CN114106346B - Rare earth bimetallic electrochemiluminescence material and preparation method and application thereof - Google Patents
Rare earth bimetallic electrochemiluminescence material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a rare earth bisA metal electrogenerated chemiluminescence material, a preparation method and application thereof. Which takes 3,5-dicarboxyphenyl boric acid as ligand and Tb 3+ And Ce 3+ Is a metal center and is prepared by a solvothermal method. The invention solves the problems of low sensitivity and poor accuracy of detection of epinephrine and the like in the prior art, and has the advantages of high sensitivity, high accuracy, good stability and wider linear range.
Description
Technical Field
The invention relates to the technical field of electrochemiluminescence, in particular to a rare earth bimetal electrochemiluminescence material and a preparation method and application thereof.
Background
Adrenalin, which is a kind of catecholamine, is derived from tyrosine, and is used as a neurotransmitter and hormone, has a close relationship with human health and diseases, and is closely related to functional diseases such as schizophrenia, depression and organic lesions (such as parkinsonism, cardiovascular diseases and the like), as well as the regulation of vegetative nerve functions such as blood pressure, heart rate, respiration and sleep. Patients with certain tumors, such as neuroblastoma, often have elevated levels of norepinephrine or epinephrine in their blood.
At present, the detection of epinephrine level generally includes high performance liquid chromatography, enzyme linked immunosorbent assay, radioimmunoassay, and the like. However, these methods all have disadvantages, such as long time consumption, high cost, difficulty in batch determination, lack of accuracy and reproducibility in enzyme-linked immunoassay, cross reaction and false positive reaction in radioimmunoassay, and radioactive contamination. Therefore, the establishment of a method for rapidly, accurately and sensitively detecting the epinephrine level has important significance.
Compared with the detection method, ECL (Electrochemiluminescence) detection has the characteristics of high sensitivity and simple operation, and can be applied to clinical disease diagnosis, drug detection, food safety, environmental monitoring, pathogenic microorganism research and the like. The ECL sensor can realize ECL detection, and is a luminescence phenomenon generated by an unstable excitation state due to oxidation-reduction reaction of a luminophor under a certain voltage after the luminophor (luminophor) is modified on the surface of an electrode, and the detection of a substance component is realized by detecting a luminescence signal. Therefore, the core of ECL detection is the synthesis and development of luminescent materials with stable and strong ECL signals.
Currently, the ECL luminescent materials which are researched more comprise organic substances (hydrazide and acridine), inorganic substances (complexes of Ru and Ir) and nano materials (quantum dots and noble metal nanoclusters), and the ECL luminescent materials have good luminescent properties but still have defects. For example, the synthesis of the luminescent material is complicated, time-consuming, and poor in stability, and even the luminescent material falls off from the surface of the electrode during the detection process, resulting in signal loss. In addition, some luminescent materials have high toxicity and must generate strong ECL emission under high excitation potential, and the high excitation potential easily causes the release of oxygen in the electrolyte, thereby causing electrode damage and biomolecule damage, and limiting the practical application thereof to a certain extent. However, the fluorescent property of the luminescent material is more and less studied, and the research on the electrochemiluminescence property is less.
Therefore, it is an urgent need to solve the problem of finding a new luminescent material using rare earth metals as raw materials and detecting epinephrine by its electrochemiluminescence property, thereby obtaining an epinephrine detection method with high sensitivity, high accuracy, high stability, and environmental friendliness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a rare earth bimetallic electrochemiluminescence material, a preparation method and application thereof, and solves the problems of low sensitivity and poor accuracy in epinephrine detection in the prior art.
The invention provides a rare earth bimetal electrochemiluminescence material which takes 3,5-dicarboxyphenyl boric acid as a ligand and Tb 3+ And Ce 3+ Is a metal center and is prepared by a solvothermal method.
Preferably, tb 3+ And Ce 3+ In a molar ratio ofIs 9:1-1:9.
Tb 3+ And Ce 3+ In the range of the molar ratio, rare earth bimetal electrochemiluminescence materials with different appearances can be obtained; ECL luminous intensity of rare earth bimetal electrochemiluminescence materials with different morphologies is different. Tb 3+ And Ce 3+ When the molar ratio is within the range, the ECL luminescence intensity of the synthesized rare earth bimetallic electrochemiluminescence material is the strongest.
