between cationic OD and the GOx (pI = 4.2) may contribute to retain the activity of adsorbed-GOx on the CF surface. The resulting biosensor enabled the detection of glucose in the concentration range from 0.1 mM to 10 mM (detection limit, 0.05 mM) with sampling rate (ca.50 samples/h) at carrier flow rate of 4.1 ml/min. The GOx-MB/CF retained ca.45 % of its original activity after 131 days storage in 0.1 M phosphate buffer (pH 5.0) at 4℃.

 

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33.

酵素固定化用モノリスカラムの開発と微量計測への応用

神奈川工科大工a、秋田大工資b

○飯田泰広a、安藝 翔a、村山尚子a、塚田結香a、佐藤生男a、山本 修b

DEVELOPEMNT OF SILICA MONOLITH FOR IMMOBILIZATION OF ENZYMES AND THE APPLICATION OF THE PREPARATION TO MICRO BIOSENSING

Yasuhiro IIDAa, Sho AKIa, Naoko MURAYAMAa, Yuka TSUKADAa, Ikuo SATOHa, Osamu YAMAMOTOb

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

bCenter for Geo-Environmental Science, Faculty of Engineering and Resource Science,
Akita University
1-1 Tegata Gakuen-machi, Akita 010-8502

A novel synthetic method of silica monolith having amino groups in the structure of the silica was developed as supporting materials for enzymes and the properties of the monolithic silica column was investigated. Boc-γ-APTES was synthesized and used as an element for the fabrication of novel silica monolith. Synthesized Boc-?γ-APTES was mixed with TMOS (tetramethoxysilane) and PEG to fabricate a monolithic silica column. Influence of the synthetic condition on the properties of the silica monolith was investigated. The optimized silica monolith was used as a support for immobilization of L-Histidine decarboxylase and was applied to L-histidine sensing.

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34.

酵素反応によるOs錯体酸化体の蓄積/電解還元過程を利用した酸化酵素活性の高感度測定

兵庫県立大院 a・産総研北海道b、産総研つくばc

○太田 栄次a・三重 安弘b・丹羽 修c水谷 文雄a

HIGHLY SENSITIVE DETERMINATION OF OXIDASE ACTIVITY BASED ON THE CHARGE ACCUMULATION AND ELECTROCHEMICAL REDUCTION AT OSMIUM COMPLEX-PEROXIDASE-COATED ELECTRODE

EIJI OTAa ,YASUHIRO MIEb ,OSAMU NIWAc and FUMIO MIZUTANIa

aGraduate School of Material Science ,University of Hyogo
3-2-1 Kouto ,Kamigori ,Ako-gun ,Hyogo 678-1297
bHokkaido Center ,National Institute of Advanced Industrial Science and Technology,
2-17-2-1 Tsukisamu-Higashi ,Sapporo 062-8517
cTsukuba Center ,National Institute of Advanced Industrial Science and Technology,
1-1-1Higashi ,Tsukuba ,Ibaraki 305-8566

The highly sensitive determination of hydrogen peroxide have been strongly required for clinical field to develop enzyme sensors and immunosensors with enzyme labels.
In this study, an electrode coated with poly(vinylpyridine) containing [Os(bpy)2sub>]2+and horseradish peroxidase (Os(II)/HRP-polymer) was used for determining hydrogen peroxide. Hydrogen peroxide oxidized [Os(bpy)2sub>]2+ to produce [Os(bpy)]3+, and the [Os(bpy)]3+accumulated under the open-circuit condition was then reduced cathodically. The accumulation process is inherently advantageous for increasing the sensitivity of the analyte. The proposed method has been applied to the determination of glucose oxidase, a hydrogen peroxidase-producing an enzyme.

 

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35.

