CN112285185A - Application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as hydrogen phosphate ion selective electrode active carrier - Google Patents
Application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as hydrogen phosphate ion selective electrode active carrier Download PDFInfo
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- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 title claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- -1 nitrate ions Chemical class 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012088 reference solution Substances 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 4
- NBQXYAJLUDQSNV-UHFFFAOYSA-N 1-[(4-methylphenyl)methyl]-5-oxopyrrolidine-3-carboxylic acid Chemical compound C1=CC(C)=CC=C1CN1C(=O)CC(C(O)=O)C1 NBQXYAJLUDQSNV-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 238000007605 air drying Methods 0.000 abstract 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 26
- 239000004800 polyvinyl chloride Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 11
- 230000004044 response Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QJFYQROMGWGJIC-UHFFFAOYSA-N cyclopenta-1,3-diene 5-cyclopenta-2,4-dien-1-ylbenzene-1,3-dicarbonyl chloride iron(2+) Chemical compound [CH-]1C=CC=C1.C1=C[C-](C=C1)C2=CC(=CC(=C2)C(=O)Cl)C(=O)Cl.[Fe+2] QJFYQROMGWGJIC-UHFFFAOYSA-N 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229910013804 M2HPO4 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 235000014510 cooky Nutrition 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 235000010855 food raising agent Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- KCUNTYMNJVXYKZ-JTQLQIEISA-N methyl (2s)-2-amino-3-(1h-indol-3-yl)propanoate Chemical group C1=CC=C2C(C[C@H](N)C(=O)OC)=CNC2=C1 KCUNTYMNJVXYKZ-JTQLQIEISA-N 0.000 description 1
- XNFNGGQRDXFYMM-PPHPATTJSA-N methyl (2s)-2-amino-3-(1h-indol-3-yl)propanoate;hydrochloride Chemical compound Cl.C1=CC=C2C(C[C@H](N)C(=O)OC)=CNC2=C1 XNFNGGQRDXFYMM-PPHPATTJSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses an application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as a hydrogen phosphate ion selective electrode active carrier, which comprises the following steps: dissolving an active carrier, a plasticizer and PVC powder in tetrahydrofuran in proportion to obtain an electrode membrane solution; the electrode membrane solution is placed at room temperature for air drying to obtain a PVC active membrane, the PVC active membrane is hermetically bonded at the bottom of an electrode tube, and 0.01mol/L K is added2HPO4The solution is used as an internal reference solution, and an Ag-AgCl internal reference electrode is inserted to obtain HPO4 2‑An ion selective electrode. The test finds that: when 5-ferrocene isophthaloyl-L-tryptophan methyl ester is used as an active carrier for preparing the hydrogen phosphate ion selective electrode, the prepared electrode HPO4 2‑The lower limit of detection of ion concentration is as low as 8.4X 10‑6mol/L, and is little interfered by anions such as chloride ions, nitrate ions and sulfate ions.
Description
Technical Field
The invention belongs to the technical field of electrode preparation, and particularly relates to application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as a hydrogen phosphate ion selective electrode active carrier.
Background
Phosphoric acid and its salts are closely related to human daily life and are widely used in industries such as agriculture, food, and medicine. In the food industry, phosphate is one of the most widely applied food additives in the world at present, and can be used as an acidulant, a water retention agent, a leavening agent, a stabilizer, a coagulant, an anticaking agent and the like, for example, the water retention property, the gel strength and the like of meat products can be improved by adding the phosphate; the addition of phosphate greatly increases the bulk of baked goods, such as cakes, cookies, breads and pancakes. Although the use of a phosphoric acid system in a synthetic detergent is greatly limited by the country but is influenced by the use of fertilizers in agricultural production, industrial pollution and the like, the influence of the application of phosphorus compounds on the environment still exists widely recently, such as: the phosphorus compound and the organic phosphine enter into lakes, rivers and other water bodies in large quantities to be seriously damaged, and meanwhile, the organic phosphine is soaked underground along with surface water, thereby causing serious threat to human water. Therefore, a method for rapidly and accurately measuring the phosphorus content is necessary in the fields of food, clinical chemistry, industrial engineering monitoring, environment and the like.
