阅读说明：本技术 多巴胺检测装置以及多巴胺检测电极的制作方法 (Dopamine detection device and manufacturing method of dopamine detection electrode ) 是由 詹义强 努曼·阿尔希德 秦亚杰 胡来归 于 2021-07-27 设计创作，主要内容包括：本发明提供了一种多巴胺检测装置,玻璃碳电极的表面采用还原性氧化石墨烯-Co3O4-金属纳米复合材料进行修饰。本发明提供了一种多巴胺检测电极的制作方法,包括如下步骤：合成氧化石墨烯；制备还原性氧化石墨烯-Co3O4复合材料；将金属纳米颗粒沉积在还原性氧化石墨烯-Co3O4复合材料上,获得还原性氧化石墨烯-Co3O4-金属纳米复合材料；抛光玻璃碳电极表面；将还原性氧化石墨烯-Co3O4-金属纳米复合材料修饰于玻璃碳电极表面。提出rGO、-Co-(3)O-(4)和金属的三元纳米复合材料可以作为玻璃碳和丝网印刷电极改性的连贯平台。rGO可以为-Co-(3)O-(4)纳米粒子提供支撑和导电平台。rGO基本计划上的官能团将有助于提高在极性溶剂中的选择性和分散性。-Co-(3)O-(4)将作为DA氧化的催化剂,而贵金属将通过促进电荷转移来催化氧化。(The invention provides a dopamine detection device.A surface of a glassy carbon electrode is modified by adopting a reducing graphene oxide-Co 3O 4-metal nano composite material. The invention provides a manufacturing method of a dopamine detection electrode, which comprises the following steps: synthesizing graphene oxide; preparing a reducing graphene oxide-Co 3O4 composite material; depositing metal nanoparticles on the reductive graphene oxide-Co 3O4 composite material to obtain a reductive graphene oxide-Co 3O 4-metal nanocomposite material; polishing the surface of the glassy carbon electrode; and modifying the reducing graphene oxide-Co 3O 4-metal nano composite material on the surface of the glassy carbon electrode. Providing rGO, -Co 3 O 4 And of metalsThe ternary nanocomposite can be used as a coherent platform for glassy carbon and screen printing electrode modification. rGO can be-Co 3 O 4 The nanoparticles provide a supporting and conductive platform. The basic intended functionality of rGO will help to improve selectivity and dispersibility in polar solvents. -Co 3 O 4 Will act as a catalyst for the oxidation of DA, while the noble metal will catalyze the oxidation by promoting charge transfer.)

1. The dopamine detection device is characterized in that the surface of a glassy carbon electrode adopts reductive graphene oxide-Co₃O₄-metal nanocomposites.

2. A manufacturing method of a dopamine detection electrode is characterized by comprising the following steps:

synthesizing graphene oxide;

preparation of reduced graphene oxide-Co₃O₄A composite material;

depositing metal nanoparticles on reduced graphene oxide-Co₃O₄On the composite material, obtaining the reductive graphene oxide-Co₃O₄-a metal nanocomposite;

polishing the surface of the glassy carbon electrode;

reducing graphene oxide-Co₃O₄The metal nano composite material is decorated on the surface of the glassy carbon electrode.

3. The method for manufacturing a dopamine-detecting electrode according to claim 2, wherein the step of synthesizing graphene oxide further comprises:

cleaning graphene with a mixed solution of sulfuric acid and phosphoric acid;

soaking the graphite oxide in a potassium permanganate solution to obtain graphite oxide;

carrying out ultrasonic treatment on the graphite oxide solution to strip the graphite oxide solution to obtain a graphene oxide suspension;

and carrying out centrifugal treatment on the graphene oxide suspension to obtain the graphene oxide.

4. The method for manufacturing the dopamine detecting electrode according to claim 2, wherein a hydrothermal method is adopted to prepare the reductive graphene oxide-Co₃O₄A composite material.

5. The method for manufacturing the dopamine detecting electrode according to claim 2, wherein the surface of the glassy carbon electrode is polished by using alumina powder.

6. A manufacturing method of a dopamine detection electrode is characterized by comprising the following steps:

synthesizing graphene oxide;

mixing Co₃O₄And combining the precursor solution of the metal with graphene oxide to obtain reduced graphene oxide-Co₃O₄-a metal nanocomposite;

polishing the surface of the glassy carbon electrode;

reducing graphene oxide-Co₃O₄The metal nano composite material is decorated on the surface of the glassy carbon electrode.

