CN116445156A - Hybrid nanocomposite Zn-BTEC@ZIF-8, preparation method thereof, fluorescent probe and detection method - Google Patents
Hybrid nanocomposite Zn-BTEC@ZIF-8, preparation method thereof, fluorescent probe and detection method Download PDFInfo
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- CN116445156A CN116445156A CN202310229822.6A CN202310229822A CN116445156A CN 116445156 A CN116445156 A CN 116445156A CN 202310229822 A CN202310229822 A CN 202310229822A CN 116445156 A CN116445156 A CN 116445156A
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- histamine
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 55
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 49
- 238000001514 detection method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 69
- 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 abstract description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 26
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 230000001788 irregular Effects 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007822 coupling agent Substances 0.000 claims abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 4
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 claims description 255
- 229960001340 histamine Drugs 0.000 claims description 128
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 55
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000005284 excitation Effects 0.000 claims description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
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- 238000004458 analytical method Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 125000002883 imidazolyl group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-Histidine Natural products OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 229960002885 histidine Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
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- 238000002411 thermogravimetry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004098 Tetracycline Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
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- 150000003522 tetracyclines Chemical class 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- 241001089723 Metaphycus omega Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- NZBSAAMEZYOGBA-UHFFFAOYSA-N luminogren Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=CC3=CC=CC1=C23 NZBSAAMEZYOGBA-UHFFFAOYSA-N 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
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- 235000020989 red meat Nutrition 0.000 description 1
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- 235000014102 seafood Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention discloses a hybrid nanocomposite Zn-BTEC@ZIF-8, a preparation method thereof, a fluorescent probe and a detection method, wherein the Zn-BTEC@ZIF-8 is formed by coupling ZIF-8 on the surface of Zn-BTEC; the Zn-BTEC particles are in the shape of irregular blocks with smooth surfaces, the particle size range is 1-9 microns, the ZIF-8 particles are in the shape of regular polyhedrons, and the particle size range is 220-280 nanometers; the number of the faces of the regular polyhedron is not less than 6; zn-BTEC and ZIF-8 are formed by the coordination of organic ligands and metal ions; the organic ligand is at least one of pyromellitic acid, N-dimethylformamide and 2-methylimidazole; the metal ions are derived from oxides and/or zinc salts of zinc; the coupling agent used for coupling is at least one selected from polyvinylpyrrolidone and polyvinyl alcohol; the zinc salt is at least one selected from zinc nitrate, zinc sulfate and zinc chloride. The hybrid nanocomposite Zn-BTEC@ZIF-8 is coupled with ZIF-8 to form a stable structure on the surface of Zn-BTEC, has regular morphology, and shows excellent selectivity and sensitivity in sensing compared with single Zn-BTEC and ZIF-8.
Description
Technical Field
The invention relates to the field of fluorescence detection, in particular to a hybrid nanocomposite Zn-BTEC@ZIF-8, a preparation method thereof, a fluorescent probe and a detection method.
Background
Histamine (Histamine) is a heterocyclic biogenic amine formed by decarboxylation of L-histidine amino acids. In foods with high protein content, especially in some fish with green skin and red meat and products thereof, the fish contains a large amount of histidine, and if the fish is stored for a long time or is not stored properly, the fish is easy to be decomposed to generate histamine, so that the level of the histamine is closely related to the freshness of the fish, and the fish can be used as an important index for evaluating the freshness of the food. Histamine is considered by the world health organization as an important cause in the judgment of many food poisoning events. The His limit in fish and fish products is specified by many countries and organizations. For example, china (GB 2733-2015) and Turkish both specify that the limit of histamine in fish should be less than 200mgkg -1 . European, iran, indonesia and Brazil require that the histamine content in fish should not exceed 100mg kg -1 . The U.S. Food and Drug Administration (FDA) has imposed stricter limits on histamine in fish, not exceeding 50mgkg -1 。
Since exceeding histamine levels in foods does not affect the organoleptic properties of the food, a rapid quantitative determination of histamine in foods is highly desirable. The current standard detection methods of histamine mainly comprise capillary electrophoresis, gas chromatography, high Performance Liquid Chromatography (HPLC), enzyme-linked immunosorbent assay (ELISA) and the like. However, these methods generally have problems of complicated sample preparation, expensive instruments, long detection time, and the like.
Currently, optical biosensor platforms are of great interest. There are a wide variety of optical biosensors based on absorbance, photoluminescence, surface Enhanced Raman Spectroscopy (SERS), and fluorescence. As one of the most popular strategies, fluorescence sensors can obtain selectivity through a specific reaction process or functional group, overcome the difficult problems of complex detection environments, and the like, and a plurality of fluorescence probes have been used for rapidly detecting histamine in foods at present. For example, the fluorescent activity of graphite-phase carbon nitride (g-C3N 4) is used for rapidly detecting histamine in fish, and Carbon Quantum Dots (CQDs) and synthetic polypeptides are utilized to effectively quench fluorescence of the carbon quantum dots through electron transfer interaction by the polypeptides, so that the fluorescence can be recovered due to stronger interaction between the peptides and targets in the presence of histamine.
The use of fluorescent nanomaterials can provide a better development environment for fluorescent sensors. However, these rapid detection methods require complex fluorescent probe composition and preparation techniques. Therefore, it is desirable to develop a simple, low cost, rapid method for detecting histamine in an aquatic product. The metal organic framework material is a porous crystal material with wide application prospect, can be prepared by combining different organic ligands and metal ions, and the hybridized functional material can enable the porous crystal material to show better stability, selectivity and sensitivity in the histamine detection process. Some multi-emissive metal-organic framework Materials (MOFs) recognize amines by emissive red-shifting, ultimate induction enhancement, and energy transfer. Intensive research into multiple-emission metal-organic framework Materials (MOFs) led to an emerging family of MOF-on-MOF hybrid materials, consisting of two or more metal-organic framework Material (MOFs) unit conjugates. MOF-on-MOFs exhibit excellent selectivity and sensitivity in sensing compared to single metal-organic framework Materials (MOFs). In terms of histamine detection, the ZIF-8 is controllably grown on a fluorescent core of a three-dimensional (3D) anionic fluorescent metal-organic framework Material (MOF) and simultaneously encapsulated with fluorescein, so that the intelligent ratio fluorescent sensor is further constructed Biogenic amine is sensed. However, after adding conventional organic dyes to inorganic materials, the luminescence of the hybrid materials may be reduced or even quenched due to the polymerization quenching (ACQ) effect. Whereas aggregation-induced emission luminescence is an effect that emits little light in a dilute solution, but shows strong fluorescence emission in an aggregated state. The AIEgens has simple molecular structure, low background noise, high luminous efficiency, good light stability and good biocompatibility, and has been applied to electroluminescent devices, biological probes, chemical sensors and the like. However, biogenic amine aggregation-induced emission detection luminescence sensors based on hybrid metal-organic framework Materials (MOFs) have not been reported.
Therefore, a hybrid nanocomposite and a fluorescence detection method for detecting histamine content in fish are desired.
Based on the method, the invention synthesizes the MOF-on-MOF nanomaterial Zn-BTEC@ZIF-8, and establishes a fluorescence method for detecting the histamine content of fish based on a fluorescence probe Zn-BTEC@ZIF-8@Tet constructed by the fluorescence probe Zn-BTEC@ZIF-8@Tet with strong fluorescence characteristic emitted by aggregation-induced luminescence effect of tetracycline. The detection performance of the synthesized Zn-BTEC@ZIF-8@Tet heterostructure on histamine is studied through batch experiments and characterization of X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible-near infrared spectroscopy (UV-vis), fluorescence (FL) and the like. A large number of test results show that the Zn-BTEC@ZIF-8@Tet can rapidly quantify the histamine level, and a thought is provided for the simultaneous detection of an integrated system based on the design of a multifunctional MOF-on-MOF heterostructure.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a hybrid nanocomposite Zn-BTEC@ZIF-8, a preparation method thereof, a fluorescent probe and a detection method, wherein the hybrid nanocomposite Zn-BTEC@ZIF-8 is coupled with the ZIF-8 to form a stable structure on the surface of the Zn-BTEC, has regular morphology, and shows excellent selectivity and sensitivity in sensing compared with single Zn-BTEC and ZIF-8.
