CN116239783A - Double-emission rare earth metal organic framework material for detecting heavy metal lead ions and sulfonamides - Google Patents
Double-emission rare earth metal organic framework material for detecting heavy metal lead ions and sulfonamides Download PDFInfo
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- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 37
- 150000002500 ions Chemical class 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 29
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- 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
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Abstract
The invention relates to a double-emission rare earth metal organic frame material for detecting heavy metal lead ions and sulfonamides. The double-emission rare earth metal organic frame material is prepared from two rare earth salts and two rigid ligands by adopting a simple hydrothermal method, has good water stability, and can binary decode an object to be detected through the internal fluorescence intensity ratio of the two rare earth metals. Can selectively detect lead ions and sulfonamides, and can also realize quantitative detection at the same time. Compared with the traditional fluorescence sensing method based on single emission intensity, the method for double-reading orthogonal identification of the multi-emission site material through the decoding diagram can be used for built-in correction, effectively reduces interference of various factors, reduces errors, and is more reliable.
Description
Technical Field
The invention relates to the technical field of fluorescent sensing materials for detecting typical pollutants (heavy metal lead ions and sulfonamide antibiotics) in soil, in particular to preparation and application of a dual-rare earth metal-organic framework material.
Background
Soil is relatively stable in position compared with water and the atmosphere, and pollutants are easy to gather, so that the soil becomes a sink of various pollutants, such as heavy metals and antibiotics. Lead is a typical heavy metal contaminant in which most of the lead circulates in soil and groundwater, enters the human body through the food chain and accumulates in the body, thereby causing serious and long-term effects on human health. Even very small amounts of lead accumulation can cause neurological, reproductive disorders and cardiovascular problems. The sulfonamides are artificially synthesized antibiotics, have the characteristics of broad antibacterial spectrum and low cost and stability, and can be combined with antibacterial synergists, so that the sulfonamides are widely used for preventing and treating various animal diseases. However, such drugs are easy to release into the natural environment after use, destroy the flora balance in the natural environment, and also can enter the human body through the food chain to cause potential risks. Therefore, the method has important significance in environmental monitoring and detection of heavy metal lead ions and sulfonamides.
The traditional detection method of the metal ions mainly comprises an atomic absorption emission spectrometry, an inductively coupled plasma mass spectrometry and the like, and the traditional detection method of the medicines mainly comprises an instrument detection method such as a high performance liquid chromatography and the like. The methods have the defects of time and labor consumption, high cost, complex use, inconvenience in carrying and the like, and have limited application range, and are particularly applied to field actual analysis. In recent years, fluorescence has been attracting attention because of its advantages of high detection speed, high sensitivity, good selectivity, easy operation, low cost, and the like.
Rare earth metal organic frameworks (Ln-MOFs) have received increasing attention in recent years due to their rich coordination structures and special luminescence properties. The rare earth ion has the characteristics of large Stokes shift, high characteristic emission peak intensity, long fluorescence life and the like. As a metal center in Ln-MOFs, good fluorescent properties are exhibited under the energy transfer effect of the organic ligand. The invention designs a double-emission rare earth metal organic frame material, which can decode a plurality of detected objects through the internal fluorescence intensity ratio of two rare earth metals, selectively detect lead ions and sulfonamides, realize quantification and show high selectivity and sensitivity. Compared with the traditional fluorescence sensing method based on single emission intensity, the double-emission site material has richer identification information through fluorescence intensity compared with the established decoding graph, can effectively reduce the interference of various factors, and increases the reliability and accuracy of detection, thereby having higher application value.
Disclosure of Invention
The invention aims to provide a dual rare earth metal-organic framework material for selectively detecting heavy metal lead ions and sulfonamides and a preparation method thereof. The prepared rare earth metal organic frame material has double emission sites, can decode various detected objects through the internal fluorescence intensity ratio of two rare earth metals, selectively detect lead ions and sulfonamides, realize quantification and show high selectivity and sensitivity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention adopts a simple hydrothermal method to synthesize the double-emission rare earth metal organic frame material, and the preparation method comprises the following specific steps:
weighing pyromellitic acid, 4, 5-imidazole dicarboxylic acid, europium nitrate hexahydrate and terbium nitrate hexahydrate in different molar ratios, placing into a polytetrafluoroethylene reaction vessel, adding ultrapure water, after ultrasonic homogenization, placing the polytetrafluoroethylene reaction vessel into a high-temperature high-pressure hydrothermal reaction kettle, reacting for 48 hours at a constant temperature of 100 ℃, and naturally cooling to room temperature. Finally, the white solid is collected by centrifugal separation and dried for 10 to 12 hours at the temperature of 60 to 80 ℃ to obtain the double-emission rare earth metal organic frame material.
