JPS6355662B2 - - Google Patents
Info
- Publication number
- JPS6355662B2 JPS6355662B2 JP56062775A JP6277581A JPS6355662B2 JP S6355662 B2 JPS6355662 B2 JP S6355662B2 JP 56062775 A JP56062775 A JP 56062775A JP 6277581 A JP6277581 A JP 6277581A JP S6355662 B2 JPS6355662 B2 JP S6355662B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- block
- upper block
- flow channel
- detector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000007788 liquid Substances 0.000 claims description 18
- 125000006850 spacer group Chemical group 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000004832 voltammetry Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003943 catecholamines Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Automatic Analysis And Handling Materials Therefor (AREA)
Description
【発明の詳細な説明】
本発明は、改良された電極構造を有するマイク
ロフローセル型ボルタンメトリー検出器に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a microflow cell voltammetric detector having an improved electrode structure.
マイクロフローセル型ボルタンメトリー検出器
は、液体クロマトグラフイーやフローインジエク
シヨンアナリシス等の検出器として用いられ、キ
ヤリヤ流体中に含まれる酸化又は還元性の原子団
（感応基）をもつ物質や無機イオンに感応するも
のである。マイクロフローセルは、その名称が示
す通り、被験液が流通する極微サイズのフローチ
ヤンネルを形成するために、上部ブロツクと下部
ブロツクとをわずかな間隙で対向させ、この間隙
中でチヤンネル四周を区画するための開口を備え
たスペーサを用いるものである。従来、上下各ブ
ロツクはテフロン（登録商標名）系又はアクリル
系樹脂等の電気絶縁物からなり、下部ブロツクに
は前記フローチヤンネルに露出する作用電極を埋
設し、上部ブロツクにはフローチヤンネルへの液
入口及び出口を形成すると共に、液出口となる埋
設パイプ（金属製）を作用電極に対する補助電極
（対極）として用いるのが一般的である。 Micro flow cell type voltammetry detectors are used as detectors for liquid chromatography, flow injection analysis, etc., and are used to detect substances with oxidizing or reducing atomic groups (sensitive groups) and inorganic ions contained in the carrier fluid. It is something to be sensitive to. As the name suggests, a micro flow cell is a system in which an upper block and a lower block are opposed to each other with a small gap, and the four circumferences of the channel are divided in this gap to form an extremely small flow channel through which the test liquid flows. This uses a spacer with an opening. Conventionally, the upper and lower blocks are made of an electrical insulator such as Teflon (registered trademark) or acrylic resin, the lower block has a working electrode embedded in it that is exposed to the flow channel, and the upper block has a working electrode that is exposed to the flow channel. It is common to use a buried pipe (made of metal), which forms an inlet and an outlet and serves as a liquid outlet, as an auxiliary electrode (counter electrode) for the working electrode.
この場合、上部ブロツクには液出口付近の流通
液に接する参照電極をさらに設け、この参照電極
電位を制御信号として作用電極―対極間印加電圧
を制御し、その正確を期すものであるが、前記の
ような対極位置の片寄り、すなわちフローチヤン
ネルの要部に露出した作用電極に対し、比較的細
長い流路を経て対極が位置していることによる電
極間インピーダンスによる検出電流の応答遅れが
生じたり、フローチヤンネルの液流の脈動などが
検出ノイズとなり種々の不都合を生じることにな
る。 In this case, the upper block is further provided with a reference electrode in contact with the flowing liquid near the liquid outlet, and the applied voltage between the working electrode and the counter electrode is controlled using this reference electrode potential as a control signal to ensure accuracy. In other words, the response of the detection current may be delayed due to the impedance between the electrodes due to the counter electrode being located through a relatively long and narrow flow path with respect to the working electrode exposed in the main part of the flow channel. , pulsation of the liquid flow in the flow channel, etc. become detection noise and cause various inconveniences.
このことは、本発明者が先に発明した複数作用
電極型ボルタンメトリー検出器においては、電極
数に応じて顕著に現れる問題である。 This is a problem that becomes more pronounced depending on the number of electrodes in the multiple working electrode type voltammetry detector that the present inventor previously invented.
