CN114047178B - Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material - Google Patents
Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material Download PDFInfo
- Publication number
- CN114047178B CN114047178B CN202111292148.3A CN202111292148A CN114047178B CN 114047178 B CN114047178 B CN 114047178B CN 202111292148 A CN202111292148 A CN 202111292148A CN 114047178 B CN114047178 B CN 114047178B
- Authority
- CN
- China
- Prior art keywords
- zif
- composite material
- core
- shell
- aptamer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 239000011258 core-shell material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910007564 Zn—Co Inorganic materials 0.000 title claims abstract description 8
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 claims abstract description 96
- 108091023037 Aptamer Proteins 0.000 claims abstract description 48
- 239000002126 C01EB10 - Adenosine Substances 0.000 claims abstract description 48
- 229960005305 adenosine Drugs 0.000 claims abstract description 48
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 210000002700 urine Anatomy 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 18
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 18
- 239000008055 phosphate buffer solution Substances 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 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
- 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
- 229920006395 saturated elastomer Polymers 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940067157 phenylhydrazine Drugs 0.000 claims description 5
- -1 superoxide radicals Chemical class 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 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
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical compound 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
- 229950006790 adenosine phosphate Drugs 0.000 claims description 2
- 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 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000008363 phosphate buffer Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 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
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002965 ELISA Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000004614 tumor growth Effects 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a preparation method of a Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material catalyst and an application technology thereof in a chemiluminescent sensor, and is mainly technically characterized in that: the preparation method comprises the steps of preparing a core-shell ZIF-9@ZIF-8 composite material, and modifying an aptamer on the surface of the composite material to obtain a core-shell ZIF-9@ZIF-8 composite material catalyst with high specific recognition capability on adenosine molecules, wherein 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, which applies the aptamer functionalized ZIF-9@ZIF-8 composite material to the detection of adenosine by using a chemiluminescent sensor, has the advantages of high sensitivity, good selectivity, convenient operation, simple instrument and the like, is successfully used for detecting adenosine in human urine samples, shows high accuracy and precision, provides possibility for application to actual 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 material catalyst and an application technology thereof in a chemiluminescent 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 material and an application thereof in detecting adenosine in the chemiluminescent sensor.
Background
Metal-organic framework (MOFs) materials are emerging metal-organic materials, which are usually 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 usually organic carboxylic acids and nitrogen-containing heterocyclic compounds, the ZIFs material is used as one of the MOFs materials, and has higher catalytic performance and chemical stability, and the metal-organic framework materials usually have wider application range in the catalytic field than other nano materials due to the unique physical and chemical properties, and the number of special structures is quite remarkable, so that the potential application prospect is very wide, wherein the effect in chemical catalysis is particularly prominent.
Adenosine plays an important role in signal expression of central nervous system and peripheral nervous system, so that researches are widely focused by researchers, and researches show that rapid growth of solid tumor cells can cause hypoxia and necrosis of the solid tumor cells, a large amount of adenosine is released, environment is provided for rapid growth of tumors, and thus higher concentration of adenosine is accumulated in the solid tumors, adenosine level in urine reflects degradation level of adenosine in human bodies, so that selectivity and sensitivity detection of adenosine are of great significance, and at present, methods for detecting adenosine such as electrochemical sensors, enzyme-linked immunosorbent assay, photoelectric sensors and fluorescent sensors exist, but the methods have respective problems such as poor reproducibility, complex operation, high price of enzyme-linked immunosorbent assay and the like, and therefore, a method for detecting adenosine with high sensitivity and high selectivity is urgently needed to be established.
The flow injection-chemiluminescence technology integrates the advantages of flow injection, such as autoinjection, 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 disadvantage, such as poor selectivity, because various coexisting substances are extremely easy to cause the change of chemiluminescence intensity, and the disadvantage can be overcome by introducing specific recognition materials, such as a molecularly imprinted material, an antigen-antibody material, an aptamer material and the like.
