CN112694547A - Fluorescent sensor material and preparation method and application thereof - Google Patents
Fluorescent sensor material and preparation method and application thereof Download PDFInfo
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- CN112694547A CN112694547A CN202011563144.XA CN202011563144A CN112694547A CN 112694547 A CN112694547 A CN 112694547A CN 202011563144 A CN202011563144 A CN 202011563144A CN 112694547 A CN112694547 A CN 112694547A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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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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- 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
Abstract
The invention provides a fluorescent sensor material and a preparation method and application thereof. The general molecular structure formula of the fluorescent sensor material is as follows: eu (beta-diketones)Xdinitrogen‑CDYEu is europium ion, β -diketones is β -diketone ligand, dinitrogen is dinitrogen ligand, CD is β -cyclodextrin, X ═ 1 or 2, Y ═ 1 or 2; the invention also provides a preparation method and application of the fluorescent sensor material. The fluorescent sensor material contains rare earth europium complexes of three ligands of beta-cyclodextrin, beta-diketone ligand and dinitrogen ligand, and the three ligands are Eu3+The luminescence has sensitization, combines the good luminescence property of rare earth europium and the hydrophilic and lipophilic characteristics of beta-cyclodextrin, and selectively identifies Fe3+High selectivity, reversibility, application in organism and environmental water solution system3+Detection of (3).
Description
Technical Field
The invention relates to the technical field of fluorescent sensors, in particular to a fluorescent sensor material and a preparation method and application thereof.
Background
The identification and sensing of metal ions is an important research direction and is currently receiving attention in the biological and environmental fields. Excess or lack of metal ions can lead to various diseases and toxic reactions, such as: if the body is lack of iron, the synthesis of hemoglobin can be influenced, and the activity of enzymes such as cytochrome c, ribonucleotide reductase, succinate dehydrogenase and the like can be reduced, so that serious body dysfunction is caused; fe in human body3+The change in the content is associated with many diseases, such as anemia, cancer, diabetes, organ dysfunction due to iron deficiency, etc., and the excess of iron induces Alzheimer's disease, Huntington's disease, Parkinson's disease, etc., by producing reactive oxygen species through Fenton's reaction.
The fluorescence detection method has the advantages of simple method, high sensitivity, good selectivity, in-situ and real-time detection and the like, and becomes an essential detection means in modern analytical chemistry, supermolecular chemistry, environmental chemistry and life science research. In the moleculeIn the identification technology, the fluorescence sensor method has obvious advantages over other traditional detection methods, and is attracting more and more attention of researchers. Therefore, as an effective and simple detection method, the fluorescence sensing technology has been widely applied to ferric ion (Fe)3+) Identification of (1).
The rare earth metal complex, particularly europium and terbium, has longer fluorescence life, characteristic fluorescence and larger Stokes shift in a long wavelength region, fluorescent emission is not easily interfered by a background, and the rare earth metal complex has unique fluorescent property and is widely used for a fluorescent sensor. At present, the existing rare earth ion complex for the fluorescence sensor needs to identify metal ions in an organic solvent, and the organic solvent has toxicity, pollutes the environment and has toxic and harmful effects on cells, so that Fe is limited3+The application of the rare earth metal complex for the fluorescence sensor in a water system; therefore, it cannot be used for the detection of ferric ions in organisms and the environment.
Disclosure of Invention
The invention aims to provide a fluorescent sensor material, a preparation method and application thereof, and aims to solve the problem that in the prior art, a rare earth ion complex for a fluorescent chemical sensor detection technology can identify metal ions only in an organic solvent, so that secondary pollution is caused, and the fluorescent chemical sensor material cannot be used for detecting ferric ions in organisms and environment.
In order to solve the technical problem, the technical scheme of the invention is realized as follows:
in one aspect, the invention provides a fluorescent sensor material, which has a molecular structural formula: eu (beta-diketones)Xdinitrogen-CDYIn the formula: eu is europium ion, β -diketones is a β -diketone ligand, dinitrogen is a dinitrogen ligand, CD is β -cyclodextrin, X ═ 1 or 2, Y ═ 1 or 2.
The fluorescent sensor material is a unique rare earth europium complex which contains three ligands of beta-cyclodextrin, beta-diketone ligand and dinitrogen ligand, and the three ligands are used for trivalent europium ions (Eu)3+) Has sensitization effect on luminescenceThe good luminescent property of rare earth and the amphiphilic characteristic of the beta-cyclodextrin which is hydrophilic and lipophilic are fused, the obtained fluorescent sensor material has stable performance and can be used for Fe3+Selective recognition of, with respect to, Fe3+High selectivity and reversibility of Fe, and application of Fe in organism and environmental water solution system3+The detection method is simple to operate, does not contain organic solvent, has no toxicity, does not pollute the environment, does not have toxic action on cells, does not cause secondary pollution, and is safe to use. In the fluorescent sensor material of the present invention, europium ion (Eu)3+) The molar percentage of the beta-diketone ligand (beta-diketones) is 20-25%, the molar percentage of the beta-diketone ligand (beta-diketones) is 20-40%, the molar percentage of the dinitrogen ligand (dinitrogen) is 20-25%, and the molar percentage of the beta-Cyclodextrin (CD) is 20-40%.
