Vol. 33, Supplement B (2017)

Proceedings of the 62th Chemical Sensor Symposium
Nagasaki, September 10-11, 2017

 

Abstracts



1.

NASICONを利用した固体電解質型COセンサの開発 -Pt検知極への酸化物添加の影響Ⅱ-

長崎大院工

○上田太郎、大隅祐李、鎌田 海、兵頭健生、清水康博

IMPROVEMENT OF CO-SENSING PROPERTIES OF SOLID-ELECTROLYTE GAS
SENSORS USING NASICON −EFFECTS OF OXIDE ADDITION TO THE Pt SENSING
ELECTRODE ON THE CO-SENSING PROPERTIES II−

Taro UEDA, Yuri OSUMI, Kai KAMADA, Takeo HYODO and Yasuhiro SHIMIZU

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

CO sensing properties of NASICON (Na3Zr2Si2PO12)-based solid electrolyte-type gas sensors attached with Pt mixed with a metal oxide (MO: Bi2O3, CeO2, Cr2O3, CuO, Fe2O3, In2O3, La2O3, Mn2O3, NiO, V2O5, WO3) as a sensing electrode (Pt(15MO), the additive amount of MO: 15 wt%) and Pt as a counter electrode, which were denoted as Pt(15MO)/Pt, were examined at operating temperature in the range of −10~300°C. The magnitude of responses to 300 ppm CO of the examined sensors except for the Pt(15MO)/Pt (MO: Fe2O3 and In2O3) were the largest at 30°C. Among them, the Pt(15Bi2O3)/Pt and Pt(15Cr2O3)/Pt sensors showed relatively large CO response with a change in electromotive force to a positive direction at 30°C, while the Pt(15CeO2)/Pt sensor showed relatively large negative CO response at 30°C. The Pt(15MO)/Pt sensors (MO: Bi2O3, CeO2, Cr2O3) also showed the clear CO responses even at the temperature below freezing point. Among them, the Pt(15Bi2O3)/Pt sensor showed relatively large CO response (ca. −148 mV) with quick response and recovery behavior even at −10°C. The CO response mechanism of the sensors was discussed based on mixed potential theory.

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2.

酸化グラフェンのプロトン導電性とガス検知特性

熊大院自然科学研究科a、熊大パルスパワー科学研究所b

○桑木裕大a、宮本杏未a、キタイン アルマンドa、佐々木 満b、木田徹也a

PROTON CONDUCTION AND GAS DETECTION PROPERTIES
OF GRAPHENE OXIDE

Yuta KUWAKIa, Azumi MIYAMOTOa, Armando QUITAINa, Mitsuru SASAKIb, Tetsuya KIDAa

a Department of Applied Chemistry and Biochemistry, Kumamoto University,
2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555
b Institute of Pulsed Power Science, Kumamoto University
2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555

Graphene oxide (GO) is a two-dimensional carbon nanosheet with various oxygen functional groups. GO has been attracting much attention as a material that can be applied in a wide range of applications such as capacitors and solar cells, because GO has unique electrical properties. Here, we report the development of solid electrolyte gas sensor using proton conductivity of GO. GO was synthesized by the Hummers’ method, and the GO membrane was prepared by vacuum filtration of the obtained solution. The GO membrane exposed to humid air showed good proton-conducting properties at room temperature, as confirmed by hydrogen concentration cell measurements, complex impedance analyses, and proton pumping. The gas sensor using the GO membrane with a platinum-supporting carbon (Pt/C) sensing electrode showed a high hydrogen response at room temperature. The sensing mechanism is explained by the mixed-potential theory. Our results showed the possibility of GO which can electrochemically detect hydrogen leakage without external heating.

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3.

金属酸化物検知極を用いた高分子電解質型ガスセンサのCO検知特性

長崎大院工

○高森まり、上田太郎、鎌田 海、兵頭健生、清水康博

CO-SENSING PROPERTIES OF POLYMER ELECTROLYTE-TYPE GAS SENSORS
USING METAL-OXIDE SENSING ELECTRODES

Mari TAKAMORI, Taro UEDA, Kai KAMADA, Takeo HYODO and Yasuhiro SHIMIZU

Graduate School of Engineering, Nagasaki University,
1-14 Bunkyo-machi, Nagasaki 852-8521

CO-sensing properties of potentiometric gas sensors using an anion-conducting polymer (ACP) as an electrolyte and metal oxide (MO) loaded with and without a noble metal (N) as a sensing-electrode material (EC(nN/MO) or EC(MO), respectively, MO: Bi2O3, CeO2 or SnO2, n: the loading amount of a noble metal (0.5–10 wt%), N = Ag, Au, Ir, Rh, Ru, Pt) have been investigated in wet synthetic air (57%RH) at 30°C. All the EC(MO) sensors showed quite small responses to both CO and H2. The N loading onto MO was effective in improving the CO response in some cases, and the Au and Pt loading onto SnO2 especially enhanced the CO response of the EC(SnO2) sensor. In addition, the CO responses of all the EC(nPt/SnO2) sensors showed a good linear relationship with CO concentration. Among them, the H2 responses of the EC(nPt/SnO2) (n = 0.5–5.0) sensors were much smaller than their CO responses, indicating their excellent CO selectivity against H2.

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4.

起電力式アンモニアセンサにおける電極被覆膜の影響

愛媛大学院理工

○板垣吉晃、川渕貴史、猿丸英理、青野宏通

EFFECT OF ELECTRODE COVERING IN POTENTIOMETRIC
AMMONIA SENSORS

Yoshiteru ITAGAKI, Takafumi KAWABUCHI, Eri SARUMARU, and Hiromichi AONO

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

Human breath from a controlled human body contains <1 ppm NH3, while that from a lever disease patient is known to increase to 50 ppm. Therefore, exhaled NH3 can be a biomarker in a non-invasive breath test for lever disease. We reported that covering the Pt sensing electrode with hexagonal boron nitride (h-BN) supported catalysts (Pt, Pd, Ag) increased the EMF response. In particular, Ag loaded h-BN (Ag/h-BN) was the most effective catalyst, and the EMF response increased with an increase in the amount of Ag loading between 2 and10 wt%. However, Ag-loading tended to increase the sensor response time. In this study, a beads-milling technique was applied to increase surface area of the h-BN powder. It was found that increasing surface area of the h-BN powder significantly enhance the sensor response and decrease the sensor response time.

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5.

ハイドロソーダライト系ゼオライトを用いた
 固体電解質インピーダンス型センサのガス応答特性

九工大院工

○弓場優也、高瀬聡子、清水陽一

SOLID ELECTROLYTE IMPEDANCEMETRIC GAS SENSOR
USING HYDRO-SODALITE RECEPTOR

Masaya YUMIBA, Satoko TAKASE and Youichi SHIMIZU*

Department of Applied Chemistry, Kyushu Institute of Technology,
1-1 Sensui-cho, Tobata, City of Kitakyushu, Fukuoka 804-8550
*shimizu.youichi366@mail.kyutech.jp

These days, disease diagnostics using breath analysis have attracted a lot of attentions as a non-invasive method. Therefore, it has been coming very important to develop high performance gas sensors for maker gases, i. e., ammonia, acetone, toluene, etc. It is well known that hydro-sodalites show high ion-exchange capacity, tunable surface charge, and large surface area. In this study, we have focused on the use of hydro-sodalite as a new receptor for an impedancemetric solid-electrolyte gas sensor. Hydro-sodalites, Na8(AlSiO4)6(OH)2 and NA8(AlSiO4)6Cl2, powders could be synthesized by a hydrothermal method. It was found that the impedance response of the Na8(AlSiO4)6Cl2 / Na5DySi4O12 sensor device showed high sensitivity and selectivity to NH3 at 400ºC, 50 Hz.

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6.

