JPH0792448B2 - Probe electrode - Google Patents
Probe electrodeInfo
- Publication number
- JPH0792448B2 JPH0792448B2 JP63078698A JP7869888A JPH0792448B2 JP H0792448 B2 JPH0792448 B2 JP H0792448B2 JP 63078698 A JP63078698 A JP 63078698A JP 7869888 A JP7869888 A JP 7869888A JP H0792448 B2 JPH0792448 B2 JP H0792448B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- carbon
- probe
- probe electrode
- carbon material
- 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
- 239000000523 sample Substances 0.000 title claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000008280 blood Substances 0.000 description 7
- 210000004369 blood Anatomy 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 102000001554 Hemoglobins Human genes 0.000 description 5
- 108010054147 Hemoglobins Proteins 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 241000555678 Citrus unshiu Species 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- IQUGDGIIAQZHGL-UHFFFAOYSA-L iron(2+);dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Fe+2] IQUGDGIIAQZHGL-UHFFFAOYSA-L 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Ceramic Products (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、シャープペンシル用芯と同様な方法で製造
された炭素棒を電極として使用するプローブ電極に関す
る。TECHNICAL FIELD The present invention relates to a probe electrode using a carbon rod manufactured by a method similar to that of a mechanical pencil lead as an electrode.
（従来の技術） 従来、プローブ電極としてはグラファイト、グラッシー
カーボン等の炭素電極、白金、銀、金或は水銀等が使用
されてきた。(Prior Art) Conventionally, carbon electrodes such as graphite and glassy carbon, platinum, silver, gold or mercury have been used as probe electrodes.
（発明が解決しようとする課題） しかし、白金，銀、金等は高価であり、また水銀につい
ては毒性の問題がある。(Problems to be Solved by the Invention) However, platinum, silver, gold and the like are expensive, and mercury has a problem of toxicity.
一方、炭素電極についてはグラファイト、アモルファス
カーボン等の炭素材を焼結して得られた炭素棒が電極と
して使用されているが、このような炭素電極については
炭素材の焼結体であるため、機械的な強度を大にするこ
とができず、したがって径の太いものしか得られず、被
測定物に突き刺して使用できるような径の細い丈夫なも
のは得られない。On the other hand, for the carbon electrode, a carbon rod obtained by sintering a carbon material such as graphite or amorphous carbon is used as an electrode, but since such a carbon electrode is a sintered body of the carbon material, The mechanical strength cannot be increased, and therefore, only the one having a large diameter can be obtained, and the durable one having a small diameter which can be used by piercing the object to be measured cannot be obtained.
また炭素電極棒の機械的な強度を大にするために、炭素
材中に粘土などの結合材を混入すると、電極反応を阻害
する不純物などのため高感度の測定ができない等の難点
がある。Further, if a binding material such as clay is mixed in the carbon material in order to increase the mechanical strength of the carbon electrode rod, there is a problem that high sensitivity measurement cannot be performed due to impurities that hinder the electrode reaction.
そこで、この発明においては機械的な強度が大で、しか
も純粋な炭素材の焼結体と同様な正確な電極反応が再現
性よく得られるような炭素電極棒を開発する目的で鋭意
研究の結果、シャープペンシル用芯、例えば市販されて
いるシャープペンシル用芯（商品名：三菱ユニ、三菱鉛
筆株式会社製）は炭素材、不活性雰囲気中又は非酸化性
雰囲気中で焼成すると炭素化物を残す有機物の粘結剤及
び重金属を含まない鉱油を混練、押し出し形成した後、
高温で焼成し、更に油含浸して製造されるが（化学技術
誌MOL昭和57年10月号別冊１〜６頁三菱鉛筆株式会社研
究部 川窪隆昌著「鉛筆の芯」）、これと同様な製造方
法で得られた炭素棒が以上のような条件に適う電極とな
ることを見出し、この発明を完成したものである。Therefore, in the present invention, as a result of earnest research for the purpose of developing a carbon electrode rod having a large mechanical strength and capable of reproducibly obtaining an accurate electrode reaction similar to that of a sintered body of a pure carbon material. , Mechanical pencil lead, for example, commercially available mechanical pencil lead (trade name: Mitsubishi Uni, manufactured by Mitsubishi Pencil Co., Ltd.) is a carbon material, an organic substance that leaves a carbonized product when fired in an inert atmosphere or a non-oxidizing atmosphere. After kneading and extruding the mineral oil containing no binder and heavy metal,
It is produced by baking at high temperature and further impregnating with oil (Chemical Technical Journal MOL October 1982, Supplement, pages 1-6, Takamasa Kawakubo, Research Department, Research Department, Mitsubishi Pencil Co., Ltd.). The inventors have found that the carbon rod obtained by the manufacturing method serves as an electrode that meets the above conditions, and completed the present invention.
