CN108287187B - Electrochemical luminescence sensor - Google Patents
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Abstract
The invention discloses an electrochemiluminescence sensor. The electrochemical luminescence sensor is a metal organic framework thin layer electrode modified by luminescent compounds, and consists of an electrode and a metal organic framework thin layer modified by the luminescent compounds and positioned on the surface of the electrode. The electrode is a glassy carbon electrode, a carbon paste electrode, a carbon fiber electrode or ITO conductive glass. The luminescent compound may be ruthenium terpyridyl. The invention combines the electrochemical deposition technology to fix the luminescent compound in the metal organic framework thin layer and modify the surface of the electrode, the coreactant or the object to be detected can directly enter the thin layer for detection, and the construction of a novel electrochemical luminescence sensing interface and the hypersensitive immunoassay thereof are realized by combining the immunoreaction. The method is simple and low in cost, can detect the acute myocardial infarction marker with extremely low concentration, can be used for single-target analyte detection and multi-target analyte multi-channel detection based on bioaffinity, and has huge application prospect.
Description
Technical Field
The invention belongs to the field of sensors, and relates to an electrochemiluminescence sensor.
Background
Acute myocardial infarction is one of the most common causes of death in the world today. Aiming at the urgent needs of the acute myocardial infarction with high morbidity and mortality for the rapid, sensitive and low-cost in-vitro diagnosis technology, the development of the unmarked nano chemiluminescence new generation in-vitro diagnosis technology and the application research thereof in the rapid diagnosis of the acute myocardial infarction are urgently needed, and the novel rapid diagnosis method of the acute myocardial infarction with high sensitivity and high specificity is developed. For the immunoassay method of a designated immune pair, the immune system has excellent specific recognition characteristics and shows excellent selectivity, so that the improvement of the sensitivity of the immunoassay has become a key entry point of the innovative immunoassay method. Since most of the immunoassay targets (such as proteins) have no direct output of significant analysis signals, the application of nanomaterials has become an important strategy in immunoassay. So far, nano materials such as metal nano materials like gold and silver, metal sulfide (or metal selenide and metal telluride) equivalent Quantum Dots (QDs), metal oxide nano materials, nano silicon and nano carbon have unique optical, electrical, electrochemical, catalytic and mechanical properties, and can be used for electrochemiluminescence immunoassay to obtain high-sensitive immune signal output. The Metal Organic Framework (MOFs) material is a novel zeolite-like porous material formed by self-assembling central metal ions and organic ligands, so that organic ligands with specific structures can be designed to coordinate with different central metal ions, and a plurality of functional compounds with novel structures are constructed. As a novel porous material which is green and environment-friendly, has easily designed and controlled structure, diversified functions and wide sources, the material has unique properties of light, electricity, magnetism, catalysis, adsorption and the like, so that the material shows attractive application prospects and is practically applied to electrochemical luminescence immunoassay. For example, Yuan et al synthesized N- (4-aminobutyl) -N-ethyl isoluminol modified MOFs as an electrochemiluminescence indicator labeled on a secondary antibody, and constructed a sandwich-type immunosensor on a glassy carbon electrode, thereby realizing the ultra-sensitive detection of mucin in human breast cancer cells. Similarly, the ruthenium complex modified MOFs can be used for in vivo and in vitro labeling, biological light analysis and biological optical imaging, and can also be used for electrochemiluminescence immunoassay. For example, Yin et al drop-coat the mixture of MOFs functionalized with ruthenium complex and graphene oxide onto the surface of a glassy carbon electrode for electrochemical and electrochemiluminescence detection. However, the MOFs-modified biosensors synthesized by using these luminescent reagents generally adopt a strategy of synthesizing a functionalized MOFs marker and then modifying the electrode surface for electrochemiluminescence analysis, so that inevitable complicated operations limit urgent needs of electrochemiluminescence immunoassay for rapid and sensitive in vitro diagnosis techniques in acute myocardial infarction, and the complexity of experimental operations is increased by replacing solutions.
Disclosure of Invention
The invention aims to provide an electrochemiluminescence sensor.
The invention claims an electrochemical luminescence sensor, namely a metal organic framework thin layer electrode modified by luminescent compounds, which consists of an electrode and a metal organic framework thin layer modified by the luminescent compounds and positioned on the surface of the electrode.
In the metal organic framework thin-layer electrode modified by the luminescent compound, the electrode is a glassy carbon electrode, a carbon paste electrode, a carbon fiber electrode or ITO conductive glass.
The luminescent compound is at least one of terpyridyl ruthenium and a terpyridyl ruthenium derivative;
the metal organic framework thin layer is prepared from metal salt and trimesic acid by an electrodeposition method;
the metal salt is zinc salt or copper salt; more particularly, the zinc salt is zinc nitrate, zinc acetate or zinc chloride.