In the present invention, Eu3+D-f transition of (D) to make rare earth Eu3+Produce intense fluorescence when Eu3+After being coordinated with beta-diketone ligands and dinitrogen ligands, the ligands are used for Eu3+The luminescence has sensitization, so-called 'antenna effect', so that the rare earth europium complex is more dynamic, the final fluorescent sensor material has the potential performance of a reversible fluorescent switch, and the fluorescent reaction of the type can change the fluorescent intensity of rare earth by changing the stimulation drive of a ligand. In addition, the rare earth europium complex is a dynamically combined high polymer material, has potential coordination, and has more advantages in biological systems and environmental detection systems.
beta-Cyclodextrin (CD) is the most widely used cyclodextrin product, and is a cyclic glucose oligomer consisting of seven glucoses, and the interior of the cyclic glucose oligomer has a hydrophobic cavity capable of being connected with Eu3+Coordination occurs, the fluorescence characteristic is adjusted, and the water solubility and the stability are improved. The beta-cyclodextrin has the excellent performances of no toxicity, amphipathy, inclusion of host and guest, and the like, and has wide application in the fields of food, medicaments, gene transfer, and the like. Beta-cyclodextrin and Eu3+The complex is integrated into an aggregate, namely a fluorescent sensor material, is an amphiphilic material with excellent luminescence property, and the material integrates the good luminescence property of rare earth and beta-cyclodextrin which is hydrophilic and lipophilicThe amphiphilic character of (a). The key point is that the beta-cyclodextrin can simultaneously regulate Eu3+The fluorescence intensity of (2), the water solubility is enhanced, and the toxicity is reduced. In the present invention, Eu is added3+The complex is self-assembled with nontoxic beta-cyclodextrin with amphiphilic property to prepare beta-cyclodextrin enhanced Eu3+The luminescent aggregate, namely the fluorescent material, has the advantages of high luminescent intensity, large Stokes shift, low detection limit, good water solubility and the like, and realizes the selective identification of iron ions in an aqueous solvent.
As a preferred embodiment, the beta-diketone ligand is any one or more of 2-thenoyl trifluoroacetone, 2-thenoyl trichloroacetone and dibenzoyl methane. The beta-diketone ligand has strong coordination capability with the rare earth europium, and the beta-diketone is used as the ligand of the rare earth europium, so that the fluorescent sensor material emits the characteristic fluorescence of the rare earth europium through the strong ultraviolet absorption of the beta-diketone and the energy transfer to the rare earth europium, and has excellent fluorescence performance.
In a preferred embodiment, the dinitrogen ligand is any one of 1, 10-phenanthroline and 2, 2' -bipyridine. The dinitrogen ligand has strong coordination capability with rare earth europium, and can obviously enhance Eu3+The luminescence sensitization effect of (1); the double-nitrogen ligand is used as the ligand of the rare earth europium, and the fluorescent sensor material emits the characteristic fluorescence of the rare earth europium through the strong ultraviolet absorption of the double-nitrogen ligand and the energy transfer to the rare earth europium, so that the fluorescent sensor material has excellent fluorescence performance.
The general molecular structure formula of the fluorescent sensor material in the invention can also be expressed as:
wherein R is1And R2Saturated or saturated group with carbon number of 1-8, cyclohexyl, cyclopentyl, phenyl, substituted phenyl, naphthyl, biphenyl, pyridine, bipyridine, imidazole, pyrrole, imidazole, naphthyridine, quinoline and substituted derivatives thereof, etc.; r3And R4Hydrogen radicals, methyl radicals, vinyl radicals and the like.
When X is 1 and Y is 1, the molecular structural formula of the fluorescent sensor material is as follows:
when X is 1 and Y is 2, the molecular structural formula of the fluorescent sensor material is as follows:
as a preferred embodiment, the morphology of the fluorescent sensor material is a network structure. The fluorescent sensor material is a reticular structure formed by stacking nanoparticles observed under a transmission electron microscope after being dried, a large number of hydroxyl groups exist in the reticular structure, oxygen atoms on the hydroxyl groups can generate coordination with ferric ions, and meanwhile, the ferric ions can form a competitive relationship with rare earth europium to compete for coordination with beta-diketone ligands, dinitrogen ligands and beta-cyclodextrin, so that the fluorescent sensor material can be used for identifying the ferric ions.
