JPH04204368A - Hydrocarbocate ion measuring electrode - Google Patents
Hydrocarbocate ion measuring electrodeInfo
- Publication number
- JPH04204368A JPH04204368A JP2339919A JP33991990A JPH04204368A JP H04204368 A JPH04204368 A JP H04204368A JP 2339919 A JP2339919 A JP 2339919A JP 33991990 A JP33991990 A JP 33991990A JP H04204368 A JPH04204368 A JP H04204368A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ion concentration
- ion
- bicarbonate
- concentration
- 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.)
- Pending
Links
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 47
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical class FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- GJNWUVBDBVUZKP-UHFFFAOYSA-N 1-(4-decylphenyl)-2,2,2-trifluoroethanone Chemical compound CCCCCCCCCCC1=CC=C(C(=O)C(F)(F)F)C=C1 GJNWUVBDBVUZKP-UHFFFAOYSA-N 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- -1 hydrogen ions Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- LCMKCXQZUDEWSJ-UHFFFAOYSA-N FC(C(=O)CCCCCCCCCCC1=CC=CC=C1)(F)F Chemical compound FC(C(=O)CCCCCCCCCCC1=CC=CC=C1)(F)F LCMKCXQZUDEWSJ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- URWYVXBYQUNESG-UHFFFAOYSA-N (2,2,2-trifluoroacetyl) benzoate Chemical compound FC(F)(F)C(=O)OC(=O)C1=CC=CC=C1 URWYVXBYQUNESG-UHFFFAOYSA-N 0.000 description 1
- ITYFZOKZBNDKOF-UHFFFAOYSA-N 2,2,2-trifluoro-1-(4-octoxyphenyl)ethanone Chemical compound CCCCCCCCOC1=CC=C(C(=O)C(F)(F)F)C=C1 ITYFZOKZBNDKOF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- LZBCVRCTAYKYHR-UHFFFAOYSA-N acetic acid;chloroethene Chemical compound ClC=C.CC(O)=O LZBCVRCTAYKYHR-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- ZWLHEJXGDIROAT-UHFFFAOYSA-N n,n-dioctyl-4-(2,2,2-trifluoroacetyl)benzamide Chemical compound CCCCCCCCN(CCCCCCCC)C(=O)C1=CC=C(C(=O)C(F)(F)F)C=C1 ZWLHEJXGDIROAT-UHFFFAOYSA-N 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- IYPZIBYQZWSIHB-UHFFFAOYSA-N n-fluoro-n-phenylacetamide Chemical compound CC(=O)N(F)C1=CC=CC=C1 IYPZIBYQZWSIHB-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- OCWNMDUAUUAHSJ-UHFFFAOYSA-N silver;sulfanylidenesilver Chemical compound [Ag].[Ag]=S OCWNMDUAUUAHSJ-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RIECPYZYOLVSJK-UHFFFAOYSA-N tert-butyl 2-dimethylsilyl-5-methylindole-1-carboxylate Chemical compound C[SiH](C)c1cc2cc(C)ccc2n1C(=O)OC(C)(C)C RIECPYZYOLVSJK-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は医療用および理化学分析用の化学センサに用い
られる炭酸水素塩イオン測定用電極に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrode for measuring bicarbonate ions used in chemical sensors for medical use and physical and chemical analysis.
体液、特に血液中の炭酸水素塩イオン
（ＨＣＯ３−）は、呼吸および代謝の状態を把握する重
要な因子であり、その濃度を計測することは極めて重要
である。Bicarbonate ions (HCO3-) in body fluids, especially blood, are important factors for understanding the state of respiration and metabolism, and it is extremely important to measure their concentration.
従来、この炭酸水素塩イオンの濃度は、二酸化炭素ガス
の分圧（ＰＣＯ２）と水素イオン濃度（ｐＨ）とを測定
し、これらの値からヘンダーソン・ハッセルバルヒの式
により間接的に求狛ていた。そして、二酸化炭素ガスの
濃度はセパリングハウスのＣＯ２センサで測定し、一方
水素イオン濃度はガラス電極で測定していた。Conventionally, the concentration of bicarbonate ions has been determined indirectly by measuring the partial pressure of carbon dioxide gas (PCO2) and hydrogen ion concentration (pH), and using the Henderson-Hasselbalch equation from these values. The concentration of carbon dioxide gas was measured with a CO2 sensor in the separation house, while the concentration of hydrogen ions was measured with a glass electrode.