In the patent, a core-shell type ZIF-9@ZIF-8 composite material is prepared, and an adenosine aptamer is modified on the surface of the core-shell type ZIF-9@ZIF-8 composite material to obtain a functionalized core-shell type ZIF-9@ZIF-8 composite material which is easy to separate, excellent in fixing performance and high in specific recognition capability, and the functionalized core-shell type ZIF-9@ZIF-8 composite material is used together with a flow injection-chemiluminescence technology, so that a chemiluminescent sensor for detecting adenosine with high sensitivity and high selectivity is constructed, and a novel method for detecting adenosine with simplicity, high sensitivity and good selectivity is invented.
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 mainly prepares a core-shell ZIF-9@ZIF-8 composite material, and modifies an aptamer on the surface of the catalyst to obtain the functionalized core-shell ZIF-9@ZIF-8 composite material with high specific recognition capability on adenosine.
The invention is realized by the following technical scheme:
(1) Preparation of a core-shell ZIF-9@ZIF-8 composite material: mixing 0.70-0.78 g of zinc nitrate hexahydrate and 0.80-0.85 g of 2-methylimidazole with 50mL of methanol respectively, carrying out ultrasonic treatment for 20-30 min, mixing the two solutions, and stirring at room temperature for 1-2 h to obtain a ZIF-8-containing solution; gradually adding the ZIF-8-containing solution into 120mL methanol suspension containing 0.4-0.55 g of ZIF-9, carrying out ultrasonic treatment for 20-30 min, stirring at room temperature for 2-4 h, centrifuging at a rotating speed of 8000r/min for 5min, removing the supernatant, and carrying out vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ZIF-8 crystal with the ZIF-9 as a core and the ZIF-8 as a shell, namely the core-shell type ZIF-9@ZIF-8 composite material;
(2) Preparation of 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 30mL of 0.02mol/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 centrifuge tube for 3-5 h, and then incubating at the room temperature of 25 ℃ for 24-h; finally centrifuging for 10min at a rotating speed of 8000r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ZIF-8 composite material;
the preparation method of ZIF-9 comprises the following steps: respectively weighing 0.630g cobalt nitrate hexahydrate and 0.180g benzimidazole, putting into 60mL of N, N-dimethylformamide, stirring and dissolving, mixing the two solutions to obtain a pink solution, vigorously stirring the solutions for 20min, heating and stirring at 140 ℃ and refluxing for 24h, cooling to room temperature, continuously stirring at room temperature for 48h, centrifuging at 8000r/min for 10min, and removing supernatant; finally, vacuum drying is carried out at the temperature of 80 ℃ to obtain purple crystals, namely ZIF-9.
The invention further aims to apply the aptamer functionalized core-shell ZIF-9@ZIF-8 composite material to a chemiluminescent sensor for detecting adenosine, and when the adenosine exists, the adenosine molecules and the aptamer thereof are specifically identified and combined together, so that a composite material catalyst is released, the released composite material catalyst catalyzes a luminol-hydrogen peroxide chemiluminescent system to cause the change of chemiluminescent intensity, and the detection of the adenosine is realized; the chemiluminescent chemical sensor is characterized in that the detection of adenosine is as follows: the method has the advantages of high sensitivity, good selectivity, convenient operation and simple instrument, and in the construction of the chemiluminescent chemical sensor, the immobilization performance of the synthetic material is researched, the chemiluminescent conditions are optimized, the working curve is drawn, the anti-interference capability is researched, and the method is finally used for detecting the adenosine in the human urine sample.
The invention has the advantages and effects that:
(1) The invention prepares the core-shell ZIF-9@ZIF-8 composite material, connects ZIF-9 and ZIF-8 together through hydrothermal reaction, prepares the core-shell ZIF-9@ZIF-8 composite material through vacuum drying, has the advantages of large specific surface area, abundant active sites and the like, provides a large number of action sites for the aptamer, and ensures that the saturation fixation amount of the core-shell ZIF-9@ZIF-8 composite material to the adenosine aptamer is 7.5x10 -11 mol/L；
(2) The preparation method prepares the aptamer functionalized core-shell ZIF-9@ZIF-8 composite material, has simple preparation process and easily controlled conditions, and can obviously improve the specific recognition capability of the composite material;
(3) The aptamer functionalized core-shell ZIF-9@ZIF-8 composite material prepared by the invention is applied to a chemiluminescent sensor for detecting adenosine, the sensor for detecting adenosine shows a wide linear range and a low detection limit, and the sensor for detecting adenosine in a human urine sample shows high accuracy and precision, provides possibility for application to actual detection, and 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 graph of the prepared core-shell ZIF-9@ZIF-8 composite material;
FIG. 3 is a Zeta potential diagram of the prepared core-shell ZIF-9@ZIF-8 composite material.