The metal organic framework thin-layer electrode modified by the luminescent compound can be prepared by the following method provided by the invention.
The invention provides a method for preparing a terpyridyl ruthenium modified metal organic framework thin-layer electrode, which comprises the following steps:
carrying out electrodeposition on a working electrode by using an in-situ electrodeposition method to obtain the terpyridyl ruthenium modified metal organic frame thin-layer electrode;
the working electrode is a glassy carbon electrode, a carbon paste electrode, a carbon fiber electrode or ITO conductive glass;
the reaction solution contains a luminescent compound, a ligand for forming a metal organic framework thin layer, a supporting electrolyte and water;
the luminescent compound is specifically at least one of terpyridyl ruthenium and a terpyridyl ruthenium derivative;
the ligand for forming the metal organic framework is zinc salt and trimesic acid; the zinc salt is zinc nitrate, zinc acetate or zinc chloride;
the supporting electrolyte is at least one selected from potassium nitrate, sodium chloride and potassium sulfate.
In the method, the reaction solution consists of an aqueous solution of zinc salt, an aqueous solution of ruthenium terpyridyl, an ethanol solution of trimesic acid and potassium nitrate; the reaction solution can be prepared by the following method: mixing the materials to form the reaction solution, and stirring at room temperature; the stirring time may be specifically 2.5 to 3.5 hours, more specifically 3 hours;
the electrode radius of the working electrode is 1-5mm, specifically 3 mm.
The concentration of the zinc salt aqueous solution is 0.1 mg/mL-1.8 g/mL, specifically 0.089 g/mL;
the concentration of the aqueous solution of the terpyridyl ruthenium is 1 mmol/L-0.1 mol/L;
the concentration of the ethanol solution of the trimesic acid is 1 mg/mL-3.5 g/mL, and is specifically 0.035 g/mL;
the using ratio of the zinc salt aqueous solution, the terpyridyl ruthenium aqueous solution, the trimesic acid ethanol solution and the potassium nitrate is 3 mL: 100 μ L of: 3mL of: 0.0303 g.
The electrolytic cell is a two-electrode or three-electrode system;
specifically, in the three-electrode system, the counter electrode is a platinum sheet electrode; the reference electrode used was a saturated calomel electrode.
In the electrodeposition step, the negative potential is 0V (vs. SCE) to-2.0V (vs. SCE); sce "means the potential relative to a saturated calomel electrode;
the electrodeposition time is 1-10800s, specifically 1500 s.
The method may further comprise the steps of:
cleaning the metal organic framework thin-layer electrode according to a conventional method before the electrochemical deposition step; the cleaning method specifically comprises the following steps: grinding and polishing the metal organic framework thin-layer electrode in 0.5 and 0.05 mu m aluminum oxide suspension liquid, then fully washing the surface of the electrode by using ultrapure water, and then performing ultrasonic treatment in ultrapure water, ethanol and ultrapure water for 5min respectively to remove the aluminum oxide powder remaining on the surface of the electrode; then, a concentrated H is dropped on the surface of the electrode2SO4Washing liquid, keeping for 15s, and washing with ultrapure water; finally, the pollutants are thoroughly removed by electrochemical cleaning, and the sewage is blown dry by nitrogen after being washed by a large amount of ultrapure water.
In addition, the application of the terpyridyl ruthenium modified metal organic framework thin-layer electrode in electrochemical luminescence immunoassay or photoelectrocatalysis and the application of the terpyridyl ruthenium modified metal organic framework thin-layer electrode in the detection of the acute myocardial infarction marker also belong to the protection scope of the invention. Wherein the acute myocardial infarction marker can be heart-type fatty acid binding protein;
in the detection step, the electrode system is a three-electrode system;
the working electrode is the immune modified terpyridyl ruthenium modified metal organic framework thin-layer electrode; the method of immunological modification is a conventional method.
The counter electrode is a platinum wire;
the reference electrode is an Ag/AgCl electrode;
the electrolyte is 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine, and the pH value is 7.0;
the scanning interval is 0V-1.35V (vs. Ag/AgCl), and the photomultiplier PMT is set to 800V.