しかしながら、ＣＯ□センサの応答時間は１〜２分であ
り、ガラス電極の応答時間（数秒）に比較して時間を要
する。このため、二酸化炭素ガスの濃度と水素イオン濃
度との間には時間のずれが生じる。したがって、各々の
値が変化している場合、これらの値より算出した炭酸水
素塩イオン濃度に誤差が含まれる。また、二酸化炭素ガ
スおよび水素イオン濃度の２つの値の各々の誤差が加算
されるたｔ、直接炭酸水素塩イオン濃度を測定する場合
に比べて誤差が大きくなると考えられる。However, the response time of the CO□ sensor is 1 to 2 minutes, which is longer than the response time of a glass electrode (several seconds). Therefore, a time lag occurs between the concentration of carbon dioxide gas and the concentration of hydrogen ions. Therefore, if each value changes, the bicarbonate ion concentration calculated from these values includes an error. Furthermore, since the errors between the two values of carbon dioxide gas and hydrogen ion concentration are added, the error is considered to be larger than when directly measuring the bicarbonate ion concentration.
これに対して、近年、このような理論式を用いることな
く炭酸水素塩イオンの濃度を求釣るものとして、ワイズ
等が炭酸塩イオンに応答する電極を開示（米国特許公報
３７２３２８１ 号）し、また、シモン等は炭酸水素塩
イオンに応答するキャリアとり、テｘり／ −ｍ７ ミ
ン（Ａｎａｌ、Ｃｈｅｍ、５４．４２３−４２９（１９
８２） ） 、あるいは有機スズ化合物を用いたセン
サを開示した（国内公表公報７９００６６１ 号）。On the other hand, in recent years, Wise et al. have disclosed an electrode that responds to carbonate ions (US Pat. No. 3,723,281) to determine the concentration of bicarbonate ions without using such a theoretical formula. , Simon et.
82) ) or disclosed a sensor using an organic tin compound (Domestic Publication No. 7900661).
しかしながら、従来の炭酸塩イオンに応答する電極の場
合は、血液中では大部分が炭酸塩イオンではなく、炭酸
水素塩イオンの形で存在しているため、試料溶液にアル
カリ物質、たとえば三塩化水素緩衝液（ｐＨ＝８．６＞
を添加し、炭酸水素塩イオンを炭酸塩イオンに変換した
後に測定する必要があり、その操作が煩雑であるという
問題があった。However, in the case of conventional carbonate ion-responsive electrodes, the majority of blood exists in the form of bicarbonate ions rather than carbonate ions, so the sample solution contains alkaline substances, such as hydrogen trichloride. Buffer solution (pH=8.6>
It is necessary to convert the bicarbonate ions into carbonate ions and then perform the measurement, which poses a problem in that the operation is complicated.
また、炭酸水素塩イオンセンサの場合は、直接に炭酸水
素塩イオンの濃度を測定できるものの、炭酸水素塩イオ
ンに応答するばかりでなく、試料溶液の水素イオン濃度
（ｐ Ｈ）にも応答してしまい、炭酸水素塩イオンの選
択性が低下し、そのため感度が高くないという問題があ
った。In addition, although a bicarbonate ion sensor can directly measure the concentration of bicarbonate ions, it responds not only to bicarbonate ions but also to the hydrogen ion concentration (pH) of the sample solution. However, there was a problem in that the selectivity for hydrogen carbonate ions was reduced, and therefore the sensitivity was not high.
本発明はかかる問題点に鑑みてなされたものであって、
その目的は、試料溶液の水素イオン濃度に応答すること
がなく、炭酸水素塩イオンの選択性が向上し、測定感度
が向上した炭酸水素塩イオン測定用電極を提供すること
にある。The present invention has been made in view of such problems, and includes:
The purpose is to provide an electrode for measuring bicarbonate ions that does not respond to the hydrogen ion concentration of a sample solution, has improved selectivity for bicarbonate ions, and has improved measurement sensitivity.
本発明による炭酸水素塩イオン測定用電極は、基準電極
と、重合不活性支持体材料に可塑剤と炭酸水素塩イオン
キャリア物質とを含有させるとともに、水素イオン濃度
の影響を排除する化合物を含有させてなり、前記基準電
極に電気化学的に接触された炭酸水素塩イオン選択性膜
とを備えている。The electrode for measuring bicarbonate ions according to the present invention includes a reference electrode and a polymerized inert support material containing a plasticizer and a bicarbonate ion carrier substance, as well as a compound that eliminates the influence of hydrogen ion concentration. and a bicarbonate ion selective membrane electrochemically contacted with the reference electrode.