（課題を解決するための手段） 即ち、この発明においては炭素材、有機物の粘結剤及び
重金属を含まない鉱油を混練、押出形成した後、高温で
焼成し、更に油含浸して製造された炭素棒を電極として
使用するプローブ電極を提案するものである。(Means for Solving the Problems) That is, in the present invention, a carbon material, an organic binder, and a mineral oil that does not contain a heavy metal are kneaded, extruded and formed, followed by firing at a high temperature and further impregnated with oil. A probe electrode using a carbon rod as an electrode is proposed.
この発明において炭素材としてはグラファイト、アモル
ファスカーボン等を使用するとことができる。In the present invention, graphite, amorphous carbon or the like can be used as the carbon material.
また有機物の粘結剤としては、不活性雰囲気中または非
酸化性雰囲気中で焼成すると炭素化物を残す有機物であ
って、具体的に酸化ビニル樹脂、ポリエチレン樹脂、ア
クリル樹脂等の熱可塑性樹脂、フェノール樹脂、エポキ
シ樹脂等の熱硬化性樹脂の初期縮合物、コールタールピ
ッチ、アスファルト、セルロース誘導体、ルグニン誘導
体等の公知の有機物質が挙げられるが、その中でも酢酸
ビニル樹脂、エポキシ樹脂或はフェノール樹脂が望まし
い。The organic binder is an organic substance that leaves a carbonized product when baked in an inert atmosphere or a non-oxidizing atmosphere, and specifically includes a thermoplastic resin such as vinyl oxide resin, polyethylene resin, acrylic resin, or phenol. Resins, initial condensates of thermosetting resins such as epoxy resins, and known organic substances such as coal tar pitch, asphalt, cellulose derivatives, and lignin derivatives are listed. Among them, vinyl acetate resins, epoxy resins, or phenol resins are desirable.
更に、重金属を含まない鉱油としては、スピンドル油、
シリコン油等を挙げることができる。Further, as the mineral oil containing no heavy metal, spindle oil,
Silicon oil etc. can be mentioned.
この他にDOP,DBP,DBS,BPBG等の可塑剤を加えてもよく、
これらの成分は混練して棒状に押出成形した後、高温度
で焼成する。In addition to this, you may add plasticizers such as DOP, DBP, DBS, BPBG,
These components are kneaded, extruded into a rod shape, and then fired at a high temperature.
焼成は、例えば空気中で180℃にて10時間熱処理して、
可塑剤を除去した後、窒素雰囲気中で常温から300℃迄
は10℃/hr、300℃から1000℃迄は30℃/hrで昇温させ、1
000℃にて１時間焼成する。Firing is, for example, heat treatment at 180 ℃ in air for 10 hours,
After removing the plasticizer, increase the temperature from room temperature to 300 ° C at 10 ° C / hr and from 300 ° C to 1000 ° C at 30 ° C / hr in a nitrogen atmosphere.
Bake at 000 ° C for 1 hour.
なお、この発明における好ましい成分例及び配合割合を
示すと、下記の通りである。In addition, the preferable component example and compounding ratio in this invention are as follows.
天然グラファイト75〜85％。フェノール樹脂の初期縮合
物12〜13％をスピンドル油で混練して焼成するものであ
る。Natural graphite 75-85%. 12-13% of the initial condensate of phenol resin is kneaded with spindle oil and fired.
（発明の効果） 以上のように、この発明に係るブローブ電極は有機物の
粘結剤、炭素材、重金属を含まない鉱油を混練、押出成
形した後、高温で焼成し、更に油含浸して得られた炭素
棒を電極とするものであり、このため機械的な強度が大
であり、径を細くしても十分な機械的な強度が得られる
と同時に、炭素材の焼結体からなる炭素電極棒と同様に
バックグランド電流が小さく、再現性のよい良好な電極
反応を行なわせることができる。(Effects of the Invention) As described above, the probe electrode according to the present invention is obtained by kneading and extruding an organic binder, a carbon material, and a mineral oil containing no heavy metal, firing at high temperature, and further impregnating with oil. The resulting carbon rod is used as an electrode, so it has a high mechanical strength, and even if the diameter is reduced, sufficient mechanical strength can be obtained, and at the same time, a carbon made of a sintered carbon material is used. Similar to the electrode rod, the background current is small, and good electrode reaction with good reproducibility can be performed.
