CN115791941A - Preparation method of dopamine electrochemical sensor and product - Google Patents
Preparation method of dopamine electrochemical sensor and product Download PDFInfo
- Publication number
- CN115791941A CN115791941A CN202211110794.8A CN202211110794A CN115791941A CN 115791941 A CN115791941 A CN 115791941A CN 202211110794 A CN202211110794 A CN 202211110794A CN 115791941 A CN115791941 A CN 115791941A
- Authority
- CN
- China
- Prior art keywords
- solution
- electrochemical sensor
- cnts
- dopamine
- co3o4
- 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
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229960003638 dopamine Drugs 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 17
- 238000002484 cyclic voltammetry Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000002659 electrodeposit Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 238000001903 differential pulse voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 3
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 description 3
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 description 3
- 235000009498 luteolin Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 102000014150 Interferons Human genes 0.000 description 2
- 108010050904 Interferons Proteins 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 229940079322 interferon Drugs 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002858 neurotransmitter agent Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010012335 Dependence Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000663 muscle cell Anatomy 0.000 description 1
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The application relates to a preparation method and a product of a dopamine electrochemical sensor, niCo-TPA is synthesized through a traditional hydrothermal method, then the NiCo-TPA is pyrolyzed to obtain NiO-Co3O4@ CNTs, then the NiO-Co3O4@ CNTs is electrodeposited on the surface of reduced graphene oxide, and the NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensor is prepared by means of the excellent electronic conductivity of rGO and the active sites of the NiCo @ CNTs, and has the advantages of lower detection limit, wide detection range, outstanding selectivity and stability.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection, and particularly relates to a preparation method of a bimetal MOF derived magnetic NiO-Co3O4@ CNTs/rGO modified dopamine electrochemical sensor.
Background
The neurotransmitter is a very key chemical transmission signal in the human body, is connected with various organs, nerves and muscle cells of the human body, promotes the normal operation of the human body, and plays a very important role in regulating the functions of various organs, and dopamine is one of the most important neurotransmitters. Many studies have demonstrated that dopamine plays an important role in many physiological systems in the human body. Other studies have shown that dopamine is also associated with addictive phenomena, and some drugs cause addiction by controlling dopamine secretion in the brain. Dopamine is an important mark of human health, and the index of the dopamine is the key for diagnosing and treating dopamine dysfunction in clinical practice. Therefore, research and development are of great practical significance for in vivo and in vitro dopamine detection. In recent years, various detection methods aiming at the content of dopamine in human serum and urine have been researched and developed, and for example, spectrophotometry, high performance liquid chromatography and the like have been applied to the in vitro detection of dopamine.
However, the above method is expensive, the measurement time is long, and a professional technician is required to perform the measurement, so that the efficiency is low, and at this time, an efficient, sensitive and low-cost electrochemical sensor enters the field of a researcher, and the electrochemical sensor mainly depends on an electrocatalytic material modified on the surface of an electrode, and the two adjacent phenolic hydroxyl groups of dopamine provide the electrochemical activity of molecules of the dopamine, and then a strong electric signal can be formed through the catalytic oxidation of the surface material of the electrode. However, the electrode surface materials generally have the defects of poor conductivity and less active site exposure, and the oxidation electric signal of dopamine is prevented to a certain extent.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the defects in the prior art, the preparation method and the product of the dopamine electrochemical sensor with more exposed active sites and high electrocatalytic activity are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a dopamine electrochemical sensor comprises the following steps:
s1: taking terephthalic acid, polyvinylpyrrolidone, nickel nitrate and cobalt nitrate, dissolving the terephthalic acid, polyvinylpyrrolidone, nickel nitrate and cobalt nitrate into a mixed solution of deionized water, DMF and ethanol, performing ultrasonic dispersion for more than half an hour to ensure complete dissolution, transferring the solution into a reaction kettle after the solution is clear, placing the reaction kettle in an oven for reaction, after the reaction is naturally cooled, centrifuging the solution by using a high-speed centrifuge, sequentially washing the solution with DMF, methanol and water, and finally performing vacuum drying to obtain NiCo-MOF; putting the prepared NiCo-MOF in a tube furnace for annealing, finally obtaining magnetic black powder, namely NiO-Co3O4@ CNTs, weighing the NiO-Co3O4@ CNTs powder, adding the NiO-Co3O4@ CNTs powder into a DMF solution, adding NaCl, and performing ultrasonic dispersion on the suspension to obtain NiO-Co3O4@ CNTs electrodeposition solution;
inserting the polished and dried glassy carbon electrode into the graphite oxide electrodeposition liquid, scanning the glassy carbon electrode by using a cyclic voltammetry method, and drying to obtain the glassy carbon electrode subjected to graphite oxide deposition;
s2: scanning and electrodepositing NiO-Co3O4@ CNTs electrodeposition liquid on graphite oxide of a glassy carbon electrode by a cyclic voltammetry method and reducing graphene oxide on the glassy carbon electrode;
s3: and (3) placing the glassy carbon electrode obtained in the step (S2) in a blank PBS buffer solution, and then scanning by using a cyclic voltammetry method to reduce the graphite oxide to obtain the dopamine electrochemical sensor.