In another aspect, the invention provides a method for preparing a fluorescent sensor material, comprising the following steps: 1) preparing a europium salt into a europium salt ethanol solution, wherein the molar concentration of the europium salt ethanol solution is 0.001-0.1M; preparing beta-diketone ligand ethanol solution with the molar concentration of 0.001-0.1M by taking the beta-diketone ligand; preparing a dinitrogen ligand ethanol solution from the dinitrogen ligand, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.001-0.1M; mixing an europium salt ethanol solution and a beta-diketone ligand ethanol solution, wherein the molar ratio of beta-diketone ligand to europium salt is 1:1-2:1, stirring at normal temperature for 1-2h, adjusting the pH value to 7-8, adding a double-nitrogen ligand ethanol solution, wherein the molar ratio of double-nitrogen ligand to europium salt is 1:1-1.5:1, and stirring at normal temperature for 2-4h to obtain a rare earth europium complex ethanol solution; 2) preparing beta-cyclodextrin into a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.00033-0.033M; adding a beta-cyclodextrin aqueous solution into the rare earth europium complex ethanol solution obtained in the step 1), wherein the molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:1-2:1, and stirring at normal temperature for 1-3h to obtain the fluorescent material.
The preparation method of the fluorescent sensor material is simple, convenient to operate, low in energy consumption, free of special instruments and equipment, high in efficiency, free of toxic and harmful gas in the preparation process and free of environment pollution, and is carried out at room temperature. The fluorescent sensor material of the invention is beta-cyclodextrin enhanced Eu3+The luminescent aggregate obtains the strongest emission peak at 612nm under the excitation of 390nm, and belongs to Eu3+4f electron transport of5D0→7FJ(612nm, J ═ 2). Beta-cyclodextrin enhanced Eu3+The luminescent aggregate can be used as a fluorescent sensor applied to Fe3+Selective identification of (2). The sensor has Eu3+Bright red fluorescence of in Fe3+At a concentration of 50. mu.M, a rapid response and a high sensitivity of selectivity were exhibited. Adding Fe3+After-fluorescence quenching, the fluorescence can be enhanced by adding Ethylene Diamine Tetraacetic Acid (EDTA), which indicates that Fe3+Fluorescence quenching is reversible in the presence. Fe3+The fluorescent sensor belongs to a 'switch type' fluorescent sensor, and combines the good luminous characteristic of rare earth and the amphiphilic characteristic of the beta-cyclodextrin which is both hydrophilic and lipophilic. It is a unique enhanced Eu in an ethanol-water system3+Luminescent aggregates of p-Fe3+High selectivity and reversibility of the Fe-Fe alloy can be applied to an environmental aqueous solution system3+Detection of (3).
In a preferred embodiment, in the step 1), the molar concentration of the rare earth europium complex in the rare earth europium complex ethanol solution is 0.001-0.1M. The molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:1-2:1, the molar concentration of the rare earth europium complex in the rare earth europium complex ethanol solution is controlled, and the dosage of the rare earth europium complex ethanol solution can be more conveniently controlled, so that the reaction process of the rare earth europium complex ethanol solution and the beta-cyclodextrin aqueous solution is controlled, and the fluorescent material with high fluorescence intensity is obtained.
As a preferred embodiment, in step 1), the europium salt is any one of europium chloride, europium acetate and europium nitrate. The europium salt of the present invention is a soluble europium salt, for example: europium salt is dissolved to obtain europium ions, so that the europium ions coordinate with the ligand.
As a preferred embodiment, in the step 1), the stirring speed is 400-800 r/min. The reaction of the rare earth europium complex ethanol solution is carried out at normal temperature, the operation is convenient, the energy consumption is low, the reaction is easy to realize, and the industrialization is easy.
As a preferred embodiment, in the step 2), the stirring speed is 400-800 r/min. The coordination reaction of the rare earth europium complex ethanol solution and the beta-cyclodextrin aqueous solution is also carried out at normal temperature, so that the simplicity and convenience of the preparation method are further improved, the control is convenient, and the industrialization is easy to realize; by comparing the fluorescence intensities of the fluorescent sensor materials with different proportions of the beta-cyclodextrin and the rare earth europium complex, the fluorescent sensor material has stronger fluorescence intensity when the molar ratio of the beta-cyclodextrin to the rare earth europium complex is 1:1-2: 1.
In a further aspect, the invention relates to the application of the fluorescent sensor material, and the application of the fluorescent sensor material in the detection of ferric ions in organisms and environmental aqueous solution systems.
The fluorescent sensor material of the invention is beta-cyclodextrin enhanced Eu3+Luminescent aggregates for the preparation of selectively recognising Fe3+The fluorescent sensor can be directly applied to the detection of ferric ions in organisms and environmental aqueous solution systems, and has the function of detecting Fe3+High selectivity and reversibility.
