Vol. 19, Supplement A (2003)

Proceedings of the 36th Chemical Sensor Symposium
April 1-3, 2003

Abstracts

1.

バイオケモメカニカルゲルを利用したディスポーザブルバイオセンサ

筑波大物質工、筑波大応生化*

○熊谷あゆみ、鈴木博章、小川和義*、國府田悦男*

A DISPOSABLE BIOSENSER USING A BIOCHEMOMECHANICAL GEL

Ayumi KUMAGAI, Hiroaki SUZUKI, Kazuyoshi OGAWA*, Etsuo KOKUFUTA*

Institute of Materials Science, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8573
*Institute of Applied Biochemistry, University of Tsukuba, 1-1-1
Tennodai, Tsukuba, Ibaraki 305-8565

A disposable biosensor was fabricated by employing a pH-sensitive copolymerized poly(N-isopropylacrylamide) / acrylic acid gel with immobilized glucose oxidase. When the gel makes contact with a sample solution containing glucose, the pH of the gel decreases as a result of the enzymatic reaction inducing the collapse of the gel. The volume change of the gel could be converted into the movement of a dye solution in a flow channel faithfully with the help of a silicone rubber diaphragm. By using a gel of 2 mm in diameter and 1 mm in thickness, the response time was shortened to the order of several minutes. The response time to the shrinking change depended upon the activity of the enzyme and the concentration of glucose, although the final ratio of shrinkage settled approximately around the same value irrespective of their concentration. The transient stage could be used for sensing. Clear dependence of the length of the dye solution on the concentration of glucose was observed. By measuring the change at a predetermined time, glucose concentration could be measured. The lower detection limit was 200 μM when the measurement time was 10 min. The sensor will be an ultimate style of a disposable sensor, which does not need any external
circuits or spectroscopic procedures for detection.

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2.

微細針状バイオセンサの作製

徳島大工・東洋精密工業*

○安澤幹人、西浦慎二、村上淳也*、清水利泰*、今井信治*

FABRICATION OF FINE NEEDLE TYPE BIOSENSORS FOR IN VIVO MEASUREMENTS

Mikito YASUZAWA, Shinji NISHIURA, Junya MURAKAMI, Toshiyasu SHIMIZU, Shinji IMAI

Department of Chemical Science and Technology, Faculty of Engineering The University of Tokushima,
2-1 Minamijosanjima, Tokushima 770-8506
Toyo Precision Parts MFG. Co., Ltd.,
97-1 Higashinaka, Yamatotakada, Nara 635-0066

New needle type glucose oxidase immobilized glucose sensors were prepared by the electropolymerization of 1-(6-D-gluconamidohexyl) pyrrole (GHP) on the platinum wire electrode precoated with the solution of GHP, polydimethylsiloxane, and Nafion. In vitro measurement was performed in the phosphate buffer solution (pH 7.4) containing NaCl and bovine serum at 40C.
The response current obtained in bovine serum was similar with that in phosphate buffer solution. This indicated that the sensor itself have excellent biocompatibility and the adsorption of protein was hardly prevented. Therefore, the outer coating of biocompatible film such as polyurethane, was not essential. In vivo measurement was performed using rats under gas anesthesia of isoflurane. The sensor was implanted in subcutaneous tissue. After the intraperitoneal injection of glucose (30% solution, 1.0 g kg-1 body weight), the sensor response increased and behaved good agreement with the blood glucose level measured in vitro ith glucose meter.

 

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3.

集積化電気化学的送液機構とその応用

筑波大物質工

○鈴木博章、米山　玲

INTEGRATED ELECTROCHEMICAL FLUID TRANSPORT SYSTEM AND ITS APPLICATION

Hiroaki SUZUKI, Rei YONEYAMA

Institute of Materials Science, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8573

A microfluidic system was constructed by integrating on-chip micro pumps and check valves that function by means of a hydrogen bubble generated or extinguished electrochemically. Essential elements consisted of thin-film three-electrode systems with platinum black working electrodes. Micro flow channels and containers for electrolyte solutions were formed on a polydimethylsiloxane (PDMS) substrate. The growth and shrinkage of the bubble were controlled reproducibly by setting the working electrode potential at a constant value. The elastic nature of the bubble clogged in a valve compartment in the middle of a flow channel hindered the passage of the solution effectively. The bubble was also effective in separating two different solutions. By making the valves open and close cooperatively, a solution could be introduced into the system and transported in the flow channel. When two dye solutions were transported and merged in a flow channel, sheath flows were observed reflecting low Reynolds number. As a model system, two solutions containing luciferin and luciferase were introduced separately, transported, and mixed. Chemiluminescence originating from the enzymatic reaction was observed.

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4.

酵素固定化マイクロおよびナノ電極を組み込んだマイクロ流体システムの作製と電気化学的評価

東北大院工，グラスゴー大工，旭化成中研

○ 安川智之，Andrew Glidle，野村昌行，末永智一，Jonathan M Cooperb

FABRICATION AND ELECTROCHEMICAL CHARACTERISATION OF THE MICROFLUIDIC SYSTEMS INCLUDING MICRO AND NANO ELECTRODES IMMOBILISED ENZYMES.

Tomoyuki YASUKAWA, Andrew GLIDLE, Masayuki NOMURA, Tomokazu MATSUE, Jonathan M COOPER

Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University
07 Aoba, Aramaki, Aoba, Sendai, Sendai, 980-8579,
Bioelectronics Research Centre, Department of Electronics & Electrical Engineering, University of Glasgow
Oakfield Ave, Glasgow G12 8QQ U.K.
Central Technology Laboratory, ASAHI KASEI CORPORATION
2-1, Samejima, Fuji, Shizuoka 416-8501

For the sensitive detection of minute samples of analytes using immobilised biomolecules, microfluidic systems including micro and nano electrodes were fabricated and electrochemically characterised. Enzymes were immobilised on electrodeposited polymers via covalent bonding of molecular recognizing mot ifs. The polymer films were characterised at each step using XPS, FT-IR and electrochemical methods in order to investigate non-specific and specific p rotein binding at both sensor surface and those of other system components. The immobilised enzyme activity was estimated using scanning electrochemica l microscopy. Results are presented that demonstrate the success of this me thod in allowing us to optimise both electrodeposited polymer surface coatin gs designed to inhibit non-specific adsorption and strategies designed to sp ecifically immobilise various enzymes (e.g. via avidin-biotin constructs).

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5.

集積型血液ガスセンサ２

筑波大物質工、NTTマイクロシステムインテグレーション研*、国立循環器病センター**

○王　シャウ文、鈴木博章、林　勝義*、砂川賢二**

INTEGRATED BLOOD GAS SENSORS 2

Xiaowen WANG, Hiroaki SUZUKI, Katsuyoshi HAYASHI*, Kenji SUNAGAWA**

Institute of Materials Science, University of Tsukuba, 1-1-1 Tennodai,
Tsukuba, Ibaraki 305-8573
*NTT Microsystem Integration Laboratories, 3-1 Morinosato Wakamiya,
Atsugi, Kanagawa, 243-0198
**National Cardiovascular Center, 5-7-1 Fujishirodai, Suita, Osaka
565-8565

A micro Severinghaus-type carbon dioxide electrode which can be incorporated in a syringe needle or a catheter was fabricated for in vivo monitoring of carbon dioxide. The chip was 0.3 mm wide and 60 mm long. The patterns of an iridium oxide indicator electrode and a Ag/AgCl reference electrode were formed and stacked on a polyimide substrate. The electrolyte layer was formed by casting a 20wt% polyvinylpyrrolidone solution containing 3 M KCl dissolved in 20 mM NaHCO3 solution. A silicone rubber gas-permeable membrane was formed to cover the entire structure except for the pads. A peculiar feature of the electrode is its Ag/AgCl reference electrode whose AgCl layer is grown at a small constant current during the use of the electrode. The reference electrode could maintain an expected potential for longer than 24h. Clear response curves were obtained with a 90% response time of 2 min. Calibration curves were linear in the clinically important range of pCO2 with a slope of 98 mV/decade at 37℃.

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6.

