Vol. 28, Supplement A (2012)

Proceedings of the 53rd Chemical Sensor Symposium
March 29-31, 2012

 

Abstracts



1.

カーボンナノチューブとプラズマ重合膜および電子伝達媒介物質を用いるアンペロメトリックバイオセンサ

芝浦工大

井上貴博、星野達也、○六車仁志

AMPEROMETRIC BIOSENSOR WITH CARBON NANOTUBE, PLASMA-POLYMERIZED
FILM, AND ELECTRON TRANSFER MEDIATOR

Takahiro INOUE, Tatsuya HOSHINO, and Hitoshi MUGURUMA

Shibaura Institute of Technology

We report on an amperometric biosensor that is based on carbon nanotubes (CNT) and plasma-polymerized film (PPF) for lower potential detection. The CNTs were sandwiched with 2 nm-thick acetonitrile PPFs. Under PPF layer was deposited onto sputtered gold electrode. We examined the three kinds of electron transfer mediator, Dimethylaminomethlferrocene (DMAMFc), Iron(III) ferrocyanide (Prussian blue; PB), Pottasium ferricyanide (Prussian red; PR). The electron transfer mediator was positioned between under PPF layer and CNT layer. It plays an important roles for lower potential detection; the polarized potential vs Ag/AgCl was reduced from +0.6V down to +0.4V. In those mediators, the DMAMFc showed the most valuable property. It is probably attributed to the good affinity between enzyme and DMAMFc for effective electron transportation. We also optimized the CNT and electron transfer mediator concentration for casting formation onto the under PPF layer. This high performance is attributed that CNTs offer excellent electrocatalytic activity and enhance electron transfer.

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2.

米の鮮度評価のための
電気化学的マイクロデバイス

筑波大院数理物質a、筑波大院生命環境b

○小谷内 絵梨a、小嶋 謙一a、佐竹 隆顕b、鈴木 博章a

ELECTROCHEMICAL MICRODEVICE FOR FRESHNESS CHECK OF RICE

Eri KOYACHIa, Kenichi KOJIMAa, Takaaki SATAKEb and Hiroaki SUZUKIa

a Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8573
b Graduate School of Life and Environmental Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8572

Freshness is an important factor that determines the quality of rice. In this study, we have developed an electrochemical microdevice that can measure the freshness of rice based on the measurement of the activity of peroxidase. In the existence of hydrogen peroxide and hydroquinone, the enzymatic reaction produced benzoquinone, which was reduced on a gold working electrode electrochemically and generated current was detected. The measurement on the chip showed larger currents with fresh rice, suggesting the accumulation of benzoquinone in the solution. The observed current clearly reflected harvest years and the condition of storage. The same tendency was observed by other conventional methods. The results demonstrated that on-site rapid measurement of freshness of rice can actually be carried out using our device.

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3.

ヒト血漿アミノ酸計測のための
電気化学酵素センサの開発

富山大院理工a、富山県立大工b

○三浦将典a、篠原寛明a、堀江 肇a、須加 実a、浅野泰久b

DEVELOPMENT OF ELECTROCHEMICAL ENZYME SENSOR
FOR MEASUREMENT OF AMINO ACIDS IN HUMAN BLOOD PLASMA

Masanori MIURAa, Hiroaki SHINOHARAa, Hajime HORIEa, Minoru SUGAa
and Yasuhisa ASANOb

a Graduate School of Science and Engineering, University of Toyama,
3190 Gofuku, Toyama 930-8555
b Biotechnology Research Center and Department of Biotechnology,
Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama 939-0398

We have previously developed the electrochemical enzyme sensors for several amino acids with our originally designed gold electrode chip on which amino acid dehydrogenase and diaphorase are co-immobilized, and the automatic measurement system using pre-electrolysis. For example, developed Leu sensor system was successfully detected only branched chain amino acids by elimination of the interference from ascorbic acid (Chemical Sensors, Suppl. B, 95-97, 2011). Detection range of this Leu sensor was from 50 to 400 M. In this study, The Leu sensor was applied to measure Leu concentration in human blood plasma (HBP). However, Leu concentration in HBP, which was calculated from the calibration curve with PBS as a medium was significantly lower than expected value from HPLC analysis. Therefore new calibration curve for the Leu sensor was made with HBP as a medium on a trial basis.

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4.

炭素繊維を固定化用担体として用いたフローインジェクション計測

神奈川工科大工1・神奈川工科大院工2

○佐藤 生男1、 神崎 愷2

FLOW-INJECTION DETERMINATIONS USING CARBON FIBERS
AS SUPPORTS FOR IMMOBILIZING ENZYMES

Ikuo SATOH1 and Yasushi KANZAKI 2

Department of Applied Chemistry, Faculty of Engineering1,
Graduate School of Engineering2
Kanagawa Institute of Technology,
1030 Shimo-Ogino, Atsugi-shi, 243-0292, Kanagawa-ken

 Use of carbon fibers as supports for immobilizing enzymes was investigated. Ascorbate oxidase was applied to immobilization onto the fibers chemically modified and their characteristics as the enzyme sensor were tested.

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5.

半導体性カーボンナノチューブを用いる
NADHセンサ

芝浦工大

星野達也、○六車 仁志

NADH SENSOR WITH SEMICONDUCTOR-RELATED CARBON NANOTUBE

Tatsuya HOSHINO, and Hitoshi MUGURUMA

Shibaura Institute of Technology

We report an amperometric NADH sensor based on the semiconductor-related CNTs. Although carbon nanotube (CNT) showed the attractive properties for biosensor application, heterogeneity of as-synthesized CNTs was still limitation in order to get the designate and excellent characteristics. For example, about one-third of all possible single-walled CNTs exhibit metallic properties and the remaining two-thirds act as semiconductors. Recently, as-synthesized CNTs were sorted by metallic and semiconducting, using the technique of density-gradient ultracentrifugation. The configuration of the sensor was a nanocomposite of CNTs and a nano-thin plasma-polymerized film (PPF). A CNT film is sandwiched with 15-nm-thick acetonitrile PPFs. Under PPF layer was deposited onto a sputtered gold electrode. It showed the more than excellent sensor performance than that with metallic CNTs.

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6.


ウェーブレット変換を用いた妨害物質除去法の提案と
ラクトースバイオセンサへの応用

東理大理工

○四反田 功, 田中 沙織, 板垣 昌幸

ELIMINATION OF INTERFERING SUBSTANCE ON LACTOSE BIOSENSOR BY THE
WAVELET TRANSFORMATION

Isao SHITANDA, Saori TANAKA, Masayuki ITAGAKI

Department of Pure and Applied Chemistry, Faculty of Science and Technology,
Tokyo University of Science Noda, Chiba 278-8510, Japan

The wavelet transformation (WT) has been shown a powerful tool for the deconvolution of the electrochemical signals. The WT can decompose a signal as a function of the frequency in time domain. In the present study, the authors applied the WT to the amperometric response of a lactose biosensor to eliminate the interfering substance such as ascorbic acid. A power spectum density (PSD) signal related to the response of lactose was detected in low frequency range around 0.125 Hz. On the contrary, the PSD signal related to the response of ascorbic acid was detected in high frequency range around 0.05 Hz. The concentrations of lactose and ascorbic acid in the sample solution were estimated separately by the WT since the time constants of lactose and ascorbic acid of the biosensor are considerably different.

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清山賞受賞講演1

ドライプロセスを基盤とするバイオナノ界面の作製評価およびバイオセンサへの応用

芝浦工大

六車 仁志

FABRICATION AND CHARACTERIZATION OF BIONANOINTERFACE BASED ON DRY
PROCESS AND APPLICATION FOR BIOSENSORS

Hitoshi MUGURUMA

Shibaura Institute of Technology

Biosensors are devices that use a biological reaction for detecting target analytes by generating a quantifiable electronic signal. They are powerful tools used in medical diagnostics, food quality control, and environmental monitoring. A typical biosensor is an integrated product incorporating biological elements and transducers. It has been consistently shown that dry process, plasma-polymerized thin films (PPFs), have potential for use as the interface between the two components of biosensors. To date, transducers have been amenable to miniaturization, and the concept of biochips has concomitantly expanded to encompass interdisciplinary fields such as microchips, arrayed sensors, nanotechnology, chemistry, and materials science. The roles and advantages of plasma-polymerized films in biochip design are highlighted. The main issues are that (i) plasma-polymerized films play an important role in the control and manipulation of biological components on the spatial region (patterning formation) of biochip surfaces while retaining their activity, and (ii) dry-process-based plasma-polymerized films are compatible and continuous with whole biochip processes.