Preferably, the preparation method of the dopamine electrochemical sensor of the present invention uses cyclic voltammetry in step S2 to obtain a voltage in the potential range of-0.2V-1.2V- 1 Scanning at the speed of 20 half circles, keeping stirring in the period, and drying under an infrared lamp after scanning; then NiO-Co3O4@ CNTs is electrodeposited on the graphene oxide, and the cyclic voltammetry is used for the treatment of the NiO-Co3O4@ CNTs -1 The scanning speed of the method is within a potential range of-1.2V-2.0V for 5 times to enable graphene oxide to be electrodeposited on the surface of an electrode, then the electrode is taken out and dried under an infrared lamp, the obtained electrode is placed in a blank PBS buffer solution with the concentration of 0.1M and the pH =5.5, the graphite oxide is reduced by scanning the electrode at the scanning speed of 0.1 V.s < -1 > within a potential range of-0.9V-0V by using a cyclic voltammetry method, and finally the NiCo @ CNTs/rGO/GCE electrochemical sensing platform is successfully prepared.
Preferably, in the preparation method of the dopamine electrochemical sensor, before step S1, a glassy carbon electrode is treated, the glassy carbon electrode is polished by using alumina powders with particle sizes of 1.0um, 0.3um and 0.05um in sequence, and then the polished electrode is immersed in absolute ethyl alcohol and deionized water in sequence for ultrasonic washing, wherein in step S1, the volume ratio of the deionized water to the DMF-ethanol mixed solution is 1.
Preferably, in the preparation method of the dopamine electrochemical sensor, the oven temperature in the step S1 is 150 ℃, and the reaction time is 10 hours.
Preferably, in the preparation method of the dopamine electrochemical sensor, in the step S1, the annealing temperature of the tubular furnace is 400 ℃, and the heating rate is 2 ℃ min -1 The annealing time is 4h, and the NaCl concentration in the step S1 is 15 mmol.L -1 。
Preferably, in the preparation method of the dopamine electrochemical sensor, the concentration of the NiO-Co3O4@ CNTs electrodeposition solution in the step S1 is 2 mg/mL -1 。
Preferably, in the preparation method of the dopamine electrochemical sensor of the present invention, the method for synthesizing graphene oxide in step S2 includes: firstly, mixing graphite powder with sodium nitrate and slowly adding cold concentrated H 2 SO 4 The solution was stirred in an ice-water bath while maintaining the overall temperature of the reaction below 5 ℃, and KMnO was slowly added during the stirring reaction 4 Removing the ice bath device, then carrying out reaction at room temperature, continuously stirring, adding deionized water into a reaction solution, raising the reaction temperature to 80-120 ℃, adding deionized water and a hydrogen peroxide solution into the reaction until the reaction is stopped and the solution is light brown, keeping the solution, standing and filtering to obtain a brown precipitate, repeatedly washing the brown precipitate with dilute hydrochloric acid, finally centrifuging the brown precipitate with deionized water, drying the precipitate in a vacuum drying oven, collecting graphene oxide, weighing graphene oxide powder, adding the graphene oxide powder into deionized water, adding NaCl serving as a supporting electrolyte, and placing the dispersion at room temperature for ultrasonic mixing to obtain the graphene oxide electrodeposition solution.