Detailed Description
Example 1
(1) Preparation of a core-shell ZIF-9@ZIF-8 composite material: mixing 0.70 g zinc nitrate hexahydrate and 0.80 g 2-methylimidazole with 50mL methanol respectively, performing ultrasonic treatment for 20min, mixing the two solutions, and stirring at room temperature for 1 h to obtain ZIF-8-containing solution; gradually adding the ZIF-8-containing solution into 120mL methanol suspension containing 0.4 g of ZIF-9, carrying out ultrasonic treatment for 20min, stirring for 2h at room temperature, centrifuging for 5min at a rotation speed of 8000r/min, removing supernatant, and vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ZIF-8 crystal with the ZIF-9 as a core and the ZIF-8 as a shell, namely a core-shell type ZIF-9@ZIF-8 composite material;
(2) Preparation of an aptamer functionalized ZIF-9@ZIF-8 composite material: weighing 0.1mg of ZIF-9@ZIF-8 composite material into a 50mL centrifuge tube, adding 30mL of 0.02mol/L phosphate buffer solution with pH=7.4 into the centrifuge tube, and adding 0.5 ng/mL adenosine aptamer into the centrifuge tube; vibrating the centrifuge tube for 3 h, and then incubating for 24h at the room temperature of 25 ℃; and finally centrifuging for 10min at a rotating speed of 8000r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ZIF-8 composite material.
Example 2
(1) Preparation of a core-shell ZIF-9@ZIF-8 composite material: mixing 0.72 g zinc nitrate hexahydrate and 0.82 g 2-methylimidazole with 50mL methanol respectively, performing ultrasonic treatment for 25 min, mixing the two solutions, and stirring at room temperature for 1.5 h to obtain ZIF-8-containing solution; gradually adding the ZIF-8-containing solution into 120mL methanol suspension containing 0.50 g of ZIF-9, carrying out ultrasonic treatment for 25 min, stirring for 3 h at room temperature, centrifuging for 5min at a rotation speed of 8000r/min, removing supernatant, and vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ZIF-8 crystal with the ZIF-9 as a core and the ZIF-8 as a shell, namely a core-shell type ZIF-9@ZIF-8 composite material; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Preparation of an aptamer functionalized ZIF-9@ZIF-8 composite material: weighing 0.3 mg of ZIF-9@ZIF-8 composite material into a 50mL centrifuge tube, adding 30mL of 0.02mol/L phosphate buffer solution with pH=7.4 into the centrifuge tube, and adding 0.7 ng/mL adenosine aptamer into the centrifuge tube; vibrating the centrifuge tube to 4h, and then incubating at the temperature of 25 ℃ for 24h; and finally centrifuging for 10min at a rotating speed of 8000r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ZIF-8 composite material.
Example 3
(1) Preparation of a core-shell ZIF-9@ZIF-8 composite material: mixing 0.78g zinc nitrate hexahydrate and 0.85g 2-methylimidazole with 50mL methanol respectively, performing ultrasonic treatment for 30min, mixing the two solutions, and stirring at room temperature for 2h to obtain ZIF-8-containing solution; gradually adding the ZIF-8-containing solution into 120mL methanol suspension containing 0.55g of ZIF-9, carrying out ultrasonic treatment for 30min, stirring for 4h at room temperature, centrifuging for 5min at a rotation speed of 8000r/min, removing supernatant, and vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ZIF-8 crystal with the ZIF-9 as a core and the ZIF-8 as a shell, namely a core-shell type ZIF-9@ZIF-8 composite material;
(2) Preparation of an aptamer functionalized ZIF-9@ZIF-8 composite material: weighing 0.5mg of ZIF-9@ZIF-8 composite material into a 50mL centrifuge tube, adding 30mL of 0.02mol/L phosphate buffer solution with pH=7.4 into the centrifuge tube, and adding 1ng/mL adenosine aptamer into the centrifuge tube; vibrating the centrifuge tube for 5h, and then incubating for 24h at the room temperature of 25 ℃; and finally centrifuging for 10min at a rotating speed of 8000r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ZIF-8 composite material.