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特別講演1

MICROFLUIDIC PAPER-BASED ANALYTICAL DEVICES (microPADs)
FABRICATED BY INKJET PRINTING TECHNOLOGY

Daniel CITTERIO

Department of Applied Chemistry, Keio University
Yokohama-shi, Kanagawa 223-8522

Microfluidic paper-based analytical devices, generally referred to as µPADs, are recently drawing attention as low-cost and simple to use alternatives of conventional microfluidic analytical systems (e.g. µTAS). The fact that µPADs do not require external pumping and high-tech signal detection systems makes them applicable to low infrastructure settings, such as they are for example encountered in the developing world, in field use or in home healthcare settings. Our group has been able to demonstrate that piezo inkjet printing is a useful method for both the microfluidic patterning of paper substrates and for the deposition of reagents required for (bio)chemical sensing onto the microfluidic system. In our first approach, an inkjet printing device has been used to fabricate three-dimensional hydrophilic microfluidic patterns on filter paper by inkjet etching. These patterned substrates have been used to realize inkjet printed quantitative chemical assays (glucose, pH and total protein in model urine) and lateral-flow immunoassays. Furthermore, the development of polymer nanoparticle-based "chemical sensing inks" has lead to improved quantitative performance of our µPADs. More recently, we have developed an environmentally friendly hydrophobic UV curable acrylate ink composition made of non-volatile and non-flammable compounds. With this ink composition, high-resolution microfluidic structures can now be patterned within less than 5 minutes on the surface of untreated filter paper. What makes inkjet printing technology so attractive is the fact that it is so far the only method allowing fabricating entire µPADs on a single standard manufacturing device, in some cases a device as simple as an off-the-shelf office inkjet printer.

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7.

白金錯体の電解還元による触媒電流を利用したDNAセンシング

兵庫県立大院物質理a,JST-CRESTb,産業技術総合研究所c

○安川智之a, b,山下裕也a,中山大地a,飯島誠一郎c,水谷文雄a

DETERMINATION OF DOUBLE-STRANDED DNA FORMED WITH HYBRIDIZATION
BASED ON DEPOSITION OF PLATINUM COMPLEXES

Tomoyuki YASUKAWA,a, b Yuuya YAMASHITAa, Daichi NAKAYAMAa, Seiichiro IIJIMAc,
Fumio MIZUTANIa

a Graduate School of Material Science, University of Hyogo,
3-2-1, Kouto, Kamigori, Ako, Hyogo 678-1297
b JST-CREST, 5, Sanbancho, Chiyoda, Tokyo 102-0075
c National Institute of Advanced Industrial Science and Technology, Tsukuba, 305-8566

Electrochemical determination systems of DNA sequence have been developed by a simple electrochemical deposition of chloro-2,2':6',2''-terpyridine platinum (II) chloride dihydrate on a glassy carbon electrode without immobilization steps on solid substrate. The intercalation of platinum complexes with dsDNA, which is formed with the complementary recognition of probe DNA to target DNA, caused to suppress the electroreduction of platinum complexes due to the steric hindrance and decrease of the diffusion coefficient. Thus, the catalytic current for reducing proton by the platinum deposited on the glassy carbon electrode decreased with the increase of the concentration of target DNA. An amplified response for measuring the current for reducing proton as compared with that for reducing platinum complexes itself could provide the highly sensitive measurement of dsDNA.

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8.

電気化学発光によるメチル化DNAの検出

産総研a、筑波大b

栗田僚二a、中元浩平a,b、加藤大a、丹羽修a,b

DETERMINATION OF DNA METHYLATION BY
ELECTROGENERATED CHEMILUMINESCENCE

Ryoji KURITA a, Kohei Nakamotoa,b, Dai KATO a, Osamu NIWA a,b

a National Institute of Advanced industrial Science and Technology
1-1-1 Higashi, Tsukuba, Ibaraki 305-8566
b University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki, Japan 305-8573

Cytosine methylation in DNA was determined by an enzyme linked immunosorbent assay (ELISA) with electrogenerated chemiluminescence (ECL) detection and employed for the DNA methylation assay of a long and real genomic sample for the first time. The developed method employed an anti-methyl cytosine antibody labeled with acetylcholinesterase, which was added to recognize single methylated cytosine in a DNA oligomer. The acetylcholinesterase converted acetylthiocholine (substrate) to thiocholine (product), which was accumulated on a gold electrode surface via gold-thiol binding. This surface accumulated pre-concentration made it possible to observe bright and distinctive ECL by applying a potential to the gold electrode in the presence of a tris(2,2-bipyridyl)ruthenium complex luminophore when the analyte DNA contained a methylation region. Methyl-cytosine was measured quantitatively in the 1 to 100 pmol range, which exhibits sufficiently high sensitivity to achieve real DNA measurements without amplification by a polymerase chain reaction. The proposed ECL method also exhibited high selectivity for methyl-cytosine against non-methylated cytosine, guanine, thymine and adenine nucleotides. Finally, original and methylated DNA samples were clearly distinguished with our method using a real DNA bacteriophage sample (48502 base pairs).

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9.

酵素前駆体を用いる電気化学エンドトキシンセンサ
のための高感度検出法の検討

東北大院環境a、東北大μSICb、東北大WPI-AIMRc

井上(安田)久美a,b,高橋 里子a,児玉 隼人,伊野 浩介a,珠玖 仁a,b,c,末永 智一a,b,c

DEVELOPMENT OF HIGHLY SENSITIVE ELECTROCHEMICAL ENDOTOXIN
DETECTION METHOD USING LIMULUS AMEBOCYTE LYSATE ASSAY TECHNIQUE

Kumi Y. INOUEa,b, Hayato KODAMAb, Satoko TAKAHASHIa, Kosuke INOa,
Hitoshi SHIKUa,b,c and Tomokazu MATSUEa,b,c

a Graduate School of Environmental Studies, Tohoku University, 6-6-11 Aoba, Aramaki,
Aoba, Sendai 980-8579, Japan
b R&D Center of Excellence of Integrated Microsystems (μSIC), Tohoku University, 6-6-11
Aoba, Aramaki, Aoba, Sendai 980-8579, Japan
c Advanced Institute of Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira,
Aoba, Sendai 980-8579, Japan

We have developed highly sensitive electrochemical sensors for endotoxin, potentially toxic compounds inducing septic shock. The endotoxin activates reactions of zymogens contained in the Limulus amebocyte lysate (LAL). In this study, we used Boc-Leu-Gly-Arg-p-aminophenol (LGR-pAP) as a substrate for the last step of the LAL cascade reaction. To detect a released pAP (signal molecule) with high sensitivities, substitutional stripping voltammetry was employed. We fabricated a chip consisting of two cells: a sample cell containing mixture of 50 L of endotoxin solution and 50 μL LAL regents with 1 mM LGR-pAP, and a stripping cell containing 70 μL of 10 mM AgNO3. A liquid junction was set between the cells to construct a battery cell like circuit. By connecting the electrodes in the cells, Ag+ in the stripping cell was reduced to Ag to be deposited on the electrode only in the presence of endotoxin in the sample cell. By quantifying the deposited Ag by anode stripping, we could detect as low as 0.1 endotoxin units (EU) L−1 within 2 h.

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10.

核内受容体のアゴニストスクリーニングを
目的としたナノ粒子センサ

九工大院 生命体工

○高辻 義行、 池野 慎也、 春山 哲也

FUNCTIONAL PEPTIDE MODIFIED GOLD NANOPARTICLE FOR AGONIST
SCREENING OF NUCLEAR RECEPTOR

Yoshiyuki Takatsuji, Shinya Ikeno, and Tetsuya Haruyama

Dept. of Biological Functions and Engineering, Kyushu Institute of Technology
Kitakyushu Science and Research Park, Kitakyushu, Fukuoka 808-0196, Japan

It is proposed the novel agonist assay for nuclear receptor (NR) using functional peptide modified gold nanoparticles (GNPs: 15nm). GNPs have unique optical property that spectra of GNPs can change drastically depending on close to each other. This screening system employs functionalized GNPs whose surface were modified with 12 amino acid peptide in sequence of co-activator within nuclear system. Due to the affinity of the peptide, the functionalized GNPs are aggregated faster when nuclear receptor and agonist ligand are co-existed. This agonist screening system can recognize improper ligand(s) through simple method in 30 min. It can be systemized as high through-put screening (HTS) with good reproducibility. It is also possible to expand this system for the other NR. Moreover, it is expected that the method can estimate the force of agonist activity to NR and determine quantity of agonist ligand.

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11.

デジタルホログラフィック顕微鏡による
単一PC12細胞の3次元形態変化の非標識観察と
細胞利用薬物センシングへの応用

富山大院生命融合科学a、富山大院理工b

○ミーア タンビール アハマドa、篠原寛明a, b、須加 実a, b

LABEL-FREE OBSERVATION OF 3D-MORPHOLOGY CHANGE OF A SINGLE PC12
CELL BY DIGITAL HOLOGRAPHIC MICROSCOPY FOR CELL-BASED DRUG SENSING

Tanveer Ahamd MIRa, Hiroaki SHINOHARAa,b, and Minoru SUGAa, b

a Course of Life, Information System Sciences, Graduate School of Innovative Life Science
for Education, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan.
b Field of Life, Information and System Sciences, Graduate School of Science and
Engineering for Research, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan.

