CN113960140B - Screen printing electrode for detecting vitamin B1 content in blood plasma - Google Patents
Screen printing electrode for detecting vitamin B1 content in blood plasma Download PDFInfo
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- CN113960140B CN113960140B CN202111123567.4A CN202111123567A CN113960140B CN 113960140 B CN113960140 B CN 113960140B CN 202111123567 A CN202111123567 A CN 202111123567A CN 113960140 B CN113960140 B CN 113960140B
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- 229960003495 thiamine Drugs 0.000 title claims abstract description 35
- 229930003451 Vitamin B1 Natural products 0.000 title claims abstract description 33
- 235000010374 vitamin B1 Nutrition 0.000 title claims abstract description 33
- 239000011691 vitamin B1 Substances 0.000 title claims abstract description 33
- 238000007650 screen-printing Methods 0.000 title claims abstract description 21
- 210000002381 plasma Anatomy 0.000 title claims abstract description 13
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 title claims abstract 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 73
- 239000002131 composite material Substances 0.000 claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000012986 modification Methods 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims abstract 14
- 239000000243 solution Substances 0.000 claims description 43
- 239000002244 precipitate Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 12
- 210000004369 blood Anatomy 0.000 abstract description 9
- 239000008280 blood Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000001548 drop coating Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- JZRWCGZRTZMZEH-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 28
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 235000008170 thiamine pyrophosphate Nutrition 0.000 description 4
- 239000011678 thiamine pyrophosphate Substances 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 238000000835 electrochemical detection Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019157 thiamine Nutrition 0.000 description 2
- 239000011721 thiamine Substances 0.000 description 2
- 229960002363 thiamine pyrophosphate Drugs 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- YXVCLPJQTZXJLH-UHFFFAOYSA-N thiamine(1+) diphosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N YXVCLPJQTZXJLH-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000037149 energy metabolism Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 235000020955 thiamine monophosphate Nutrition 0.000 description 1
- 239000011621 thiamine monophosphate Substances 0.000 description 1
- -1 thiamine triphosphates Chemical class 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The application discloses an electrode modification liquid and a screen printing electrode based on the electrode modification liquid for detecting vitamin B1 content in blood plasma. The electrode modification liquid is composite nanoparticle dispersion liquid, and is prepared by adopting a normal-temperature in-situ polymerization method, specifically, nickel nanoparticles are prepared firstly, cobalt-nickel composite nanoparticles are prepared through the nickel nanoparticles, and finally, cobalt-nickel composite nanoparticle uniform suspension liquid is prepared, so that the required composite nanoparticle dispersion liquid is obtained. And (3) dripping a proper amount of electrode modification liquid on the surface of the working electrode through a rapid enzyme-pointing machine, and standing for 30min at room temperature to obtain the modified screen printing electrode. The electrode modification liquid disclosed by the application is coated and modified on the surface of a working electrode of a commercial screen printing electrode, so that the detection and analysis of the vitamin B1 content in blood can be realized; based on the electrode modification liquid, a mature rapid micro-drop coating technology is used, so that a test paper electrode with high uniformity can be conveniently prepared in a large scale, and the industrial implementation is facilitated.
Description
Technical Field
The application relates to the technical field of screen printing electrodes, in particular to an electrode modification liquid and a screen printing electrode based on the electrode modification liquid and used for detecting the vitamin B1 content in blood plasma.
Background
Vitamin (Vitamin) is a nutrient that maintains normal human activity and plays an important role in metabolism of the body, wherein Vitamin B1 (thiamine) is a sulfur-containing compound having both pyrimidine and thiazole rings. Coenzyme thiamine pyrophosphate (Thiamine Pyrophosphate, TPP) plays an important biochemical role in the energy metabolism process of the body, and vitamin B1 is the main raw material for synthesizing TPP. Vitamin B1 is also present in various human tissues in the form of thiamine monophosphates, thiamine triphosphates, etc., and plays an important biochemical role therein. Vitamin B1 is readily soluble in water and ethanol, relatively stable under acidic conditions, and unstable at high temperatures, in the presence of alkalinity and oxidants.