The different molar ratios of europium nitrate hexahydrate and terbium nitrate hexahydrate in the above steps are as follows: 1:0,8:2,6:4,4:6,2:8,1:9,0:1.
Application:
the double-emission rare earth metal organic frame material has good water stability, double-emission sites, can be used for binary decoding through the internal fluorescence intensity ratio of two rare earth metals, and is applied to the selective detection of heavy metal lead and sulfonamides. The specific detection method comprises the following steps: adding 2mg of double-emission rare earth metal organic frame material into 20ml of different metal nitrate solutions or different medicines with the same concentration, and measuring an emission spectrum when the excitation wavelength is 300nm after ultrasonic homogenization to obtain characteristic emission of rare earth metal europium and terbium. By terbium separationInternal fluorescence intensity ratio I of the seed 545 /I 490 I of europium ion in abscissa 615 /I 590 And drawing a two-dimensional decoding diagram for the ordinate, wherein each analyte corresponds to a unique decoding position, different analytes can be effectively perceived through two-dimensional reading, and particularly heavy metal lead ions and sulfonamides can be clearly distinguished. This internal calibration can effectively improve the error caused by uncontrollable factors when a single-shot sensor detects. Wherein I is 545 、I 490 、I 615 、I 590 The fluorescence intensities at 545nm, 490nm, 615nm and 590nm are shown, respectively.
The invention has the remarkable advantages that:
(1) The preparation method is simple and feasible, is simple and convenient to operate, and is easy to popularize and use.
(2) The dual-emission rare earth metal organic frame material prepared by the invention has good water stability and stable performance.
(3) The material prepared by the invention can selectively detect heavy metal lead ions and sulfonamides through a binary decoding diagram, realizes quantification in a certain concentration range, and has higher selectivity and sensitivity.
(4) Compared with the traditional fluorescence sensing method based on single emission sites, the material prepared by the method has the advantages that the quantity of identification information of the binary decoding diagram constructed by the multi-emission site material through intensity ratio is more abundant, and the internal correction method also ensures that the data is more reliable.
Drawings
FIG. 1 shows fluorescence spectra (a) of Eu/Tb-MOF at 300nm, XRD spectra (b) of Eu/Tb-MOF-1 and its dispersion in water for 60h, and emission spectra (c) of Eu/Tb-MOF-1 at 300nm, according to the present invention;
FIG. 2 is a two-dimensional decoding diagram (a) and quantitative detection (b) of lead ions obtained after detection of aqueous solutions of different metal ions at a concentration of 1mM by Eu/Tb-MOF-1 in the present invention;
FIG. 3 shows a two-dimensional decoding chart (a) and a quantitative detection (b) of sulfamethoxazole obtained after detection of different drug solutions with a concentration of 0.1mM by Eu/Tb-MOF-1 in the present invention.
Detailed Description
In order to make the description of the present invention easier to understand, the technical solutions in the embodiments of the present invention will be further described with reference to the drawings in the embodiments of the present invention, but the present invention is not limited thereto.
Example 1
The rare earth metal organic frame material for detecting heavy metal lead ions and sulfonamides comprises the following specific preparation processes:
weighing 0.1mmol of pyromellitic acid, 0.1mmol of 4, 5-imidazole dicarboxylic acid, europium nitrate hexahydrate and terbium nitrate hexahydrate in different molar ratios, putting into a polytetrafluoroethylene reaction vessel, adding 8ml of ultrapure water, carrying out ultrasonic homogenization, putting the polytetrafluoroethylene reaction vessel into a high-temperature high-pressure hydrothermal reaction vessel, carrying out constant-temperature reaction at 100 ℃ for 48 hours, and naturally cooling to room temperature. Finally, the white solid is collected by centrifugal separation and dried at 60 ℃ for 10 hours, and the dual-emission rare earth metal organic frame material Eu/Tb-MOFs is obtained.
Further, in the process, the different molar ratios of europium nitrate hexahydrate and terbium nitrate hexahydrate are as follows: 1:0,8:2,6:4,4:6,2:8,1:9,0:1. Eu was selected by fluorescence test 3+ ：Tb 3+ The Eu/Tb-MOF-1 sample with a doping molar ratio of 1:9 was the best ratio product, as shown in FIG. 1 (a), and this doping ratio sample was used for the subsequent experiments.