Preferably, in the preparation method of the dopamine electrochemical sensor, in step S2, the mass fraction of hydrogen peroxide is 30%, and the dilute hydrochloric acid is prepared from a concentrated hydrochloric acid solution and water at a volume ratio of 5.
Preferably, in the preparation method of the dopamine electrochemical sensor, the NaCl concentration in the step S2 is 5 mmol.L -1 In step S2, the concentration of the graphite oxide electrodeposition solution is 2 mg/mL -1 。
Preferably, the preparation method of the dopamine electrochemical sensor of the invention uses cyclic voltammetry to perform the measurement in the potential range of-0.2V-1.2V with 0.1 V.s- 1 Scanning at the speed of 20 and a half circles, keeping stirring in the period, and drying under an infrared lamp after scanning; then NiO-Co3O4@ CNTs is electrodeposited on the graphene oxide, and the cyclic voltammetry is used for the treatment of the NiO-Co3O4@ CNTs -1 The method comprises the steps of scanning for 5 circles within a potential range of-1.2V-2.0V to enable graphene oxide to be electrodeposited on the surface of an electrode, taking out the electrode and drying the electrode under an infrared lamp, finally reducing the graphene oxide on the electrode, placing the obtained electrode in a blank PBS buffer solution with the pH =5.5 and the scanning speed of 0.1 V.s < -1 > within a potential range of-0.9V-0V to reduce the graphite oxide by using a cyclic voltammetry scanning method, and finally successfully preparing a NiCo @ CNTs/rGO/GCE electrochemical sensing platform.
The invention also provides a dopamine electrochemical sensor prepared by the preparation method.
The beneficial effects of the invention are:
the NiO-TPA is synthesized by a traditional hydrothermal method, then is pyrolyzed to obtain NiO-Co3O4@ CNTs, and then is electrodeposited on the surface of reduced graphene oxide, and the NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensor is prepared by means of the excellent electronic conductivity of rGO and the active site of the NiO @ CNTs, and has the advantages of lower detection limit, wide detection range, excellent selectivity and stability.
The invention combines the advantages of large specific surface area of NiO-Co3O4@ CNTs, more active sites, excellent conductivity of reduced graphene oxide, active groups on the surface and the like, greatly increases the dopamine detection effect, and obtains the following experimental conclusion after experimental optimization conditions and the use of a differential pulse voltammetry to determine the working curve of dopamine: when the dopamine concentration is in two linear segments at 100 nM-7 μ M and 7 μ M-22 μ M, the linear equations are Ip1 (μ A) =0.0064C (nM) -0.6783 (R) 2 ＝0.9975)，Ip2(μA)＝0.0013C(nM)+33.787(R 2 = 0.9916) detection Limit (LOD) of 45nM (S/N = 3), and the sensor thus produced also has good effect on interferents in the solution to be testedA counteracting effect. In addition, the sensor has good reproducibility and stability, and has been successfully used for detecting dopamine in actual samples.
Drawings
The technical solution of the present application is further explained below with reference to the drawings and the embodiments.
FIG. 1A is an SEM picture of NiCo-TPA-MOF in example 1 and FIG. 1B is an SEM picture of NiO-Co3O4@ CNTs/rGO in example 1.
FIG. 2A is the DPV spectra of NiO-Co3O4@ CNTs/rGO/GCE in example 1 for different concentrations of dopamine, and FIG. 2B is the working curve of NiO-Co3O4@ CNTs/rGO/GCE in example 1 for dopamine detection.