本発明はマイクロフローセル型ボルタンメトリ
ー検出器における上述したような不都合を改良す
るために、作用電極と向かい合う上部ブロツクそ
のものを、導電性材料からなる対極として形成し
たボルタンメトリー検出器を提供しようとするも
のである。 In order to improve the above-mentioned disadvantages of micro flow cell type voltammetry detectors, the present invention aims to provide a voltammetry detector in which the upper block itself facing the working electrode is formed as a counter electrode made of a conductive material. .
第１図は、本発明のマイクロフローセル型ボル
タンメトリー検出器の実施例を示すもので、検出
器本体１は、上部ブロツク２、スペーサ３及び下
部ブロツク４からなる三層構造を有する。上部ブ
ロツク２は、本発明に従つて補助電極（すなわ
ち、対極）を兼用するため、ステンレス、白金、
グラシカーボン等の電気良導体であつて、適度な
鋼性を有するものが採用される。スペーサ３及び
下部ブロツク４はテフロン系樹脂又はアクリル系
樹脂等の絶縁性物質からなつている。スペーサ３
は細長いフローチヤンネル５を上、下ブロツク
２，４間に形成するための開口を打抜いたもので
あり、チヤンネル５の範囲内で対向する上、下ブ
ロツク２，４の面は平滑に仕上げられている。上
部ブロツク２には、フローチヤンネル５の一端に
通ずる液入口管６が填設されると共に、フローチ
ヤンネル５の他端に通ずる参照電極支持孔７が形
成される。この支持孔７には上方より、参照電極
８が挿入されると共に、上部ブロツク２の図にお
ける左端面から挿入された液出口管９が連通して
いる。 FIG. 1 shows an embodiment of the micro flow cell type voltammetry detector of the present invention, in which the detector main body 1 has a three-layer structure consisting of an upper block 2, a spacer 3 and a lower block 4. The upper block 2 is made of stainless steel, platinum,
A good electrical conductor, such as glassy carbon, with appropriate steel properties is used. The spacer 3 and the lower block 4 are made of an insulating material such as Teflon resin or acrylic resin. Spacer 3
An opening is punched out to form an elongated flow channel 5 between the upper and lower blocks 2 and 4, and the surfaces of the upper and lower blocks 2 and 4 that face each other within the range of the channel 5 are finished smooth. ing. A liquid inlet pipe 6 communicating with one end of the flow channel 5 is inserted into the upper block 2, and a reference electrode support hole 7 communicating with the other end of the flow channel 5 is formed. A reference electrode 8 is inserted into the support hole 7 from above, and a liquid outlet pipe 9 inserted from the left end face of the upper block 2 in the figure is communicated with it.
下部ブロツク４には、この実施例ではマルチエ
レクトロードセルとするために、10個の作用電極
１１，１２〜２０が填設され、各作用電極の上端
面が下部ブロツク４の上面においてフローチヤン
ネル５に露出するようになつている。 The lower block 4 is filled with ten working electrodes 11, 12 to 20 in order to form a multi-electrode cell in this embodiment, and the upper end surface of each working electrode is connected to the flow channel 5 on the upper surface of the lower block 4. It's becoming more exposed.
検出器のための電気回路は、各作用電極に接続
された入力線を有する電流検出回路２１と、この
検出回路の各入力に対応する出力線に接続された
増幅回路２２と、この増幅回路の出力に接続され
た信号処理装置２３及び指示記録計２４を備えて
いる。 The electrical circuit for the detector includes a current detection circuit 21 having an input line connected to each working electrode, an amplifier circuit 22 connected to an output line corresponding to each input of this detection circuit, and It includes a signal processing device 23 and an indicator recorder 24 connected to the output.
各作用電極１１，１２〜２０は、さらに電流検
出回路２１を介して電圧制御回路２５に接続され
る。電圧制御回路２５は、導線２６によつて参照
電極８に接続された参照入力端子２７と、導線２
８によつて補助電極たる上部ブロツク２に接続さ
れた対極電位端子２９とを有する。 Each working electrode 11, 12-20 is further connected to a voltage control circuit 25 via a current detection circuit 21. The voltage control circuit 25 includes a reference input terminal 27 connected to the reference electrode 8 by a conductor 26, and a reference input terminal 27 connected to the reference electrode 8 by a conductor 26.