Preferably, tb 3+ The compound exists in a terbium salt form, wherein the terbium salt is one of terbium nitrate and terbium chloride; said Ce 3+ The cerium nitrate is in the form of cerium salt, and the cerium salt is one of cerium nitrate and cerium chloride.
Preferably, its specific surface area is 95.83m 2 ·g -1 The total pore volume is 0.2265cm 3 ·g -1 The most probable pore diameter was 37.4nm.
The invention also provides a preparation method of the rare earth bimetal electrochemiluminescence material, tb is used 3+ And Ce 3 + Mixing, dissolving in a DMF/water mixed solvent, adding 3,5-dicarboxyphenyl boric acid under stirring, carrying out hydrothermal reaction, centrifuging, and collecting precipitate to obtain the rare earth bimetallic electrochemiluminescence material.
Preferably, in the DMF/water mixed solvent, the molar ratio of DMF and water is 7:3; in mol/L, tb 3+ And a DMF/water mixed solvent in a molar volume ratio of 0.1 to 0.9; ce 3+ And a DMF/water mixed solvent at a molar volume ratio of 0.1-0.9; 3,5-dicarboxyphenylboronic acid and DMF/water mixed solvent in a molar volume ratio of 1;
preferably, the stirring temperature is room temperature, and the stirring time is 30min;
or the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 12h;
or the rotating speed of the centrifugation is 6000r/min, the time is 3min, and the times are 3-4.
In another aspect, the invention provides a kit for detecting epinephrine, comprising the rare earth bimetallic electrochemiluminescent material;
preferably, the rare earth bimetallic electrochemiluminescence material exists in the form of solution, and the concentration of the solution is 1.5mg/mL;
preferably, it also comprises a compound containing K 2 S 2 O 8 PBS (g).
In still another aspect, the present invention provides an electrochemiluminescence sensor, comprising a substrate electrode, wherein the surface of the substrate electrode is coated with the above rare earth bimetallic electrochemiluminescence material;
preferably, the substrate electrode is a glassy carbon electrode.
In another aspect, the invention provides a method for preparing an electrochemiluminescence sensor, which comprises the steps of polishing, cleaning and airing a substrate electrode, and coating the rare earth bimetallic electrochemiluminescence material on the surface of the substrate electrode to obtain the electrochemiluminescence sensor.
The invention further provides the application of the rare earth bimetal electrochemiluminescence material, the kit and the electrochemiluminescence sensor in detecting the adrenaline level.
In still another aspect of the present invention, there is provided a method for detecting the level of epinephrine by dissolving the epinephrine to be detected in a solution containing K 2 S 2 O 8 In the PBS solution, the signal intensity is detected by an electrochemiluminescence sensor and calculated according to a linear equation;
preferably, said K 2 S 2 O 8 The concentration of (A) is 0.1mol/L; the concentration of the PBS solution is 0.1mol/L.
The technical principle of the invention is as follows: because the rare earth metal ions have flexible coordination environments, the spatial structure of the product is difficult to predict and control after the rare earth metal ions are combined with the ligand, and the design and synthesis of the rare earth complex face huge challenges. We have screened different ligands and rare earth metal ions by a number of tests and have surprisingly found that Ce is present in the ligand 3,5-dicarboxyphenylboronic acid (5-BOP) 3+ And Tb 3+ When the rare earth metal complex is used as metal ions together, the obtained rare earth metal complex has stronger stability and fluorescence signals. This is mainly due to the fact that the 5-BOP ligand contains a benzene ring and a borate, and the single 5-BOP molecules are aggregated together to form the electrochemiluminescent materialIn the process, the energy gap is reduced, the efficient recombination of electron holes is realized, the non-radiative transition is inhibited, and the aggregation-induced enhanced ECL emission is realized. Meanwhile, single 5-BOP molecules are orderly arranged in the luminescent material, so that intramolecular free rotation of a benzene ring is limited, and hollow P at the center of a boron atom in the 5-BOP n The orbital and the benzene ring have P n -n conjugation, which reduces non-radiative relaxation, further enhances the ECL strength of rare earth bimetallic electrochemiluminescent materials (Tb: ce-MOF) by the "antenna effect". As the conjugation degree of the 5-BOP molecules becomes higher after the 5-BOP molecules are orderly arranged in the luminescent material, the band gap is reduced, and simultaneously the ECL pathway transition of Tb: ce-MOF (or named as Tb: ce-COP) causes the spectrum red shift through the 'double sensitization effect' formed by the 'antenna effect' and the energy resonance transfer. Therefore, the interference to the background of visible light is low, the tissue penetration is deep, and the method has application prospects in the aspects of ECL sensing and biological imaging. Furthermore, ce is added 3+ And Tb 3+ The doping into Tb: ce-MOF can not only adjust the appearance of Tb: ce-MOF, but also adjust the appearance of Tb: ce-MOF 3+ To Tb 3+ 3,5-dicarboxyphenylboronic acid to Ce 3+ And Tb 3+ The antenna effect of (1) forms a 'double sensitization effect', and Ce is added at the same time 3+ As a co-reaction promoter, S is effectively promoted 2 O 8 2- More SO is generated 4 ·- The combined action of the two elements improves the ECL strength of the Tb: ce-MOF, realizes direct ECL of the rare earth elements, and the light-emitting principle of the element is shown in figure 13.
