CN114047178A - Preparation and application of functionalized Zn-Co bimetal core-shell ZIF-9@ ZIF-8 composite material - Google Patents
Preparation and application of functionalized Zn-Co bimetal core-shell ZIF-9@ ZIF-8 composite material Download PDFInfo
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- 238000001291 vacuum drying Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008363 phosphate buffer Substances 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940067157 phenylhydrazine Drugs 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- UDMBCSSLTHHNCD-UHFFFAOYSA-N Coenzym Q(11) Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(O)=O)C(O)C1O UDMBCSSLTHHNCD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical class C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O UDMBCSSLTHHNCD-KQYNXXCUSA-N 0.000 claims description 2
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- 238000002474 experimental method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 6
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- 230000017074 necrotic cell death Effects 0.000 description 1
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 210000004881 tumor cell Anatomy 0.000 description 1
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- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
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- 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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Abstract
The invention discloses a preparation method of a Zn-Co bimetallic core-shell ZIF-9@ ZIF-67 composite catalyst and an application technology thereof in a chemiluminescence sensor, and the main technical characteristics are as follows: the core-shell ZIF-9@ ZIF-67 composite material is prepared, and an aptamer is modified on the surface of the core-shell ZIF-9@ ZIF-67 composite material to obtain the core-shell ZIF-67 composite material catalyst with high specificity recognition capability on adenosine molecules, so that the preparation process is simple, the conditions are easy to control, and the production cost is low; the invention also provides a novel method for detecting adenosine, the aptamer functionalized ZIF-9@ ZIF-67 composite material is applied to a chemiluminescence sensor for detecting adenosine, the method has the advantages of high sensitivity, good selectivity, convenience in operation, simple instrument and the like, and the method is successfully applied to the detection of adenosine in human urine samples, shows high accuracy and precision, provides possibility for practical detection, and has important biological significance in human health.
Description
Technical Field
The invention relates to a preparation method of a Zn-Co bimetallic core-shell ZIF-9@ ZIF-8 composite catalyst and an application technology thereof in a chemiluminescence sensor, belongs to the technical field of photochemical sensing, and particularly relates to a preparation method of an aptamer functionalized core-shell ZIF-9@ ZIF-8 composite catalyst and an application thereof in adenosine detection of the chemiluminescence sensor.
Background
The metal-organic framework (MOFs) material is an emerging metal-organic material, which is generally formed by connecting various metal ions or metal clusters and organic ligands, wherein the metal ions mainly comprise atoms of transition metals, rare earth metals and alkaline earth metal elements, the organic ligands are generally organic carboxylic acids and nitrogen-containing heterocyclic compounds, the ZIFs material is one of MOFs materials and has higher catalytic performance and chemical stability, the metal-organic framework material generally exceeds other nano materials in the application range in the field of catalysis due to unique physical and chemical properties, and the number of special structures of the metal-organic framework material is quite remarkable, so that the metal-organic framework material has a very wide potential application prospect, and the effect in chemical catalysis is particularly outstanding.
Adenosine plays an important role in signal expression of central nervous system and peripheral nervous system, thus being widely noticed by researchers, researches show that the rapid growth of solid tumor cells can cause hypoxia and necrosis thereof, release a large amount of adenosine, provide environment for the rapid growth of tumors, resulting in the accumulation of higher concentrations of adenosine in solid tumors, the adenosine levels in the urine reflect the degradation levels of adenosine in the human body, therefore, the selectivity and sensitivity detection of adenosine have important significance, and at present, some methods for detecting adenosine exist, such as electrochemical sensors, enzyme-linked immunosorbent assay, photoelectric sensors, fluorescence sensors and the like, however, these methods have problems such as poor reproducibility of electrochemical methods, complicated operation, and high price of the enzyme-linked immunosorbent assay, and thus, there is an urgent need to establish a method for detecting adenosine with high sensitivity and high selectivity.
The flow injection-chemiluminescence technology integrates the advantages of flow injection, automatic sample injection, convenient operation, high sensitivity of a chemiluminescence analysis method, simple instrument, wide linear range, high analysis speed, no pollution and the like, and is widely applied in the analysis field, but the chemiluminescence method has a great defect of poor selectivity, because various coexisting substances easily cause the change of chemiluminescence intensity, and the defect can be overcome by introducing specific recognition materials, such as a molecular imprinting material, an antigen-antibody material, an aptamer material and the like.