Observation of three-dimensional (3D) morphology changes of a single mammalian cell is very useful to understand cell response for various stimuli. Conventional techniques to evaluate morphology changes with sufficient precision and high temporal resolution are limited. Recently, a novel imaging method based on digital holographic microscopy (DHM) was developed for non-labeling microscopic observation of three-dimensional morphology. In this study, DHM was applied to monitor three-dimensional morphology change of individual PC12 cell, a nerve model cell, subjected to high K+ stimulation. Phase images of the rapidly swelling cell were acquired and time-lapse reconstruction of 3D cell morphology was performed from phase images.

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12.

変異型Gタンパク質の最適化による電気生理バイオセンサの高出力化

パナソニックa,京大院工b,パナソニックエレクトロニックデバイスc

○鈴木雅登a,下野 健a, 清中茂樹b,沼田朋大b,森 泰生b,岡 弘章c

OPTIMIZATION OF MUTATED G-PROTEIN FOR ELECTROPHYSIOLOGICAL
BIOSENSOR

○Masato SUZUKIa, Ken SHIMONOa, Shigeki KIYONAKAb, Tomohiro NUMATAb,
Yasuo MORIb and Hiroaki OKAc

1-1a BTDO, Panasonic Corporation, Souraku-gun, Kyoto 619-0237, b Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-shi, Kyoto 615-8510
c Panasonic Electrinic Device Co. Ltd, Kadoma-shi, Osaka 571-8506

We have previously reported to have developed an electrophysiological biosensor for detecting chemical compounds binding to a GPCR by using a chimera G-protein and the inward rectifier potassium channels (Kir 3). The chimera G-protein has determined the performance of this sensor. To improve the sensor output current, thirteen types of mutated G-proteins were designed by swapping C-terminal domain of Gαi protein to corresponding amino acids of Gαolf protein. For evaluation of signal transduction from GPCR to ion channel, the mutated G-protein was heterogeneously expressed in HEK-293T cells with mutated potassium channel (Kir 3.1 (F137S)) and β1 adrenergic receptor. By utilizing of the mutated G-protein dramatically change of inwardly rectifying K+ current was occurred in the presence of β1 agonist (30 nM isoproterenol). As a result, the sensor output current increased 1.5 times by using a new chimera G-protein (Gi/olf94) than reported previously c! himera G-protein (Gi/olfC-ter)

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13.

表面プラズモン共鳴を用いた血液凝固測定

NTTマイクロシステムインテグレーション研究所

○林 勝義、井上鈴代、岩崎 弦、瀬山倫子、堀内 勉、為近恵美

DETERMINATION OF BLOOD COAGULATION BY USING SURFACE PLASMON
RESONANCE

Katsuyoshi HAYASHI, Suzuyo INOUE, Yuzuru IWASAKI, Michiko SEYAMA,
Tsutomu HORIUCHI, Emi TAMECHIKA

NTT Microsystem Integration Laboratories,
Atsugi-shi, Kanagawa 243-0198

We studied on a method of blood coagulation test by using surface plasmon resonance(SPR). We have already reported that SPR measurement method allows us to measure flow velocity near the bottom face of a microchannel. Microchannels with inlet and outlet were fabricated using polydimethyl siloxane (PDMS). First, coagulation trigger regent was introduced into the microchannel, and then standard human plasma was dropped in the inlet. The plasma was introduced into the microchannel by a surface tension driven pump. After the introduction of the plasma, it was mixed with the coagulation trigger regent at an interface between the plasma and the trigger regent. We succeeded in measurement of flow velocity of the interface in the microchannels whose height were less than 100 μm(width:1.0mm, length: 10 mm). And, we also confirmed that the flow velocity correlates with the coagulation activity of plasma.

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14.

マイクロ流体デバイスを用いた微生物の
最小発育阻止濃度測定

筑波大院数理物質a、筑波大院生命環境b

○高木 理香a、長田 啓司b、福田 淳二a、 野村 暢彦b、鈴木 博章a

DETERMINATION OF THE MINIMUM INHIBITORY CONCENTRATION OF ANTIBIOTICS
AGAINST BACTERIA USING A MICROFLUIDIC DEVICE

Rika TAKAGIa, Keiji NAGATAb, Junji FUKUDAa, Nobuhiko NOMURAb
and Hiroaki SUZUKIa

aGraduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8572
bGraduate School of Life and Environmental Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8572

We have developed a disposable and user-friendly microfluidic device that could be used to estimate an appropriate antibiotic and its minimum inhibitory concentration. In this device, a microbial suspension solution was introduced into multiple chambers simultaneously with a very simple procedure. Microbes (Escherichia coli, K-12) introduced into the chambers were exposed to various concentrations of antibiotics (gentamicin) and their growth was quantified using a non-invasive and three-dimensional visualization technique. The length of time required for the determination of the minimum inhibitory concentration was only 12 h after cell seeding.

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15.

電気化学マイクロデバイスによる
ATPase活性測定

筑波大院数理物質

○蔡 智、 木村 翔平、 横川 雅俊、 鈴木 博章

MEASUREMENT OF THE ACTIVITY OF ATPase USING AN ELECTROCHEMICAL MICRODEVICE

Zhi CAI, Shohei KIMURA, Masatoshi YOKOKAWA and Hiroaki SUZUKI

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

A microfluidic device for electrochemical determination of the activity of ATPase, which catalyzes the hydrolysis of ATP into ADP, was fabricated. In a series of enzymatic reactions, one of the final reaction products, hydrogen peroxide (H2O2), was used as an indicator for the ATPase activity and was detected by coulometry. Intermediates, pyruvate and ADP, were detected and linear relationships were observed between the output charge and their concentration, which indicated smooth enzymatic conversion by the experimental protocol. The obtained activity of sample ATPase (GroEL) was consistent with that measured by a conventional spectrophotometric method, which indicated that a highly sensitive measurement of ATPase activity in a sample of a small volume (294 nL) could be achieved using the electrochemical microdevice.

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16.

電気化学チップデバイスを用いた
1細胞からの分泌タンパク質の検出

東北大院・環境a,東北大・WPIb

○伊野浩介a、Mustafa Şena、珠玖仁a、末永智一a,b

ELECTROCHEMICAL CHIP DEVICE
FOR DETECTION OF A SECRETED PROTEIN FROM SINGLE CELLS

Kosuke Inoa, Mustafa Şena, Hitoshi Shikua and Tomokazu Matsuea,b

a JaGraduate School of Environmental Studies, Tohoku University, 6-6-11-604, Aramaki-Aoba,
Aoba, Sendai 980-8579
b World Premier International Research Center, Advanced Institute for Materials Research,
Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577

In this study, we have developed a local redox cycling-based electrochemical chip device for high-throughput cell analyses. In the device, two arrays of band microelectrodes were arranged orthogonally to fabricate a 256 (n2) array of crossing points with only 32 (2n) connector pads for external connection. The crossing points can be used as individual sensors by setting potentials at the column and row electrodes to appropriate values. For detection of the secreted proteins from single cells, the cells were trapped into the microwells on the chip device and cultured to immobilize the secreted proteins. After the cells were removed from the microwells, the immobilized proteins were electrochemically detected. The electrochemical images show that the secreted proteins from the single cells were successfully detected, which indicates that the chip device can be used as high-throughput single cell analyses, such as cell screening, reporter gene assay. We believe that the chip device can provide high-throughput electrochemical assays on cell analysis.

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17.

ELISA法によるBisphenol A測定用マイクロ流体デバイス

創価大工

○久保いづみ、森脇一樹、板津貴之、古谷俊介、金松知幸

A Microfluidic Device for Bisphenol A Sensing Based on ELISA

Izumi KUBO, Kazuki MORIWAKI, Takayuki ITATSU, Shunsuke FURUTANI and
Tomoyuki KANAMATSU

Faculty of engineering, Soka University
Hachioji, Tokyo, 192-8577, Japan

Bisphenol A (BPA) is a major material of polycarbonate, which is used as a food container in our life and known as endocrine disruptor. Animal experiments should be performed to study the effect of BPA on life. To determine the intake of BPA with food in animals, we need a sensing system of BPA with a small amount of biological sample. We have developed a disk-shaped microfluidic device for ELISA with 32 microchannels and chambers. In order to establish a rapid and sensitive assay system of BPA in biological sample, anti BPA antibody was immobilized on micro beads and introduced into microchambers on the microchannels on the device, in this study. Competitive immunoassay was performed using HRP conjugated BPA with a small amount of sample solution with in 20 min.

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18.