Compared with the prior art, the invention has the following beneficial effects:
1. the ECL sensor has high sensitivity, low detection limit and wide linear range, and the detection range of the ECL sensor for epinephrine is 0.1 nmol.L -1 -10mmol·L -1 The detection limit is 0.25 nmol.L -1 (ii) a The stability is good, and the results have no obvious difference when the epinephrine is continuously measured for 23 times; the accuracy is high, the detection result is close to the adrenaline content of the injection, the adrenaline labeling recovery rate is 96.0-107.0 percent, and the relative standard deviation is less than or equal to 0.89 percent;
2. the electrochemiluminescence material has the characteristic of infrared fluorescence emission, the maximum emission wavelength is 693nm, the background interference is small, the photochemical damage is small, the tissue penetrability is strong, and the application range is wider;
3. the electrochemiluminescence material has long fluorescence life, the fluorescence life is 9.82ns, interference signals in detection can be effectively eliminated, the obtained signals are more accurate, and high-flux detection of an object to be detected can be realized;
4. the electrochemiluminescence material has low excitation potential of-2.0-0V, can emit signals in an aqueous medium in the presence of oxygen, improves the chemical stability in water, effectively reduces the oxidation damage of the excitation potential to biomolecules, has controllability on the excitation potential, and is favorable for improving the detection accuracy;
5. the electrochemiluminescence material is directly fixed on the surface of an electrode in a coating mode, so that an ECL reagent directly interacts with the electrode, direct ECL of rare earth metal is realized, and the electrochemiluminescence efficiency is enhanced;
6. the method has the advantages of simple and controllable synthesis steps, suitability for expanded production, convenient operation, no need of an external light source and capability of realizing rapid detection of the epinephrine level.
In conclusion, the sensor constructed by the rare earth bimetallic electrogenerated chemiluminescence material can simply, quickly, accurately and sensitively measure epinephrine, has important research significance in the aspects of diagnosis, treatment and the like of diseases, opens up a new path for direct ECL luminescence of rare earth elements, and provides a new idea for the research of novel ECL inorganic luminophores.