Example 4
The method for detecting adenosine by using the aptamer functionalized ZIF-9@ZIF-8 composite material in a chemiluminescent sensor comprises the following steps: the composite material is used together with a flow injection-chemiluminescence technology, and the change of chemiluminescence intensity caused by adenosine with different concentrations is used for quantitatively detecting the adenosine, and the chemiluminescent sensor is constructed as follows:
(1) Core-shell ZIF-9@ZIF-8 composite material pairSaturated adsorption amount study of aptamer: accurately transferring 8 parts of 0.7-mL core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, respectively placing into 50mL colorimetric tubes, and adding 2.0362 ×10 solutions with different volumes -8 The MOL/L aptamer phosphate buffer solution is used for measuring the chemiluminescence intensity of the solution in each colorimetric tube by using a flow injection-chemiluminescence instrument, and the saturated adsorption quantity of ZIF-9@ZIF-8 to the aptamer can be calculated according to the chemiluminescence intensity change value, the aptamer concentration and the volume thereofQ；
(2) Saturated adsorption time study of core-shell ZIF-9@ZIF-8 composite material on aptamer: accurately transferring 8 parts of 0.7. 0.7mL core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, respectively placing into 50mL colorimetric tubes, and adding a known optimal saturated adsorption quantity of 7.5X10 -11 The optimal adsorption time of ZIF-9@ZIF-8 to the aptamer can be obtained according to the variation value of the chemiluminescence intensity and the difference of the adsorption time by measuring the chemiluminescence intensity in the colorimetric tubes with different adsorption times by using a flow injection-chemiluminescence instrument;
(3) Drawing a working curve: preparing a series of standard concentration adenosine phosphate buffer solutions, adding 0.7mL core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, measuring the chemiluminescence intensity of the adenosine with the standard concentration under the optimal experimental conditions, namely the optimal main and auxiliary pump speeds 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 an abscissa and the chemiluminescence intensity as an ordinate;
(4) Stability study: accurately transferring 0.7mL core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, respectively placing the core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution into 11 colorimetric tubes of 50mL, measuring the chemiluminescence intensity by using a flow injection-chemiluminescence instrument under a chemiluminescence system of sodium hydroxide-luminol-hydrogen peroxide, and detecting whether the chemiluminescence values of 11 identical samples are stable;
(5) Free radical experimental study: respectively transferring phenylhydrazine and thiourea with the concentration of 1mg/mL and different volumes (2 mL, 3mL and 4 mL) into 6 50mL colorimetric tubes, adding luminol to fix the volume at a 50mL scale mark, preparing an independent luminol colorimetric tube as a control, measuring the chemiluminescence intensity by using a flow injection-chemiluminescence instrument, and detecting the existence of superoxide radicals and hydroxyl radicals according to the chemiluminescence intensity value and the added phenylhydrazine and thiourea;
(6) And (3) detecting an actual sample: under the optimal experimental conditions, the adenosine content in human urine is detected, a standard adding and recycling experiment is carried out, a urine sample of 5.00mL people is accurately removed and placed into a 10mL centrifuge tube, the sample is centrifuged for 10min at the rotating speed of 8000r/min, a supernatant of 0.1mL is accurately removed and placed into a 50mL colorimetric tube for constant volume, and the adenosine content in the sample is measured.
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 saturation fixation amount of 7.5X10 to aptamer -11 mols/L; the optimal experimental conditions are as follows: 35 r/min main pump speed, 25 r/min auxiliary pump speed, 0.07 mol/L NaOH solution, 0.04 mol/L H 2 O 2 Solution and 6.5X10 -5 A mol/L luminol solution; the linear equation of the working curve is deltaI=326.82+103.35 lgc (r=0.9982), linear range 1.5×10 -12 ~2.5×10 -10 mol/L, detection limit of 5X 10 -13 mol/L; meanwhile, the anti-interference capability is strong; the recovery rate is 98.3% -102.2% when the detection of the adenosine content in human urine is carried out, and the relative standard deviation is in a smaller range, so that the detection method has higher accuracy and precision, and provides possibility for application to actual sample detection.