7. The method for manufacturing a dopamine-detecting electrode according to claim 6, wherein the step of synthesizing graphene oxide further comprises:

cleaning graphene with a mixed solution of sulfuric acid and phosphoric acid;

soaking the graphite oxide in a potassium permanganate solution to obtain graphite oxide;

carrying out ultrasonic treatment on the graphite oxide solution to strip the graphite oxide solution to obtain a graphene oxide suspension;

and carrying out centrifugal treatment on the graphene oxide suspension to obtain the graphene oxide.

8. The method for manufacturing the dopamine detecting electrode according to claim 6, wherein Co is subjected to hydrothermal reaction₃O₄And combining the precursor solution of the metal with graphene oxide.

9. The method for manufacturing the dopamine detecting electrode according to claim 6, wherein the surface of the glassy carbon electrode is polished by using alumina powder.

Technical Field

The invention relates to the field of electrochemical detection, in particular to a dopamine detection device and a manufacturing method of a dopamine detection electrode.

Background

Dopamine (DA) (3,4 dihydroxyphenylethylamine) is an organic electrochemical neurotransmitter and has received continuous attention from a variety of neurotransmitters due to its indispensable role in maintaining physiological functions and pathogenesis of diseases. It is responsible for the normal functioning of the nervous system and has also been identified as a clinical biomarker for a variety of diseases, such as parkinson's disease, schizophrenia and cardiovascular disease. Therefore, it is important to regularly monitor abnormal levels of important chemical neurotransmitters (such as DA) as it reflects the overall health. This also helps screen out many neurological disorders and constantly monitor mental health. Monitoring the DA level throughout will help adjust the patient's therapeutic dose.

Neurological disorders and DA levels are closely related to a pre-accurate diagnosis. To fill this gap in diagnosis and therapy, there is an urgent need for rapid, efficient, low-cost diagnostic tools to lead to optimal use of drugs in human medicine. Most important is the accurate detection of dopamine, which can be used to guide the initiation of the correct treatment by minimizing overuse or misuse of the drug. Both the speed of detection and the initiation of treatment play an important role in disease conditions. For example, healthy adults have plasma DA concentrations in the range of 0.1nM, while patients with head and neck paraganglioma have plasma DA concentrations in the range of up to 6 nM. In this case, sensing DA with high sensitivity and selectivity is disadvantageous to both application science and basic science.

The conventional analysis method for DA detection is high-precision liquid chromatography (HPLC) or enzyme-linked immunosorbent assay (ELISA) as an analyte separation tool, and combines electrochemistry or mass spectrometry, coulometry and fluorescence as detection technologies. However, the previously reported dopamine assay methods have some limitations. These techniques require a significant amount of capital for installation and instrument purchase, training professionals, and are time consuming. Conventional assay testing requires laboratory processing time, which often results in unnecessary time delays. Therefore, in order to avoid such economic burden and achieve rapid detection of DA, the present invention proposes a detection procedure based on nanomaterials. It can help save the patient's life by timely, rapid and more accurate testing, ultimately reducing treatment time, minimizing unnecessary drug use, and helping to better determine the prescription, including the selected drug, dosage, duration, etc.

Nanomaterials can have advantages in speed, specificity and sensitivity over other biochemical methods based on micron-sized materials. Because nanomaterials have unique electrical properties, easily functionalized surfaces and high surface area to volume ratios.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a dopamine detection device and a manufacturing method of a dopamine detection electrode, which have advantages in speed, specificity and sensitivity.

In order to solve the problems, the invention provides a dopamine detection device, wherein the surface of a glassy carbon electrode is modified by adopting a reducing graphene oxide-Co 3O 4-metal nano composite material.

In order to solve the above problems, the present invention provides a method for manufacturing a dopamine detection electrode, comprising the following steps: synthesizing graphene oxide; preparing a reducing graphene oxide-Co 3O4 composite material; depositing metal nanoparticles on the reductive graphene oxide-Co 3O4 composite material to obtain a reductive graphene oxide-Co 3O 4-metal nanocomposite material; polishing the surface of the glassy carbon electrode; and modifying the reducing graphene oxide-Co 3O 4-metal nano composite material on the surface of the glassy carbon electrode.

Optionally, the step of synthesizing graphene oxide further comprises: cleaning graphene with a mixed solution of sulfuric acid and phosphoric acid; soaking the graphite oxide in a potassium permanganate solution to obtain graphite oxide; carrying out ultrasonic treatment on the graphite oxide solution to strip the graphite oxide solution to obtain a graphene oxide suspension; and carrying out centrifugal treatment on the graphene oxide suspension to obtain the graphene oxide.