Pt-Ti-OゲートSi-MISFET型水素ガスセンサの
水素類似ガスへの応答特性

日立 中研

○宇佐川利幸、笹子佳孝

HYDROGEN-RELATED GAS RESPONSE FROM PT-TI-O GATE Si-MISFETS
GAS SENSORS

Toshiyuki USAGAWA and Yoshitaka SASAGO

Center for Technology Innovation-Electronics, Hitachi, Ltd.,
Kokubunji-shi, Tokyo 185-8601

We have applied the platinum-titanium-oxygen (Pt-Ti-O) gate silicon-metal-insulator-semiconductor field-effect transistors (Si-MISFETs) hydrogen gas sensor to gas sensing study for H2S, NH3, CH3OH, C2H5OH gases. We demonstrated the H2S gas response for wide concentration range from 500ppm to 10ppm at operation temperature of 200C. The H2S gas response shows steep threshold operation-temperature around 180 C. As the Pt-Ti-O gate Si-MISFETs are operated around 115 C for H2 gas sensing, it is possible to discriminate H2S gases and H2 gases. The high threshold temperature will be an advantage for H2S gas sensing compared with previous 100nm-thick Pd-gate MOSFETs H2S gas sensors, which work at a low temperature of 70 C. The sensing characteristics of our Pt-Ti-O gate structures to NH3, CH3OH, and C2H5OH gases were much different from the previous simple Pd-gate or Pt-gate Si-MOSFETs. The sensor responses of our Pt-Ti-O gate structures to 500ppm NH3 gas exposures showed no response at 115C, 320mV Vth shift at 185C, and 360mV Vth shift at 220C. These NH3 sensing behavior is much different from the hitherto-developed Pt-gate Si-MOSFETs sensors,which showed large sensing amplitude like 400~800 mV depending operation temperature between 70~200C. We also investigate CH3OH, and C2H5OH gas sensing.

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特別講演

味と匂いを測る化学バイオセンサ

九大院

○都甲 潔

CHEMICAL BIOSENSORS TO MEASURE TASTE AND SMELL

Kiyoshi TOKO

Graduate School of Information Science and Electrical Engineering
Research and Development Center for Taste and Odor Sensing
Kyushu University, Fukuoka 819-0395

Chemical biosensors to measure taste and smell have made rapid progress recently. They are named electronic tongues (e-tongues) and noses (e-noses), respectively. A taste sensor, which is a kind of e-tongue, has a property of global selectivity that implies ability to decompose taste into five basic taste qualities (sourness, sweetness, bitterness, saltiness, umami) and quantify them without identifying each chemical substance. Each sensor electrode of the taste sensor is specific to each taste quality. This sensor has been applied to many kinds of foods such as beer, coffee, tea, meat, rice, milk and wine. It can provide a scale of taste, and can be utilized to produce new foods and medicines or control/monitor their qualities.
E-noses are chemical biosensors to detect smell of foods, perfumes and circumstance. Whereas various types of materials and methods are reported, an “electronic dog nose” based on both surface plasmon resonance (SPR) and an antigen–antibody interaction is explained here. The detecting surface is chemically modified by a self-assembled monolayer. As a result, TNT was detected at about 6 ppt using the optimized surface with indirect competitive assay. In the near future, mobile phones mounting the above kinds of e-tongues and e-noses will be developed.

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7.

希土類複合酸化物を触媒として用いた
接触燃焼式エチレンガスセンサ

阪大院工

〇渡邉美寿貴、中谷 遥、田村真治、今中信人

CATALYTIC COMBUSTION-TYPE C2H4 GAS SENSOR
EMPLOYING THE Ce-Zr COMPLEX OXIDE SOLID SOLUTION CATALYST

Mizuki WATANABE, Haruka NAKATANI, Shinji TAMURA, and Nobuhito IMANAKA

Graduate School of Engineering, Osaka University,
Suita-shi, Osaka 565-0871

Ethylene (C2H4) gas, which is a essential material in petrochemical industry, leads to the potential for explosion accidents, because of its high flammability (explosive limits: 2.7 vol. % in the air), Thus, a C2H4 gas sensor is required to detect C2H4 leakage for preventing the following accidents. In this study, a new catalytic combustion-type C2H4 gas sensor was developed by using Pt-loaded CeO2-ZrO2-ZnO (CZZn) solid solution as a C2H4 oxidizing catalyst. The sensor employing 10wt%Pt/CZZn catalyst responded to C2H4 gas smoothly and reproducibly with linear response to C2H4 gas concentration change even at 135°C.

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8.

金属-酸化物複合触媒を用いた接触燃焼式
MEMSガスセンサに関する研究

九大院

〇末松昂一、高山真緒、有馬理菜、渡邉 賢、西堀麻衣子、島ノ江憲剛

COMBUSTION-TYPE MEMS GAS SENSORS USING METAL – METAL OXIDE
COMPOSITE CATALYSTS

Koichi SUEMATSU a, Mao TAKAYAMA b, Rina ARIMA b, Ken WATANABE a,
Maiko NISHIBORI a, Kengo SHIMANOE a

aDepartment of Advanced Materials Science and Engineering, Faculty of
Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
bDepartment of Molecular and Material Sciences, Interdisciplinary Graduate
School of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan

The catalytic activity and gas sensing property of Pd-loaded Al2O3 (Pd/AL) and Pd and LaMnO3 co-loaded Al2O3 (Pd/LM/AL) to detect hydrocarbons, especially isobutane and methane were investigated. For gas sensing properties, the combustion type MEMS gas sensor was driven by pulse-heating mode to reduce the power consumption. The isobutane conversion using Pd/LM/AL showed higher catalytic activity than that using Pd/AL at 300oC, because Pd of Pd/LM/AL was more dispersed in the particles than that of Pd/AL. On the other hand, however, the sensor response to isobutane using Pd/AL was higher than that using Pd/LM/AL. Thus, it is indicated that the distribution state of Pd particles such as particles aggregation and chemical state affect to the thermal conductivity of sensing layers and the enhancement of the sensor response.

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9.

アパタイト型ケイ酸ランタンを用いた
新規な接触燃焼式アンモニアガスセンサ

阪大院工

○渡邊結香、田村真治、今中信人

CATALYTIC COMBUSTION-TYPE NH3 GAS SENSOR EMPLOYING
THE APATITE-TYPE OXIDE

Yuka WATANABE, Shinji TAMURA, and Nobuhito IMANAKA

Graduate School of Engineering, Osaka University,
Suita-shi, Osaka 565-0871

Ammonia gas is one of the useful gas species in the industrial field. However, ammonia gas is very toxic, and the ammonia gas sensor showing the exact gas detection with a rapid response is greatly requested for prevening the serious accidents. In this study, we fabricated the catalytic combustion-type sensor which can detect NH3 at low temperature by incorporating a Pt-loaded appatite-type La10Si6O27 solid solution as the NH3 oxidizing catalyst. The sensor showed the superior sensing performance of smooth and rapid response to NH3 gas at 200°C. Moreover, since the present sensor exhibited linear response to the NH3 gas concentration change, it is expected that the sensor can detect NH3 quantitatively at around 200°C.

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10.

貴金属-金属酸化物共担持メソポーラスアルミナ触媒
を用いた吸着燃焼式マイクロガスセンサのVOC検知特性

長崎大院工a、矢崎エナジーシステムb

○兵頭健生a、永江和徳a、笹原隆彦b、鎌田 海a、上田太郎a、清水康博a

VOC-SENSING PROPERTIES OF ADSORPTION/COMBUSTION-TYPE GAS SENSORS
UTILIZING MESOPOROUS ALUMINA CO-LOADED WITH NOBLE METAL AND
METAL OXIDE AS A CATALYST

Takeo HYODOa, Kazunori NAGAEa, Takahiko SASAHARAb, Kai KAMADAa, Taro UEDAa,
and Yasuhiro SHIMIZUa

aGraduate School of Engineering, Nagasaki University,
1-14 Bunkyo-machi, Nagasaki 852-8521
bGas Equipment R&D Center, Yazaki Energy System Corporation,
23 Minamikajama, Shizuoka 431-3393

Sensing properties of adsorption/combustion-type gas sensors utilizing mesoporous alumina co-loaded with 10 wt% noble metal and 10 wt% metal oxide, (10N/10MO/mp-Al2O3, N: noble metal (Pd or Pd), MO: metal oxide (Bi2O3 or CeO2)) to volatile organic compounds (VOCs, ethanol or 1-hexanol in this study) have been investigated and their sensor-signal profiles have been analyzed by differential and integral processing. The sensor-signal profiles to ethanol and 1-hexanol were drastically dependent on the kind of N and MO loaded onto the mp-Al2O3, and 10Pt/10CeO2/mp-Al2O3 and 10Pd/10CeO2/mp-Al2O3 sensors showed the largest dynamic responses to ethanol and 1-hexanol, which probably originated from flash combustion (450°C) of adsorbed partially decomposed products and/or polycondensates produced at 150°C, respectively. In addition, the differential processing obviously differentiated their dynamic-response behavior. On the other hand, the integral processing of static responses revealed that the catalytic-combustion activities of ethanol and 1-hexanol over mp-Al2O3 largely depended on the kind of loaded MO (Bi2O3 or CeO2).