また、この発明に係るプローブ電極はPb,Cd,As,Fe,Si,A
l,Sb,Cr,Ca,Mg,k,Na,Ti,Hg,Baなどの重金属類が含まれ
ていないため、毒性がない。Further, the probe electrode according to the present invention is Pb, Cd, As, Fe, Si, A
It is not toxic because it does not contain heavy metals such as l, Sb, Cr, Ca, Mg, k, Na, Ti, Hg and Ba.
したがって、この発明の電極は、電気分析装置、電流電
位を測定する装置用の電極及び電解反応、電池反応検出
用電極、液クロマトグラフイ、電気泳動用のプローブ電
極などとして使用可能であり、また環境分析用プロー
ブ、センサーとして使用可能であり、更に生体内の電
流、電位検出用プローブ、ンサ電極として使用可能であ
り、またおもちゃなど毒性安全性を問題とする部位の電
極として使用可能である。Therefore, the electrode of the present invention can be used as an electroanalyzer, an electrode for an apparatus for measuring a current potential and an electrolytic reaction, an electrode for detecting a battery reaction, a liquid chromatograph, a probe electrode for electrophoresis, and the like. It can be used as an environmental analysis probe and sensor, as well as an in-vivo current and potential detection probe and a sensor electrode, and can also be used as an electrode at a site where toxicity safety is a problem, such as toys.
なお、この発明に係るプローブ電極の表面を酵素等で修
飾することによって生体内の電流を、電位検出用プロー
ブ、センサー電極として使用することもでき、またその
表面に酸化物を蒸着することにより酸素等のガスセンサ
ー電極として使用することもできる。It should be noted that by modifying the surface of the probe electrode according to the present invention with an enzyme or the like, the current in the living body can be used as a potential detection probe or a sensor electrode, and by depositing an oxide on the surface, oxygen can be obtained. Etc. can also be used as a gas sensor electrode.
（実施例） 以下、この発明の実施例を示す。(Example) Hereinafter, the Example of this invention is shown.
実施例１ クロマトグラフ、電気泳動などの分離流出液系のプロー
ブ電極として使用した例 0.3mmφのシャープペンシル用芯（商品名：三菱ユニ，
三菱鉛筆株式会社製）をプローブ電極として使用し、第
１図に示すようにクロマトグラフ分離後流出するフラク
ションの液溜１中にプローブ電極２及び参照極３と対極
４を挿入し、２回以上サイクリックボルタモグラム（c,
v曲線）を測定した。Example 1 Example of use as a probe electrode for separation effluent system for chromatography, electrophoresis, etc. Lead for 0.3 mmφ mechanical pencil (trade name: Mitsubishi Uni,
Mitsubishi Pencil Co., Ltd.) is used as a probe electrode, and the probe electrode 2 and the reference electrode 3 and the counter electrode 4 are inserted into the liquid reservoir 1 of the fraction flowing out after chromatographic separation as shown in FIG. Cyclic voltammogram (c,
v curve) was measured.
この曲線のピーク電位、平衡電位などからイオンの定性
を行ない、ピーク高さから半定量を行なった（第２図c,
v曲線、例はFeイオン）。Ions were qualitatively determined from the peak potential and equilibrium potential of this curve, and semi-quantitative determination was performed from the peak height (Fig. 2, c,
v curve, example Fe ion).
フラクション中のイオンの定量を行なうには、パルスボ
ルタモグラムをとり、あらかじめ作成した検量線などを
利用すると、やや時間は掛るが、±１％の精度で定量が
でき、プローブ電極により鉄イオンを分析した結果（パ
ルスボルタモグラム）を第３図に示した。To quantify the ions in the fraction, if you take a pulse voltammogram and use a calibration curve prepared in advance, it will take a little time, but it will be possible to quantify with an accuracy of ± 1%. The results (pulse voltammogram) are shown in FIG.
実施例２ フロー型電池の充放電状態をモニターするプローブ電極
として使用した例 0.5mmφのシャープペンシル用芯（商品名：三菱ユニ，
三菱鉛筆株式会社製）をプローブ電極として使用してレ
ドックスフロー型電池の充放電過程において充放電の状
態をモニターする２つの方法を以下に示した。Example 2 Example of use as probe electrode for monitoring charge / discharge state of flow type battery 0.5 mmφ lead for mechanical pencil (trade name: Mitsubishi Uni,
Two methods for monitoring the state of charge / discharge in the charge / discharge process of a redox flow type battery using Mitsubishi Pencil Co., Ltd.) as a probe electrode are shown below.