Claims (5)
1. The preparation method of the aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material is characterized by comprising the following steps of:
(1) Preparation of ZIF-9
Respectively weighing 0.630g of cobalt nitrate hexahydrate and 0.180g of benzimidazole, putting into 60mL of N, N-dimethylformamide, stirring and dissolving, mixing the two solutions to obtain a pink solution, vigorously stirring the solutions for 20min, heating, stirring and refluxing at 140 ℃ for 24h, cooling to room temperature, continuously stirring at room temperature for 48h, centrifuging at 8000r/min for 10min, and removing supernatant; finally, vacuum drying is carried out at 80 ℃ to obtain purple crystals, namely ZIF-9;
(2) Preparation of core-shell ZIF-9@ZIF-8 composite material
Mixing 0.70-0.78 g of zinc nitrate hexahydrate and 0.80-0.85 g of 2-methylimidazole with 50mL of methanol respectively, carrying out ultrasonic treatment for 20-30 min, mixing the two solutions, and stirring at room temperature for 1-2 h to obtain a ZIF-8-containing solution; gradually adding the ZIF-8-containing solution into 120mL of methanol suspension containing 0.4-0.55 g of ZIF-9, carrying out ultrasonic treatment for 20-30 min, stirring at room temperature for 2-4 h, centrifuging at 8000r/min for 5min, removing supernatant, and vacuum drying at 80 ℃ to obtain a core-shell type ZIF-9@ZIF-8 crystal with the ZIF-9 as a core and the ZIF-8 as a shell, namely the core-shell type ZIF-9@ZIF-8 composite material;
(3) Preparation of aptamer functionalized ZIF-9@ZIF-8 composite material
Weighing 0.10-0.5 mg ZIF-9@ZIF-8 composite material in a 50mL centrifuge tube, adding 30mL of 0.02mol/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 centrifuge tube for 3-5 h, and then incubating for 24h at the room temperature of 25 ℃; and finally, centrifuging for 10min at a rotating speed of 8000r/min, and removing supernatant to obtain the aptamer functionalized ZIF-9@ZIF-8 composite material.
2. The method for preparing the aptamer functionalized Zn-Co bimetallic core-shell type ZIF-9@ZIF-8 composite material according to claim 1, wherein in the step (1), the ZIF-8-containing solution is gradually added into 120mL of methanol suspension containing 0.4-0.55 g of ZIF-9, so as to promote the generation of core-shell type ZIF-9@ZIF-8 crystals with the ZIF-9 as a core and the ZIF-8 as a shell.
3. The preparation method of the aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material according to 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 with high specific recognition capability on adenosine molecules.
4. The application of the aptamer functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material prepared by the preparation method according to claim 1 in detection of adenosine by a chemiluminescent sensor.
5. The use of claim 4 for detecting adenosine by chemiluminescent sensor, wherein the chemiluminescent sensor is constructed by flow injection-chemiluminescent method comprising the steps of:
(1) Determination of aptamer saturated adsorption quantity by core-shell ZIF-9@ZIF-8 composite material
Accurately transferring 8 parts of 0.7mL of core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, respectively placing into 50mL colorimetric tubes, and adding 2.0362 ×10 solutions with different volumes -8 The MOL/L aptamer phosphate buffer solution is used for measuring the chemiluminescence intensity of the solution in each colorimetric tube by using a flow injection-chemiluminescence instrument, and the saturated adsorption quantity Q of ZIF-9@ZIF-8 to the aptamer can be calculated according to the chemiluminescence intensity change value, the aptamer concentration and the volume thereof;
(2) Determination of aptamer saturation adsorption time by core-shell ZIF-9@ZIF-8 composite material
Accurately transferring 8 parts of 0.7mL of core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, respectively placing into 50mL colorimetric tubes, and adding a known optimal saturated adsorption quantity of 7.5X10 -11 The optimal adsorption time of ZIF-9@ZIF-8 to the aptamer can be obtained according to the variation value of the chemiluminescence intensity and the difference of the adsorption time by measuring the chemiluminescence intensity in the colorimetric tubes with different adsorption times by using a flow injection-chemiluminescence instrument;
(3) Working curve drawing