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11.

呼気水素、CO、メタン分析用の熱電式アレー型ガスセンサの開発

産総研a、阪大b

○申ウソクa、伊藤敏雄a、後藤知代b、鶴田彰宏a、赤松貴文a

THERMOELECTRIC ARRAY SENSORS FOR BREATH H2, CO, and CH4 ANALYSIS

Woosuck SHIN a, Toshio ITOH a, Tomoyo GOTO b, Akihiro TSURUTA a,
and Takafumi AKAMATSUa

a National Institute of Advanced Industrial Science and Technology (AIST),
Shimo-shidami, Moriyama-ku, Nagoya 463-8560
bThe Institute of Scientific and Industrial Research, Osaka University,
Ibaraki 567-0047

Calorimetric gas sensors take advantages of micro-machined devices using the heat of combustion reaction generated on catalytic metals and inflammable gas. Micro-thermoelectric array sensors (TAS) have been developed for the ppm level gas detection, which includes H2, CO, and CH4 in human breath, heating catalyst combustor temperatures by using micro heaters built on the membrane of the sensor device. For the purpose of simultaneous detection of the gases in exhaled breath, an array sensor of thermoelectric devices with 3 different combustion catalysts is developed. Using the micro-heaters the temperatures of the Pd/Al2O3, Au/Co3O4 and Pt/Al2O3 catalysts were controlled for the selective combustion of CH4, CO and H2, respectively, and the gas sensing performance of the sensor for the simulated breath of the gas mixture including 100 ppm H2, 25 ppm CO, 50 ppm CH4, and 199 ppm CO2 in air is investigated.

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12.

ポリアニリングラフト膜の作製とそのアンモニアガス検知特性

愛大院理工

○北方暁朗、八木 創、松口正信

FABRICATION OF SURFACE-GRAFTED FILM OF POLYANILINE AND ITS
AMMONIA GAS SENSING PROPERTIES

Tokirou KITAGATA,, Hajime YAGI, and Masanobu MATSUGUCHI

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

It is well known that sensing properties of a polyaniline (PANI) gas sensor depend on the morphology of the PANI film. In this study, the surface-grafted PANI film was fabricated and its sensing properties towards NH3 gas were investigated. Fabrication of the grafted PANI sensor was performed in two steps. First, parylene A was deposited by chemical vapor deposition onto an alumina substrate having a pair of interdigitated gold electrodes. Second, polyaniline was then immobilized onto the parylene A surface by oxidative graft polymerization of aniline. The response of the grafted sensor was approximately five times larger than that of the simply deposited (non-grafted) sensor. Also, the grafted sensor was fabricated in several conditions. Among the sensors tested, the grafted sensor prepared in 0.5 M H2SO4 for 24 hours had much higher response. However, the there was little difference in the reversibility of the grafted sensors, irrespective of fabrication conditions.

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13.

シリコンマイクロリング共振器水素ガスセンサの基礎検討

横国大院工

○山作直貴、松浦壮佑、西島喜明、荒川太郎、岡崎慎司

BASIC STUDY OF SILICON MICRORING RESONATOR HYDROGEN GAS SENSOR

Naoki YAMASAKU, Sosuke MATSUURA, Yoshiaki NISHIJIMA, Taro ARAKAWA,
and Shinji OKAZAKI

Graduate School of Engineering, Yokohama National University, Faculty of Engineering,
79-5 Tokiwadai, Hodogaya-ku, Yokohama-city 240-8501, Japan

A novel optic sensor using platinum-loaded tungsten oxide (Pt/WO3) and silicon microring-resonator (MRR) for detection of hydrogen gas at room temperature was proposed and examined. The sensing principle is based on the resonant wavelength shift caused by the change in optical properties of hydrogen sensitive layer. 140 pm resonant wavelength shift was observed when the sensor was exposed to 4 vol.% H2/N2 for 5 minutes, however, according to the optical microscope image of the surface of it, the part of microring was not completely covered with Pt/WO3. Maybe it was because this part was so small that the surface tension of Pt/WO3 precursor prevented to entirely cover it. We think this sensor will be much more sensitive if the microring portion is fully covered with Pt/WO3 by mixing a surfactant into its precursor.

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14.

共貧溶媒効果を利用したPNIPAM微粒子膜の作製とそのHClガス吸着特性

愛大院理工

○藤井慎之輔、八木 創、松口正信

FABRICATION OF PNIPAM NANOPARTICLE FILMS BY USING A CONONSOLVENCY EFFECT AND
THEIR HCl GAS ADSORPTION PROPERTIES

Shinnosuke FUJII, Hajime YAGI, and Masanobu MATSUGUCHI

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

Poly(N-isopropylacrylamide) (PNIPAM) nanoparticle films were fabricated easily at room temperature on the surface of a quartz resonator by using a cononsolvency effect. The surface morphology of the films was observed by SEM and nanoparticles with the diameter of several hundreds nm were successfully formed. Moreover, images obtained at high magnification(×500k) revealed that these nanoparticles were secondary particles formed by aggregation of primary particles (about 10 nm in diameter). The amount of HCl gas adsorption of PNIPAM nanoparticle films increased in proportion to the PNIPAM loading on the resonator surface, while the reversibility was unexpectedly less than 90%.

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15.

p型半導体酸化物によるCO2ガス検知

北九州高専

○小畑賢次、本郷雄也、松嶋茂憲

CO2 DETECTION OF P-TYPE SEMICONDUCTOR OXIDE

Kenji OBATA, Yuya HONGOU, Shigenori MATSUSHIMA

Department of Creative Engineering, National Institute of Technology (NIT),
Kitakyushu College, Shii 5-20-1, Kokuraminami-ku, Kitakyushu 802-0985

CO2 sensing properties of Zr-added CaFe2O4 powders prepared from a malic acid complex (MAC) and a polymerized complex (PC) methods were examined in the temperature range of 250 to 450 °C in dry air. In the MAC method, the CO2 sensitivity of Zr-added CaFe2O4 powder was higher than that of unadded CaFe2O4 powder and it reached maximum at measuring temperature from 300 to 350 °C. On the other hand, Zr-added CaFe2O4 powder in the PC method had a low CO2 sensitivity as well as the unadded one.

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16.

酸化スズ半導体MEMSガスセンサにおける
パルス駆動条件の検討

九大院総理工

原野 航、大山旬春、末松昂一、○渡邉 賢、西堀麻衣子、島ノ江憲剛

EFFECT OF PULSE HEATED CONDITION ON SENSING PERFORMANCE OF SnO2
MEMS GAS SENSORS

Wataru HARANO a, Tokiharu OHYAMA a, Koichi SUEMATSU b, Ken WATANABE b, Maiko NISHIBORI b, Kengo SHIMANOE b

aInterdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga, Fukuoka 816-8580
b Faculty of Engineering Sciences, Kyushu University,
Kasuga, Fukuoka 816-8580, Japan

MEMS-type gas sensor, for which benefits of the pulse heating are not only reduction of power consumption but also its specific sensing performance, was investigated the effect of the pulse heating condition on the sensing property. In this pulse heating, sensor signal includes the transformation of the unsteady state to the steady state. Sensing properties to H2, CO and C7H8 gases were measured and compared within such transformation. As a result, it was found that the resistance change in 1 pulse heating strongly depends on the kind of gas and the rest time. Thus, the measurements of resistance change during a one pulse were discussed for high sensitivity and selectivity in gas detection.