Compared with the prior art, the invention has the beneficial effects that: the fluorescent sensor material is a unique rare earth europium complex which contains three ligands of beta-cyclodextrin, beta-diketone ligand and dinitrogen ligand, and the three ligands are used for trivalent europium ions (Eu)3+) The obtained product has sensitization effect, combines the good luminescence property of rare earth and the amphiphilic characteristics of the beta-cyclodextrin which is both hydrophilic and lipophilicThe fluorescent sensor material has stable performance and is used for Fe3+The Fe-based nano-material has the advantages of selective identification, quick response and high selectivity, and can be applied to Fe in organisms and environmental aqueous solution systems3+The detection is simple to operate, and the detection does not contain organic solvent, has no toxicity, does not pollute the environment, does not have toxic action on cells, does not cause secondary pollution and is safe to use; fe is added into the fluorescent sensor material3+Then, the fluorescence intensity is weakened and quenched, the fluorescence quenching is reversible, and after EDTA is continuously added, the fluorescence can be enhanced, so that the beta-cyclodextrin provided by the invention enhances Eu3+The luminescent aggregate, i.e. the fluorescent sensor material has reversibility, i.e. the fluorescence has switching performance, so that the beta-cyclodextrin enhances Eu3+Luminescent aggregates, i.e. fluorescent sensor materials, belong to the "on-off" fluorescent sensors.
Drawings
FIG. 1 is a transmission electron microscope image of a fluorescent material obtained in accordance with an embodiment of the present invention;
FIG. 2 is a transmission electron microscope image of a fluorescent material obtained in example two of the present invention;
FIG. 3 is a transmission electron microscope image of a fluorescent material obtained in example III of the present invention;
FIG. 4 shows a phosphor and Fe and phosphor thereof obtained in accordance with an embodiment of the present invention3+Fluorescence emission spectrogram of a test solution consisting of the aqueous solution;
FIG. 5 shows the fluorescent material obtained in the second embodiment of the present invention and Fe3+Fluorescence emission spectrogram of a test solution consisting of the aqueous solution;
FIG. 6 shows the fluorescent material obtained in the third embodiment of the present invention and Fe3+Fluorescence emission spectrogram of a test solution consisting of the aqueous solution;
FIG. 7 is a graph showing the fluorescence response of the fluorescent material obtained in the third embodiment of the present invention to different metal ions;
FIG. 8 shows the fluorescent material obtained in the third embodiment of the present invention for different concentrations of Fe3+Fluorescence emission spectrum of (a);
FIG. 9 shows Fe in the presence of different concentrations of ethylenediaminetetraacetic acid (EDTA)3+And fluorescent material obtained in example III of the present inventionFluorescence emission spectrogram of the formed fluorescence quenching solution;
FIG. 10 is a fluorescence emission spectrum of the fluorescent material obtained in the third embodiment of the present invention and a rare earth europium ion complex without added beta-cyclodextrin ligand.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a fluorescent sensor material, which has a molecular structure general formula as follows: eu (beta-diketones)Xdinitrogen-CDYIn the formula: eu is europium ion, β -diketones is a β -diketone ligand, dinitrogen is a dinitrogen ligand, CD is β -cyclodextrin, X ═ 1 or 2, Y ═ 1 or 2.
Preferably, the beta-diketone ligand is any one or more of 2-thenoyl trifluoroacetone, 2-thenoyl trichloroacetone and dibenzoyl methane.
Preferably, the bis-nitrogen ligand is any one of 1, 10-phenanthroline and 2, 2' -bipyridine.
Preferably, the morphology of the fluorescent sensor material is a mesh structure.
The invention discloses a preparation method of a fluorescent sensor material, which comprises the following steps:
1) preparation of rare earth europium complex
Preparing europium salt into a europium salt ethanol solution, wherein the molar concentration of the europium salt ethanol solution is 0.001-0.1M; preparing beta-diketone ligand ethanol solution with the molar concentration of 0.001-0.1M by taking the beta-diketone ligand; preparing a dinitrogen ligand ethanol solution from the dinitrogen ligand, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.001-0.1M;
mixing an europium salt ethanol solution and a beta-diketone ligand ethanol solution, wherein the molar ratio of beta-diketone ligand to europium salt is 1:1-2:1, stirring at normal temperature for 1-2h, adjusting the pH value to 7-8, adding a double-nitrogen ligand ethanol solution, wherein the molar ratio of double-nitrogen ligand to europium salt is 1:1-1.5:1, and stirring at normal temperature for 2-4h to obtain a rare earth europium complex ethanol solution;
2) preparation of fluorescent materials
Preparing beta-cyclodextrin into a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.00033-0.033M; adding a beta-cyclodextrin aqueous solution into the rare earth europium complex ethanol solution obtained in the step 1), wherein the molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:1-1:2, and stirring at normal temperature for 1-3h to obtain the fluorescent material.