Point of Care(POC)診断用プリンテッド
マイクロチップの構築

産総研健康工学a、クラスターテクノロジーb

○渕脇 雄介a、矢部 雄一 b、 安達 良紀 、田中 正人a、 阿部 佳織a、 中原 伴徳a
  山瓶子 勇次a、 片岡 正俊a、 大家 利彦a

FABRICATION OF THE PRINTED MICROCHIP TOWARD POINT-OF-CARE TESTING

Yusuke FUCHIWAKIa, Yuichi YABEb, Yoshinori ADACHIb, Masato TANAKAa, Kaori ABEa, Tomonori NAKAHARAa, Yuji YAMACHOSHIa, Masatoshi KATAOKAa, Toshihiko Ooiea

a Health Research Institute, National Institute of Advanced Industrial Science and
Technology (AIST), Hayashicho 2217-14, Takamatsu, Kagawa 761-0395
b Cluster Technology Co., LTD., Shibukawa-cho 4-5-28, Higashi-Osaka, Osaka 577-0836

Microchips with biological functions now are powerful tools for point-of-care testing. However, the microtechnical production of microchips is very sophisticated and quite expensive. Ink-jet printing technology has developed over recent years into a preferred method of dispensing liquid micro-droplets for the purpose of printing and microfabrication. Advantages offered by this approach include precise volumetric control of dispensed material, data-driven flexibility, low cost, high speed and low environmental impact. In this study, we fabricated multiple single immunoassay chip with the piezoelectric inkjet printing system for the deposition and fixation of the 1st antibody on the microchannel. The microchip determined serum procollagen type I C-peptide (PICP) of a biomarker for bone formation with accuracy, high sensitivity, time saving ability, and low consumption of sample.

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19.

生体成分計測用バイオFETの研究開発(VIII)
緊張ストレス被験者実験の予備的検討

産総研a、近畿能開大b、神大院海事科学c

○脇田 慎一a、宮道 隆a,b、北村 健一c、村井 康二c、福士 惠一c、林 祐司c

R & D OF BIOFET FOR BIOLOGICAL MONITORING(VIII)
PRELIMINARY STUDIES ON SALIVAR SAMPLING FOR STRESS EXPERIMENT

Shin-ichi WAKIDAa, Takashi MIYADOa,b, Ken-ichi KITAMURAc,
Koji MURAIc, Keiichi FUKUSHIc and Yuji HAYASHIc

a National Institute of Advanced Industrial Science and Technology (AIST),
Hayashi 2217-14, Takamatsu, Kagawa 761-0395
Midorigaoka 1-8-31, Ikeda, Osaka 563-8577
b Department of Industrial Chemistry, Kinki Polytechnic College,
Inaba 1778, Kishiwada, Osaka 596-0103
c Graduate School of Maritime Sciences, Kobe University
Fukae-minami 5-1-1, Higashinada, Kobe 658-0022

To measure salivary NO metabolites in clinical study and human engineering study, we have investigated sensing materials and also original biocompatible polymer membrane materials for high performance nitrate ion-selective field-effect transistors (ISFETs).

We prepared highly sensitive and selective prototype of FET NO3- checkers based on NO3--ISFETs using the suitable copper(I) complex as a nitrate-sensing material, 2-nitrophenyldodecylether (NPDDE) as a liquid membrane material (plasticizer) and a segmented poly(urethane-urea) (KP-13) as a bio-compatible polymer material using the commercialized FET pH checker. The FET NO3- checker showed linear characteristics from 10-5.5 M to 10-0.5 M with a response time of less than a few seconds.

The FET NO3- checker showed specific NO3- selectivity against coexisting major Cl- in human saliva. So, we carried out preliminary application of whole human saliva on a ship handling simulator using direct potentiometry with several salivary sampling. We will report preliminary results of salivary sampling for the FET NO3- checker.

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20.


蒸気圧を利用した超高速PCR
マイクロ流体デバイスの開発

産総研健康工学a, b、阪大院工c

○渕脇 雄介a、 永井 秀典b、 斉藤 真人c、 脇田 慎一a、 片岡 正俊a、 大家 利彦a
 民谷 栄一c

DEVELOPMENT OF ULTRA-RAPID FLOW-THROUGH PCR MICROFLUIDICS DEVICE USING VAPOR PRESSURE

Yusuke FUCHIWAKI a, Hidenori NAGAI b, Masato SAITO c,
Shin-ichi WAKIDA a, Masatoshi KATAOKA a, Toshihiko Ooie a, Eiichi TAMIYA c

a Health Research Institute, National Institute of Advanced Industrial Science and
Technology (AIST), Hayashicho 2217-14, Takamatsu, Kagawa 761-0395
b Health Research Institute, National Institute of Advanced Industrial Science and
Technology (AIST), Midorigaoka 1-8-31, Ikeda, Osaka 563-8577
c Department of Applied Physics Graduate School of Engineering,
Yamadaoka 2-1, Suita, Osaka 565-0871

A novel flow-through polymerase chain reaction (PCR) microfluidic system using vapor pressure was developed that can achieve ultra-rapid, small volume, DNA amplification on a chip. The 40cycle amplification can be completed in as little as 120 s, making this device the fastest PCR system in the world. The chip device is made of a pressure sensitive polyolefin (PSP) film and cyclo-olefin polymer (COP) substrate which was processed by cutting work to fabricate the microchannel. The enclosed structure of the microchannel was fabricated solely by weighing the PSP film on the COP substrate, resulting in superior practical application. The vapor pressure in the denaturation zone of the destabilizing flow source was applied to the flow force, and ultra-rapid, efficient amplification was accomplished with a minimal amount of PCR reagents for detection. The flowing rhythm created by vapor pressure minimized the residual PCR products, leading to highly efficient amplification. For field test analysis, airborne dust was collected from a public place and tested for the presence of anthrax. The PCR chip had sufficient sensitivity for anthrax identification. The fastest time from aerosol sampling to detection was theoretically estimated as 8 min.

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21.

分子インプリント高分子固定電極を用いた血液中ヘパリンセンシング

芝浦工業大学応用化学科

○ 吉見 靖男, 佐藤 邦昭, 大島 正規

REAGENTLESS SENSING OF HEPARIN IN WHOLE BLOOD USING AN
ELECTRODE GRAFTED WITH MOLECULARLY IMPRINTED POLYMER

Yasuo YOSHIMI, Kuniaki SATO, Masaki OHSHIMA

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

Control of blood-coagulation is very important for safe operation of extra corporeal circulation. However suitable technology for monitoring anticoagulant in blood is yet to be developed. The purpose of this study is development of a sensor for level of heparin, which is the most well-used coagulant, using an electrode grafted with heparin-imprinted polymer. Indium-tin oxide (ITO) electrode was grafted with poly (methacryloxyethyl trimethylamine chloride-co-acrylamide-co-methylenebisacrylamide) in the presence of heparin. A cyclic voltammetry of bovine whole blood was performed with the grafted electrode. The anodic current was sensitive to the heparin. The result indicates that the electrode grafted with heparin-imprinted polymer can work as a reagentless sensor for heparin in blood.

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22.

分子鋳型技術を利用する細菌センサの開発

阪府大院工a,阪府大21機構b,シャープ(株)c

床波志保b,高橋茉里c,池水麦平c,門馬哲也c ,椎木 弘a,○長岡 勉a

DEVELOPMENT OF BACTERIAL SENSORS FABRICATED BY
MOLECULARLY IMPRINTED POLYMER TECHNIQUES

Shiho TOKONAMI,b Mari TAKAHASHI,c Mugihei IKEMIZU,c
Tetsuya KADOMA,c Hiroshi SHIIGI,a and Tsutomu NAGAOKAa

a Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture
University, 1-2 Gakuen-cho, Sakai, 599-8570
bNanoscience and Nanotechnology Research Center, Osaka Prefecture University, 1-2
Gakuen-cho, Sakai, 599-8570
charp Co., 3-1-72, Kitakamei-cho, Yao, 581-8585

We have successfully developed bacterial sensors based on molecularly imprinted polymers using overoxidized polypyrrole. The molecularly imprinted polymer was prepared by electrochemical overoxidation of polypyrrole, which had been doped with bacilli as a template. The sensor was fabricated on a gold-coated quartz microbalance sensor, and the results of dielectrophoretic QCM measurements demonstrated that the greatest responses resulted from template bacilli rebinding.

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23.