Product characterization
FIG. 1 (b) is an X-ray powder diffraction pattern of the double-emission rare earth metal-organic framework Eu/Tb-MOF-1 obtained in example 1, which was dispersed in water for 60 hours. It can be found that the diffraction peak of the synthesized Eu/Tb-MOF-1 sample is very sharp, indicating that the sample prepared under this condition has a better crystallinity. Meanwhile, the Eu/Tb-MOF-1 can be found to be dispersed in water for 60 hours, and the diffraction pattern of the Eu/Tb-MOF-1 is basically unchanged, so that the Eu/Tb-MOF-1 double-emission rare earth metal organic framework has good water stability.
FIG. 1 (c) is a fluorescence emission spectrum of the double-emission rare earth metal organic framework Eu/Tb-MOF-1 obtained in example 1. The emission spectra obtained for Eu/Tb-MOF-1 at 300nm excitation are shown in the figure, and the results show that there are 4 typical emission peaks at 490nm, 545nm, 590nm and 615nm,due to the fact that 5 D 4 → 7 F 6 、 5 D 4 → 7 F 5 、 5 D 0 → 7 F 1 And 5 D 0 → 7 F 2 a transition; wherein Eu is 3+ And Tb 3+ The strongest peaks of (2) are at 615nm and 545nm, respectively.
Performance testing
And (3) researching the identification detection and quantitative analysis of Eu/Tb-MOF-1 on heavy metal lead ions and sulfonamides.
FIG. 2 (a) is a two-dimensional decoding diagram of the metal ion detection by the dual emission rare earth metal organic framework Eu/Tb-MOF-1 obtained in example 1. The metal ion detection method comprises the following steps: the Eu/Tb-MOF-1 sample amount is 2mg, and the reaction system is 20mL M (NO) with the same concentration 3 ) x (M X+ ＝Na + ,Ag + ,Cd 2+ ,Pb 2+ ,Co 2+ ,Mg 2+ ,Ni 2+ ,Zn 2+ ,Fe 2+ ,Cr 3+ ) (1 mM) aqueous solution. And then carrying out ultrasonic treatment on the mixture to form a uniform and stable metal ion-containing solution, and carrying out fluorescence test under the excitation wavelength of 300nm to obtain the characteristic emission of rare earth europium and terbium. In the internal fluorescence intensity ratio I of terbium ion 545 /I 490 I of europium ion in abscissa 615 /I 590 A two-dimensional decoding map is obtained for the ordinate.
Metal ion detection experimental results: as can be seen from fig. 2 (a), each metal ion corresponds to a unique coordinate value, and most of the metal ions are concentrated in the region (1.8-2.4), with the exception of heavy metal lead ions (1.22,1.17). Therefore, different metal ions can be effectively distinguished through the decoding diagram, and particularly heavy metal lead ions can be clearly distinguished; this is due to the significant quenching of the fluorescence intensity of the solution by the lead ions compared to other metal ions, and the significant decrease in the Eu and Tb fluorescence peak intensities, indicating that Eu/Tb-MOF-1 can selectively detect lead ions.
FIG. 2 (b) shows the quantitative analysis of lead ions by Eu/Tb-MOF-1, a double-emission rare earth metal organic framework, obtained in example 1. Experimental conditions for quantitative analysis: eu/Tb-MOF-1 sampleThe dosage is 2mg, and the reaction systems are respectively 0, 100, 150, 200, 250, 300, 350, 400, 700 and 1000 mu M Pb 2+ The solution (20 mL) was sonicated and fluorescence tested at 300nm excitation wavelength.
Quantitative analysis results of lead ions: fluorescence tests show that the fluorescence emission peak intensity at 545nm follows Pb 2+ The concentration increases and gradually decreases. As can be seen from fig. 2 (b), there is no (I 0 ) And presence (I) 545 ) Ratio of fluorescence intensity I at 545nm for analyte lead ions 0 /I 545 Along with Pb 2+ The concentration increases and increases. Wherein a good linear relationship is exhibited in the range of 200-700. Mu.M (I 0 /I 545 ＝0.01169[Q]0.99498), the concentration of lead ions can thus be quantified using this relationship. ([ Q)]Is the molar concentration of the analyte).
Detection limit and sensitivity of Eu/Tb-MOF-1 to lead ions: the quantitative analysis result of the lead ions shows that the fluorescence intensity and the concentration of the lead ions show good linear relation, so that the detection limit of Eu/Tb-MOF-1 on the lead ions is further calculated. A common method of calculating the detection limit is dl= (kxs) b ) Where k represents a confidence factor, m represents a calibration sensitivity, S b Is the standard deviation of the blank signal. According to IUPAC standards, k here takes 3. To calculate S b We repeatedly measured the fluorescence intensity of 20 blank samples to determine the standard deviation of the blank signal. The standard deviation calculation formula of the blank signal is
Here I i Fluorescent intensity of blank signal, I a Is the average intensity of all the repetitions, N is the number of repetitions, and the result S is calculated after repeating 20 times b = 0.02935. The calibration sensitivity m is the slope of the calibration curve, here 0.01169. Final detection limit calculation result DL (Pb) = 7.5315 ×10 -6 M, the method is shown to have a lower detection limit for detecting lead ions.