The existing vitamin B1 detection method mainly comprises a liquid chromatography method, a spectrophotometry method, a tandem mass spectrometry method, an electrochemical detection method and the like. Electrochemical detection is a widely used method for monitoring and analyzing biological and environmental samples. The most commonly used electrochemical detection methods are voltammetry and polarography, wherein the voltammetry is widely applied to the detection of biomarkers, such as blood sugar, uric acid, cholesterol and other biomarkers. Voltammetry generally consists of a three-electrode system, namely a working electrode, a reference electrode and a counter electrode. The physical and chemical properties of the working electrode material and the electrode surface, the modification layer material applied on the electrode surface for improving the detection effect, and thermodynamic and kinetic factors such as external potential and adsorption have great influence on the detection result of the voltammetry. The working electrodes commonly used at present mainly comprise carbon-based electrodes, including glassy carbon electrodes, carbon paste electrodes, carbon fiber electrodes, carbon film electrodes, carbon nanotube electrodes, graphene electrodes, screen-printed carbon electrodes and the like.
Screen-printed Electrode (SPE) is a three-electrode system which is low in cost, can be industrially produced and is highly integrated by printing a specific pattern on a substrate by using different inks through a Screen printing method. Carbon materials are often used as the material for the working electrode in screen printed electrodes because of their relatively good stability and wide electrochemical window. The conductive carbon paste is a complex mixture composed of various compounds, and is formed by printing the conductive carbon pasteThe electrochemical performance of the working electrode is generally less pure than that of the glassy carbon electrode. The content of vitamin B1 in human blood is 10 -8 In m/L, vitamin B1 at this concentration is undetectable by working electrodes printed with typical commercial conductive carbon pastes.
Disclosure of Invention
Aiming at the problem that the working electrode printed by common commercial conductive carbon paste cannot detect the vitamin B1 content in human blood plasma, the application realizes the detection of the vitamin B1 content in blood by dripping an electrode modification liquid with catalytic oxidation effect on the vitamin B1 on the surface of the screen printing electrode.
The application provides an electrode modification liquid, which is composite nanoparticle dispersion liquid and is prepared by adopting a normal-temperature in-situ polymerization method, specifically, nickel nanoparticles are prepared firstly, cobalt-nickel composite nanoparticles are prepared through the nickel nanoparticles, and finally cobalt-nickel composite nanoparticle uniform suspension liquid is prepared, so that the required composite nanoparticle dispersion liquid is obtained.
The preparation method of the composite nanoparticle dispersion liquid is specifically described as follows:
1. preparation of Nickel nanoparticles
1. Taking a proper amount of nickel chloride solution, adding a proper amount of absolute ethyl alcohol and deionized water into the nickel chloride solution, uniformly stirring, adding a proper amount of sodium hydroxide solution, and regulating the pH to 14;
2. gradually heating and dropwise adding a proper amount of hydrazine hydrate, heating to 50 ℃, and keeping for 30min until the reaction is complete, so as to generate a precipitate;
3. centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for multiple times to obtain a brownish-black precipitate;
4. and (3) placing the brown-black precipitate in a vacuum drying oven, and drying at 50 ℃ for 24 hours to constant weight to obtain the nickel nano particles.
2. Preparation of cobalt-nickel composite nano particles
1. Adding proper amount of nickel nano particles, aniline and room temperature ionic liquid [ BMIM ] PF6 into proper amount of hydrochloric acid solution with concentration of 1.5mol/L in sequence, and stirring to obtain uniform mixed solution;
2. adding a proper amount of cobalt chloride solution with the concentration of 1mol/L into the uniform mixed solution to obtain a mixture solution of pink mixing and black precipitation, and fully stirring until uniform;
3. dropwise adding a proper amount of ammonium persulfate solution with the concentration of 0.1g/mL into the mixture solution, and continuously stirring at a constant speed during the dropwise adding process until the color of the solution turns into dark brown;
4. filtering, and washing with deionized water and absolute ethyl alcohol until the filtrate is colorless;
5. and (3) placing the filtered product in a vacuum drying oven, and drying for 24 hours at 70 ℃ to obtain the cobalt-nickel composite nano particles.
3. Preparation of a cobalt-nickel composite nanoparticle uniform suspension: and (3) taking a proper amount of cobalt-nickel composite nano particles, and dispersing the cobalt-nickel composite nano particles in a proper amount of absolute ethyl alcohol by ultrasonic. The mass concentration of the cobalt-nickel composite nano particles in the uniform suspension is preferably 5mg/mL.
The application also protects a screen printing electrode based on the electrode modification liquid, and realizes the detection of the vitamin B1 content in blood plasma. The screen printing electrode comprises a substrate, a working electrode, a reference electrode and a counter electrode, wherein the working electrode, the reference electrode and the counter electrode are arranged on the substrate. The conventional structure is that a working electrode is printed into a round shape, and a reference electrode and a counter electrode are arranged around the working electrode; the working electrode and the counter electrode are both printed by conductive carbon paste, and the reference electrode is printed by conductive silver paste.
