CN112557470A - Preparation method and detection method of modified electrode for detecting vitamin B1 - Google Patents
Preparation method and detection method of modified electrode for detecting vitamin B1 Download PDFInfo
- Publication number
- CN112557470A CN112557470A CN202011528721.1A CN202011528721A CN112557470A CN 112557470 A CN112557470 A CN 112557470A CN 202011528721 A CN202011528721 A CN 202011528721A CN 112557470 A CN112557470 A CN 112557470A
- Authority
- CN
- China
- Prior art keywords
- electrode
- vitamin
- nitrate
- detecting
- modified electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229960003495 thiamine Drugs 0.000 title claims abstract description 58
- 229930003451 Vitamin B1 Natural products 0.000 title claims abstract description 57
- 239000011691 vitamin B1 Substances 0.000 title claims abstract description 57
- 235000010374 vitamin B1 Nutrition 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001514 detection method Methods 0.000 title claims abstract description 14
- 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 10
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 239000008280 blood Substances 0.000 claims abstract description 29
- 210000004369 blood Anatomy 0.000 claims abstract description 29
- 238000005498 polishing Methods 0.000 claims abstract description 28
- 229940088594 vitamin Drugs 0.000 claims abstract description 22
- 229930003231 vitamin Natural products 0.000 claims abstract description 22
- 235000013343 vitamin Nutrition 0.000 claims abstract description 22
- 239000011782 vitamin Substances 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003722 vitamin derivatives Chemical class 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000009713 electroplating Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 239000001103 potassium chloride Substances 0.000 claims abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 239000011159 matrix material Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000003115 supporting electrolyte Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000000970 chrono-amperometry Methods 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004832 voltammetry Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 49
- 239000000523 sample Substances 0.000 description 24
- 239000012488 sample solution Substances 0.000 description 10
- 239000012086 standard solution Substances 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 206010047601 Vitamin B1 deficiency Diseases 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 208000002894 beriberi Diseases 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 208000007287 cheilitis Diseases 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- 208000005232 Glossitis Diseases 0.000 description 1
- 206010029240 Neuritis Diseases 0.000 description 1
- 206010036105 Polyneuropathy Diseases 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- 201000003465 angular cheilitis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000023852 carbohydrate metabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001903 differential pulse voltammetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008558 metabolic pathway by substance Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 208000019629 polyneuritis Diseases 0.000 description 1
- 238000000083 pulse voltammetry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004365 square wave voltammetry Methods 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- G01N27/416—Systems
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- 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)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention belongs to the technical field of vitamin detection methods, and particularly relates to a preparation method of a modified electrode for detecting vitamin B1, which comprises the following steps of selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use; dripping or electroplating a modification solution on the surface of the substrate electrode, and drying by using an infrared lamp to obtain the modified electrode; the modification solution is composed of one or more of hydrochloric acid, nitric acid, acetic acid, bismuth nitrate, mercuric nitrate, silver nitrate, potassium chloride, sodium chloride, cadmium nitrate, lead nitrate and amino black 10B, and the concentration range of each component is 0.0001-1 mol/L. Overcomes the defects of the prior art, has the advantages of high sensitivity, good reproducibility, convenient and quick operation and the like, and accurately measures the content of the vitamin B1 in the blood sample.
Description
Technical Field
The invention belongs to the technical field of vitamin detection methods, and particularly relates to a preparation method and a detection method of a modified electrode for detecting vitamin B1.
Background
As is well known, vitamins are trace organic substances which must be ingested through food to maintain normal physiological functions of the body, and play important roles in regulating substance metabolism, maintaining physiological functions and the like. Wherein, vitamin B1 is called thiamine, is an important biological molecule, has very important catalytic action in glycometabolism, especially has very important influence on the function of the nervous system, corresponding diseases can be caused by long-term deficiency or excessive intake, diseases such as beriberi, polyneuritis and the like can be caused by vitamin B1 deficiency, and cheilitis, glossitis, angular cheilitis and the like can also occur.
The existing methods for detecting vitamin B1 are different, and mainly comprise gravimetric methods, titration methods, fluorescence analysis methods, high performance liquid chromatography methods, electrochemical methods and the like. Gravimetric methods and titration methods are complex to operate, measurement errors for low-content components are large, large errors can be caused if end point judgment is not sharp, pretreatment processes of spectroscopic analysis methods and chromatography methods are excessively complicated and time-consuming, more organic solvents are used, and the quantity of blood samples is large.
The electrochemical method is sensitive and rapid, needs less samples, does not need pretreatment, and is particularly suitable for detecting the vitamins in the biological samples. The existing electrochemical analysis technology for detecting vitamins is mainly realized by the traditional linear sweep voltammetry, the conventional pulse voltammetry, the differential pulse voltammetry, the square wave voltammetry, the stripping voltammetry and the like, although the methods can be used for detecting the vitamins, the sensitivity is low, and particularly when the vitamin B1 in a blood sample is detected, the detection limit is high, and the concentration level of the vitamin B1 in the blood sample cannot be reached.
Disclosure of Invention
The invention aims to provide a preparation method of a modified electrode for detecting vitamin B1, overcomes the defects of the prior art, has the advantages of high sensitivity, good reproducibility, convenient and quick operation and the like, and accurately measures the content of vitamin B1 in a blood sample.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a modified electrode for detecting vitamin B1 comprises the following steps:
(1) pretreatment of a substrate electrode: selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use;
(2) preparing a modified electrode: dripping or electroplating a modification solution on the surface of the matrix electrode prepared in the step (1), and drying by using an infrared lamp to prepare the modified electrode;
the modification solution is composed of one or more of hydrochloric acid, nitric acid, acetic acid, bismuth nitrate, mercuric nitrate, silver nitrate, potassium chloride, sodium chloride, cadmium nitrate, lead nitrate and amino black 10B, and the concentration range of each component is 0.0001-1 mol/L.
Further, the polishing and cleaning treatment of the substrate electrode specifically comprises: firstly, polishing a matrix electrode on metallographic abrasive paper of different models to ensure that the surface of the matrix electrode is smooth like a mirror surface; then mirror polishing is carried out on the polished substrate electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright substrate electrode in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surface of the substrate electrode, and drying the substrate electrode by using nitrogen for later use.
Further, the method for electroplating in the step (2) is selected from one of cyclic voltammetry, a potential step method or a chronoamperometry.
The invention also provides a detection method of the modified electrode for detecting vitamin B1, which comprises the following steps:
taking a blood sample to be detected to react with a vitamin releasing agent, so that the vitamin in a combined state in the blood sample to be detected is converted into the vitamin in a free state, wherein the vitamin releasing agent consists of a solvent and an inert supporting electrolyte; detecting the redox current generated by the vitamin in the blood sample to be detected on the modified electrode by using a convolution current voltammetry; the vitamin content in the blood sample to be detected is calculated through a linear equation according to the current signal values of the samples to be detected under the same condition.
Further, when the content of vitamin B1 in a blood sample is detected, the initial electrode potential of instrument parameters is 0.6-0.6V, the final electrode potential is-0.6-2.2V, the scanning speed is 10-800 mV/s, the working mode is a differential mode of 0.5 times, 1.5 times or 2.5 times, and the noise filtering is a low-pass mode; the vitamin B1 releasing agent is composed of a solvent and an inert supporting electrolyte, the solvent is one or more aqueous solutions of sodium hydroxide, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid and boric acid, the concentration of the solvent is 0.0001-5 mol/L, the inert supporting electrolyte is one or more of potassium chloride, sodium citrate, disodium hydrogen phosphate, sodium dihydrogen phosphate, silver nitrate and lead nitrate, and the concentration of the inert supporting electrolyte is 0.001-20 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the method is modified on the basis of a glassy carbon electrode or a copper electrode, has the advantages of high sensitivity, good reproducibility, convenience and quickness in operation and the like, and can be used for accurately measuring the content of vitamin B1 in a blood sample.
The invention adopts the standard addition method to determine the content of the vitamin B1 in the sample, eliminates the interference caused by the matrix effect of the sample, reduces the detection limit of the vitamin B1 and has accurate and reliable measurement result.
Drawings
FIG. 1 is a linear equation measured when the concentration of vitamin B1 added by using the modified electrode pair prepared in example 1 is changed from 40 to 200 nmol/L.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment discloses a preparation method of a modified electrode for detecting vitamin B1, which comprises the following steps:
(1) pretreatment of a substrate electrode: selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use;
(2) preparing a modified electrode: dripping or electroplating a modification solution on the surface of the matrix electrode prepared in the step (1), and drying by using an infrared lamp to prepare the modified electrode; the modification solution is prepared by mixing 0.001mol/L hydrochloric acid, 0.005mol/L bismuth nitrate and 0.002mol/L aminoblack 10B.
The polishing and cleaning treatment of the substrate electrode specifically comprises the following steps: firstly, polishing a matrix electrode on metallographic abrasive paper of different models to ensure that the surface of the matrix electrode is smooth like a mirror surface; then mirror polishing is carried out on the polished substrate electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright substrate electrode in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surface of the substrate electrode, and drying the substrate electrode by using nitrogen for later use.
The electroplating method in the step (2) is selected from one of cyclic voltammetry, potential step method or chronoamperometry.
Example 2
The embodiment discloses a preparation method of a modified electrode for detecting vitamin B1, which comprises the following steps:
(1) pretreatment of a substrate electrode: selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use;
(2) preparing a modified electrode: dripping or electroplating a modification solution on the surface of the matrix electrode prepared in the step (1), and drying by using an infrared lamp to prepare the modified electrode; the modification solution was prepared by mixing 0.05mol/L nitric acid, 0.01mol/L sodium chloride and 0.02mol/L lead nitrate.
The polishing and cleaning treatment of the substrate electrode specifically comprises the following steps: firstly, polishing a matrix electrode on metallographic abrasive paper of different models to ensure that the surface of the matrix electrode is smooth like a mirror surface; then mirror polishing is carried out on the polished substrate electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright substrate electrode in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surface of the substrate electrode, and drying the substrate electrode by using nitrogen for later use.
The electroplating method in the step (2) is selected from one of cyclic voltammetry, potential step method or chronoamperometry.
Example 3
The embodiment discloses a preparation method of a modified electrode for detecting vitamin B1, which comprises the following steps:
(1) pretreatment of a substrate electrode: selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use;
(2) preparing a modified electrode: dripping or electroplating a modification solution on the surface of the matrix electrode prepared in the step (1), and drying by using an infrared lamp to prepare the modified electrode; the modifying solution is prepared by mixing 1mol/L acetic acid, 0.5mol/L cadmium nitrate and 0.2mol/L potassium chloride.
The polishing and cleaning treatment of the substrate electrode specifically comprises the following steps: firstly, polishing a matrix electrode on metallographic abrasive paper of different models to ensure that the surface of the matrix electrode is smooth like a mirror surface; then mirror polishing is carried out on the polished substrate electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright substrate electrode in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surface of the substrate electrode, and drying the substrate electrode by using nitrogen for later use.
The electroplating method in the step (2) is selected from one of cyclic voltammetry, potential step method or chronoamperometry.
Detection method
Method for determining content of vitamin B1 in blood sample by single standard addition method
The specific implementation process comprises the following steps:
1. pretreatment of the vitamin B1 sensor probe: a commercially available glassy carbon electrode or copper electrode with the diameter of 2mm is selected as a vitamin B1 sensor probe, and the electrode is firstly ground on metallographic abrasive paper of different models, so that the surface of the electrode is smooth like a mirror surface. Then mirror polishing is carried out on the polished electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright electrodes in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surfaces of the electrodes, and drying the electrodes by using nitrogen for later use.
2. Activation of vitamin B1 sensor probe: preparation of vitamin B1 modified electrode: the processed electrode was used as a working electrode, a platinum wire electrode was used as an auxiliary electrode, and a silver/silver chloride electrode was used as a reference electrode, and the working motor was modified by the preparation method of example 1. Setting instrument parameters: the initial electrode potential is-0.6V (relative to the reference electrode), the final electrode potential is-0.8-2V (relative to the reference electrode), the scanning speed is 20-120 mV/s, the cyclic scanning is carried out for 5-20 circles under the stirring condition, then the deionized water is used for cleaning, and the nitrogen is used for blow-drying for standby.
3. Preparation of vitamin B1 releasing agent: and (2) taking a proper amount (100-1000 mL) of the single solvent or the mixed solvent into a volumetric flask, weighing the single or composite inert supporting electrolyte according to the proportion, adding the single or composite inert supporting electrolyte into the volumetric flask, covering a bottle stopper, slightly shaking, adding the same solvent to the scale mark of the volumetric flask after the supporting electrolyte is dissolved, wherein the concentration of the inert supporting electrolyte in the solution is 0.001-20 mol/L.
4. Release of vitamin B1 in blood samples: quantitatively transferring a blood sample (10-20 mu L) into a 5.0mL test tube by using a micropipette, quantitatively adding 0.1-2.0 mL vitamin B1 releasing agent, covering a test tube plug, gently shaking uniformly, standing for 5 minutes, and detecting by using an on-machine after vitamin B1 combined in the blood sample is released and becomes free micromolecules.
5. Determination of vitamin B1 in blood samples:
firstly, fixing a test tube containing a sample solution to be detected on a workbench of a vitamin detector, taking the vitamin B1 modified electrode as a working electrode, taking a platinum wire electrode as an auxiliary electrode and taking a silver/silver chloride electrode as a reference electrode, and inserting the electrodes into the sample solution to be detected together for detection. The working mode of the vitamin detector can be selectively set to be 0.5, 1.5 or 2.5 differential modes, and the noise filtering is a low-pass mode. The test parameters are: the initial electrode potential of the instrument parameters is 0.6 to-0.6V, the final electrode potential is-0.6 to-2.2V, the scanning speed is 10 to 800mV/s, and the convolution current obtained by detecting the sample solution is recorded as h.
Then quantitatively transferring Vs mL of the standard solution of vitamin B1 by using a micropipette, adding the Vs mL of the standard solution into the sample solution, uniformly stirring, detecting under the same condition, and recording the obtained convolution current as H.
6. Calculation of vitamin B1 concentration in blood samples:
the concentration of vitamin B1 in the blood sample was calculated according to formula (1):
in the formula, cA is the concentration of vitamin B1 in the blood sample, H is the convolution current value obtained by detecting the sample solution, H is the convolution current value obtained by detecting after adding the standard solution, Vx is the volume of the diluent, Vs is the volume of the added standard solution, cs is the concentration of the standard solution, and k is the dilution multiple of the sample. The volume and concentration of the added vitamin B1 standard solution meet the following requirements:
Vs<100Vx，cs>100cA
second, multi-standard addition method for determining content of vitamin B1 in blood sample
The specific implementation process comprises the following steps:
1. pretreatment of the vitamin B1 sensor probe: the same as in example 1.
2. Activation of vitamin B1 sensor probe: the same as in example 1.
3. Preparation of vitamin B1 releasing agent: the same as in example 1.
4. Release of vitamin B1 in blood samples: the same as in example 1.
5. Determination of vitamin B1 in blood samples:
firstly, fixing a test tube containing a sample solution to be detected on a workbench of a vitamin detector, taking a modified vitamin B1 sensor as a working electrode, a platinum wire electrode as an auxiliary electrode and a silver/silver chloride electrode as a reference electrode, and inserting the test tube and the sensor into the sample solution to be detected together for detection. The working mode of the vitamin detector can be selectively set to be 0.5, 1.5 or 2.5 differential modes, and the noise filtering is a low-pass mode. The test parameters are: the initial electrode potential of the instrument parameters is 0.6 to-0.6V, the final electrode potential is-0.6 to-2.2V, the scanning speed is 10 to 800mV/s, and the convolution current obtained by detecting the sample solution is recorded as h 0.
Then, a micropipette is used for quantitatively transferring standard solutions V1 mL, V2 mL, V3mL,. cnmL and VnmL of vitamin B1 in sequence, the standard solutions are added into the sample solution respectively, detection is carried out in sequence under the same condition, the obtained convolution currents are recorded as h1, h2, h3,. cndot. hn, and the concentrations of the correspondingly added vitamin B1 are respectively c1, c2, c3,. cndot. cndot. (which can be obtained by volume conversion of the standard solution added each time). FIG. 1 shows the linear equation measured when the concentration of vitamin B1 added was varied from 40 to 200 nmol/L.
6. Calculation of vitamin B1 concentration in blood samples:
a minimum linear fit was performed using the convolution current and concentration (concentration c0 of vitamin B1 of the sample solution without standard addition was 0) resulting in the following linear relationship:
h＝kc+B (2)
it is thus possible to obtain a vitamin B1 concentration in the blood sample of
cA＝-B (3)
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. A preparation method of a modified electrode for detecting vitamin B1 is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of a substrate electrode: selecting a glassy carbon electrode or a copper electrode as a substrate electrode, and polishing and cleaning the surface of the substrate electrode for later use;
(2) preparing a modified electrode: dripping or electroplating a modification solution on the surface of the matrix electrode prepared in the step (1), and drying by using an infrared lamp to prepare the modified electrode;
the modification solution is composed of one or more of hydrochloric acid, nitric acid, acetic acid, bismuth nitrate, mercuric nitrate, silver nitrate, potassium chloride, sodium chloride, cadmium nitrate, lead nitrate and amino black 10B, and the concentration range of each component is 0.0001-1 mol/L.
2. The preparation method of the modified electrode for detecting vitamin B1 as claimed in claim 1, wherein the modified electrode comprises: the polishing and cleaning treatment of the substrate electrode specifically comprises the following steps: firstly, polishing a matrix electrode on metallographic abrasive paper of different models to ensure that the surface of the matrix electrode is smooth like a mirror surface; then mirror polishing is carried out on the polished substrate electrode on the alumina polishing powder with the grain diameter of 1.0 mu m, 0.3 mu m and 0.05 mu m in sequence; and finally, respectively placing the polished and bright substrate electrode in ethanol and deionized water for 2 minutes by ultrasonic treatment to remove organic matters and adsorbed alumina powder remained on the surface of the substrate electrode, and drying the substrate electrode by using nitrogen for later use.
3. The preparation method of the modified electrode for detecting vitamin B1 as claimed in claim 1, wherein the modified electrode comprises: the method for electroplating in the step (2) is selected from one of cyclic voltammetry, potential step method or chronoamperometry.
4. A method of detecting a modified electrode of vitamin B1 using convolution voltammetry as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
taking a blood sample to be detected to react with a vitamin releasing agent, so that the vitamin in a combined state in the blood sample to be detected is converted into the vitamin in a free state, wherein the vitamin releasing agent consists of a solvent and an inert supporting electrolyte; detecting the redox current generated by the vitamin in the blood sample to be detected on the modified electrode by using a convolution current voltammetry; the vitamin content in the blood sample to be detected is calculated through a linear equation according to the current signal values of the samples to be detected under the same condition.
5. The detection method for detecting the modified electrode of vitamin B1, according to claim 4, wherein the detection method comprises the following steps: when the vitamin B1 content in a blood sample is detected, the initial electrode potential of instrument parameters is 0.6-0.6V, the final electrode potential is-0.6-2.2V, the scanning speed is 10-800 mV/s, the working mode is a differential mode of 0.5 times, 1.5 times or 2.5 times, and the noise filtering is a low-pass mode; the vitamin B1 releasing agent is composed of a solvent and an inert supporting electrolyte, the solvent is one or more aqueous solutions of sodium hydroxide, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid and boric acid, the concentration of the solvent is 0.0001-5 mol/L, the inert supporting electrolyte is one or more of potassium chloride, sodium citrate, disodium hydrogen phosphate, sodium dihydrogen phosphate, silver nitrate and lead nitrate, and the concentration of the inert supporting electrolyte is 0.001-20 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528721.1A CN112557470A (en) | 2020-12-22 | 2020-12-22 | Preparation method and detection method of modified electrode for detecting vitamin B1 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528721.1A CN112557470A (en) | 2020-12-22 | 2020-12-22 | Preparation method and detection method of modified electrode for detecting vitamin B1 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112557470A true CN112557470A (en) | 2021-03-26 |
Family
ID=75032133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011528721.1A Pending CN112557470A (en) | 2020-12-22 | 2020-12-22 | Preparation method and detection method of modified electrode for detecting vitamin B1 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112557470A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650330A (en) * | 2009-06-26 | 2010-02-17 | 上海大学 | Preparation method and application of didodecyldimethylammonium bromide modified glassy carbon electrode |
| CN102192944A (en) * | 2011-03-23 | 2011-09-21 | 天津市兰标电子科技发展有限公司 | Linear scanning stripping voltammetry method for detecting content of vitamins in blood sample |
| CN103308574A (en) * | 2013-05-21 | 2013-09-18 | 上海师范大学 | Carbon nano tube-graphene composite membrane modified electrochemical sensor as well as preparation method and application thereof |
| CN103399055A (en) * | 2013-08-15 | 2013-11-20 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensors for detecting vitamins B in plasma of human body based on gold nanoparticle modified electrode |
| CN105784818A (en) * | 2016-03-08 | 2016-07-20 | 中逸安科生物技术股份有限公司 | Fast detecting method of vitamin K1 used for preventing coupling hemorrhage after vaccine injection |
| CN106053568A (en) * | 2016-08-12 | 2016-10-26 | 浙江大学 | Composite material modified electrode for measurement of vitamin C concentration and application thereof |
| CN109164153A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Rhodamine 6G-palladium membranes modification ITO electrode preparation method and applications |
| CN110646495A (en) * | 2019-09-30 | 2020-01-03 | 合肥天一生物技术研究所有限责任公司 | Convolution current voltammetry for detecting vitamin content in blood sample |
| US20200141891A1 (en) * | 2018-11-07 | 2020-05-07 | King Fahd University Of Petroleum And Minerals | Detection of serum methionine and glucose by graphite pencil electrode |
-
2020
- 2020-12-22 CN CN202011528721.1A patent/CN112557470A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650330A (en) * | 2009-06-26 | 2010-02-17 | 上海大学 | Preparation method and application of didodecyldimethylammonium bromide modified glassy carbon electrode |
| CN102192944A (en) * | 2011-03-23 | 2011-09-21 | 天津市兰标电子科技发展有限公司 | Linear scanning stripping voltammetry method for detecting content of vitamins in blood sample |
| CN103308574A (en) * | 2013-05-21 | 2013-09-18 | 上海师范大学 | Carbon nano tube-graphene composite membrane modified electrochemical sensor as well as preparation method and application thereof |
| CN103399055A (en) * | 2013-08-15 | 2013-11-20 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensors for detecting vitamins B in plasma of human body based on gold nanoparticle modified electrode |
| CN105784818A (en) * | 2016-03-08 | 2016-07-20 | 中逸安科生物技术股份有限公司 | Fast detecting method of vitamin K1 used for preventing coupling hemorrhage after vaccine injection |
| CN106053568A (en) * | 2016-08-12 | 2016-10-26 | 浙江大学 | Composite material modified electrode for measurement of vitamin C concentration and application thereof |
| CN109164153A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Rhodamine 6G-palladium membranes modification ITO electrode preparation method and applications |
| US20200141891A1 (en) * | 2018-11-07 | 2020-05-07 | King Fahd University Of Petroleum And Minerals | Detection of serum methionine and glucose by graphite pencil electrode |
| CN110646495A (en) * | 2019-09-30 | 2020-01-03 | 合肥天一生物技术研究所有限责任公司 | Convolution current voltammetry for detecting vitamin content in blood sample |
Non-Patent Citations (6)
| Title |
|---|
| 张胜男等: "维生素B6在修饰掺硼金刚石薄膜电极上的测定", 《人工晶体学报》 * |
| 潘攀: "VC和VB2的电化学传感器制备及其分析应用", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
| 王春燕等: "聚氨基黑10B修饰电极检测维生素B_6", 《应用化学》 * |
| 袁倬斌等: "维生素K_3的单扫描示波极谱法和新极谱法研究", 《分析化学》 * |
| 顾小燕等: "盐酸吡哆辛在聚烟酸修饰电极上的电化学行为及测定", 《化学分析计量》 * |
| 马红燕等: "《现代分析测试技术与实验》", 31 December 2012, 西安：陕西科学技术出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110646495A (en) | Convolution current voltammetry for detecting vitamin content in blood sample | |
| CN108344792B (en) | Method for rapidly detecting total arsenic in water body | |
| Liu et al. | Determination of sunset yellow and tartrazine using silver and poly (L-cysteine) composite film modified glassy carbon electrode | |
| Ostapczuk | Direct determination of cadmium and lead in whole blood by potentiometric stripping analysis | |
| CN110779971A (en) | Sample treatment fluid for trace vitamin A detection and electrochemical detection method thereof | |
| CN101581688B (en) | Electrochemical detection method for dihydrogen phosphate ions in water system | |
| CN114184710A (en) | Method for detecting content of lithium hexafluorophosphate in lithium ion battery electrolyte | |
| CN110823970A (en) | Electrochemical detection method for rapidly determining content of L-cystine in acidic solution | |
| CN108732222B (en) | Method for simultaneously and rapidly detecting glycosylated hemoglobin and glycosylated serum protein in blood | |
| CN112557470A (en) | Preparation method and detection method of modified electrode for detecting vitamin B1 | |
| Scherson et al. | Thin-layer spectroelectrochemical cell | |
| CN109001289A (en) | The method of bipyridyl ruthenium system electrogenerated chemiluminescence method measurement nefopam hydrochloride | |
| CN114609219A (en) | Microelectrode for monitoring inorganic nitrogen ion concentration in real time and preparation method and application thereof | |
| CN112557468A (en) | Preparation method of modified electrode for simultaneously detecting vitamins B2 and C and electrochemical detection method | |
| CN112557471B (en) | Preparation method and detection method of modified electrode capable of simultaneously detecting vitamins B6 and B9 | |
| CN110208356B (en) | Electrochemical sensor and preparation and application thereof | |
| CN112557469A (en) | Convolution current voltammetry for simultaneously detecting vitamin A, D, E | |
| Wang et al. | Trace metal speciation by adsorptive stripping voltammetry of metal chelates of solochrome violet RS | |
| CN111551595B (en) | Composite material modified acetylene black carbon paste electrode for measuring content of triclosan and preparation method and application thereof | |
| RU2818446C1 (en) | Voltammetric method of determining methylparaben in eye drops | |
| CN110208342B (en) | Chemically modified electrode for sensitively detecting sulphaguanidine and preparation method and application thereof | |
| CN106198698A (en) | A kind of measure the method for micro cyanide content in complex sample | |
| CN110779968A (en) | Sample treatment fluid for trace vitamin A detection and differential pulse detection method thereof | |
| Zhang et al. | In vivo determination of tetrahydrobiop-terin and monoamine neurotransmitters in rat brain by liquid chromatography with a nano crystalline Mn-doped lead dioxide film modified electrode | |
| Franks et al. | Analysis of inorganic solids by laser ablation inductively coupled plasma spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210326 |
|
| RJ01 | Rejection of invention patent application after publication |