マイクロフロー型抗体チップによるCo-PCBのモニタリング

北陸先端科技大　材料科学 （１）,（株）　エンバイオテック・ラボラトリーズ（２）

○遠藤達郎（１）,奥山　亮（２）,松原泰孝（１）,小林正昭（１）,森田資隆（１）,水上春樹（２）,民谷栄一（１）

MONITORING OF Co-PCB BY THE MICRO FLOW ANTIBODY CHIP

Tatsuro ENDO(1), Akira OKUYAMA(2), Yasutaka MATSUBARA(1), Masaaki KOBAYASHI(1), Yasutaka MORITA(1), Haruki MIZUKAMI(2), Eiichi TAMIYA(1)

(1)School of Materials Science, Japan Advanced Institute of Science and Technology, Japan,
1-1, Asahidai, Tatsunokuchi, Ishikawa 923-1292 Japan
(2)EnBioTec Laboratories Co., Ltd.,
Time24 Bldg., 4th Floor 2-45 Aomi, Koto-ku Tokyo 135-8073, Japan

We report a fabrication of a simple and convenient micro flow antibody chip for the measurement of Co-PCB using Co-PCB antibody. This chip is fabricated by rapid prototyping technique. And the polystyrene beads immobilized with Co-PCB antibodies were placed in the flow channel. The concentration of a Co-PCB in the sample mixture was achieved based on a competitive assay between HRP conjugated Co-PCB hapten, non HRP conjugated Co-PCB hapten using AmplexTM red and the detection signal was captured by a CCD camera built-in fluorescence microscope.

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t1.

「特別講演」分子認識を重さで測る-水晶発振子マイクロバランス法-

東工大・生命理工

岡畑恵雄

GRAVIMETRIC MOLECULAR RECOGNITION STUDIES BY QUARTS CRYSTAL MICROBALANCE

Yoshio OKAHATA

Department of Biomolecular Engineering, Tokyo Institute of Technology
Nagatsuda, Midori-ku, Yokohama 226-8501, Japan

Biomolecular interations such as DNA-DNA hybridization, DNA-protein interation have been studied by using a quartz-crystal microbalance (QCM). Kinetic parameters such as binding or dissociation rate constants and real binding amout have been obtained by this method.

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7.

ELECTROCHEMICAL OXIDATION OF UNDERIVATIZED-NUCLEIC ACIDS AT HIGHLY BORON-DOPED DIAMOND ELECTRODES

○Tribidasari A. IVANDINI, Bulusu V. SARADA, Tata N. RAO and Akira FUJISHIMA

Department of Applied Chemistry, Undergraduate School of Engineering, The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

Boron doped-diamond (BDD) electrode was examined for the electrochemical oxidation of underivatized-nucleic acids in terms of single stranded (ss-) or double stranded (ds-) DNA. As-deposited diamond film with predominantly H-terminated surface has shown the superiority over O-terminated diamond in terms of sensitivity. Linear calibration result shows linearity of the
current with concentration was observed in the range 1-8 ppm at as-deposited BDD. The detection limits (S/N =3) of 5.2 and 10 ng/mL for adenine or guanine residue in ss-DNA, respectively, and 3.7 and 10 ng/mL for adenine and guanine residue in ds-DNA, respectively. This work shows promising use of BDD for direct detection of nucleic acids.

 

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8.

白金－ダイヤモンドマイクロ電極での過酸化水素の電気化学的検出

東大院工

○Olivia Herlambang, Bulusu V. Sarada, 本多健介,Tata N. Rao, 藤嶋 昭

INTERFERENCE-FREE H2O2 MONITORING AT　PLATINIZED-DIAMOND MICROFIBER ELECTRODES

Olivia HERLAMBANG, Bulusu SARADA, Kensuke HONDA, Tata RAO, Akira FUJISHIMA

Department of Applied Chemistry, Undergraduate School of Engineering, The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

Pt-modified highly boron-doped diamond microfiber (BDDMF) electrodes have been used for the detection of H2O2. Deposition conditions for Pt were optimized. BSA/OPPy/Pt-modified BDDMF electrodes were used for continuous interference-free H2O2 monitoring. Amperometric measurements of H2O2 performed at 0.6 V gave a linear calibration curves in the range of 100 nM
to 10 mM, with an RSD of 0.84% for 5 injections of 0.1 mM H2O2. LOD for H2O2 detection was 30 nM (S/N = 3). The electrodes have shown good stability during 1-month period of measurements with perfect suppression of AA as interfering compounds.

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9.

走査型電気化学顕微鏡（SECM）によるヒト白血病細胞（HL-60）の制癌剤感受性評価

東北大院工・山形県企業振興公社

○鳥澤勇介，珠玖　仁，葛西重信，西澤松彦・末永智一

ANTICANCER DRUG SENSITIVITY TEST OF HL-60 USING SCANNING ELECTROCHEMICAL MICROSCOPY

Yu-suke TORISAWA, Hitoshi SHIKU, Shigenobu KASAI, Matsuhiko NISHIZAWA, Tomokazu MATSUE

Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579
Yamagata Public Corporation for Development of Industry, 2-2-1 Matsuei, Yamagata 990-2473, Japan

We report here a novel anticancer drug sensitivity assay applicable for tumors removed from in vivo mammalians. In vivo- and in vitro- cultured human promyelecytic leukemia cell line (Hl-60) cells were embedded in a small volume of collagen-gel matrix and entrapped in a silicon microstructure. For the in vivo- cultured HL-60, the cells were inoculated subcutaneously in SCID mice and removed 31 days after the inoculation. Respiration activity of the cell-collagen mixture on the silicon chip was monitored using scanning electrochemical microscopy (SECM). The proliferation rate of HL-60 in collagen-gel was smaller than that cultured in flask, and conformed to that in mice. The sensitivity for cisplatin and etoposide of HL-60 removed from SCID mice was in good agreement with that cultured in flask. Our results suggest that the SECM-based assay is appropriate for biopsy specimens with relatively short-time evaluation.

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10.

導電性高分子/DNA複合膜によるDNAセンサの開発

山口大院理工

○木島大介，椎木 弘，長岡 勉

DEVELOPMENT OF DNA SENSOR USING CONDUCTING POLYMER/DNA FILM

Daisuke KIJIMA, Hiroshi SHIIGI, and Tsutomu NAGAOKA

Division of Applied Chemistry, Graduate School of Science and Engineering, Yamaguchi University
Tokiwadai, Ube 755-8611，Japan

We have studied on a novel detection method of DNA using polypyrrole (PPy) / DNA film. PPy doped with a single-strand DNA (12 mer) as a capture was synthesized by potentiostatic electrolysis onto a quartz crystal microbalance (QCM) electrode. Although the hybridization with the complementary DNA strand led to the decrease in the resonance requency of the film, the frequency change was unresponsive and unstable. To improve the sensitivity of the measurement, the complementary 3’-thiol substituted single-strand DNA (12 mer) was tagged with Au particle (50 nm). Moreover, we have also confirmed by imaging the Au colloid modified with complementary DNA strands bound on the film through the hybridization.

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11.

マルチプル層流を用いた細胞パターンへの局所薬剤投与

東北大院工

○梶　弘和，小谷松大祐，西澤松彦，末永智一

LOCALIZED CHEMICAL STIMULATION TO MICROPATTERNED CELLS USING MULTIPLE LAMINAR FLOWS

Hirokazu KAJI, Daisuke OYAMATSU, Matsuhiko NISHIZAWA, Tomokazu MATSUE

Department of Biomolecular Engineering, Graduate School of Engineering,Tohoku University,
Sendai 980-8579, Japan

Micropatterned cardiac tissue model was prepared by microcontact printing (μCP), and the localized chemical stimulation was applied to the cellular pattern by using multiple laminar flows. An inhibitor of gap junctional communication, 1-octanol, inactivated only the targeted part of cardiomyocytes, while the others remained the activity to excite spontaneously and synchronously. Our method has an important advantage that experimental system is simple and understandable since both of cells and flows have well-defined pattern. This research was carried out with the objective of developing a bioassay system based on a cellular network.

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12.

アルカリホスファターゼカラム・電気化学的アポ酵素再生法による微量亜鉛(Ⅱ)イ オ ンの計測

神奈川工科大学・応用化学科

佐藤生男，○関根正史，飯田泰広

Microdetermination of Zn(II) Ions by Using an Alkaline Phosphatase Column Based on an Electrochemical Apoenzyme Regeneration Method

Ikuo SATOH, Masashi SEKINE, and Yasuhiro IIDA

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

A novel regeneration method of apoenzyme, i.e. metal-free enzyme, for determination of heavy metal ions was investigated. Alkaline phosphatase (ALP) from Escherichia coli was covalently immobilized onto porous glass beads (CPG) and then, packed into a small polymer column. The column was mounted in a water-jacketed holder (303 K). Two pieces of metal tubings as a joint were connected with the inlet and the outlet of the column, respectively. The main part of the flow-injection system was assembled with the enzyme-packed column and a flow-through photometric device. Tris-HCl buffer (0.1 M, pH 8.0, 1.0 M NaCl, 0.1 uM citrate) as the carrier solution was successively pumped into the system. The catalytic activity of the column was assessed by injecting 0.1 mL of 2.0 mM p-nitrophenyl phosphate (pH 8.0) as a substrate. Removal of zinc(II) ions from the enzymes immobilized onto the glass beads was made by applying constant current (2.0 mA, 5 min) between the joints under acidic onditions (50 mM citrate buffer (pH 4.5)). Subsequent injection of the substrate solution showed significant decrease in absorbance at 405 nm in the effluents from the column. Subsequent injection of 1.0 mM standard zinc(II) ions into the system exhibited sufficient recovery of the column activity. Reversible variations in the enzyme activity between the regeneration and the reactivation processes could be observed. Thus, determination of zinc(II) ions in nanomolar levels was demonstrated.

