JPH0545180B2 - - Google Patents
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- Publication number
- JPH0545180B2 JPH0545180B2 JP62033310A JP3331087A JPH0545180B2 JP H0545180 B2 JPH0545180 B2 JP H0545180B2 JP 62033310 A JP62033310 A JP 62033310A JP 3331087 A JP3331087 A JP 3331087A JP H0545180 B2 JPH0545180 B2 JP H0545180B2
- Authority
- JP
- Japan
- Prior art keywords
- reference electrode
- sample
- liquid
- flow path
- solution
- 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 - Lifetime
Links
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000523 sample Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- 230000005484 gravity Effects 0.000 description 7
- 230000005404 monopole Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 210000000601 blood cell Anatomy 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Landscapes
- Investigating Or Analysing Biological Materials (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はオープン流絡方式の比較電極に係り、
特に流絡部の接液面の電位が安定でかつ小量検体
に適した比較電極に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an open flow type reference electrode,
In particular, the present invention relates to a reference electrode that has a stable potential on the liquid-contacted surface of the flow junction and is suitable for small-volume specimens.
従来のこの種の比較電極として、H.F
Osswoldの比較電極がある（Diss・ETH 6480
注 Hidgen Ossischen Technisehen
Hochshule Zurich Jurir Druch＋Verlang
Zurich1979）。また、実開昭59−29759号に示され
たものがある。
As a conventional reference electrode of this type, HF
There is an Osswold reference electrode (Diss・ETH 6480
Note Hidgen Ossischen Technisehen
Hochshule Zurich Jurir Druch＋Verlang
Zurich1979). There is also one shown in Utility Model Application Publication No. 59-29759.
〔発明が解決しようとする問題点］
ところが、上記Ｈ・Ｆ Osswoldの比較電極で
は、上下に直線上に置かれたφ0.8mmの試料流路に
上方から試料を流し、その中間部へ斜下方から試
料流路より細い流路から比較電極液を流し込むこ
とにより、接液面の乱れを極力小さくしている。
しかるに、比較電極液を細い流路に導く為の継手
部に気泡が付着し、微小気泡が流路部に時々流れ
込んだり、比較電極中の極微小夾雑物が細い流路
を閉塞させるなど、長時日の安定性が得られない
欠点があつた。[Problems to be Solved by the Invention] However, in the H.F. By pouring the reference electrode solution through a channel that is narrower than the sample channel, turbulence on the surface in contact with the liquid is minimized.
However, air bubbles may adhere to the joint for guiding the reference electrode solution into a narrow channel, and microbubbles may occasionally flow into the channel, or microscopic contaminants in the reference electrode may clog the narrow channel. The drawback was that it did not provide stability over time or day.
また、実開昭59−29759号記載のものにおいて
は、比較電極流路又は試料流路に開閉弁を設け、
接液面の乱れを防止することを特徴としている。
しかし、試料液と比較電極液との間に比重の差が
ある場合、接液面における長時間の安定性が得ら
れないうえ、開閉弁のない流路に圧力変動が発生
した場合に、接続面の乱れが瞬時に発生するなど
の欠点があつた。 In addition, in the method described in Utility Model Application Publication No. 59-29759, an on-off valve is provided in the reference electrode flow path or the sample flow path,
The feature is that it prevents disturbance of the liquid contact surface.
However, if there is a difference in specific gravity between the sample solution and the reference electrode solution, long-term stability on the surface in contact with the liquid cannot be achieved, and if pressure fluctuations occur in a flow path without an on-off valve, connection may be difficult. There were drawbacks such as surface disturbance occurring instantaneously.
その他従来例として第４図の縦断面図および第
５図の下面図に示すように構成されたものがあ
る。これは、試料液と比較電極液との間の比重差
については、比較電極流路２９を長くとることが
でき改良はなされているが、比較電極液中の気泡
による問題、試料入口２７より供給される標準液
中の気泡による問題、比較電極２２、接地電極２
１の寿命の点について配慮がされておらず、装置
の信頼性について問題があつた。 Other conventional examples include those constructed as shown in the vertical sectional view of FIG. 4 and the bottom view of FIG. 5. This is because the difference in specific gravity between the sample liquid and the reference electrode liquid has been improved by making the reference electrode flow path 29 longer; Problems caused by bubbles in the standard solution, reference electrode 22, ground electrode 2
No consideration was given to the lifespan of the device, and there were problems with the reliability of the device.