低侵襲針状酵素センサの作製およびその評価

徳島大工

○安澤幹人、山本美穂、森山健史、高岡宏樹

PREPARATION AND EVALUATION OF A LOW INVASIVE NEEDLE TYPE ENZYME SENSOR

Mikito YASUZAWA, Miho YAMAMOTO, Kenji MORIYAMA, Hiroki TAKAOKA

Department of Chemical Science and Technology, The University of
Tokushima,
Tokusima 770-8506, Japan

A unique needle type glucose sensor which can be used by inserting only the tip of the sensor in the sample was fabricated. In order to maintain enough area for enzyme immobilization and platinum electrode surface, a cave with platinum surface was formed at the tip of the sensor. The enzyme glucose oxidase was immobilized on the platinum surface located in the cave by the combination of electrodeposition and electropolymerization of o-phenylenediamine. Amperometric responses of the prepared electrodes to glucose were examined by measuring the electrooxidation current at a potential of 0.60 V (for hydrogen peroxide detection) in 0.1 mol dm-3 phosphate buffer solution (pH 7.4). The obtained sensor showed good response with good linear relationship with glucose concentration up to 24 mmol dm-3, which is actually wider than general sensor with sensing part outside of the electrode. This may due to the effective reproduction of oxygen generated by the electrooxidation of hydrogen peroxide, which all occurred in the cave. The application of this sensor to a low invasive glucose sensor fabrication is highly feasible.

 

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36.

無水リン酸結合を共通構造として有する生体エネルギー分子の網羅的検知を目的とした人工酵素バイオセンサ

九工大

池野慎也、淺川 雅、○春山哲也

Molecular commonality detection of diphsphoric acid anhydride structured substances using an artificial-enzyme membrane for in situ one-step bio-surveillance

Shinya IKENO, Hitoshi ASAKAWA, and Tetsuya HARUYAMA*

Department of Biological Functions and Engineering, Kyusyu Institute of Technology
Kitakyushu Science and Research Park, Kitakyushu, Fukuoka 808-0196, Japan

In the fields of hygiene, public safety and security including fighting bioterriorism, the detection of biological contaminants, e.g. microorganisms, spores and viruses, is a constant challenge. However, there is as yet no sophisticated method of detecting such contaminants in situ witnout oversight. The autnors focused their attention on diphosphoric acid anhydride which is a structure common to all biological phosphoric substances, Interestingly, biological phosphoric substances are peculiar substances present in all living things, and include many different substances, e.g. ATP. ADP.dNTP. pyrophosphate(PPi) this common structure as the basis of their development of an artificial-enzyme membrane with selectivity for the structure common to all biological phosphoric substances and studied the possibility of its application to in situ bio-surveillance sensoes. This in situ detection method of the common diphosphoric acid anhydride structure bring a unique advantage to the fabrication of in situ bio-surveilance sensors for monitoring biological contaminants without an oversighit, even if they were transformed.

 

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37.

フェニルボロン酸アゾ色素を用いる糖センサの開発

東北大

○江川祐哉、後藤良太、新名 聖、安斉順一

PHENYLBORONIC ACID-APPENDED AZO DYES FOR SUGAR SENSING

Yuya EGAWA, Ryota GOTOH, Aatoshi NINA and Jun-ichi ANZAI

Graduate School of Pharmaceutial Sciences, Tohoku University,
Aramaki, Aoba, Sendai 980-8578

We synthesized new boronic acid-appended azo dyes(BAs) in which a boronic acid group was arranged to the ortho-position of azo group. BAs show a significant change in UV-visible spectra upon sugar binding. A new mechanism for the spectral change of the dyes is proposed based on the formation and cleavage of B-N dative bond between boronic acid and azo groups. To improve the selectivity for D-glucose, BA was attached to poly(ethyleneimine) (polyBA). The binding constants for D-glucose(Kglu) and D-glucose (Kfru) were calculated to be 54 and 110 M-1, respectively. The selectivity for D-glucose was improved compared to monomeric BA(Kglu = 1.2M-1, Kflu = 17M-1 ). Multilayered films composed of polyBA and polyanions {poly(vinyl sulface)(PVS), carboxymethylcellulose (CMC)} were prepared using a layer-by-layer deposition technique. In(PVS/polyBA)10 films, the affinity for D-glucose was low (kglu = 1.7M-1, Kflu = 28M-1). In contrast, (CMC/polyBA)5film showed a relatively high affinity for D-glucose(Kglu = 18M-1, Kflu = 42M-1). The loosely packed structure and flexibility of polymer chains in the (CMC/polyBA)5 film may lead to the imprioved affinity for D-glucose.

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38.