The first aspect of the invention provides a hybrid nanocomposite Zn-BTEC@ZIF-8, wherein the Zn-BTEC@ZIF-8 is formed by coupling the ZIF-8 on the surface of the Zn-BTEC;
the Zn-BTEC particles are in the form of irregular blocks with smooth surfaces, and the particle size ranges from 1 to 9 microns, preferably from 3 to 7 microns;
the ZIF-8 particles are in the shape of regular polyhedrons, and the particle size ranges from 220 nm to 280 nm, preferably from 240 nm to 260 nm;
the number of the faces of the regular polyhedron is not less than 6;
Zn-BTEC and ZIF-8 are formed by the coordination of organic ligands and metal ions;
the organic ligand is at least one of pyromellitic acid, N-dimethylformamide and 2-methylimidazole;
the metal ions are derived from oxides and/or zinc salts of zinc;
the coupling agent used for coupling is at least one selected from polyvinylpyrrolidone and polyvinyl alcohol;
The zinc salt is at least one selected from zinc nitrate, zinc sulfate and zinc chloride.
The second aspect of the invention provides a preparation method of the hybrid nanocomposite Zn-BTEC@ZIF-8, which comprises the following steps:
1) Mixing pyromellitic acid, zinc oxide, ultrapure water and N, N-dimethylformamide, carrying out ultrasonic treatment, transferring and sealing the mixture into a polytetrafluoroethylene autoclave for reaction, sequentially carrying out primary centrifugal separation, ultrasonic water washing and secondary centrifugal separation on a reaction product to obtain a white solid, washing the white solid with absolute ethyl alcohol, carrying out vacuum drying to obtain Zn-BTEC, and refrigerating and storing the Zn-BTEC;
2) Dissolving Zn-BTEC in deionized water, performing ultrasonic treatment to obtain a uniform solution, adding polyvinylpyrrolidone into the uniform solution, stirring to obtain a first mixture, dissolving zinc nitrate hexahydrate in water to obtain a second mixture, adding the second mixture into the first mixture, stirring to obtain a third mixture, dissolving 2-methylimidazole in water to obtain a fourth mixture, adding the fourth mixture into the third mixture, sequentially stirring, centrifuging, washing with water, and vacuum drying to obtain Zn-BTEC@ZIF-8, and/or,
and adding the fourth mixture into the second mixture, and sequentially stirring, centrifugally separating, washing with water and drying in vacuum to obtain ZIF-8.
The third aspect of the invention provides a fluorescent probe Zn-BTEC@ZIF-8@Tet for detecting the histamine content of fish, wherein the Zn-BTEC@ZIF-8@Tet comprises the following components:
1) Zn-BTEC@ZIF-8;
2) Tetracycline hydrochloride;
3) Tris-HCl buffer;
based on the volume of Zn-BTEC@ZIF-8@Tet, the concentration of Zn-BTEC@ZIF-8 is 1.00-1.50mg/L, and the concentration of tetracycline hydrochloride is 0.9-1.2mM.
The fourth aspect of the invention provides a fluorescence detection method for detecting the histamine content of fish, which utilizes the Zn-BTEC@ZIF-8@Tet to carry out fluorescence detection on the histamine content of fish;
the linear range of the fluorescence detection of the histamine concentration of the fish is 2-1000mg/L;
the detection limit of fluorescence detection is not more than 1.458mg/L;
the excitation wavelength for fluorescence detection is 365-395nm, preferably 380-390nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the hybrid nanocomposite Zn-BTEC@ZIF-8 provided by the invention is coupled with ZIF-8 to form a stable structure on the surface of Zn-BTEC, has regular morphology, and shows excellent selectivity and sensitivity in sensing compared with single Zn-BTEC and ZIF-8.
2. The preparation method of the hybrid nanocomposite Zn-BTEC@ZIF-8 provided by the invention is simple, the raw material cost is low, and the prepared nanocomposite Zn-BTEC@ZIF-8 has good consistency.
3. The fluorescence probe Zn-BTEC@ZIF-8@Tet for detecting the histamine content of fish provided by the invention can be used for rapidly quantifying the histamine level, the fluorescence intensity is stable within 20 minutes, the stable storage time is longer than 20 days, and the selectivity and the anti-interference capability are strong.
4. The fluorescence probe Zn-BTEC@ZIF-8@Tet for detecting the content of the fish histamine provided by the invention competes for the tetracycline hydrochloride in the aggregation-induced emission complex based on the unique interaction between the histamine and Zn-BTEC@ZIF-8, so that fluorescence is quenched, and compared with the existing method, the sensor has a larger detection range and a lower detection limit, and the detection limit of the method is 1.458mg/L, which is superior to a plurality of methods reported in the prior art.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is a Scanning Electron Microscope (SEM) image (A, B, C) of Zn-BTEC@ZIF-8, and Zn-BTEC@ZIF-8, a comparison chart (D) of X-ray diffraction (XRD) spectra of Zn-BTEC, ZIF-8, and Zn-BTEC@ZIF-8, a comparison chart (E) of Fourier Transform Infrared (FTIR), and a comparison chart (F) of X-ray photoelectron spectroscopy (XPS), respectively, of a hybrid nanocomposite material proposed by the invention.
FIG. 2 is a schematic diagram (A) of a preparation process of the hybrid nanocomposite Zn-BTEC@ZIF-8 and a schematic diagram (B) of a mechanism of a fluorescent probe Zn-BTEC@ZIF-8@Tet for histamine detection.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart (A), a potential analysis chart (B), a C1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (C), an N1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (D), an O1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (E) and a Zn2p orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (F) of the hybrid nanocomposite Zn-BTEC@ZIF-8, the fluorescent probe Zn-BTEC@ZIF-8@Tet after adding histamine.
FIG. 4 is a graph showing the aggregation-induced emission (AIE) effect mechanism of the hybrid nanocomposite Zn-BTEC@ZIF-8 combined with tetracycline hydrochloride (Tet) and Zn-BTEC@ZIF-8@Tet on histamine detection.
FIG. 5 is a graph (A) of fluorescence spectrum of a probe in the presence of histamine (curve representing increase of histamine concentration from top to bottom), a graph (B) of relationship between histamine concentration and probe quenching efficiency at 525nm, a graph (C) of specificity analysis of fluorescence analysis, and a graph (D) of time variation of quenching efficiency of fluorescence analysis of a fluorescent probe Zn-BTEC@ZIF-8@Tet of the hybridized nanocomposite material Zn-BTEC@ZIF-8.
FIG. 6 is a C1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (A), an N1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (B), an O1 s orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (C) and a Zn2p orbit high-resolution X-ray photoelectron spectroscopy (XPS) chart (D) of the hybrid nanocomposite Zn-BTEC@ZIF-8 provided by the invention.
FIG. 7 shows the nitrogen (N) at 77K of Zn-BTEC@ZIF-8, ZIF-8 and Zn-BTEC@ZIF-8 of the hybrid nanocomposite proposed by the invention 2 ) Adsorption isotherm plot.
FIG. 8 is a graph of thermogravimetric analysis of Zn-BTEC, ZIF-8 and Zn-BTEC@ZIF-8 in the hybrid nanocomposite proposed by the invention.
FIG. 9 is a graph (D) comparing fluorescence spectra of Zn-BTEC at 1mg/mL of histamine (Zn-BTEC at 1.5mM of tetracycline hydrochloride (Tet), 1000mg/L of histamine, incubation time at 20 minutes) in the presence and absence of histamine, fluorescence spectra of ZIF-8 at 1.5mM of histamine (Tet), 1000mg/L of histamine, incubation time at 20 minutes) in the presence and absence of histamine, fluorescence spectra of Zn-BTEC at 1.5mM of Zn-BTEC at ZIF-8 at histamine (tetracycline hydrochloride (Tet), 1000mg/L of histamine, incubation time at 20 minutes) in the presence and absence of histamine, quenching efficiencies of Zn-BTEC, ZIF-8 and Zn-BTEC at ZIF-8.