Preparing a series of standard concentration adenosine phosphate buffer solutions, adding 0.7mL of core-shell type ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL, measuring the chemiluminescence intensity of the adenosine with the standard concentration under the optimal experimental conditions, namely the optimal main and auxiliary pump speeds 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 an abscissa and the chemiluminescence intensity as an ordinate;
(4) Stability study
Accurately transferring 0.7mL of core-shell ZIF-9@ZIF-8 composite material phosphate buffer solution with the concentration of 0.1mg/mL into 11 colorimetric tubes with the concentration of 50mL, respectively, measuring the chemiluminescence intensity by using a flow injection-chemiluminescence instrument under a chemiluminescence system of sodium hydroxide-luminol-hydrogen peroxide, and detecting whether the chemiluminescence values of 11 identical samples are stable;
(5) Free radical experimental study
Respectively transferring phenylhydrazine and thiourea with the concentration of 1mg/mL and the volumes of 2mL, 3mL and 4mL respectively, putting the phenylhydrazine and thiourea into 6 50mL colorimetric tubes, adding luminol to the positions of 50mL graduation marks for constant volume, preparing an independent luminol colorimetric tube as a contrast, measuring the chemiluminescence intensity by using a flow injection-chemiluminescence instrument, and detecting the existence of superoxide radicals and hydroxyl radicals according to the chemiluminescence intensity value and the added phenylhydrazine and thiourea;
(6) Actual sample detection
Under the optimal experimental conditions, the adenosine content in human urine is detected, a standard adding and recycling experiment is carried out, 5.00mL of human urine sample is accurately removed and placed into a 10mL centrifuge tube, the centrifuge tube is centrifuged for 10min at the rotating speed of 8000r/min, 0.1mL of supernatant is accurately removed and placed into a 50mL colorimetric tube for constant volume, and the adenosine content in the supernatant is measured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111292148.3A CN114047178B (en) | 2021-11-03 | 2021-11-03 | Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111292148.3A CN114047178B (en) | 2021-11-03 | 2021-11-03 | Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114047178A CN114047178A (en) | 2022-02-15 |
| CN114047178B true CN114047178B (en) | 2023-12-22 |
Family
ID=80206959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111292148.3A Active CN114047178B (en) | 2021-11-03 | 2021-11-03 | Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114047178B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007211A (en) * | 2022-05-05 | 2022-09-06 | 济南大学 | Preparation and application of aptamer functionalized magnetic bead/Au @ ZIF-67-ssDNA composite material |
| CN115201310A (en) * | 2022-09-16 | 2022-10-18 | 湖南大学 | Method for detecting trace disinfection byproducts in water body |
| CN116754348B (en) * | 2023-06-06 | 2024-03-08 | 华北理工大学 | ZIF-8-90 material-based effervescent tablet, preparation method and application thereof |
| CN116632219B (en) * | 2023-07-19 | 2023-10-24 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076427A1 (en) * | 2016-10-31 | 2018-05-03 | 内蒙古天奇中蒙制药股份有限公司 | Method for detecting gallic acid in zhachong pills containing thirteen kinds of traditional chinese medicine ingredients |
| CN109553797A (en) * | 2018-11-13 | 2019-04-02 | 济南大学 | A kind of preparation and its Application in Sensing of functionalization three-dimensional graphene composite material |
| CN110441294A (en) * | 2019-08-26 | 2019-11-12 | 济南大学 | One kind wrapping up Co based on ferritin3O4The preparation method of the biosensor of core-shell structure |
| CN111562255A (en) * | 2020-05-27 | 2020-08-21 | 济南大学 | Preparation method of chemiluminescence sensor based on reduced graphene oxide quenching luminol @ gold nanoparticles |
| WO2020228291A1 (en) * | 2019-05-14 | 2020-11-19 | 大连理工大学 | Immobilised enzyme method for improving the stability of horseradish peroxidase, and application therefor |
| CN113109406A (en) * | 2021-04-19 | 2021-07-13 | 江苏大学 | Method for constructing electrochemiluminescence aptamer sensor for omethoate detection |
-
2021