すなわち、本発明の炭酸水素塩イオン測定用電極では、
炭酸水素塩イオン選択性膜に、水素イオン濃度の影響を
排除する化合物を含有することにより、試料溶液中の水
素イオン濃度に依存することがなくなり、これにより選
択的に炭酸水素塩イオンに応答し、測定感度が向上する
。That is, in the electrode for measuring bicarbonate ions of the present invention,
By containing a compound in the bicarbonate ion-selective membrane that eliminates the effect of hydrogen ion concentration, it becomes independent of the hydrogen ion concentration in the sample solution, thereby selectively responding to bicarbonate ions. , measurement sensitivity is improved.
重合不活性支持体材料としては、可塑化効率が高い塩化
ビニル重合体あるいは塩化ビニル−酢酸、ビニルの共重
合体を用いることが好ましい。また、可塑剤としてはセ
バシン酸エステル、フタル酸エステル、トリメリット酸
エステル等が用いられるが、特にセバシン酸ジ（２−エ
チルヘキシル）が好ましい。As the polymerized inert support material, it is preferable to use a vinyl chloride polymer or a vinyl chloride-acetic acid, vinyl copolymer, which has a high plasticization efficiency. Further, as the plasticizer, sebacic acid ester, phthalic acid ester, trimellitic acid ester, etc. are used, and di(2-ethylhexyl sebacate) is particularly preferred.
水素イオン濃度の影響を排除する化合物としては、トリ
フルオロアセトフェノン誘導体が用いられる。このトリ
フルオロアセトフェノン誘導体を用いることにより、膜
中の疏水性が高まり、荷電物質つまりイオンの膜中への
進入を阻止することができ、親油的な性質を持つ炭酸水
素塩イオンの選択性を高めることができる。A trifluoroacetophenone derivative is used as a compound that eliminates the influence of hydrogen ion concentration. By using this trifluoroacetophenone derivative, the hydrophobicity in the membrane is increased, and charged substances, that is, ions, can be prevented from entering the membrane, and the selectivity of bicarbonate ions, which have lipophilic properties, can be increased. can be increased.
トリフルオロアセトフェノン誘導体は、一般に次式で表
すことができる。Trifluoroacetophenone derivatives can generally be represented by the following formula.
ここに、Ｒ＝Ｃ＋ ｏ Ｈ２１（）リフルオロアセチル
−ｐ−デシルベンゼン） 、ＣＩｌ ８２３ （）リフ
ルオロアセチル−ｐ−ウンデシルベンゼン）、Ｃ１２８
２Ｓ（）リフルオロアセチル−ｐ−ト′デジーメチル−
ｐ−）！Ｊフルオロアセチルアニリン）、ＯＣｓ Ｈ
Ｉ３ （ｐ−オクチルオキシトリフルオロアセチルヘン
ゼン） 、−３−Ｃ１２Ｈ２Ｓ （４ｎ−ドデシルチオ
−１−トリフルオロアセチルベンゼン）、
−４−）リフルオロアセチルアニリン）−ＣＯＮ （Ｃ
ＩＩＨＩ７） ２ （Ｎ、 Ｎ−ジオクチル−４−
トリフルオロアセチルベンザミド）、−ＣＯＯＣ７Ｈ，
Ｓ （ヘプチル−ｐ−）リフルオロアセチルベンゾエー
ト）、−８○２ ＣＩ ２ Ｈ２５（４−（ｎ−ドデ
シルサルフォニル） −１−）リフルオロアセチルベン
ゼン）
この中で、特に好ましいものとしてはトリフルオロアセ
チルデシルベンセンを挙げることができる。Here, R=C+ o H21 () Lifluoroacetyl-p-decylbenzene), CIl 823 () Lifluoroacetyl-p-undecylbenzene), C128
2S()Lifluoroacetyl-p-to'dimethyl-
p-)! J fluoroacetylaniline), OCs H
I3 (p-octyloxytrifluoroacetylbenzene), -3-C12H2S (4n-dodecylthio-1-trifluoroacetylbenzene), -4-)lifluoroacetylaniline) -CON (C
IIHI7) 2 (N, N-dioctyl-4-
trifluoroacetylbenzamide), -COOC7H,
S (heptyl-p-)lifluoroacetylbenzoate), -8○2 CI 2 H25 (4-(n-dodecylsulfonyl)-1-)lifluoroacetylbenzene) Among these, trifluoroacetylbenzoate is particularly preferred. Mention may be made of fluoroacetyldecylbenzene.