In the patent, a core-shell ZIF-9@ ZIF-8 composite material is prepared, an adenosine aptamer is modified on the surface of the core-shell ZIF-9@ ZIF-8 composite material to obtain a functionalized core-shell ZIF-9@ ZIF-8 composite material which is easy to separate, excellent in fixing performance and high in specific identification capacity, and the functionalized core-shell ZIF-9@ ZIF-8 composite material is used together with a flow injection-chemiluminescence technology to construct a chemiluminescence sensor for detecting adenosine with high sensitivity and high selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of an aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material catalyst, which is mainly used for preparing a core-shell ZIF-9@ ZIF-8 composite material, and an aptamer is modified on the surface of the core-shell ZIF-9@ ZIF-8 composite material to obtain the functionalized core-shell ZIF-9@ ZIF-8 composite material with high specificity recognition capability on adenosine.
The invention is realized by the following technical scheme:
(1) preparing a core-shell ZIF-9@ ZIF-8 composite material: respectively blending 0.70-0.78 g of zinc nitrate hexahydrate and 0.80-0.85 g of 2-methylimidazole with 50mL of methanol, performing ultrasonic treatment for 20-30 min, mixing the two solutions, and stirring at room temperature for 1-2 h to obtain a solution containing ZIF-8; gradually adding a solution containing ZIF-8 into 120 mL of methanol suspension containing 0.4-0.55 g of ZIF-9, performing ultrasonic treatment for 20-30 min, stirring for 2-4 h at room temperature, centrifuging for 5 min at a rotation speed of 8000 r/min, removing supernatant, and performing vacuum drying at 80 ℃ to obtain a core-shell ZIF-9@ ZIF-8 crystal with a ZIF-9 core and a ZIF-8 shell, namely a core-shell ZIF-9@ ZIF-8 composite material;
(2) preparing an aptamer functionalized ZIF-9@ ZIF-8 composite material: weighing 0.10-0.5 mg of ZIF-9@ ZIF-8 composite material into a 50mL centrifuge tube, adding 30 mL of 0.02 mol/L phosphate buffer solution with pH =7.4 into the centrifuge tube, and then adding 0.5-1 ng/mL adenosine aptamer into the centrifuge tube; vibrating the centrifugal tube for 3-5 h, and then incubating for 24 h at 25 ℃ room temperature; finally, centrifuging for 10 min at the rotating speed of 8000 r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ ZIF-8 composite material;
the preparation method of ZIF-9 is as follows: respectively weighing 0.630 g of cobalt nitrate hexahydrate and 0.180 g of benzimidazole, putting the cobalt nitrate hexahydrate and the benzimidazole into 60 mL of N, N-dimethylformamide, stirring and dissolving, mixing the two solutions to obtain a pink solution, violently stirring the solution for 20 min, heating at 140 ℃, stirring and refluxing for 24 h, cooling to room temperature, continuously stirring for 48 h at room temperature, then centrifuging at the rotating speed of 8000 r/min for 10 min, and removing the supernatant; and finally, performing vacuum drying at 80 ℃ to obtain a purple crystal, namely ZIF-9.
The invention also aims to apply the aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material to a chemiluminescence sensor for detecting adenosine, when adenosine exists, the adenosine molecules and the aptamer specificity are identified and combined together, so that the composite material catalyst is released, and the released composite material catalyst catalyzes a luminol-hydrogen peroxide chemiluminescence system to cause the change of chemiluminescence intensity, thereby realizing the detection of the adenosine; the chemiluminescence chemical sensor is characterized in that: the method has the advantages of high sensitivity, good selectivity, convenient operation and simple instrument, researches the fixing performance of the synthetic material, optimizes the chemiluminescence condition, draws a working curve, researches the anti-interference capability and finally is used for detecting adenosine in a human urine sample.