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17.

セリア厚膜型ガスセンサの真空中水素検知特性

新コスモス電機a、宇宙航空研究開発機構b、産業技術総合研究所c

○鈴木健吾a、宮崎 洋a、杠 泰成a、丸 祐介b、伊豆典哉c

CHARACTERIZATION OF A CERIA THICK FILM TYPE GAS SENSOR
FOR HYDROGEN DETECTION IN VACUUM CONDITIONS

Kengo SUZUKIa, Hiroshi MIYAZAKIa, Yasunari YUZURIHAa, Yusuke MARUb and Noriya IZUc

a New Cosmos Electric Co., Ltd., Osaka 532-0036
b JAXA Institute of Space and Astronautical Science,Kanagawa, 252-5210
c National Institute of Advanced Industrial Science and Technology (AIST), Nagoya 463-8560

Detection of trace amounts of hydrogen in vacuum conditions is essential in reusable space transportation systems and for safety control in manned space exploration. We evaluated the H2 detection in vacuum conditions by a novel gas sensor using sintered ceria (cerium oxide) nanoparticles. The results show that sensor resistance depended on H2 and O2 partial pressure ratios at any pressure from 10-5 Pa to atmospheric pressure. We conclude that the ceria resistance does not depend on total pressure but on H2 and O2 adsorption. The increase in sensor resistance resulted from a decrease in oxygen vacancies dependent on the O2 storage of ceria at a high O2 partial pressure. On the other hand, H2 dissociated and formed a cluster with ceria oxygen atoms when the H2 partial pressure was higher than the O2 partial pressure. Sensor resistance markedly decreased in these conditions because Ce3+ with free electrons were generated. In summary, the proposed sensor can convert gas adsorption into an electrical signal even in vacuum conditions, and has the potential to be a highly durable device with high sensitivity.

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18.

小型においセンサを目指した微細電位型
ガスセンサアレイの作製と応答パターンによるガス識別

豊橋技科大a、アロマビットb

○新名直也a、岩田達哉a、橋詰賢一b、黒木俊一郎b、澤田和明a

DEVELOPMENT OF POTENTIOMETRIC MINIATURE GAS SENSOR ARRAYS
FEASIBLE FOR SMALL OLFACTORY CHIPS AND GAS RECOGNITION
FROM THEIR RESPONSE PATTERNS

Naoya SHINMYO a, Tatsuya IWATA a, Kenichi HASHIZUME b, Shunichiro KUROKI b,
and Kazuaki SAWADA a

aToyohashi University of Technology, Toyohashi-shi, Aichi 441-8122
bAroma Bit, Inc., chuo-ku, Tokyo 104-0061

We propose a novel sensing device for small olfactory chip which can be installed on mobile such as smart phone. Three kinds of the gas-sensitive films were separately deposited on surface potential sensor arrays, which is integrated in a single chip with the area of 7.3 mm2. The chip has 128 × 128 elements with the element size of 37.30 × 37.30 μm2, and the manufactured device was exposure to three gases, ethanol, ammonia, acetic acid. The output voltage changes -17 to -41, -58 to -115, and -19 to -58 mV depending on ethanol, ammonia, and acetic acid, respectively. Response pattern of three gases can be obtained from the comparison of voltage difference by the type of film. Furthermore, the time responses have been proposed to be used for gas identification. These results indicate the promising property of the proposed device as a small olfaction chip.

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19.

半導体式センサによる呼気VOC検知器の開発と統計解析

産総研a、愛知県がんセンターb、愛知県立大c、フィガロ技研d

○伊藤敏雄a、三輪俊夫a、鶴田彰宏a、赤松貴文a、伊豆典哉a、申ウソクa、朴 将哲b
樋田豊明b、作村論一c,e、江田 健d、瀬戸口泰弘d

DEVELOPMENT OF EXHALED BREATH VOCS MONITORING SYSTEMS WITH
SEMICONDUCTIVE GAS SENSORS AND STATISTICAL ANALYSIS

Toshio ITOH a, Toshio MIWA a, Akihiro TSURUTA a, Takafumi AKAMATSU a, Noriya IZU a,
Woosuck SHIN a, Jangchul PARK b, Toyoaki HIDA b, Yuichi SAKUMURA c,e, Takeshi EDA d
and Yasuhiro SETOGUCHI d

aNational Institute of Advanced Industrial Science and Technology (AIST),
Shimo-shidami, Moriyama-ku, Nagoya 463-8560
bAichi Cancer Center, 1-1 Kanokoden, Chikusa-ku, Nagoya 464-8681
cDepartment of Information Science and Technology, Aichi Prefectural University,
Nagakute 480-1198
dFigaro Engineering Inc., 1-5-11 Sembanishi, Minoh, Osaka 562-8505
ePresent address: Graduate School of Biological Sciences, Nara Institute of Science and
Technology, Ikoma, Nara 630-0192

Exhaled breath air includes a lot of volatile organic compounds (VOCs) related to halitosis, metabolism, and diseases. It will be easy to check the health condition if the breath analysis, one of the noninvasive analysis, will be improved to monitor the specific VOCs related to them. Especially for diseases, it is expected as a screening method leading to early detection. In this study, we developed semiconductive gas sensors and exhaled breath VOCs monitoring systems using the gas sensors for screening lung cancer. The exhaled breath VOCs monitoring systems consist of Tenax TA as a gas condensing unit, two GC columns, and two semiconductive gas sensors as detectors. We used Pt, Pd, and Pd-loaded SnO2 (Pt,Pd,Au/SnO2) sensors for detecting various VOCs. The target VOCs were selected according to the results of GC/MS analysis. In statistical analyses, we firstly carried out the t-test and the correlation coefficient analysis, and compared the results from the GC/MS and the exhaled breath VOCs monitoring system. Next, we carried out the support vector machine algorithm (SVM) for other target VOCs with high percentage of correct answers, and prepared the second version of exhaled breath VOCs monitoring system.

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20.

インターカレータ型白金錯体の電解還元析出を利用したDNA計測

兵庫県大a、パナソニックb

○安川智之a、有本 聡b、下野 健b、吉岡俊彦b、水谷文雄a

DNA SENSING BASED ON THE DEPOSITION OF PLATINUM COMPLEX WORKED AS
A DNA INTERCALATOR

Tomoyuki YASUKAWA a, Satoshi ARIMOTO b, Ken SHIMONO b, Toshihiko YOSHIOKA b,
Fumio MIZUTANI a

aGraduate School of Material Science, University of Hyogo,
3-2-1 Kouto, Kamigori, Ako, Hyogo 678-1297
bAdvanced Research Division, Panasonic Corporation,
3-4 Hikaridai, Seika, Soraku, Kyoto 619-0237

An electrochemical detection system for DNA has been investigated based on the current increase due to the catalytic oxidation of hydrogen peroxide with platinum deposited by the electrochemical reduction of chloro-2,2':6',2''-terpyridine platinum (II) chloride dihydrate (Pt complex) on a screen-printed carbon electrode. The platinum deposited on the screen-printed carbon electrode that has shown no catalytic activity for oxidation of hydrogen peroxide gives rise to catalytic activity. Cyclic voltammetry was used to reduce the Pt complex to deposit platinum metal on the carbon electrode. The oxidation current of hydrogen peroxide increased with increasing concentration of the Pt complex in the electrolytic deposition. The intercalation of the Pt complex into double-stranded DNA (dsDNA) decreased the concentration of free Pt complex and caused a decrease in the diffusion coefficient of the intercalated Pt complex. Moreover, the reduction of Pt complex was inhibited due to steric hindrance. Thus, the oxidation current for hydrogen peroxide by platinum deposited on the carbon electrode decreased with an increase in the concentration of dsDNA. The present procedure is absolutely simple without the need of the immobilization of DNA. Furthermore, the use of inexpensive screen-printed carbon electrodes will allow for the development of disposable sensing systems.

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21.