分子の導電性を利用した化学センサ構築用ナノコンポジット薄膜基板の作製と評価

産総研

Dae-Gun Kim, 小山恵美子, 桐原和大, 徳久英雄, ○越崎直人

FABRICATION AND EVALUATION OF NANOCOMPOSITE FILM SUBSTRATES FOR CHEMICAL SENSOR UTILIZING MOLECULAR CONDUCTANCE

Dae-Gun Kim, Emiko Koyama, Kazuhiro Kirihara, Hideo Tokuhisa, Naoto Koshizaki

Nanoarchitectonics Research Center (NARC)
National Institute of Advanced Industrial Science and Technology (AIST)
Central 5, 1-1-1 Tsukuba, Ibaraki, 305-8565

Au/SiO2 nanocomposite films consisted of an extremely high number density of Au nanoparticles dispersed in SiO2 matrix a few nanometers thick were deposited by co-sputtering method, and employed for molecular conductance measurement by immobilizing and bridging conjugated biphenyl molecules on dispersed Au nanoparticles. The number density of Au nanoparticles in the insulating SiO2 matrix was approximately 14000 /μu, and the average interparticle distance with their neighbors was about 8 nm. The current increased considerably up to the range of nanoamperes after the immobilization of the conjugated biphenyl molecules, 105 times larger than without molecules before immobilization. Although the Au nanoparticles can be connected to only 30% of all combinations of neighboring Au nanoparticles by biphenyl molecules 2.4 nm long from the topological analysis, the biphenyl molecules can bridge most of the Au nanoparticles, and their bridging continuity is over 100 nm in length. Thus the measured current is suggested to be come from the continuously bridged molecules between the Au nanoparticles. Furthermore the I-V data of the whole Au/SiO2 nanocomposite film immobilized with conjugated molecules are confirmed to be in a reasonable range in comparison with the scanning tunneling spectroscopy data of similar conjugated molecules.

 

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39.

固相抽出を組み合わせた尿中8-OHdG測定法の改良―測定条件の最適化と基本性能の評価―

産総研 バイオニクス研究センターa、(株)タニタb、東京工科大c

○稲葉 洋平a、水品 昌之b、木村 純b、伊藤 成史b、横山 憲二a、輕部 征夫 a,c

IMPROVEMENT OF URINARY 8-OHDG MEASUREMENT METHOD COMBINED WITH SOLID PHASE EXTRACTION −OPITIMAIZATION OF MEASUREMENT CONDITION AND EVALUTION OF BASIC PERFORMANCE−

Yohei INABAa, Masayuki MIZUSHINA b, Jun KIMURAb, Narushi ITOb, Kenji
YOKOYAMAa and Isao KARUBE a,c

aNational Institute of Advanced Industrial Science and Technology (AIST),
c/o Katayanagi Advanced Research Laboratories, 1404-1 Katakura-Machi,
Hachiouji, Tokyo 192-0982

bTANITA Corporation, 1-14-2, Maeno-cho, Itabashi-ku, Tokyo 174-8630

cTokyo University of Technology, 1404-1 Katakura-Machi, Hachiouji, Tokyo
192-0982

8-Hydroxy-2’-deoxyguanosine (8-OHdG) contained in urine is known as a biomarker of oxidative stress. Standardization of urinary 8-OHdG determination is significant. We have reported an effective solid phase extraction (SPE) method when urinary 8-OHdG is measured by high performance liquid chromatography coupled to an electrochemical detector (HPLC-ECD). In this study, the 8-OHdG measurement optimized method condition and evaluated basic performance. The optimized measurement was highly reproducible (CV=2.0-2.9%, n=10) and removed the urinary interference materials. A correlation was observed between the proposed HPLC method and the column switching method (r = 0.96).

 

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40.

インクジェットプリンタを用いたフレキシブル基板電極の作製と化学センサへの応用

国立リハ研、東洋大、富山大

○高橋健一、田原祐助、山口昌樹、加藤誠志、外山 滋

PREPARATION OF FLEXIBLE ELECTRODE WITH AN INKJET PRINTER AND ITS APPLICATION TO CHEMICAL SENSORS

Kenichi TAKAHASHIa, Yuusuke TAHARAb, Masaki YAMAGUCHIb, Seishi KATOc, and Shigeru TOYAMAc

aDepartment of Chemical Engineening, Faculty of Engineering, Toyo University,
2100 Nakanodai, Kujirai, Kawagoe-shi, Saitama 350-8585
aDepartment of material systems engineering & lifescience, Faculty of Engineering,
Toyama University, 3190 Gohoku, Toyama-shi, Toyama 930-8555
cResearch Institute, National Rehabilitation Center for Persons with Disabilities,
4-1 Namiki, Tokorozawa-shi, Saitama 359-8555

Metal electrodes for chemical sensors have been fabricatedon an overhead-transparency film by a kind of liftoff method using an inkjet printer. Furthermore, a glucose sensor using this electrode on film was fabricated. The new method to fabricate electrode is comprised of i) inkjet-pronting of the reversal pattern of the electrode with a water-soluble ink, ii) vapor-deposition of metal layers, iii) and removal of the ink with the upper metal layers. This method has an advantage that the reveral pattern of the ink and the metal layers used water, although our previous method used organic solvents.

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(清山賞受賞講演2)

高機能性バイオインターフェイスを用いた高感度バイオセンサの開発

産総研

黒澤 茂

R&D OF ADVANCED BIOSENSORS USING HIGH PERFORMANCE BIOINTERFACES

Shigeru KUROSAWA

National Institute of Advanced Industrial Science and Technology (AIST),
AIST Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba 305-8565

There is growing concern about the necessity of strategic technological innovation in Japan. Monitoring the physical condition of people is vital for health management to realize a safe and secure society, and it is important to develop biosensors to detect markers of stress and disease. At the same time, we need highly sophisticated technology for analyses of chemical substances at levels from parts per million (ppm) to parts per trillion (ppt) for monitoring exposure to environmental pollutants, such as dioxins or pesticide residues. In this research, we tried to develop equipment for high-sensitivity, high-precision, rapid, and simplified measurement that could be applied in environmental monitoring, medical applications, food testing, or in the detection of pathogenic microbes. We have proposed and developed Advanced Biosensors using high performance Biointerfaces for detection of environmental pollutants, and disease makers. Here, we attempted to put the flow-type QCM immunosensor system to practical use to overcome weaknesses of the batch-type method.

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41.

交流インピーダンス法によるタンパク質検出装置の開発

(財)富山県新世紀産業機構a、富山県工業技術センターb、立山科学グループc  
  
○常川 直子a、横山 義之b、牧村 めぐみb、寺澤 孝志b、清水 孝晃b、深沢 正樹c、角崎 雅博b、藤城 敏史b、谷野 克巳

Development of impedimetric protein sensor system

Naoko TSUNEKAWAa, Yoshiyuki YOKOYAMAb, Megumi MAKIMURAb, Takashi
TERASAWAb, Takaaki SHIMIZUb, Masaki FUKAZAWAc, Masahiro KADOSAKIb,
Satoshi FUJIKIb and Katsumi TANINOb

aToyama New Industry Organization, 529 Takada, Toyama-shi, Toyama
930-0866 bToyama Industrial Technology Center, 383 Takada, Toyama-shi,
Toyama 930-086 cTateyama Kagaku Group, 30 Shimonoban, Toyama-shi, Toyama 930-1305

Specific protein detection is important and necessary for the clinical assay, the early detection and rapid cure. Since electrochemical reactions directly emit an electronic signal, expensive signal transduction equipment is not required. Impedance spectroscopy enables label-free detection and is nondestructive and useful in equivalent circuit models for interpretation on an electrode surface. In this study, we developed the system to detect a specific protein using impedance spectroscopy and antigen-antibody complex reaction on gold electrodes. Self-assembly technique was utilized to modify the Au-electrode surface. We also investigated the method to modify Au-electrodes with an antibody directly and simply. The results suggest that it is possible to detect antigen simply by comparing the measurement values of a.c. impedance.

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42.

片面電極から励起可能な水晶振動子バイオセンサの開発

東北大

○加藤 寛、橋本昌彦、樋口 誠、岸 宏樹、梶 弘和、西澤松彦、安部 隆

DEVELOPMENT OF A QCM BASED BIOSENSOR HAVING THE ELECTRODES FOR EXITING THE VIBRATIONS ON ONE SIDE

Hiroshi KATO, Masahiko HASHIMOTO, Makoto HIGUCHI, Hiroki KISHI, Hirokazu KAJI, Matsuhiko NISHIZAWA, Takashi ABE

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

A new type of quartz crystal microbalance(QCM) in which the electrodes are located on one side has been developed for biosensing. The QCM sensor has two electrodes for exciting thickness sheer vibration on one side of the crystal and a conductive layer(gold) on the other side. The excited vibration by the electrode configuration has asymmetric desplacement. Design and evaluation for miniaturizing the QCM sensor have been studied as to the convex height and the electrode ratio. The optimum height and the optimum electrode ratio to convex-diameter are 2.0 μm and 0.6〜0.8 for the QCM(17MHz,AT-cut), respectively. We also reported adsorption measurements of of bovine serum albumin(BSA) on the gold electrode using the optimized QCM sensor.

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43.

TNTを超高感度検出するための金ナノ粒子を用いたSPR信号増幅

九大産学連携センターa、JSPS b、九大院農c 、九大院情シd

○川口俊一a、デシン ラビシャンカランa,b、松本 清c、都甲 潔d、三浦則雄a

SPR SIGNAL AMPLIFICATION USING AU NANOPARTICLE FOR ULTRA-HIGHLY SENSITIVE TNT DETECTION

○Toshikazu KAWAGUCHIa, Dhesingh RAVI SHANKARANa,b,
Kiyoshi MATSUMOTOc , Kiyoshi TOKOd, Norio MIURAa

a Art, Science and Technology Center for Cooperative Research, Kyushu
University,
Kasuga-shi, Fukuoka, 816-8580
b Japan Society for the Promotion of Science, Tokyo, 102-8471
c Graduate School of Agriculture, Kyushu University, Fukuoka-shi,
812-8581
d Graduate School of Information Science and Electrical Engineering,
Kyushu University, Fukuoka-shi, 819-0395

We report here the novel signal amplification technique using Au nanoparticle for surface plasmon resonance (SPR) sensor. Localized surface plasmon resonance (LSPR) effect using Au nanoparticle is well-known as one of the way to amplify SPR signal. In the previous work, we proposed the innovative theory, “the extended Mie theory”, which depicted how to fabricate adequate immunosurface using Au nanoparticle to amplify the SPR signal by LSPR effect. The present work employed the immunosurface fabricated with the Au nanoparticle (40 to 150 nm) for detection of TNT. The surface stability was improved significantly, since the Au nanoparticle did not aggregate on the sensor surface in this case. The degree of SPR signal amplification depended on the Au particle size, as the extended Mie theory predicted. The TNT detectable range was between 10 ppt and 100 ppb, which was comparable with that without Au nanoparticle.

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44.

レセプターとの相互作用を利用したSPRによる神経伝達物質の検出

九大、日本学術振興会、JNV大

○デシン ラビシャンカラ、キム スクジン、スニタ クンバット、カウベリ ゴビ、川口俊一、三浦則雄

DETECTION OF NEUROTRANSMITTER BY SPR SENSOR UTILIZING ITS INTERACTION WITH RECEPTOR

○Dhesingh RAVI SHANKARANa,b, Sook Jin KIMa, Sunita KUMBHATc, K. Vengatajalabathy GOBIa, Toshikazu KAWAGUCHIa, Norio MIURAa

aArt, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi,Fukuoka, 816-8580, Japan
bJapan Society for the Promotion of Science, Tokyo, 102-8471, Japan
cDepartment of Chemistry, Jodhpur University, Jodhpur, 342 003, India

This report describes the development and characteristics of a new kind of biosensor for detection of dopamine(DA), an important neurotransmitter implicated in the regulation on mood, motivation and movement. The specific interaction of DA with its recepter (D3. DA-RC) has been utilized for sensing of DA by surface-plasmon of resonance (SPR) technique. A conjugate of DA was synthesized using bovine serum albumin(BSA) and was immobilized onto an SPR gold surface by simple physical adsorption. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and atomic force microscopy (AFM) techniques were used to characterize the conjyugate and the biosensor surface. Based on the principle of indirect competitive inhibition, the biosensor exhibited excellent sensitivity to DA in the concentration range from 85 pg/ml (ppt) to 700 ng/ml (ppb). The experimantal results indicate that the biosensor exhibits remarkable selectivity to DA with good reproducibility and stability.

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45.