8 and a counter electrode potential terminal 29 connected to the upper block 2 as an auxiliary electrode.
以上の構成において、フローチヤンネル５に液
入口管６から導入した被験液を液出口管９に向け
て流通させ、補助電極ブロツク２と各作用電極と
の間に流れる電流を検出することにより、被験液
を、正確かつ高感度、及び速応的に分析すること
ができる。指示記録計２４は、電極電流を並列的
に作図するが、信号処理装置２３は例えば、各電
極電位を横軸に、対応する各同一成分ピークの各
電流を縦軸にしたボルタモグラムを演算すること
ができる。この場合、電圧制御回路２５は、参照
電極８の電位を基準として上部ブロツク（補助電
極）２と、各作用電極１１，１２〜２０との間に
各所定の電圧を印加する。 In the above configuration, the test liquid introduced from the liquid inlet pipe 6 into the flow channel 5 is caused to flow toward the liquid outlet pipe 9, and the current flowing between the auxiliary electrode block 2 and each working electrode is detected. Liquids can be analyzed accurately, with high sensitivity, and quickly. The indicator recorder 24 plots the electrode currents in parallel, but the signal processing device 23 calculates, for example, a voltammogram with each electrode potential on the horizontal axis and each current of the corresponding same component peak on the vertical axis. I can do it. In this case, the voltage control circuit 25 applies each predetermined voltage between the upper block (auxiliary electrode) 2 and each of the working electrodes 11, 12-20 with reference to the potential of the reference electrode 8.
第２図及び第３図は、いずれも試料としてカテ
コーラミンの標準品を用い、それぞれ従来型（液
出口パイプを補助電極とするもの）、及び本発明
の実施例によるボルタンメトリー検出器で測定し
た場合の記録曲線である。 Figures 2 and 3 show the results of measurements using a conventional type (using a liquid outlet pipe as an auxiliary electrode) and a voltammetry detector according to an embodiment of the present invention, respectively, using a standard catecholamine as a sample. This is a recording curve.
第２図のグラフA1，A2……A10はそれぞれ補助
電極との電位差が200、300、……1100mVと、順
次100mVずつ高い電位とした各作用電極につい
ての測定電流である。また、第３図のB1，B2…
…B10も同様に順次100mVずつ高い電位とした各
作用電極の測定電流である。 Graphs A 1 , A 2 . . . A 10 in FIG. 2 are the measured currents for each working electrode whose potential difference with the auxiliary electrode was 200, 300, . Also, B 1 , B 2 ... in Fig. 3
... B10 is the measured current of each working electrode, which was similarly raised in potential by 100 mV.
第２図から明らかな通り、従来型検出器では電
位の低い電極のグラフ（A1が最も顕著である）
ほど、成分ピーク（右方突出）の前に、負（左方
突出）の干渉を受けピークの大きさも全体として
比較的小さい。一方、第３図に示す本発明の検出
器によるグラフでは、上記のような負の干渉又は
ノイズはほとんどなく、ピークも全体として比較
的大きいことが明らかである。従つて、本発明に
より、感度、応答性及び分析精度を高めうること
は明らかである。 As is clear from Figure 2, in the conventional detector, the graph of electrodes with low potential (A 1 is the most prominent)
Therefore, negative interference (leftward protrusion) occurs before the component peak (rightward protrusion), and the size of the peak is relatively small as a whole. On the other hand, in the graph of the detector of the present invention shown in FIG. 3, it is clear that there is almost no negative interference or noise as described above, and that the peaks are relatively large as a whole. Therefore, it is clear that the present invention can improve sensitivity, responsiveness, and analytical accuracy.
また、本発明によれば、単体の補助電極を要し
ないため、構造的にも簡単になる。 Further, according to the present invention, since a single auxiliary electrode is not required, the structure is also simplified.