And (3) dripping a certain volume of composite nanoparticle dispersion liquid on the surface of the working electrode through a rapid enzyme-pointing machine, and standing for 30min at room temperature to obtain the modified screen printing electrode. When the working electrode diameter is 2mm, the drop-on amount of the composite nanoparticle dispersion is preferably 5. Mu.l.
The electrode modification liquid disclosed by the application is coated and modified on the surface of a working electrode of a commercial screen printing electrode, so that the detection and analysis of the vitamin B1 content in blood can be realized; the electrochemical response of the working electrode to vitamin B1 can be realized without using special formula ink; based on the electrode modification liquid, a mature rapid micro-drop coating technology is used, so that a test paper electrode with high uniformity can be conveniently prepared in a large scale, and the industrial implementation is facilitated.
Drawings
FIG. 1 is a front view of a screen printed electrode for use in the detection of vitamin B1 content in blood plasma;
FIG. 2 is a schematic diagram showing the electrochemical performance change of screen printing electrodes before and after the coating modification of the composite nanoparticle dispersed liquid;
fig. 3 is a graph showing a minimum linear fit of the peak current value IP to the corresponding concentration value C.
Description of the reference numerals
1-base plate, 2-working electrode, 3-reference electrode, 4-counter electrode, 5-electrode insulating layer, 6-counter electrode terminal, 7-working electrode terminal, 8-reference electrode terminal.
Detailed Description
The application will now be described in further detail with reference to the drawings and to specific examples. The embodiments of the application have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the application in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, and to enable others of ordinary skill in the art to understand the application for various embodiments with various modifications as are suited to the particular use contemplated.
Example 1 electrode preparation
A screen printing electrode for detecting vitamin B1 content in blood plasma comprises a substrate 1, a working electrode 2, a reference electrode 3 and a counter electrode 4 which are arranged on the substrate, wherein the reference electrode 3 is shown in figure 1. The working electrode 2 and the counter electrode 4 are both printed by conductive carbon paste, and the reference electrode 3 is printed by conductive silver paste.
And (3) dripping a certain volume of composite nanoparticle dispersion liquid on the surface of the working electrode through a rapid enzyme-pointing machine, and standing for 30min at room temperature to obtain the modified screen printing electrode. When the working electrode diameter is 2mm, the drop-on amount of the composite nanoparticle dispersion is preferably 5. Mu.l. Different dripping amounts, different amounts of electrode surface modification substances after drying and different distribution can be achieved, and the final detection effect is directly affected.
The composite nanoparticle dispersion liquid is prepared by adopting a normal-temperature in-situ polymerization method, specifically, nickel nanoparticles are prepared firstly, cobalt-nickel composite nanoparticles are prepared through the nickel nanoparticles, and finally, cobalt-nickel composite nanoparticle uniform suspension liquid is prepared, so that the required composite nanoparticle dispersion liquid is obtained. The preparation of the composite nanoparticle dispersion liquid by the normal temperature in-situ polymerization method can be completed at normal temperature without high temperature and complex and harsh experimental conditions.
The preparation method of the composite nanoparticle dispersion liquid is specifically described as follows:
1. preparation of Nickel nanoparticles
1. Taking 20mL of 0.1mol/L nickel chloride solution, adding 13.6mL of absolute ethyl alcohol and 6.7mL of deionized water into the solution, uniformly stirring the solution, adding a proper amount of 5mol/L sodium hydroxide solution, and adjusting the pH to 14;
2. gradually heating and dropwise adding 20mL of hydrazine hydrate, heating to 50 ℃, and keeping for 30min until the reaction is complete, so as to generate a precipitate;
3. centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for multiple times to obtain a brownish-black precipitate;
4. and (3) placing the brown-black precipitate in a vacuum drying oven, and drying at 50 ℃ for 24 hours to constant weight to obtain the nickel nano particles.