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13.

匂い及び味複合センサシステムを用いた日本酒の甘辛の識別

金沢工業大学　高度材料科学研究開発センター

南戸秀仁，関川祐司，宮竹智樹，北出康人，中慎太郎，東　崇利，竹井義法

DISCRIMINATION OF TYPES OF JAPANESE SAKE USING TASTE AND ODOR SENSORS

Hidehito NANTO, Yuuji SEKIKAWA, Tomoki MIYATAKE, Yasuto KITADE, Shintarou NAKA, Takatoshi HIGASHI, Yoshinori TAKEI

Advanced Materials Science R&D Center, Kanazawa Institute of Technology

Quality of four types of Japanese sake is estimated using a surface plasmon resonance (SPR) taste sensor and a quartz crystal microbalance (QCM) sensor. The SPR taste sensor responds to quality change of Japanese sake such as sweetness and dry. On the other hand, QCM odor sensor responds to the alcohol content of Japanese sake. It is found that the discrimination of four types of Japanese sake can be possible by plotting the output of QCM odor sensor as a function of output of SPR taste sensor.

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14.

環境要因に対する観葉植物の生体信号変化

金沢星稜大学*，富山大学工学部**，金沢工業大学***，東京電機大学****，埼玉大学工学部*****

○新保 達也*，大薮 多可志*，広林 茂樹**，南戸 秀仁***，原 和裕****，勝部 昭明*****

Bioelectric potential characteristics of potted Schefflera for room temperature change and sprinkling

Tatsuya SHINBO*, Takashi OYABU*, Shigeki HIROBAYASHI**, Hidehito NANTO***Kazuhiro HARA****, Teruaki KATSUBE*****

*Kanazawa Seiryo University, Kanazawa 920-8620, Japan
**Faculty of Engineering, Toyama University, Toyama 930-8555, Japan
***Kanazawa Institute of Technology, Nonoichi 921-8501, Japan
****Tokyo Denki University, Chiyoda-ku 101-8457, Japan
*****Faculty of Engineering, Saitama University, Saitama 338-8570, Japan

Plants are affected by various kinds of environmental factors and artificial deed, and its bioelectric potential is changed. In this study, Schefflera arboricola was adopted as a subjective plant and the potential change among the leaves was input into a mobile computer through a control circuit including an A-D converter. The characteristics were analyzed using a statistical method. In the method, the potential characteristics were squared and its square root characteristics vpsq were introduced. The relationship of the room temperature tr and vpsq was analyzed and FFT(Fast Fourier Transform) analysis was also used. As for the results, It was obvious that vpsq became lower as the environmental temperature tr was higher. When a potted plant close to the subjective plant was sprinkled, the potential was changed largely and also the subject was sprinkled. The principal frequency component at the sprinkling was 1[Hz] from the FFT analysis.

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15.

表面プラズモン共鳴センサによる電析された銀薄層の屈折率測定

国立リハビリ研、東洋大工*

柘植将示*、武居修*、宇佐美論*、加藤誠志、○外山滋

EVALUATION OF ELECTROPLATED SILVER USING AN SPR SENSOR

Masashi TSUGE*, Osamu TAKEI*, Ron USAMI*, Seishi KATO, Shigeru TOYAMA

Research Institute, National Rehabilitation Center for the Disabled
4-1 Namiki, Tokorozawa, Saitama 359-8855
*Department of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Nakanodai, Kujirai, Kawagoe, Saitama 350-8585

Silver thin layer was electrochemically deposited on a Au-coated glass plate, and its growth was evaluated with an SPR sensor. It was found that the silver deposited plates exhibited broad absorbance in the SPR curves. The absorptions of the two silver deposited plates with different electroplating solution were appeared at different angles. These observations are probably originated from the surface roughness of the electroplated silvers.

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16.

ポータブルＳＰＲ免疫センサを用いた低分子化合物の高感度検出

九大先端センター

○原田良平、カウベリ・ゴビ、キム・スクジン、三浦則雄

HIGHLY SENSITIVE DETECTION OF SMALL-MOLECULE COMPOUNDS BY USING A PORTABLE SPR IMMUNOSENSOR

〇Ryohei HARADA, Kauveri V. Gobi, Sook Jin KIM, Norio Miura

Advanced Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580, Japan


A sensor-chip-module integrated portable miniature SPR sensor is developed to determine the concentration of 2-hydroxybiphenyl (HBP) by monitoring the immunoreaction between the antibody against HBP (anti-HBP Ab) and the HBP-protein conjugate immobilized on sensor chip that could be inhibited by the presence of HBP in the analyte solution. The portable immunosensor is found to detect HBP sensitively in the concentration range of 0.1 ? 1000 ppb with a response time of ca. 15 min. It detects HBP selectively and shows no cross-sensitivity to the presence of benzo(a)pyrene and anthracene. The SPR sensor chip is found to be reusable for several times with a negligible decrease in the sensor performance.

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17.

携帯型SPRセンサシステムの開発とその応用

富山大工

○鈴木正康，八木澤壮平，松島功治

DEVELOPMENT OF A PORTABLE SPR SENSOR SYSTEM AND ITS APPLICATION

Masayasu SUZUKI, Sohei YAGISAWA, Koji MATSUSHIMA

Department of Electric and Electronic Engineering, Faculty of Engineering,
Toyama University, Toyama-shi, Toyama 930-8555

A portable surface plasmon resonance (SPR) sensor system consisting of a miniature SPR sensor chip SpreetaTM, a hydrostatic pressure driven flow system using a Marionette bottle and a sample injector, was developed. The sensor system worked for 12 hours with a 9volts dry cell. The size of the sensor system was 7cm width x 7cm depth x 23cm height. The developed portable SPR sensor system was applied for a food analysis and immunosensors. Anti-human IgG antibody was immobilized onto the SPR sensor chip and a human IgG sensor was developed. The sensor could measure 1 to 30mg/l human IgG. Furthermore, 2,4-dinitrophenol (DNP) was measured by using this sensor system. DNP was measured based on the competition between sample DNP and DNP-albumin immobilized on the sensor chip. DNP in the range of 0.001 to 1mg/l could be measured by using this sensor system.

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18.

マイクロステップ制御法を使ったSPR測定装置

東大先端研、アイシンコスモス研究所*、東大医学系研究科**

斎藤逸郎、遠山貴博*、○中川英元、奥村幸司*、鎮西恒雄、井街宏**

DEVELOPMENT OF A SURFACE PLASMON RESONANCE MEASUREMENT SYSTEM WITH A MICROSTEP-CONTROLLED PULSE MOTOR.

Itsuro SAITO, Takahiro TOHYAMA*, Hidemoto NAKAGAWA, Kouji OKUMURA*, Tsuneo CHINZEI, Kou IMACHI**

Research Center for Advanced Science and Technology, the University of Tokyo
Komaba 4-6-1, Meguroku, Tokyo 153-8904, Japan
* Aishin Cosmos R & D Co., Ltd,
Hachikencho 5-50, Kariya,Aichi 448-8650, Japan
**Graduate School of Medicine, the University of Tokyo,
Hongo 7-3-1, Bunkyo, Tokyo, 113-0033, Japan

A small-size surface plasmon resonance measurement system was constructed. It is aimed to shrink the existing bulky equipments without loss of versatility and sensitivity as well as easy operation. To achieve this goal, we adopted a stepping motor with micro-step control circuit for angular scanning. The measurement is performed by a flow system with a built-in peristaltic pump and sample injection valve. A small sub-note type personal computer is utilized to gather the data and system control. Preliminary data exhibited very promising results.

 

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19.