Drawings
FIG. 1 is a process diagram of the preparation of Tb: ce-MOF in the invention;
FIG. 2 is an SEM image of a series of Tb: ce-MOFs prepared in example 1;
FIG. 3 is a graph comparing the signals of a series of ECL sensors prepared in example 2;
FIG. 4 is a TEM image of Tb: ce-MOF in example 3;
FIG. 5 is an electron diffraction pattern of Tb: ce-MOF selected region in example 3;
FIG. 6 is the EDS and element distribution plots for Tb: ce-MOF in example 3;
FIG. 7 is an XPS plot of Tb: ce-MOF in example 3;
FIG. 8 is a graph showing the nitrogen adsorption isotherms and pore size distributions of Tb Ce-MOF in example 3;
FIG. 9 is a graph showing the luminescence properties of Tb: ce-MOF in example 3, wherein A is a fluorescence analysis graph of Tb: ce-MOF, B is a fluorescence lifetime detection graph, C is a 3D ECL spectrum, D is a heat map image, E is a 2D ECL spectrum, and F is an ECL signal stability graph (continuous scanning 800 s);
FIG. 10 is a graph showing the results of sensitivity evaluation of the ECL sensor in example 4; wherein, A is a response graph of the light signal and the concentration of epinephrine, and B is a correction curve graph of the light signal and the logarithm of the concentration of epinephrine;
FIG. 11 is a graph showing the results of stability evaluation of the ECL sensor in example 4;
FIG. 12 is a graph showing the results of evaluating the specificity of the ECL sensor in example 4;
FIG. 13 is a schematic diagram of ECL luminescence principle of Tb: ce-MOF.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1 Synthesis and morphology detection of rare earth bimetallic electrogenerated chemiluminescence material
1. Synthesis of rare-earth bimetallic electrogenerated chemical luminophor material
Tb (NO) 3 ) 3 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 O was mixed in the amount shown in Table 1, and 10mL of DMF/H was added 2 O (7:3) mixed solvent to Tb (NO) 3 ) 3 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 The O was completely dissolved. Then 5-BOP (0.1 mmol) was added and stirred at room temperature for 30min to give a clear solution. The clear solution was then placed in a teflon lined autoclave and maintained at 150 ℃ for 12 hours. And after the reaction is finished, centrifugally washing the mixture for 3 to 4 times at the rotating speed of 6000r/min, 3min each time, and taking the precipitate to prepare a series of rare earth bimetal electrogenerated chemiluminescence body materials Tb: ce-MOF.
TABLE 1 Tb (NO) 3 ) 3 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Proportioning of O amount
| Group of | Tb(NO 3 ) 3 ·6H 2 O(/mmol) | Ce(NO 3 ) 3 ·6H 2 O(/mmol) |
| Group A | 0.09 | 0.00 |
| Group B | 0.09 | 0.01 |
| Group C | 0.07 | 0.03 |
| Group D | 0.05 | 0.05 |
| Group E | 0.03 | 0.07 |
| Group F | 0.01 | 0.09 |
| Group G | 0.00 | 0.09 |
2. Topography detection
The Scanning Electron Microscope (SEM) observation is carried out on the prepared rare earth bimetallic electrochemiluminescence material (A group-G group), the result is shown in figure 2, and the shapes of the independent Tb-MOF (A group) and Ce-MOF (G group) are respectively rod-shaped and hollow column-shaped; the shape of the series Tb: ce-MOFs (B group-F group) is gradually changed from needle shape, rod shape to spherical shape. Wherein, the B group appearance is needle-like, the average diameter is 0.1 μm, the average length is 2.5 μm, and the length-diameter ratio is 25.
EXAMPLE 2ECL sensor preparation and ECL Signal detection
1. Preparation of ECL sensor
1) Preparing a rare earth bimetal electrochemiluminescence material solution: the rare earth bimetallic electrochemiluminescent materials (A-G groups) prepared in example 1 are respectively dispersed in water and are magnetically stirred for 2 hours to prepare 1.5mg/mL -1 A solution;
2) Polishing a bare Glassy Carbon Electrode (GCE), respectively ultrasonically cleaning the polished bare glassy carbon electrode with ethanol and water, and airing the polished bare glassy carbon electrode at room temperature. Then, 10 mu L of the solution prepared in the step 1) is respectively dripped on the surface of the polished GCE, and is dried at room temperature to prepare an ECL sensor Tb, ce-MOF/GCE, wherein an ECL sensor prepared from the group A rare earth bimetallic electroluminescent material is denoted as a group, an ECL sensor prepared from the group B rare earth bimetallic electroluminescent material is denoted as B group, an ECL sensor prepared from the group C rare earth bimetallic electroluminescent material is denoted as C group, an ECL sensor prepared from the group D rare earth bimetallic electroluminescent material is denoted as D group, an ECL sensor prepared from the group E rare earth bimetallic electroluminescent material is denoted as E group, an ECL sensor prepared from the group F rare earth bimetallic electroluminescent material is denoted as F group, and an ECL sensor prepared from the group G rare earth electroluminescent material is denoted as G group.