気泡の発生する要因は、供給される比較電極
液、標準液は室温以下であるのに対して、装置内
部では種々の電気部品からの放熱によつて40℃〜
50℃に上昇するため、試薬に溶存している空気が
温度上昇と共に過飽和となつて気泡となる等の温
度変化によるものと、配管の都合上配管径に変化
があり、流路内部で流れが乱流となり、この時に
気泡が発生する等、装置内流路系での物理的変化
によるものである。また、比較電極セル２０内の
試料流路２８が直角に曲つているため、試料入口
２７より供される試薬中の気泡が完全に抜けない
ことがある。一般に、イオン濃度分析計の流路の
構成としては気泡等を考慮して鉛直方向にするこ
とが条件とされている。 The reason for the generation of bubbles is that while the reference electrode solution and standard solution supplied are at room temperature or below, the temperature inside the device is 40℃ or higher due to heat dissipation from various electrical components.
As the temperature rises to 50℃, the air dissolved in the reagent becomes supersaturated and forms bubbles as the temperature rises, and the diameter of the piping changes due to the flow inside the flow path. This is due to physical changes in the flow path system within the device, such as turbulent flow and the generation of bubbles at this time. Furthermore, since the sample channel 28 in the reference electrode cell 20 is curved at a right angle, air bubbles in the reagent supplied from the sample inlet 27 may not be completely removed. Generally, the configuration of the flow path of an ion concentration analyzer is required to be vertical in consideration of air bubbles and the like.
第４図に示す比較電極セル２０の場合、比較電
極２２、接地電極２１をセル内に挿入している
が、測定感度を高めるため電極表面積をできる限
りとることで図示のように流路径が異なつてい
る。更に、流路が袋小路状となつている。このた
め、一旦微細な気泡が混入するとかど部（Ａ部）
に蓄積してしまい正確な測定ができなくなる。 In the case of the comparison electrode cell 20 shown in Fig. 4, the comparison electrode 22 and the ground electrode 21 are inserted into the cell, but in order to increase the measurement sensitivity, the electrode surface area is taken as much as possible, so that the flow path diameters are different as shown in the figure. It's on. Furthermore, the flow path is in the shape of a dead end. For this reason, once fine air bubbles are mixed in, the corner part (A part)
It accumulates and makes accurate measurements impossible.
本発明の目的は、比較電極セル内に供給される
比較電極液、標準液中の微細な気泡の影響がな
く、液絡部の接液面の多少の乱れにもかかわらず
安定した液間電位が得られ、かつ小量試料にも適
した比較電極を提供することにある。 The purpose of the present invention is to provide a liquid junction potential that is not affected by minute bubbles in the reference electrode solution and standard solution supplied into the reference electrode cell, and that has a stable liquid junction potential despite some disturbance of the liquid contact surface of the liquid junction. It is an object of the present invention to provide a reference electrode that can be obtained and is also suitable for small-volume samples.
上記目的は、試料流路を鉛直方向にクランク状
にし、比較電極液の流入口をクランク部の鉛直上
に開口させることにより、達成される。
The above object is achieved by making the sample channel vertically crank-shaped and opening the reference electrode liquid inlet vertically above the crank part.
試料流路を鉛直方向にクランク状にし、比較電
極液の流入口をクランク部の鉛直上に開口させ
る。それによつて、試料の比重，比較電極液の比
重差からくる接液面の乱れ、及び比較電極液がイ
オン濃度検知器へ落下して影響を与えることを排
除することになるので、誤測定することがなくな
る。
The sample channel is shaped like a crank in the vertical direction, and the inlet for the reference electrode solution is opened vertically above the crank part. This eliminates disturbances on the wetted surface due to differences in the specific gravity of the sample and the reference electrode solution, as well as the influence of the reference electrode solution falling onto the ion concentration detector, thereby preventing erroneous measurements. Things will disappear.
以下、本発明の一実施例を第１図の縦断面図お
よび第２図の下断面図により説明する。
Hereinafter, one embodiment of the present invention will be described with reference to the longitudinal cross-sectional view of FIG. 1 and the bottom cross-sectional view of FIG. 2.