金属ナノ構造標識を用いたバクテリアセンシング

阪府大院工

○椎木 弘、木下隆将、Dung Quang NGUYEN、長岡 勉

BACTERIAL SENSING USING NANOMETAL LABEL

Hiroshi SHIIGI, Takamasa KINOSHITA, Dung Quang NGUYEN,
and Tsutomu NAGAOKA

Department of Applied Chemistry, Osaka Prefecture University,
Sakai, Osaka 599-8570

In this study, an organic-inorganic nanostructure that was composed of polyaniline (PANI) and gold nanoparticles has been prepared. The presence of PANI offered us a potential application as electrochemical label for bacteria. Therefore, we have attempted to use this nanostructure as an electrochemical label for E. coli O157:H7 cell which is the leading cause of foodborne diseases. It is well known that the specific antibody-antigen reaction is one of the most effective ways for bacteria detection. So, the anti-E. coli O157:H7 antibody was immobilized on the nanostructure to ensure the specific binding to the target cells. It was confirmed that the antibody-modified nanostructure bound selectively to the target bacteria by using a dark-field microscopy. The bacterial detection was carried out by differential pulse voltammetry (DPV). The results showed that the electrochemical response based on the nanostructure was obtained for the pathogenic E. coli O157:H7 while there was no response for other types of bacteria.

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22.

SPRバイオセンサを用いたウシ尿中のβアゴニストの高感度検出

北大院環境a、ウシオ電機b、北大院国際食資源学院c

Dulal KABIRAZa、森田金市b、○川口俊一c、高橋昌志c

SPR BIOSENSING FOR DETECTION OF BETA AGONIST IN URINE OF COW

Dulal KABIRAZa, Kinichi MORITAb, Toshikazu KAWAGUCHIc, Masashi TAKAHASHIc

aGraduate School of Environmental Science, Hokkaido University,
Sapporo-shi, Hokkaido 060-0810
bUSHIO INC. Tokyo 100-8150
cGraduate School of Global Food Resources, Hokkaido University,
Sapporo-shi, Hokkaido 060-8589

Surface Plasmon Resonance (SPR) biosensor has been developed for a practical application in small molecule detection. However, the real sample may contain many kinds of inhibitors. There are challenges for real sample analysis, even though the high sensitivity was realized in an ideal condition. In this study, the indirect competitive inhibition immunoassay with secondary immunoreaction was employed for detection of beta agonist. Although the sensitivity of 150 ppq (fg mL-1) was achieved, SPR did not respond to the monoclonal antibody of beta agonist in non-pretreated urine. First, the pH was adjusted by mixing with PBS buffer solution (1:1). The pH of sample solution became always 7.4 by the buffer effect. Next, the filtration methods for urine of cows were investigated. It was found that the filtration using pore size could not remove inhibitors. But, the inhibitors were totally removed by the filter modified with functional group such as –CH3, -NH2, or –COOH. It was noticed that the COOH-modified silica filter showed the best performance. It was almost comparable sensitivity to that in PBS buffer solution. It will be discussed that the mechanism of inhibitors in urine.

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23.

分子インプリント高分子グラフトグラファイトの
ペースト電極による薬剤濃度測定

芝浦工大

○吉見靖男、林 俊介、山口莉奈、関 真希

DRUG SENSING USING PASTE ELECTRODE OF GRAPHITE PARTICLE DIRETLY
GRAFTED WITH MOLECULARLY IMPRINTED POLYMER

Yasuo YOSHIMI, Shunsuke HAYASHI, Rina YAMAGUCHI and Maki SEKI

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

Graphite particles grafted with a polymer imprinted with unfractionated heparin and kneaded with silicone oil to fabricate a paste electrode. The redox current at of ferrocyanide at the paste electrode was sensitive to unfractionated heparin and low molecular weight heparin but was insensitive to chondroitin sulfate C. The contact angle of saline on the surface of the paste electrode was decreased by addition of heparin but insensitive to chondroitin sulfate C. The results indicate that the sensing of heparin by the molecularly imprinted polymer on graphite paste electrode controls the effective area of the paste electrode by oil movement.

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24.

きゅうりの皮の細片を炭素繊維に固定化した
充填物を用いた計測システムとその特性

神奈川工科大

○佐藤生男、廣田優希、神崎 愷

A MEASUREMENT SYSTEM AND ITS CHARACTERISTICS
USING PACKINGS WITH FRAGMENTS FROM CUCUMBER'S
PEELS IMMOBILIZED ONTO CARBON FIBERS

Ikuo SATOH,Yuuki HIROTA, and Yasushi KANZAKI

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

Finely cut fragments from cucumber’s peels immobilized onto carbon fibers chemically treated were prepared. The disk type of the immobilized preparations were packed into a small plastic column and then,this column was assembled into a flow-injection system. The system was applied to a flow-injection determination of L-ascorbate based on an amperometric monitoring of decrease in amounts of dissolved oxygen in the substrate solutions. The performance characteristics of the flow system were reported.

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25.

高指数面を有する白金の形態制御が
グルコースセンシングに与える影響

中央大学

○松澤拓哉、松永真理子

EFFECT OF MORPHOLOGICAL CONTROL OF PLATINUM EXPOSING
HIGH-INDEX PLANES ON GLUCOSE SENSING

Takuya MATSUZAWA and Mariko MATSUNAGA

Chuo University,
1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551

A platinum electrode with a mesoporous structure was prepared by electrodeposition of the platinum. The mesoporous platinum electrode showed a large electrochemical active surface. In the glucose solution, the obtained electrode show reductive peak at around 0.35 V vs. Ag/AgCl in the cyclic voltammograms, which was not observed in the electrolyte of 0.5 M H2SO4 solution. The peak current value show a good linear relationship with the concentration of not only D- but also L-glucose in the range between 2 mM and 10 mM. Glucose sensing using cyclic voltammograms in the mixed solution of D-, and L-glucose solution with the constant glucose concentration (5 mM), showed that the peak current value slightly increase with increasing the ratio of L-glucose. Therefore, the influence of L-glucose should be taken into account for a more accurate detection of D-glucose with the mesoporous Pt. Therefore, the influence of L-glucose should be taken into account for a more accurate detection of D-glucose with the mesoporous Pt.

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26.

ペルオキシダーゼの直接電子移動型触媒電流に及ぼす有機色素の効果と
グルコースセンシングへの応用

埼玉工大

○長谷部靖、持田裕貴、吉澤直哉

EFFECT OF ORGANIC DYES ON DIRECT ELECTRON TRANSFER-BASED
CATALYTIC CURRENT OF PEROXIDASE
AND IT’S APPLICATION TO GLUCOSE-SENSING

Yasushi HASEBE, Hiroki MOCHIDA and Naoya YOSHIZAWA

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

Horseradish peroxidase (HRP) was physically adsorbed onto plastic formed carbon (PFC) electrode together with various redox-active organic dyes. Bioelectrocatalytic reduction current to H2O2 were increased by co-adsorption of some redox-active dyes. In the case of phenazine and phenoxazine dyes, typical mediated currents were observed. However, in the case of phenothiazine (PTZ) dyes such as thionine (TN) and methylene blue (MB), the PTZ facilitated direct electron transfer (DET), and the DET-based bioelectrocatalytic reduction current to H2O2 increased. Glucose oxidase (GOx) was further adsorbed onto the HRP/PTZ-PFC electrodes, and the resulting bi-enzyme electrode (GOx/HRP/PTZ-PFC) showed cathodic responses to glucose in a concentration depending manner. When the electrode was changed to carbon-felt (CF), essentially similar behavior was observed, and these sensors allowed highly sensitive and selective determinations of H2O2 and glucose.

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27.