2. Signal detection for ECL sensors
The signals of the ECL sensors (a-g groups) were detected by an MPI-E electrochemiluminescence analyzer (Seaanrei electronic science and technology Co., ltd., china), and the results are shown in FIG. 3.
From the results, the ECL signals of the b groups were the largest.
Example 3 detection of the Properties of rare-earth bimetallic electrogenerated chemiluminescence materials (group B)
The results of Transmission Electron Microscopy (TEM), EDS elemental distribution, XPS spectroscopy, nitrogen adsorption analysis, and fluorescence spectroscopy analysis on the rare earth bimetallic electrochemiluminescent material (group B) are shown in fig. 4-9.
As can be seen from FIG. 4, the average particle size of Tb: ce-MOF was 2.5. Mu.m; as can be seen from FIG. 5, tb: ce-MOF has no specific crystal configuration; as can be seen from FIGS. 6 and 7, tb is Ce-MOF containing five elements of C, B, O, ce and Tb; as can be seen from FIG. 8, the isothermal nitrogen adsorption curve of the Tb: ce-MOF shows type IV characteristics, and the electrochemiluminescence material is of a mesoporous structure; the specific surface area (BET) is about 95.83m 2 ·g -1 The total pore volume is about 0.2265cm 3 ·g -1 . The pore size distribution curve obtained by Barrett-Joyner-Halenda (BJH) shows that the pore size of Tb: ce-MOF is concentrated at about 37.4 nm; as can be seen from FIG. 9A, tb: ce-MOF showed four strong emission peaks corresponding to Tb 3+ Is/are as follows 5 D 4 → 7 F J (J/6,5,4,3, 491.0nm 5 D 4 → 7 F 6 550.8nm 5 D 4 → 7 F 5 586.6nm 5 D 4 → 7 F 4 623.2nm 5 D 4 → 7 F 3 ) Transmitting; the weak and wide-band emission band at 300-400nm is Tb to Ce in Ce-MOF 3+ D-f radiative transitions of (a); as can be seen from FIG. 9B, the PL lifetime of Tb: ce-MOF is 9.82ns, and the PL lifetime of Tb-MOF is 6.60ns; the long Photoluminescence (PL) lifetime of Tb: ce-MOF is increased by about 3.22ns compared to Tb-MOF; as can be seen from FIGS. 9C-9E, the maximum ECL emission wavelength of Tb: ce-MOF is 693nm, and as can be seen from FIG. 9F, the ECL signal of Tb: ce-MOF does not change significantly after 23 cycles, indicating that the ECL signal has high stability.
Example 4 evaluation of the Performance of ECL Sensors (group b)
1. Sensitivity assessment of ECL sensors
The prepared ECL sensor is used for detecting epinephrine, and an MPI-E electrochemiluminescence analyzer (Siennamei electronic scientific and technology Co., ltd., china) is used, and a three-electrode system comprises the following components: using a glassy carbon electrode working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire as a counter electrode, wherein the excitation potential is-2.0-0V, and the detection base solution contains 0.1mol/L K 2 S 2 O 8 0.1mol/L PBS (pH = 7.4). The working electrode was immersed in 4mL of a detection base solution to obtain an EP concentration of 0.1 nmol.L -1 Change to 100 mmol. L -1 . The results are shown in FIG. 10. From the results, it is clear that there is a good positive correlation between the ECL signal change and the logarithm of the PE concentration, and the linear equation is Δ I (Δ I = I) blank -I)＝16676.7+1730.4lgc(R 2 ＝0.981)(ΔI＝I 0 –I，I 0 And I represents sensor ECL intensity at blank and different EP concentrations; c: the EP concentration; r: correlation coefficient), detection Limit (LOD) of 0.25 nmol.L -1 。
2. Stability evaluation of ECL sensors
The prepared ECL sensors are used for respectively measuring 10 nmol.L -1 And 1. Mu. Mol. L -1 The results of 23 consecutive measurements of EP (1) are shown in FIG. 11, and it is found that the obtained ECL signal has high stability.
3. Specific evaluation of ECL sensors
The prepared ECL sensors are respectively used for measuring the concentration of 10 mmol.L -1 Na (b) of + 、K + 、Mg 2+ 、Zn 2+ The results of tests on L-cysteine, L-lysine, L-valine, L-alanine, L-arginine, uric Acid (UA), ascorbic Acid (AA), bovine Serum Albumin (BSA) and glucose are shown in FIG. 12, and it can be seen from the results that the ECL signals of single interferents in the measured ECL signals are similar to those of the blank, and the ECL signal of target epinephrine is obviously reduced, which indicates that the ECL sensor has good specificity.
