KR100330739B1 - Compositions of calcium ion-selective membranes based on polyurethane matrix - Google Patents
Compositions of calcium ion-selective membranes based on polyurethane matrix Download PDFInfo
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- KR100330739B1 KR100330739B1 KR1019990016564A KR19990016564A KR100330739B1 KR 100330739 B1 KR100330739 B1 KR 100330739B1 KR 1019990016564 A KR1019990016564 A KR 1019990016564A KR 19990016564 A KR19990016564 A KR 19990016564A KR 100330739 B1 KR100330739 B1 KR 100330739B1
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- South Korea
- Prior art keywords
- calcium ion
- electrode
- selective membrane
- ion
- membrane
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 122
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 5
- 239000011159 matrix material Substances 0.000 title description 2
- 150000002500 ions Chemical class 0.000 claims abstract description 64
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000012472 biological sample Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- UOBBAWATEUXIQF-UHFFFAOYSA-N tetradodecylazanium Chemical compound CCCCCCCCCCCC[N+](CCCCCCCCCCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC UOBBAWATEUXIQF-UHFFFAOYSA-N 0.000 claims description 4
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- RUMQAIMLSBNZGK-UHFFFAOYSA-N C(C)C(CC(C(=O)O)(CCCC(=O)O)CC(CCCC)CC)CCCC.C(CCCCC(=O)OCC(CCCC)CC)(=O)OCC(CCCC)CC Chemical compound C(C)C(CC(C(=O)O)(CCCC(=O)O)CC(CCCC)CC)CCCC.C(CCCCC(=O)OCC(CCCC)CC)(=O)OCC(CCCC)CC RUMQAIMLSBNZGK-UHFFFAOYSA-N 0.000 claims 1
- NZSPOMNUNQSXMI-UHFFFAOYSA-N bis(2-ethylhexyl) decanedioate;2,2-bis(2-ethylhexyl)decanedioic acid Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC.CCCCC(CC)CC(C(O)=O)(CC(CC)CCCC)CCCCCCCC(O)=O NZSPOMNUNQSXMI-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 33
- 239000008280 blood Substances 0.000 abstract description 13
- 210000004369 blood Anatomy 0.000 abstract description 13
- 102000004169 proteins and genes Human genes 0.000 abstract description 8
- 108090000623 proteins and genes Proteins 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 210000002700 urine Anatomy 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 230000004044 response Effects 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 229910001415 sodium ion Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- URAUKAJXWWFQSU-UHFFFAOYSA-N n,n-dicyclohexyl-2-[2-(dicyclohexylamino)-2-oxoethoxy]acetamide Chemical compound C1CCCCC1N(C1CCCCC1)C(=O)COCC(=O)N(C1CCCCC1)C1CCCCC1 URAUKAJXWWFQSU-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- CJAONIOAQZUHPN-KKLWWLSJSA-N ethyl 12-[[2-[(2r,3r)-3-[2-[(12-ethoxy-12-oxododecyl)-methylamino]-2-oxoethoxy]butan-2-yl]oxyacetyl]-methylamino]dodecanoate Chemical compound CCOC(=O)CCCCCCCCCCCN(C)C(=O)CO[C@H](C)[C@@H](C)OCC(=O)N(C)CCCCCCCCCCCC(=O)OCC CJAONIOAQZUHPN-KKLWWLSJSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical group CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- GGZSJLYEDRTYEA-UHFFFAOYSA-N C1(CCCCC1)N(C(CC(CC(=O)N(C1CCCCC1)C1CCCCC1)=O)=O)C1CCCCC1 Chemical compound C1(CCCCC1)N(C(CC(CC(=O)N(C1CCCCC1)C1CCCCC1)=O)=O)C1CCCCC1 GGZSJLYEDRTYEA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZMLXOTHKYKUMLO-UHFFFAOYSA-N 2-(2-amino-1,1-dicyclohexyl-2-oxoethoxy)-2,2-dicyclohexylacetamide Chemical compound C1CCCCC1C(C1CCCCC1)(C(=O)N)OC(C(N)=O)(C1CCCCC1)C1CCCCC1 ZMLXOTHKYKUMLO-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000004159 blood analysis Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002555 ionophore Substances 0.000 description 1
- 230000000236 ionophoric effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
본 발명은 칼슘이온 센서의 전극에 구비되는 칼슘이온선택성 막 조성물에 관한 것으로, 구체적으로는 칼슘이온 센서의 재래식 전극 및 고체상 전극에 장착되는, 폴리우레탄을 지지체로 사용하고 가소제, 이온선택성 물질 및 친유성 첨가제를 사용한 칼슘이온선택성 막 조성물에 관한 것이며, 본 발명에 의한 칼슘이온선택성 막 조성물을 칼슘이온 센서의 전극에 구비하면 혈액이나 뇨 등의 생체시료 중의 칼슘이온 농도 측정시 단백질 흡착으로 인한 비대칭 전위가 발생되지 않을 뿐 만 아니라 여러 가지 이온종에 의한 방해작용을 받지 않는 등 우수한 전기화학적 성질을 지니며, 특히 본 발명에 의한 칼슘이온선택성 막 조성물을 칼슘이온 센서의 고체상 전극에 구비하면 그 표면과의 접착력이 우수하기 때문에 감응성의 감소가 방지되고 수명이 연장되며 전기화학적 성질이 우수하여 칼슘이온 센서의 소형화 및 대량생산를 촉진한다.The present invention relates to a calcium ion selective membrane composition provided in the electrode of the calcium ion sensor, specifically, a polyurethane, which is mounted on the conventional electrode and the solid-state electrode of the calcium ion sensor as a support, and a plasticizer, an ion-selective substance and The present invention relates to a calcium ion selective membrane composition using an oil-based additive, wherein when the calcium ion selective membrane composition according to the present invention is provided on an electrode of a calcium ion sensor, an asymmetric potential due to protein adsorption when measuring calcium ion concentration in a biological sample such as blood or urine Not only does not occur, but also has excellent electrochemical properties such as not being disturbed by various ionic species. In particular, when the calcium ion selective membrane composition according to the present invention is provided on the solid-state electrode of the calcium ion sensor, Excellent adhesion prevents loss of sensitivity and extends lifespan It said superior electrochemical properties and to facilitate miniaturization and mass saengsanreul of calcium ion sensor.
Description
본 발명은 칼슘이온선택성 막 조성물에 관한 것으로, 구체적으로 폴리우레탄 (polyurethane, 이하 'PU'로 약칭함)을 지지체 (matrix)로 사용하며 이온선택성 물질 (ionophore), 가소제 (plasticizer) 및 일정량의 친유성 첨가제 (lipophilic additive) 들을 첨가하는 칼슘이온선택성 막 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calcium ion selective membrane composition, specifically using polyurethane (abbreviated as "PU") as a matrix, an ion selective material (ionophore), a plasticizer and a certain amount of A calcium ion selective membrane composition is added to add lipophilic additives.
