CN113155916B - Solid-state electrochemiluminescence probe and preparation method thereof - Google Patents
Solid-state electrochemiluminescence probe and preparation method thereof Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000007790 solid phase Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000004020 luminiscence type Methods 0.000 claims abstract description 24
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910007926 ZrCl Inorganic materials 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 238000004873 anchoring Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 22
- 229910052707 ruthenium Inorganic materials 0.000 description 11
- 239000013208 UiO-67 Substances 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- -1 liCl Chemical compound 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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Abstract
The invention relates to the technical field of electrochemiluminescence, in particular to a solid-state electrochemiluminescence probe and a preparation method thereof. The preparation method of the solid-state electrochemical luminescence probe comprises the following steps: a) 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 Mixing with acetic acid, reacting, and drying to obtain a solid phase carrier; b1 (ii) subjecting the solid support, water and Ru (bpy) 2 Cl 2 Stirring for reaction, and drying the obtained precipitate to obtain an electrochemiluminescence material; or B2) reacting the solid phase carrier, ruthenium trichloride hydrate, liCl, 2' -bipyridine and an organic solvent, and drying the obtained precipitate to obtain the solid-state electrochemiluminescence probe. The invention adopts an in-situ molecular anchoring strategy to realize electrochemical on the basis of retaining the morphology of MOFAnd the immobilization of the chemiluminescent probe, and the finally prepared solid-state electrochemiluminescent probe has better load stability on the surface of the electrode.
Description
Technical Field
The invention relates to the technical field of electrochemiluminescence, in particular to a solid-state electrochemiluminescence probe and a preparation method thereof.
Background
Electrochemiluminescence (ECL) has the advantages of high sensitivity, low background signal, simple equipment, good space-time resolution and the like, and has been successfully applied to diagnosis of clinical diseases. Currently, the most commonly used electrochemiluminescent material is ruthenium terpyridyl. Compared with the solution phase electrochemiluminescence, the solid-state electrochemiluminescence is more economical and has higher luminous efficiency and no luminous reagent consumption because the solid-state electrochemiluminescence is stably attached to the surface of the electrode after the luminescent probe molecules are fixed on the carrier by means of the electrochemiluminescence probe and the coreactant are diffused and react on the surface of the electrode to generate the electrochemiluminescence.
The electrochemiluminescence probe immobilization method reported in the literature is mainly realized by loading the luminescence probe molecules on a carrier through physical embedding or electrostatic adsorption and through subsequent dripping or physical action of an externally applied magnetic field. Wherein stable immobilization of luminescent probe molecules on a material carrier is particularly important for developing a stable solid-state electrochemical luminescence sensing platform. And electrostatic adsorption requires introducing a charged carrier, and the probe carrier material obtained by electrostatic adsorption is aggregated and is directly dripped on the surface of an electrode, so that the load stability is poor. The physical embedding method usually adopts silicon dioxide, and has poor conductivity. And the electrochemical luminescence probes cannot be directly loaded in situ chemically at present, and a complex covalent process is required.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a solid-state electrochemical luminescence probe and a preparation method thereof, wherein the solid-state electrochemical luminescence probe prepared by the present invention has excellent load stability on the electrode surface.
The invention provides a preparation method of a solid-state electrochemical luminescence probe, which comprises the following steps:
a) 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 Mixing with acetic acid, and performingReacting and drying to obtain a solid phase carrier;
b1 (ii) subjecting the solid support, water and Ru (bpy) 2 Cl 2 Stirring for reaction, and drying the obtained precipitate to obtain an electrochemiluminescence material;
or (b)
B2 And (3) reacting the solid phase carrier, ruthenium trichloride hydrate, liCl, 2' -bipyridine and an organic solvent, and drying the obtained precipitate to obtain the solid-state electrochemiluminescence probe.
Preferably, in step A), the solvent in the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution is DMF;
the concentration of the 2,2 '-dipyridine-5, 5' -dicarboxylic acid solution is 3.5-4.5 mg/mL.
Preferably, in step A), the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 The mass ratio of (2) is 0.5-1.5: 0.5 to 1.5;
the ZrCl 4 And acetic acid in an amount of 35 to 40g: 1-3 mL.
Preferably, in step A), the reaction temperature is 95-105 ℃ and the reaction time is 23-25 h.
Preferably, in step a), after the reaction, the method further includes: centrifuging the product after the reaction, and then washing with absolute ethyl alcohol;
the drying temperature is 55-65 ℃.