（１）正極液（塩化鉄−塩酸系）の開回路電圧を測定し
て、電解液中での［Fe3+］／［Fe2+］の割合により変化
する開回路電圧から電池の残存容量をモニターした。そ
の方法は、タンクから取り出した電解液槽にプローブ電
極を挿入し、参照電極を対極として開回路電圧を測定す
ることによって行なった。(1) The open circuit voltage of the positive electrode solution (iron chloride-hydrochloric acid system) is measured, and the remaining capacity of the battery is calculated from the open circuit voltage that changes depending on the ratio of [Fe 3 + ] / [Fe 2+ ] in the electrolytic solution. Was monitored. The method was performed by inserting a probe electrode into an electrolytic solution tank taken out from the tank and measuring an open circuit voltage with the reference electrode as a counter electrode.
（２）［Fe3+］／［Fe2+］の濃度比を直接測定するた
め、パルスボルタモグラムを利用した。(2) A pulse voltammogram was used to directly measure the concentration ratio of [Fe 3+ ] / [Fe 2+ ].
プローブ電極に流れる正電流と負電流はおおよそ［F
e3+］（Fe3+濃度）と［Fe2+］（Fe2+濃度）に比例する
のであらかじめ作成した検量線による各濃度を定量し
た。The positive and negative currents flowing in the probe electrode are approximately [F
Since it is proportional to [e 3+ ] (Fe 3+ concentration) and [Fe 2+ ] (Fe 2+ concentration), each concentration was quantified by a calibration curve prepared in advance.
実施例３ 血液中のヘモグロビンのレドック反応の測定例ヒトの血
液中のヘモグロビンは血液のpHなどの存在条件によって
レドックス電位が変動する。それはヘモグロビンの中心
金属であるFeイオンの周りを取り巻くヘムの構造がpHな
どにより異なるためと推定され、取り出された血液中の
ヘモグロビンのレドックス電位の測定は体内での血液の
状態を推定する上で重要である。Example 3 Example of measurement of redock reaction of hemoglobin in blood The redox potential of hemoglobin in human blood varies depending on the existence conditions such as pH of blood. It is presumed that the structure of the heme surrounding the Fe ion, which is the central metal of hemoglobin, differs depending on the pH, etc.The measurement of the redox potential of hemoglobin in the extracted blood is useful for estimating the blood state in the body. is important.
採血直後の少量（数ml以下）の血液に実施例１のプロー
ブ電極及び微小参照極（飽和甘汞電極:SCE）及び対極を
浸し、ボルタングラムを測定した。その結果、ヘモグロ
ビンのレドックス電位はpH6で0.17V,pH7で0.15V vsSCE
であった。Immediately after blood collection, a small amount (less than a few ml) of blood was immersed in the probe electrode, the micro reference electrode (saturated sweet field electrode: SCE) and the counter electrode of Example 1, and the voltamgram was measured. As a result, the redox potential of hemoglobin was 0.17 V at pH 6 and 0.15 V vs SCE at pH 7.
Met.
実施例４ 柑橘類の中のアスコルビン酸の量の測定例 みかんの袋に実施例２のプローブ電極を突き刺し、対極
として銅線（あるいは白金線）及び微小甘汞電極を参照
電極としてみかんの中のアスコルビン酸（ビタミンＣ）
の反応を測定した。Example 4 Example of measurement of amount of ascorbic acid in citrus fruits A bag of mandarin oranges was pierced with the probe electrode of Example 2, and a copper wire (or platinum wire) as a counter electrode and a fine sweet potato electrode were used as reference electrodes. Acid (vitamin C)
Was measured.
伊予柑、温州ミカン、グレープフルーツなどの種類によ
り、また鮮度によりアスコルビン酸の量が異なる。The amount of ascorbic acid varies depending on the type of Iyokan, Satsuma mandarin, grapefruit, etc. and depending on the freshness.
この測定結果を、第４図に示す。The measurement result is shown in FIG.