이온선택성 막을 장착한 전극은 크게 두 가지 형태로 나누어 질 수 있다. 이온선택성 막과 내부기준전극 (inner reference metal electrode) 사이에 내부기준용액 (inner reference filling solution)을 가지고 있어야 하는 재래식 이온선택성 막전극 (conventional ion-selective membrane electrode)과 이를 필요로 하지 않는 고체상 이온선택성 막전극 (solid-state ion-selective membrane electrode)이다. 이온선택성 막전극의 일반적인 형태는도 1에 나타내었는데,도 1a는 재래식 이온선택성 막전극의 단면도이고,도 1b는 고체상 이온선택성 막전극의 단면도이다.Electrodes equipped with ion selective membranes can be divided into two types. Conventional ion-selective membrane electrodes that must have an inner reference filling solution between the ion-selective membrane and the inner reference metal electrode and solid phase ion-selective electrodes that do not require them It is a solid-state ion-selective membrane electrode. The general form of the ion selective membrane electrode is shown in FIG. 1 , where FIG. 1A is a cross sectional view of a conventional ion selective membrane electrode, and FIG. 1 B is a cross sectional view of a solid phase ion selective membrane electrode.
고체상 전극이 갖는 장점은 내부기준용액을 필요로 하지 않기 때문에 소형화에 유리하며, 한 개의 소자 (chip)에 여러 이온을 동시에 검출할 수 있는 다중센서(multisensor)를 제작하는 것이 쉽고, 대량생산이 용이하여 가격의 저렴함까지 가져올 수 있다는 것이다. 또한 이와 같이 소자 자체가 갖는 장점 외에도 감응부의 소형화에 따라 시료를 미량으로 사용할 수 있다는 장점을 갖는다.The advantage of solid-state electrodes is that they do not require an internal reference solution, which is advantageous for miniaturization, and it is easy to manufacture a multisensor that can simultaneously detect several ions on a single chip, and to facilitate mass production. It is possible to bring in the cheapness of the price. In addition, in addition to the advantages of the device itself, there is an advantage that the sample can be used in a small amount according to the miniaturization of the sensitive portion.
이와 같은 장점에 기인하여 고체상 전극은 자동화 분석장치의 개발과 연계되어 상업적인 개발에 있어서 주된 전극형태가 될 것으로 판단되어 왔다. 그러나 이러한 고체상 전극의 형태에서 주지해야 할 점은도 1에서 볼 수 있듯이, 재래식 이온선택성 막전극은 전극체에서 이온선택성 막 (50)을 고정체 (20)로 고정시켜 막 (50)의 이탈을 막아줄 수 있으나 고체상 전극의 경우 이온선택성 막(50)이 전극 표면에 아무런 고정체도 없이 노출되어 있기 때문에, 이온선택성 막의 고체상 전극 표면에 대한 접착력이 전극의 수명 및 전기화학적인 특성을 결정짓는 가장 중요한 요인으로 작용한다는 것이다.Due to these advantages, solid-state electrodes have been considered to be the main electrode type in commercial development in connection with the development of automated analysis devices. However, it should be noted that in the form of the solid-state electrode, as shown in FIG. 1 , the conventional ion-selective membrane electrode fixes the ion-selective membrane 50 to the fixture 20 in the electrode body to prevent the separation of the membrane 50. In the case of a solid-state electrode, since the ion-selective membrane 50 is exposed to the electrode surface without any fixture, the adhesion of the ion-selective membrane to the solid-state electrode surface determines the lifetime and electrochemical characteristics of the electrode. It is an important factor.
이러한 이온선택성 막의 일반적인 조성은, 지지체로 사용되는 고분자 (polymer), 특정 이온과 결합하여 전하분리를 일으키는 이온선택성 물질 및 비휘발성 유기용매인 가소제로 이루어져 있으며, 이온선택성 막에 따라서는 친유성 첨가제를 넣어주는 경우도 있다. 이때, 고분자 지지체가 고체상 전극 표면과의 접착력을 결정하는 가장 중요한 요소로 작용한다.The general composition of the ion-selective membrane is composed of a polymer used as a support, an ion-selective material that binds to specific ions to cause charge separation, and a plasticizer, which is a nonvolatile organic solvent. You can also put it. At this time, the polymer support serves as the most important factor in determining the adhesion to the surface of the solid electrode.
상기 이온선택성 막을 제작하는데 있어 지금까지 가장 널리 사용되고 있는 고분자 지지체는 폴리(비닐클로라이드) (poly(vinyl cholide), 이하 'PVC'로 약칭함)이다. PVC는 지지체로 사용이 가능하다고 지금까지 알려진 고분자 물질 중에서전기화학적인 특성, 즉 감응기울기 (slope), 감응한계 (detection limit), 선택성 (selectivity) 등이 가장 우수하기 때문에 각종 이온선택성 막의 지지체로 널리 이용되어 왔다. 그러나, 이러한 PVC-지지체 이온선택성 막은 고체상 전극 표면과의 접착력이 떨어지기 때문에 이온선택성 막과 고체상 전극 표면 사이의 계면이 불안정하여 전기화학적 특성이 저하되고, 고체상 전극의 수명이 단축된다는 단점이 있다. 또한, PVC-지지체 이온선택성 막은 혈액이나 생체액 등에 삽입될 경우 생체적합성 (biocompatibility)이 떨어져 단백질 등이 전극막 표면에 흡착하여 막의 전기화학적 특성이 저하된다는 단점을 가지고 있다.The polymer support most widely used so far in producing the ion selective membrane is poly (vinyl chloride) (hereinafter, abbreviated as 'PVC'). PVC is widely used as a support for various ion-selective membranes because of its excellent electrochemical properties, namely slope, detection limit, and selectivity, among polymer materials known to be able to be used as a support. Has been used. However, such a PVC-supported ion selective membrane has a disadvantage in that the interface between the ion selective membrane and the solid electrode surface is unstable and thus the electrochemical properties are lowered and the life of the solid electrode is shortened because the adhesion between the solid phase electrode and the solid surface is poor. In addition, PVC-supported ion-selective membranes have a disadvantage in that biocompatibility is lowered when inserted into blood or biological fluids, so that proteins and the like are adsorbed onto the electrode membrane surface, thereby degrading the electrochemical properties of the membrane.