Test example detection of epinephrine
Two different doses of EP hydrochloric acid injection (1mg and 5mg specificationHuman serum was analyzed. The hydrochloric acid EP injection is respectively used with a solution containing 0.1mol/L K 2 S 2 O 8 Diluted to an appropriate concentration with 0.1mol/L PBS (pH = 7.4), and then detected using the ECL sensor prepared in example 3. At the same time, the standard addition method is adopted, and the concentration of the solution is 50 times diluted human serum (0.1 mol. L) -1 PBS, pH = 7.4) were added with various concentrations of epinephrine, and the ECL sensor prepared in example 3 was used for detection, and the results are shown in table 2.
TABLE 2 detection of epinephrine hydrochloride in the serum of epinephrine hydrochloride injection and healthy persons
a Provided by China Jilin province Hua mu animal health products Limited company, the product specification is as follows: 5 mg.
b Provided by Shanghai Quanyu Biotechnology (Limb shop) animal pharmaceutical industry Co., ltd., china, the product specification is as follows: 1mg.
c Provided by the ninth people hospital in Chongqing City
As can be seen from Table 2, the EP test results in the injections were 1.020mg, 1ml and 5.015mg, respectively, which are close to the stated epinephrine content of the injections, the recovery rate of adrenaline in the sample is 96.0-107.0%, the relative standard deviation is less than or equal to 0.89%, and the detection effect is good, which indicates that the sensor can be used for detecting adrenaline in biological samples.
Comparative example 1 rare earth bimetallic electrogenerated chemiluminescence material TbPO 4 Synthesis and Performance detection of Ce
0.09mmol of Tb (NO) 3 ) 3 ·6H 2 O and 0.01mmol Ce (NO) 3 ) 3 ·6H 2 Mixing O, adding 20mL of water, and stirring at room temperature for 10 minutes to obtain a clear solution; adding 0.2mmol of NaH 2 PO 4 ·2H 2 Stirring O into the solution for 3h, centrifuging at 5000rpm for 1min, washing and drying to obtain TbPO 4 :Ce。
Scanning Electron Microscope (SEM) for TbPO 4 Form of CeThe appearance is characterized, and the appearance is detected to be needle-shaped, the diameter is about 20nm, the average length is 600nm, and the length-diameter ratio is 30. The specific surface area is about 130.63m 2 ·g -1 The total pore volume is about 0.4690cm 3 ·g -1 The pore diameter is concentrated about 12.1 nm.
Comparative example 2ECL sensor TbPO 4 Preparation and performance detection of Ce/GCE
1、TbPO 4 Preparation of Ce/GCE: tbPO 4 Ce (2.0 mg) is put in 5mL chitosan (CS, 0.5%) solution and stirred evenly. Then, 5 μ L of the luminescent nano material is dripped on the polished GCE surface and dried at room temperature, and is recorded as TbPO 4 :Ce/GCE。
2. Performance detection
Detected by fluorescence analysis, tbPO 4 ECL luminescence wavelength of Ce/GCE: tbPO 4 The maximum ECL luminescence wavelength of Ce/GCE is 651nm. For TbPO 4 Ce/GCE was evaluated for sensitivity. Meanwhile, the ECL sensors of the group a and the group g in example 2 were subjected to sensitivity evaluation.
The signal intensity of the group g of ECL sensors in example 2 was almost unaffected, while the group a of ECL sensors in example 2 and the ECL sensors prepared in comparative example 2 were less sensitive than the ECL sensors in example 4. This is probably because the ECL sensor prepared by the group g and the comparative example 2 has different compositions and morphologies of the electrochemiluminescent materials from those of the ECL sensor, thereby affecting the sensing properties of the ECL sensor, and causing different detection sensitivity for epinephrine detection.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (16)
1. A rare earth bimetallic electrochemiluminescence material is characterized in that: which takes 3,5-dicarboxyphenyl boric acid as a ligand,with Tb 3+ And Ce 3+ Is a metal center and is prepared by a solvothermal method;
the average diameter of the luminescent material is 0.1 μm, the average length is 2.5 μm, the aspect ratio is 25 2 ·g -1 The total pore volume is 0.2265cm 3 ·g -1 The most probable pore diameter was 37.4nm.