分子鋳型技術を用いるコレステロールセンサの
開発と実用化

阪府大院工a,日本制禦機器(株)b

○長岡 勉a,椎木弘a,高橋 靖典b, 高木 靖浩b

DEVELOPMENT OF PRACTICAL CHOLESTEROL SENSORS BASED ON
MOLECULARLY IMPRINTED POLYMER

Tsutomu NAGAOKAa, Hiroshi SHIIGIa, Yasunori TAKAHASHIb, Yasuhiro TAKAGIb

aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture
University, 1-2 Gakuen-cho, Sakai, Osaka, 599-8570
bJSK Co. Ltd., 1-5-1 Higashi-amakawa, Takatsuki, Osaka, 560-0012

We have developed chemical sensors based on alkanethiol self-assembled monolayers. For fabricating the monolayer based sensor, intermixed monolayers consisting of the alkanethiol and cholesterol were formed on both amorphous and single crystal gold electrodes via the self-assembly precess, and the cholesterol was extracted to produce a slot for rebinding. In this report, the responses of the sensors thus assembled are discussed along with some basic characteristics, such as selectivity. Sensor systems developed based on this concept have been recently commercialized from JSK Co. Ltd, and are validated for food cholesterol quantification.

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24.

イオン注入によるPTFE改質膜を用いたCOセンサの検討

理研計器a、理化学研究所b

○今屋浩志a、岡村 圭a、中野信夫a、石地 徹a、鈴木嘉昭b、高橋勝緒b

DEVELOPMENT OF ELECTROCHEMICAL CO GAS SENSOR USING EXPANDED
POLYTETRAFLUOROETHYLENE MEMBRANE MODIFIED BY ION IMPLANTATION

Hiroshi IMAYAa, Kei OKAMURAa, Nobuo NAKANOa, Toru ISHIJIa,
Yoshiaki SUZUKIb and Katsuo TAKAHASHIb

aRiken Keiki Co., Ltd.,
Itabashi-ku, Tokyo 174-8744
b RIKEN (The Institute of Physical and Chemical Research),
Wako-shi, Saitama 351-0198

An amperometric gas sensor based on electrolysis of CO gas has been developed by using gas permeable membrane made of polytetrafluoroethylene (PTFE))modified by ion implantation technology. The ion implantations of several kinds of ion into PTFE membranes with fluenses of 1×1014 ~5×1015 ions/cm2 was carried out to modify the gas permeable membranes. Gas permeable electrodes were prepared by Au coating on the ion-implanted PTFE membranes. For CO detection, sensors constructed with the ion-implanted gas permeable electrode showed 5.5~38 times higher sensitivity than that used non-ion-implanted one. The selectivity for organic vapor gas such as methanol and iso-propyl alcohol, was improved to more than twice compared with using Pt-Black electrode sensor. In the case of CO detection, the modification of membranes brings an active nature of electrode process of CO oxidation, which improves selectivity of CO. The surface modification of PTFE by ion implantation will be useful method for development of a practical CO gas sensor.

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25.

マルチ電解修飾カーボン電極を用いる可逆的な水素酸化還元波の測定

埼玉工大工

内山俊一、山脇曜輔、林田恵梨子、丸山詩織、松浦宏昭

MEASUREMENT OF REVERSIBLE REDOX WAVES OF HYDROGEN USING
ELECTROLYTICALLY MULTIMODIFIED CARBON ELECTRODE

Shunichi UCHIYAMA, Yosuke YAMAWAKI, Eriko HAYASHIDA, Shiori MARUYAMA and
Hiroaki MATSUURA

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

We obtained a very interesting result of a large electrode oxidation wave of hydrogen molecule appearing after the long-term electrode reduction of the aminated carbon felt electrode in sulphuric acid. The reversible redox waves between the hydrogen ion and the hydrogen molecule can be observed by the introduction of diazo and sulpho groups into the surface of the carbon felt electrode. The introduced diazo group must be stabilised by the introduction of a sulphonic acid group; because an ionic pair (or chemical bond) may form between the positive diazonium ion and the negative sulphonic acid ion. Moreover, we also found that the reduction wave of oxygen appears in the significantly positive potential region after the electrolytic introduction of a sulpho group. In these catalytic electrode reactions, it can be considered that the diazo group and the hydrazino group (or azo group) consist of the catalytic sites for the cell reactions.

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26.

マルチ電解修飾カーボン電極の作製とその溶存水素センサへの応用

埼玉工大工

松浦宏昭、山脇曜輔、佐々木洸輔、内山俊一

FABRICATION OF MULTIELECTROLYTIC MODIFIED CARBON ELECTRODE AND ITS
APPLICATION TO DISSOLVED HYDROGEN SENSOR

Hiroaki MATSUURA, Yosuke YAMAWAKI, Kosuke SASAKI and Shunichi UCHIYAMA

Department of Life Science & Green Chemistry, Faculty of Engineering,
Saitama Institute of Technology, 1690 Fusaiji, Fukaya, Saitama 369-0293

Multielectrolytic modified carbon electrode (MEMCE) was fabricated by using the following electrolytic-oxidation/reduction processes. First, diazo group is introduced by the electrode oxidation of carbon felt electrode in an ammonium carbamate aqueous solution, and next, sulfonic acid group is introduced by the electrode reduction of diazotated carbon felt electrode in sulfuric acid. We found that the reversible redox waves between hydrogen ion and hydrogen molecule at highly positive potential range appear in the cyclic voltammogram obtained by using the MEMCE. A coulometric cell using MEMCE was constructed and was used for the measurement of dissolved hydrogen. The typical current vs. time curve was obtained by the repetitive measurement of the dissolved hydrogen. These curves indicate that the measurement of dissolved hydrogen is finished completely in a short time (~20 s). Hence the present coulometric method could be used for the measurement of the dissolved hydrogen concentration.

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27.

電気化学的に析出させたフタロシアニン薄膜のH2O2検出挙動

九工大

○髙瀨 聡子、清水 陽一

H2O2 SENSING PROPERTIES OF METALLOPHTHALOCYANINE THIN FILM
PREPARED BY ELECTROCHEMICAL DEPOSITION

Satoko TAKASE and Youichi SHIMIZU

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

There are Highly-sensitive H2O2 detection devices need for bio-sensing devices. Also, industrial processes need the devices as control of H2O2 concentration. Metal phthalocyanines (MPc) are known as catalysts for oxygen reduction reaction, and can use as H2O2 detection materials. In this study, MPcs with various centered metal thin-film prepared by electrochemical deposition ITO electrodes. XRD patterns shows that unsubstituted MPcs (M=Co, Ni, Cu, Zn) thin films are α forms. The MPcs thin-films were composed with fibrous crystals and the morphologies were largely dependent on the centered metals in MPcs. Among the MPc electrode, only CoPc-ITO showed the potentiometric response for H2O2 concentration. On the other hand the fluoro-CoPc-ITO showed amperometric highly-sensing for H2O2.

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28.

ポリカチオン含有マンガン酸化物を利用した
全固体型塩化物イオン選択性電極

東京理科大理

○赤塚 達也, 鈴木 千裕, 藪内 直明, 駒場 慎一

ALL-SOLID-STATE CHLORIDE ION-SELECTIVE ELECTRODES
USING POLYCATION-CONTAINING MANGANESE OXIDES

Tatsuya AKATSUKA, Chihiro SUZUKI, Naoaki YABUUCHI, and Shinichi KOMABA

Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku,
Tokyo 162-8601

Manganese oxides can reversibly insert/extract alkali cation, which can be utilized as electrodes for an ion-sensing. Additionally, polycation-containing manganese oxides can reversibly insert/extract anions into/from manganese dioxide inter layers by the electrochemical process. In this study, we examine poly(allylamine)-containing manganese oxides (PAAm-MnOx) for the sensing of chloride ions. The Pt/PAAm-MnOx electrodes show stable potential response to chloride ion in KCl aqueous solution. The PAAm-MnOx electrode, covered with chloride ion selective membrane (Pt/PAAm-MnOx/PVC), exhibits quick and Nernstian response to chloride ion activity, and better potential stability than the electrode without PAAm-MnOx (Pt/PVC). Chronopotentiometric mesurments and AC impedance analysis suggested that PAAm-MnOx as the inner layer effectively reduces the resistance of the all-solid-state electrode, and thus improves the stability for ion-sensing.

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29.

イオノフォア含有可塑化PVC膜
CCD型カルシウムイオンイメージセンサの開発

豊技大電気a, 豊技大物質b,豊技大研究基盤セc

○服部敏明a,加藤絢巳b,加藤亮c,澤田和明b

DEVELOPMENT OF CCD-TYPE CALCIUM ION IMAGE SENSOR
WITH PLASTICIZED PVC MEMBRANE CONTAINED IONOPHORE

Toshiaki Hattoria,b, Ayami Katob, Ryo Katoc and Kazuaki Sawada b

aDepartment of Electrical and Electronic Engineering, bDepartment of Materials Science, cCooperative
Research Facility Center, Toyohashi University of Technology, Toyohashi 441-8580

We developed a CCD-type calcium ion image sensor with plasticized poly(vinyl chloride) (PVC) membrane contained a calcium ionophore. The plasticized PVC membrane contained 4,6-Di-N-octadecylcarbamoyl-3-oxabutyryl-1,7,10,13,19-pentaoxa-4,16-diaza cyclohenicosane (K23E1) as Ca2+ ionophore was prepared by a solution casting method. The out-put signal of sensing pixels linearly increased with logarithmic concentration of calcium ion from 10-5 M to 10-2 M. The sensitivity of calcium ion was high, and the presence of sodium, potassium and magnesium ions little affected the sensor response. The membrane content and the response were comprehensively discussed with our previously reported CCD-type calcium ion image sensor with plasticized PVC membrane contained alkylphosphate exchanger. The CCD sodium ion image sensor displayed real-time images of calcium ion concentration, and can dynamically monitor instant changes of calcium ion concentration.