이러한 PVC-지지체 이온선택성 막의 단점을 개선하기 위하여 접착제나 외부 고정체을 사용하는 방법과 기존의 PVC를 변형시킨 히드록시화된 PVC나 카르복시화된 PVC 유도체 등을 이용하는 방법이 연구되어 왔다. 그러나 이러한 방법을 이용한 이온선택성 막은 전기화학적 특성이 저하되고, 외부 고정체를 사용할 경우 전극의 소형화 및 대량생산에 불리하며, PVC를 변형시켜 사용하는 경우 PVC 유도체들의 접착력에 한계가 있기 때문에 기존 PVC-지지체 이온선택성 막의 단점을 개선시킬 수 없었다.In order to improve the disadvantages of the PVC-supported ion selective membrane, a method of using an adhesive or an external fixture and a method of using a hydroxylated PVC or a carboxylated PVC derivative modified from existing PVC have been studied. However, ion-selective membranes using this method have poor electrochemical properties, disadvantages in miniaturization and mass production of electrodes when using external fixtures, and limited adhesion of PVC derivatives when using modified PVC. The disadvantages of the support ion-selective membrane could not be improved.
최근 새로운 물질을 지지체로 사용하여 이온선택성 막을 제조하는 방법이 연구되었으며, 이러한 대체 지지체 중 우수한 생체적합성과 강한 접착력을 갖는 PU를 이온선택성 막의 지지체로 이용하고자 하는 연구가 활발히 진행되어 왔다.Recently, a method of preparing an ion-selective membrane using a new material as a support has been studied, and studies have been actively conducted to use PU having excellent biocompatibility and strong adhesion among these alternative supports as a support for an ion-selective membrane.
한편 PVC를 지지체로 사용하여 형성한 칼슘이온선택성 막은, 혈액 내 2.1 -2.65 mM 정도 존재하는 칼슘이온을 분석할 경우 혈액 내에 130 - 145 mM 정도로 다량 존재하는 나트륨이온 (sodium; Na+)이 심각한 방해작용을 하기 때문에 실용적 사용이 불가능하다는 문제점이 있었다. 이러한 문제점을 해결하기 위한 방법으로, 친유성 첨가제로 포타슘 테트라키스(4-클로로페닐)보레이트를 사용하고 있고, 미소전극 (microelectrode)에서 PVC막의 저항을 줄여주기 위하여 테트라도데실암모늄 테트라키스(4-클로로페닐)보레이트와 포타슘 테트라키스(4-클로로페닐)보레이트를 혼합하여 사용한 연구가 보고되었으나 선택성의 개선과는 무관한 것이었다.On the other hand, the calcium ion selective membrane formed by using PVC as a support has severe disturbance of sodium ions (Na + ) present in the blood in a large amount of 130-145 mM when analyzing the calcium ions present in the blood of 2.1 -2.65 mM. There was a problem that practical use is impossible because it works. To solve this problem, potassium tetrakis (4-chlorophenyl) borate is used as a lipophilic additive, and tetradodecylammonium tetrakis (4- is used to reduce the resistance of the PVC film in the microelectrode. A study using a mixture of chlorophenyl) borate and potassium tetrakis (4-chlorophenyl) borate has been reported but has not been related to the improvement in selectivity.
또한 PVC-지지체 이온선택성 막의 경우는, 혈액분석시 혈액 내에 존재하는 단백질 (protein)이 막 표면에 흡착됨으로 인해 생기는 비대칭 전위 (asymmetric potential)로 인해 잘못된 분석 신호를 발생시킨다는 문제점을 지니고 있다.In addition, PVC-supported ion selective membranes have a problem in that false analysis signals are generated due to asymmetric potentials caused by the adsorption of proteins in the blood onto the membrane surface during blood analysis.
이에 본 발명자들은 전술한 칼슘이온선택성 막의 문제점을 해결하고자 연구한 결과, PU를 지지체로 사용하고 친유성 첨가제, 가소제 및 이온선택성 물질이 적절한 비율로 혼합된 본 발명의 조성물로 제조된 칼슘이온선택성 막이, 기존의 PVC-지지체 막에 비하여 혈액이나 뇨와 같은 생체시료 중의 칼슘이온 농도 측정시 단백질 흡착으로 인한 비대칭 전위가 발생하지 않을 뿐만 아니라 나트륨이온, 칼륨이온 (potassium; K+), 리튬이온 (lithium; Li+), 마그네슘이온 (magnesium; Mg2+), 수소이온 (hydrogen ion; H+) 등과 같은 여러 가지 이온종에 의한 방해작용을 받지 않으며, 고체상 전극 표면과의 접촉 계면의 안정을 가져와 감응성의 감소를 방지하고,고체상 전극 표면과의 접착력을 향상시켜 고체상 전극의 수명을 연장시킬 수 있으며, 또한 전기화학적 성질이 우수하다는 것을 알아내어 본 발명을 완성하였다.Accordingly, the present inventors have studied to solve the above-mentioned problems of calcium ion selective membranes. As a result, the calcium ion selective membranes prepared from the composition of the present invention using PU as a support and a mixture of lipophilic additives, plasticizers and ion selective materials in an appropriate ratio are Compared to conventional PVC-supported membranes, asymmetric potentials due to protein adsorption do not occur when measuring calcium ion concentrations in biological samples such as blood or urine, as well as sodium, potassium ions (K + ), and lithium ions (lithium). ; Li + ), magnesium ions (Mg 2+ ), hydrogen ions (Hgen) (H + ), etc. are not disturbed by various ionic species, and the stability of the contact interface with the surface of the solid-state electrode It can prevent the decrease of, improve the adhesion with the surface of the solid electrode can extend the life of the solid electrode, and also has excellent electrochemical properties It was found that the present invention was completed.
본 발명의 목적은 칼슘이온 센서의 전극에 구비되는 칼슘이온선택성 막 조성물을 제공하는 것이다.An object of the present invention is to provide a calcium ion selective membrane composition provided on the electrode of the calcium ion sensor.