第１図は本発明の検出器の実施例を示す断面及
びブロツク線図、第２図は従来の検出器による測
定曲線図、第３図は本発明の検出器による同一試
料の測定曲線図である。
２……上部ブロツク兼対極、３……スペーサ、
４……下部ブロツク、５……フローチヤンネル、
６……液入口管、７……参照電極支持孔、８……
参照電極、９……液出口管、１１，１２〜２０…
…作用電極。
Fig. 1 is a cross-sectional and block diagram showing an embodiment of the detector of the present invention, Fig. 2 is a measurement curve diagram by a conventional detector, and Fig. 3 is a measurement curve diagram of the same sample by the detector of the present invention. be. 2... Upper block and counter electrode, 3... Spacer,
4... lower block, 5... flow channel,
6...Liquid inlet pipe, 7...Reference electrode support hole, 8...
Reference electrode, 9...Liquid outlet pipe, 11, 12-20...
...working electrode.
Claims (1)
鋼性材料からなり、一面を平滑に仕上げた上部ブ
ロツクと、 絶縁材料からなり、前記上部ブロツクの平滑面
に対応する平滑面を有する下部ブロツクと、前記
上部及び下部ブロツク間に位置し、それらブロツ
クの間隔中で被験液を流通させるためのフローチ
ヤンネルを画成する開口を有してなるスペーサ
と、 前記フローチヤンネルに連通するように前記上
部ブロツクに形成された液入口及び液出口、並び
に 一端面が前記フローチヤンネル内で前記下部ブ
ロツクの平滑面上に露出するように同ブロツクに
埋設された少くとも１個の作用電極とを備え、 前記上部ブロツクを前記少くとも１個の作用電
極と協同する対極として用いることを特徴とする
マイクロフローセル型ボルタンメトリー検出器。 ２ 前記液出口に参照電極を付設し、参照電極電
位を基準として前記作用電極と、前記補助電極と
の間の電位差を制御するようにした特許請求の範
囲第１項記載の検出器。 ３ 下部ブロツクに順次間隔して埋設された複数
の前記作用電極を備えた特許請求の範囲第１項又
は第２項記載の検出器。[Claims] 1. An upper block made of metal or other electrically conductive and chemically stable steel material with a smooth finish on one side, and an insulating material that corresponds to the smooth surface of the upper block. a lower block having a smooth surface; a spacer located between the upper and lower blocks and having an opening defining a flow channel for allowing a test liquid to flow through the space between the blocks; a liquid inlet and a liquid outlet formed in the upper block so as to communicate with each other; and at least one function embedded in the lower block such that one end surface is exposed on the smooth surface of the lower block within the flow channel. a microflow cell type voltammetric detector, comprising: an electrode, wherein the upper block is used as a counter electrode in cooperation with the at least one working electrode. 2. The detector according to claim 1, wherein a reference electrode is attached to the liquid outlet, and the potential difference between the working electrode and the auxiliary electrode is controlled based on the reference electrode potential. 3. The detector according to claim 1 or 2, comprising a plurality of the working electrodes embedded in the lower block at sequential intervals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56062775A JPS57175950A (en) | 1981-04-24 | 1981-04-24 | Micro-flow cell type voltammetry detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56062775A JPS57175950A (en) | 1981-04-24 | 1981-04-24 | Micro-flow cell type voltammetry detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57175950A JPS57175950A (en) | 1982-10-29 |
| JPS6355662B2 true JPS6355662B2 (en) | 1988-11-04 |
Family
ID=13210080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56062775A Granted JPS57175950A (en) | 1981-04-24 | 1981-04-24 | Micro-flow cell type voltammetry detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57175950A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0295955U (en) * | 1989-01-14 | 1990-07-31 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3307154C2 (en) * | 1983-03-01 | 1986-08-21 | Gerhard Dipl.-Ing. 8000 München Rall | Method and device for electrochemical detection |
| JPS6085359A (en) * | 1983-10-14 | 1985-05-14 | Matsushita Electric Works Ltd | Substance quantification |
-
1981
- 1981-04-24 JP JP56062775A patent/JPS57175950A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0295955U (en) * | 1989-01-14 | 1990-07-31 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57175950A (en) | 1982-10-29 |
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