炭酸水素塩イオンキャリア物質としては、高級アルキル
置換された有機スズ化合物が用いられる。As the bicarbonate ion carrier material, a higher alkyl-substituted organotin compound is used.
この有機スズ化合物のスズは４価で、ハロゲン化あるい
はエーテル化した１ないし３のヒドロキシル基を有する
もの、または０３〜ＣＩ ２の炭化水素からなる１ない
し３のアルキル基を有するものであることが望ましい。The tin of this organotin compound is tetravalent and has 1 to 3 halogenated or etherified hydroxyl groups, or has 1 to 3 alkyl groups consisting of 03 to CI 2 hydrocarbons. desirable.
これは、炭酸水素イオンに応答するキャリアの条件とし
ては、イオン交換基（ハロゲン基、ヒドロキシル基〉を
有するが、荷電をもたないことが必要であるからである
。４級アミンのようにハロゲン基を有しても、荷電を有
するものは、イオン交換基でＨＣ１３−とイオン交換し
、塩化物イオン応答を示すため適さない。This is because the carrier that responds to bicarbonate ions must have an ion exchange group (halogen group, hydroxyl group) but be uncharged. Even if it has a group, a charged one is not suitable because it exchanges ions with HC13- in the ion exchange group and exhibits a chloride ion response.
また、本発明の炭酸水素塩イオン測定用電極では、可塑
剤中をキャリア物質が移動して炭酸水素塩イオンに応答
性を示すたｔに、キャリア物質としては可塑剤中に溶解
する必要がある。二のたｔ、キャリア物質としては０３
〜ＣＩ２の炭化水素からなるアルキル基を有することが
望ましい。Furthermore, in the electrode for measuring bicarbonate ions of the present invention, in order for the carrier substance to move through the plasticizer and exhibit responsiveness to bicarbonate ions, the carrier substance must be dissolved in the plasticizer. . Second, as a carrier substance, 03
It is desirable to have an alkyl group consisting of a hydrocarbon of ~CI2.
なお、基準電極は、酸化還元電位を有する酸化還元物質
を用いたものが好ましく、酸化還元物質としては、銀−
ハロゲン化銀、キノン−ヒドロキノン型酸化還元物質、
アミン−キノイド型酸化還元物質、銀−硫化銀等から選
択することが好ましい。Note that the reference electrode preferably uses a redox substance having a redox potential, and the redox substance is silver.
silver halide, quinone-hydroquinone type redox substance,
It is preferable to select from amine-quinoid type redox substances, silver-silver sulfide, and the like.
以下、図面を参照して本発明の実施例を具体的に説明す
る。Embodiments of the present invention will be specifically described below with reference to the drawings.
実施例１
以下の組成の溶液を調整後、直径５ｍｍ、深さ１ｍｍの
アルミニウム缶に流し込み、１７０℃で１分間加熱し、
ゲル化させることにより、電極膜としての炭酸水素塩イ
オン選択性膜を作成した。Example 1 After preparing a solution with the following composition, it was poured into an aluminum can with a diameter of 5 mm and a depth of 1 mm, heated at 170 ° C. for 1 minute,
By gelation, a bicarbonate ion selective membrane was created as an electrode membrane.