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30.

PVCと水との界面を横切る促進イオン移動ボル
タンメトリー応答に基づく金属イオンのフローインジェクション分析

九大院工

 ○石松亮一、中野幸二、今任稔彦

FLOW INJECTION ANALYSIS OF METAL CATIONS BASED ON
FACILITATED ION TRANSFER ACROSS THE PVC AND WATER INTERFACE

Ryoichi ISHIMATSU, Koji NAKANO and Toshihiko IMATO

Graduate School of Engineering, Kyushu University,
744 Motooka, Nishi-ku, Fukuoka 819-0395

We have revealed that the facilitated ion transfer of metal cations, such as K+, Li+, and Ca2+, across the interface between plasticized PVC and water interface is electrochemically quasireversible. The heterogeneous rate constant (k0) is estimated in the range of 10-2-10-3 cm s-1. The kinetic information is very important for sensor applications because the response time should depend on the kinetics. For the better understanding, we simulated the effect of kinetics on the hydrodynamic voltammetry. The kinetics affects on the shape of voltammogram. To reach the diffusion-limited steady state current of metal cation from water to PVC, more negative potential is applied. The slower kinetics decrease current response slightly for the flow injection analysis.

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31.

Pt-Ti-OゲートSi-MISFETの窒素ガス環境下水素および酸素の応答特性

日立中研

○宇佐川 利幸、 菊池 洋太

HYDROGEN AND OXYGEN RESPONSE OF Pt-Ti-O GATE Si-MISFETs
UNDER NITROGEN ATMOSPHERE

Toshiyuki USAGAWA , Yota KIKUCHI

Central Research Laboratory, Hitachi, Ltd.,
Kokubunji, Tokyo 185-8601

We have reported N2 gas-diluted 1% hydrogen gas response properties for Pt-Ti-O gate Si-MISFET hydrogen gas sensors. We also reported a stability data of sensing amplitude for 9 repeated hydrogen expose every 7minitutes. The average sensing amplitude is 624.4 mV with standard deviation of 7.27mV. The rising response time is so fast around 0.4s. The turning off properties of the sensor shows similar tailing like air-dilured hydrogen gas response. According to the logarithm-linear sensor characteristics of hydrogen concentration dependence, the accuracy of the measured hydrogen concentration will be less influenced by this tailing behavior. We also investigated the Pt-Ti-O gate Si-MISFETs as for oxygen gas sensors. The oxygen removing response of the FETs after N2-gas expose show a long tail behavior which will be approximately described logarithmic linear function of time expected from Elovich (or Roginsky-Zeldovich) equation. The direction of Vth shift is identical to hydrogen gas expose, which is reverse change for the hitherto-developed Si-MIS type oxygen sensors

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32.

陽極酸化TiO2膜とPd-Pt電極を用いた
ダイオード型H2センサの特性改善
-電極へのポリマーコーティング-

長崎大院工1,長崎大院生産2

○山本 剛1,山下 友樹2,松尾 勝秀1,兵頭 健生1,清水 康博1

IMPROVEMENT IN H2 SENSING PROPERTIES OF DIODE-TYPE GAS SENSORS FABRICATED WITH ANODIZED TiO2 FILMS AND POLYMER-COATED Pd-Pt ELECTODES

Go YAMAMOTO1, Tomoki YAMASHITA2, Katsuhide MATSUO1, Takeo HYODO1 and Yasuhiro SHIMIZU1

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

Diode-type gas sensors (Pd-Pt/TiO2) have been fabricated with anodized TiO2 films and Pd-Pt alloy electrodes and the improvement in the H2 sensing properties of Pd-Pt/TiO2 by polytetrafluoroethylene (PTFE) or polyvinyl alcohol (PVA) coating on their electrodes has been performed in this study. The H2 response of all sensors in wet air was larger than that in dry air. The coating of relatively thin polymer films on the Pd-Pt electrodes was effective for improving the H2 response of Pd-Pt/TiO2, but the H2 response tended to decrease with an increase in the thickness of the polymer films on the electrodes. In addition, O2 concentration dependence of H2 response of the sensor was not improved, but the humidity dependence was improved in some cases, by the polymer coating of the Pd-Pt electrodes.

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33.

安定化ポリ(N-イソプロピルアクリルアミド)微粒 子の作製とそのHClガス吸着特性

愛媛大院理工

大森智史、○松口正信

PREPARATION OF STABILIZED POLY(N-ISOPROPYLACRYLAMIDE)
NANOPARTICLES AND ITS HCl GAS ADSORPTION PROPERTIES

Satoshi OMORI and Masanobu MATSUGUCHI

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

Stabilized nanoparticles, composed of cross-linked Poly(N-isopropylacrylamide) (PNIPAM) with ethyleneglycol dimethacrylate (EGDMA), were prepared by precipitation polymerization via atom transfer radical polymerization (ATRP). The PNIPAM nanoparticles without crosslinking (P-PNIPAM) were soluble in water below the lower critical solution temperature (LCST) at 32ºC, however, PNIPAM nanoparticles cross-linked with 1.5 mol % EGDMA (SP-PNIPAM) were stable in water below LCST. SP-PNIPAMs were loaded on the quartz crystal and its HCl gas adsorption/desorption properties were investigated. Adsorption/desorption properties were affected by the SP-PNIPAM loads on the crystal. Especially the reversibility worsened and the response time lengthned with increasing the SP-PNIPAM loads, although the P-PNIPAM showed the fast and reversible response even at larger loads.

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34.

カーボンナノチューブアレイ電極とガス選択性

立命大院理工

○大前 政輝,橋新 剛,玉置 純,小島 一男

CARBON NANOTUBES ARRAY ELECTRODES AND GAS SELECTIVITY

Masaki OMAE, Takashi HASHISHIN, Jun TAMAKI, Kazuo KOJIMA

Department of Applied Chemistry,
Ritsumeikan University, Kusatsu-shi, Shiga 525-8577

Multi-walled carbon nanotubes (MWCNTs) array with about 40 nm in diameter and 500 to 1300 nm in length was directly grown on the Au interdigitated electrodes by radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD). The growth catalyst at the tip of MWCNTs array was clarified to be Ni/Ni3C/MWCNT by transmission electron microscope (TEM) and selected area electron diffraction (SAED). The sensing properties of MWCNTs array to NO2, H2S, CH3SH and C8H10 were investigated at operating temperature from 100 to 250°C. The resistance changes to sulfur gases were higher than those to NO2sub and C8subH10. It was suggested that Ni at the tip was sulfidized to be NiS in sulfur gases and that the p-n junction was formed at the interface between p-type NiO and n-type NiS leading to selectivity to sulfur gases.

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35.

球状酸化セリウムナノ粒子から作製したCOセンサ

産総研

○伊豆典哉、松原一郎、伊藤敏雄、申ウソク、西堀麻衣子

CO SENSOR PREPARED FROM SPHERICAL CERIUM OXIDE NANOPARTICLES

Noriya IZU, Ichiro Matsubara, Toshio ITOH, Woosuck SHIN, Maiko NISHIBORI
National Institute of Advanced Industrial Science and Technology (AIST),
Nagoya, Aichi 463-8560

Last time we reported very fast response CO sensors. However we needed to increase response of the sensor to apply for industry. In this study, we prepared cerium oxide thick films which consisted of clustered grains prepared from core-shell cerium oxide / polymer hybrid nanoparticles as a raw material and investigated sensing properties of them. As a result, it is clarified that the response to CO gas of the cerium oxide thick film made from the core-shell nanoparticles are better than that of cerium oxide thick film made from nanoparticles prepared by precipitation. Furthermore, the response increased when Au nanoparticles are added on the surface of the cerium oxide thick films.

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36.