Up to now, various methods such as High Performance Liquid Chromatography (HPLC), spectroscopic method, ion selective electrode method (ISEs), etc. have been used for measuring the concentration of phosphorus in various samples. Among them, the HPLC method has high requirements for equipment and test conditions, and the spectroscopic method is often greatly interfered by other examples. The electrochemical sensors for measuring the activity or concentration of ions in solution by using membrane potential, such as Ion Selective Electrode (ISEs) methods, are widely applied to various fields such as theoretical research, agricultural production, industrial production, environmental detection, medicine and the like due to the advantages of simplicity, rapidness, high sensitivity, small amount of measuring articles, no damage to a test solution system during measurement and the like. Using HPO4 2-Ion selective electrode rapid detection system HPO4 2-The ion content has practical significance for detecting the phosphorus content of food, the phosphorus content of soil and phosphorus in a hydrogen phosphate system produced in a factory.
Disclosure of Invention
The invention aims to provide application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as a hydrogen phosphate ion selective electrode active carrier by taking a ferrocenyl-containing pincer-shaped compound of a life-simulating system based on an L-tryptophan methyl ester fragment as a PVC (polyvinyl chloride) membrane ion selective electrode active carrier, so that the application of the pincer-shaped compound serving as the hydrogen phosphate ion selective electrode active carrier is expectedRapid HPO assay4 2-Ion content.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as a hydrogen phosphate ion selective electrode active carrier.
The application of the 5-ferrocene isophthaloyl-L-tryptophan methyl ester as the hydrogen phosphate radical ion selective electrode active carrier specifically comprises the following steps: dissolving an active carrier, a plasticizer and PVC powder in tetrahydrofuran in proportion to obtain an electrode membrane solution; the electrode membrane solution is placed at room temperature and air-dried to obtain a PVC active membrane, the PVC active membrane is hermetically bonded at the bottom of an electrode tube, and 0.01mol/L K is added into the electrode tube2HPO4The solution is used as an internal reference solution, and an Ag-AgCl internal reference electrode is inserted into the internal reference solution to obtain HPO4 2-An ion selective electrode.
Specifically, the active carrier, the plasticizer and the PVC powder account for 100 percent of the total mass, the active carrier is 0.5 to 2 percent, the plasticizer is 50 to 70 percent, and the balance is PVC (polyvinyl chloride) powder. The active carrier is 5-ferrocene isophthaloyl-L-tryptophan methyl ester.
In order to obtain a better measurement effect, it is further preferable that the electrode membrane solution further contains an additive of tridodecylmethylammonium chloride (molecular formula: C)37H78NCl, abbreviated as TDMACl), and the additive is added in an amount of 0.05-0.2% of the sum of the mass of the active carrier, the mass of the plasticizer and the mass of the PVC powder.
Wherein, the structure of the active carrier 5-ferrocene isophthaloyl-L-tryptophan methyl ester is shown as follows:
specifically, the plasticizer may be one or a mixture of two or more of dioctyl sebacate (DOS), dibutyl phthalate (DBP), o-nitrophenyloctyl ether (NPOE), and the like.
Further preferably, the PVC active membrane is circular, the thickness is 0.05-0.3 mm, and the diameter is 7-13 mm.
When 5-ferrocene isophthaloyl-L-tryptophan methyl ester is applied as hydrogen phosphate ion selective electrode active carrier, HPO prepared4 2-The ion selective electrode is suitable when the pH value is 9; the calomel electrode is used as a reference electrode, and the inner filling liquid of the reference electrode is saturated KCl solution.