（溶液）
トリオクチルティンクロライド ３．０重量％（（ｃａ
Ｈｌｌ＞ ３ Ｓ ｎ ｃ １）トリフルオロア
セチルデシルベンゼン（ＴＦＡＤＢ）（Ｃ，。Ｈ２１（
Ｃｓ Ｈ４） ＣＯＣＦ３ ） １ 、 ８重量％セ
バシン酸ジ（２−エチルヘキシル）６３．５（（ＣＨ２
） ４ ＣＯＯＣａ Ｈ＋ｉ） ２ 重量％ポリ塩
化ビニル ３１．７重量％次に、第１ＥＩ
に示すように、この炭酸水素塩イオン選択性膜１１を塩
化ビニル樹脂製のチューブ１２の端面に、上記電極膜組
成物のＴＨＦ溶液で接着した。続いて、チューブ１２内
に５０ｍＭ’Ｊン酸塩緩衝液、０．０１Ｍ塩化ナトリウ
ム水溶液からなる内部液１３とともにリード線１４が接
続された銀・塩化銀電極１５を充填し、炭酸水素塩イオ
ン測定用電極を作製した。(Solution) Trioctyl tin chloride 3.0% by weight ((ca
Hll> 3 S n c 1) Trifluoroacetyldecylbenzene (TFADB) (C,.H21(
Cs H4) COCF3) 1, 8 wt% di(2-ethylhexyl) sebacate 63.5 ((CH2
) 4 COOCa H+i) 2% by weight Polyvinyl chloride 31.7% by weight Next, 1st EI
As shown in FIG. 2, this bicarbonate ion selective membrane 11 was adhered to the end face of a tube 12 made of vinyl chloride resin using a THF solution of the above electrode membrane composition. Next, a silver/silver chloride electrode 15 to which a lead wire 14 was connected was filled into the tube 12 together with an internal solution 13 consisting of a 50mM'J phosphate buffer solution and a 0.01M sodium chloride aqueous solution, and hydrogen carbonate ion measurement was performed. An electrode for this purpose was prepared.
（比較例１）
実施例１のトリフルオロアセチルデシルベンゼンの濃度
を０，１．３．５．２０重量％に変化させて、実施例と
同様に炭酸水素塩イオン測定用電極を作製した。(Comparative Example 1) An electrode for measuring bicarbonate ions was prepared in the same manner as in Example, except that the concentration of trifluoroacetyldecylbenzene in Example 1 was changed to 0, 1, 3, 5, and 20% by weight.
実験例１
実施例１および比較例１の各電極を作用極とし、基準電
極に５ＳＣＥ（飽和塩化ナトリウムカロメル電極）を用
いて、試料溶液中の炭酸水素塩イオン濃度に対する両電
極間の起電力の関係を調べた。Experimental Example 1 Each electrode of Example 1 and Comparative Example 1 was used as a working electrode, and a 5SCE (saturated sodium chloride calomel electrode) was used as a reference electrode. I investigated the relationship.
その結果、炭酸水素塩イオン濃度の対数に対して直線性
が得られた。この直線の勾配、すなわち感度ヲトリフル
オロアセチルデシルベンゼンのａ度に対してプロットし
たものを第３図に示す。トリフルオロアセチルデシルベ
ンゼンの濃度が５． ０重量％以下であれば、５０ ｍ
Ｖ ／ｄｅｃａｄｅ以上の感度となり、実用上問題は
ないことがわかった。As a result, linearity was obtained with respect to the logarithm of the bicarbonate ion concentration. The slope of this straight line, that is, the sensitivity plotted against the degree a of trifluoroacetyldecylbenzene is shown in FIG. The concentration of trifluoroacetyldecylbenzene is 5. If it is 0% by weight or less, 50 m
It was found that the sensitivity was greater than V/decade, and there was no problem in practical use.
次に、水素イオン濃度（ｐＨ）の変化に対して起電力の
変化を調べ、水素イオン濃度に対する依存性ヲトリフル
オロアセチルデシルベンゼンの濃度に対してブロー／
）したものを第４図に示す。実施例１で示した１、８重
量％の濃度において、水素イオン濃度に対する依存性が
殆ど無いことを示している。したがって、実施例１の組
成を用いて作製した炭酸水素塩イオン測定用電極は水素
イオン濃度の影響を受けることなく、選択的に炭酸水素
塩イオンに応答することがわかった。Next, we investigated the change in electromotive force with respect to changes in hydrogen ion concentration (pH), and determined the dependence on hydrogen ion concentration and the blow /
) is shown in Figure 4. This shows that at the concentration of 1.8% by weight shown in Example 1, there is almost no dependence on the hydrogen ion concentration. Therefore, it was found that the electrode for measuring bicarbonate ions prepared using the composition of Example 1 selectively responded to bicarbonate ions without being affected by the hydrogen ion concentration.
（実施例２）
第２図に示すように周囲を絶縁剤１６で絶縁した銀・塩
化銀電極１７上に実施例１で作製した炭酸水素塩イオン
選択性膜１１を被覆させて炭酸水素塩イオン測定用電極
を作製した。(Example 2) As shown in FIG. 2, the hydrogen carbonate ion selective membrane 11 prepared in Example 1 was coated on the silver/silver chloride electrode 17 whose periphery was insulated with an insulating material 16, and the hydrogen carbonate ion Measurement electrodes were prepared.