FIG. 3 is a graph of the effect of interferon on 5 μ M dopamine as tested in example 1.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be considered limiting of the scope of the present application. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the invention, "a plurality" means two or more unless otherwise specified.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art through specific cases.
The technical solutions of the present application will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
Example 1
The embodiment provides a preparation method of a dopamine electrochemical sensor, which comprises the following steps:
s1: preparing NiO-Co3O4@ CNTs electrodeposition liquid, taking 0.15g of terephthalic acid (TPA), 1.5g of polyvinylpyrrolidone (PVP), 0.067g of nickel nitrate and 0.132g of cobalt nitrate, dissolving the materials in deionized water, DMF and ethanol solution with the volume ratio of 1 -1 Temperature rising speed) and keeping for 3h, and finally obtaining magnetic black powder, namely NiO-Co3O4@ CNTs. Weighing 20mg of NiO-Co3O4@ CNTs powder, adding the powder into 10mL of DMF solution, adding 15mmol of NaCl, and ultrasonically dispersing the suspension for 2h to obtain 2 mg/mL-1 NiO-Co3O4@ CNTs electrodeposition solution.
S2, synthesizing Graphene Oxide (GO), namely mixing 6g of graphite powder and 3g of sodium nitrate and slowly adding cold concentrated H 2 SO 4 The solution was stirred in an ice-water bath and the overall temperature of the reaction was kept below 5 ℃. During the stirring reaction, 15g of KMnO was slowly added 4 After removal of the ice bath, the reaction was continued at room temperature with constant stirring. Then 200mL of deionized water was added to the reaction solution while the reaction temperature was raised to 98 deg.C, and 500mL of deionized water was then addedWater and 30mL of 30% hydrogen peroxide solution are added into the reaction until the reaction is stopped and the solution is light brown, the mixture is left overnight, and is kept still for filtering to obtain a brown precipitate, and then the brown precipitate is washed repeatedly by dilute hydrochloric acid (the dilute hydrochloric acid is prepared by concentrated hydrochloric acid solution and water with the volume ratio of 5. And finally, centrifuging by using deionized water, drying in a vacuum drying oven, and collecting to obtain the graphene oxide. Weighing 10mg of graphene oxide powder, adding the graphene oxide powder into 10mL of deionized water, adding 5mmol of NaCl serving as supporting electrolyte, placing the dispersion liquid at 25 ℃ and ultrasonically mixing for 6 hours to obtain 2 mg-mL -1 GO electrodeposition bath of (1).
S3: construction of a NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensing platform: before the glassy carbon electrode is used for testing experiments, aluminum oxide powder with the grain size of 1.0um, 0.3um and 0.05um is used for polishing in sequence, then the polished electrode is immersed into absolute ethyl alcohol and deionized water in sequence for ultrasonic washing, and after the washing is finished, the clean electrode is placed under an infrared lamp for drying. Firstly, graphene oxide is attached to the surface of an electrode, the operation is carried out according to the literature description, the prepared electrode is firstly inserted into the electrodeposition solution of GO, and the cyclic voltammetry is used for carrying out the operation in the potential range of-0.2V-1.2V at the voltage of 0.1 V.s -1 Scanning at the speed of (2) for 20 and a half circles, keeping stirring in the period, and baking under an infrared lamp after the scanning is finished. Then NiCo @ CNTs is electrodeposited on the graphene oxide with CV of 0.1 V.s -1 The method comprises the steps of scanning for 5 circles within a potential range of-1.2V-2.0V to enable graphene oxide to be electrodeposited on the surface of an electrode, taking out the electrode and drying the electrode under an infrared lamp, finally reducing the graphene oxide on the electrode, placing the obtained electrode in a blank PBS (phosphate buffer solution) with the pH of 0.1M =5.5 according to the description in the literature, scanning by using a CV (constant voltage) technology within a potential range of-0.9V-0V at a scanning speed of 0.1 V.s < -1 > to reduce GO to generate rGO (reduced graphite oxide), and finally successfully preparing the NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensing platform.