FIG. 10 is a Transmission Electron Microscope (TEM) image of a fluorescent probe Zn-BTEC@ZIF-8@Tet in a hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention.
FIG. 11 is a graph showing the size distribution and comparison of Zn-BTEC, ZIF-8, zn-BTEC@ZIF-8, fluorescent probe Zn-BTEC@ZIF-8@Tet and histamine-added fluorescent probe Zn-BTEC@ZIF-8@Tet in the hybrid nanocomposite proposed by the invention (A, B, C, D, E, respectively).
FIG. 12 is a graph (A) of fluorescence spectrum of a hybridized nanocomposite Zn-BTEC@ZIF-8 with and without addition of 200. Mu.L histamine at a concentration of 1000mg/L, a graph (B) of fluorescence spectrum of tetracycline hydrochloride (Tet) with and without addition of 200. Mu.L histamine at a concentration of 1000mg/L, and a graph (C) of fluorescence spectrum of tetracycline hydrochloride (Tet) in the presence of different concentrations of histamine, according to the present invention.
FIG. 13 is a color comparison chart of the fluorescent probe Zn-BTEC@ZIF-8@Tet (A), the fluorescent probe Zn-BTEC@ZIF-8@Tet (B) after adding histamine, and the fluorescent probe Zn-BTEC@ZIF-8@Tet (C) after adding histamine in the hybridized nanocomposite Zn-BTEC@ZIF-8 according to the invention, which are exposed for the same time under ultraviolet irradiation.
FIG. 14 is a Transmission Electron Microscope (TEM) image of the fluorescence probe Zn-BTEC@ZIF-8@Tet in the hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention decomposed by histamine.
FIG. 15 is a graph showing the change of fluorescence intensity with time after addition of histamine to the hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention.
FIG. 16 is a graph showing the change of fluorescence intensity with time of a fluorescent probe Zn-BTEC@ZIF-8@Tet in the hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention by a fluorescence analysis method.
FIG. 17 is a graph showing the change of fluorescence intensity of a fluorescent probe Zn-BTEC@ZIF-8@Tet in the hybridized nanocomposite Zn-BTEC@ZIF-8 according to the invention with time after 500mg/L histamine is added.
FIG. 18 is a graph (A) of fluorescence spectra of a fluorescent probe Zn-BTEC@ZIF-8@Tet in a hybrid nanocomposite Zn-BTEC@ZIF-8 according to the invention at seven different excitation wavelengths (excitation wavelengths: 365, 370, 375, 380, 385, 290, 395nm, histamine concentration: 500 mg/L) after histamine addition, and a graph (B) of the effect of the different excitation wavelengths on histamine detection.
FIG. 19 is a schematic representation of the proposed hybrid nanocomposite Zn-BTEC@ZIF-8 in the presence (I) and absence (I) of histamine 0 ) At this time, different concentrations (1, 1.25, 1.5, 2, 2.5, 5, 10 mg/L) of Zn-BTEC@ZIF-8 were used for histamine determination (histamine concentration: 1000mg/L; culturing time: 0 minutes; incubation time is 40 minutes; tetracycline hydrochloride (Tet) concentration: quenching efficiency of 1.5 mM), with (I) and without (I) 0 ) Zn-BTEC@ZIF-8 solubles of histamineIn the solution, the quenching efficiency (B) of tetracycline hydrochloride (Tet) (histamine: 1000mg/L; incubation time: 40 min; detection time: 40 min) was varied at different concentrations (0.5, 1.0, 1.5, 2.0, 2.5, 3.0 mM).
FIG. 20 is a graph (A) showing the effect of the concentration of the hybridized nanocomposite Zn-BTEC@ZIF-8 on the quenching efficiency value of the fluorescent probe Zn-BTEC@ZIF-8@Tet, and a graph (B) showing the effect of the concentration of tetracycline hydrochloride on the quenching efficiency value of the fluorescent probe Zn-BTEC@ZIF-8@Tet.
FIG. 21 is a Stern-Volmer plot of histamine determination for a hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention.
FIG. 22 is a color comparison chart of a fluorescent probe Zn-BTEC@ZIF-8@Tet (B) added with histamine under ultraviolet irradiation and a fluorescent probe Zn-BTEC@ZIF-8@Tet (A) added with histamine under ultraviolet irradiation.
FIG. 23 is a graph showing repeated measurement of fluorescence intensity of a fluorescent probe Zn-BTEC@ZIF-8@Tet at 525nm after addition of 500mg/L histamine in the hybrid nanocomposite Zn-BTEC@ZIF-8 according to the present invention.
FIG. 24 is a standard graph of a commercial ELISA detection kit for detecting histamine concentrations of 0.2-16 ng/mL for the hybrid nanocomposite Zn-BTEC@ZIF-8 proposed by the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples and the accompanying drawings, which are given by way of illustration only and are not intended to be limiting.
According to a first aspect of the present invention, as shown in FIG. 1C, the present invention provides a hybrid nanocomposite Zn-BTEC@ZIF-8, the Zn-BTEC@ZIF-8 being formed by coupling ZIF-8 onto the surface of Zn-BTEC;
the Zn-BTEC particles are in the form of irregular blocks with smooth surfaces, and the particle size ranges from 1 to 9 microns, preferably from 3 to 7 microns;
the ZIF-8 particles are in the shape of regular polyhedrons, and the particle size ranges from 220 nm to 280 nm, preferably from 240 nm to 260 nm;
the number of the faces of the regular polyhedron is not less than 6;
Zn-BTEC and ZIF-8 are formed by the coordination of organic ligands and metal ions;
the organic ligand is at least one of pyromellitic acid, N-dimethylformamide and 2-methylimidazole;
the metal ions are derived from oxides and/or zinc salts of zinc;
the coupling agent used for coupling is at least one selected from polyvinylpyrrolidone and polyvinyl alcohol;
the zinc salt is at least one selected from zinc nitrate, zinc sulfate and zinc chloride.
In the invention, the hybrid nanocomposite Zn-BTEC@ZIF-8 is coupled on the surface of Zn-BTEC by ZIF-8 to form a stable structure, and the hybrid nanocomposite Zn-BTEC has regular morphology and shows excellent selectivity and sensitivity in sensing compared with single Zn-BTEC and ZIF-8.
According to a second aspect of the present invention, the present invention provides a preparation method of the hybrid nanocomposite Zn-btec@zif-8, including the steps of:
1) Mixing pyromellitic acid, zinc oxide, ultrapure water and N, N-dimethylformamide, carrying out ultrasonic treatment, transferring and sealing the mixture into a polytetrafluoroethylene autoclave for reaction, sequentially carrying out primary centrifugal separation, ultrasonic water washing and secondary centrifugal separation on a reaction product to obtain a white solid, washing the white solid with absolute ethyl alcohol, carrying out vacuum drying to obtain Zn-BTEC, and refrigerating and storing the Zn-BTEC;
2) Dissolving Zn-BTEC in deionized water, performing ultrasonic treatment to obtain a uniform solution, adding polyvinylpyrrolidone into the uniform solution, stirring to obtain a first mixture, dissolving zinc nitrate hexahydrate in water to obtain a second mixture, adding the second mixture into the first mixture, stirring to obtain a third mixture, dissolving 2-methylimidazole in water to obtain a fourth mixture, adding the fourth mixture into the third mixture, sequentially stirring, centrifuging, washing with water, and vacuum drying to obtain Zn-BTEC@ZIF-8, and/or,
and adding the fourth mixture into the second mixture, and sequentially stirring, centrifugally separating, washing with water and drying in vacuum to obtain ZIF-8.
According to the invention, in step 1), the moles of pyromellitic acid and zinc oxide are the same and are 1.3-3.5mM;
the dosage of the ultrapure water is 0.5-2mL;
the dosage of the N, N-dimethylformamide is 8-12mL.
The ultrasonic treatment time is 5-20 minutes;
the reaction temperature is 160-200 ℃ and the reaction time is 2.5-4.5 days.