2. The rare earth bimetallic electrochemiluminescence material as set forth in claim 1, wherein: tb 3+ And Ce 3+ In a molar ratio of 9:1-1:9.
3. The rare earth bimetallic electrochemiluminescent material as set forth in claim 1, wherein: tb 3+ The compound exists in a terbium salt form, wherein the terbium salt is one of terbium nitrate and terbium chloride; the Ce 3+ The cerium salt exists in the form of cerium salt, and the cerium salt is one of cerium nitrate and cerium chloride.
4. A method for preparing a rare earth bimetallic electrochemiluminescence material as described in any one of claims 1 to 3, wherein: tb is to be 3+ And Ce 3+ Mixing, dissolving in a DMF/water mixed solvent, adding 3,5-dicarboxyphenyl boric acid under the stirring condition, carrying out hydrothermal reaction, centrifuging, and collecting precipitate to obtain the rare earth bimetallic electrochemiluminescent material.
5. The method for preparing a rare earth bimetallic electrochemiluminescence material as claimed in claim 4, wherein the method comprises the following steps: in the DMF/water mixed solvent, the molar ratio of DMF to water is 7:3; in mol/L, tb 3+ And a DMF/water mixed solvent in a molar volume ratio of 0.1 to 0.9; ce 3+ And a DMF/water mixed solvent at a molar volume ratio of 0.1-0.9; 3,5-dicarboxyphenylboronic acid and DMF/water mixed solvent molar volume ratio of 1.
6. The method for preparing a rare earth bimetallic electrochemiluminescence material as claimed in claim 4, wherein the method comprises the following steps: the stirring temperature is room temperature, and the stirring time is 30min.
7. The method for preparing rare earth bimetallic electrochemiluminescence material as in claim 4, wherein the method comprises the following steps: the temperature of the hydrothermal reaction is 150 ℃, and the time is 12h.
8. The method for preparing a rare earth bimetallic electrochemiluminescence material as claimed in claim 4, wherein the method comprises the following steps: the rotation speed of the centrifugation is 6000r/min, the time is 3min, and the times are 3-4.
9. A kit for detecting epinephrine, comprising: comprising a rare earth bimetallic electrochemiluminescent material as claimed in any one of claims 1 to 3.
10. The kit for detecting epinephrine according to claim 9, wherein: the rare earth bimetallic electrochemiluminescence material exists in the form of solution, and the concentration of the solution is 1.5mg/mL.
11. The kit for detecting epinephrine according to claim 9, wherein: also includes compounds containing K 2 S 2 O 8 PBS (g).
12. An electrochemiluminescence sensor, comprising: comprising a base electrode coated on its surface with a rare earth bimetallic electrochemiluminescent material as claimed in any one of claims 1 to 3.
13. An electrochemiluminescence sensor as defined in claim 12, wherein: the substrate electrode is a glassy carbon electrode.
14. A method of making an electrochemiluminescence sensor as defined in claim 12, wherein: and polishing, cleaning and airing the substrate electrode, and coating the rare earth bimetallic electrochemiluminescence material on the surface of the substrate electrode to obtain the rare earth bimetallic electrochemiluminescence material.
15. Use of a rare earth bimetallic electrochemiluminescent material according to any of claims 1-3, a kit according to claim 9 or an electrochemiluminescent sensor according to claim 12 for detecting epinephrine levels.
16. A method of detecting epinephrine levels using a rare earth bimetallic electrochemiluminescent material of any one of claims 1-3, a kit of claim 9, or an electrochemiluminescent sensor of claim 12, wherein: dissolving the adrenaline to be detected in a solution containing K 2 S 2 O 8 In the PBS solution, the signal intensity is detected by the rare earth bimetallic electrochemiluminescence material, the kit or the electrochemiluminescence sensor, and the signal intensity is calculated according to a linear equation;
wherein, K is 2 S 2 O 8 The concentration of (A) is 0.1mol/L; the concentration of the PBS solution is 0.1mol/L.
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