Effects of the embodiment
The Co3O4/N-CNFs/MoS2-MWCNTs/GCE electrochemical sensor prepared in example 1 is taken as an example for detecting the concentration of dopamine.As shown in FIG. 2a, by adding luteolin with different concentrations (100 nM-7 μ M and 7 μ M-22 μ M), a Differential Pulse Voltammetry (DPV) of response of the Co3O4/N-CNFs/MoS2-MWCNTs/GCE electrochemical sensor to luteolin can be obtained, 2b is a calibration curve of response current and concentration of luteolin, and it can be seen that when the dopamine concentration is 100 nM-7 μ M and 7 μ M-22 μ M, the two-stage linearity is achieved, and the linear equations are Ip1 (μ A) =0.0064C (nM) -0.6783 (R) respectively 2 ＝0.9975)，Ip2(μA)＝0.0013C(nM)+33.787(R 2 = 0.9916), the limit of detection (LOD) was 45nM (S/N = 3).
The prepared NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensor is taken as an example to test the influence of interferon on 5 mu M dopamine. As shown in FIG. 3, the performance of the sensor for measuring dopamine by adding different interferents is almost not reduced, which indicates that the prepared NiO-Co3O4@ CNTs/rGO/GCE electrochemical sensor has good anti-interference capability.
A bimetallic MOF: niCo-MOF, and after carbonizing at 400 ℃, electrodeposit on reduced graphene oxide, thus constructing a novel dopamine electrochemical sensing platform NiO-Co3O4@ CNTs/rGO/GCE, the electrode material combines the advantages of large specific surface area, many active sites, excellent conductivity of the reduced graphene oxide, active groups on the surface and the like, so that the detection effect of the electrode material on dopamine is greatly increased, and after experimental optimization conditions and the working curve of dopamine is determined by using a differential pulse voltammetry method, the following experimental conclusion is obtained: when the dopamine concentration is in two linear segments at 100 nM-7 μ M and 7 μ M-22 μ M, the linear equations are Ip1 (μ A) =0.0064C (nM) -0.6783 (R) 2 ＝0.9975)，Ip2(μA)＝0.0013C(nM)+33.787(R 2 = 0.9916), the limit of detection (LOD) is 45nM (S/N = 3), and the sensor thus produced is also very resistant to interferents in the solution to be tested. In addition, the sensor has good reproducibility and stability, and has been successfully used for detecting dopamine in actual samples.
In light of the foregoing description of the preferred embodiments according to the present application, it is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of a dopamine electrochemical sensor is characterized by comprising the following steps:
s1: taking terephthalic acid, polyvinylpyrrolidone, nickel nitrate and cobalt nitrate, dissolving the terephthalic acid, polyvinylpyrrolidone, nickel nitrate and cobalt nitrate into a mixed solution of deionized water, DMF and ethanol, performing ultrasonic dispersion for more than half an hour to ensure complete dissolution, transferring the solution into a reaction kettle after the solution is clear, placing the reaction kettle in an oven for reaction, after the reaction is naturally cooled, centrifuging the solution by using a high-speed centrifuge, sequentially washing the solution with DMF, methanol and water, and finally performing vacuum drying to obtain NiCo-MOF; placing the prepared NiCo-MOF in a tube furnace for annealing to obtain magnetic black powder, namely NiO-Co3O4@ CNTs, weighing the NiO-Co3O4@ CNTs powder, adding the NiO-Co3O4@ CNTs powder into a DMF solution, adding NaCl, and performing ultrasonic dispersion on the suspension to obtain NiO-Co3O4@ CNTs electrodeposition liquid;
inserting the polished and dried glassy carbon electrode into the graphite oxide electrodeposition solution, scanning the glassy carbon electrode by using a cyclic voltammetry method, and drying to obtain the glassy carbon electrode subjected to graphite oxide deposition;
s2: scanning and electrodepositing NiO-Co3O4@ CNTs electrodeposition liquid on graphite oxide of a glassy carbon electrode by a cyclic voltammetry method and reducing graphene oxide on the glassy carbon electrode;
s3: and (3) placing the glassy carbon electrode obtained in the step (S2) in a blank PBS buffer solution, and then scanning by using a cyclic voltammetry method to reduce the graphite oxide to obtain the dopamine electrochemical sensor.