Preferably, in the step 1), the molar concentration of the rare earth europium complex in the rare earth europium complex ethanol solution is 0.001-0.1M.
Further, in the step 1), the europium salt is any one of europium chloride, europium acetate and europium nitrate.
Preferably, in the step 1), the stirring speed is 400-800 r/min.
Preferably, in the step 2), the stirring speed is 400-800 r/min.
The invention relates to an application of a fluorescent sensor material, in particular to an application of the fluorescent sensor material in ferric ion detection in organism and environmental aqueous solution systems.
Example one
The invention discloses a preparation method of a fluorescent sensor material, which comprises the following steps:
preparation of S1 rare earth europium complex
1) Taking europium chloride, and adding absolute ethyl alcohol to prepare a europium chloride ethanol solution, wherein the molar concentration of the europium chloride ethanol solution is 0.001M for later use;
2) taking beta-diketone ligand 2-thenoyl trichloroacetone, and adding absolute ethyl alcohol to prepare a beta-diketone ligand ethanol solution, wherein the molar concentration of the beta-diketone ligand ethanol solution is 0.001M for later use;
3) taking a dinitrogen ligand 2, 2' -bipyridine, and adding absolute ethanol to prepare a dinitrogen ligand ethanol solution, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.001M for later use;
4) mixing the europium chloride ethanol solution obtained in the step 1) with the beta-diketone ligand ethanol solution obtained in the step 2), wherein the molar ratio of beta-diketone ligand to europium chloride is 1:1, stirring at normal temperature for 1h, adjusting the pH value to 7, adding the dinitrogen ligand ethanol solution obtained in the step 3), wherein the molar ratio of dinitrogen ligand to europium chloride is 1:1, and stirring at normal temperature for 2h to obtain a rare earth europium complex ethanol solution;
preparation of S2 fluorescent material
5) Adding water into beta-cyclodextrin to prepare a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.00033M for later use;
6) adding the beta-cyclodextrin aqueous solution obtained in the step 5) into the rare earth europium complex ethanol solution obtained in the step 4), wherein the molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:1, and stirring at normal temperature for 1h to obtain the fluorescent material.
Example two
The invention discloses a preparation method of a fluorescent sensor material, which comprises the following steps:
preparation of S1 rare earth europium complex
1) Taking europium nitrate, and adding absolute ethyl alcohol to prepare a europium nitrate ethanol solution, wherein the molar concentration of the europium nitrate ethanol solution is 0.1M for later use;
2) taking a beta-diketone ligand 2-thenoyl trifluoroacetone, and adding absolute ethyl alcohol to prepare a beta-diketone ligand ethanol solution, wherein the molar concentration of the beta-diketone ligand ethanol solution is 0.1M for later use;
3) taking the dinitrogen ligand-1, 10-phenanthroline, and adding absolute ethanol to prepare dinitrogen ligand ethanol solution, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.1M for later use;
4) mixing the europium nitrate ethanol solution obtained in the step 1) with the beta-diketone ligand ethanol solution obtained in the step 2), wherein the molar ratio of beta-diketone ligand to europium nitrate is 2:1, stirring at normal temperature for 2 hours, the stirring speed is 400r/min, adjusting the pH value to 8, adding the dinitrogen ligand ethanol solution obtained in the step 3), the molar ratio of dinitrogen ligand to europium nitrate is 1.5:1, stirring at normal temperature for 4 hours, and the stirring speed is 400r/min to obtain a rare earth europium complex ethanol solution;
preparation of S2 fluorescent material
5) Adding water into beta-cyclodextrin to prepare a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.033M for later use;
6) and (3) adding the beta-cyclodextrin aqueous solution obtained in the step 5) into the rare earth europium complex ethanol solution obtained in the step 4), wherein the molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:2, stirring for 3 hours at normal temperature and the stirring speed of 400r/min, and thus obtaining the fluorescent material.
EXAMPLE III
The invention discloses a preparation method of a fluorescent sensor material, which comprises the following steps:
preparation of S1 rare earth europium complex
1) Taking europium acetate, and adding absolute ethyl alcohol to prepare a europium acetate ethanol solution, wherein the molar concentration of the europium acetate ethanol solution is 0.01M for later use;
2) taking beta-diketone ligand dibenzoyl methane, adding absolute ethyl alcohol to prepare beta-diketone ligand ethanol solution, wherein the molar concentration of the beta-diketone ligand ethanol solution is 0.01M for later use;
3) taking a dinitrogen ligand 2, 2' -bipyridine, and adding absolute ethanol to prepare a dinitrogen ligand ethanol solution, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.01M for later use;
4) mixing 1mL of the europium acetate ethanol solution obtained in the step 1) with 1mL of the beta-diketone ligand ethanol solution obtained in the step 2), stirring at normal temperature for 1.5h at the stirring speed of 800r/min, adjusting the pH value to 7.5, adding 1mL of the dinitrogen ligand ethanol solution obtained in the step 3), stirring at normal temperature for 3h at the stirring speed of 800r/min, and obtaining a rare earth europium complex ethanol solution;
preparation of S2 fluorescent material
5) Preparing beta-cyclodextrin into a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.0033M for later use;
6) adding 1mL of the beta-cyclodextrin aqueous solution obtained in the step 5) into the rare earth europium complex ethanol solution obtained in the step 4), and stirring at the normal temperature for 2h at the stirring speed of 800r/min to obtain the fluorescent material.