The invention utilizes hydrogen bond donor (-NH) -and hydrogen bond acceptor (-COOMe) sites existing in the active carrier compound 5-ferrocene isophthaloyl-L-tryptophan methyl ester and pincerlike cavities capable of performing spatial micro-assembly through the thermal motion of molecules to realize the reaction with target anion HPO4 2-By the host-guest action of (A), and further prepare ISEs for HPO4 2-Concentration determination of (1), HPO in optimized Membrane ion-Selective electrode example4 2-The lower limit of detection of the ion concentration is 8.4X 10-6mol/L, to HPO in the detection range4 2-The ions show better Nernst response, are slightly interfered by anions such as nitrate ions, chloride ions, sulfate ions and the like, and can be applied to industrial online measurement. Compared with the prior art, the invention has the following beneficial effects:
PVC active Membrane (i.e. HPO) in the invention4 2-Ion selective membrane) adopts 5-ferrocene isophthaloyl-L-tryptophan methyl ester as an active carrier, has high sensitivity and selectivity and HPO4 2-The lower limit of detection of ion concentration is as low as 8.4X 10-6mol/L, HPO in the detection range4 2-The ions show excellent Nernst response and are slightly interfered by anions such as nitrate ions, chloride ions, sulfate ions and the like; the selective electrode is suitable for HPO with the pH value of 94 2-The method has the advantages of good stability and rapid determination, and can be used for industrial on-line measurement and realize real continuous measurement.
Drawings
FIG. 1 is a HPO of the present invention4 2-The structure of the ion selective electrode is shown in the figure, wherein 1 is an electrode tube, 2 is a PVC active membrane, and 3 is an Ag | AgCl internal reference electrode; the bottom of the electrode tube is opened, and the PVC active membrane 2 is sealed and adhered by 5 percent of PVC solutionKnot formation; the upper part and the lower part of the electrode tube 1 are detachable structures and are connected through threads; the electrode tube structure is a conventional structure in the art, and thus, the description thereof is omitted.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
The active carrier 5-ferrocene isophthaloyl-L-tryptophan methyl ester can be prepared by the following method:
3.3 mL of triethylamine (Et) were added with stirring3N) was added dropwise to 20 mL of anhydrous CH containing 1.91g L-tryptophan methyl ester hydrochloride2Cl2In solution. After stirring at room temperature for 30 min, 10 mL of anhydrous CH containing 0.97g of 5-ferrocenyl isophthaloyl chloride (5-ferrocenyl lithium dichloride) was added dropwise2Cl2Continuously stirring the solution for reaction for 12 hours; the reaction mixture was filtered, the solvent was evaporated under reduced pressure, and the residue was taken up with CH2Cl2/ CH3The desired product is obtained in high yield by rinsing with COOEt (4:1) and column chromatography. Yield: 90% yield, M.p., 124-42H38FeN4O6Na [M + Na]+requires: 773.2038 found: 773.2037; IR νmax (KBr): 3411,1739, 1655, 1598, 1515, 1436, 1346, 1216, 1101, 744 cm-1; 1H NMR (400 MHz, CDCl3)δ ppm: 3.32-3.51 (m, 4H, CH2), 3.80 (s, 6H, OCH3), 3.98 (s, 5H, Cp-H), 4.34 (s, 2H, Cp-H), 4.60 (s, 2H, Cp-H), 5.10 [m, 2H, CH (COOMe)], 6.64 (d, 2H, J= 7.4 Hz, CONH), 6.76 (s, 2H, CH), 7.06-7.53 (m, 8H, Ar-H), 7.39 (s, 1H, Ar-H), 7.92 (s, 2H, Ar-H), 8.36 (s, 2H, NH). 13C NMR (100 MHz, CDCl3)δ ppm: 27.58, 52.69, 53.22, 66.88, 66.95, 69.79, 69.89, 82.91, 109.74, 111.60, 118.63, 119.71, 121.42, 122.38, 122.99, 127.34, 128.18, 134.12 136.17, 141.76, 166.14, 172.66. ESI-MS found: [M ]+: 750.4, [M + Na]+: 773.4。
The synthesis of 5-ferrocenylisophthaloyl chloride can be found in the literature Wei Liu, Synthesis, chromatography, and Electrochemical Anion Recognition Investigation of New N-5-ferrocenylisophtalic Amino Acid Methyl esters, Z Anarg. Allg chem. 2010, 636, 236-.
Example 1:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparation of an ion selective electrode comprising the following steps (as shown in figure 1):
1) dissolving 3mg of active carrier, 200mg of plasticizer (NPOE) and 100mg of PVC powder in 5mL of Tetrahydrofuran (THF) according to a ratio to obtain an electrode membrane solution;
2) sticking a glass ring with the diameter of 40mm on a glass sheet;
3) pouring the electrode membrane solution into a glass ring, covering the glass ring with filter paper, and naturally volatilizing the glass ring for 48 hours at room temperature to obtain an electrode membrane;
4) punching a small circular membrane with a diameter of 10mm from the electrode membrane by a puncher to obtain a PVC active membrane 2 (the thickness is about 0.2 mm);
5) the PVC active membrane 2 is hermetically bonded at the bottom of the electrode tube 1;
6) adding 0.01mol/L KCl solution into the electrode tube 1 as internal reference solution, and soaking the platinum wire 3 in the internal reference solution to obtain HPO4 2-An ion selective electrode.
Example 2:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (DBP) and PVC powder is respectively as follows: 3mg, 200mg and 100 mg; other steps refer to example 1.
Example 3:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (DOS) and PVC powder is respectively as follows: 3mg, 200mg and 100 mg; other steps refer to example 1.
Example 4:
5-ferrocene isophthaloylApplication of (E) -L-tryptophan methyl ester serving as active carrier to HPO (HPO)4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder is respectively as follows: 4.2mg, 200mg and 100 mg; other steps refer to example 1.
Example 5:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder is respectively as follows: 5mg, 200mg and 100mg, the other steps refer to example 1.
Example 6:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder in the step 1) is respectively as follows: 3.0mg, 200mg and 100 mg; with the addition of 0.2mg TDMACl, the other steps refer to example 1.
Example 7:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder is respectively as follows: 3.0mg, 200mg and 100 mg; with the addition of 0.3mg TDMACl, the other steps refer to example 1.
Example 8:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder is respectively as follows: 3mg, 200mg and 100 mg; with the addition of 0.6mg TDMACl, the other steps refer to example 1.
Example 9:
application of 5-ferrocene isophthaloyl-L-tryptophan methyl ester serving as active carrier in HPO4 2-Preparing an ion selective electrode, wherein the dosage of an active carrier, a plasticizer (NPOE) and PVC powder is respectively as follows: 0mg, 200mg and 100 mg; with the addition of 0.3mg TDMACl, the other steps refer to example 1.
And (3) testing the performance of the electrode:
1. and (3) detecting the slope of the electrode: arrangement 10-1M、10-2M、10-3M、10-4M、10-5M、10-6K of M2HPO4And (4) standard solution. HPO prepared in examples 1-94 2-An ion selective electrode and a calomel electrode (commercially available product) as a reference electrode, sequentially adding K2HPO4And (4) measuring in the standard solution (the concentration is increased from small to large), and recording the potential value after the reading number is stabilized.
HPO prepared in examples 1-94 2-The electrode slope and detection range for the ion selective electrode test are shown in the following table:
2. selectivity of the electrode:
usually, the selectivity coefficient is determined by the IUPAC recommended fixed interference method or the separate solution method. Both methods are however based on the nernst equation, which is a good agreement for membrane electrodes when the ions under consideration all have the same charge. However, this equation is not well suited when the ions under consideration have different valences. Here we formulate 10 separately-5－10-2Determination of HPO by using Glazier recommended ion activity ratio method in mol/L anion solution4 2-Coefficient of selectivity (Logk) of ions to other anionsPOT i/j). Testing of display electrode pairs HPO4 2-There is better selectivity and less interference of other anions to the electrode, especially chloride, since chloride is a very serious interfering ion in the actual analytical determination, which further indicates that the electrode has good selectivity. HPO prepared in example 14 2-Ion selective electrode pair Cl-Has a selectivity coefficient of (-1.43) to Br-Has a selectivity coefficient of (-2.16) for I-Has a selectivity coefficient of (-1.13) for NO3 -Has a selectivity coefficient of(-1.75) to SO4 2-Has a selectivity coefficient of (-1.12) for CO3 2-The selectivity coefficient of (A) is (-0.07).
3. Measuring the detection range of the electrode: and detecting the same slope.
4. Due to HPO4 2-It can generate H under different pH values2PO4 -And PO4 3-Different morphologies of conversion, the test showed that the electrode test results were superior at pH 9.