ヘテロコア型光ファイバを用いるSPRセンサ

創価大学工学部

○関　篤志、伊賀光博、中澤　毅、渡辺一弘

SPR SENSOR BASED ON A HETERO-CORE TYPE FIBER OPTIC

Atsushi SEKI, Mitsuhiro IGA*, Tsuyoshi NAKAZAWA*, Kazuhiro WATANABE*
Department of Bioenginnering, *Department of Information systems, Faculty of Engineering, Soka University
1-236 Tangi, Hachioji, Tokyo 192-8577 Japan

SPR sensor based on a hetero-core fiber optic was fabricated by depositing gold and/or silver film on surface of a hetero-core portion of the fiber. Single mode fiber of 2 - 3 cm was inserted in a multi mode fiber. Then metal film was formed on the surface of the hetero-core portion by using sputtering method. The fiber was rotated under RF-sputtering. SEM images show that the metal film on the fiber surface was uniform. The propagation loss spectra of the metal-coated fiber immersed in glycerine/water solution was measured. According to increasing of refractive index of the solution, a shift in the resonance wavelength was observed.

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20.

光導波路の表面構造変化による化学物質のセンシング

横浜国立大学大学院環境情報研究院

○許一太、雨宮隆、伊藤公紀

Chemical Sensing Based on Surface Structure Changes of Optical Waveguides

Y. Xu, T. Amemiya, and K. Itoh

Graduate School of Environment and Information Sciences, Yokohama National University

Chemical sensing techniques based on optical waveguides are discussed. Evanescent wave absorption; most of the guided lightwave energy is located in the guided layer, and hence, its sensitivity remains relatively small although the use of a thin layer of high index material (e.g., TiO2) largely improves this disadvantage. Phase change; appropriate thickness of TiO2 gives a condition where a TE mode and a TM mode are guided in different guiding layers, thus, can provide very high sensitivity for refractive index changes. Surface structure change; chemical reactions leading to thickness changes in guiding layers and/or glad layer can be utilized especially when combined with the phase change method.

 

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21.

表面光電圧法(LAPS)による血漿浸透圧のための集積バイオセンサ構築とその非線形解析

埼玉大工

○青木一仁，森本賢則，石丸雄大，飯田武揚

Construction and nonlinear analysis of the integrated biosensor for blood plasma osmometry by means of light addressable potentiometric sensor (LAPS)

K.Aoki, M.Morimoto, Y.Ishimaru, T.Iida

Department of Functional Materials Science, Faculty of Engineering, Saitama University,
255 Shimo-okubo, Sakura-ku, Saitama-shi, Saitama-ken 338-8570, Japan

Simplification of blood plasma osmometer is desired since blood plasma osmometry should be applied to pathological diagnosis for some disease such as dehydration. Then we studied the integration of biosensors for glucose, urea and alkali cations by the use of Light Addressable Potentiometric Sensor (LAPS) in order to predict the osmotic pressure on the blood plasma by simultaneous determination of those analytes. Simultaneous determination between glucose and urea caused decreases of sensor responses. Besides, the glucose sensor using glucokinase was influenced by Na+ and K+ ions concentration. Moreover, the behavior might be used for an alkali cation sensor. These problems should be partly solved by nonlinear regression analysis. Therefore, the nonlinear regression analysis was employed.

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22.

テオフィリンインプリントポリマーのゲート効果の機構

早稲田大院理工，芝浦工業大工

○服部浩二，小堀　深，酒井清孝，伊東　徹，平野克比古，吉見靖男

MECHANISM OF THE GATE EFFECT OF THEOPHYLLINE-IMPRINTED POLYMER GRAFTED ON INDIUM-TIN OXIDE ELECTRODE

Koji HATTORI, Toru ITO, Yasuo YOSHIMI, Katsuhiko HIRANO, Fukashi KOHORI, Kiyotaka SAKAI

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

The morphology and the diffusive permeability of the nano-ordered thin layer of molecularly imprinted polymer (MIP) changes by its template, termed "gate effect". We have reported that theophylline is a key component, which causes a change in diffusive permeability of the imprinting of theophylline on copolymer of ethyleneglycol dimethacrylate and methacylic acid grafted on indium-tin oxide electrode (Theo-MIP). The gate effect is applicable to chemical sensors. The purpose of the present work is to design of a model capable of describing the gate effect.
The Faradic current of ferrocyanide with the Theo-MIP was measured by cyclic voltammetry. The degree of the gate effect was defined a percent change in the current by imprinting theophylline.
The current of ferrocyanide decreased with increasing pH. Although, currents of ferrocyanide with the Theo-MIP increased in either presence or absence of theophylline, the degree of the gate effect decreased with increasing potassium nitrate concentration. These results indicate that the nano-oredred thin layer of the grafted copolymer is swelled by repulsion among carboxyl groups in a high pH or low ionic strength solution. The thin layer is porous by AFM, and hence the porosity of the layer increased with shrinking of the polymer, and decreases with swelling of the polymer.
The gate effect is due to a variation in the porosity, which is caused by the polymer-shrinking/swelling occurring in rebinding with the template.

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23.


分子鋳型を持つ過酸化ポリピロール膜による異性体認識

山口大院理工　木島大介，椎木　弘，長岡　勉

RECOGNITION OF ISOMER WITH MOLECULARLY IMPRINTED OVEROXIDIZED POLYPYRROLE FILM

Daisuke KIJIMA, Hiroshi SHIIGI, and Tsutomu NAGAOKA
Molecular Recognition Engineering Course, Graduate School of Science and Engineering, Yamaguchi University,
Ube 755-8611, Japan

The preparation process of a molecularly imprinted overoxidized-polypyrrole film has been studied with the quartz crystal microbalance. The film has been derived from 1- naphthalenesulfonate (1-NS)-doped polypyrrole through overoxidation. The extraction of 1-NS (dedoping) has created a shape-complementary cavity at the surface. The resulting overoxidized-polypyrrole film imprinted with 1-NS exhibited an excellent selectivity to the structural isomer, 1-NS. Aqueous 0.010 M 1-NS showed a frequency decrease of 110 Hz, while 2-NS shows only a negligible change. Thus, the shape-complementary cavity can recognize the difference in the spatial configuration of the sulfonate substituent between 1- and 2- positions.

 

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24.

新規過酸化水素選択透過膜を有するグルコースセンサチップ

東陶機器（株）

　○ルイ　昌生

GLUCOSE SENSOR WITH A NEW PERMSELECTIVE MEMBRANE CONSISTING OF CELLULOSE DERIVATVE HAVING ALDEHYDE AND ACETYL GROUPS

Changsheng RUI

Research Group, TOTO LTD.
2-1-1 Nakashima, Kokurakita-ku, Kitakyushu 802-8601, Japan

Aimed at the development of biosensor with long-term stability for urine assay in a toilet, cellulose derivatives having aldehyde and acetyl groups (ACA) have been synthesized, and their application has been tested as the permselective membrane in biosensors based on the detection of hydrogen peroxide. As a result, the ACA membranes show strong adhesion to the base of the sensor chip and high permselectivity for hydrogen peroxide. The membranes with acetylation degree of 2.1-2.3 give the best results. A glucose sensor chip, with ACA and immobilized glucose oxidase membranes formed onto Pt electrode printed on ceramic plate, shows high selectivity to glucose and excellent stability. The ratio of the current from uric acid or ascorbic acid to glucose at the same concentration is less than 6% after 3000 times of assay.

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25.

カテコールアミンセンシングデバイスの高選択性化

NTT MI研、NTT-AT、国立循環器病センター

○林　勝義、岩崎　弦、栗田僚二、丹羽　修、砂川賢二

IMPROVEMENT OF SELECTIVITY FOR CATECHOLAMINE SENSING DEVICE

Katsuyoshi HAYASHI, Yuzuru IWASAKI, Ryoji KURITA, Osamu NIWA, and Kenji SUNAGAWA

NTT Microsystem Integration Labs.,
3-1 Morinosato Wakamiya, Atsugi, Kanagawa 243-0198、
NTT Advanced Technology Corporation,
3-1 Morinosato Wakamiya, Atsugi, Kanagawa 243-0124、
National Cardiovascular Center,
5-7-1 Fujishirodai, Suita, Osaka 565-8565

We developed an electrochemical microfluidic sensing device combined with an interdigitated array electrode (IDA) and enzyme modified pre-reactor for highly sensitive and selective detection of catecholamines in blood. We studied two types of catecholamine sensing devices. One device is integrated an IDA electrode with a pre-reactor modified with ascorbate
oxidase on a same chip. The other one consists two devices which are IDA electrode chip and an pre-reactor modified with uricase and catalase. This pre-reactor has a large number of micropillars to increase the conversion efficiency of the acid. We improved selectivity for the catecholamine sensing device against ascorbic acid and uric acid.