도 1a는 일반적인 재래식 이온선택성 막전극의 단면도이고, 1A is a cross-sectional view of a conventional conventional ion selective membrane electrode,
도 1b는 고체상 이온선택성 막전극의 단면도이고, 1B is a cross-sectional view of a solid state ion selective membrane electrode,
도 2a는 이온선택성 물질로 N,N,N',N'-테트라시클로헥실-3-옥사펜탄디아미드를 사용한, PVC-지지체 (●), 친유성 첨가제가 첨가되지 않은 PU-지지체 (▲), 친유성 첨가제가 첨가된 PU-지지체 (■) 칼슘이온선택성 막을 재래식 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이고, Figure 2a shows a PVC-support (●), a PU-support without lipophilic additives (▲), using N, N, N ', N'-tetracyclohexyl-3-oxopentanediamide as an ion-selective material. , PU-support (■) calcium ion selective membrane to which the lipophilic additive was added to the conventional electrode, a graph showing the sensitivity characteristics when the sensitivity test,
도 2b는 이온선택성 물질로 (-)-(R,R)-N,N'-[비스(11-에톡시카르보닐)운데실]-N,N'-4,5-테트라메틸-3,6-디옥사옥탄디아미드를 사용한, PVC-지지체 (●), 친유성 첨가제가 첨가되지 않은 PU-지지체 (▲), 친유성 첨가제가 첨가된 PU-지지체 (■) 칼슘이온선택성 막을 재래식 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이고, Figure 2b is an ion-selective material (-)-(R, R) -N, N '-[bis (11-ethoxycarbonyl) undecyl] -N, N'-4,5-tetramethyl-3, PVC-supported (●), 6-dioxaoctanediamide, PU-supported without lipophilic additives (▲), PU-supported with lipophilic additives (■) calcium ion selective membranes were added to conventional electrodes. It is a graph showing the response characteristics when the sensitivity test when installed,
도 3a는 이온선택성 물질로 N,N,N',N'-테트라시클로헥실-3-옥사펜탄디아미드를 사용한, PVC-지지체 및 친유성 첨가제가 첨가된 PU-지지체 칼슘이온선택성 막을 고체상 전극에 장착하여 칼슘이온 (ㄱ)과 나트륨이온 (ㄴ)에 대한 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이고, 3A shows a PU-supported calcium ion selective membrane to which a PVC-supported and lipophilic additive is added, using N, N, N ', N'-tetracyclohexyl-3-oxopentanediamide as an ion-selective material, to a solid-state electrode. It is a graph showing the sensitivity characteristics when the sensitivity test for calcium ions (a) and sodium ions (b) by mounting,
(가) : PVC-지지체 막의 감응성 그래프(A): Sensitivity graph of PVC-supported membrane
(나) : 친유성 첨가제가 첨가된 PU-지지체 막의 감응성 그래프(B): Sensitivity graph of PU-supported membrane to which lipophilic additive is added
도 3b는 이온선택성 물질로 (-)-(R,R)-N,N'-[비스(11-에톡시카르보닐)운데실]-N,N'-4,5-테트라메틸-3,6-디옥사옥탄디아미드를 사용한, PVC-지지체 및 친유성 첨가제가 첨가된 PU-지지체 칼슘이온선택성 막을 고체상 전극에 장착하여 칼슘이온 (ㄱ)과 나트륨이온 (ㄴ)에 대한 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이고, Figure 3b is an ion-selective material (-)-(R, R) -N, N '-[bis (11-ethoxycarbonyl) undecyl] -N, N'-4,5-tetramethyl-3, When the PU-supported calcium ion-selective membrane with PVC-supported and lipophilic additives using 6-dioxaoctanediamide was mounted on a solid-state electrode, the sensitivity test for calcium ions (a) and sodium ions (b) was carried out. Is a graph showing the response characteristics of
(가) : PVC-지지체 막의 감응성 그래프(A): Sensitivity graph of PVC-supported membrane
(나) : 친유성 첨가제가 첨가된 PU-지지체 막의 감응성 그래프(B): Sensitivity graph of PU-supported membrane to which lipophilic additive is added
도 4는 이온선택성 물질로 N,N,N',N'-테트라시클로헥실-3-옥사펜탄디아미드 및 (-)-(R,R)-N,N'-[비스(11-에톡시카르보닐)운데실]-N,N'-4,5-테트라메틸-3,6-디옥사옥탄디아미드를 사용한, PVC-지지체 및 친유성 첨가제가 첨가된 PU-지지체 칼슘이온선택성 막의 고체상 전극에서의 시간에 따른 칼슘이온에 대한 감응성을 나타낸 그래프이다. 4 is N, N, N ', N'-tetracyclohexyl-3-oxapentanediamide and (-)-(R, R) -N, N'-[bis (11-ethoxy) as ion-selective materials. Solid-state electrode of PU-supported calcium ion-selective membrane with added PVC-support and lipophilic additive, using carbonyl) undecyl] -N, N'-4,5-tetramethyl-3,6-dioxaoctanediamide This is a graph showing the sensitivity to calcium ions over time.
* 도면의 주요 부분에 대한 부호의 설명* Explanation of symbols for the main parts of the drawings
(10) : 전극 몸체 (20) : 고정체10: electrode body 20: fixture
(30) : 내부기준전극 (Ag/AgCl) (40) : 내부기준용액(30): Internal reference electrode (Ag / AgCl) (40): Internal reference solution
(50) : 이온선택성 막 (60) : Ag 막대50: ion-selective membrane 60 Ag rod
(70) : 세라믹판 (80) : 절연체70: ceramic plate 80: insulator
상기 목적을 달성하기 위하여, 본 발명에서는 PU, 가소제, 이온선택성 물질 및 친유성 첨가제로 이루어진 칼슘이온선택성 막 조성물을 제공한다.In order to achieve the above object, the present invention provides a calcium ion selective membrane composition consisting of PU, a plasticizer, an ion selective material and a lipophilic additive.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 우선, 칼슘이온선택성 막의 제조에 있어서 PU를 지지체로 사용한 칼슘이온선택성 막 조성물을 제공한다.In the present invention, first, a calcium ion selective membrane composition using PU as a support in the preparation of a calcium ion selective membrane is provided.
또한, 본 발명에서는 칼슘이온선택성 막 조성물로서 가소제, 이온선택성 물질 및 친유성 첨가제를 포함할 수 있다.In addition, in the present invention, a calcium ion selective membrane composition may include a plasticizer, an ion selective material, and a lipophilic additive.
구체적으로 전술한 칼슘이온선택성 막 조성물에서 지지체로 사용한 PU는 전체 막 조성의 24.6 - 41.0 중량로 포함될 수 있다.Specifically, the PU used as a support in the aforementioned calcium ion selective membrane composition may be included as 24.6-41.0 weight of the total membrane composition.
또한 상기 PU-지지체 칼슘이온선택성 막의 제조를 위한 조성물로서 가소제로는 비스(2-에틸헥실) 아디페이트 (bis(2-ethylhexyl) adipate, 이하 'DOA'라 약칭함); 비스(2-에틸헥실) 세바케이트 (bis(2-ethylhexyl) sebacate, 이하 'DOS'라 약칭함); 및 2-니트로페닐 옥틸 에테르 (2-nitropheny octyl ether, 이하 'NPOE'라 약칭함) 로 이루어진 그룹에서 선택되는 물질을 사용할 수 있다. 이때 가소제는 전체 막 조성의 49.4 - 74.6 중량로 포함될 수 있다.In addition, the plasticizer as a composition for the production of the PU-supporting calcium ion-selective membrane is bis (2-ethylhexyl) adipate (bis (2-ethylhexyl) adipate, hereinafter abbreviated as 'DOA'); Bis (2-ethylhexyl) sebacate (bis (2-ethylhexyl) sebacate, hereinafter abbreviated as 'DOS'); And 2-nitropheny octyl ether (hereinafter abbreviated as 'NPOE') may be used. The plasticizer may be included at 49.4-74.6 weight of the total membrane composition.