電解析出法を用いたカーボンナノチューブ/酵素固定電極の作製

徳島大院社会産業理工a、産総研b、近藤化学工業c

○安澤幹人a、内丸正宏a、倉科 昌a、渕脇雄介b、原田俊彦c

PREPARATION OF CARBON NANOTUBE/ENZYME-IMMOBILIZED
ELECTRODE USINGELECTRODEPOSITION METHOD

Mikito YASUZAWA a, Masahiro UCHIMARU a, Masashi KURASHINA a,
Yusuke FUCHIWAKI b and Toshihiko HARADA c

aDepartment of Applied Chemistry, Tokushima University, Tokushima 770-8506
bHealth Research Institute, AIST, Takamatsu, Kagawa 761-0395
c Kondo Chemical Industry, Higashiosaka, Osaka 578-0932

A stable dispersed solution of glucose oxidase (GOx) and carbon nanotube (CNT) was prepared using gellan gum and was applied as a solution for electrodeposition. Both GOx and CNT was successfully immobilized on Pt-Ir electrode by applying a constant potential of 1.3 V(vs. Ag/AgCl), while it was followed by o-phenylenediamine electropolymerization in order to fabricate a stable enzyme-immobilized electrode. The obtained electrode performed as a glucose sensor with high sensor sensitivity. This indicate that the introduction of CNT in GOx-immobilized film increased the efficiency of electron transfer between the electrode and generated hydrogen peroxide. In addition, the reproductivity of electrode fabrication was satisfactorily improved by the use of gellan gum as a dispersing agent.

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清山賞受賞講演1

極微量分子センシングのためのナノカーボン薄膜電極の開発

産総研

○加藤 大

DEVELOPMENT OF NANOCARBON FILM ELECTRODES FOR
DETECTING TRACE AMOUNTS OF (BIO)MOLECULES

Dai KATO

Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology,
1-1-1, Higashi, Tsukuba, Ibaraki, 305-8566, Japan

We have been studying nanocarbon film electrodes formed by some sputtering methods. The film provides a nanocrystalline sp2 and sp3 mixed bond structure with an atomically flat surface and high conductivity without doping. The film electrode has excellent properties including a low background current, a wide potential window, and little surface fouling, while maintaining relatively high electrode activity for various (bio) molecules. These characteristics allow the detection of (bio)molecules (e.g., all DNA bases and cerebral gliotransmitter), especially ultratrace amount of biomolecules, which are difficult to measure at conventional carbon electrodes. The nanocarbon film surface can be also easily modified with other atoms/nanoparticle without losing its ultraflatness. For example, we developed electrochemically stable fluorinated nanocarbon (F-nanocarbon) film by CF4 plasma treatment. We successfully used F-nanocarbon film electrode for selective detection of hydrophobic antioxidants (vitamin E) and highly-sensitive detection of LPS. Our developed nanocarbon film-based electrodes can extend ability to detect analytes, which are difficult to detect at conventional carbon electrodes.

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清山賞受賞講演2

希土類化合物をキーマテリアルとした
環境汚染ガスセンサの開発

阪大院工

○田村真治

DEVELOPMENT OF GAS SENSORS WITH RARE EARTH CONTAINING MATERIALS
AS THE KEY COMPONENT

Shinji TAMURA

Department of Applied Chemistry, Graduate School of Engineering, Osaka University,
2-1 Yamadaoka, Suite, Osaka 565-0871

We have developed various kinds of gas sensors in which the rare earth containing materials were strategically selected as the key component of the sensor for realizing the superior sensing performances such as high gas selectivity, high durability, and low temperature operation. Although we have developed the solid electrolyte-type CO2, SO2, NOx, Cl2, and NH3 gas sensors and the catalytic combustion-type CO and H2 gas sensors, I introduce, here, the water durable solid electrolyte-type NH3 gas sensor and the low temperature operable catalytic combustion-type CO gas sensor.

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28.

呼気計測のため二級アルコール脱水素酵素の
正・逆反応を用いたイソプロパノール・アセトン用
バイオスニファ(気相用バイオセンサ)

医科歯科大院a、医科歯科大・生材研b

○簡 伯任a、辻井誠人a、鈴木卓磨a、叶 明b、 當麻浩司b、荒川貴博2、三林浩二a,b

ISOPROPANOL & ACETONE BIO-SNIFFERS (BIOCHEMICAL GAS SENSORS) USING
FORWARD & REVERSE REACTIONS OF SECONDARY ALCOHOL DEHYDROGENASE
FOR ANALYSIS OF EXHALED AIR

Po-Jen CHIENa1, Masato TSUJIIa, Takuma SUZUKIa, Ming YE2, Koji TOMAb,
Takahiro ARAKAWAb, and Kohji MITSUBAYASHIa,b

aGraduate School of Medical and Dental Sciences, Tokyo Medical and Dental University,
1-5-45 Yushima, Bunkyo-ku, Tokyo 113-8549
bnstitute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10
Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan

In this study, highly sensitive bio-sniffers (gas phase biosensor) for analysis of breath acetone and IPA were constructed and demonstrated. Secondary alcohol dehydrogenase (S-ADH) can reduce acetone to isopropanol (IPA) and oxidize nicotinamide adenine dinucleotide (NAD+ to NADH) in a weak acid environment. Furthermore, S-ADH can reversely oxidize IPA to acetone and reduce NADH to NAD+ in an alkaline condition. NADH has unique optical property that it emits fluorescence at 490 nm when it is exposed to 340 nm ultraviolet lights. Therefore, the acetone sniffer detected the decrease of NADH fluorescence to determine the concentration of gaseous acetone and the IPA sniffer measured the increase of NADH. The bio-sniffers were composed of an UV–LED, a photomultiplier tube and an optical fiber probe equipped with a flow-cell and enzyme immobilized membrane. Buffer (pH 7.0 or pH 8.5) solution containing coenzyme (NAD+ or NADH) was circulated in the flow-cell. Both bio-sniffers showed rapid response, highly sensitivity and selectivity to acetone/IPA in the gas phase. The analysis of breath acetone in healthy volunteers found higher concentrations when during the fasting. Additionally, the IPA in exhaled air of healthy subjects observed the concentration of 15.4±11.3 ppb, which was consisted with other researches.

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29.

超好熱古細菌Aeropyrum pernix由来DNAメチル化酵素の特性評価

神奈川工大

○飯田泰広、菅原啓亮、前田翔太

CLONING, OVEREXPRESSION AND CHARACTERIZATION OF DNA
METHYLTRANSFERASE FROM AEROPYRUM PERNIX.

Yasuhrio IIDA, Keiichi SUGAHARA and Shota MAEDA

Department of Applied Bioscience, Faculty of Applied Bioscience, Kanagawa
Institute of Technology
1030 Shimo-Ogino, Atsugi, Kanagawa, 243-0292

Methyltransferase from Aeropyrum pernix was constructed and the active properties were investigated. A. pernix is known as hyperthermophilic archaea and the methyltransferase will have a thermostability, therefore, the methyltransferase can be expected for industrial applications. On the other hand, there is little knowledge of methyltransferase from archaea. APE_0872.1 is a gene in A. pernix genome and is presumed to be a gene encoding DNA(cytosin-5) methyltransferase by homology search. The sequence is homologous to motif I, IV, VI, VIII, and X region of Dnmt I which is known as a DNA methyltransferase of human. And more, A. pernix has a APEK I encoded by a gene of restriction enzyme which recognize GCWGC. From the view point of the restriction modification system, it is considered that DNA methyltransferase of A. pernix will recognize the sequence of GCWGC. However, there is no report of the recognition sequence and thermostability about a protein encoded APE_0872.1. Therefore, in this study, we investigate the properties.

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30.

マイクロ流路ディスクを用いた食肉中の
サルモネラ菌迅速検出

創価大a、産総研b

○久保いづみa、鍛冶屋光俊a、古谷俊介b

RAPID DETECTION OF SALMONELLA ENTERICA IN
CHICKEN MEAT UTILIZING A MICROFLUIDIC DISC

Izumi KUBOa, Mitsutoshi KAJIYAa, Shunsuke FURUTANIb

aIGraduate School of Engineering, Soka University
Hachioji, Tokyo, 192-8577
bBiomedical Research Institute, AIST
Ikeda, Osaka 563-8577

Cells of Salmonella enterica contaminate food and cause foodborne illnesses. It takes long time to detect the existence of S. enterica because of enrichment and several times of separation cultures from samples. Bacterial cells can be isolated in microchamber on a microfluidic disc for single cell isolation, which was developed in our group. Through the PCR of the gene using fluorescent probe the amplicon of the gene in the isolated cell can be detected on the disc and small numbers of S. enterica cells were detected selectively by PCR of invA gene. The aim of this study is rapid detection of S. enterica spiked to chicken meat, as a model of food, by PCR of invA gene on the disc. The collected bacteria from the meat was mixed with PCR reagents and applied to the disc, and single cell isolation and PCR was performed. PCR amplicon of each micro chamber was detected by a fluorescent microscope. The number of the microchamber with PCR amplicon depended on the concentration of S. enterica cells. On a microfluidic disc we could successfully detect S. enterica cells at range of 104 -105 CFU/g within 8 hours including enrichment culture.