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26.

ADP応答性bienzymeセンサを用いたクレアチンキナーゼ活性測定

産総研

○水谷文雄，矢吹聡一，澤口隆博，飯島誠一郎

DETERMINATION OF CREATINE KINASE WIT AN ADP-SENSING BIENZYME ELECTRODE

Fumio MIZUTANI, Soichi YABUKI, Takahiro SAWAGUCHI, Seiichiro IIJIMA

National Institute of Advanced Industrial Science and Technology
Central 6, Tsukuba, Ibaraki 305-8566, Japan

An amperometric ADP-sensing bienzyme electrode was prepared by immobilizing pyruvate kinase and pyruvate Oxidase on an electrode coated with an oxygen-permeable poly(dimethylsiloxane) layer. The concentration of ADP (2 mm - 0.4 mM) could be measured from the decrease in the cathodic current at -0.4 V vs. Ag/AgCl. The bienzyme electrode was applied to the determination of creatine kinase; the enzyme activity ( 4 - 1000 U L-1) was determined from the rate of current decrease, which was caused by the production of ADP through the creatine kinase-catalyzed reaction.

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27.

マレイミド基ペンダントポリスチレンを酵素固定化担体とするポテンショメトリックバイオセンサー

（埼玉工大工、筑波物質情報研＊、三菱鉛筆＊＊）

○内山俊一、萩原時男、長谷部靖、金子浩子＊、須田吉久＊＊、山田邦生＊＊

POTENTIOMETRIC BIOSENSORS USING MALEIMIDE PENDANT POLYSTYLENE AS AN ENZYME IMMOBILIZATION MATERIAL

Shunichi Uchiyama, Tokio Hagiwara, Yasushi Hasebe, Hiroko Kaneko*, Yoshihisa Suda**, Kunio Yamada**

Department of Applied Chemistry, Faculty of Engineering,Saitama Institute of Technology,
1690, Fusaiji, Okabe Saitama 369-0293
＊TMIL Ltd., 3-23-4, Ninomiya, Tsukuba 305-0051
＊＊Mitsubishi Pencil Co. Ltd., Fujioka, Gumma 375

We have utilized maleimide pendant polystylene (poly-(4-vinylphenyl)maleimide, PMS) as an enzyme immobilization carrier,
and the enzyme immobilized PMS coated porous carbon materials were combined with ammonia and carbon dioxide electrodes. As enzymes, urease and adenosine deiminase were used and the response characteristics of urea and adenosine sensors have been investigated. The lifetime of the sensors were more than two months and very stable enzyme electrodes could be fabricated. The enzyme immobilization tothispolymer is very simple because the thiol and amine of amino acid residues are reacted directly with maleimide by covalent bond in aqueous solution.

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28.

チロシナーゼ・ペルオキシダーゼ修飾電極を用いたフェノール誘導体の分離定量検出（２）

東大生研

○野津英男、立間徹

SIMULTANEOUS DETERMINATION OF PHENOL DERIVATIVES BY USING TYROSINASE/PEROXIDASE-MODIFIED ELECTRODES (2)

Hideo NOTSU, Tetsu TATSUMA

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

Most phenol derivatives are known as harmful and/or useful compounds. However, when a sample solution contains some different phenol derivatives, a monoenzyme electrode cannot determine them separately. As a solution for this problem, multienzyme systems may be envisaged. In the present work, we used a tyrosinase (TYR) electrode and TYR-peroxidase (POD) bienzyme (MIX) electrodes, because TYR and POD can oxidize catechol derivatives, while their enzymatic selectivities are different. Moreover, MIX electrodes with different component of enzymes exhibited different sensitivities to each substrate. By using a TYR electrode and two different MIX electrodes with different POD amounts, simultaneous determination of catechol, p-cresol, and m-cresol (or phenol) was possible.

 

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29.


酸性ウレアーゼカラム・FIAシステムによる微量尿素の蛍光計測

神奈川工科大学・応用化学科

○飯田泰広，青砥舞子，佐藤生男

FLUOROMETRIC MEASUREMENT OF TRACE UREA BY USING AN FIA SYSTEM WITH AN ACID UREASE COLUMN

Yasuhiro IIDA, Maiko AOTO, and Ikuo SATOH

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

A fluorometric flow-injection analysis (FIA) system with an acid urease column as a recognition element was developed and applied to determination of trace urea. An acid urease was covalently immobilized onto porous glass beads with controlled pore size and then, packed into a small polymer column. The flow-type of the biosensing system was assembled with a sample injection
valve, the immobilized enzyme column, and a flow-through quartz cell attached to a fluorescent spectrophotometer. Fluorometer intensity attributable to fluorescent isoindole derivates generated by coupling with ammonia molecules released in the enzymatic
hydrolysis of urea and orthophthalaldehyde reagents were measured under the conditions of λex = 415 nm and λem = 485 nm. A wide, linear relationship was obtained between the concentration of urea (1.0 - 100 uM) and the change in fluorescent intensity. The monitoring wasn’t affected by ethanol and various amino acids contained in rice wine. This FIA system presented
highly sensitive, highly selective and convenient analysis of urea in alcoholic beverages.

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30.

PFC電極に被覆したマレイミド基ペンダントポリスチレン膜を酵素固定層とするアンペロメトリックバイオセンサ

埼玉工大工・筑波物質情報研*・三菱鉛筆**

○長谷部　靖、萩原 時男、内山 俊一、金子 浩子*、須田 吉久**、山田 邦生**

AMPEROMETRIC BIOSENSORS USING MALEIMIDE-PENDANT POLYSTYRENE AS AN ENZYME IMMOBILIZATION MATRIX

Yasushi HASEBE, Tokio HAGIWARA, Shunichi UCHIYAMA, Hiroko KANEKO*, Yoshihisa SUDA** and Kunio YAMADA**

Department Applied Chemistry, Faculty of Engineering, Saitama Institute of Technology
1690, Fusaiji, Okabe, Saitama 369-0293
*TMIL Ltd., 3-23-4, Nimomiya, Tsukuba 305-0051
**Gunma Research and development center, Mitsubishi Pencil Co. Ltd.,
1091 Tatsuishi, Fujioka, Gunma, 375-8501

Plastic Formed Carbon (PFC) electrode was used as transducer for amperometric biosensor, on which maleimide-pendant polystylene [poly-vinylphenyl)maleimide, PMS] was coated as enzyme immobilization layer. γ-Aminopropyl-triethoxy silane (APTES)-activated PFC electrode is suitable for MPS-coating for rapid electron transfer of catechol and qiunone.
Tyrosinase was selected as a model enzyme for detection of catechol compounds. Based on the rapid electron transfer with o-quinone produced by tyrosinase-catalyzed reaction, highly sensitive catechol sensor could be developed. Calibration curve of catechol is linear from 1 × 10-8M to 2 × 10-5M catechol with the detection limit of 5×10-9 M.

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31.

吸着ストリッピングボルタンメトリーによる高感度アセチルコリンエステラーゼ活性測定とそのペプチドホルモン検出への応用（1）

筑波大化1・産総研2

○松浦宏昭1、佐藤　縁2、澤口隆博2、水谷文雄1,2

HIGH SENSITIVE DETERMINATION OF ACETYLCHOLINESTERASE ACTIVITY BY USING ADSORPTIVE STRIPPING VOLTAMMETRY AND ITS APPLICATION FOR MEASUREMENT OF PEPTIDE HORMONE (1)

Hiroaki MATSUURA 1, Yukari SATO 2, Takahiro SAWAGUCHI 2, and Fumio MIZUTANI 1,2

1 Department of Chemistry, University of Tsukuba,
1-1-1 Tsukuba, Ibaraki 305-8571
2 National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba Central 6, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8566

A novel enzyme-linked immunosorbent assay (ELISA) system was developed for the trace analysis of a peptide hormone, B-type natriuretic peptide (BNP). For the high sensitive determination of labeled enzyme activity at ELISA, we have utilized an adsorptive stripping voltammetric method. Thiocholine, which was produced through the reaction catalyzed by the labeled enzyme,
acetylcholinesterase, was chemisorbed on a silver electrode, and then was electrochemically desorbed in an alkaline solution. The electrical charge passed through the desorption process was proportional to the number of adsorbed thiocholine molecules on the silver electrode, hence to the acetylcholinesterase activity. Using competitive immunoreaction of antigen and antibody-enzyme conjugate, we demonstrated that the BNP could be determined in the concentration range from 20 to 100 ppb.