본 발명에서는 상기 PU-지지체 칼슘이온선택성 막의 제조를 위한 조성물로서 이온선택성 물질로는 N,N,N',N'-테트라시클로헥실-3-옥사펜탄디아미드 (N,N,N'N'- tetracyclohexyl-3-oxapentanediamide, 이하 'ETH 129'라 약칭함); (-)-(R,R)- N,N'-[비스(11-에톡시카르보닐)운데실]-N,N'-4,5-테트라메틸-3,6-디옥사옥탄디아미드 ((-)-(R,R)-N,N'-[bis(11-ethoxycarbonyl)undecyl]-N,N'-4,5-tetramethyl-3,6- dioxaoctanediamide, 이하 'ETH 1001'라 약칭함 ); 및 N,N-디시클로헥실-N,N'-디옥타데실-3-옥사펜탄디아미드 (N,N-dicyclohexyl-N,N'-dioctadecyl-3-oxapnetanediamide) 로 이루어진 그룹에서 선택되는 물질을 사용할 수 있다. 이때 이온선택성 물질을 전체 막 조성의 0.5 - 5.5 중량포함할 수 있다.In the present invention, as the composition for preparing the PU-supporting calcium ion selective membrane, the ion-selective substance is N, N, N ', N'-tetracyclohexyl-3-oxopentanedamide (N, N, N'N'). tetracyclohexyl-3-oxapentanediamide, hereafter abbreviated as 'ETH 129'; (-)-(R, R) -N, N '-[bis (11-ethoxycarbonyl) undecyl] -N, N'-4,5-tetramethyl-3,6-dioxaoctanediamide ((-)-(R, R) -N, N '-[bis (11-ethoxycarbonyl) undecyl] -N, N'-4,5-tetramethyl-3,6-dioxaoctanediamide, hereinafter abbreviated as' ETH 1001' )); And N, N-dicyclohexyl-N, N'-dioctadecyl-3-oxapentanediamide (N, N-dicyclohexyl-N, N'-dioctadecyl-3-oxapnetanediamide). Can be used. In this case, the ion-selective material may include 0.5-5.5 weight of the total membrane composition.
또한 상기 PU-지지체 칼슘이온선택성 막의 제조를 위한 조성물에서 친유성 첨가제로는 포타슘 테트라키스(4-클로로페닐)보레이트 (potassium tetrakis(4- chlorophenyl)borate, 이하 'KTpClPB'라 약칭함); 테트라도데실암모늄 테트라키스(4-클로로페닐)보레이트 (tetradodecylammonium tetrakis(4-chlorophenyl) borate, 이하 'ETH 500'라 약칭함); 및 이들의 혼합물로 이루어진 그룹에서 선택되는 물질을 사용할 수 있다. KTpClPB와 ETH 500의 혼합물을 사용하는 것이 더 바람직하며, 그 경우 KTpClPB와 ETH 500을 각각 전체 막 조성의 0.3 -3.3 중량로 포함할 수 있다.In addition, the lipophilic additive in the composition for preparing the PU-supporting calcium ion-selective membrane is potassium tetrakis (4-chlorophenyl) borate (hereinafter abbreviated as 'KTpClPB'); Tetradodecylammonium tetrakis (4-chlorophenyl) borate (tetradodecylammonium tetrakis (4-chlorophenyl) borate, hereinafter abbreviated as 'ETH 500'); And materials selected from the group consisting of mixtures thereof. It is more preferred to use a mixture of KTpClPB and ETH 500, in which case KTpClPB and ETH 500 may each comprise 0.3-3.3 weight of the total film composition.
본 발명의 PU-지지체 칼슘이온선택성 막은, 칼슘이온 센서의 고체상 전극 및 재래식 전극에 장착될 수 있다.The PU-supported calcium ion selective membrane of the present invention may be mounted on solid state electrodes and conventional electrodes of calcium ion sensors.
구체적으로 본 발명은 칼슘이온 센서의 재래식 전극에 칼슘이온선택성 막을 장착하는 방법에 있어서, 상기 칼슘이온선택성 막 조성물을 유기 용매에 녹인 후 그 혼합물을 유리판 또는 테프론판 위에 고정시킨 유리링에 부어 실온에서 1-3일 정도 건조시켜 성형하고, 이와 같이 제조된 이온선택성 막을 통상의 절단 기구로 원하는 모양으로 잘라낸 후 재래식 전극에 상기 칼슘이온선택성 막을 장착하는 공정을 포함하는 칼슘이온센서의 제조방법을 제공한다.Specifically, in the method for mounting a calcium ion selective membrane on a conventional electrode of a calcium ion sensor, the calcium ion selective membrane composition is dissolved in an organic solvent, and then the mixture is poured into a glass ring fixed on a glass plate or a teflon plate at room temperature. It is dried for 1 to 3 days, and the ion-selective membrane prepared as described above is cut into a desired shape with a conventional cutting device, and then the method of manufacturing a calcium ion sensor comprising the step of mounting the calcium ion-selective membrane on a conventional electrode. .
또한 본 발명은 칼슘이온 센서의 고체상 전극에 칼슘이온선택성 막을 장착하는 방법에 있어서, 상기 칼슘이온선택성 막 조성물을 유기 용매에 녹인 후 그 혼합물을 마이크로시린지를 사용하여 고체상 전극 표면에 코팅하고 실온에서 1-3일 정도 건조시켜 성형하는 공정을 포함하는 칼슘이온센서의 제조방법을 제공한다.In addition, the present invention is a method of mounting a calcium ion selective membrane on the solid-state electrode of the calcium ion sensor, the calcium ion-selective membrane composition is dissolved in an organic solvent and then the mixture is coated on the surface of the solid-state electrode using a micro syringe and 1 at room temperature It provides a method for producing a calcium ion sensor comprising a step of drying to form -3 days.