2. Preparation of cobalt-nickel composite nano particles
1. 2g of nickel nano particles, 1mL of aniline and 0.2mL of room temperature ionic liquid [ BMIM ] PF6 are taken, added into 70mL of hydrochloric acid solution with the concentration of 1.5mol/L in sequence, and stirred to obtain uniform mixed solution;
2. adding 10mL of cobalt chloride solution with the concentration of 1mol/L into the uniform mixed solution to obtain a mixture solution of pink mixing and black precipitation, and fully stirring until uniform;
3. dropwise adding 30mL of ammonium persulfate solution with the concentration of 0.1g/mL into the mixture solution, and continuously stirring at a constant speed during the dropwise adding process until the color of the solution turns into dark brown;
4. filtering, and washing with deionized water and absolute ethyl alcohol until the filtrate is colorless;
5. and (3) placing the filtered product in a vacuum drying oven, and drying for 24 hours at 70 ℃ to obtain the cobalt-nickel composite nano particles.
3. Preparation of a cobalt-nickel composite nanoparticle uniform suspension: and (3) taking a proper amount of cobalt-nickel composite nano particles, and dispersing the cobalt-nickel composite nano particles in a proper amount of absolute ethyl alcohol by ultrasonic. The mass concentration of the cobalt-nickel composite nano particles in the uniform suspension is preferably 5mg/mL.
Example 2 electrochemical Performance test of working electrode
And (3) comparing and testing the screen printing electrode of which the working electrode is not coated with the composite nanoparticle dispersion liquid and the screen printing electrode of which the composite nanoparticle dispersion liquid is coated with the working electrode. By adding 5mL Fe (CN) 6 3- /Fe(CN) 6 4- The change in electrochemical performance of the electrode in the solution (containing 1mol/L KCl) was explained. The test results are shown in fig. 2, and it can be seen from fig. 2 that the modified electrode shows higher peak current response and smaller peak potential difference, which indicates that the composite nanoparticle is successfully modified to the surface of the working electrode, and the electrochemical performance of the working electrode is significantly improved.
Example 3 verification of the effect of detecting the vitamin B1 content in blood
In this example, the vitamin B1 content in blood was measured by a multi-standard addition method, and the specific procedure was as follows: taking 50 mu L of blood to be detected, adding 50 mu L of vitamin B1 releasing agent, uniformly mixing, and taking 50 mu L of mixed liquid drops in a detection area of a screen printing electrode; and inserting the modified test paper electrode into a vitamin detector to detect the concentration of vitamin B1.
The implementation process of the multi-standard addition method comprises the following steps: sequentially and accurately transferring vitamin B1 standard solutions V1mL, V2mL, V3mL, V4mL, V5mL, V6mL and V7mL by using a micropipette, and respectively adding the solutions into the mixed solution; sequentially measuring corresponding peak currents of IP1, IP2, IP3, IP4, IP5, IP6 and IP7 by a vitamin detector, and calculating the concentration of the mixed liquid which is changed after the vitamin B1 standard liquid is added each time to obtain seven concentration values corresponding to the peak currents of C1, C2, C3, C4, C5, C6 and C7; performing minimum linear fitting on the peak current value IP and the corresponding concentration value C to obtain a linear relation ip=kc+b, as shown in fig. 3, wherein k is a linear coefficient and b is an intercept; by calculating B, the concentration value of vitamin B1 in blood is 2 (IP-B) k. As can also be seen from the better linear relationship presented in fig. 3, the vitamin B1 detection based on the screen-printed electrode disclosed by the application has sufficient reliability.
It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art and which are included in the embodiments of the present application without the inventive step, are intended to be within the scope of the present application.
Claims (5)
1. The application of the electrode modification liquid in detecting the vitamin B1 content in blood plasma is characterized in that the electrode modification liquid is composite nanoparticle dispersion liquid, and is prepared by adopting a normal-temperature in-situ polymerization method, specifically, nickel nanoparticles are prepared firstly, cobalt-nickel composite nanoparticles are prepared through the nickel nanoparticles, and finally cobalt-nickel composite nanoparticle uniform suspension liquid is prepared, so that the required composite nanoparticle dispersion liquid is obtained;
the preparation method of the nickel nanoparticle comprises the following steps:
step A1, taking a proper amount of nickel chloride solution, adding a proper amount of absolute ethyl alcohol and deionized water into the nickel chloride solution, uniformly stirring the nickel chloride solution, adding a proper amount of sodium hydroxide solution, and regulating the pH to 14;
step A2, gradually heating and dropwise adding a proper amount of hydrazine hydrate, heating to 50 ℃, and keeping for 30min until the reaction is complete, so as to generate a precipitate;
step A3, centrifuging the precipitate, and washing the precipitate for a plurality of times by using deionized water and absolute ethyl alcohol in sequence to obtain a brownish-black precipitate;
step A4, placing the brown-black precipitate in a vacuum drying oven, and drying at 50 ℃ for 24 hours to constant weight to obtain nickel nanoparticles;
the preparation method of the cobalt-nickel composite nano particle comprises the following steps:
step B1, adding a proper amount of nickel nano particles, aniline and room temperature ionic liquid [ BMIM ] PF6 into a proper amount of hydrochloric acid solution with the concentration of 1.5mol/L in sequence, and stirring to obtain a uniform mixed solution;
step B2, adding a proper amount of cobalt chloride solution with the concentration of 1mol/L into the uniform mixed solution to obtain a mixture solution of pink mixing and black precipitation, and fully stirring until the mixture solution is uniform;
step B3, dropwise adding a proper amount of ammonium persulfate solution with the concentration of 0.1g/mL into the mixture solution, and continuously stirring at a constant speed in the dropwise adding process until the color of the solution becomes dark;
step B4, filtering, and washing with deionized water and absolute ethyl alcohol in sequence until the filtrate is colorless;
and B5, placing the filtered product in a vacuum drying oven, and drying at 70 ℃ for 24 hours to obtain the cobalt-nickel composite nano particles.