The invention constructs a novel metal organic framework thin-layer electrode modified by luminescent compounds such as terpyridyl ruthenium and the like by using an electrochemical deposition method. The invention adopts a three-electrode system, required reaction liquid is added into an electrolytic cell, negative potential is applied to a working electrode, the electrolytic cell generates electrochemical reaction, hydroxide ions are generated in situ on the surface of the electrode, a neutral ligand is activated to deprotonate, and the growth of a metal organic framework crystal thin layer is regulated and controlled. Due to the electrostatic attraction effect of the ligand of trimesic acid with negative electricity and the ruthenium ions of the terpyridyl with positive electricity, the molecules of luminescent compounds such as the terpyridyl ruthenium and the like are brought into the crystal of the metal organic framework, and thus the metal organic framework thin-layer electrode modified by the terpyridyl ruthenium is obtained by a one-step in-situ electrodeposition method. The modified electrode is used for label-free electrochemical luminescence immunoassay, so that quantitative analysis of target analytes in a sample is indirectly realized, and the electrochemical luminescence method can detect proteins with the level as low as fg/mL. Compared with the prior art, the method is simple and low in cost, can detect the acute myocardial infarction marker (heart-type fatty acid binding protein, FABP) with extremely low concentration, and can be used for single-target analyte detection and multi-target analyte multi-channel detection based on bioaffinity. Has great application prospect in the aspects of researching electrochemical luminescence, photoelectrocatalysis and the like based on the terpyridyl ruthenium.
Drawings
Fig. 1 is a schematic diagram of a novel metal organic framework thin layer device for constructing a terpyridyl ruthenium modified by a (conventional) electrochemical deposition method in example 1, wherein 1 is an electrochemical workstation, 2 is a solution, 3 is a working electrode, 4 is a counter electrode, 5 is a reference electrode, and 6 is a terpyridyl ruthenium modified metal organic framework thin layer electrode.
FIG. 2 is a schematic representation of the immune response of example 1. The research system is the immunoreaction of heart-type fatty acid binding protein on a modified electrode.
FIG. 3 is a graph of the electrochemiluminescence signals of example 1.
FIG. 4 is a standard graph of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
(1) Preparation of an electrodeposition solution: 0.266g of zinc nitrate was dissolved in 3mL of water, and 0.0303g of potassium nitrate was added as a supporting electrolyte. 0.105g of trimesic acid was dissolved in 3mL of ethanol, added to an aqueous solution of zinc nitrate, mixed well, added to 100. mu.L of a 0.1M aqueous solution of terpyridyl ruthenium, and stirred vigorously at room temperature for 3 hours.
(2) Preparing a modified electrode: grinding and polishing a Glassy Carbon Electrode (GCE) in alumina suspension of 0.5 and 0.05 mu m in sequence, then fully washing the surface of the electrode by using ultrapure water, and then respectively carrying out ultrasonic treatment in the ultrapure water, ethanol and the ultrapure water for 5min to remove alumina powder remained on the surface of the electrode; then, a concentrated H is dropped on the surface of the electrode2SO4Washing liquid, keeping for 15s, and washing with ultrapure water; finally, electrochemical cleaning is carried out to thoroughly remove pollutants, and nitrogen is used for blow-drying after the pollutants are washed by a large amount of water.
The electrochemical cleaning steps are as follows: at 10mL of 0.50mol/L H2SO4The sweep rate of 0.1V/s is 0.0V to 1.0V to be stable. The treated glassy carbon electrode was rinsed with copious amounts of water and then blown dry with nitrogen.
The electrode was placed in the electrodeposition solution in (1) above, and 1500s (vs. SCE (saturated calomel electrode)) was electrodeposited at-1.3V. And then washing with water for the second time to obtain the metal organic framework thin layer electrode (Ru-MOFs/GCE) modified by terpyridyl ruthenium.
(3) An immuno-electrode without label was prepared. Dropping 3.0 μ L of 0.5% Chitosan (CS) on MOFs modified glassy carbon electrode (Ru-MOFs/GCE), drying, dropping 6 μ L of 2.5% Glutaraldehyde (GA) for reaction for 2h, and dropping 6.0 μ L of primary antibody (AbAb) containing 1.0mg/mL1) The PBS solution is dripped on a GA-CS/Ru-MOFs/GCE electrode, and the GA-CS/Ru-MOFs/GCE electrode is stored in a refrigerator (4 ℃) overnight to ensure the saturated adsorption of the antibody on the surface of the electrode to obtain Ab1the/GA-CS/Ru-MOFs/GCE modified electrode. Washing and drying the electrode with PBS solution in sequence, dripping 6.0 mu L of PBS solution containing 3% BSA onto the electrode, keeping the temperature at 4 ℃ for 1h to block the nonspecific adsorption sites to obtain BSA/Ab1the/GA-CS/Ru-MOFs/GCE modified electrode. When not in use, the electrodes were stored in PBS at 4 ℃.
The prepared BSA/Ab1The electrode modified with/GA-CS/Ru-MOFs/GCE was incubated at 37 ℃ for 1 hour with 6.0. mu.L of PBS containing antigens (FABP, human heart fatty acid binding protein) at different concentrations 150fg/mL, 15fg/mL, 1.5pg/mL, 15pg/mL, 150pg/mL, 1.5ng/mL, 15ng/mL or 150ng/mL for 1 hour, and then the electrode surface was washed with PBS solution to obtain FABP/BSA/Ab1the/GA-CS/Ru-MOFs/GCE modified electrode. (Ab)1、Ab2Is an anti-human heart fatty acid binding protein).