The invention has the advantages and effects that:
(1) the invention prepares a core-shell ZIF-9@ ZIF-8 composite material, and ZIF-9 and ZIF-8 are bonded together through a hydrothermal reactionThe core-shell ZIF-9@ ZIF-8 composite material is prepared by vacuum drying, has the advantages of large specific surface area, rich active sites and the like, provides a large number of action sites for aptamers, and has the saturated fixation quantity of 7.5 multiplied by 10 to adenosine aptamers-11 mol/L；
(2) The aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material is prepared, the preparation process is simple, the conditions are easy to control, and the specific recognition capability of the composite material can be obviously improved;
(3) the aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material prepared by the invention is applied to a chemiluminescence sensor for detecting adenosine, the sensor shows a wide linear range and a low detection limit when detecting adenosine, and the sensor shows high accuracy and precision when being used for detecting adenosine in human urine samples, so that the application to actual detection is possible, and the aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material has important biological significance in human health.
Drawings
FIG. 1 is an SEM image of a prepared core-shell ZIF-9@ ZIF-8 composite material;
FIG. 2 is a Mapping diagram of a prepared core-shell ZIF-9@ ZIF-8 composite;
FIG. 3 is a zeta potential diagram of the prepared core-shell ZIF-9@ ZIF-8 composite material.
Detailed Description
Example 1
(1) Preparing a core-shell ZIF-9@ ZIF-8 composite material: respectively blending 0.70 g of zinc nitrate hexahydrate and 0.80 g of 2-methylimidazole with 50mL of methanol, performing ultrasonic treatment for 20 min, mixing the two solutions, and stirring at room temperature for 1 h to obtain a solution containing ZIF-8; gradually adding a solution containing ZIF-8 into 120 mL of methanol suspension containing 0.4 g of ZIF-9, performing ultrasonic treatment for 20 min, stirring for 2 h at room temperature, centrifuging for 5 min at the rotation speed of 8000 r/min, removing supernatant, and performing vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ ZIF-8 crystal with a ZIF-9 core and a ZIF-8 shell, namely a core-shell type ZIF-9@ ZIF-8 composite material;
(2) preparing an aptamer functionalized ZIF-9@ ZIF-8 composite material: weighing 0.1 mg of ZIF-9@ ZIF-8 composite material into a 50mL centrifuge tube, adding 30 mL of 0.02 mol/L phosphate buffer with pH =7.4 into the centrifuge tube, and then adding 0.5 ng/mL of adenosine aptamer into the centrifuge tube; shaking the centrifuge tube for 3 h, and then incubating for 24 h at 25 ℃ room temperature; and finally, centrifuging at the rotating speed of 8000 r/min for 10 min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ ZIF-8 composite material.
Example 2
(1) Preparing a core-shell ZIF-9@ ZIF-8 composite material: respectively blending 0.72 g of zinc nitrate hexahydrate and 0.82 g of 2-methylimidazole with 50mL of methanol, performing ultrasonic treatment for 25 min, mixing the two solutions, and stirring at room temperature for 1.5 h to obtain a solution containing ZIF-8; gradually adding a solution containing ZIF-8 into 120 mL of methanol suspension containing 0.50 g of ZIF-9, performing ultrasonic treatment for 25 min, stirring for 3 h at room temperature, centrifuging for 5 min at the rotation speed of 8000 r/min, removing supernatant, and performing vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ ZIF-8 crystal with a ZIF-9 core and a ZIF-8 shell, namely a core-shell type ZIF-9@ ZIF-8 composite material; (ii) a
(2) Preparing an aptamer functionalized ZIF-9@ ZIF-8 composite material: weighing 0.3 mg of the ZIF-9@ ZIF-8 composite material into a 50mL centrifuge tube, adding 30 mL of 0.02 mol/L phosphate buffer with pH =7.4 to the centrifuge tube, and then adding 0.7 ng/mL adenosine aptamer into the centrifuge tube; shaking the centrifugal tube for 4 h, and then hatching for 24 h at 25 ℃ room temperature; and finally, centrifuging at the rotating speed of 8000 r/min for 10 min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ ZIF-8 composite material.
Example 3
(1) Preparing a core-shell ZIF-9@ ZIF-8 composite material: respectively blending 0.78 g of zinc nitrate hexahydrate and 0.85 g of 2-methylimidazole with 50mL of methanol, performing ultrasonic treatment for 30 min, mixing the two solutions, and stirring at room temperature for 2 h to obtain a solution containing ZIF-8; gradually adding a solution containing ZIF-8 into 120 mL of methanol suspension containing 0.55 g of ZIF-9, performing ultrasonic treatment for 30 min, stirring for 4 h at room temperature, centrifuging for 5 min at the rotation speed of 8000 r/min, removing supernatant, and performing vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ ZIF-8 crystal with a ZIF-9 core and a ZIF-8 shell, namely a core-shell type ZIF-9@ ZIF-8 composite material;
(2) preparing an aptamer functionalized ZIF-9@ ZIF-8 composite material: weighing 0.5 mg of the ZIF-9@ ZIF-8 composite material into a 50mL centrifuge tube, adding 30 mL of 0.02 mol/L phosphate buffer with pH =7.4 to the centrifuge tube, and then adding 1 ng/mL adenosine aptamer into the centrifuge tube; shaking the centrifugal tube for 5 h, and then hatching for 24 h at 25 ℃ room temperature; and finally, centrifuging at the rotating speed of 8000 r/min for 10 min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ ZIF-8 composite material.
Example 4
The method for applying the aptamer functionalized ZIF-9@ ZIF-8 composite material to the chemiluminescence sensor for detecting adenosine comprises the following steps: the composite material is used together with a flow injection-chemiluminescence technology, the change of chemiluminescence intensity caused by different concentrations of adenosine is used for quantitatively detecting the adenosine, and the construction process of the chemiluminescence sensor is as follows:
(1) the saturated adsorption capacity of the core-shell ZIF-9@ ZIF-8 composite material on the aptamer is researched: accurately transferring 8 parts of 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, respectively putting the core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution into 50mL of colorimetric tubes, and adding 2.0362 multiplied by 10 concentrations with different volumes-8Determining chemiluminescence intensity of the solution in each colorimetric tube by using a flow injection-chemiluminescence apparatus, and calculating the saturated adsorption capacity of ZIF-9@ ZIF-8 to the aptamer according to the chemiluminescence intensity change value, the aptamer concentration and the volume thereofQ；
(2) The saturated adsorption time of the core-shell ZIF-9@ ZIF-8 composite material on the aptamer is researched: accurately transferring 8 parts of 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, respectively placing the core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution into 50mL of colorimetric tubes, and adding the known optimal saturated adsorption amount of 7.5 multiplied by 10-11Determining chemiluminescence intensity in colorimetric tubes with different adsorption times by using a flow injection-chemiluminescence apparatus for moll/L aptamer phosphate buffer solution, and obtaining the optimal adsorption time of ZIF-9@ ZIF-8 on the aptamer according to the chemiluminescence intensity change value and the different adsorption times;
(3) drawing a working curve: preparing a series of adenosine phosphate buffer solutions with standard concentration, adding 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, determining the chemiluminescence intensity of the adenosine with the standard concentration under the optimal experimental conditions, namely the optimal main and auxiliary pump speed and the optimal concentration of luminol, hydrogen peroxide and sodium hydroxide solution, and drawing a working curve by taking the concentration of the adenosine as a horizontal coordinate and the chemiluminescence intensity as a vertical coordinate;
(4) stability study: accurately transferring 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL into 11 colorimetric tubes with the concentration of 50mL, respectively, determining chemiluminescence intensity by using a flow injection-chemiluminescence apparatus under a sodium hydroxide-luminol-hydrogen peroxide chemiluminescence system, and detecting whether chemiluminescence values of 11 identical samples are stable;
(5) experimental study of free radicals: respectively transferring phenylhydrazine and thiourea with the concentration of 1 mg/mL and different volumes (2 mL, 3 mL and 4 mL) into 6 colorimetric tubes with the concentration of 1 mg/mL, adding luminol to perform constant volume at a 50mL scale line, preparing an independent luminol colorimetric tube for comparison, determining chemiluminescence intensity by using a flow injection-chemiluminescence apparatus, and detecting existence of superoxide radical and hydroxyl radical according to the chemiluminescence intensity value and the amount of the phenylhydrazine and thiourea;
(6) and (3) actual sample detection: under the best experimental conditions, detecting the adenosine content in human urine and carrying out a standard adding recovery experiment, accurately transferring 5.00 mL of human urine sample into a 10 mL centrifuge tube, centrifuging for 10 min at the rotating speed of 8000 r/min, accurately transferring 0.1 mL of supernatant, putting into a 50mL colorimetric tube for constant volume, and determining the adenosine content.