5. Reproducibility, stability and response time of the electrodes:
reproducibility: the preparation concentrations are respectively 10-3 mol/L and 10-2 mol/L of K2HPO4The solutions are 50 mL each, and the standard deviation of the electrode potential is measured to be 1.5 mV by continuously measuring the two solutions for 5 times by using electrodes alternately, and the reproducibility is good.
Stability: the preparation concentration is 10-3 mol/L of K2HPO4The solution was 50 mL, and then the potential was measured by an electrode, and the experiment was continuously carried out for 8 hours. As a result, the stability of the electrode was found to be excellent, and the potential drift was within 1.5 mV.
Response time: response time is a very important factor in electrode analysis applications. Electrode response time: (t 95% ) Is measured at 10-5~10-3 mol/L concentration range, K2HPO4The concentration of the solution is rapidly increased by 10 times in turn, and the measured concentration is from 10-5 mol/L to 10-4 mol/L，10-4 mol/L to 10-3 mol/L，10-3 mol/L to 10-2 mol/L (rapid injection of greater concentrations of K with microsampler)2HPO4Solution), the time required to reach its 95% stable potential. The experimental results show that: the electrode potential response is fast, and the response time is within 35 s.
The invention has the following beneficial effects: the PVC active membrane in the electrode of the invention adopts 5-ferrocene isophthaloyl-L-tryptophan methyl ester as an active carrier, has high sensitivity and selectivity, and in the given example 7, HPO4 2-The lower limit of detection of ion concentration is as low as 8.4X 10-6The mol/L is small, the interference of anions such as chloride ions, sulfate radicals and the like is small, carbonate radicals interfere the test system, but the carbonate radicals can be removed by heating and boiling under an acidic condition, and then the test system is cooled, the pH value is adjusted, and the interference is eliminated; the electrode can be used for HPO under the environment condition of pH 94 2-And (4) measuring ions. The invention has good stability and rapid determination, can be used for industrial on-line measurement and can realize real continuous measurement.
The foregoing detailed description is given by way of example only, to better enable a person skilled in the art to understand the patent, and is not to be construed as limiting the scope of the patent; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Claims (6)
1.5-ferrocene isophthaloyl-L-tryptophan methyl ester is used as an active carrier of a hydrogen phosphate ion selective electrode.
2. The application of 5-ferrocenyl isophthaloyl-L-tryptophan methyl ester as defined in claim 1 as a hydrogen phosphate ion selective electrode active carrier, wherein the active carrier, a plasticizer and PVC powder are dissolved in tetrahydrofuran in proportion to obtain an electrode membrane solution; the electrode membrane solution is placed at room temperature and air-dried to obtain a PVC active membrane, the PVC active membrane is hermetically bonded at the bottom of an electrode tube, and 0.01mol/L K is added into the electrode tube2HPO4The solution is used as an internal reference solution, and an Ag-AgCl internal reference electrode is inserted to obtain HPO4 2-An ion selective electrode.
3. The application of 5-ferrocenyl isophthaloyl-L-tryptophan methyl ester as the hydrogen phosphate ion selective electrode active carrier in claim 2, wherein the active carrier, the plasticizer and the PVC powder account for 100% by mass of the total of 0.5-2% by mass of the active carrier, 50-70% by mass of the plasticizer and the balance of PVC powder.
4. The use of 5-ferrocenylisophtalic-L-tryptophan methyl ester as the hydrogen phosphate ion selective electrode active carrier as claimed in claim 2, wherein the electrode membrane solution further contains an additive of tridodecylmethylammonium chloride, and the additive amount is 0.05-0.2% of the sum of the active carrier, the plasticizer and the PVC powder.
5. The use of 5-ferrocene isophthaloyl-L-tryptophan methyl ester as a hydrogen phosphate ion-selective electrode active carrier according to claim 2 or 3, wherein the plasticizer is one or a mixture of two or more of dioctyl sebacate, dibutyl phthalate and o-nitrophenyloctyl ether.
6. The use of 5-ferrocenyl isophthaloyl-L-tryptophan methyl ester as a hydrogen phosphate ion-selective electrode active carrier according to claim 2, wherein the PVC active membrane is circular, has a thickness of 0.05-0.3 mm and a diameter of 7-13 mm.
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