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31.

レンズレスイメージングに基づく血中循環腫瘍細胞の
培養モニタリングシステムの開発

東京農工大a、マルコムb

○小木曽淳a、高林知弘a、吉野知子a、前田義昌a、林 泰圭b、原田 学b、松永 是a、田中 剛a

DEVELOPMENT OF MONITORING SYSTEM BASED ON LENS-LESS
IMAGING TOWARD CULTIVATION OF CIRCULATING TUMOR CELLS

Atsushi KOGISOa, Tomohiro TAKABAYASHIa, Tomoko YOSHINOa, Yoshiaki MAEDAa,
Tae-kyu LIMb, Manabu HARADAb, Tadashi MATSUNAGAa, Tsuyoshi TANAKAa

a Institute of Engineering, Tokyo University of Agriculture and Technology,
Koganei-shi, Tokyo 184-8588
bMalcom Co., Ltd.,
Shibuya-ku, Tokyo 151-0071

Circulating tumor cells (CTCs) are defined as tumor cells circulating in the peripheral blood of patients with metastatic cancer. CTCs could provide useful information regarding malignancy, metastatic property of primary tumor and its response to anticancer agent. However, it is still extremely difficult to cultivate CTCs and examine multiple anticancer agents toward identical CTCs. This could be due to the lack of knowledge of division and proliferation behavior of CTCs. The critical difficulty in investigation of CTC proliferation is that cell division events of CTCs are very rare, and thus conventional microscopy might overwork them. Additionally, it is essential that CTCs are discriminated from the blood cells which contaminate CTCs. In this study, we propose to use a wide-field imaging system for investigation of CTC cultivation. The imaging system is composed of a LED and CMOS image sensor, called for lens-less imaging. Using this lens-less imaging system, we attempted to observe tumor cell proliferation and distinguish tumor cells from blood cells. This study indicates that the lens-less imaging can be a powerful tool to investigate the CTC proliferation and cultivation.

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32.

血中循環腫瘍細胞の遺伝子変異検出に向けた
ハイスループット単一細胞単離システムの構築

東京農工大

○根岸 諒、高井香織、松永 是、田中 剛、吉野知子

DEVELOPMENT OF HIGH-THROUGHPUT SINGLE CELL ISOLATION SYSTEM TOWARD
DETECTION OF GENE MUTATION OF CIRCULATING TUMOR CELL

Ryo NEGISHI, Kaori TAKAI, Tadashi MATSUNAGA,
Tsuyoshi TANAKA and Tomoko YOSHINO

Institute of Engineering, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588

Circulating tumor cells (CTCs) are defined as the tumor cells circulating in the peripheral blood of patients with metastatic cancer. Genetic analysis of CTCs at single cell level is believed to provide detailed information of cancer patients. Our research group has developed the size- and deformability-based CTC recovery system using microcavity array (MCA). Recently, we have also developed the single-cell isolation method using photopolymerizable hydrogel encapsulation called “gel-based cell manipulation (GCM)”. GCM allows us to isolate single-cells by tweezers without microscopic observation. However, light irradiation using fluorescent microscopy for each cell is required to hydrogel encapsulation of single-cell, resulting in low throughput. If a number of single-CTCs on MCA are simultaneously encapsulated in hydrogel, high-throughput isolation of CTCs is achieved. In this study, we developed the multiple light irradiation system using two dimensional (2D) complementary metal oxide semiconductor (CMOS) photosensor and digital micromirror device (DMD), and integrated it with the MCA system.

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33.

カリウムイオン電池正極活物質を用いた
全固体型イオン選択性電極の高性能化

東京理科大学a、KOAb

〇土屋和彦a、堀場達雄a、青木 仁b、駒場慎一a

HIGH PERFORMANCE OF ALL-SOLID-STATE
ION SELECTIVE ELECTRODES BASED ON POSITIVE ELECTRODE
ACTIVE MATERIALS FOR POTASSIUM-ION BATTERIES

Kazuhiko TSUCHIYA a, Tatsuo HORIBA a, Hitoshi AOKI b and Shinichi KOMABA a

aDepartment of Applied Chemistry, Tokyo University of Science
1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601
bKOA Corporation
14016, Oaza Naka-minowa, Minowa-machi, Kamiina-gun, Nagano 399-4697

We have developed all-solid-state K ion-selective electrodes by using a K insertion material placed between metal substrate and ion selective membrane. Three different Prussian blue analogues were employed as insertion materials which are known as candidate materials for positive electrodes of K-ion batteries and allow K+ to reversibly be inserted/extracted into/from their crystal structures associated with electrochemical redox reactions. The electrodes of Pt/K insertion material/K+-ISM exhibited an ideal Nernstian response in the range of 10-4.5 – 10-1 mol dm-3 with high selectivity for potassium ions and good potential stability. AC impedance analysis of the all-solid-state electrodes revealed that the insertion materials were capable of reducing the electrode impedance at the interface between metal substrate and ion selective membrane, which was responsible for their improved potential stability.

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34.

溶液中保存の安定性向上を目指した
電界効果トランジスタバイオセンサゲート絶縁膜への酸化グラフェン被覆

早大院先進理工a、早大ナノ・ライフ機構b

○竹内 亮a、秀島 翔b、黒岩繁樹b、中西卓也b、門間聰之a、逢坂哲彌a,b

GRAPHENE OXIDE COATING ON GATE INSULATOR OF FIELD EFFECT TRANSISTOR
BIOSENSOR FOR IMPROVEMENT OF ITS LONG-TERM STABILITY
DURING STORAGE IN SOLUTION

Ryo TAKEUCHI a, Sho HIDESHIMA b, Shigeki KUROIWA b, Takuya NAKANISHI b,
Toshiyuki MOMMA a and Tetsuya OSAKA a,b

aGraduate School of Advanced Science and Engineering, Waseda University,
Shinjuku, Tokyo 169-8555
bResearch Organization for Nano & Life innovation, Waseda University,
Shinjuku, Tokyo 162-0041

A field effect transistor (FET) biosensor that can directly detect target molecules is expected to be applied in healthcare and medical fields due to its potential as a diagnosis tool. When the FET sensors are stored in solution environments, a silicon dioxide insulating layer might be damaged, resulting in the degradation of the reproducibility of sensor response. In this study, to stabilize sensor response for long term immersion in solution, graphene oxide (GO) was selected as a coating layer on the gate insulator of FET sensors. The GO sheets were deposited on a self-assembled monolayer, aminopropylsilane (APS), to obtain GO-coated APS-modified FET (GO/APS/SiO2) sensor. The sensor response, which is observed as a change in the Vg - Id characteristics, was evaluated before and after storing the sensors in buffer solution environments.

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35.

フッ素終端ダイヤモンドを用いた全固体pHセンサ

横河電機a、早大理工b

○新谷幸弘a, b,川原田洋b

All-SOLID-STATE PH SENSOR WITH FLUORINE-TERMINATED DIAMOND SURFACE

Yukihiro SHINTANIa, b , Hiroshi KAWARADA b

aR&D Dept., Yokogawa Electric Corp.,
Musashino-shi, Tokyo 180-8750
bSchool of Science and Engineering Waseda University,
Shinjyuku-ku, Tokyo 169-8555

A fluorine-terminated boron-doped diamond surface is successfully employed as a pH-insensitive solution-gate field-effect transistor for an all-solid-state pH sensor. The fluorinated polycrystalline boron-doped diamond (BDD) channel possesses a pH-insensitivity of less than 3mV/pH. With differential field-effect transistor sensing method, a sensitivity of ca. 0.03 v/pH was obtained in the pH range of 2–10.