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32.

WO3ゲート電極を接合したFET型 NO2センサ

(九大院総理工,*九大先端センター)　

○中田聖士、島ノ江憲剛、三浦則雄*、山添　曻

FET NO2 SENSOR ATTACHED WITH WO3 GATE

Seiji NAKATA, Kengo SHIMANOE*, Norio MIURA**, Noboru YAMAZOE*

Department of Molecular and Materials Sciences,
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University,
*Department of Materials Science, Faculty of Engineering Sciences, Kyushu University,
**Advanced Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580

A field effect transistor (FET) device fitted with a WO3 layer over the gate area exhibited almost ideal FET behavior at 150 and 180℃ in air containing various concentrations of NO2. Under the conditions of fixed source-drain voltage (3.0 V) and fixed drain current (450 μA), the gate-source voltage (VGS) was found to increase linearly with an increase in the logarithm of NO2 concentration over the range of several tens to 700 ppb NO2, proving its potentiality to work as an environmental NO2 sensor.
However the times of 90%-response and -recovery to switching-on and -off 50 ppb NO2 were as long as 10 and 25 min even at 180℃, respectively. Cross sensitivity tests revealed that the device was totally insensitive to CO2, but rather sensitive to NO. Water vapor was found to give a serious disturbance to the device: The VGS response to NO2 as well as its dependence on NO2 concentration changed with a change in relative humidity.

 

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33.

ガラス固体電解質によりNi参照電極を密閉した炭酸ガスセンサ

（愛媛大工）

○青野宏通、橋本泰英、定岡芳彦

CO2 GAS SENSOR USING Ni REFERENCE ELECTRODE COVERED BY GLASSY Na+ CONDUCTING SOLID ELECTROLYTE

Hiromichi AONO, Yasuhide HASHIMOTO, and Yoshihiko SADAOKA

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

EMF type CO2 gas sensor using a Ni reference electrode covered by a glassy Na2O-Al2O3-4SiO2 electrolyte was prepeared and those sensing properties were investigated in the range of 10-10000ppm at 310-510 oC. The sensor exhibited a good sensitivity and fast response at 360-510 oC. The electron number for the reaction was ca. n=2.1 which was agreed with theoretical 2.0.
The electrical potential at Ni reference electrode would be fixed by O2 concentration from an equiliblium of Ni, NiO, and oxygen diffusion from solid electrolyte.

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34.

Li2CO3-BaCO3系補助相による室温作動型CO3センサの安定化

九大院総理工、九大先端センター*

○小畑賢次、島ノ江憲剛、三浦則雄*、山添　曻

STABILIZATION OF ROOM TEMPERATURE TYPE CO2 SENSOR BY USING Li2CO3-BaCO3 AUXILIARY PHASE

Kenji OBATA, Kengo SHIMANOE*, Norio MIURA* * and Noboru YAMAZOE*

Department of Molecular and Material Sciences, Interdisciplinary Graduate
School of Engineering Sciences, Kyushu University
*Department of Materials Science, Faculty of Engineering Sciences, Kyushu University,
* * Advanced Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580


The NASICON (Na3Zr2Si2PO12)-based electrochemical device attached with a metal oxide (ITO: indium tin oxide) sensing electrode and a metal carbonate auxiliary phase (NaHCO3 or Na2CO3) responded well to CO2 at room temperature (30 oC) under fixed humidity conditions. With a change in relative humidity, however, the Nernstian correlation between EMF and CO2 concentration shifted up or down seriously. It was tried to reduce this humidity dependence by incorporating novel auxiliary phases. Although incorporation of Li2CO3 was fairly effective, that of Li2CO3-BaCO3 binary carbonates was found to be very effective in reducing the humidity dependence. With Li2CO3-BaCO3 (1:2 in molar ratio), the Nernstian correlation was almost independent of a change in relative humidity (RH) between 30 and 70 %. Based on this finding, a planar type CO2 sensor was
also fabricated, which could work stably under the conditions of 30 %RH and above. A CO2 sensing mechanism, facilitated by the presence of physisorbed water, was proposed.

 

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35.

LaGaO3系酸化物を電解質とする電流検出型炭化水素センサ
（３）カソード電極の性能向上

大分大工

○石原達己、Atanu Dutta、西口宏泰、滝田祐作

AMPEROMETRIC HYDROCARBON SENSOR USING LaGaO3 BASED ELECTROLYTE (3)IMPROVEMENT OF ANODE CATALYST ACTIVITY

Tatsumi ISHIHARA, Atanu DUTTA, Hiroyasu NISHIGUCHI, and Yusaku TAKITA

Department of Applied Chemistry, Faculty of Engineering, Oita University
Dannoharu 700, Oita 870-1192

Amperometric hydrocarbon sensor using Ni doped LaGaO3 based oxide was investigated and it was found that the sensitivity of the sensor using Ni doped LaGaO3 for electrolyte was much improved by improving surface catalyst activity. In this study, effects of cathode on the sensitivity was first investigated and it was found that La0.5Sr0.5MnO3 gives much higher sensitivity that that of La0.6Sr0.4CoO3. On the other hand, sensitivity to hydrocarbon was much improved by improving the anode catalyst activity. In particular, it was found that the addition of small amount of Fe added for Pt anode is effective for increasing sensor sensitivity and the developed sensor is highly selective to C3H6 and hardly dependent on O2 concentration.

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36.

環境計測用高感度NO2センサのフィールド試験特性

九大先端センターa、九大院総理工b、グリーンブルー c、フィガロ技研d

三浦則雄a 、山添曻b 、○越智俊治c 、二田穂積c 、兼安一成d

FIELD-TEST PERFORMANCES OF HIGHLY SENSITIVE NO2 SENSOR FOR AMBIENT AIR MONITORING

Norio MIURA a，Noboru YAMAZOE b，Toshiharu OCHI c，Hozumi FUTATA c，
Kazunari KANEYASU d

a Advanced Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580, Japan
b Department of Materials Science, Faculty of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580, Japan
c Green Blue Corporation, Oota-ku, Tokyo 144-0033, Japan
d Figaro Engineering Inc., Mino, Osaka 562-8508, Japan

A compact NO2 sensing device fabricated based on NASICON (Na+ conductor) and NaNO2 was operated at 150℃ in amperometric mode for monitoring ambient air. In order to improve the long-term stability of the sensor, a voltage of －150 mV was applied in pulses with an electric relay between the sensing electrode and the reference electrode. The voltage-pulse period was set to 8 s, followed by the open-circuit condition for 40 s, in each operation cycle. The data-acquisition timing was fixed at 5 s just after starting each pulse. The field-test data collected at a traffic intersection in Tokyo has confirmed that the performance of the present NO2 sensor is comparable to that of a commercial chemiluminescence NOx analyzer with a limited error over the tested period of 6 months.

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37.

Pd-PdOを内部参照極とした密封型ジルコニア酸素センサーの応答特性

*秋田大工資、**東北フジクラ

○岡村崇之*、泰松斉*、金児紘征*、西田裕**、浅田昭良**

RESPONSE CHARACTERISTICS OF A ZIRCONIA OXYGEN SENSOR WITH A Pd-PdO INTERNAL REFERENCE


Takayuki OKAMURA*, Hitoshi TAIMATSU*, Hiroyuki KANEKO*,Hiroshi NISHIDA** and Akiyoshi ASADA**

*Department of Materials Science and Engineering,Faculty of Engineering and Resource Science,Akita University,
Akita 010-8502, JAPAN
**Sensor Department, Tohoku Fujikura Ltd.,
Akita 010-1415, JAPAN

We developed a disk-type zirconia oxygen sensor with an internal reference using the equilibrium oxygen pressure of Pd-PdO. The oxygen pressure dependence of the sensor emfs was investigated at about 450 ℃. Emfs of the sensor were a little lower than those calculated from the literature formation energy of PdO. However, the sensor worked well at low oxygen pressures until 2×10-6 atm. The response of the sensor emfs was investigated on an abrupt change of oxygen pressure using a zirconia oxygen pump. It took about 12 s to detect 90% of pulse-injected oxygen amount. For a step-functional injection of oxygen, the sensor detected oxygen pressures almost at 100% efficiency. It was ascertained that the sensor was very effective for low oxygen pressure use.

 

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38.