Experiment 1
Through calculation, in the fluorescent material obtained in the first embodiment of the invention, the molar concentration of the rare earth europium ion is 0.25 mM; in the fluorescent material obtained in the second embodiment of the invention, the molar concentration of the rare earth europium ions is 25 mM; in the fluorescent material obtained in the third embodiment of the invention, the molar concentration of the rare earth europium ion is 2.5 mM.
The fluorescent material obtained in the first embodiment of the present invention was dried and placed on a JEM-1200CXII type transmission electron microscope manufactured by Japan Electron Ltd for observation. As can be seen from the attached drawings 1, 2 and 3, the fluorescent material obtained by the method has a net-shaped structure, the net-shaped structure is formed by stacking nano ions, a large number of hydroxyl groups exist in the net-shaped structure, oxygen atoms on the hydroxyl groups can generate coordination with ferric ions, and meanwhile, the ferric ions can form a competitive relationship with rare earth europium to compete for coordination with beta-diketone ligands, dinitrogen ligands and beta-cyclodextrin, so that the fluorescent material can be used as a fluorescent sensor material to identify the ferric ions.
Experiment 2
The three parts of fluorescent materials obtained in the first to third embodiments of the invention are respectively used for measuring ferric ions in an environmental aqueous solution system, and the Fe pairs of the fluorescent materials are verified3+The identification performance of (1). The determination method comprises the following steps: firstly, three parts of the fluorescent material obtained by the invention are taken and are excited by 390nm on an F-4500 type spectrum determinator manufactured by Hitachi company to determine the fluorescence property; then, 3 parts of 60. mu. L0.1mol/L Fe were added3+The solution was added to 4mL of the three fluorescent materials obtained in the present invention to obtain a test solution, and the fluorescence properties thereof were measured on a type F-4500 spectrometer manufactured by Hitachi under the same parameters. Wherein, in the three test solutions, Fe3+The molar concentrations of (A) and (B) were all 1500. mu.M.
As can be seen from the attached figures 4, 5 and 6, when the fluorescence property of the three parts of fluorescent materials obtained by the invention is tested, under the excitation of 390nm, the fluorescence properties are all at 612nmShows a strong fluorescence intensity peak; this shows that the fluorescent material obtained by the invention has good fluorescence performance. As can be further seen from the attached FIGS. 4, 5 and 6, when the ferric ion aqueous solution is added into the fluorescent material of the present invention for the fluorescence performance test again, under the excitation of 390nm, the fluorescence is quenched at 612 nm; therefore, the fluorescent material of the invention can be used as a reagent of a fluorescence sensor for Fe3+Identification of (1). Furthermore, in the experimental process, Fe is added into the fluorescent material of the invention3+After the aqueous solution is shaken for 1-2 seconds, the mixture can be uniformly mixed, and the fluorescence test is immediately carried out, so that the fluorescence response can be generated and the quenching can be carried out. Thus, the fluorescent material of the present invention is paired with Fe3+The response speed of (2) is fast.
Experiment 3
Taking the fluorescent material obtained in the third embodiment of the invention as an example, the fluorescent material is used for determining the identification condition of other metal ions in an environmental aqueous solution system, such as: ca2+、K+、Mg2+、Na+、Mn2+、Al3+、Cr3+、Zn2+、Cu2+、Co2+And Ni2+Verification of its pairing with Fe3+Selective identification of performance. The determination method comprises the following steps: 11 parts of the fluorescent material obtained in the third example of the invention were taken, 4mL of each fluorescent material (the molar concentration of europium ions in the fluorescent material was 2.5mM) was added with 50. mu.L of 0.1mol/L of Ca2+、K+、Mg2+、Na+、Mn2+、Al3+、Cr3 +、Zn2+、Cu2+、Co2+And Ni2+The fluorescence property was measured under excitation at 390nm on a spectrometer F-4500, manufactured by Hitachi corporation, using an aqueous solution of metal ions as a reference. The molar concentrations of the metal ions in 11 control test solutions were also 1500. mu.M. The obtained fluorescence intensity I and the fluorescence intensity I of the fluorescence sensor material obtained in the invention measured in experiment 2 are used0And comparing to obtain the ratio of the two, namely: I/I0(ii) a And compared with the test results of ferric ions under the same conditions as in experiment 2.