Optionally, a hydrothermal method is adopted to prepare the reducing graphene oxide-Co 3O4 composite material.

Optionally, the surface of the glassy carbon electrode is polished by using alumina powder.

In order to solve the above problems, the present invention provides a method for manufacturing a dopamine detection electrode, comprising the following steps: synthesizing graphene oxide; combining Co3O4 and a precursor solution of metal with graphene oxide to obtain a reducing graphene oxide-Co 3O 4-metal nanocomposite; polishing the surface of the glassy carbon electrode; and modifying the reducing graphene oxide-Co 3O 4-metal nano composite material on the surface of the glassy carbon electrode.

Optionally, the step of synthesizing graphene oxide further comprises: cleaning graphene with a mixed solution of sulfuric acid and phosphoric acid; soaking the graphite oxide in a potassium permanganate solution to obtain graphite oxide; carrying out ultrasonic treatment on the graphite oxide solution to strip the graphite oxide solution to obtain a graphene oxide suspension; and carrying out centrifugal treatment on the graphene oxide suspension to obtain the graphene oxide.

Optionally, a hydrothermal method is adopted to combine the precursor solution of Co3O4 and the metal with the graphene oxide.

Optionally, the surface of the glassy carbon electrode is polished by using alumina powder.

The above solution presents a commercialization capability and development path for sensors from the laboratory to the market. rGO-Co₃O₄-metal modified screen printed electrodes for ultra-selective and ultra-sensitive detection of DA. Due to rGO-Co₃O₄The 4 nanocubes exhibit excellent electrochemical properties and high affinity for DA and suitable ligands for specific recognition of DA. Considering the detection of DA, the main obstacle is the selectivity due to the oxidation potential of Ascorbic Acid (AA), whereas Dopamine (DA) is very close to each other. This problem can be solved by using GO/rGO based platforms. The oxygen-containing functional groups aid in the adsorption of DA (oxidation occurs), while Ascorbic Acid (AA) is repelled by electrostatic forces, resulting in pure electrical response of DAShould be used. In addition, these functional groups aid in dispersion of rGO in polar solvents.

However, cobalt oxide (-Co)₃O₄) Has unique characteristics such as large surface area to volume ratio, rapid electron transfer kinetics, excellent biocompatibility and excellent electrocatalytic activity, which makes the electrochemical sensing typical prospect. -Co₃O₄Having a ridge crystal structure with two Co²⁺Two of Co³⁺And four O^2-And two of Co³⁺And four O^2-And (4) ending. -Co₃O₄These different polar sites of the crystal, along with the high surface area to volume ratio and unique catalytic activity, help to detect charge and impart rapid charge transfer kinetics at the electrode surface. However, -Co₃O₄The higher band gap of (a) can hinder charge transport. This problem can be corrected by adding small amounts of noble metals (Pt, Pd, Au, Ag), which can provide an extended channel for fast charge transport.

Based on the above discussion, the above technical scheme provides rGO and-Co₃O₄And the ternary nanocomposite of metal can be used as a coherent platform for glassy carbon and screen printed electrode modification. rGO can be-Co₃O₄The nanoparticles provide a supporting and conductive platform. The basic intended functionality of rGO will help to improve selectivity and dispersibility in polar solvents. -Co₃O₄Will act as a catalyst for the oxidation of DA, while the noble metal will catalyze the oxidation by promoting charge transfer.

Drawings

FIG. 1 is a schematic diagram showing the steps of the method according to one embodiment of the present invention,

fig. 2 is a specific flow chart of the method for synthesizing graphene oxide according to an embodiment of the present invention.

FIG. 3 is a flow chart illustrating the method of making a coating according to one embodiment of the present invention.

Figure 4 is a schematic diagram showing the steps of the method according to one embodiment of the present invention,

FIG. 5 is a flow chart illustrating the method of making a coating according to one embodiment of the present invention.

Detailed Description

The following describes in detail specific embodiments of a dopamine detecting device and a method for manufacturing a dopamine detecting electrode according to the present invention with reference to the accompanying drawings.

FIG. 1 is a schematic diagram illustrating the steps of the method according to an embodiment of the present invention, including: step S10, synthesizing graphene oxide; step S11, preparing reductive graphene oxide-Co₃O₄A composite material; step S12, depositing metal nanoparticles on the reduced graphene oxide- -Co₃O₄On the composite material to obtain reducing graphene oxide-Co₃O₄-a metal nanocomposite; step S13, polishing the surface of the glassy carbon electrode; step S14, reducing graphene oxide-Co₃O₄The metal nano composite material is decorated on the surface of the glassy carbon electrode.

Referring to step S10, graphene oxide is synthesized, i.e., the first stage of the present embodiment: and (3) synthesizing Graphene Oxide (GO). The synthetic route will be simplified to Hummur's method. Later, the GO will be used to make rGO- -Co₃O₄. For GO synthesis, graphite flakes will be used to synthesize graphene oxide. The simplified hummers method will be used for the synthesis of graphene. Sulfuric acid and phosphoric acid will be used to oxidize graphite, which is then obtained with potassium permanganate. After stirring for three days, the solution was added to ice and further hydrogen peroxide. The material obtained was then washed with HCl and deionized water to reach a pH equal to 7. The obtained graphite oxide solution was then sonicated for exfoliation to obtain a graphene oxide suspension and centrifuged at 4000rpm for a short period of time to remove the voluminous layer. A detailed flow chart of the above method is shown in fig. 2.

Referring to step S11, reduced graphene oxide- -Co is prepared₃O₄A composite material. Namely, the second stage of the present embodiment: rGO-Co₃O₄Preparation of @ metal nanocomposite. The preparation at this stage adopts a one-step hydrothermal methodrGO--Co₃O₄@ metal nanocomposites. The synthesis scheme used will be a hydrothermal process. The method is simple and can be commercialized. The optimized morphology will be prepared by adjusting the pH, reaction time and temperature.

Referring to step S12, metal nanoparticles are deposited on the reduced graphene oxide-Co₃O₄On the composite material to obtain reducing graphene oxide-Co₃O₄-a metal nanocomposite. Namely, the third stage of the present embodiment: synthesizing rGO- @ metal nano composite material. The present embodiment employs a two-step synthetic route. In the first step, the first rGO- -Co will be prepared₃O₄The nanocomposite (optimized in step S11). Second, deposit metal nanoparticles on rGO-Co using hydrothermal method₃O₄On the nanocomposite.

The structural and morphological characteristics of the coating prepared by the above method, including composition, purity and structural crystallinity, are analyzed by fourier transform infrared spectroscopy (FTIR), raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD) and energy dispersive X-ray spectroscopy (EDX). The morphology and particle size of the metal oxide/sulfide nanostructures will be confirmed by High Resolution Transmission Electron Microscopy (HRTEM), Field Emission Scanning Electron Microscopy (FESEM). For samples that are qualified for characterization, the electrode fabrication process can be further performed. A detailed flow chart of the above method is shown in fig. 3.

And step S13, polishing the surface of the glassy carbon electrode. Before modification, the glassy carbon electrode surface will be polished with alumina powder (0.3 and 0.05 μm). The glassy carbon electrode will be rinsed with Deionized (DI) water and dried under an Infrared (IR) lamp. Aliquoted rGO-Co₃O₄The @ metal nanocomposite was used to modify the glassy carbon electrode surface in deionized water and subsequent electrochemical studies were performed.

Step S14, reducing graphene oxide-Co₃O₄The metal nano composite material is decorated on the surface of the glassy carbon electrode. The prepared sample was drop cast into aliquots and the electrodes were prepared on clean and dry glassy carbon electrode surfaces. To go intoIn one step of electrochemical studies, it was further dried under an infrared lamp.

The manufactured electrode can be used for analyzing rGO-Co₃O₄@ metal nanocomposite material performance for electrochemical sensing of DA. The surface of the glassy carbon electrode will be modified with an ink of [email protected] metal nanocomposite. The performance parameters of LOD, sensitivity, selectivity, and linearity range will be determined by Differential Pulse Voltammetry (DPV), Chronoamperometry (CA), and Electrochemical Impedance Spectroscopy (EIS).

The development of functional biosensors for dopamine detection is increasingly under investigation, showing the importance and strong demand for commercial applications of such devices. Although various reports on the detection of dopamine using electrochemical sensors have been published, the commercial market still lacks products for practical sample applications. Challenges exist in the path such as ideally low detection limits, high selectivity, short analysis, cost efficiency, skill not required to perform the detection, and portability of the sensor for field monitoring purposes. The integration of nanomaterials into biosensors has made a significant advance in the analysis time and selectivity of the biosensing process. It is important to consider the type of nanomaterials used in sensor applications, since most materials are either costly or require extensive synthesis processes. Thus, the process from the laboratory bench to the end user is typically lengthy.