電池駆動半導体式COセンサの検知機構

エフアイエス株式会社a、長崎大院工b、長崎大院生産c

栗林 晴美a、島袋 宗春a、松本 晋一a、稲澤 領a、清水 康博b、兵頭 健生b、阿久津 竜馬c

DETECTION MECHANISM OF A BATTERY DRIVEN SEMICONDUCTOR CO SENSOR

Harumi KURIBAYASHIa, Muneharu SHIMABUKUROa, Shinichi MATSUMOTOa,
Osamu INAZAWAa, Yasuhiro SHIMIZUb, Takeo HYODOb, and Ryoma AKUTSUc

a FIS Inc., 3-36-3 Kitazono, Itami, Hyogo 664-0891
bGraduate School of Engineering, Nagasaki University,
1-14 Bunkyo-machi, Nagasaki 852-8521
c Graduate School of Science and Technology, Nagasaki University,
1-14 Bunkyo-machi, Nagasaki 852-8521

We have been developing a battery driven mini-bead type semiconductor CO sensor using a periodic heater ON/OFF operating method. In this report, we have focused on the mechanism of CO response at room temperature during the OFF period. Using a TPD-MS analysis, we have found that the CO response arose mainly from CO adsorption on Pd loaded SnO2.

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37.

SnO2ナノ粒子ガスセンサにおける水素応答
メカニズムの検討

九大院総理工

○末松 昂一、湯浅 雅賀、木田 徹也、山添 曻、島ノ江 憲剛

STUDY ON THE SENSING MECHANISM TO HYDROGEN GAS FOR GAS SENSORS USING
SnO2 NANO PARTICLES

Koichi SUEMATSUa, Masayoshi YUASAb, Tetsuya KIDA b,
Noboru YAMAZOEb, Kengo SHIMANOEb

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

In the previous work, we reported that the oxygen adsorbs as an O2- in extremely dry atmosphere over 350oC. In this study, we aimed to confirm the oxygen adsorption species and sensing mechanism to the hydrogen in dry or wet atmosphere. They were investigated by the relationships between the electric resistance and oxygen partial pressure and between sensor response and hydrogen partial pressure. The obtained results indicated that the oxygen adsorbs as O- and O2- by the competitive adsorption below 350oC in dry atmosphere. Additionally, in wet atmosphere, O2- adsorption seems to be disturbed by H2O adsorption which decreases the electric resistance, and thus the oxygen adsorbs as O-. On the other hand, the sensor response to hydrogen in wet atmosphere was lower than that in dry atmosphere because the O- adsorption species react with hydrogen after consuming the O2- adsorption species.

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38.

水熱処理法によるパラジウム担持 酸化スズクラスターの調製とそのガス検知特性

九大院総理工

進 由佳、○末松 昂一、湯浅 雅賀、木田 徹也、島ノ江 憲剛

GAS SENSING PROPERTIES OF PD-LOADED SNO2 CLUSTER SOLS PREPARED BY HYDROTHERMAL TREATMENT

Yuka SHINa, Koichi SUEMATSUa, Masayoshi YUASAb, Tetsuya KIDA b,
Kengo SHIMANOEb

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

Based on material designs of receptor function and utility factor, Pd-loaded SnO2 cluster sols were prepared by hydrothermal treatment. A mixture of stannic acid gel (SnOH4) and Pd(NO2)2(NH3)2 solution was hydrothermally treated at 200oC for 3h at 10MPa. In the process, the pH control in hydrothermal treatment was important for controlling the cluster size. The suitable loading amount of Pd was 0.1 mol%, which was very lower than those of usual Pd-loaded SnO2 prepared by impregnation method, meaning that the loaded Pd is dispersed finely on SnO2 cluster. The obtained Pd-loaded SnO2 cluster was deposited on alumina substrate with Au electrodes by spin coating method to fabricate thin film type sensors. The sensor of Pd-loaded SnO2 cluster showed higher gas response compared with the devices fabricated from SnO2 sols, SnO2 cluster and Pd-loaded SnO2 sols. Especially the response to toluene gas, large size gas molecule, was enhanced by introducing designs of receptor function and utility factor.

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清山賞受賞講演2

酸化スズ系半導体ガスセンサの
基礎および応用技術の研究開発

大阪ガス株式会社

大西 久男

BASIC AND APPLIED RESEARCH AND DEVELOPMENT OF
TIN OXIDE-BASED SEMICONDUCTOR GAS SENSORS

Hisao OHNISHI

Energy Technology Laboratories, Osaka Gas Co., Ltd.,
Konohana-ku, Osaka 554-0051

The fundamental sensing mechanism of tin oxide semiconductor gas sensors put to practical use for gas alarms was revealed by the model to clarify the electrical conduction mechanism and the reaction mechanism on the tin oxide surface. By utilizing of this knowledge, we have developed a highly selective methane sensor based on the highly sensitive tin oxide thin film with nano-columnar structure and a selective catalyst layer. By combining the MEMS technology with highly selective methane sensors, ultrashort pulse driving become possible, and a battery-powered micro methane sensor has been developed.

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特別講演2

匂いセンシングと嗅覚ディスプレイ

東京工業大学理工学研究科

中本 高道

ODOR SENSING SYSTEM AND OLFACTORY DISPLAY

Takamichi NAKAMOTO

Graduate School of Science and Engineering, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152-8552

An odor sensing system using multiple sensors with different characteristics and pattern recognition technique has been studied. Here we focus on the sensing system robust against environmental changes such as concentration, temperature and humidity. We introduced short-time Fourier Transform for preprocessing of sensor responses to odors with irregularly changing concentrations. It was found that short-time Fourier Transform was effective to extract the feature related to sensor-response speed. It was implemented into an odor recognition chip for real-time application. Moreover, the novel preconcentrator without adsorbent will be presented. Another topic is an olfactory display, smell-presentation device. The multi-component olfactory display, the exploration of odor components and its application to a new multimedia platform will be explained at the conference.

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39.

アルミニウムイオン伝導体を用いた
低温作動型炭酸ガスセンサ

阪大院工a、学振b

○永井つかさa, b、田村真治a、今中信人a

LOW TEMPERATURE OPERABLE CO2 GAS SENSOR BASED ON
TRIVARENT ALUMINUM CATION CONDUCTING SOLID ELECTROLYTE

Tsukasa NAGAIa, b, Shinji TAMURAa, Nobuhito IMANAKAa

aDepartment of Applied Chemistry, Faculty of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b Japan Society for the Promotion of Science
1-8 Chiyoda-ku, Tokyo 102-8472, Japan

Solid electrolyte type carbon dioxide gas (CO2) sensor operable at moderate temperature was fabricated by using trivalent aluminum cation conducting (Al0.2Zr0.8)20/19Nb(PO4)3 solid electrolyte. The Nd2O2CO3-(0.52Li2CO3-0.48Na2CO3) solid and Al metal thin film were selected as the auxiliary sensing electrode and reference electrode, respectively, to produce a sensor that exhibits superior sensing performance in terms of a quantitative, continuous and reproducible response with obeying the theoretical Nernst relationship at the temperature as low as 350°C. Since the sensor exhibited stable CO2 gas detection over 2 months, it is expected to be a practical on-site CO2 gas detecting tool.

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40.

室温作動型固体電解質 CO2 センサの NO2 雰囲気の影響

a北九州高専, b九工大院

○小畑 賢次a,b, 松嶋 茂憲a,b.

INFLUENCE OF NO2 GAS IN SOLID-STATE ELECTROLYTE-BASED CO2 SENSOR OPERATIVE AT ROOM TEMPERATURE

Kenji OBATAa,b and Shigenori MATSUSHIMAa,b

aDepartment of Materials Science and Chemical Engineering,
Kitakyushu National College of Technology,
5-20-1 Shii, Kokuraminami-ku, Kitakyushu-shi 802-0985
bGraduate School of Life Science and Systems Engineering,
Kyushu Institute of Technology,
Kitakyushu Science and Research Park, 2-4 Hibikino, Wakamatsu-ku, Kitakyushu-shi
808-0196

The CO2 sensor operative at room temperature was fabricated by applying a solid-state electrolyte (NASICON (Na3Zr2Si2PO12) or LISICON (LiTi2(PO4)3)), ITO (indium tin oxide) and an auxiliary phase (Li2CO3-BaCO3 (1:2 in molar ratio) or Li2CO3-In2O3 (4:1 in molar ratio)). Their CO2 sensing properties and the cross sensitivities to NO2 (2 – 7 ppm) were measured under 30 %RH (relative humidity) between 30 and 100 °C. The NO2 cross sensitivities of the ITO-attached NASICON sensor with Li2CO3-BaCO3 was estimated to be 29.0 mV at 30 oC. In contrast, the ITO-attached NASICON sensor with Li2CO3-In2O3 demonstrated fairly good CO2 sensing properties and were not affected much by NO2 coexisting in the atmosphere. The 90 % response time was within 10 min and the EMF values were proportional to the logarithm of CO2 concentration. When the sensor was operated in the range of 250 – 2500 ppm CO2 at 30 oC, the EMF (electromotive force) change was 30.4 mV. In addition, when the sensor operated in the range of 2 – 7 ppm NO2 at 30 oC, the NO2 cross sensitivity was estimated to be 3.7 mV.

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41.