본 발명의 조성물로 형성된 PU-지지체 칼슘이온선택성 막을 장착한 재래식 전극을 사용한 칼슘이온 센서는, 혈액이나 뇨와 같은 생체시료 중의 칼슘이온 농도를 측정할 때 단백질 흡착으로 인한 비대칭 전위를 발생시키지 않을 뿐만 아니라 나트륨이온, 칼륨이온, 리튬이온, 마그네슘이온, 수소이온 등 여러 가지 이온종에 의한 방해작용이 제거된다. 반면 PVC를 지지체로 사용한 칼슘이온선택성 막은 혈액 내 다량 존재하는 나트륨이온에 의해 방해작용을 받기 때문에 선택성에 문제가있으며, 또한 생체시료 분석시 단백질이 막 표면에 흡착되기 때문에 비대칭 전위가 발생하고 이로 인하여 잘못된 분석 신호를 발생시킨다.The calcium ion sensor using a conventional electrode equipped with a PU-supporting calcium ion selective membrane formed from the composition of the present invention does not generate an asymmetric potential due to protein adsorption when measuring the calcium ion concentration in a biological sample such as blood or urine. In addition, the interference by various ionic species such as sodium ions, potassium ions, lithium ions, magnesium ions and hydrogen ions is eliminated. On the other hand, calcium ion selective membranes using PVC as a support have a problem of selectivity because they are interrupted by sodium ions present in the blood, and asymmetric potentials occur because proteins are adsorbed on the membrane surface in biological samples. It generates a false analysis signal.
또한, 본 발명의 조성물로 형성된 PU-지지체 칼슘이온선택성 막을 고체상 전극에 코팅한 칼슘이온 센서에 대해 감응성 변화 실험을 수행한 결과, PU를 지지체로 사용함으로써 그 이온선택성 막은 고체상 전극 표면과의 접촉 계면의 안정성이 증대되어 감응성의 감소를 방지하고, 고체상 전극 표면과의 접착력을 향상시켜 고체상 전극의 수명을 연장시킬 수 있으며, 또한 PVC-지지체 칼슘이온선택성 막을 사용한 것보다도 전기화학적 성질이 우수하다. 반면에 기존의 PVC-지지체 이온선택성 막은 이온선택성 막과 고체상 전극 표면 사이의 계면이 불안정하므로 전기화학적 특성이 저하되며 접착력이 약하여 고체상 전극의 수명이 단축된다.In addition, as a result of performing a sensitivity change experiment on a calcium ion sensor coated on a solid-state electrode with a PU-supporting calcium ion-selective membrane formed from the composition of the present invention, the ion-selective membrane was contacted with the surface of the solid-state electrode by using PU as a support. The stability of the resin can be increased to prevent a decrease in sensitivity, to improve the adhesion to the surface of the solid phase electrode, thereby to extend the life of the solid phase electrode, and the electrochemical property is superior to that of the PVC-supported calcium ion selective membrane. On the other hand, the conventional PVC-supported ion selective membrane has an unstable interface between the ion selective membrane and the surface of the solid electrode, thereby deteriorating electrochemical properties and weak adhesion, thereby shortening the life of the solid electrode.
또한 본 발명의 조성물로 형성된 이온선택성 막을 고체상 전극에 장착한 칼슘이온 센서는, 혈액이나 뇨와 같은 생체시료 중의 칼슘이온 농도를 측정할 때 단백질 흡착으로 인한 비대칭 전위를 발생시키지 않으며 나트륨이온, 칼륨이온, 리튬이온, 마그네슘이온, 수소 이온 등 여러 가지 이온종에 의한 방해작용이 제거된다.In addition, a calcium ion sensor equipped with an ion-selective membrane formed of the composition of the present invention on a solid-state electrode does not generate an asymmetric potential due to protein adsorption when measuring the calcium ion concentration in a biological sample such as blood or urine, and does not generate sodium or potassium ions. The interference by various ionic species such as lithium ions, magnesium ions and hydrogen ions is eliminated.
이하 본 발명을 실시예에 의하여 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
단, 하기 실시예들은 본 발명을 예시하는 것으로 본 발명의 내용이 실시예에 의해 한정되는 것은 아니다.However, the following examples are illustrative of the present invention, and the content of the present invention is not limited by the examples.
<실시예 1-2 및 비교예 1-4> 칼슘이온선택성 막 조성물의 제조<Example 1-2 and Comparative Example 1-4> Preparation of calcium ion selective membrane composition
본 발명의 칼슘이온선택성 막 중, ETH 129를 이온선택성 물질로 한 조성은표 1에 나타내었고, ETH 1001을 이온선택성 물질로 한 조성은표 2에 나타내었다.In the calcium ion selective membrane of the present invention, the composition using ETH 129 as an ion selective material is shown in Table 1 , and the composition using ETH 1001 as an ion selective material is shown in Table 2 .
<실시예 3> 재래식 전극을 사용한 칼슘이온 센서의 제조Example 3 Fabrication of Calcium Ion Sensor Using a Conventional Electrode
칼슘이온 센서의 재래식 전극에 구비되는 이온선택성 막을 제조하기 위하여, 상기 실시예 1-2 및 비교예 1-4의 막 조성물을 유기용매인 테트라히드로푸란 (tetrahydrofuran, 이하 'THF'라 약칭함)에 녹인 후 그 혼합물을 유리판이나 테프론판 위에 고정시킨 유리링에 부어 실온에서 1 - 3 일 정도 건조시켜 성형하고, 이와 같이 제조된 이온선택성 막을 펀치 등을 사용하여 잘라낸 후 재래식 전극의 고정체에 장착하여 실험하였다.In order to manufacture an ion-selective membrane provided in the conventional electrode of the calcium ion sensor, the membrane compositions of Examples 1-2 and Comparative Examples 1-4 are added to tetrahydrofuran (hereinafter, abbreviated as 'THF') as an organic solvent. After melting, the mixture is poured into a glass ring fixed on a glass plate or a teflon plate, dried at room temperature for 1 to 3 days, and molded. The ion-selective membrane thus prepared is cut out using a punch or the like and mounted on a fixture of a conventional electrode. Experiment.
칼슘이온 센서의 전기화학적 수행 능력을 알아보기 위하여, 재래식 전극에 칼슘이온선택성 막을 장착하여 각각의 감응 기울기를 조사했다.In order to investigate the electrochemical performance of the calcium ion sensor, the slope of each response was investigated by mounting a calcium ion selective membrane on the conventional electrode.
고분자 지지체의 종류와 첨가제 사용 여부에 따른 감응성의 변화 조사Investigation of the sensitivity change according to the type of polymer support and the use of additives
도 2a는 이온선택성 물질로 ETH 129를 사용한 칼슘이온선택성 막을 재래식 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이다. FIG. 2A is a graph showing the sensitivity characteristics when a calcium ion selective membrane using ETH 129 as an ion selective material was mounted on a conventional electrode and subjected to a sensitivity test. FIG.
기존에 널리 사용되고 있는 PVC-지지체 막 (-●-)의 조성은표 1의 비교예 1과 같으며, 이것을 기준으로 하여 다른 조성의 것과 비교하였다.The composition of the conventionally widely used PVC-supported membrane (-●-) is the same as in Comparative Example 1 of Table 1 , and compared with that of other compositions based on this.