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36.

RuO2-Ta2O5触媒上での炭酸水素イオンの 酸化に対する触媒組成の影響

同志社大院理工a、同志社大研究開発推進機構b、同志社大理工c

○池谷ちなみa、川口健次b、盛満正嗣c

EFFECTS OF OXIDE COMPOSITION OF AMORPHOUS RuO2-Ta2O5
CATALYST ON OXIDATION OF HYDROGEN CARBONATE ION

Chinami IKETANIa, Kenji KAWAGUCHIb, and Masatsugu MORIMITSUc

aDepartment of Science of Environment and Mathematical Modeling,
bOrganization for Research Initiatives and Development,
cDepartment of Environmental Systems Science,
Doshisha University, Kyotanabe, Kyoto 610-0394

Amorphous RuO2-Ta2O5 catalysts at different Ru:Ta ratios were prepared by thermal decomposition on titanium disk and the electrochemical measurements of HCO3- in KCl solutions were carried out with the catalysts using rotating disk electrode method. The onset potential for HCO3- oxidation, the linearity between the HCO3- concentration and the oxidation current density, the sensitivity, and the linear concentration range were examined by cyclic voltammetry and chronoamperometry, and the results were compared to those obtained with HPO42-. The Ru ratio of the catalyst ranging from 20 mol% to 80 mol% examined in this work gave little influence on the onset potential of HCO3- oxidation as well as that of HPO42-, in which the oxidation of HCO3- occurs at the less novel potential than that of HPO42-. The sensitivity to each ion showed a strong dependence on the catalyst’s composition, which was maximum at Ru = 50 mol% for both the ions, suggesting that the catalyst at 50 mol% Ru is favorable to quantify HCO3- and HPO42-.

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37.

RuO2-Ta2O5触媒を用いる
リン酸水素イオンと炭酸水素イオンの分離定量

同志社大院理工a、同志社大研究開発推進機構b、同志社大理工c

○本田 愛a、川口健次b、盛満正嗣a,c

QUANTIFICATION OF HPO42- AND HCO3- ON RuO2-Ta2O5 CATALYST

Ai HONDAa, Kenji KAWAGUCHIb, and Masatsugu MORIMITSUa,c

aDepartment of Science of Environment and Mathematical Modeling,
bOrganization for Research Initiatives and Development,
cDepartment of Environmental Systems Science,
Doshisha University, Kyotanabe, Kyoto 610-0394

The oxidation reactions of HPO42- and HCO3- on amorphous RuO2-Ta2O5 catalytic coatings prepared by thermal decomposition on titanium disk were investigated by electrochemical measurements. Cyclic voltammetry and square wave voltammetry indicated that HPO42- and HCO3- were oxidized and the oxidation wave of HPO42- appeared prior to that of HCO3- . The separation in oxidation potential was about 0.14 V measured in SWV, which suggests that both the ions are quantified separately by changing the detection potential. Chronoamperometry was also performed with the KCl solutions with HPO42-, HCO3-, or both of them to know the diffusion limited current density at different potentials. The results showed that the net current density for the oxidation of both HPO42- and HCO3- is almost the same as the sum of that of HPO42- and that of HCO3-, implying that the quantification of each ion in the solution, where both ions are dissolved, is possible electrochemically with the novel catalyst, amorphous RuO2-Ta2O5 mixed oxide.

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38.

Liイオン伝導性ガラスセラミックスを用いた起電力
  検出型センサの溶存CO2に対する応答の安定化

琉球大理

○又吉直子、藤井貴博

STABILIZATION OF THE SENSING RESPONSES FOR DISSOLVED CO2 OF A
POTENTIOMETRIC SENSOR USING LI+-ION CONDUCTIVE GLASS-CERAMICS

Naoko MATAYOSHI and Takahiro HUJII

Faculty of Science, University of the Ryukyus,
1 Senbaru, Nishihara-cho, Okinawa 903-0213

A planar-type sensor using a Li3Zr2Si2PO12 glass-ceramics (Li+ ionic conductor : LICGC) as a transducer and metal carbonates as an auxiliary phase was fabricated for monitoring dissolved CO2 in liquid solution. The electrochemical cell of this sensor element was as follows, (reference electrode) Pt-black, Au / LICGC / Au, Pt-black, Li2CO3+Na2CO3 (sensing electrode). It had no water-proof coating layer on the sensing electrode and the reference electrode. Various mixed solutions were prepared by varying a volume ratio of Li2CO3 saturated solution and Na2CO3 saturated solution, and Li2CO3+Na2CO3 layer was formed on Pt-black by dropping and drying one of them. Among the various ratio of Li2CO3 and Na2CO3 examined, the sensor with a ratio of 1:0.25 was found to show good sensing properties to dissolved CO2. The EMF response of this sensor was found to vary logarithmically with a change in dissolved CO2 concentration in the range of 300 to 1300 ppm in a phosphate buffer solution of pH 7.0 at 30℃. The 90% response time to1300 ppm was ca. 2 min.

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39.

インクジェット法による微細パターン
K+-H+マルチイオンイメージセンサの作製

豊橋技科大

○松葉聡太、高宮貴一、武田和樹、加藤 亮、澤田和明、服部敏明

DEVELOPMENT OF MICROSCALE-PATTERNED POTASSIUM AND PROTON
MULTI-ION IMAGE SENSOR USING AN INK-JET PRINTING METHOD

Sota MATSUBA a , Kiichi TAKAMIYA a , Kazuki TAKEDA a , Ryo KATO b ,
Kazuaki SAWADA a  and Toshiaki HATTORI a

aDepartment of Electrical & Electronic Information Engineering,
Toyohashi University of Technology, Toyohashi-shi, Aichi 441-8580
bCooperative Research Facility Center, Toyohashi University of Technology,
Toyohashi-shi, Aichi 441-8580

Cells control a variety of ion concentrations with ion pumps and channels. The simultaneous monitoring of plural ions is very useful to reveal the behavior of cells and tissues. We have recently developed multi-ion image sensors with ion-sensitive membranes using an ink-jet printing. The Ca2+-K+ multi-ion image sensor divided with two sensing regions successfully observed dynamic multi-ion images of living cells. In this study, we fabricated a microscale-patterned K+-H+ multi-ion image sensor that had 64 sensing lines (line width: 70 µm). The half of these lines were coated with K+ sensitive membrane, and the sensitivity to K+ of each sensing pixel had the average of 50.1 mV/decade. While the other half lines worked as pH sensing pixels. The sensor could compare the local response of K+ and H+ since K+ sensitive lines and H+ sensitive lines were alternately aligned on the sensing area. The sensor would be helpful to analyze cell events accompanying with locally changing K+ and/or H+ concentration.

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40.

ソフトマター分子の動的挙動の周波数依存性

産総研a、鹿大院理工b

○黒澤 茂a、田中睦生a、吉本 稔b

FREQUENCY DEPENDENCE OF DYNAMIC
PROPERTIES OF SOFT MATTER MOLECULES

Shigeru KUROSAWA a, Mutsuo TANAKA a, and Minoru YOSHIMOTO b

aHealth Research Institute, National Institute of Advanced Industrial Science and
Technology (AIST), Central 6, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8566
bDepartment of Information Science and Biomedical Engineering,
Graduate School of Science and Engineering, Kagoshima University,
1-21-40 Korimto, Kagoshima 890-0065

We examined the frequency dependence of the resonant length of polyethylene glycol (PEG) on a solid-liquid interface oscillating at MHz area by using a quartz crystal microbalance (QCM). In order to study it in detail, the QCM frequency and a number-average molecular weight of PEG were changed systematically. As results, the study led to the fact that, in all the frequencies used, the series-resonant frequency shift, ΔF, of the QCM against the square root of the density-viscosity product of the PEG solutions was linear and had intercept. Moreover, the analysis made it clear that the ΔF slope was able to be explained by the Debye process and the ΔF intercept became constant above the resonant length. These results revealed that the resonant length of the PEG molecules formed by physisorption was equal to that in the region of the viscous penetration depth and that the frequency dependency of resonant length of physisorption and chemisorption was equal to each other.

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