As can be seen from FIG. 7, the fluorescence of the present inventionMaterial and metal ion Ca2+、K+、Mg2+、Na+、Mn2+、Al3+、Cr3 +、Zn2+、Cu2+、Co2+、Ni2+And Fe3+When the test solution consisting of the aqueous solution is used for testing the fluorescence property, the test solution added with the ferric ion aqueous solution has the most obvious reduction of the fluorescence intensity, and the I/I0The ratio of (A) to (B) is minimum; the fluorescence intensity of the test solution added with the aqueous solution of other metal ions is basically unchanged or slightly reduced. The fluorescent material obtained by the invention has strong fluorescence intensity, and the obvious change of the fluorescence intensity can selectively identify Fe after the ferric ion aqueous solution is added3+. Therefore, the fluorescent material of the invention can selectively identify Fe3+And, the selectivity is high.
Experiment 4
Taking the fluorescent material obtained in the third embodiment of the invention as an example, reversible experiments are carried out to verify that the fluorescent material is Fe3+Has reversibility. The determination method comprises the following steps: 11 parts of the fluorescent material obtained in the third example of the present invention (molar concentration of europium ion in the fluorescent material: 2.5mM) were taken, and 4mL of each was added to 2. mu.L, 5. mu.L, 8. mu.L, 10. mu.L, 15. mu.L, 20. mu.L, 25. mu.L, 30. mu.L, 40. mu.L, 50. mu.L, and 60. mu.L of 0.1mol/L of Fe3+The fluorescence property was measured under excitation at 390nm on a spectrometer model F-4500, manufactured by Hitachi corporation. Then, 6 parts of the fluorescent material obtained in example III of the present invention (the molar concentration of europium ions in the fluorescent material was 2.5mM) were each 4mL, and 60. mu.L of 0.1mol/L Fe was added to each of the 6 parts3+To obtain a fluorescence quenching solution; then, 50. mu.L, 100. mu.L, 150. mu.L, 200. mu.L, 300. mu.L, and 400. mu.L of a 0.1mol/L EDTA aqueous solution were added to the above-mentioned fluorescence quenching solution, respectively, and the fluorescence properties were measured under excitation at 390nm on a spectral measuring instrument of F-4500 type manufactured by Hitachi corporation.
As can be seen from FIG. 8, with Fe3+Increasing concentration (50. mu.M, 125. mu.M, 200. mu.M, 250. mu.M, 375. mu.M, 500. mu.M, 625. mu.M, 750. mu.M, 1000. mu.M, 1250. mu.M, 1500. mu.M) and gradually decreasing fluorescence intensity; when Fe3+Mole ofAt a concentration of 1500. mu.M, the fluorescence was quenched. As can be seen from FIG. 9, in Fe3+And a fluorescence quenching solution (Fe) composed of the fluorescent material of the present invention3+1500 μ M), with increasing EDTA solution concentration (1.25 x 10)-3M、2.5*10-3M、3.75*10-3M、5*10-3M、6.25*10-3M、7.5*10-3M), the fluorescence intensity is gradually enhanced; this is due to the EDTA chelating Fe3+Has stronger capability of making Fe3+Stripping from the fluorescent material obtained by the invention; therefore, the fluorescence intensity is enhanced.
Therefore, the fluorescent sensor material of the invention can also be said to be beta-cyclodextrin enhanced Eu3+The luminescent aggregate, beta-cyclodextrin can enhance the luminescence of the rare earth europium complex, because the oxygen atom in the beta-cyclodextrin and Eu3+Coordination occurs to generate a new chemical bond Eu-O, so that the beta-cyclodextrin serves as a ligand to sensitize the rare earth europium ions to emit light (see figure 10). Fe3+Can weaken beta-cyclodextrin to strengthen Eu3+The fluorescence intensity of the luminescent aggregate is due to Fe3+The coordination is carried out with two oxygen atoms on the beta-diketone ligand, two nitrogen atoms in the double-nitrogen ligand and oxygen atoms in the beta-cyclodextrin, and the three ligands are weakened to Eu3+Energy transfer of (2). Thus, with Fe3+The increase in the amount gradually decreased the fluorescence intensity until quenching (see FIG. 8). Furthermore, chelation of Fe by EDTA3+Can enhance beta-cyclodextrin to enhance Eu3+Fluorescence intensity of the luminescent aggregate. This is due to EDTA and Fe3+Has particularly strong coordination ability, and EDTA obtains Fe3+Release beta-cyclodextrin, beta-diketone ligand and dinitrogen ligand, which react with Eu again3+Coordinated so that fluorescence is enhanced (see FIG. 9). Thus, the beta-cyclodextrin of the present invention enhances Eu3+The luminescent aggregate has reversibility, that is, fluorescence has switching performance, so that beta-cyclodextrin enhances Eu3+The luminescent aggregates belong to the "switch-mode" fluorescent sensor material.