実験例２
実験例１と同様の方法で、炭酸水素塩イオンおよび水素
イオンに対する応答性を調べた結果、実験例１と同様の
結果が得られた。Experimental Example 2 As a result of examining the responsiveness to bicarbonate ions and hydrogen ions in the same manner as in Experimental Example 1, the same results as in Experimental Example 1 were obtained.
以上説明したように本発明の炭酸水素塩イオン測定用電
極によれば、炭酸水素塩イオン選択性膜中に水素イオン
濃度の影響を排除する化合物を含有させたことにより、
試料溶液中の水素イオン濃度に依存することがなくなり
、炭酸水素塩イオンの選択性が向上し、測定感度が向上
する。As explained above, according to the hydrogen carbonate ion measuring electrode of the present invention, by containing a compound that eliminates the influence of hydrogen ion concentration in the hydrogen carbonate ion selective membrane,
This eliminates dependence on the hydrogen ion concentration in the sample solution, improves selectivity for hydrogen carbonate ions, and improves measurement sensitivity.
第１図は本発明の実施例１に係る炭酸水素塩イオン選択
性膜電極の構成を示す縦断面図、第２図は本発明の実施
例２に係る炭酸水素塩イオン選択性膜電極の構成を示す
縦断面図、第３図は実施例１の電極の炭酸水素塩イオン
センサの感度のＴＦＡＤＢ依存性を示す特性図、第４図
は同じく水素イオン濃度に対する依存性を示す特性図で
ある。
１１・・・炭酸水素塩イオン選択性膜
１２・・・チニーブ
１３・・・内部液
１４・・・リード線
１５．１７・・・銀・塩化銀電極FIG. 1 is a longitudinal cross-sectional view showing the structure of a bicarbonate ion-selective membrane electrode according to Example 1 of the present invention, and FIG. 2 is a longitudinal cross-sectional view showing the structure of a bicarbonate ion-selective membrane electrode according to Example 2 of the present invention. FIG. 3 is a characteristic diagram showing the TFADB dependence of the sensitivity of the hydrogen carbonate ion sensor of the electrode of Example 1, and FIG. 4 is a characteristic diagram showing the dependence on hydrogen ion concentration. 11...Hydrocarbonate ion selective membrane 12...Tinibu 13...Internal liquid 14...Lead wire 15.17...Silver/silver chloride electrode
Claims (1)
水素塩イオンキャリア物質とを含有させるとともに、水
素イオン濃度の影響を排除する化合物を含有させてなり
、前記基準電極に電気化学的に接触された炭酸水素塩イ
オン選択性膜とを備えたことを特徴とする炭酸水素塩イ
オン測定用電極。 ２、水素イオン濃度の影響を排除する化合物としてトリ
フルオロアセトフェノン誘導体を用いてなる請求項１記
載の炭酸水素塩イオン測定用電極。[Claims] 1. A reference electrode and a polymerized inert support material containing a plasticizer and a bicarbonate ion carrier material as well as a compound that eliminates the influence of hydrogen ion concentration, An electrode for measuring bicarbonate ions, comprising a bicarbonate ion-selective membrane electrochemically contacted with a reference electrode. 2. The electrode for measuring bicarbonate ions according to claim 1, which uses a trifluoroacetophenone derivative as the compound that eliminates the influence of hydrogen ion concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339919A JPH04204368A (en) | 1990-11-30 | 1990-11-30 | Hydrocarbocate ion measuring electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339919A JPH04204368A (en) | 1990-11-30 | 1990-11-30 | Hydrocarbocate ion measuring electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04204368A true JPH04204368A (en) | 1992-07-24 |
Family
ID=18332006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2339919A Pending JPH04204368A (en) | 1990-11-30 | 1990-11-30 | Hydrocarbocate ion measuring electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04204368A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635683B1 (en) | 1998-07-28 | 2003-10-21 | Tokuyama Corporation | Film responsive to bicarbonate ion |
-
1990
- 1990-11-30 JP JP2339919A patent/JPH04204368A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635683B1 (en) | 1998-07-28 | 2003-10-21 | Tokuyama Corporation | Film responsive to bicarbonate ion |
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