- 2021-11-03 CN CN202111292148.3A patent/CN114047178B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076427A1 (en) * | 2016-10-31 | 2018-05-03 | 内蒙古天奇中蒙制药股份有限公司 | Method for detecting gallic acid in zhachong pills containing thirteen kinds of traditional chinese medicine ingredients |
| CN109553797A (en) * | 2018-11-13 | 2019-04-02 | 济南大学 | A kind of preparation and its Application in Sensing of functionalization three-dimensional graphene composite material |
| WO2020228291A1 (en) * | 2019-05-14 | 2020-11-19 | 大连理工大学 | Immobilised enzyme method for improving the stability of horseradish peroxidase, and application therefor |
| CN110441294A (en) * | 2019-08-26 | 2019-11-12 | 济南大学 | One kind wrapping up Co based on ferritin3O4The preparation method of the biosensor of core-shell structure |
| CN111562255A (en) * | 2020-05-27 | 2020-08-21 | 济南大学 | Preparation method of chemiluminescence sensor based on reduced graphene oxide quenching luminol @ gold nanoparticles |
| CN113109406A (en) * | 2021-04-19 | 2021-07-13 | 江苏大学 | Method for constructing electrochemiluminescence aptamer sensor for omethoate detection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114047178A (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114047178B (en) | Preparation and application of functionalized Zn-Co bimetallic core-shell ZIF-9@ZIF-8 composite material | |
| Zhang et al. | DNAzyme-triggered visual and ratiometric electrochemiluminescence dual-readout assay for Pb (II) based on an assembled paper device | |
| An et al. | A novel molecularly imprinted electrochemical sensor based on Prussian blue analogue generated by iron metal organic frameworks for highly sensitive detection of melamine | |
| CN109696430B (en) | Method for measuring concentration of microcystin | |
| Sun et al. | based electrochemical immunosensor for carcinoembryonic antigen based on three dimensional flower-like gold electrode and gold-silver bimetallic nanoparticles | |
| WO2011022921A1 (en) | Reactor-type rapid measuring instrument for biochemical oxygen demand (bod) and measurement method thereof | |
| Wu et al. | Accelerating peroxidase-like activity of gold nanozymes using purine derivatives and its application for monitoring of occult blood in urine | |
| CN110987843B (en) | Phosphate radical colorimetric detection method based on bimetallic MOF nano-oxidase | |
| CN103616361A (en) | Fluorescent glucose nano biosensor and preparation method thereof | |
| CN106525943A (en) | Construction method and application of surface protein-embossed self-energized biological fuel cell sensor | |
| Xing et al. | Triple-enzyme mimetic activity of Fe 3 O 4@ C@ MnO 2 composites derived from metal–organic frameworks and their application to colorimetric biosensing of dopamine | |
| Chen et al. | An eco-friendly near infrared fluorescence molecularly imprinted sensor based on zeolite imidazolate framework-8 for rapid determination of trace trypsin | |
| Asghar et al. | Real-time and online monitoring of glucose contents by using molecular imprinted polymer-based IDEs sensor | |
| CN107727720A (en) | HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared | |
| CN109651249A (en) | A kind of fluorescence probe detecting endocytoplasmic reticulum cysteine and its synthesis and application | |
| CN106370634A (en) | Application of CdTe QD@ZIF-8 core-shell nano composite material in detection of oxidase activity | |
| CN104122215A (en) | Preparation and application of regenerable photometry probe | |
| Ni et al. | Research progress of sensors based on molecularly imprinted polymers in analytical and biomedical analysis | |
| Li et al. | Biomimetic enzyme MOF-NADH-mediated and 3, 3′, 5, 5′-tetramethylbenzidine-based colorimetric assay for formaldehyde detection | |
| CN110568050B (en) | Preparation method of enzyme-free catalytic hydrogen peroxide electrochemical sensor based on flexible electrode | |
| CN100489496C (en) | Method for measuring sludge dehydrogenase activity | |
| CN104020169A (en) | Chemical detection method for dissolved organic matters in organic fertilizer | |
| Ouyang et al. | A Simple and Sensitive Nanocatalytic Fluorescence Method for the Determination of Folic Acid in Foods Using Fe 3 O 4 Nanoparticle-K 2 S 2 O 8 System | |
| CN109030599B (en) | Preparation method of glucose oxidase sensor and detection of glucose by glucose oxidase sensor | |
| CN103185737B (en) | Method for detecting lead ion in water sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |