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Molecularly imprinted electrochemical sensor based on electro-copper-based mofs sensitive membrane modified electrode and preparation method and detection method thereof

A technology of molecular imprinting and modified electrodes, which is applied in the field of electrochemical sensing, can solve the problems of shape, unclear crystal form, and unclear explanation of influence, etc., and achieve the effects of good conductivity, time saving and high stability

Active Publication Date: 2022-07-08
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is no report on the synthesis of MOFs sensitive membranes by electrochemical reduction method for modifying electrodes to prepare molecularly imprinted electrochemical sensors.
The effect of the ligands used on the properties (e.g., morphology, electrochemical properties, etc.) of electrochemically synthesized MOFs and their application in combination with molecular imprinting techniques is also not clearly addressed in the literature.
Moreover, the stability changes (e.g., morphology, crystal form, etc.)

Method used

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  • Molecularly imprinted electrochemical sensor based on electro-copper-based mofs sensitive membrane modified electrode and preparation method and detection method thereof
  • Molecularly imprinted electrochemical sensor based on electro-copper-based mofs sensitive membrane modified electrode and preparation method and detection method thereof
  • Molecularly imprinted electrochemical sensor based on electro-copper-based mofs sensitive membrane modified electrode and preparation method and detection method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] 1. a molecularly imprinted electrochemical sensor of an electro-copper-based MOFs sensitive membrane modified electrode, comprising a working electrode, characterized in that, outside the working electrode, Cu-MOF sensitive membrane, chitosan membrane, cross-linking agent are successively connected The insulating layer with the target protein and the polypyrrole molecular imprinting layer, the polypyrrole molecular imprinting layer has imprinted holes of the target protein.

[0040] 2. The working electrode is a glassy carbon electrode, and the electro-copper-based MOF sensitive membrane is a modified electrode, which is a new type of highly ordered porous material with the advantages of large specific surface area, porosity and adjustable function. The surface film is formed by the accumulation of 100nm MOFs, and the surface is relatively dense. MOFs were directly electrodeposited on the conductive substrate through electrochemical reduction process, and the layered st...

Embodiment 2

[0047] 1) Weigh 10 mmol of copper nitrate trihydrate (Cu(NO) 3 ) 2 ·3H 2 O), 15mmol 1,3,5- trimesic acid (H 3 BTC) and 10 mmol triethylamine hydrochloride (Et 3 NHCl) was dissolved in 50 mL of N,N-dimethylformamide (DMF);

[0048] 2) Cu-MOF was deposited on the surface of glassy carbon electrode by electrodeposition method. The electrodeposition process was carried out in potentiostatic mode, with -1.3V electrodeposition for 5 minutes. After the end, the electrode was quickly taken out from the deposition bottom solution and dried for later use. The prepared electrode was named Cu-MOF / GCE.

[0049] The specific steps of preparing the human immunoglobulin G molecularly imprinted electrochemical sensor in the present invention are as follows:

[0050] 3) Weigh 3 μL of 0.25 mg / mL (in 0.02 mol / L acetic acid) chitosan solution dropwise onto the electrode surface, dry at room temperature and name it CS / Cu-MOF / GCE.

[0051] 4) Drop 10 μL of 2.5% glutaraldehyde solution on the...

Embodiment 3

[0057] Detection based on the molecularly imprinted electrochemical sensor prepared in Example 2:

[0058] 1) Immerse the modified electrode to 50mmol / l[K 3 Fe(CN) 6 ] in 1 mol / l KCl solution, each modified electrode was then scanned by electrochemical voltammetry and measured by AC impedance method, and the corresponding cyclic voltammetry (CV) and AC impedance (EIS) maps were obtained after scanning.

[0059] 2) The prepared electrochemical sensor was immersed in a standard solution of human immunoglobulin G containing 0, 0.001, 0.01, 0.05, 0.1, 0.5, 1, 5 ng / mL, and measured by differential pulse voltammetry (DPV) to dissolve Degrees are plotted against DPV response values.

[0060] 3) Lysozyme, Human Serum Albumin and Bovine Serum Albumin were selected as the structural analogs of human immunoglobulin to determine the selectivity of MIP / CS / Cu-MOF / GCE.

[0061] as attached Figure 4 As shown, the peak current value and IgG concentration showed a good linear relationship ...

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Abstract

The invention studies a molecularly imprinted electrochemical sensor based on an electrode modified by an electro-copper-based MOFs sensitive film, and a preparation method and detection method thereof, belonging to the field of electrochemical sensing. The present invention selects the specific protein human immunoglobulin G (IgG) in serum as the research object, and successfully constructs a new type of high-sensitivity molecular imprinting electrode by combining nanocomposite materials, a new imprinting method, a new template processing idea and a new detection method. chemical sensor. First, copper-based MOFs were synthesized on the surface of glassy carbon electrode by electrodeposition to modify the electrode to improve conductivity and increase specific surface area, then chitosan and glutaraldehyde were sequentially modified to provide attachment sites for IgG, and then directly on the surface of the modified electrode A polymer film is formed by electropolymerization of pyrrole, and the template is finally eluted to obtain a molecularly imprinted polymer-modified electrode. The molecularly imprinted electrochemical sensor has high sensitivity and good selectivity, and has been successfully applied to the detection of target proteins in actual samples.

Description

technical field [0001] The invention belongs to the field of electrochemical sensing, and particularly relates to a preparation method and a detection method of a molecularly imprinted electrochemical sensor with an electro-copper-based MOFs sensitive film modified electrode. Background technique [0002] Immunoglobulins are roughly classified into immunoglobulin A (IgA), immunoglobulin D (IgD), immunoglobulin E (IgE), immunoglobulin G (IgG) and immunoglobulin according to their chemical structure and mode of action. Globulin M (IgM). In the role of the human body, immunoglobulins usually play the role of antibodies, and in the process of combining with pathogenic factors such as antigens, they play a certain defense and protection role for the body. Human immunoglobulin G (IgG) is the most important immunoglobulin in the human body. In addition, IgG is the only immunoglobulin that can cross the placenta and plays a crucial role in neonatal immunity against infection. IgG...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): G01N27/327G01N27/48
CPCG01N27/3277G01N27/48
Inventor 罗爱芹梁阿新侯慧鹏唐珊珊刘毅权刘宗坤
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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