2. The method for preparing a dopamine electrochemical sensor according to claim 1, wherein cyclic voltammetry is used in step S2 at 0.1 V.s- 1 Scanning at the speed of 20 half circles, keeping stirring in the period, and drying under an infrared lamp after scanning; then NiO-Co3O4@ CNTs is electrodeposited on the graphene oxide, and the cyclic voltammetry is used for 0.1 V.s -1 The scanning speed of the method is within a potential range of-1.2V-2.0V for 5 times to enable graphene oxide to be electrodeposited on the surface of an electrode, then the electrode is taken out and dried under an infrared lamp, the obtained electrode is placed in a blank PBS buffer solution with the concentration of 0.1M and the pH =5.5, the graphite oxide is reduced by scanning the electrode at the scanning speed of 0.1 V.s < -1 > within a potential range of-0.9V-0V by using a cyclic voltammetry method, and finally the NiCo @ CNTs/rGO/GCE electrochemical sensing platform is successfully prepared.
3. The method for preparing a dopamine electrochemical sensor according to claim 1 or 2, characterized in that before step S1, a glassy carbon electrode is treated, the glassy carbon electrode is polished by using alumina powders with particle sizes of 1.0um, 0.3um and 0.05um in sequence, and then the polished electrode is immersed in absolute ethyl alcohol and deionized water in sequence for ultrasonic washing, wherein in step S1, the volume ratio of the deionized water to the DMF to the ethanol mixed solution is 1.
4. The method for preparing the dopamine electrochemical sensor according to claim 1, wherein the oven temperature in step S1 is 150 ℃ and the reaction time is 10 hours.
5. The method for preparing the dopamine electrochemical sensor according to claim 1, wherein the annealing temperature of the tube furnace in step S1 is 400 ℃, and the temperature rise rate is 2 ℃. Min -1 The annealing time is 4h, and the NaCl concentration in the step S1 is 15 mmol.L -1 。
6. The method for preparing the dopamine electrochemical sensor according to claim 1, wherein the concentration of the NiO-Co3O4@ CNTs electrodeposit solution in the step S1 is 2 mg-mL -1 。
7. The method for preparing the dopamine electrochemical sensor according to claim 1, wherein the method for synthesizing graphene oxide in step S2 comprises: firstly, mixing graphite powder with sodium nitrate and slowly adding cold concentrated H 2 SO 4 In (1), the solution is stirred in an ice-water bathMaintaining the overall temperature below 5 deg.C, and adding KMnO slowly while stirring 4 Removing an ice bath device, then carrying out a subsequent reaction at room temperature, continuously stirring, adding deionized water into a reaction solution, simultaneously raising the reaction temperature to 80-120 ℃, then adding deionized water and a hydrogen peroxide solution into the reaction until the reaction is stopped and the solution is light brown, keeping and standing for filtering to obtain a brown precipitate, then repeatedly washing with dilute hydrochloric acid, finally centrifuging with deionized water, drying in a vacuum drying oven, collecting graphene oxide, weighing graphene oxide powder, adding the graphene oxide powder into deionized water, adding NaCl serving as a supporting electrolyte, and placing the dispersion liquid at room temperature for ultrasonic mixing to obtain the graphene oxide electrodeposition liquid.
8. The method for preparing a dopamine electrochemical sensor according to claim 7, wherein the mass fraction of hydrogen peroxide in step S2 is 30%, and the dilute hydrochloric acid is prepared from a concentrated hydrochloric acid solution and water at a volume ratio of 5.