Preferably, in the step 1), ultrasonic washing is ultrasonic treatment after each washing, the ultrasonic washing times are not less than 3 times, and the time of each ultrasonic treatment is 5-15 minutes;
the rotation speed of the primary centrifugal separation is 7000-9000 rpm, and the time is 8-12 minutes;
the rotational speed of the secondary centrifugal separation is 4000-6000 rpm, and the time is 2-8 minutes;
washing with absolute ethanol for not less than 3 times;
vacuum drying at 40-60deg.C for 12-24 hr;
the temperature of the refrigerated storage is 2-6 ℃.
According to the invention, in step 2), the Zn-BTEC is used in an amount of 10-30mg and deionized water is used in an amount of 8-12mL;
the dosage of the zinc nitrate hexahydrate is 0.3-0.7g, and the dosage of the water for dissolving the zinc nitrate hexahydrate is 8-12mL;
the dosage of 2-methylimidazole is 2.2-2.7g, and the dosage of water for dissolving 2-methylimidazole is 8-12mL.
Preferably, in step 2), polyvinylpyrrolidone is added to the homogeneous solution and stirred for a period of 10 to 14 hours;
Adding the second mixture into the first mixture, and stirring for 2-6 hours;
adding the fourth mixture into the third mixture, and stirring for 2-6 hours;
the rotation speed of centrifugal separation is 7000-9000 rpm, and the time is 8-12 minutes;
the times of water washing are not less than 3 times, and the water consumption is 18-22mL each time;
the temperature of vacuum drying is 60-80 ℃ and the time is 10-14 hours.
In the invention, the preparation method of the hybrid nanocomposite Zn-BTEC@ZIF-8 is simple, the cost of raw materials is low, and the prepared nanocomposite Zn-BTEC@ZIF-8 has good consistency.
According to a third aspect of the present invention, there is provided a fluorescent probe Zn-BTEC@ZIF-8@Tet for detecting the histamine content of fish, the fluorescent probe Zn-BTEC@ZIF-8@Tet comprising:
1) Zn-BTEC@ZIF-8;
2) Tetracycline hydrochloride;
3) Tris-HCl buffer;
based on the volume of Zn-BTEC@ZIF-8@Tet, the concentration of Zn-BTEC@ZIF-8 is 1.00-1.50mg/L, and the concentration of tetracycline hydrochloride is 0.9-1.2mM.
According to the invention, the Zn-BTEC@ZIF-8@Tet is prepared by a method comprising the following steps of:
1) Adding the Zn-BTEC@ZIF-8 aqueous solution according to any one of claims 1-4 into Tris-HCl buffer solution, and uniformly mixing to obtain a buffer primary solution;
2) Adding tetracycline hydrochloride into the buffer primary solution, and uniformly mixing to obtain Zn-BTEC@ZIF-8@Tet;
the pH value of the Tris-HCl buffer solution is 7-9;
based on the volume of Zn-BTEC@ZIF-8@Tet, the concentration of Zn-BTEC@ZIF-8 is 1.00-1.50mg/L, and the concentration of tetracycline hydrochloride is 0.9-1.2mM.
According to the invention, the fluorescence probe Zn-BTEC@ZIF-8@Tet for detecting the content of the histamine in fish can rapidly quantify the histamine level, the fluorescence intensity is stable within 20 minutes, the stable storage time is longer than 20 days, and the selectivity and the anti-interference capability are strong.
According to a fourth aspect of the invention, the invention provides a fluorescence detection method for detecting the content of the histamine in fish, which utilizes the Zn-BTEC@ZIF-8@Tet to carry out fluorescence detection on the content of the histamine in fish;
the linear range of the fluorescence detection of the histamine concentration of the fish is 2-1000mg/L;
the detection limit of fluorescence detection is not more than 1.458mg/L;
the excitation wavelength for fluorescence detection is 365-395nm, preferably 380-390nm.
In the invention, the fluorescence probe Zn-BTEC@ZIF-8@Tet for detecting the content of the fish histamine competes with tetracycline hydrochloride in the aggregation-induced emission complex based on unique interaction between the histamine and Zn-BTEC@ZIF-8, so that fluorescence is quenched, and compared with the existing method, the sensor has a larger detection range and a lower detection limit, and the detection limit of the method is 1.458mg/L, which is superior to a plurality of methods reported in the prior art.
The following describes the invention in detail by way of examples.
Materials and reagents for use in the examples of this application
The water used was ultrapure water (18 M.OMEGA.cm); nano zinc oxide (99.8% purity, 50.+ -.10 nm, shanghai A Ding Shenghua reagent Co., ltd.), pyromellitic acid (98% purity, shanghai Yi En chemical technology Co., ltd.), N, N-dimethylformamide (99% purity, shanghai Yi En chemical technology Co., ltd.), polytetrafluoroethylene reactor liner (25 mL), polyvinylpyrrolidone (average molecular weight 58000, K29-32, shanghai A Ding Shenghua reagent Co., ltd.), zinc nitrate hexahydrate (99% purity, shanghai laboratory equipment Co., ltd.), tris-HCl buffer (1 mmol/L, pH 8.0) (Sigma-Aldrich Co., ltd.), 2-methylimidazole (98% purity, shanghai Yi En chemical technology Co., ltd.), tetracycline hydrochloride (Solarbio, 95% purity), histamine (98% purity, shanghai source leaf biotechnology Co., ltd.).
Instruments and devices used in embodiments of the present application
F97pro fluorescence spectrophotometer (Shanghai optical technologies Co., ltd.); UH4150 ultraviolet-visible-near infrared spectrophotometer (Hitachi, japan); field emission scanning electron microscopy (ZEISS Sigma 500); l-200 analytical balance (Metrehler-Todoli instruments, switzerland); DH-101-0BY electric vacuum drying oven (Tianjin middle ring experiment electric furnace Co., ltd.); SB25-12D ultrasonic cleaner (Ningbo Xinzhi biotechnology Co., ltd.).
Example 1
MOF was synthesized by solvothermal method, pyromellitic acid (2.5 mm,0.6375 g), zinc oxide (2.5 mm,0.2034 g), 1mL of ultrapure water and 10mL of n, n-Dimethylformamide (DMF) were added to a beaker and sonicated for 10 minutes. They were then transferred to a polytetrafluoroethylene vessel, subsequently sealed in an autoclave, and reacted at 180 ℃ for 3.5 days. After the completion of the reaction, the product was centrifuged, washed 3 times with ultrapure water, sonicated for 10 minutes each time, and centrifuged for 5 minutes (5000 r/min). The resulting white solid product was then centrifuged, washed 3 times with absolute ethanol and dried overnight in a vacuum oven at 50 ℃ to give Zn-BTEC. Finally, it was stored in a refrigerator at 4 ℃.
Example 2
0.5g of zinc nitrate hexahydrate was dissolved in 10mL of water and stirred continuously for 4 hours. Then, 2.5g of 2-methylimidazole was dissolved in 10mL of water and quickly added to the above mixture. The mixture was stirred for 4 hours, centrifuged for 10 minutes, washed 3 times with water (20 mL) and dried under vacuum at 70 ℃ to give ZIF-8.
Example 3
20mg of Zn-BTEC synthesized in example 1 was dissolved in 10mL of deionized water and sonicated to form a homogeneous solution. Then 20mg of polyvinylpyrrolidone was added and stirred for 12 hours. Then, 0.5g of zinc nitrate hexahydrate was dissolved in 10mL of water and added to the above mixture, followed by stirring for 4 hours. Then, 2.5g of 2-methylimidazole was dissolved in 10mL of water and quickly added to the above mixture. The mixture was stirred for 4 hours, centrifuged for 10 minutes, washed 3 times with water (20 mL) and dried under vacuum at 70 ℃ to give Zn-btec@zif.
Example 4
The three MOFs synthesized in examples 1-3 were dissolved in water to prepare a 1mg/mL solution for use. Then, 300. Mu.L of three MOF solution stock solutions (1 mg/mL) were added to 1.7mL of Tris-HCl buffer (10 mM, pH=8), and then, tetracycline hydrochloride (1.5 mM) was added to the above solutions, and then, 1mg/mL of histamine solution was added to observe the fluorescence change after the addition, 3 sets of parallel controls were made for each test sample, and pure water was added as a control to calculate fluorescence quenching efficiency.
Example 5
The fluorescent probe Zn-BTEC@ZIF-8@Tet configured in example 4 was pipetted into a centrifuge tube with 200. Mu.L and then added with different mass concentration gradients (2 mg/L, 20mg/L, 50 mg-L, 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 1000 mg/L) of histamine solution standard 200. Mu.L, and after incubation at 25℃for 20min, stable fluorescence was measured. Collecting fluorescence spectrum at 420-720 nm under 385nm laser excitation by a fluorescence spectrophotometer, marking fluorescence intensity at 525nm as I, making 3 groups of parallel control for each detection sample, adding pure water as control, marking as I 0 Fluorescence quenching efficiency was calculated from this. Three replicates were used for each experiment. (I) 0 -I)/I 0 Is determined under optimal conditions.
Test example 1
The particle size and morphology of the hybrid nanocomposite Zn-BTEC@ZIF-8 were characterized by using a Scanning Electron Microscope (SEM). Zn-BTEC has an irregular block structure, the size is about several micrometers, and the surface is relatively smooth, as shown in A of FIG. 1, which is consistent with the literature report. The ZIF-8 synthesized independently has regular and uniform polyhedral shape and uniform size distribution of about 250nm, as shown in B of FIG. 1. The Zn-BTEC@ZIF-8 was prepared by coupling ZIF-8 to the Zn-BTEC surface by MOF-on-MOF synthesis, and as shown in FIG. 1C, a Scanning Electron Microscope (SEM) showed that ZIF-8 particles were densely distributed on the nano-sized blocks. ZIF-8 is smaller in size, probably due to the reduced surface energy of the Zn-BTEC nano-block, which limits the spatial growth of ZIF-8 during synthesis. The ZIF-8 with smaller size can enlarge the specific surface area and enhance the interaction site with the target area. In this process, the size and morphology of Zn-BTEC did not change significantly.
To further confirm the formation of the hybrid nanocomposite Zn-BTEC@ZIF-8, the main characteristic lattice planes of each MOF material were found in the hybrid nanocomposite Zn-BTEC@ZIF-8 by in situ X-ray diffraction (XRD) patterns (as in FIG. 1D), illustrating the crystal integrity and stability of Zn-BTEC@ZIF-8Zn-BTEC@ZIF-8 during interfacial coupling. In addition, FIG. 1E records 4000-400cm -1 Fourier Transform Infrared (FTIR) spectra at. In Zn-BTEC, 3000-3600cm -1 Broad peaks in between belong to O-H stretches, 1615 and 1400cm -1 The nearby peaks represent symmetrical and asymmetrical carboxylate stretching vibrations, indicating carboxylate saltsThe coordination ends of the groups are not identical. V of Zn-BTEC (215 cm-1) as (COO) and v s (COO) is less than Na 4 BTEC(95cm -1 ) This is because the carboxyl groups coordinated to the Zn (II) atom are monodentate and bidentate. Fourier Transform Infrared (FTIR) characterization of ZIF-8 was shown at 1307cm -1 、1148cm -1 And 994cm -1 The characteristic peak at this point corresponds to the in-plane bending of the imidazole ring at 423cm -1 The characteristic peak at which corresponds to the stretching of Zn-N. At 1572cm -1 The tensile vibration of C=N was observed at 2932cm-1 and the tensile vibration of aromatic and aliphatic C-H was also observed at 3129 cm-1. Fourier Transform Infrared (FTIR) spectra of Zn-BTEC@ZIF-8 also showed the presence of Zn-N bonds (424 cm) -1 ) Stretching vibration of imidazole ring (1149 cm) -1 ，995cm -1 ) Stretching vibration of c=n (1566 cm -1 ) Stretching vibration of C-H (2919 cm) -1 ,3172cm -1 ) At 3000-3600cm -1 The broad peak at this point is the stretch from O-H, which is more diffuse and broader than ZIF-8. Stretching vibration of C=N at 1572cm -1 More remarkable. The infrared characteristic peaks of both MOFs are covered in Zn-BTEC@ZIF-8.
The formation and chemical groups of the hybrid nanocomposite Zn-BTEC@ZIF-8 were further studied using X-ray photoelectron spectroscopy (XPS). As shown in F of fig. 1, signals of C, N, O and Zn elements were detected in the measured spectra of the three MOFs. Since no other element is added, the peak position of each element is fixed, but the content of each element is changed. Analysis of the relative content of X-ray photoelectron spectroscopy (XPS) showed that the hybrid nanocomposite Zn-BTEC@ZIF-8 had lower C and N content than MOF alone and higher O content than MOF alone, as shown in Table 1. The chemical state and surface bonding information were analyzed by comparing the high resolution spectra of C1s, O1s, N1 s and Zn2p of Zn-BTEC, ZIF-8 and Zn-BTEC@ZIF-8, as shown in C-F of FIG. 3. The C1s XPS spectrum of Zn-BTEC@ZIF-8 is divided into three peaks of 284.7eV, 285.9eV and 288.6eV, which correspond to C-C, C-O/C-N and OCO respectively. O1s XPS spectra fit to two peaks at 531.8 and 532.4eV corresponding to C-O and C=O of Zn-BTEC and ZIF-8, respectively. All changes in the binding energy of electron C1s and O1s in the complex spectrumThe formation is evidence of the redistribution of electron density in the O-C-O segment by complexing of metal ions through ligand oxygen atoms. The bond energy of Zn-BTEC@ZIF-8 is shifted to a higher binding energy by comparison with the bond energy of C-N and C=N in ZIF-8. N1 s XPS spectrum in Zn-BTEC@ZIF-8 fitted to two peaks of 399 and 400.6eV, corresponding to C-N and C=N of the imidazole ring in ZIF-8. The bond energy also varies toward higher binding energy than ZIF-8. The change in binding energy in binding Zn-BTEC@ZIF-8 with the binding energy of Zn-BTEC and ZIF-8 alone can be found that in the formed Zn-BTEC@ZIF-8, due to the electronic nature of the Zn-BTEC and ZIF-8 interface, there is a certain interaction between Zn-BTEC and ZIF-8. In addition, zn2p is given 3/2 And Zn2p 1/2 X-ray photoelectron spectroscopy (XPS) of (C) with two peaks respectively. The Zn-BTEC@ZIF-8 nanocomposite material shows obvious coexistence of N1 s and O1 s signals, wherein the O element of Zn-BTEC@ZIF-8 is mainly from OCO in Zn-BTEC, and the N element is mainly from C-N and C=N in 2-methylimidazole.
TABLE 1X quantitative results of ray photoelectron Spectrometry (XPS)
Test example 2
The present test example tested the Zn-BTEC@ZIF-8 formation mechanism, and N2 adsorption-desorption isotherms of Zn-BTEC, ZIF-8 and Zn-BTEC@ZIF-8 are shown in FIG. 7. The BET specific surface areas of the three MOFs were 36.92m2/g, 967.9695m2/g and 409.6026m2/g, respectively. The specific surface area of Zn-BTEC@ZIF-8 is lower than that of ZIF-8, which is probably because the ZIF-8 is partially embedded with Zn-BTEC, and the adsorption specific surface area of the object to be detected can be increased by the load of ZIF-8 as shown in Table 2. FIG. 8 is a thermogravimetric analysis (TGA) curve of Zn-BTEC, ZIF-8 and Zn-BTEC@ZIF-8. It can be clearly seen that the mass loss of synthetic Zn-BTEC@ZIF-8 can be divided into three main stages. The first stage is evaporation to remove water molecules and Zn-BTEC degradation (< 250 ℃). The second phase temperature is between 250 and 550 c with a small mass loss (about 10%). The TGA curves of Zn-BTEC and ZIF-8 were compared, mainly because ZIF-8 decomposed slowly. The third stage is then from 550 ℃ to 800 ℃. It is due to the decomposition of ZIF-8. However, the graphic trend of Zn-BTEC@ZIF-8 was milder than Zn-BTEC, which further confirmed that the mass loss of Zn-BTEC was reduced when ZIF-8 was coated on the surface of Zn-BTEC, indicating successful attachment of ZIF-8 to Zn-BTEC.
Table 2 specific surface area, pore volume and pore size of three MOFs
Test example 3
The test example utilizes fluorescence spectrum to study the optical properties of Zn-BTEC, ZIF-8 and Zn-BTEC@ZIF-8 hybrid nano composite materials and the performances of the constructed fluorescent probes. Notably, the three MOF materials were not fluorescent themselves, and intense fluorescence emission occurred after addition of tetracycline hydrochloride (Tet), as shown in fig. 9 (wherein the three curves in A, B, C of fig. 9 represent the fluorescence spectra of the probe of the MOF material, the probe of the histamine-added MOF material, and the MOF material itself from top to bottom). In the case of tetracycline hydrochloride (Tet), the X-ray photoelectron spectroscopy (XPS) spectrum showed no significant change, as shown in FIG. 3A, indicating that no chemical reaction occurred between Zn-BTEC@ZIF-8 and tetracycline hydrochloride (Tet). As can be seen from FIG. 10, the morphology of Zn-BTEC@ZIF-8 remained well after the introduction of tetracycline hydrochloride (Tet), and the skeletal structure was not deformed. Dynamic light scattering analysis of FIG. 11 shows that Zn-BTEC@ZIF-8 particle size increases upon addition of tetracycline hydrochloride (Tet). The zeta potential results showed that the absolute value of Zn-BTEC@ZIF-8@Tetzeta potential (-7.5371 mV) was reduced by nearly half as compared to the absolute value of Zn-BTEC@ZIF-8 (-14.1 mV) after addition of tetracycline hydrochloride (Tet), as shown in FIG. 3B. Through electrostatic interaction, the added tetracycline hydrochloride (Tet) can interact with Zn-BTEC@ZIF-8 to form an aggregate. In addition, X-ray photoelectron spectroscopy (XPS) further confirmed the formation of agglomerates. The increase of the carbon oxygen content in Zn-BTEC@ZIF-8@Tet proves that tetracycline hydrochloride (Tet) is adsorbed on the surface of Zn-BTEC@ZIF-8 or enters the skeleton of Zn-BTEC@ZIF-8. After addition of tetracycline hydrochloride (Tet), the relative content of C-C in the C1 s XPS spectrum (C of fig. 3) decreased from 62.73% to 28.74%, the relative content of C-O/C-N increased from 23.30% to 45.69%, and the relative content of c=o increased from 13.96% to 25.57% (table 3). This reveals a redistribution of electrons during fluorescent probe formation due to pi-pi interactions. Furthermore, the relative content of C-N in the N1 s XPS spectrum was reduced from 70.33% to 59.08% (D in FIG. 3). This phenomenon is presumed to be due to the complexation of Zn nodes with N in Zn-BTEC@ZIF-8. The high resolution XPS spectrum of O1 s consists mainly of two peaks, corresponding to C-O and c=o bands, respectively. After addition of tetracycline, the relative content of C-O was reduced from 62.01% to 43.59%, the relative content of C=O was reduced from 37.99% to 32.39%, and was converted to O-H, this is due to the hydrogen bonding interaction of-COOH/-OH of tetracycline hydrochloride with-NH 2/-COOH in Zn-BTEC@ZIF-8 during probe formation. The decrease in the relative amounts of C-O and c=o converted from XPS spectra of O1 s (E of fig. 3) to O-H is due to hydrogen bonding interactions between-NH 2/-OH and-NH 2/-COOH of Tet in Zn-btec@zif-8 during probe composition. As can be seen from the above discussion, zn-BTEC@ZIF-8 interacts with tetracycline hydrochloride (Tet) through hydrogen bonding, pi-pi interactions, coordination of Zn atoms with N in tetracycline hydrochloride (Tet), while the excellent void structure of Zn-BTEC@ZIF-8 provides adsorption sites for tetracycline hydrochloride (Tet) to aggregate in the pores of MOF. During the polymerization, the intramolecular rotation is restricted or the intramolecular rotation restriction process is activated, so that the fluorescence emission of the luminogen is turned on, which is why it can be used as a fluorescent probe.
TABLE 3 peak area distribution for different chemical bonds
In the synthesis process, zn-BTEC is used as a host of MOF-on-MOF, ZIF-8 is used as an ideal guest to be loaded on the host to prepare various nano materials Zn-BTEC and ZIF-8, and the nano materials Zn-BTEC and ZIF-8 can be independently polymerized with tetracycline hydrochloride (Tet) to induce luminescence, and larger particles of Zn-BTEC can provide more loading sites for ZIF-8. ZIF-8 has abundant micro-mesopores and larger specific surface area, can provide more space for tetracycline hydrochloride (Tet), and can generate aggregation luminescence effect with the tetracycline hydrochloride (Tet). Following histamine attachment, the fluorescence intensities of all three MOFs decreased as shown in figure 9. For histamine detection, the Quenching Efficiency (QE) of Zn-BTEC was (45.2388 + -0.7727)%, ZIF-8 was (52.1830 + -1.8860)%, zn-BTEC@ZIF-8 was (62.8548 + -1.7765)%, and the QE difference between the three MOFs was statistically significant (p < 0.001). The QE of Zn-BTEC@ZIF-8 is higher than that of Zn-BTEC and ZIF-8 (p < 0.001).
Fluorescence measurements of histamine using Zn-BTEC@ZIF-8 and tetracycline hydrochloride (Tet), respectively, are shown in FIG. 12 (wherein the curves in FIG. 12C represent fluorescence spectra from high to low histamine concentrations, respectively, from top to bottom). MOF and histamine do not fluoresce, whereas the mixture of tetracycline hydrochloride (Tet) and histamine has a distinct fluorescent signal. At the same time, an immediate darkening of the color was found, indicating that tetracycline hydrochloride (Tet) plays an important role in the construction of polymerization-induced luminescence probes. The special structure of tetracycline hydrochloride (Tet) contains a large number of Lewis acid-base sites, can provide a large number of proton donor-acceptor pairs, and is easy to form hydrogen bonds. The histamine is positively charged when dissolved in water, and the aqueous solution is the pi-pi interaction between the benzene ring of the basic (pka=9.8) tetracycline hydrochloride (Tet) molecule of the protonation of the aliphatic amino group and the imidazole ring of histamine brings them closer together, effectively limiting the rotation of the aromatic ring in tetracycline hydrochloride (Tet), further increasing the green fluorescence, with a macroscopic color change, and even browning reactions under uv light, as shown in fig. 13. A series of concentration gradient histamine solutions reacted with tetracycline hydrochloride (Tet), but low concentrations of histamine reacted with tetracycline hydrochloride (Tet) alone failed to obtain a distinct fluorescent signal.
Notably, the Zn-BTEC@ZIF-8zeta potential test showed that it was negatively charged, as was the synthesized Zn-BTEC@ZIF-8@Tet. There is a strong pi-pi interaction between the benzene ring of the host MOFZn-BTEC and the imidazole ring of histamine, and a hydrogen bond is formed between the guest ZIF-8 and histamine. XPS results showed that after histamine addition, the OCO (C1 s) area of Zn-BTEC was reduced from 25.57% to 4.27% (C as in FIG. 1), and C=O (O1 s) was also completely disappeared (E as in FIG. 3), indicating that its carboxyl group could be destroyed. It is speculated that hydrogen bond interactions are formed between H on the histamine amino group and O on the carboxyl group in MOFs. At the same time, the H of the amino group also forms hydrogen bonds with the N of the pyridine ring of ZIF-8, so that these interactions may lead to some bonds in the Zn-BTEC@ZIF-8@Tet structure being altered, which is presumably supported by the post-reaction Transmission Electron Microscopy (TEM) results plot (FIG. 14), with only scattered fragments being observed in the TEM image after histamine addition, and the MOF structure being destroyed. The zeta potential results also showed a slight increase in zeta potential (-9.193 mV) after histamine addition over Zn-BTEC@ZIF-8@Tet (-7.5371 mV) (B of FIG. 3), confirming that coagulated Zn-BTEC@ZIF-8@Tet became dispersed. The area of the main peak in the Zn2pXPS spectrum decreases and the proportion of satellite peaks increases (F in FIG. 3), indicating that the binding energy of this site 1023.13eV may be that the synthesized Zn-BTEC@ZIF-8 is a container, into which tetracycline hydrochloride (Tet) is attracted by hydrogen bonding, pi-pi interactions and complexation. At this time, aggregation-induced emission luminescence effect occurs, and addition of histamine damages the Zn-BTEC@ZIF-8 container, and the supported tetracycline hydrochloride (Tet) cannot aggregate, so that fluorescence intensity is lowered, as shown in FIG. 4.
Test example 4
The test example optimizes the effect of reaction time, excitation wavelength and concentration of Zn-BTEC@ZIF-8 and tetracycline hydrochloride on fluorescence values, respectively. By adopting an orthogonal experimental design (L20 matrix), the MOF concentration (factor A) and the tetracycline hydrochloride concentration (factor B) are analyzed for 4 variables, and the two variables are found to have obvious influence on the quenching efficiency value of the fluorescent probe parameter. The matrix consists of two factors, four and five levels, respectively. Selected MOFs were configured to different concentrations (5.0 mg/mL, 2.5mg/mL, 1.25mg/mL, 1 mg/mL) and tetracycline hydrochloride concentrations (1.0 mM, 1.5mM, 2.0mM, 2.5mM, 3.0 mM) to prepare fluorescent probes, and the quenching efficiencies of the probe combinations at the different concentrations were compared to obtain optimal probe concentrations. Design L according to the principle of orthogonality 20 (4 1 ×5 1 ) And (3) checking the matrix, and examining the influence of the matrix on the quenching efficiency value of the fluorescent probe.
Calculation of fluorescence quenching efficiency:
calculation of fluorescence quenching efficiency of the collection probes:
fluorescence spectra (excitation wavelength 385 nm) of the probe before and after addition of histamine solution were collected, and the quenching efficiency (%) was calculated as
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I 0 Refers to the original fluorescence intensity of the sample without the test, and I refers to the fluorescence intensity after exposure to the sample.
Before detection by using the probe, the stability time and incubation time of the probe were optimized first, as can be seen from FIG. 15, the Zn-BTEC@ZIF-8@Tet fluorescent probe was stable at 20min, and the fluorescence stability of the probe was measured, and the fluorescence was found to remain stable for 20 days under the condition of avoiding light, as shown in FIG. 16. After histamine was added to the prepared probe table, fluorescence was immediately turned off, slightly decreased with incubation time, and stabilized at 20min, as shown in fig. 17. In addition, the fluorescence behavior of Zn-BTEC@ZIF-8@Tet as a fluorescent probe for the detection of histamine was studied by recording fluorescence emission spectra at different excitation wavelengths of 365-395 nm. The fluorescence intensity gradually increased, reaching a maximum at 385nm, while the emission peak at 525nm remained unchanged, as shown in fig. 18.
As shown in FIG. 20, the quenching efficiency values of the fluorescent probes at different concentrations are significantly different. The quenching efficiency was highest (A2B 1) when the MOF concentration was 1.25mg/L and the tetracycline hydrochloride (Tet) concentration was 1.0mM, as shown in tables 4-5. By comparing the mean square values corresponding to the different factors, the MOF concentration (ms= 535.585) was found to be greater than the tetracycline hydrochloride (Tet) concentration (ms= 98.214). The concentration change of MOF with larger MS value can obviously influence the quenching efficiency of the fluorescent probe, while the concentration of tetracycline hydrochloride (Tet) with smaller MS value has smaller influence on the quenching efficiency of the fluorescent probe.
TABLE 4 factors and level matrix
Table 5 parameter combinations based on a 2-factor 4/5 horizontal orthogonal table
TABLE 6 inter-subject Effect test
a QSE:Quadraticsumoferror
b DF:Degreeoffreedom
c MS:MeanSquare
Test example 5
The test example tests the effect of quantitative detection of histamine by a probe Zn-BTEC@ZIF-8@Tet, and the A of FIG. 5 shows the spectral response of the probe Zn-BTEC@ZIF-8@Tet to histamine with different concentrations, and the characteristic emission band is shown at 525 nm. With increasing histamine concentration, the fluorescence intensity of Zn-BTEC@ZIF-8@Tet is obviously reduced, the difference between the fluorescence intensity of the emission intensity and the histamine concentration in the range of 2-1000mg/L and the fluorescence intensity of the control fluorescence value is Logistic related to the histamine concentration, the coefficient is 0.9978, and in the range of 2-400mg/L, (I) 0 -I)/I100 has a good linear correlation with histamine concentration (r2= 0.9978) (B of fig. 5). The resulting equation is (I 0 -I)/i×100=4.899+0.1279c, wherein I0 and I are the fluorescence intensities of Zn-btec@zif-8@tet in the absence and presence of histamine, respectively. Histamine can be quantitatively detected according to a calibration equation. The estimated detection Limit (LOD) is 1.458mg/L, as defined by the 3-fold blank signal deviation (3σ). Compared with the traditional quenching fluorescent probe, the histamine detection sensitivity is higher, and the linear range is wider. Compared with most reported histamine sensors, the histamine sensor has the advantages of lower detection limit and wider detection range, and can be suitable for fish inspection with high histamine.
In the present invention, the Stern-Volmer (SV) equation is usedQuantitative study of quenching efficiency, wherein Ksv is the quenching constant (M -1 ). In FIG. 21, it can be observed that it exhibits a good linear correlation, the correlation coefficient (R2) is 0.9904, and the Ksv value of Zn-BTEC@ZIF-8@Tet is 2.380 ×103M -1 . At the same time, the yellow-green fluorescence of the solution under the uv lamp gradually faded and was visible to the naked eye (fig. 22).
Test example 6
In order to examine the selectivity and the anti-interference capability of the method, various substances such as putrescine, cadaverine, beta-phenethylamine, histidine, mgCl, KCl, glucose and the like are selected as the interfering agents. The data were analyzed using SPSS software. Figure 5C shows that all interferons were significantly different from histamine (p < 0.05). The amine contains primary amine, secondary amine and tertiary amine due to the existence of imidazole ring in the structure of the amine. In aqueous solution, the basicity of secondary amine is highest, and the dissociation constant of histamine (pka=9.8) is weaker than that of the main analogues, such as cadaverine (pka=9.13), putrescine (pka=9.35), β -phenylethylamine (pka=9.33), which are all primary amines, and the electron withdrawing effect of aryl ring is present in β -phenylethylamine, which is weaker in basicity, and also weaker in attraction with fluorescent probe.
Test example 7
The present test example investigated the signal reproducibility of Zn-BTEC@ZIF-8@Tet fluorescent probes and the parallel response to multiple histamine samples at the same concentration. As shown in FIG. 23, the fluorescence intensity after quenching is basically unchanged in 8 repeated measurements, which shows that the developed Zn-BTEC@ZIF-8@Tet fluorescent probe has good signal reproducibility and can ensure accurate detection of histamine. D of fig. 5 shows that the fluorescent probe can have a significant stabilizing effect within 20 days. The CV range of the daytime fluorescence response signal is 0.5874% -4.887%, and the average CV is 2.455%. These results indicate that the Zn-BTEC@ZIF-8@Tet fluorescent probe has good long-term stability and high repeatability in quantitative histamine detection.
Test example 8
The test example adopts a Zn-BTEC@ZIF-8@Tet nano probe to detect histamine in different fish samples so as to evaluate the reliability of the fish samples. The tuna sample of this test example was purchased from a local supermarket in the state of Tianjin. The sample treatment method was as follows, the sample was ground into a homogenate using a meat grinder, 10g of the homogenate sample was mixed with 20mL of ultrapure water, and then, the mixture was shaken for 5 minutes. After centrifugation (10000 rpm,10 minutes) filtration was performed and the supernatant was stored at 4 ℃ for subsequent use. Then, a histamine solution with a certain concentration is added into the sample, the prepared Zn-BTEC@ZIF-8@Tet nano probe is used for quantifying the histamine solution, and meanwhile, ELISA is adopted for comparing detection results.
To verify the possibility of the method of the invention to detect histamine in an actual sample, the fluorescent probe was used for quantitative detection of histamine in fish. The initial fluorescence was used to calculate the fluorescence intensity after detection, and the measured fluorescence intensity was interpolated using a linear calibration chart to determine the histamine concentration, and the results shown in Table 7 are presented. The results obtained by the method are not statistically different from the results obtained by the ELISA method (FIG. 24), which shows that the sensing application of the method in complex actual samples is accurately feasible. For comparison, other methods of detecting histamine using MOF are compiled in table 8, and it can be seen from the results that the method of the present invention results in lower LOD and shorter detection times, which are more convenient.
Table S7 Zn-BTEC@ZIF-8@Tet comparison with ELISA detection results
Sample detection differential analysis: the histamine content in the samples was determined by Zn-BTEC@ZIF-8@Tet fluorescent probe and ELISA method, respectively. Paired t-test was performed using ibm sp statistics27 to distinguish data differences between the two methods. The results in table S7 show that there is no difference between the two methods (t=1.626, p > 0.05).
Table 8 analytical performance comparisons of different histamine determination methods
As can be seen from test examples 1-8, the Zn-BTEC@ZIF-8@Tet fluorescent probe established in the examples is suitable for sensitive detection of histamine in seafood. The formed MOF-on-MOF hybrid material has better response than the single MOF material, and the mechanism is based on unique interaction between histamine and Zn-BTEC@ZIF-8, so that tetracycline hydrochloride in the aggregation-induced emission complex is competed down, and fluorescence is quenched. Compared with the prior methods, the sensor has a larger detection range and a lower detection limit, and the detection limit of the method is 1.458mg/L, which is superior to a plurality of prior reported methods. The method has application in the determination of histamine in fish samples. Further advances in the fields of analysis and materials research have been facilitated by combining the specific and superior properties of MOFs.
The embodiments of the present invention have been described above, the description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. The hybrid nanocomposite Zn-BTEC@ZIF-8 is characterized in that the Zn-BTEC@ZIF-8 is formed by coupling the ZIF-8 on the surface of the Zn-BTEC;
the Zn-BTEC particles are in the form of irregular blocks with smooth surfaces, and the particle size ranges from 1 to 9 microns, preferably from 3 to 7 microns;
the ZIF-8 particles are in the shape of regular polyhedrons, and the particle size ranges from 220 nm to 280 nm, preferably from 240 nm to 260 nm;
the number of the faces of the regular polyhedron is not less than 6;
Zn-BTEC and ZIF-8 are formed by the coordination of organic ligands and metal ions;
the organic ligand is at least one of pyromellitic acid, N-dimethylformamide and 2-methylimidazole;
the metal ions are derived from oxides and/or zinc salts of zinc;
the coupling agent used for coupling is at least one selected from polyvinylpyrrolidone and polyvinyl alcohol;
the zinc salt is at least one selected from zinc nitrate, zinc sulfate and zinc chloride.
2. The method for preparing the hybrid nanocomposite Zn-BTEC@ZIF-8 according to claim 1, which is characterized by comprising the following steps:
1) Mixing pyromellitic acid, zinc oxide, ultrapure water and N, N-dimethylformamide, carrying out ultrasonic treatment, transferring and sealing the mixture into a polytetrafluoroethylene autoclave for reaction, sequentially carrying out primary centrifugal separation, ultrasonic water washing and secondary centrifugal separation on a reaction product to obtain a white solid, washing the white solid with absolute ethyl alcohol, carrying out vacuum drying to obtain Zn-BTEC, and refrigerating and storing the Zn-BTEC;
2) Dissolving Zn-BTEC in deionized water, performing ultrasonic treatment to obtain a uniform solution, adding polyvinylpyrrolidone into the uniform solution, stirring to obtain a first mixture, dissolving zinc nitrate hexahydrate in water to obtain a second mixture, adding the second mixture into the first mixture, stirring to obtain a third mixture, dissolving 2-methylimidazole in water to obtain a fourth mixture, adding the fourth mixture into the third mixture, sequentially stirring, centrifuging, washing with water, and vacuum drying to obtain Zn-BTEC@ZIF-8, and/or,
and adding the fourth mixture into the second mixture, and sequentially stirring, centrifugally separating, washing with water and drying in vacuum to obtain ZIF-8.
3. The hybrid nanocomposite Zn-btec@zif-8 according to claim 2, wherein in step 1) the moles used for pyromellitic acid and zinc oxide are the same, both being 1.3-3.5mM;
the dosage of the ultrapure water is 0.5-2mL;
the dosage of the N, N-dimethylformamide is 8-12mL.
4. The hybrid nanocomposite Zn-btec@zif-8 according to claim 2, wherein in step 1), the time of the ultrasonic treatment is 5 to 20 minutes;
the reaction temperature is 160-200 ℃ and the reaction time is 2.5-4.5 days.
5. The hybrid nanocomposite Zn-btec@zif-8 according to claim 2, wherein in step 1), the ultrasonic water washing is ultrasonic treatment after each water washing, and the number of ultrasonic water washing is not less than 3, and the time of each ultrasonic treatment is 5-15 minutes;
the rotation speed of the primary centrifugal separation is 7000-9000 rpm, and the time is 8-12 minutes;
the rotational speed of the secondary centrifugal separation is 4000-6000 rpm, and the time is 2-8 minutes;
washing with absolute ethanol for not less than 3 times;
vacuum drying at 40-60deg.C for 12-24 hr;
the temperature of the refrigerated storage is 2-6 ℃.
6. The hybrid nanocomposite Zn-btec@zif-8 according to claim 2, wherein in step 2) the amount of Zn-BTEC is 10-30mg and the amount of deionized water is 8-12mL;
The dosage of the zinc nitrate hexahydrate is 0.3-0.7g, and the dosage of the water for dissolving the zinc nitrate hexahydrate is 8-12mL;
the dosage of 2-methylimidazole is 2.2-2.7g, and the dosage of water for dissolving 2-methylimidazole is 8-12mL.
7. The hybrid nanocomposite Zn-btec@zif-8 according to claim 2, wherein in step 2), polyvinylpyrrolidone is added to the homogeneous solution and stirred for a period of 10 to 14 hours;
adding the second mixture into the first mixture, and stirring for 2-6 hours;
adding the fourth mixture into the third mixture, and stirring for 2-6 hours;
the rotation speed of centrifugal separation is 7000-9000 rpm, and the time is 8-12 minutes;
the times of water washing are not less than 3 times, and the water consumption is 18-22mL each time;
the temperature of vacuum drying is 60-80 ℃ and the time is 10-14 hours.
8. A fluorescent probe Zn-BTEC@ZIF-8@Tet for detecting histamine content of fish is characterized by comprising the following components:
1) The Zn-btec@zif-8 of any one of claims 1 to 4;
2) Tetracycline hydrochloride;
3) Tris-HCl buffer;
based on the volume of Zn-BTEC@ZIF-8@Tet, the concentration of Zn-BTEC@ZIF-8 is 1.00-1.50mg/L, and the concentration of tetracycline hydrochloride is 0.9-1.2mM.
9. The fluorescent probe Zn-btec@zif-8@tet according to claim 8, wherein said Zn-btec@zif-8@tet is prepared by a method comprising the steps of:
1) Adding the Zn-BTEC@ZIF-8 aqueous solution according to any one of claims 1-4 into Tris-HCl buffer solution, and uniformly mixing to obtain a buffer primary solution;
2) Adding tetracycline hydrochloride into the buffer primary solution, and uniformly mixing to obtain Zn-BTEC@ZIF-8@Tet;
the pH value of the Tris-HCl buffer solution is 7-9;
based on the volume of Zn-BTEC@ZIF-8@Tet, the concentration of Zn-BTEC@ZIF-8 is 1.00-1.50mg/L, and the concentration of tetracycline hydrochloride is 0.9-1.2mM.
10. A fluorescence detection method for detecting the histamine content of fish, which is characterized in that the Zn-BTEC@ZIF-8@Tet as claimed in claim 8 or 9 is used for carrying out fluorescence detection on the histamine content of fish;
the linear range of the fluorescence detection of the histamine concentration of the fish is 2-1000mg/L;
the detection limit of fluorescence detection is not more than 1.458mg/L;
the excitation wavelength for fluorescence detection is 365-395nm, preferably 380-390nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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