Preferably, in step B1), the solid support and Ru (bpy) 2 Cl 2 The mass ratio of (2.5-3.5): 1, a step of;
the dosage ratio of the solid phase carrier to the water is 8-12 mg: 0.5-1.5 mL.
Preferably, in the step B1), the reaction time is 23-25 hours;
the obtained precipitate is further centrifuged and washed before being dried;
the drying temperature is 55-65 ℃.
Preferably, in the step B2), the mass ratio of the solid phase carrier, ruthenium trichloride hydrate, liCl and 2,2' -bipyridine is 4-6: 2 to 4:2 to 4:6 to 8;
the dosage ratio of the solid phase carrier to the organic solvent is 4-6 mg:3mL.
Preferably, in step B2), the precipitate obtained, before drying, further comprises centrifugation and washing;
the drying temperature is 55-65 ℃.
The invention also provides a solid-state electrochemical luminescence probe prepared by the preparation method.
The invention provides a preparation method of a solid-state electrochemical luminescence probe, which comprises the following steps: a) 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 Mixing with acetic acid, reacting, and drying to obtain a solid phase carrier; b1 (ii) subjecting the solid support, water and Ru (bpy) 2 Cl 2 Stirring for reaction, and drying the obtained precipitate to obtain an electrochemiluminescence material; or B2) reacting the solid phase carrier, ruthenium trichloride hydrate, liCl, 2' -bipyridine and an organic solvent, and drying the obtained precipitate to obtain the solid-state electrochemiluminescence probe. The invention provides a coordination environment by utilizing a metal organic framework material (solid phase carrier MOF-UiO-67 (N)), and utilizes the MOF ligand structure to form the electrochemiluminescence probe-ruthenium pyridine in situ locally by introducing the ruthenium-based ligand, thereby realizing the immobilization of the loaded electrochemiluminescence probe-ruthenium pyridine on the MOF carrier, and the in-situ molecular anchoring strategy provides a new idea for the immobilization of the electrochemiluminescence probe on the basis of retaining the morphology of the MOF. Meanwhile, the solid-state electrochemiluminescence probe prepared by the invention has better load stability on the surface of the electrode.
Drawings
FIG. 1 is a schematic diagram of a solid state electrochemiluminescence probe made by in situ atomic anchoring in accordance with the present invention;
FIG. 2 is a TEM image and an elemental scan of solid state electrochemiluminescence probes prepared in examples 1-2 of the present invention;
FIG. 3 is a stability test chart of a solid state electrochemical luminescence sensor platform constructed in example 1 of the present invention;
FIG. 4 is a chart showing the stability test of the solid-state electrochemical luminescence sensor platform constructed in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a solid-state electrochemical luminescence probe, which comprises the following steps:
a) 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 Mixing with acetic acid, reacting, and drying to obtain a solid phase carrier;
b1 (ii) subjecting the solid support, water and Ru (bpy) 2 Cl 2 Stirring for reaction, and drying the obtained precipitate to obtain an electrochemiluminescence material;
or (b)
B2 And (3) reacting the solid phase carrier, ruthenium trichloride hydrate, liCl, 2' -bipyridine and an organic solvent, and drying the obtained precipitate to obtain the solid-state electrochemiluminescence probe.
The invention firstly uses 2,2 '-dipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 And mixing with acetic acid, reacting, and drying to obtain the solid phase carrier MOF-UiO-67 (N).
In certain embodiments of the present invention, the solvent in the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution is DMF. In certain embodiments of the present invention, the concentration of the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution is 3.5 to 4.5mg/mL.
In certain embodiments of the present invention, the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 The mass ratio of (2) is 0.5-1.5: 0.5 to 1.5. In certain embodiments, the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 The mass ratio of (2) is 1:0.95.
in certain embodiments of the present invention, the ZrCl 4 And acetic acid in an amount of 35 to 40g: 1-3 mL. In certain embodiments, the ZrCl 4 And the acetic acid usage ratio was 37.28g:2mL.
In certain embodiments of the invention, the reaction is carried out at a temperature of 95 to 105℃for a period of 23 to 25 hours. In certain embodiments, the temperature of the reaction is 100 ℃. In certain embodiments, the reaction time is 24 hours.
In certain embodiments of the present invention, after the reacting, further comprising: the product after the reaction was centrifuged and then washed with absolute ethanol.
The method of centrifugation is not particularly limited, and centrifugation methods well known to those skilled in the art may be employed.
In certain embodiments of the invention, the drying temperature is 55-65 ℃. In certain embodiments, the temperature of the drying is 60 ℃.
After obtaining the solid support MOF-UiO-67 (N), there are two methods for the treatment of the solid support: one method is to mix the solid support, water and Ru (bpy) 2 Cl 2 Stirring for reaction, and drying the obtained precipitate to obtain the electrochemiluminescence material.
In certain embodiments of the invention, the solid support, water and Ru (bpy) 2 Cl 2 The stirring reaction comprises the following steps:
mixing the solid phase carrier with water, and adding Ru (bpy) 2 Cl 2 The reaction was stirred.
In certain embodiments of the invention, the water is ultrapure water.
In certain embodiments of the invention, the solid support and water are used in a ratio of 8 to 12mg: 0.5-1.5 mL. In certain embodiments, the solid support and water are present in an amount ratio of 10mg:1mL.
In certain embodiments of the invention, the solid support and Ru (bpy) 2 Cl 2 The mass ratio of (2.5-3.5): 1. in certain embodiments, the solid support and Ru (bpy) 2 Cl 2 The mass ratio of (2.9): 1.
in certain embodiments of the invention, the solid support, water and Ru (bpy) 2 Cl 2 The stirring reaction time is 23-25 h. The stirring speed of the stirring reaction is not particularly limited, and the stirring speed of the stirring reaction known to those skilled in the art may be used.
In certain embodiments of the invention, the resulting precipitate is further comprised of centrifugation and washing prior to drying. The method and parameters of the centrifugation and washing are not particularly limited in the present invention, and those known to those skilled in the art may be used.
In certain embodiments of the invention, the drying temperature is 55-65 ℃.
Another method for treating the solid phase carrier is to react the solid phase carrier, ruthenium trichloride hydrate, liCl and 2,2' -bipyridine with an organic solvent, and then drying the obtained precipitate to obtain the solid-state electrochemiluminescence probe.
In certain embodiments of the invention, reacting the solid support, ruthenium trichloride hydrate, liCl and 2,2' -bipyridine with an organic solvent comprises:
firstly, reacting a solid phase carrier with ruthenium trichloride hydrate in an organic solvent, and then adding LiCl and 2,2' -bipyridine into a product obtained after the reaction to carry out reflux reaction.
In certain embodiments of the invention, the mass ratio of the solid phase carrier, ruthenium trichloride hydrate, liCl and 2,2' -bipyridine is 4 to 6:2 to 4:2 to 4:6 to 8. In certain embodiments, the mass ratio of the solid support, ruthenium trichloride hydrate, liCl, and 2,2' -bipyridine is 5:3:3:7.
in certain embodiments of the present invention, the ruthenium content of the ruthenium trichloride hydrate is from 35.0% to 42.0% by weight.
In certain embodiments of the invention, the ratio of the solid support to the organic solvent is from 4 to 6mg:3mL. In certain embodiments, the ratio of solid support to organic solvent is 5mg:3mL.
In certain embodiments of the invention, the organic solvent is DMF.
In certain embodiments of the invention, the reaction temperature of the solid support and ruthenium trichloride hydrate in the organic solvent is room temperature for a period of time ranging from 5 to 7 hours. In certain embodiments, the reaction time is 6 hours. In certain embodiments of the invention, the reaction of the solid support and ruthenium trichloride hydrate in the organic solvent is a stirred reaction. The stirring method of the stirring reaction is not particularly limited, and stirring methods well known to those skilled in the art may be employed.
In certain embodiments of the invention, the reflux reaction is for a period of from 23 to 25 hours. In certain embodiments, the reflux reaction is for 24 hours.
In certain embodiments of the invention, the resulting precipitate is further comprised of centrifugation and washing prior to drying. The method and parameters of the centrifugation and washing are not particularly limited in the present invention, and those known to those skilled in the art may be used.
In certain embodiments of the invention, the drying temperature is 55-65 ℃.
FIG. 1 is a schematic diagram of a solid state electrochemiluminescence probe made by in situ atomic anchoring according to the present invention. The stable loading of the luminescent reagent can be realized by adopting a two-step method.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The invention also provides a solid-state electrochemical luminescence probe prepared by the preparation method.
In certain embodiments of the invention, the solid state electrochemical luminescence probe has a regular octahedral morphology and a size of 300-500 nm. In certain embodiments of the present invention, the Ru, zr, and N elements are uniformly distributed on the outer surface of the regular octahedral solid state electrochemiluminescence probe.
The invention provides a coordination environment by utilizing a metal organic framework material (solid phase carrier MOF-UiO-67 (N)), and utilizes the MOF ligand structure to form the electrochemiluminescence probe-ruthenium pyridine in situ locally by introducing the ruthenium-based ligand, thereby realizing the immobilization of the loaded electrochemiluminescence probe-ruthenium pyridine on the MOF carrier, and the in-situ molecular anchoring strategy provides a new idea for the immobilization of the electrochemiluminescence probe on the basis of retaining the morphology of the MOF. Meanwhile, the solid-state electrochemiluminescence probe prepared by the invention has better load stability on the surface of the electrode.
In order to further illustrate the present invention, the following examples are provided to describe a solid state electrochemical luminescence probe and a method for preparing the same in detail, but the present invention is not limited to the scope of the present invention.
The raw materials used in the following examples are all generally commercially available.
Example 1
(1) Synthesis of solid phase Carrier MOF-UiO-67 (N):
39.12mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid was dissolved in 10mL of DMF and 37.28mg of ZrCl was added 4 Then adding 2mL of acetic acid to obtain a mixed solution, transferring the mixed solution into a 40mL reaction kettle, heating the mixed solution at 100 ℃ for 24 hours, centrifuging the reacted product, then washing the product with absolute ethyl alcohol, and drying the product at 60 ℃ to obtain the solid phase carrier MOF-UIO-67 (N).
(2) Preparation of solid-state electrochemiluminescence probe:
100mg of the solid phase carrier MOF-UiO-67 (N) was dissolved in 10mL of ultrapure water, and 34mg of Ru (bpy) was then added 2 Cl 2 After stirring for 24 hours, the obtained precipitate is centrifuged and washed, and dried at 60 ℃ to obtain the solid-state electrochemiluminescence probe.
The results of the transmission electron microscope scanning and the element scanning of the obtained solid-state electrochemiluminescence probe are shown in fig. 2. FIG. 2 is a TEM image and an elemental scan of solid state electrochemiluminescence probes prepared in examples 1-2 of the present invention. Fig. 2 a is a TEM image of a solid state electrochemical luminescence probe according to embodiment 1 of the present invention, fig. 2 b is a TEM image of a solid state electrochemical luminescence probe according to embodiment 2 of the present invention, fig. 2 c to f correspond to the element distribution of the solid state electrochemical luminescence probe according to embodiment 1 of the present invention, and fig. 2 h to k correspond to the element distribution of the solid state electrochemical luminescence probe according to embodiment 2 of the present invention. Wherein, purple represents Ru, cyan represents Zr, orange represents N, and white is an HAADF image.
As can be seen from the graph a in FIG. 2, the morphology of the resulting solid state electrochemiluminescence probe still maintains the regular octahedral morphology of UiO-67 (N), with dimensions of 300-500 nm.
As can be seen from graphs c-f in FIG. 2, uniformly distributed Ru, zr and N elements can be detected on the outer surface of the regular octahedral solid state electrochemiluminescence probe.
(3) Construction and performance research of a solid-state electrochemiluminescence sensing platform:
and dispersing 5mg of the solid-state electrochemiluminescence probe in 1mL of ultrapure water to prepare a solution, dripping 2 mu L of the solution on the surface of the glassy carbon electrode, drying, coating a layer of Nafion (0.02 wt% and 6 mu L), and drying to obtain the solid-state electrochemiluminescence sensing platform. The luminescence behavior of the solid state electrochemiluminescence sensing platform was examined using cyclic voltammetry (electrolyte solution is 0.1M PBS solution with pH 7.4, platinum wire is the counter electrode, ag/AgCl (saturated KCl solution) electrode is the reference electrode, scanning potential 0-1.3V (vs. Ag/AgCl)), and the results are shown in fig. 3. FIG. 3 is a stability test chart of a solid-state electrochemiluminescence sensing platform constructed in example 1 of the present invention, namely: ECL intensity versus time plot for a solid state electrochemiluminescence sensing platform scanned 20 consecutive cycles in the presence of 1.8mM TPrA.
As can be seen from fig. 3, the luminescence stability after 20 consecutive scans in the presence of the co-reactant (TPrA, tripropylamine) was good with a relative standard deviation of 1.24%.
Example 2
(1) Synthesis of solid phase Carrier MOF-UiO-67 (N):
39.12mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid was dissolved in 10mL of DMF and 37.28mg of ZrCl was added 4 Then adding 2mL of acetic acid to obtain a mixed solution, transferring the mixed solution into a 40mL reaction kettle, heating the mixed solution at 100 ℃ for 24 hours, centrifuging the reacted product, then washing the product with absolute ethyl alcohol, and drying the product at 60 ℃ to obtain the solid phase carrier MOF-UIO-67 (N).
(2) Preparation of solid-state electrochemiluminescence probe:
100mg of the solid phase carrier MOF-UiO-67 (N) is added into a DMF solution containing 60mg of ruthenium trichloride hydrate (the Ru content is 35.0-42.0 wt%) and stirred at room temperature for 6h, then 60mg of LiCl and 140mg of 2,2' -bipyridine are added, after refluxing for 24h, the obtained precipitate is centrifuged and washed, and dried at 60 ℃ to obtain the solid-state electrochemiluminescence probe.
The solid-state electrochemiluminescence probe obtained in this example was subjected to transmission electron microscope scanning and element scanning, and the results are shown in fig. 2.
As can be seen from FIG. 2, the morphology of the resulting solid state electrochemiluminescence probe still maintains the regular octahedral morphology of UiO-67 (N), with dimensions of 300-500 nm.
It can be seen from the graphs h to k in fig. 2 that uniformly distributed Ru, zr, and N elements can be detected on the outer surface of the solid-state electrochemiluminescence probe of the regular octahedron.
(3) Construction and performance research of a solid-state electrochemiluminescence sensing platform:
and dispersing 5mg of the solid-state electrochemiluminescence probe in 1mL of ultrapure water to prepare a solution, dripping 2 mu L of the solution on the surface of the glassy carbon electrode, drying, coating a layer of Nafion (0.02 wt% and 6 mu L), and drying to obtain the solid-state electrochemiluminescence sensing platform. The luminescence behavior of the solid state electrochemiluminescence sensing platform was examined using cyclic voltammetry (electrolyte solution is 0.1M PBS solution with pH 7.4, platinum wire is the counter electrode, ag/AgCl (saturated KCl solution) electrode is the reference electrode, scanning potential 0-1.3V (vs. Ag/AgCl)), and the results are shown in fig. 4. FIG. 4 is a stability test chart of a solid-state electrochemiluminescence sensor platform constructed in example 2 of the present invention, namely: ECL intensity versus time plot for a solid state electrochemiluminescence sensing platform scanned 20 consecutive cycles in the presence of 1.8mM TPrA.
As can be seen from fig. 4, the luminescence stability after 20 consecutive scans in the presence of the co-reactant (TPrA, tripropylamine) was good with a relative standard deviation of 1.25%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of a solid-state electrochemiluminescence probe comprises the following steps:
a) 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl 4 Mixing with acetic acid, reacting for 23-25 hours at 95-105 ℃, centrifuging the reacted product, then washing with absolute ethyl alcohol, and drying at 55-65 ℃ to obtain a solid phase carrier;
b1 After mixing the solid support with water, ru (bpy) is added 2 Cl 2 Stirring and reacting for 23-25 h, centrifuging and washing, and drying the obtained precipitate at 55-65 ℃ to obtain the electrochemiluminescence material; the solid support and Ru (bpy) 2 Cl 2 The mass ratio of (2.5-3.5): 1, a step of;
or (b)
B2 Firstly, reacting a solid phase carrier with ruthenium trichloride hydrate in an organic solvent, then adding LiCl and 2,2' -bipyridine into a product obtained after the reaction to carry out reflux reaction, centrifuging and washing, and drying the obtained precipitate at 55-65 ℃ to obtain a solid-state electrochemiluminescence probe; the mass ratio of the solid phase carrier to the ruthenium trichloride hydrate to the LiCl to the 2,2' -bipyridine is 4-6: 2-4: 2-4: 6-8;
the organic solvent is DMF.
2. The process according to claim 1, wherein in step a), the solvent in the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution is DMF;
the concentration of the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution is 3.5-4.5 mg/mL.
3. The method according to claim 1, wherein in the step A), the 2,2 '-bipyridine-5, 5' -dicarboxylic acid solution and ZrCl are mixed 4 The mass ratio of (2) is 0.5-1.5: 0.5 to 1.5;
the ZrCl 4 And the dosage ratio of acetic acid is 35-40 g: 1-3 mL.
4. The method according to claim 1, wherein in the step B1), the ratio of the solid phase carrier to water is 8-12 mg:0.5 to 1.5mL.
5. The process according to claim 1, wherein in step B2),
the dosage ratio of the solid phase carrier to the organic solvent is 4-6 mg:3mL.
6. A solid-state electrochemical luminescence probe prepared by the preparation method according to any one of claims 1 to 5.
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