Application of aptamer functionalized core-shell ZIF-9@ ZIF-8 composite material in chemiluminescence sensor detection of adenosine to obtain core-shell ZIF-9@ ZIF-8 composite material with 7.5 multiplied by 10 of saturation fixation amount of aptamer-11moL/L; the best experimental conditions are as follows: the pump speed of a main pump is 35 r/min, the pump speed of an auxiliary pump is 25 r/min, 0.07 mol/L NaOH solution and 0.04 mol/L H2O2Solutions and 6.5X 10-5A mol/L luminol solution; linear equation of the working curve is ΔI=326.82+103.35lgc (R = 0.9982), linear range 1.5 × 10-12~2.5×10-10mol/L, detection limit of 5X 10-13mol/L; meanwhile, the anti-interference capability is strong; when the content of adenosine in human urine is detected, the recovery rate is 98.3-102.2%, and the relative standard deviation is in a small range, so that the determination method has high accuracy and precision, and provides possibility for application to actual sample detection.
Claims (6)
1. A preparation method of an aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ ZIF-8 composite material catalyst is characterized by comprising the following process steps:
(1) preparation of core-shell ZIF-9@ ZIF-8 composite material
Respectively blending 0.70-0.78 g of zinc nitrate hexahydrate and 0.80-0.85 g of 2-methylimidazole with 50mL of methanol, performing ultrasonic treatment for 20-30 min, mixing the two solutions, and stirring at room temperature for 1-2 h to obtain a solution containing ZIF-8; gradually adding a solution containing ZIF-8 into 120 mL of methanol suspension containing 0.4-0.55 g of ZIF-9, performing ultrasonic treatment for 20-30 min, stirring for 2-4 h at room temperature, centrifuging for 5 min at a rotation speed of 8000 r/min, removing supernatant, and performing vacuum drying at 80 ℃ to obtain a core-shell ZIF-9@ ZIF-8 crystal with a ZIF-9 core and a ZIF-8 shell, namely a core-shell ZIF-9@ ZIF-8 composite material;
(2) preparation of aptamer functionalized ZIF-9@ ZIF-8 composite material
Weighing 0.10-0.5 mg of ZIF-9@ ZIF-8 composite material into a 50mL centrifuge tube, adding 30 mL of 0.02 mol/L phosphate buffer solution with pH =7.4 into the centrifuge tube, and then adding 0.5-1 ng/mL adenosine aptamer into the centrifuge tube; vibrating the centrifugal tube for 3-5 h, and then incubating for 24 h at 25 ℃ room temperature; and finally, centrifuging at the rotating speed of 8000 r/min for 10 min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ ZIF-8 composite material.
2. The preparation method of the aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ ZIF-8 composite catalyst according to claim 1, wherein the ZIF-9 is prepared by the following steps:
respectively weighing 0.630 g of cobalt nitrate hexahydrate and 0.180 g of benzimidazole, putting the cobalt nitrate hexahydrate and the benzimidazole into 60 mL of N, N-dimethylformamide, stirring and dissolving, mixing the two solutions to obtain a pink solution, violently stirring the solution for 20 min, heating at 140 ℃, stirring and refluxing for 24 h, cooling to room temperature, continuously stirring for 48 h at room temperature, then centrifuging at the rotating speed of 8000 r/min for 10 min, and removing the supernatant; and finally, performing vacuum drying at 80 ℃ to obtain a purple crystal, namely ZIF-9.
3. The preparation method of the aptamer functionalized Zn-Co bimetal core-shell ZIF-9@ ZIF-8 composite catalyst as claimed in claim 1, wherein the step (1) of gradually adding the solution containing ZIF-8 into 120 mL of methanol suspension containing 0.4-0.55 g of ZIF-9 is to promote the generation of core-shell ZIF-9@ ZIF-8 crystals with ZIF-9 as a core and ZIF-8 as a shell.
4. The preparation method of the aptamer-functionalized Zn-Co bimetallic core-shell ZIF-9@ ZIF-8 composite catalyst as claimed in claim 1, wherein the aptamer-functionalized ZIF-9@ ZIF-8 composite material in the step (2) is a functionalized core-shell ZIF-9@ ZIF-8 composite material having high specificity recognition capability for adenosine molecules.
5. The application of the aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ ZIF-8 composite catalyst prepared by the preparation method according to claim 1 in detecting adenosine by a chemiluminescence sensor.
6. The use of a chemiluminescent sensor for detecting adenosine according to claim 6 wherein the chemiluminescent sensor is constructed using flow injection-chemiluminescence, comprising the steps of:
(1) determination of aptamer saturated adsorption capacity of core-shell ZIF-9@ ZIF-8 composite material
Accurately transferring 8 parts of 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, respectively putting the core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution into 50mL of colorimetric tubes, and adding 2.0362 multiplied by 10 concentrations with different volumes-8Determining each colorimetric cylinder by using a flow injection-chemiluminescence apparatus through an aptamer phosphate buffer solution of moL/LThe chemiluminescence intensity of the medium solution can be calculated according to the chemiluminescence intensity change value, the aptamer concentration and the volume thereof, and the saturated adsorption capacity of the ZIF-9@ ZIF-8 to the aptamer can be calculatedQ；
(2) Determination of aptamer saturation adsorption time by core-shell ZIF-9@ ZIF-8 composite material
Accurately transferring 8 parts of 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, respectively placing the core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution into 50mL of colorimetric tubes, and adding the known optimal saturated adsorption amount of 7.5 multiplied by 10-11Determining chemiluminescence intensity in colorimetric tubes with different adsorption times by using a flow injection-chemiluminescence apparatus for moll/L aptamer phosphate buffer solution, and obtaining the optimal adsorption time of ZIF-9@ ZIF-8 on the aptamer according to the chemiluminescence intensity change value and the different adsorption times;
(3) drawing working curve
Preparing a series of adenosine phosphate buffer solutions with standard concentration, adding 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL, determining the chemiluminescence intensity of the adenosine with the standard concentration under the optimal experimental conditions, namely the optimal main and auxiliary pump speed and the optimal concentration of luminol, hydrogen peroxide and sodium hydroxide solution, and drawing a working curve by taking the concentration of the adenosine as a horizontal coordinate and the chemiluminescence intensity as a vertical coordinate;
(4) stability study
Accurately transferring 0.7 mL of core-shell ZIF-9@ ZIF-8 composite material phosphate buffer solution with the concentration of 0.1 mg/mL into 11 colorimetric tubes with the concentration of 50mL, respectively, determining chemiluminescence intensity by using a flow injection-chemiluminescence apparatus under a sodium hydroxide-luminol-hydrogen peroxide chemiluminescence system, and detecting whether chemiluminescence values of 11 identical samples are stable;
(5) experimental study of free radicals
Respectively transferring phenylhydrazine and thiourea with the concentration of 1 mg/mL and different volumes (2 mL, 3 mL and 4 mL) into 6 colorimetric tubes with the concentration of 1 mg/mL, adding luminol to perform constant volume at a 50mL scale line, preparing an independent luminol colorimetric tube for comparison, determining chemiluminescence intensity by using a flow injection-chemiluminescence apparatus, and detecting existence of superoxide radical and hydroxyl radical according to the chemiluminescence intensity value and the amount of the phenylhydrazine and thiourea;
(6) actual sample detection
Under the best experimental conditions, detecting the adenosine content in human urine and carrying out a standard adding recovery experiment, accurately transferring 5.00 mL of human urine sample into a 10 mL centrifuge tube, centrifuging for 10 min at the rotating speed of 8000 r/min, accurately transferring 0.1 mL of supernatant, putting into a 50mL colorimetric tube for constant volume, and determining the adenosine content.
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