図において、１は比較電極セルボデイ、２は内
部液封入形液膜比較電極、３は試料液入口、４は
試料液出口、５は比較電極液入口、８は試料と比
較電極液との開口部、９はクランク流路部であ
る。試料流路と比較電極液流路１９は、万一発生
した気泡が蓄積しないように、内径の変化をすく
なくする構造と（内径φ1mm程度）とされている。 In the figure, 1 is a reference electrode cell body, 2 is an internal liquid-filled liquid film reference electrode, 3 is a sample liquid inlet, 4 is a sample liquid outlet, 5 is a reference electrode liquid inlet, and 8 is an opening between the sample and the reference electrode liquid. , 9 is a crank flow path section. The sample flow path and the reference electrode liquid flow path 19 are designed to minimize changes in inner diameter (inner diameter approximately 1 mm) to prevent any air bubbles from accumulating.
第３図により本発明の使用例を説明する。試料
液出管１３が配設された比較電極２の下位に試料
流入管１６を有する例えばカリウムイオン単極１
４がある。カリウムイオン単極１４の信号線１５
は電極２ａ及び接地線１８との間に設けられた電
気回路１７により電気的に処理される。 An example of use of the present invention will be explained with reference to FIG. For example, a potassium ion monopole 1 has a sample inflow tube 16 below a reference electrode 2 in which a sample liquid outlet tube 13 is disposed.
There are 4. Signal line 15 of potassium ion monopole 14
is electrically processed by an electric circuit 17 provided between the electrode 2a and the ground line 18.
次に本発明の動作を説明する。今人間の全血が
試料流入管１６を経て試料流出管１３へ流れて系
を充流した時流れが止まる。次いで比較電極入口
５から比較電極液が試料流出管１３へ向つて流れ
る。その時点よりカリウムイオン濃度に応じた電
位差が現われる。一般的に、イオン電極を測定す
る場合約30秒間は一定の電位が必要である。 Next, the operation of the present invention will be explained. When human whole blood now flows through the sample inlet tube 16 to the sample outlet tube 13 to fill the system, the flow stops. Next, the reference electrode liquid flows from the reference electrode inlet 5 toward the sample outflow tube 13 . From that point on, a potential difference appears that corresponds to the potassium ion concentration. Generally, when measuring with an ion electrode, a constant potential is required for about 30 seconds.
今、開口部８近辺では、全血に対して比較電極
液、一般には１モル濃度の塩化カリウム水溶液で
あるので比重が大きく、若し試料流路がクランク
状でなく上下に長い管であれば、30秒間内に落下
してきてカリウムイオン単極１４に至り、誤差を
与える。また、測定時間内にカリウムイオン単極
１４に影響を与えない程度に試料流路を上下方に
延ばしてやることは可能であるが、一般に緊急検
査装置において、使用する試料量は100μlと限ら
れておりこの量がかなり増えることになり、現実
的ではない。クランク状にするということは、流
路の水平部分においては比較電極液が落下すると
いうことはなく、万一液が動いても、測定時間内
に落下するなどということはない。クランク内の
容量は13μl以下にでき、使用する試料を増やすこ
とはなくなる。 Now, in the vicinity of the opening 8, the reference electrode solution, generally a 1 molar potassium chloride aqueous solution, has a high specific gravity compared to the whole blood. , the potassium ion falls within 30 seconds and reaches the potassium ion monopole 14, giving an error. Additionally, it is possible to extend the sample flow path vertically to the extent that it does not affect the potassium ion monopole 14 within the measurement time, but the sample volume used in emergency testing equipment is generally limited to 100 μl. This amount would increase considerably, which is not realistic. The crank shape means that the reference electrode solution will not fall in the horizontal portion of the channel, and even if the solution moves, it will not fall within the measurement time. The volume inside the crank can be reduced to 13 μl or less, eliminating the need to increase the number of samples used.
人間の全血のカリウムイオン濃度は５ミリモル
程度であり0.1ミリモル程度の誤差しか許容でき
ないとすると、塩化カリウム水溶液の１万分の１
が落下してきてもいけない。また、塩化カリウム
水溶液の比重よりも血球の比重が大きいから、若
し流路１９が水平位置よりも比較電極液入口５の
側が下方に傾斜していると、試料流出口１３より
血球が落下して透過膜１２まで至り塩橋が成り立
たなくなる。しかるに、本発明の如く試料流路が
クランク状であれば、測定時間内に塩化カリウム
水溶液がカリウムイオン単極１４に落下すること
も、多少の圧力変動があつたとしても血球が透過
膜にまで到達することがない。 The potassium ion concentration in human whole blood is about 5 mmol, and if we can only tolerate an error of about 0.1 mmol, then it is 1/10,000 of the potassium chloride aqueous solution.