化学増幅型2次元SPR免疫センサによるIgG及びIL-2の高感度検出

富山大院理工

羽根新太郎、入部康敬、○鈴木正康

HIGHLY SENSITIVE DETECTION OF IGG AND IL-2 BY USING A CHEMICALLY AMPLIFIED 2D-SPR IMMUNOSENSOR

Shintaro HANE, Yasunori IRIBE, Masayasu SUZUKI

Graduate School of Science and Engineering, University of Toyama

Toyama-shi, Toyama 930-8555, Japan

We are developing a high resolution two dimensional surface plasmon resonance (2D- SPR) affinity imaging sensor for the monitoring of single cell based micro-arrayed cell chips. But the 2D-SPR sensor has lower sensitivity compared with conventional 1D-SPR sensors. This paper described biochemical amplification method of SPR signal for high sensitive detection of mouse immunoglobulin G (IgG) and interleukin 2 (IL-2). The measurement is based on sandwich method. After the sample application, peroxidase-labelled second antibody (HRP-Ab) was added. By the addition of 4-chloro-1- naphtol (CN) and H2O2, CN was polymerized and precipitated. This precipitates may cause large SPR signal changes. By the present method, the sensitivity for mouse IgG was improved over 10,000 times higher than the conventional method. In the similar way, 100 ng/ml IL-2 could be detected by the present method.

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46.

ポルフィリン固定化ポリスチレンセルを用いた光学式pHセンサの開発

愛媛大院理工

○山中暁、板垣吉晃、定岡芳彦

DEVELOPMENT OF OPTOCHEMICAL PH SENSOR USING PORPHYRIN IMMOBILIZED POLYSTYRENE CUVETTE

Satoru YAMANAKA, Yoshiteru ITAGAKI, and Yoshihiko SADAOKA

Department of Materials Science and Biotechnology, Graduate School of
Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577,
Japan
 
The optochemical pH sensor based on porphyrin dyes immobilized on a polystyrene cuvette is developed. Immobilizing chemically stable porphyrin dyes on polystyrene through the ionic bond resulted a stable pH detection in the wide range of pH values. The porphyrin dyes on the cuvette exhibited the characteristic change in the visible absorption bands to the change in the pH values. This sensor element exhibited good response for higher and lower pH values and reproducibility.

 

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47.

ポリチオエーテルを用いた銅イオン選択性電極の開発

産総研a、神戸大院総合人間b、神戸大院人間発達環境c
  
○脇田慎一a、佐藤長久a,b、齊藤惠逸c

DEVELOPMENT OF COPPER ION-SELECTIVE ELECTRODES BASED ON POLYTHIOETHER

Shin-ichi WAKIDAa, Nagahisa SATOa,b and Keiitsu SAITOc

a National Institute of Advanced Industrial Science and Technology (AIST),
Midorigaoka 1-8-31, Ikeda, Osaka 563-8577
b Graduate School of Cultural Studies and Human Science, Kobe University,
Tsurukabuto 3-11, Nada, Kobe 657-8501
c Graduate School of Human Development and Environment, Kobe University,
Tsurukabuto 3-11, Nada, Kobe 657-8501

A systematic ring-size effect of polythiocrown ether on electrochemical response of copper ion-selective electrodes (Cu2+-ISEs) was investigated, which electrodes were composed of a series of tetrathiocrown ether, n-ane-S4 (n=12〜15), sodium tetraphenylborate (NaTPB), 2-nitrophenyloctylether (NPOE) and poly(vinyl chloride) (PVC). The composition of copper ion-sensing membranes was optimized for each Cu2+-ISEs. We observed the anionic site effect and slight memory effect for the prepared Cu2+-ISEs. Among the tetrathiocrown ether, n-ane-S4 (n=12〜15), the Cu2+-ISEs based on 13-ane-S4 and 15-ane-S4 show almost Nernst theoretical response from 10-5 M and the ISEs based on 12-ane-S4 and 13-ane-S4 show relatively better selectivity for Ag+ ion. We also discussed the relationship between sensor characteristics of Cu2+-ISEs and solvent extraction characteristics in selectivity for Cu2+ and Ag+ ions.

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48.