The present embodiment proposes a new model of a simple, POC and high-sensitivity electrochemical biosensor based on integrated nanomaterials for differentiating and detecting DA. This embodiment creates a novel multifunctional electrochemical nano-platform to detect DA, with emphasis on early detection of DA, especially in countries lacking an effective healthcare system. In the composite system, rGO-Co is selected₃O₄-metal nanocomposite electrode as capture and detection platform, DA as cooperative capture and inactivation unit, rGO — Co₃O₄-a metal nanocomposite as deactivating unit. To build a platform, screen printed electrodes will be developed. Platform technology will distinguish molecular targets from surrogates to achieve precise localization. The strategyWill be based on rGO-Co₃O₄The use of metal nanocomposite electrochemical sensors in public health opens up new avenues.

FIG. 4 is a schematic diagram illustrating the steps of a method according to another embodiment of the present invention, including: step S40, synthesizing graphene oxide; step S41, mixing Co₃O₄And combining the precursor solution of the metal with graphene oxide to obtain reduced graphene oxide-Co₃O₄-a metal nanocomposite; step S42, polishing the surface of the glassy carbon electrode; step S43, reducing graphene oxide-Co₃O₄The metal nano composite material is decorated on the surface of the glassy carbon electrode.

Referring to step S40, graphene oxide is synthesized, i.e., the first stage of the present embodiment: and (3) synthesizing Graphene Oxide (GO). The synthetic route will be simplified to Hummur's method. Later, the GO will be used to make rGO- -Co₃O₄. For GO synthesis, graphite flakes will be used to synthesize graphene oxide. The simplified hummers method will be used for the synthesis of graphene. Sulfuric acid and phosphoric acid will be used to oxidize graphite, which is then obtained with potassium permanganate. After stirring for three days, the solution was added to ice and further hydrogen peroxide. The material obtained was then washed with HCl and deionized water to reach a pH equal to 7. The obtained graphite oxide solution was then sonicated for exfoliation to obtain a graphene oxide suspension and centrifuged at 4000rpm for a short period of time to remove the voluminous layer. A detailed flow chart of the above method is shown in fig. 2.

Referring to step S41, Co₃O₄And combining the precursor solution of the metal with graphene oxide to obtain reduced graphene oxide-Co₃O₄-a metal nanocomposite. Namely, the second stage of the present embodiment: rGO-Co₃O₄Preparation of @ metal nanocomposite. In this stage, one-step hydrothermal method is adopted to prepare rGO-Co₃O₄@ metal nanocomposites. The synthesis scheme used will be a hydrothermal process. The method is simple and can be commercialized. The optimized morphology will be obtained by adjusting the pH, reaction time andtemperature. The present embodiment employs a single step synthetic route. The single-step synthetic route is-Co₃O₄And the precursor solution of the noble metal will combine with GO and take a hydrothermal route.

The structural and morphological characteristics of the coating prepared by the above method, including composition, purity and structural crystallinity, are analyzed by fourier transform infrared spectroscopy (FTIR), raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD) and energy dispersive X-ray spectroscopy (EDX). The morphology and particle size of the metal oxide/sulfide nanostructures will be confirmed by High Resolution Transmission Electron Microscopy (HRTEM), Field Emission Scanning Electron Microscopy (FESEM). For samples that are qualified for characterization, the electrode fabrication process can be further performed. A detailed flow chart of the above method is shown in fig. 5.

And step S42, polishing the surface of the glassy carbon electrode. Before modification, the glassy carbon electrode surface will be polished with alumina powder (0.3 and 0.05 μm). The glassy carbon electrode will be rinsed with Deionized (DI) water and dried under an Infrared (IR) lamp. Aliquoted rGO-Co₃O₄The @ metal nanocomposite was used to modify the glassy carbon electrode surface in deionized water and subsequent electrochemical studies were performed.

And step S43, modifying the reducing graphene oxide-Co 3O 4-metal nano composite material on the surface of the glassy carbon electrode. The prepared sample was drop cast into aliquots and the electrodes were prepared on clean and dry glassy carbon electrode surfaces. For further electrochemical studies, it was further dried under an infrared lamp.

The manufactured electrode can be used for analyzing rGO-Co₃O₄@ metal nanocomposite material performance for electrochemical sensing of DA. The surface of the glassy carbon electrode is to be coated with rGO-Co₃O₄Ink modification of @ metal nanocomposites. The performance parameters of LOD, sensitivity, selectivity, and linearity range will be determined by Differential Pulse Voltammetry (DPV), Chronoamperometry (CA), and Electrochemical Impedance Spectroscopy (EIS).

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.