PVC-지지체 막 (비교예 1; -●-)의 경우 이론적 감응 기울기인 29 mV/decade에 거의 유사한 28 mV/decade를 보였다. 친유성 첨가제가 첨가되지 않은 PU-지지체 막 (비교예 2; -▲-)은 이론적인 감응 기울기보다 더 큰 47 mV/decade의 비정상적인 감응을 보였다. 반면에 두 가지 친유성 첨가제, 즉 KTpClPB와 ETH 500이 첨가된 PU-지지체 막 (실시예 1; -■-)은, PVC-지지체 막과 동일한 감응 기울기인 28 mV/decade를 보이고 있으며 다른 전기화학적 수행 능력 또한 PVC-지지체 막과 거의 유사함을 확인할 수 있었다.The PVC-supported membrane (Comparative Example 1;-●-) showed 28 mV / decade, which is almost similar to the theoretical response slope of 29 mV / decade. PU-support membranes without the addition of lipophilic additives (Comparative Example 2;-▲-) showed an abnormal response of 47 mV / decade which was greater than the theoretical response slope. On the other hand, the PU-support membrane (Example 1;-■-) with the addition of two lipophilic additives, KTpClPB and ETH 500, showed 28 mV / decade with the same sensitivity gradient as the PVC-support membrane. The performance was also found to be almost similar to the PVC-supported membrane.
도 2b는 이온선택성 물질로 ETH 1001를 사용한 칼슘이온선택성 막을 재래식 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이다. FIG. 2B is a graph showing the sensitivity characteristics when a calcium ion selective membrane using ETH 1001 as an ion selective material was mounted on a conventional electrode and subjected to a sensitivity test. FIG.
PVC-지지체 막 (-●-)의 조성은표 2의 비교예 3과 같으며, 이것을 기준으로 하여 다른 조성의 것과 비교하였다.The composition of the PVC-supporting membrane (-●-) was as in Comparative Example 3 of Table 2 , and compared with that of other compositions based on this.
PVC-지지체 막 (비교예 3; -●-)의 경우 감응 기울기는 26 mV/decade로 이론적 기울기보다 약간 작게 나오고 있다. 친유성 첨가제가 첨가되지 않은 PU-지지체 막 (비교예 4; -▲-)은 감응 기울기가 28 mV/decade를 보이고는 있지만, 감응 후 전위가 불안정해지는 단점이 있었다. 친유성 첨가제가 첨가된 PU-지지체 막 (실시예 2; -■-)은 감응 기울기가 28 mV/decade로서 이온선택성 물질로 ETH 129를 사용한 경우에서와 마찬가지로 PVC-지지체와 같은 우수한 전기화학적 성질을 나타냄을 확인하였다.In the case of PVC-supported membranes (Comparative Example 3;-●-), the response slope is 26 mV / decade, which is slightly smaller than the theoretical slope. PU-support membrane (Comparative Example 4;-▲-) to which no lipophilic additive was added showed a response slope of 28 mV / decade, but had a disadvantage in that the potential was unstable after the response. PU-support membranes with lipophilic additives (Example 2;-■-) have good electrochemical properties like PVC-support as in the case of using ETH 129 as an ion-selective material with a slope of 28 mV / decade. It confirmed that it was shown.
<실시예 4> 고체상 전극을 사용한 칼슘이온 센서의 제조Example 4 Fabrication of Calcium Ion Sensor Using Solid-State Electrode
고체상 전극에 이온선택성 막을 형성하기 위해서 THF 용매에 상기 실시예 1-2 및 비교예 1-4의 막 조성물을 녹인 혼합물을 마이크로시린지 (microsyringe) 등을 이용하여 고체상 전극 표면에 코팅한 후 실온에서 1 - 3 일 정도 건조시켜 성형하였다.In order to form an ion-selective membrane on a solid-state electrode, a mixture of the membrane compositions of Examples 1-2 and Comparative Examples 1-4 in THF solvent was coated on the surface of the solid-state electrode using a microsyringe, or the like at room temperature. Molded by drying for 3 days.
칼슘이온 센서의 전기 화학적 수행 능력을 알아보기 위하여, 고체상 전극에 칼슘이온선택성 막을 장착하여 각각의 감응 기울기를 조사하였다.In order to investigate the electrochemical performance of the calcium ion sensor, the slope of each response was investigated by mounting a calcium ion selective membrane on the solid-state electrode.
1) 고분자 지지체의 종류와 첨가제 사용 여부에 따른 감응성의 변화 조사1) Investigation of change in sensitivity depending on the type of polymer support and the use of additives
도 3a는 이온선택성 물질로 ETH 129를 사용한 칼슘이온선택성 막을 고체상 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이다. (가)는 PVC-지지체 막 (비교예 1)으로 측정하여 얻은 결과에 대한 그래프이고, (나)는 두 가지 친유성 첨가제가 첨가된 PU-지지체 막 (실시예 1)으로 측정하여 얻은결과에 대한 그래프로서, (ㄱ)은 칼슘이온에 대한 감응성 그래프이고, (ㄴ)은 혈액 중 비교적 많이 존재하는 나트륨이온 (혈액 중 정상 농도 범위 135 - 145 mV)에 대한 감응성 그래프로서 (ㄴ)의 경우는 300 mM까지의 감응을 비교하였다. FIG. 3A is a graph illustrating the sensitivity characteristics when a calcium ion selective membrane using ETH 129 as an ion selective material is mounted on a solid state electrode and subjected to a sensitivity test. FIG. (A) is a graph of the results obtained by measuring with a PVC-supporting membrane (Comparative Example 1), (B) is a graph of the results obtained by measuring with a PU-supporting membrane (Example 1) to which two lipophilic additives were added. (A) is a graph of sensitivity to calcium ions, (b) is a graph of sensitivity to sodium ions (a normal concentration range of 135-145 mV in the blood) in the blood, The response up to 300 mM was compared.
혈액 중 자유 칼슘이온의 농도는 2.1 - 2.65 mM인데 (가)의 경우는 (ㄱ)의 10 mM까지의 감응이 139 mV였고, (ㄴ)은 300mM까지의 감응이 28 mV였다. (나)의 경우도 (가)의 경우와 거의 동일하였다. 이것을 통하여, 재래식 전극에서의 전기화학적 성능이 고체상 전극에서도 잘 적용됨을 확인할 수 있었다. 반면 친유성 첨가제를 첨가하지 않은 PU-지지체 막 (비교예 2)을 고체상 전극에 응용하였을 경우 2일 정도만 작동했으며 나트륨 이온에 의해 많은 방해작용을 받았다.The concentration of free calcium ions in the blood ranged from 2.1 to 2.65 mM. In the case of (a), the response up to 10 mM in (a) was 139 mV, and (b) was up to 28 mV up to 300 mM. The case of (b) was also almost the same as the case of (a). Through this, it was confirmed that the electrochemical performance of the conventional electrode is well applied to the solid-state electrode. On the other hand, when the PU-supporting membrane (Comparative Example 2) without the addition of a lipophilic additive was applied to the solid-state electrode, it only operated for about two days and was heavily disturbed by sodium ions.