水素化物－溶融金属混合系を基準物質とした水素センサ

（株）TYK、名大名誉教授*

○林光彦、大島智子、片平幸司、岩原弘育*

HYDROGEN SENSOR USING METAL HYDRIDE-MOLTEN METAL MIXTURE AS A STANDARD MATERIAL

Mitsuhiko Hayashi, Tomoko Ohshima, Koji Katahira, Hiroyasu Iwahara*

TYK Corporation, Advanced Materials Research & Development Center,
3-1, Ohbata-cho, Tajimi, 507-8607
*Professor Emeritus of Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603

The metal hydride-molten metal mixture was investigated as a standard material of solid electrolyte-type hydrogen sensor. In the case of a titanium hydride-molten zinc mixture, EMF's of the sensor showed the value equal to 1 atm hydrogen as a standard material. These materials may be applied to a standard material of hydrogen sensors for molten metals under various conditions.

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t2.

ナノ粒子モルホロジーとその応用

触媒化成工業（株）

○小松通郎

MORPHOLOGY OF NANOPARTICLES AND THEIR APPLICATIONS

Michio Komatsu

Catalysts　&　Chemicals　IND. Co., LTD.
13-2, Kitaminato-machi, Wakamatsu-ku, Kitakyushu-shi, Japan

Novel and advanced functions are expected to be able to be achieved through controlling the surface modification and morphology of various types of nanoparticles in addition to their basic characteristics of size, shape, bulk and surface. In this presentation, some typical preparation methods for nanoparticles in the liquid phase and some examples of nanoparticles that have had their surface or morphology controlled are summarized. Moreover, some of the applications for nanoparticles controlled using these techniques are described.

 

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39.

ペロブスカイト型酸化物薄膜の湿式合成とリン酸水素イオンイオンセンサへの応用

九工大工

○樋口 直樹、高瀬 聡子、清水 陽一

SOL-GEL SYNTHESIS OF PEROVSKITE-TYPE OXIDE THIN-FILMS FOR HYDROGEN-PHOSPHATE ION SENSOR

Naoki HIGUCHI, Satoko TAKASE and Youichi SHIMIZU

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

La-based perovskite-type oxide thin-films could be fabricated from the polymer precursors using metal nitrates, acetylacetone, and polyvinyl alcohol (PVA) (or polyvinyl pyrolidone(PVP)) at lower temperatures. The obtained La-based perovskite-type oxide
thin-films have been applied to amperometric anion sensing device. Among the perovskite-type oxide thin-films, obtained La-Co-O based oxides (La1-xA'xCoO3; A'= Ca, Sr, Ba, Ce ; x = 0,0.2) showed good performance to hydrogen-phosphate ion at the concentration range between 1.0×10-6M and 1.0×10-2M. The 90% response time to 1.0×10-5M H2PO42- of the La-Co-O based amperometric sensor was ca. 3min at room temperature.

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40.

酸性ガス検知におけるハロゲン化物イオン－ハロゲン酸イオン種の影響

理研計器㈱、理研*

○今屋浩志、石地 徹、高橋勝緒*

SENSITIVITY OF ACIDIC GAS DETECTION BY ELECTROCHMEICAL SENSOR USING HALIDE-HALATE ELECTROLYTIC SOLUTION

Hiroshi IMAYA, Toru ISHIJI and Katsuo TAKAHASHI*

Riken Keiki Co., Ltd.
2-7-6 Azusawa Itabashi-ku, Tokyo 174-8744
*RIKEN (The Institute of Physical and Chemical Research),
2-1 Hirosawa, Wako, Saitama 351-0198

Amperometric sensors for the detection of acidic gases, such as hydrogen fluoride(HF) and hydrogen chloride(HCl), have been studied. The electrode reaction properties of halogen liberated from halide ion / halate ion solution by addition of hydrogen ion has been utilized for the detection of acidic gases. In this study, we have compared both types of sensors using Br-/BrO3- and
I-/IO3- electrolytic solutions for the acid gas detection. The sensitivity of Br-/BrO3- system for HF and HCl was very low, on the other hand, the I-/IO3- system showed a good sensitivity. The Br-/BrO3- system was hardly liberated Br2 by addition of acid from the results of spectroscopy. It is found that I-/IO3- system is superior to Br-/BrO3- system for the detection of acidic gases.

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41.

電気容量型湿度センサー架橋膜の使用による高温高湿ドリフトの抑制ー

愛媛大工、（株）山武*

○吉田　真、松口正信、黒岩孝朗*、小倉　勉*

CAPACITIVE-TYPE RELATIVE HUMIDITY SENSORS -CONTROL OF DRIFT PHENOMENON IN A HOT AND HUMID ATMOSPHERE BY USE OF CROSSLINKED FILM-

Makoto YOSHIDA, Masanobu MATSUGUCHI, Takaaki KUROIWA, Tsutomu OGURA

Department of Applied Chemistry, Ehime University
Matsuyama 790-8577, Japan
*Research and Development Headquarters, Yamatake Corporation
Fujisawa 251-8522, Japan

The effect of crosslinking structure of a sensing film on the drift phenomenon of capacitive-type humidity sensors in a hot and humid atmosphere was investigated. By use of the crosslinked poly(methyl methacrylate) with divinyl benzene, the irreversible increase of water sorption ability by aging the film in a 40。C and 90%RH atmosphere was depressed. This was because the swelling of the sensing film was prevented by introducing the crosslinking structure. The depression of the drift of the water sorption ability resulted in the depression of the sensor capacitance.

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42.

Pd／陽極酸化TiO2膜による水素ガスの検知

長崎大工

○兵頭健生，岩永鉄平，清水康博，江頭　誠

HYDROGEN SENSING PROPERTIES OF Pd/ANODICALLY OXIDIZED TiO2 FILM

Takeo HYODO, Teppei IWANAGA, Yasuhiro SHIMIZU and Makoto EGASHIRA

Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan

H2 sensing properties of diode-type M/TiO2 sensors (M=Pd, Pt or Au), equipped with the noble metal electrodes on the surface of the TiO2 film prepared by anodic oxidation of Ti plate, were investigated at 250℃ in air and N2 atmosphere. Among these sensors fabricated, Pd/TiO2 exhibited the highest H2 sensitivity, and the sensivitity in N2 was more than 103 times as high as that in air, indicating that the sensitivity was highly dependent on the O2 concentration. The sensitivity in N2 was nonlinearly dependent on the H2 concentration (5 ppm - 0.8%), probably due to phase transition of Pd induced by dissolution of hydrogen. The sensitivity to other inflammable gases (CH4 and C3H8) was neligibly small, except for C4H10.

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43.


ポリアニリン複合膜を用いたガスセンサの選択性とマトリックスポリマーの関係

愛媛大工

○岡本亜記、有田奈巳子、松口正信

EFFECT OF MATRIX POLYMERS ON THE SELECTIVITY OF GAS SENSORS BASED ON POLYANILINE BLEND FILMS

Aki OKAMOTO, Namiko ARITA, Masanobu MATSUGUCHI

Department of Applied Chemistry, Ehime University
Matsuyama 790-8577, Japan

The effect of matrix polymers on the selectivity of gas sensors based on polyaniline (PANI) blend films was investigated. Three kinds of matrix polymers, PMMA, PSt, and PVP were used for this purpose. It was shown that gas sorption properties of matrix polymers affected the sensitivity of the sensor using the PANI blend film. Since PVP highly sorbed ethanol vapor and water vapor, the sensitivity of the sensor using PANI-PVP blend film for these gases was the highest among the sensors tested. On the other hand, all blend films were less sensitive to the detection of NH3 than single PANI film without matrix polymer because of low NH3 sorption capacity of the matrix polymers.

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44.


酸化セリウムを使った抵抗型酸素センサの応答時間と結晶子サイズの関係

産総研

○伊豆典哉、申ウソク、松原一郎、村山宣光、神崎修三

RERATION OF RESPONSE TIME TO CRYSTALLITE SIZE IN RESISTIVE OXYGEN SENSORS USING CERIUM OXIDE

Noriya IZU, Woosuck SHIN, Ichiro MATSUBARA, Norimitsu MURAYAMA, Shuzo KANZAKI

National Institute of Advanced Industrial Science and Technology
Nagoya, Aichi 463-8569, Japan

The response time for the oxygen sensors using ceria were unaffected by particle size of ceria thick film but clearly depended on its firing temperature. The crystallite size increased as the firing temperature of thick film increased. It was concluded that the response time for the sensor using cerial strongly depended on the crystallite size.

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45.