ビスポリチオエーテルカルボン酸を用いた銅イオンセンサの開発と流れ分析への応用

産総研a、神戸大院総合人間b、神戸大院人間発達環境c

○脇田慎一a、佐藤長久a,b、齊藤惠逸c

DEVELOPMENT OF COPPER ION-SELECTIVE ELECTRODES BASED ON BIS(POLYTHIOETHER CALBOXYLATE) AND THEIR APPLICATION TO FLOW INJECTION ANALYSIS

Shin-ichi WAKIDAa, Nagahisa SATOa,b and Keiitsu SAITOc

a National Institute of Advanced Industrial Science and Technology (AIST),
Midorigaoka 1-8-31, Ikeda, Osaka 563-8577
b Graduate School of Cultural Studies and Human Science, Kobe University,
Tsurukabuto 3-11, Nada, Kobe 657-8501
c Graduate School of Human Development and Environment, Kobe University,
Tsurukabuto 3-11, Nada, Kobe 657-8501

We have studied a new calboxylated polythiocrown ether, 2-(3,6,10,13-tetrathia-cyclotetra-dec-1-oxy) hexanoic acid (TTCT-OHA) for copper-selective plasticized polyvinyl chloride (PVC) membrane electrodes. The Cu2+-ISEs shows reversible potential responses with an almost Nernstian slope for Cu2+ ions in the concentration ranges from 1.0 × 10-7 to 1.0 × 10-3 M for two month. As TTCT-OHA is very unique charged carrier, we designed more unique bischarged carrier and fundamentally studied electrochemical response for the first time as far as we know. The designed bischarged carrier was synthesized and purified as white crystal and then characterized with 1H NMR and MS. The Cu2+-ISEs based on TTCT-(DSAA)2 shows reversible responses from 1.0 × 10-6 to 1.0 × 10-3 M with a 90% response time (t90%) of 7 s. We found that the selectivity for Ag+ is much improved, however, the Cu2+-sensitive membrane seems slightly damaged. We also designed familiar bis type of neutral carrier, bis-polythiocrown ether for copper ionophore. The both Cu2+-ISEs show reversible potential responses in flow through system.

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49.

金属合金薄膜電極を用いた高性能リン酸イオンセンサ

九工大工

○城戸崎 徹,高瀬 聡子,清水 陽一

A HIGH PERFORMANCE HYDROGEN-PHOSPHATE ION SENSOR BASED ON METAL-ALLOY THIN-FILM ELECTRODE

Toru KIDOSAKI, 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 thin-film based ion-sensors were tried to prepare by electrodepositing on Au-Al2O3 substrate from aqueous solution of metal-salts. 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 × 10-4 and 1.0 × 10-2 M with a Nernst's slope of - 43mV/decade at pH 5. The sensor showed relatively fast response, high selectivity, and sensitivity. The electrode was also stable and could be used for more than 7 weeks. Thus, the sensor seems to be successfully applied as an indicating sensor in potentiometric titration of hydrogen-phosphate ion.

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50.

ペロブスカイト型酸化物厚膜型リン酸イオンセンサの作製

九工大工

〇松本 俊和、高瀬 聡子、清水 陽一

PREPARATION OF PEROVSKITE-TYPE OXIDE THICK FILM FOR PHOSPHATE ION SENSOR

Matsumoto TOSHIKAZU, 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

Perovskite-type structured LaBO3 (B=Mn, Fe, Co) powders could be prepared by a polymer precursor method at 600℃ using acetylacetone (AcAc) and polyethylene glycol (PEG) as a chelating agent and a macromolecular additive, respectively. This powder was applied for the preparation of an oxide thick-film for a phosphate ion sensor by an electrophoretic deposition
(EPD) process in acetylacetone-based suspension. The LaCoO3 thick-film on carbon cloth device prepared by the EPD method without any sintering process showed good properties of amperometric sensing for hydrogen-phosphate ion at the concentration range between 1.0×10-4 M and 1.0×10-2M.

 

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51.

電気化学並びにSPR法による尿中腫瘍マーカー/クレアチニンの同時測定

筑波大院数理物質a,産総研生物機能工学b 

○中元浩平a,関岡直行a,栗田僚二b,丹羽修a,b

SIMULTANEOUS ON-CHIP DETERMINATION OF A CANCER MARKER AND CREATININE IN A URINE SAMPLE BY INTEGRATING SURFACE PLASMON RESONANCE AND ELECTROCHEMICAL METHODS IN A MICROFLUIDIC CHANNEL

Kohei NAKAMOTOa, Naoyuki SEKIOKAa, Ryoji KURITAb, Osamu NIWAa,b

a Graduate School of Pure and Applied Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573
b National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8566