Compared with the prior art, the invention has the beneficial effects that: the fluorescent sensor material of the inventionIs a unique rare earth europium complex, which contains three ligands of beta-cyclodextrin, beta-diketone ligand and dinitrogen ligand, and the three ligands are used for trivalent europium ion (Eu)3+) The obtained fluorescent sensor material has stable performance and is used for Fe3+The Fe-based nano-material has the advantages of selective identification, quick response and high selectivity, and can be applied to Fe in organisms and environmental aqueous solution systems3+The detection is simple to operate, and the detection does not contain organic solvent, has no toxicity, does not pollute the environment, does not have toxic action on cells, does not cause secondary pollution and is safe to use; fe is added into the fluorescent sensor material3+Then, the fluorescence intensity is weakened and quenched, the fluorescence quenching is reversible, and after EDTA is continuously added, the fluorescence can be enhanced, so that the beta-cyclodextrin provided by the invention enhances Eu3+The luminescent aggregate, i.e. the fluorescent sensor material has reversibility, i.e. the fluorescence has switching performance, so that the beta-cyclodextrin enhances Eu3+Luminescent aggregates, i.e. fluorescent sensor materials, belong to the "on-off" fluorescent sensors.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A fluorescent sensor material is characterized in that the molecular structure general formula of the fluorescent sensor material is as follows:
Eu(β-diketones)Xdinitrogen-CDYin the formula: eu is europium ion, β -diketones is a β -diketone ligand, dinitrogen is a dinitrogen ligand, CD is β -cyclodextrin, X ═ 1 or 2, Y ═ 1 or 2.
2. The fluorescent sensor material of claim 1, wherein:
the beta-diketone ligand is any one or more of 2-thenoyl trifluoroacetone, 2-thenoyl trichloroacetone and dibenzoyl methane.
3. The fluorescent sensor material of claim 1, wherein:
the dinitrogen ligand is any one of 1, 10-phenanthroline and 2, 2' -bipyridine.
4. The fluorescent sensor material of claim 1, wherein:
the shape of the fluorescent sensor material is a net structure.
5. A method of preparing a fluorescent sensor material according to any of claims 1 to 4, comprising the steps of:
1) preparation of rare earth europium complex
Preparing europium salt into a europium salt ethanol solution, wherein the molar concentration of the europium salt ethanol solution is 0.001-0.1M; preparing beta-diketone ligand ethanol solution with the molar concentration of 0.001-0.1M by taking the beta-diketone ligand; preparing a dinitrogen ligand ethanol solution from the dinitrogen ligand, wherein the molar concentration of the dinitrogen ligand ethanol solution is 0.001-0.1M;
mixing an europium salt ethanol solution and a beta-diketone ligand ethanol solution, wherein the molar ratio of beta-diketone ligand to europium salt is 1:1-2:1, stirring at normal temperature for 1-2h, adjusting the pH value to 7-8, adding a double-nitrogen ligand ethanol solution, wherein the molar ratio of double-nitrogen ligand to europium salt is 1:1-1.5:1, and stirring at normal temperature for 2-4h to obtain a rare earth europium complex ethanol solution;
2) preparation of fluorescent materials
Preparing beta-cyclodextrin into a beta-cyclodextrin aqueous solution, wherein the molar concentration of the beta-cyclodextrin aqueous solution is 0.00033-0.033M; adding a beta-cyclodextrin aqueous solution into the rare earth europium complex ethanol solution obtained in the step 1), wherein the molar ratio of the beta-cyclodextrin to the rare earth europium complex in the rare earth europium complex ethanol solution is 1:1-2:1, and stirring at normal temperature for 1-3h to obtain the fluorescent material.
6. The method for preparing a fluorescent sensor material according to claim 5, wherein:
in the step 1), the molar concentration of the rare earth europium complex in the rare earth europium complex ethanol solution is 0.001-0.1M.
7. The method for preparing a fluorescent sensor material according to claim 5, wherein:
in the step 1), the europium salt is any one of europium chloride, europium acetate and europium nitrate.
8. The method for preparing a fluorescent sensor material according to claim 5, wherein:
in the step 1), the stirring speed is 400-800 r/min.
9. The method for preparing a fluorescent sensor material according to claim 5, wherein:
in the step 2), the stirring speed is 400-800 r/min.
10. Use of a fluorescent sensor material according to any one of claims 1 to 4, wherein:
the fluorescent sensor material is applied to detection of ferric ions in organisms and environmental aqueous solution systems.
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