2. The use of claim 1 for detecting vitamin B1 content in blood plasma, wherein the method for preparing the cobalt-nickel composite nanoparticle homogeneous suspension comprises the steps of: and taking a proper amount of cobalt-nickel composite nano particles, and dispersing the cobalt-nickel composite nano particles in a proper amount of absolute ethyl alcohol by ultrasonic.
3. The use of claim 2 for detecting vitamin B1 content in blood plasma, wherein the mass concentration of cobalt-nickel composite nano particles in the homogeneous suspension is 5mg/mL.
4. The application of a screen printing electrode in detecting the vitamin B1 content in blood plasma comprises a substrate, a working electrode, a reference electrode and a counter electrode which are screen printed on the substrate, and is characterized in that a proper amount of electrode modification liquid is dripped on the surface of the working electrode through a rapid enzyme-spotting machine, and the screen printing electrode is obtained after standing for 30min at room temperature;
the electrode modification liquid is composite nanoparticle dispersion liquid and is prepared by adopting a normal-temperature in-situ polymerization method, specifically, nickel nanoparticles are prepared firstly, cobalt-nickel composite nanoparticles are prepared through the nickel nanoparticles, and finally, cobalt-nickel composite nanoparticle uniform suspension liquid is prepared, so that the required composite nanoparticle dispersion liquid is obtained;
the preparation method of the nickel nanoparticle comprises the following steps:
step A1, taking a proper amount of nickel chloride solution, adding a proper amount of absolute ethyl alcohol and deionized water into the nickel chloride solution, uniformly stirring the nickel chloride solution, adding a proper amount of sodium hydroxide solution, and regulating the pH to 14;
step A2, gradually heating and dropwise adding a proper amount of hydrazine hydrate, heating to 50 ℃, and keeping for 30min until the reaction is complete, so as to generate a precipitate;
step A3, centrifuging the precipitate, and washing the precipitate for a plurality of times by using deionized water and absolute ethyl alcohol in sequence to obtain a brownish-black precipitate;
step A4, placing the brown-black precipitate in a vacuum drying oven, and drying at 50 ℃ for 24 hours to constant weight to obtain nickel nanoparticles;
the preparation method of the cobalt-nickel composite nano particle comprises the following steps:
step B1, adding a proper amount of nickel nano particles, aniline and room temperature ionic liquid [ BMIM ] PF6 into a proper amount of hydrochloric acid solution with the concentration of 1.5mol/L in sequence, and stirring to obtain a uniform mixed solution;
step B2, adding a proper amount of cobalt chloride solution with the concentration of 1mol/L into the uniform mixed solution to obtain a mixture solution of pink mixing and black precipitation, and fully stirring until the mixture solution is uniform;
step B3, dropwise adding a proper amount of ammonium persulfate solution with the concentration of 0.1g/mL into the mixture solution, and continuously stirring at a constant speed in the dropwise adding process until the color of the solution becomes dark;
step B4, filtering, and washing with deionized water and absolute ethyl alcohol in sequence until the filtrate is colorless;
and B5, placing the filtered product in a vacuum drying oven, and drying at 70 ℃ for 24 hours to obtain the cobalt-nickel composite nano particles.
5. The use of a screen printed electrode according to claim 4 for detecting vitamin B1 content in blood plasma, wherein when the working electrode is in the shape of a circle with a diameter of 2mm, 5 microliters of electrode modification liquid is dispensed.
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