医療安全用半導体エチレンオキサイドガスセンサの開発

九大院総理工

釘島裕洋、酒井　剛*、島ノ江憲剛*、山添　曻*

DEVELOPMENT OF SEMICONDUCTOR ETHYLENE OXIDE SENSOR

Masahiro KUGISHIMA, Go SAKAI, 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 Materials Sciences, Faculty of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580

An exploratory work was carried out to develop a semiconductor sensor for monitoring ethylene oxide (C2H4O) gas. Among the 5 kinds of single oxide tested with sintered block type devices, SnO2 and In2O3 were the most sensitive to C2H4O, though the sensitivity appeared to be still far from meeting the requested one, i.e. being capable of detecting 0.1 ppm C2H4O in
air. In an attempt to improve the sensitivity, a thin film device using SnO2 was fabricated from a colloidal dispersion of SnO2 by a spin coating method. The thin film device was more sensitive to C2H4O, giving fairly large sensor response to 5g～50 ppm C2H4O in air at 350℃. However, it still needed further improvements in sensitivity and rate of recovery.

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46.

熱電薄膜を用いた熱電式水素センサ

産総研

○申 ウソク、邱 法斌、松宮　正彦、伊豆　典哉、松原　一郎、村山　宣光

RF-SPUTTERED THERMOELECTRIC THIN FILMS FOR THERMOELECTRIC HYDROGEN SENSOR

W. Shin, F. Qiu, M. Matsumiya, N. Izu, I. Matsubara, N. Murayama

Synergy Materials R.C., AIST, Nagoya 463-8560, Japan,


A hydrogen gas sensor using thermoelectric Li-doped NiO thin film with platinum catalyst film on the half of its surface was fabricated and this thin film sensor has strong adhesion on the substrate. When this sensor is exposed to air mixed with the hydrogen gas, catalytic reaction heats up the platinum-coated surface, and then thermoelectric voltage appears across the hot and cold region of the oxide film. The Li doped NiO thin film was deposited by r.f. sputtering method on three different substrates and followed by thermal annealing.

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47.

レーザーアブレーション法およびゾルゲル法で作製したNiO/SiO2ナノコンポジットのCOガス応答

産総研・界面ナノ研究センター

○佐々木毅、Zbroniec Leszek、越崎直人

CO GAS SENSING PROPERTIES OF THE NiO/SiO2 NANOCOMPOSITES PREPARED BY LASER ABLATION AND SOL-GEL METHODS

Takeshi SASAKI, Leszek ZBRONIEC, Naoto KOSHIZAKI

Nanoarchitectonics Research Center, National Institute of Advanced Industrial Science and Technology
Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan,


The aim of this work is the synthesis and characterization of CO gas optical sensing properties of SiO2 sol-gel glass films doped with NiO nanocrystals and multilayered NiO/SiO2 nanocomposites prepared with alternative deposition of laser ablated NiO nanoparticles, and SiO2 layers deposited by laser ablation and/or sputtering. Various structures (number of layers, NiO particle size, particle number density, etc.) in nanocomposites were obtained by changing the deposition conditions. Optical transmittance of all the sol-gel films was higher in 1%CO/N2 gas than in air in the wavelength range from 300 to 800 nm. The differential transmittance after CO exposure was the highest for the light within 400-500 nm range. Gas sensitivity increased with increasing NiO concentration. Comparison of the gas sensing properties of the sol-gel and laser ablated films is also reported.

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48.

R.F.プラズマ溶射法による高感度NO2センサの製作

埼玉大学理工学研究科
○史　麗琴，長谷川有貴，勝部昭明

ウチヤ．サーモスタット(株)
尾上公正，中村清純

STRUCTURAL AND GAS SENSING PROPERTIES OF SnO2 GAS SENSOR BASED ON R.F. INDUCTION PLASMA SPRAY METHOD

○Liqin SHI, Yuki HASEGAWA, Teruaki KATSUBE
Department of Information and Computer Sciences, Faculty of Engineering, Saitama University
shimo-okubu 255, saitama 338, Japan

Kousei ONOUE, Kiyozumi NAKAMURA
Uchiya Thermostat Co., LTD
2-176-1 Takasu Misato-shi Saitama-ken 341-0037, Japan

SnO2-based thin film was prepared using R.F. induction plasma spray method. This paper presents results from a study on the influence of process parameters and annealing temperature on the physical properties of SnO2 gas sensor. The effect of process parameters and annealing temperature on the physical properties of SnO2 thin films were examined by XRD, SEM method. Meanwhile, in order to investigate the gas sensing properties, our sensor films was used to detect NO2 gas at a concentration from 20 ppb to 200 ppb, and the results shows that our gas sensors have achieved highly sensitive to low NO2 gas detection down to 20 ppb with the response and recovery time less than several minutes.

 

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49.

酸化タングステン薄膜センサにおける微細構造と極低濃度NO2検知特性

立命館大理工

○玉置　純、林　篤史、山本善史

MICROSTRUCTURE AND SENSING PROPERTIES TO DILUTE NITROGEN DIOXIDE OF TUNGSTEN OXIDE THIN FILM SENSORS

Jun TAMAKI, Atsushi HAYASHI, Yoshifumi YAMAMOTO

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

The effects of microstructure (WO3 crystallite size and film thickness) on NO2 sensing properties were investigated for WO3 thin film sensors equipped with Au microelectrodes. The effect of crystallite size for thin WO3 sensors was explained with conventional model. On the other hand, the high sensitivity NO2 sensor was obtained due to unique thickness effect. For
the sensors using WO3 powders calcined at 300-400 ℃ (small crystallite), th e sensitivity to dilute NO2 had a maximum at optimal thickness. The optimal thicknesses were 7 and 25 μm for 400 and 300 ℃ sensors, respective ly. The sensitivity (Rg/Ra) to 0.02-0.05 ppm NO2 ranged from 6.5 to 45 for these sensors, suggesting the possibility of environmental NO2 monitoring.
Such a behavior was not observed for the sensors having large crystallite (calcination temperature : 600-850 ℃).

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50.

ナノ多孔質材料を用いたマイクロBTXセンサ

1NTT MI研，2産総研

○上野祐子1，堀内勉1，丹羽修1，周豪慎2，山田健郎2，本間格2

MICROFLUIDIC BTX GAS SENSOR USING NANO-SIZED PORES OF MESOPOROUS SILICATE

Yuko UENO 1, Tsutomu HORIUCHI 1, Osamu NIWA 1, Hao-shen ZHOU 2, Takeo YAMADA 2, Itaru HONMA 2

1NTT Microsystem Integration Laboratories,
3-1 Morinosato Wakamiya, Atsugi, Kanagawa 243-0198, Japan,
2National Institute of Advanced Industrial Science and Technology,
1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan

We have developed a portable sensor for the detection and identification of aromatic volatile organic compound (VOC) gases, namely benzene, toluene, and xylenes (BTX), which are air pollutants, by assembling two microfluidic devices, a concentration cell and a detection cell, and peripheral devices. In this paper, we report the characteristics of our BTX gas sensor, which we studied in order to optimize the operating conditions. We optimize the total accumulation time required for spectral measurement, the gas sampling time, the arrangement of the two microfluidic devices, and we discuss the effect of cell integration without a connection tube between the concentration and detection cells. We also discuss the remaining problems, namely, the effects of temperature as regards obtaining a fast and sharp response, and then propose a device design that may improve the detection limit.

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51.

Pt/WO3薄膜を用いた分布型光ファイバ水素センサの検討

横浜国大工，東大先端研，宇宙開発事業団宇宙輸送システム本部

○住田慎太郎、岡崎慎司、朝倉祝治、中川英元、村山英晶、鷲谷正史

DISTRIBUTED HYDROGEN DETERMINATION WITH FIBER-OPTIC EVANESCENT-WAVE GAS SENSOR USING PLATINUM-SUPPORTED TUNGSTEN TRIOXIDE THIN FILM

Shintaro SUMIDA, Shinji OKAZAKI, Shukuji ASAKURA, Hidemoto NAKAGAWA, Hideaki MURAYAMA, Masahumi WASHIYA

Graduate School of Engineering, Yokohama National University
Tokiwadai 79-5, Hodogayaku, Yokohama 240-8501, Japan

A fiber-optic hydrogen gas sensor using platinum-supported tungsten trioxide (Pt/WO3) was characterized. This sensor utilizes the absorption of the evanescent field interation in the clad of Pt/WO3 thin film which was prepared by sol-gel process, coated on a silica core. The sensor showed fast response to 1 vol.% H2 balanced with nitrogen and the sensitivity was quite high at room temperature. This resulted from te color change in cladding WO3 region with the formation of tungsten bronze. After the exposure to CO or NH3 gas, the sensing characteristics were still retained. The OTDR trace considerably changed upon the exposure to hydrogen. The sensor has the potential for distributed measurement to detect the location of hydrogen leakage points.

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