第１図は、この発明に係るプローブ電極を使用した実施
例１の測定系を示す図、第２図は実施例１の測定により
得られた塩酸溶液中の鉄イオンのサイクリックボルタモ
グラム（c,v曲線）、第３図は実施例１の測定により得
られた塩酸中の鉄イオンとバナジウムイオンのパルスボ
ルタモグラム、第４図は実施例４の測定によって得られ
た柑橘類中のアスコルビン酸（ビタミンＣ）量の測定結
果を示す図（c,v曲線）である。 図中、１は電解槽、２は作用極（プローブ電極）、３は
参照電極（SCE）、４は対極（白金極）。FIG. 1 is a diagram showing a measurement system of Example 1 using the probe electrode according to the present invention, and FIG. 2 is a cyclic voltammogram (c, of iron ions in a hydrochloric acid solution obtained by the measurement of Example 1 (c, v curve), FIG. 3 is a pulse voltammogram of iron ions and vanadium ions in hydrochloric acid obtained by the measurement of Example 1, and FIG. 4 is ascorbic acid (vitamin C) in citrus fruits obtained by the measurement of Example 4. ) Is a diagram (c, v curve) showing the measurement result of the amount. In the figure, 1 is an electrolytic cell, 2 is a working electrode (probe electrode), 3 is a reference electrode (SCE), 4 is a counter electrode (platinum electrode).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−87777（ＪＰ，Ａ) 特開 昭61−7463（ＪＰ，Ａ) 特開 平１−173862（ＪＰ，Ａ) 実開 昭52−64585（ＪＰ，Ｕ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-87777 (JP, A) JP-A-61-7463 (JP, A) JP-A-1-173862 (JP, A) Practical application Sho-52- 64585 (JP, U)
Claims (1)
気中で焼成すると炭素化物を残す有機物の粘結剤及び重
金属を含まない鉱油を混練、押し出し成形した後、高温
で焼成し、更に油含浸して製造された炭素棒を電極とし
て使用することを特徴とするプローブ電極。1. A carbon material, an organic binder that leaves a carbonized product when calcined in an inert atmosphere or a non-oxidizing atmosphere, and mineral oil that does not contain heavy metals, is kneaded, extruded, and then calcined at a high temperature. A probe electrode using a carbon rod manufactured by impregnating with oil as an electrode.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63078698A JPH0792448B2 (en) | 1988-03-31 | 1988-03-31 | Probe electrode |
| US07/905,238 US5273639A (en) | 1988-03-31 | 1992-06-29 | Probe electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63078698A JPH0792448B2 (en) | 1988-03-31 | 1988-03-31 | Probe electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01250854A JPH01250854A (en) | 1989-10-05 |
| JPH0792448B2 true JPH0792448B2 (en) | 1995-10-09 |
Family
ID=13669089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63078698A Expired - Lifetime JPH0792448B2 (en) | 1988-03-31 | 1988-03-31 | Probe electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0792448B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2655742B2 (en) * | 1990-07-16 | 1997-09-24 | 工業技術院長 | Tapered carbon microelectrode and method of manufacturing the same |
| JP2816262B2 (en) * | 1991-07-09 | 1998-10-27 | 工業技術院長 | Carbon microsensor electrode and method of manufacturing the same |
| JP2783927B2 (en) * | 1991-11-29 | 1998-08-06 | 三菱鉛筆株式会社 | Carbon material for electrode and method for producing the same |
| US5503728A (en) * | 1992-09-09 | 1996-04-02 | Agency Of Industrial Science And Technology | Carbon sensor electrode and process for producing the same |
| JPH08227714A (en) * | 1995-02-21 | 1996-09-03 | Mitsubishi Pencil Co Ltd | Carbon material for negative electrode of lithium ion secondary battery and method for producing the same |
| JP2725745B2 (en) * | 1995-11-07 | 1998-03-11 | 工業技術院長 | Methods for measuring nitrogen oxides and neurotransmitters |
| JP2011128050A (en) * | 2009-12-18 | 2011-06-30 | Chubu Electric Power Co Inc | Defect detection device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442711Y2 (en) * | 1975-11-07 | 1979-12-11 | ||
| JPS5987777A (en) * | 1982-11-11 | 1984-05-21 | Matsushita Electric Ind Co Ltd | Interlayer compound electrode |
| JPS617463A (en) * | 1984-06-22 | 1986-01-14 | Sadaichi Murai | Ph and ion concentration measuring electrode equipped with carbon electrode |
| JPH0752176B2 (en) * | 1987-12-28 | 1995-06-05 | 積水化学工業株式会社 | Electrochemical detector |
-
1988
- 1988-03-31 JP JP63078698A patent/JPH0792448B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01250854A (en) | 1989-10-05 |
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