We report an integrated micro fluidic device for simultaneous determination of cancer marker (Prostate specific antigen (PSA)) and creatinine by integrating thin gold films for surface plasmon resonance (SPR) and electrochemical detection. We integrated four thin gold films for the simultaneous measurement. One is modified with anti PSA antibody for PSA detection by SPR, and the other three films for amperometric creatinine detection. The working electrode was modified with bilayer of creatininase, creatinase, sarcosine oxidase as an enzyme layer and osmium-polyvinylbilpyridine wired horseradish peroxidase (Os-gel-HRP) as an electron mediator layer. When a mixture solution of PSA and detection antibody was injected into the integrated sensor, the SPR angle increased as increasing the PSA concentration. On the other hand, when a buffer solution containing creatinine was injected, cathodic current was increased by the enzymatic reaction. We could measure both concentrations with a few micro-litter samples. As a result, PSA and creatinine concentrations could be measured with a detection limit of 1ng/mL and 5μg/mL, respectively. We could correct the PSA concentration without being affected by the fluctuating urine concentration since creatinine works as the compensation substance.

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52.

LEPを用いたジルコニア(ZrO2)中の微量元素の測定

北陸先端科学技術大、大阪大

○伴野倫子、民谷栄一、高村 禅

Measurement of trace elements in zirconium dioxide (ZrO2) by Liquid Electrode Plasma(LEP)

Michiko BANNO, Eiichi TAMIYA, Yuzuru TAKAMURA

School of Material Science, Japan Advanced Institute of Science And Technology

1-1, Asahidai, Nomi, Ishikawa, JAPANDepartment of Applied Physics Osaka University1-1, Yamadaoka, Suita, Osaka

Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) has beenemployed for the measurement of the trace element in zirconium dioxide conventionally.However, zirconium is a line-rich element, so that it is difficult to measure the trace elementin zirconium dioxide by ICP-OES. On the other hand, Liquid Electrode Plasma Optical Emission Spectrometry (LEP-OES) developed by us has many advantages; such as on-sitemonitoring, small apparatus, low cost. In addition that the sensitivity of the zirconium byLEP-OES is extremely low. So we can expect very easy measurement of trace elements in zirconium dioxide by LEP-OES. In this paper, the sensitivity of Na measurement of zirconium dioxide is studied as a view point of applied voltage dependence and concentration dependence. Na of 0.1 ppm is successfully detected in 4000 ppm Zr by LEP-OES,

 

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53.

エレクトロウェッティングによるpH応答性バルブの構築

筑波大院数理物質

○山口茂輝、森本克也、戸谷真理子、福田淳二、鈴木博章

DEVELOPMENT OF A PH-RESPONSIVE VALVE BASED ON ELECTOROWETTING

Shigeki YAMAGUCHI, Katsuya MORIMOTO, Mariko TOYA,Junji FUKUDA, and Hiroaki SUZUKI

Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8573

A pH-responsive valve based on electrowetting was realized. To operate the valve at higher pHs, an irregular three-electrode system consisting of a gold working electrode, an iridium auxiliary electrode, and a pH-sensitive reference electrode was used. With an appropriate working electrode potential, a pH change caused a potential shift of the pH-sensitive reference electrode. As a result, the wettability of the working electrode changed and a solution passed the working electrode. When the valve was used at lower pHs, the auxiliary electrode was used as the valve electrode. The valve may be used in a microsystem to collect gastrointestinal information.

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54.

マイクロ溶液プラグによる逐次反応型マイクロバイオセンシングシステム

筑波大院数理物質

○高島篤司、清水義文、佐藤航、福田淳二、鈴木博章

MICROBIOSENSING SYSTEM BASED ON THE TRANSPORT OF LIQUID PLUGS

Atsushi TAKASHIMA, Yoshifumi SHIMIZU, Wataru SATOH, Junji FUKUDA, and Hiroaki SUZUKI

Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8573

A microfluidic device which can form a row of liquid plugs in a micro flow channel and conduct sequential transport of the plugs was constructed. The liquid plugs were formed by six pumps. The plugs in a main flow channel were transported to the reaction chamber using a main pump. The pumps operate according to the volume change of the bubbles caused by the electrolysis of water. Immunoassay was carried out on the chip. First, the plugs of antigen (AFP), antibody, and buffer solutions were formed in the main flow channel and were transported to the sensing area one by one to carry out antigen-antibody reactions, cleansing, and detection. The amount of AFP was measured by the fluorescence intensity of the labeled antibody. Clear dependence of the fluorescence intensity on the concentration of AFP was observed.

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