プレナー型ジルコニアセンサのエタノール及びトルエンに対する応答性評価

愛媛大学理工学研究科a、日本特殊陶業株式会社技術開発本部b

○森 雅美a、 定岡 芳彦a、 小島 多喜男b、 喜田 真史b、 中川 伸一b

RESPONSE BEHAVIOR OF THE PLANAR-TYPE ZIRCONIA SENSOR FOR THE
ETHANOL AND TOLUENE DETECTION

Masami MORIa, Yoshihiko SADAOKAa, Takio KOJIMA b, Masahito KIDAb,
Shinichi NAKAGAWAb

a Graduate School of Science and Engineering, Ehime University,
3 Bunkyo-cho, Matsuyama, Ehime 790-8577
bFuture Products Project, New Product Planning & Development Center, Engineering R&D Group, NGK Spark Plug Co., Ltd.
2808 Iwasaki, Komaki-shi, Aichi 485-8510

A planar-type zirconia sensor having (Pt/YSZ)/YSZ/(Pt/YSZ) structure was fabricated, and one of the Pt/YSZ electrode was coated with MgAl2O4, Au, Au/YSZ powder. The EMF response of fabricated sensors to ethanol and toluene at sub-ppm levels was examined. The coating of the Pt/YSZ electrode with MgAl2O4, Au, Au/YSZ powder induced decreasing the oxide ion activity at triple phase boundary and increasing the EMF response. The response behavior depended on the thickness of the over coated layer and material. The use of the Au/YSZ working electrode instead of the Pt/YSZ working electrode resulted in the enhancement of the sensing response.

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42.

混成電位型ジルコニアセンサのC7H8検知特性に対するシミュレーション

九大院総理工a、National Research Council Canada b、九大産学連携センターc

○佐藤 伴光a、Ken Darcovichb、三浦 則雄c

SIMULATING TOLUENE SENSING BEHAVIOR
IN MIXED-POTENTIAL TYPE YSZ-BASED SENSORS

○Tomoaki SATOa, Ken DARCOVICHb, Norio MIURA c

aInterdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580
bInstitute for Chemical Process and Environmental Technology, National Research
Council Canada, Ontario K1A 0R6, Canada
cArt, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580

The toluene (C7H8) sensing behavior for a yttria-stabilized zirconia (YSZ)-based sensor utilizing a NiO sensing electrode (SE) was simulated with a computational model. The developed model considered the following simultaneous phenomenon: gas species diffusion within the microporous NiO electrode, adsorption, desorption and ionization of oxygen on NiO particles at high temperature, as well as the catalytic oxidation of toluene. The sensing signal was expressed with the Butler-Volmer equation, which was applied at the triple-phase boundary of the sensing electrode. Parameters for toluene sensitivity were fit to a mixed-potential sensing model to obtain the electromotive force (emf) of the YSZ-based sensor utilizing NiO-SE exposed to C7H8 at ppb levels. Good agreement was observed between simulated and experimental emf values within the concentration range of 50 to 300 ppb. This validated model will be used for future parametised studies.

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43.

金属酸化物修飾Au電極を用いた混成電位式アンモニアセンサ

日本特殊陶業a、北海道大b、名古屋大c

○菅谷聡a、柿元志郎a、中埜吉博a、小島多喜男a、清水研一b、薩摩篤c

MIXED POTENTIAL AMMONIA SENSORS USING Au ELECTRODE
MODIFIED BY METAL OXIDES

Satoshi SUGAYAa, Shiro KAKIMOTOa, Yoshihiro NAKANOa,
Takio KOJIMAa, Kenichi SHIMIZUb and Atsushi SATSUMA c

a NGK Spark Plug Co., Ltd.
Komaki-shi, Aichi 485-8510
bCatalysis Research Center, Hokkaido University,
Sapporo, Hokkaido 000-0021
c Graduate School of Engineering, Nagoya University,
Nagoya-shi, Aichi 464-0814

Mixed potential ammonia sensors with Au electrode modified by various metal oxides were fabricated, and influences of these metal oxides on suppression effect of interference by C3H6 and H2O were investigated. Also, stability of the metal oxides at high temperature and reactivity with YSZ were examined. As a result of model gas tests, sensors with Co3O4 added Au electrode showed favorable property; good gas selectivity and less interference by H2O. From our experiments, it was suggested that interaction between H2O and metal oxides was important factor affecting interference by H2O

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44.

SELECTIVE H2 DETECTION OF YSZ-BASED SENSOR UTILIZING SnO2
SENSING-ELECTRODE WITH AN ADDITIONAL
CATALYTIC LAYER OF Cr2O3

M. YAMAGUCHIa , S. A. ANGGRAINIa, Y. FUJIOa, M. BREEDONb,c, N. MIURAc

a Interdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580
bJapan Society for the Promotion of Science (JSPS), Tokyo 102-8472
c Art, Science and Technology Center for Cooperative Research, Kyushu
University, Kasuga-shi, Fukuoka 816-8580

A yttria-stabilized zirconia (YSZ) based mixed-potential-type sensor utilizing SnO2 (+ 30 wt.% YSZ)-SE has been fabricated, and was found to be capable of detecting H2 sensitively at 550oC. In order to enhance the selectivity towards H2, a selective C3H6 oxidation catalyst was employed to minimize unwanted responses from interfering gases. Among the examined metal oxides, Cr2O3 demonstrated the capability to oxidize C3H6 selectively, with only minimal effect on H2 sensing performance. Thus, the YSZ-based sensor using SnO2 (+ 30 wt.% YSZ)-SE coated with a catalyst layer of Cr2O3 and Al2O3 intermediate layer was constructed and its sensing characteristics were examined. The sensor was found to be capable of generating a sensitive response toward H2, with only minor responses toward HCs and NOx gases at an operating temperature of 550oC under humid conditions (21 vol.% O2 and 1.35 vol.% H2O). The sensor had a linear response relationship when plotted against H2 concentration within 20 - 800 ppm H2 on a logarithmic scale, indicating that the sensing mechanism is in good agreement with mixed-potential theory.

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45.

MECHANISM OF GAS INSESITIVITY FOR Mn-BASED
REFERENCE-ELENCTRRODE UTILIZED IN
YSZ-BASED GAS SENSORS

○Han JINa, Michael BREEDONb,c, Norio MIURAc

aInterdisciplinary Graduate School of Engineering Sciences, Kyushu University,
Kasuga-shi, Fukuoka 816-8580
bJapan Society for the Promotion of Science, Tokyo 102-8421 c Art, Science and Technology Center for Cooperative Research, Kyushu University,
Kasuga-shi, Fukuoka 816-8580

A possible working mechanism for a Mn-based reference-electrode (RE) used in the yttria-stabilized zirconia (YSZ)-based gas sensors is proposed here. It was observed visually via EDX measurements that after calcination at high temperature, Mn ions diffused into YSZ, forming a solid-solution (Mn-YSZ) with the YSZ. Additionally, the response transients toward different concentrations of oxygen for the sensors comprised of Mn-based (or Mn-YSZ) sensing-electrode (SE) and Pt/air-RE was compared. The similar sensing behavior of these sensors indicates that the Mn-YSZ solid-solution is the primary cause of the gas insensitivity of the Mn-based-RE. Furthermore, it was confirmed that the content of Mn ions in the YSZ reached its solubility limit after calcination. Based on these results, we postulated that, due to the existence of the Mn ions in the YSZ, adjacent oxygen vacanciesⅤo¨ may be trapped near the manganese ions at operational temperatures ≤550oC, resulting in insensitivity towards not only O2 but also to other various gases.

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46.

LaGaO3系固体電解質を用いた電流検出型COセンサ(6)検知特性に及ぼす酸素の影響と低減

九大院工

○石原 達己、 岩田 純、 萩原 英久、 伊田 進太郎

AMPEROMETRIC CO SENSOR USING LaGaO3 BASED SOLID ELECTROLYTE (6)REDUCTION OF OXYGEN ON SENSING PROPERTY AND THE REDUCTION

Tatsumi ISHIHARA, Jun IWATA, Hidehisa HAGIWARA and Shintaro IDA

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

In our previous study, it was found that CO can be detected sensitively by difference of catalytic activity to CO oxidation. Sensing properties for CO in various gas atmospheres were studied by using 10wt%Au-In0.95Sn0.05O1.5 cathode, RuO2-La0.6Sr0.4CoO3 anode and La0.9Sr0.1Ga0.8Mg0.2O3 electrolyte. In this study, we studied the influence of coexisting gas on CO sensing property. Coexistence of H2, CH4 and CO2 shows almost no influence on CO sensitivity, however, O2 shows large influence on CO sensitivity. Effects of additives on cathode to O2 coexistence influence were studied. It was found that addition of oxide to cathode affected the oxygen concentration dependence. In particular, addition of Ce(La,Pr)O2 to cathode was the most effective for reducing of oxygen concentration dependence.

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