9. The method for preparing the dopamine electrochemical sensor according to claim 7, wherein the NaCl concentration in step S2 is 5 mmol-L -1 In step S2, the concentration of the graphite oxide electrodeposition solution is 2 mg/mL -1 。
10. A dopamine electrochemical sensor produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211110794.8A CN115791941A (en) | 2022-09-13 | 2022-09-13 | Preparation method of dopamine electrochemical sensor and product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211110794.8A CN115791941A (en) | 2022-09-13 | 2022-09-13 | Preparation method of dopamine electrochemical sensor and product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115791941A true CN115791941A (en) | 2023-03-14 |
Family
ID=85431919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211110794.8A Pending CN115791941A (en) | 2022-09-13 | 2022-09-13 | Preparation method of dopamine electrochemical sensor and product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115791941A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104280435A (en) * | 2014-09-28 | 2015-01-14 | 上海应用技术学院 | Graphene-modified glassy carbon electrode and preparation method and application of graphene-modified glassy carbon electrode |
| CN109580741A (en) * | 2019-01-09 | 2019-04-05 | 上海应用技术大学 | It is a kind of to detect the modified electrode of dopamine, preparation method and applications |
| CN109900760A (en) * | 2019-03-28 | 2019-06-18 | 河北科技大学 | A kind of preparation method and applications of the dopamine electrochemical sensor based on polyacid |
| CN110467821A (en) * | 2019-08-30 | 2019-11-19 | 济南大学 | A kind of preparation method and application of the chitosan/oxidized graphene chirality composite material of Co-MOF/ |
| CN113267547A (en) * | 2021-05-20 | 2021-08-17 | 河南工业大学 | Preparation method of nickel-zinc-based metal organic framework material with biomass charcoal as carbon source |
| CN113624817A (en) * | 2021-07-27 | 2021-11-09 | 光华临港工程应用技术研发(上海)有限公司 | Dopamine detection device and manufacturing method of dopamine detection electrode |
| CN114113256A (en) * | 2021-11-29 | 2022-03-01 | 四川轻化工大学 | Preparation method of electrochemical sensor based on graphene oxide/carbon quantum dots and method for detecting dopamine |
| CN114674885A (en) * | 2022-03-16 | 2022-06-28 | 扬州大学 | Preparation method of flexible wearable sweat glucose electrochemical sensor |
-
2022
- 2022-09-13 CN CN202211110794.8A patent/CN115791941A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104280435A (en) * | 2014-09-28 | 2015-01-14 | 上海应用技术学院 | Graphene-modified glassy carbon electrode and preparation method and application of graphene-modified glassy carbon electrode |
| CN109580741A (en) * | 2019-01-09 | 2019-04-05 | 上海应用技术大学 | It is a kind of to detect the modified electrode of dopamine, preparation method and applications |
| CN109900760A (en) * | 2019-03-28 | 2019-06-18 | 河北科技大学 | A kind of preparation method and applications of the dopamine electrochemical sensor based on polyacid |
| CN110467821A (en) * | 2019-08-30 | 2019-11-19 | 济南大学 | A kind of preparation method and application of the chitosan/oxidized graphene chirality composite material of Co-MOF/ |
| CN113267547A (en) * | 2021-05-20 | 2021-08-17 | 河南工业大学 | Preparation method of nickel-zinc-based metal organic framework material with biomass charcoal as carbon source |
| CN113624817A (en) * | 2021-07-27 | 2021-11-09 | 光华临港工程应用技术研发(上海)有限公司 | Dopamine detection device and manufacturing method of dopamine detection electrode |
| CN114113256A (en) * | 2021-11-29 | 2022-03-01 | 四川轻化工大学 | Preparation method of electrochemical sensor based on graphene oxide/carbon quantum dots and method for detecting dopamine |
| CN114674885A (en) * | 2022-03-16 | 2022-06-28 | 扬州大学 | Preparation method of flexible wearable sweat glucose electrochemical sensor |
Non-Patent Citations (4)
| Title |
|---|
| YAO CHI等: "Ni/Co bimetallic organic framework nanosheet assemblies for high-performance electrochemical energy storage", 《NANOSCALE》, vol. 12, 23 April 2020 (2020-04-23), pages 1 * |
| 张雯主编: "《化学综合实验 第2版》", vol. 2, 31 July 2021, 西安交通大学出版社, pages: 55 - 56 * |
| 张静: "MOF 衍生过渡金属-碳基复合材料的构建及 其对生物小分子的电化学检测研究", 《中国优秀硕士学位论文全文数据库》, no. 2019, 15 January 2019 (2019-01-15), pages 3 - 2 * |
| 顾春梦: "MOFs 复合材料及其衍生物的电化学传感研究", 《中国优秀硕士学位论文全文数据库》, no. 2021, 15 February 2021 (2021-02-15), pages 1 - 4 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Fabrication of amine-functionalized metal-organic frameworks with embedded palladium nanoparticles for highly sensitive electrochemical detection of telomerase activity | |
| CN109490385B (en) | Biosensor based on Au-ZIF-8/OMC mesoporous carbon | |
| Feng et al. | MOF‐Derived Spinel NiCo2O4 Hollow Nanocages for the Construction of Non‐enzymatic Electrochemical Glucose Sensor | |
| Zheng et al. | Carbon nanohorns enhanced electrochemical properties of Cu-based metal organic framework for ultrasensitive serum glucose sensing | |
| CN109596686B (en) | Electrochemical sensor for simultaneously detecting guanine and adenine and preparation method thereof | |
| CN112110439B (en) | Preparation method and application of carbon nanotube wrapped nitrogen-doped porous carbon composite material | |
| CN110412095B (en) | Nitrogen-doped graphene composite material loaded with flower-ball-shaped copper sulfide-palladium core-shell structure and preparation method and application thereof | |
| CN110031522B (en) | Nickel metal organic framework material and preparation method and application thereof | |
| Taei et al. | Simultaneous determination of sunset yellow and tartrazine in soft drinks samples using nanocrystallites of spinel ferrite-modified electrode | |
| Bu et al. | A novel three-dimensional molecularly imprinted polypyrrole electrochemical sensor based on MOF derived porous carbon and nitrogen doped graphene for ultrasensitive determination of dopamine | |
| CN115791941A (en) | Preparation method of dopamine electrochemical sensor and product | |
| CN106568827A (en) | Preparation method of electrode for electrochemical detection of 5-hydroxyindole acetic acid in body fluid, and detection method for electrochemical detection of 5-hydroxyindole acetic acid in body fluid | |
| CN110749635B (en) | Preparation method and application of nanocomposite and electrochemical microRNA biosensor | |
| Wei et al. | A novel electrochemical sensor based on DUT-67/ZnCo2O4-MWCNTs modified glassy carbon electrode for the simultaneous sensitive detection of dopamine and uric acid | |
| CN115612115B (en) | Quinoxalinyl conjugated microporous polymer grafted graphene material, photoelectrochemical sensor, preparation method and rifampicin detection method | |
| CN110039043B (en) | Three-dimensional copper @ carbon core-shell nanoparticle, and preparation method and application thereof | |
| Solangi et al. | Phytochemicals of mustard (Brassica Campestris) leaves tuned the nickel‐cobalt bimetallic oxide properties for enzyme‐free sensing of glucose | |
| CN113697797B (en) | N-CNTs @ NiCo-LDHs tree-like nano flower material, preparation method and photoelectrochemical application thereof | |
| CN111398378B (en) | Preparation method of composite material modified electrode for detecting glucose and electrode | |
| CN114660146B (en) | Label-free photoelectric biosensor and preparation method thereof | |
| CN112010359B (en) | NiO/C nano composite electrode material and preparation method and application thereof | |
| CN114371201A (en) | Reusable glucose sensor and preparation method and application thereof | |
| Faridan et al. | Simultaneous determination of trace amounts ascorbic acid, melatonin and tryptophan using modified glassy carbon electrode based on Cuo-CeO2-rGO-MWCNTS nanocomposites | |
| CN113804737B (en) | Polyaniline loaded silver/cuprous oxide multi-element nanocomposite and preparation method of modified electrode | |
| Ghasemi et al. | A novel and ultrasensitive electrochemical DNA biosensor for pralatrexate detection |
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 |