(4) An electrochemiluminescence detection process. Using a three-electrode system (working electrode was the immuno-electrode prepared in (3) above, counter electrode was platinum wire, reference electrode was silver/silver chloride (Ag/AgCl)), 500 μ L of 0.1mol/L phosphate buffer (pH 7.0) containing 0.1mol/L triethanolamine was added to the cell. The detection conditions are as follows: the scanning interval is 0V-1.35V (vs. Ag/AgCl), and the photomultiplier PMT is set to 800V. And obtaining an electrochemiluminescence signal on the working electrode, thereby indirectly realizing the quantitative analysis of the target analyte FABP in the sample.
The electrochemical deposition device is shown in figure 1, and the immunoreaction process is shown in figure 2. The obtained electrochemiluminescence signal is shown in fig. 3, and it can be known that the electrochemiluminescence response is reduced along with the increase of the antigen concentration; the linear range of the electrochemical luminescence intensity and the antigen concentration is 150 fg/mL-150 ng/mL, and the detection limit is 2.6fg/mL (the signal-to-noise ratio is 3). The method has wide linear range and low detection limit.
Claims (12)
1. A method of preparing a luminescent compound modified metal organic framework thin layer electrode, comprising the steps of:
carrying out electrodeposition on the working electrode by using an in-situ electrodeposition method to obtain a metal organic framework thin-layer electrode modified by the luminescent compound;
the working electrode is a glassy carbon electrode, a carbon paste electrode, a carbon fiber electrode or ITO conductive glass;
the reaction solution contains a luminescent compound, a ligand for forming a metal organic framework thin layer, a supporting electrolyte and water;
the luminescent compound is at least one of terpyridyl ruthenium and a terpyridyl ruthenium derivative;
the ligand for forming the metal organic framework is zinc salt and trimesic acid.
2. The method of claim 1, wherein: the zinc salt is zinc nitrate, zinc acetate or zinc chloride;
the supporting electrolyte is at least one of potassium nitrate, sodium chloride and potassium sulfate;
the reaction liquid consists of an aqueous solution of zinc salt, an aqueous solution of terpyridyl ruthenium, an ethanol solution of trimesic acid and potassium nitrate;
the radius of the working electrode is 1-5 mm.
3. The method of claim 2, wherein: the radius of the working electrode is 3 mm.
4. The method of claim 2, wherein: the concentration of the zinc salt water solution is 0.1 mg/mL-1.8 g/mL;
the concentration of the aqueous solution of the terpyridyl ruthenium is 1 mmol/L-0.1 mol/L;
the concentration of the ethanol solution of trimesic acid is 1 mg/mL-3.5 g/mL;
the using ratio of the zinc salt aqueous solution, the terpyridyl ruthenium aqueous solution, the trimesic acid ethanol solution and the potassium nitrate is 3 mL: 100
L：3mL：0.0303g。
5. The method of claim 4, wherein: the concentration of the zinc salt aqueous solution is 0.089 g/mL;
the concentration of the ethanol solution of trimesic acid is 0.035 g/mL.
6. The method according to any one of claims 1-5, wherein: the electrolytic cell used is a two-electrode or three-electrode system.
7. The method of claim 6, wherein: in the three-electrode system, the counter electrode is a platinum sheet electrode; the reference electrode is a saturated calomel electrode;
in the electrodeposition step, the negative potential is 0V to-2.0V;
the electrodeposition time is 1500-10800 s.
8. A luminescent compound modified metal organic framework thin layer electrode prepared by the method of any one of claims 1 to 7.
9. Use of a luminescent compound modified metal organic framework thin-layer electrode according to claim 8 in electrochemiluminescence immunoassay or photoelectrocatalysis.
10. Use of the luminescent compound modified metal organic framework thin layer electrode of claim 8 for detecting acute myocardial infarction markers.
11. Use according to claim 10, characterized in that: the acute myocardial infarction marker is heart-type fatty acid binding protein.
12. Use according to claim 10, characterized in that: in the detection step, the electrode system is a three-electrode system;
the working electrode is an immune modified metal organic framework thin layer electrode modified by the luminescent compound of claim 9;
the counter electrode is a platinum wire;
the reference electrode is an Ag/AgCl electrode;
the electrolyte is 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine, and the pH value is 7.0;
the scanning interval is 0V-1.35V, and the PMT is set to be 800V.
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| CN115304781B (en) * | 2022-08-08 | 2023-12-01 | 南方医科大学皮肤病医院（广东省皮肤病医院、广东省皮肤性病防治中心、中国麻风防治研究中心） | Amplification-free high-efficiency electrochemiluminescence probe based on MOF framework and preparation method and application thereof |
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