도 3b는 이온선택성 물질로 ETH 1001을 사용한 칼슘이온선택성 막을 고체상 전극에 장착하여 감응성 테스트를 하였을 때의 감응특성을 나타낸 그래프이다. (가)는 PVC-지지체 막 (비교예 3)으로 측정하여 얻은 결과에 대한 그래프이고, (나)는 두 가지 친유성 첨가제가 첨가된 PU-지지체 막 (실시예 2)으로 측정하여 얻은 결과에 대한 그래프로서 (ㄱ)은 칼슘이온에 대한 감응성 그래프이고, (ㄴ)은 나트륨이온에 대한 감응성 그래프이다. FIG. 3B is a graph showing the sensitivity characteristics when a calcium ion selective membrane using ETH 1001 as an ion selective material is mounted on a solid state electrode and subjected to a sensitivity test. FIG. (A) is a graph of the results obtained by measuring with a PVC-supporting membrane (Comparative Example 3), (B) is a graph of the results obtained by measuring with a PU-supporting membrane (Example 2) to which two lipophilic additives were added. (A) is a graph of sensitivity to calcium ions, and (b) is a graph of sensitivity to sodium ions.
(가)의 PVC-지지체 막의 경우는 칼슘이온에 대해서는 10 mM까지의 감응성이 100 mV였고 감응 기울기가 26 mV/decade로 비교적 우수하였으나, 나트륨이온에 대해서는 300 mM까지 53 mV/decade로 많은 감응을 보여 생체물질 등 실제 시료에서 칼슘이온 측정 시 방해작용을 받을 것으로 판단된다. 그러나, (나)의 PU-지지체 막의 경우는 칼슘이온 (ㄱ)에 대해서는 10 mM까지 113 mV의 감응을 보이고 감응 기울기 또한 27 mV/decade를 보임을 알 수 있고, 나트륨이온 (ㄴ)에 대한 감응은 100 mM까지는 2 mV이고 300 mM까지는 7 mV로 생체물질 등에서 칼슘이온을 측정할 때 거의 방해작용을 받지 않을 것으로 판단된다.In case of PVC-supported membrane of (A), the sensitivity up to 10 mM for calcium ion was 100 mV and the slope of response was relatively good at 26 mV / decade, but it was 53 mV / decade up to 300 mM for sodium ion. It seems to be disturbed when measuring calcium ion in real samples such as biological materials. However, the PU-supporting membrane of (b) showed 113 mV response up to 10 mM for calcium ion (a) and a slope of response of 27 mV / decade, and response to sodium ion (b). Silver is 2 mV up to 100 mM and 7 mV up to 300 mM.
전술한 바와 같이 비교예의 조성물을 이용한 막과 실시예의 조성물을 이용한 막을 실험한 결과, 실시예의 조성물을 이용한 막의 모든 전기화학적 성질이 비교예의 조성물을 이용한 막에 비하여 현저히 개선되었음을 확인할 수 있었다.As described above, the membrane using the composition of the comparative example and the membrane using the composition of the example were tested. As a result, it was confirmed that all the electrochemical properties of the membrane using the composition of the example were significantly improved compared to the membrane using the composition of the comparative example.
2) 시간에 따른 칼슘이온에 대한 감응성의 변화 조사2) Investigation of the change in sensitivity to calcium ions over time
도 4는 이온선택성 물질로 ETH 129와 ETH 1001을 사용한 PVC-지지체 (비교예 1 및 비교예 3) 및 PU-지지체 (실시예 1 및 실시예 2) 전극막을 고체상 전극에 장착하였을 경우, 시간에 따른 칼슘이온에 대한 감응성을 나타낸 그래프이다. 4 shows the time when the PVC-support (Comparative Example 1 and Comparative Example 3) and the PU-support (Example 1 and Example 2) using the ETH 129 and ETH 1001 as ion-selective materials were mounted on the solid-state electrode. It is a graph showing the sensitivity to calcium ions according to.
PVC-지지체 막은 시간이 지남에 따라 감응 기울기가 크게 감소되었고, 또한 불안정한 전위값을 보여 일주일 이상은 더 이상 센서로 사용할 수 없게 되었지만, 두 가지 친유성 첨가제가 첨가된 폴리우레탄-지지체 막 (실시예 2)은 26 mV/decade 정도의 감응 기울기를 보이며 한달 이상 잘 작동함을 알 수 있다.While the PVC-support membranes have greatly reduced the response slope over time and also show unstable potential values, they can no longer be used as sensors for more than a week, but the polyurethane-support membranes with the addition of two lipophilic additives (Example 2) shows a response slope of 26 mV / decade and works well for over a month.
이상에서 설명한 바와 같이, 본 발명의 폴리우레탄을 지지체로 사용하고 가소제, 이온선택성 물질 및 친유성 첨가제의 조성물로 이루어진 칼슘이온선택성 막을 전극 표면에 장착한 칼슘이온 센서는, 고체상 전극 표면과의 접착력이 우수하여 감응성의 감소가 방지되고 수명이 연장되며 전기화학적 성질이 우수하고 혈액이나 뇨와 같은 생체시료 중의 칼슘이온 농도 측정시 단백질 흡착으로 인한 비대칭 전위의 발생이 없을 뿐만 아니라 나트륨이온, 칼륨이온, 리튬이온, 마그네슘이온, 수소이온 등과 같은 여러 가지 이온종에 의한 방해작용을 받지 않는다는 장점을 가지고 있으며, 따라서 본 발명에 따라 제조된 칼슘이온 센서는 생체시료, 환경시료 중의 칼슘 이온 농도를 측정하기 위한 용도로 사용이 가능하다.As described above, the calcium ion sensor using the polyurethane of the present invention as a support and having a calcium ion selective membrane composed of a composition of a plasticizer, an ion selective material and a lipophilic additive on the electrode surface has an adhesive strength with the solid electrode surface. It is excellent in preventing the reduction of sensitivity, prolonging its lifespan, and excellent in electrochemical properties, and it is not generated asymmetric potential due to protein adsorption when measuring calcium ion concentration in biological samples such as blood or urine, as well as sodium ion, potassium ion, lithium It has the advantage of not being disturbed by various ionic species such as ions, magnesium ions, hydrogen ions, etc. Therefore, the calcium ion sensor manufactured according to the present invention is used for measuring the calcium ion concentration in biological samples and environmental samples. Can be used as
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