Don't let it fall. Furthermore, since the specific gravity of blood cells is higher than the specific gravity of the potassium chloride aqueous solution, if the flow path 19 is inclined downward on the side of the reference electrode solution inlet 5 than in the horizontal position, the blood cells will fall from the sample outlet 13. It reaches the permeable membrane 12, and a salt bridge is no longer established. However, if the sample flow path is crank-shaped as in the present invention, the potassium chloride aqueous solution will not fall onto the potassium ion monopole 14 within the measurement time, and even if there is some pressure fluctuation, blood cells will not reach the permeable membrane. never reach it.
なお、開口部８の位置はクランクの鉛直上の上
下どの位置においてもよい。 Note that the opening 8 may be positioned anywhere vertically above or below the crank.
以上の説明から明らかなように本発明によれ
ば、液絡部の接液面が圧力変動又は比重の差によ
る多少の乱れにもかかわらず安定した液間電位が
得られ、かつ測定時間内に比較電極液が他の電極
まで落下影響せず、また測定時間に血球の落下に
よる液間電位の変動しない小量試料に適した比較
電極を得ることができる。
As is clear from the above description, according to the present invention, a stable liquid junction potential can be obtained even though the liquid contact surface of the liquid junction has some disturbance due to pressure fluctuations or differences in specific gravity, and within the measurement time. It is possible to obtain a reference electrode suitable for a small amount of sample in which the reference electrode solution does not fall and affect other electrodes, and the potential between the liquids does not fluctuate due to falling blood cells during the measurement time.
第１図は本発明の一実施例による比較電極の縦
断面図、第２図は本発明の一実施例による比較電
極の下面図、第３図は実施例の使用例の説明図、
第４図は従来の比較電極の縦断面図、第５図は従
来の比較電極の下面図である。
１……比較電極セルボデイ、２……内部液入形
液膜比較電極、９……クランク流路部、５……比
較電極液入口、８……開口部。
FIG. 1 is a longitudinal sectional view of a comparison electrode according to an embodiment of the present invention, FIG. 2 is a bottom view of a comparison electrode according to an embodiment of the present invention, and FIG. 3 is an explanatory diagram of an example of use of the embodiment.
FIG. 4 is a longitudinal sectional view of a conventional comparison electrode, and FIG. 5 is a bottom view of the conventional comparison electrode. DESCRIPTION OF SYMBOLS 1... Comparison electrode cell body, 2... Internal liquid filled type liquid film comparison electrode, 9... Crank channel section, 5... Reference electrode liquid inlet, 8... Opening.
Claims (1)
流路を鉛直方向でクランク状に構成し、かつ比較
電極液の流入口を試料流路クランク部の鉛直上に
開口させたことを特徴とする比較電極。1. A reference electrode of an open liquid junction type, characterized in that the sample flow path is configured vertically in the shape of a crank, and the inlet for the reference electrode liquid is opened vertically above the crank portion of the sample flow path. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62033310A JPS63201562A (en) | 1987-02-18 | 1987-02-18 | Reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62033310A JPS63201562A (en) | 1987-02-18 | 1987-02-18 | Reference electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63201562A JPS63201562A (en) | 1988-08-19 |
| JPH0545180B2 true JPH0545180B2 (en) | 1993-07-08 |
Family
ID=12382985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62033310A Granted JPS63201562A (en) | 1987-02-18 | 1987-02-18 | Reference electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63201562A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015105168A1 (en) | 2014-01-10 | 2015-07-16 | 大日本印刷株式会社 | Decorative sheet and decorative laminate, and processes for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102454114B1 (en) | 2014-06-20 | 2022-10-14 | 가부시키가이샤 호리바 세이사꾸쇼 | Reference electrode |
-
1987
- 1987-02-18 JP JP62033310A patent/JPS63201562A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015105168A1 (en) | 2014-01-10 | 2015-07-16 | 大日本印刷株式会社 | Decorative sheet and decorative laminate, and processes for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63201562A (en) | 1988-08-19 |
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