FIG. 3 (a) is a two-dimensional decoding diagram of the dual emission rare earth metal organic framework Eu/Tb-MOF-1 obtained in example 1 for drug detection. The drug detection method is the same as the metal ion, and differs in that: the reaction system is 20mL of solution of medicines (naproxen NPX, diclofenac sodium DCF, tetracycline TC, erythromycin EM, sulfadiazine SDZ, sulfamethoxazole SMZ, coumarin CM, carbamazepine CBZ, sodium nitroprusside SN, atenolol AT, p-benzoquinone PBQ, piperazine PZ) (0.1 mM) with the same concentration.
Drug detection experimental results: as can be seen from the decoding diagram in fig. 3 (a), each drug corresponds to a unique decoding position, and accurate distinction of different drugs is achieved. The Eu and Tb fluorescence intensities are almost completely quenched by the sulfonamide, so that the coordinate values of the Eu and Tb fluorescence intensities are obviously distinguished from other medicines. Therefore, the selective detection capability of the sulfonamide medicine is shown while different medicines are accurately distinguished through the decoding graph.
FIG. 3 (b) shows the quantitative analysis of sulfamethoxazole by Eu/Tb-MOF-1 in the double-emission rare earth metal organic frame obtained in example 1. Experimental conditions for quantitative analysis: the Eu/Tb-MOF-1 sample dosage is 2mg, the reaction systems are respectively 0, 5, 15, 25, 40, 50, 60, 80 and 100 mu M sulfamethoxazole solution (20 mL), and fluorescence test is carried out under the excitation wavelength of 300nm after ultrasonic homogenization.
Quantitative analysis result of sulfamethoxazole: fluorescence testing showed that the fluorescence emission peak intensity at 545nm gradually decreased with increasing SMZ concentration. As can be seen from FIG. 3 (b), the ratio I of fluorescence intensities 0 /I 545 As the SMZ concentration increases. Wherein a good linear relationship (I) is exhibited in the range of 0 to 100. Mu.M 0 /I 545 ＝0.433[Q]+ 0.65295), quenching constant K sv ＝4.33×10 5 M -1 Correlation coefficient R 2 = 0.99705, so this relationship can be used to quantify the concentration of SMZ.
Detection limit and sensitivity of Eu/Tb-MOF-1 to sulfamethoxazole: similarly, the detection limit calculation method is dl= (kxs) b ) M, where m=0.433, final calculation result DL (SMZ) = 2.033 ×10 -7 M. Compared with other metal organic frame materials, eu/Tb-MOF-1 has lower detection limit and high sensitivity to sulfamethoxazole, which shows that the method has good application value in detecting sulfanilamide medicines.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. A double-emission rare earth metal organic framework material for selectively detecting heavy metal lead ions and sulfonamides is characterized in that: the material has europium and terbium double emission sites, can perform binary decoding through the internal fluorescence intensity ratio of two rare earth metals, and is applied to qualitative and quantitative detection of heavy metal lead ions and sulfonamides;
the preparation method of the double-emission rare earth metal organic framework material specifically comprises the following steps:
weighing pyromellitic acid, 4, 5-imidazole dicarboxylic acid, europium nitrate hexahydrate and terbium nitrate hexahydrate in different molar ratios, putting into a polytetrafluoroethylene reaction vessel, adding ultrapure water, carrying out ultrasonic homogenization, putting the polytetrafluoroethylene reaction vessel into a high-temperature high-pressure hydrothermal reaction vessel, carrying out constant-temperature reaction for 48 hours at 100 ℃, naturally cooling to room temperature, finally, centrifugally separating to collect white solid, and drying at 60-80 ℃ for 10-12 hours to obtain the double-emission rare earth metal organic frame material.
2. The dual emission rare earth metal organic framework material of claim 1, wherein: the molar ratio of europium nitrate hexahydrate to terbium nitrate hexahydrate is 1:9.
3. A dual emission rare earth metal organic framework material produced by the production method according to claim 1 or 2.
4. Use of the dual-emission rare earth metal organic framework material according to claim 3 for detecting heavy metal lead ions and sulfonamides, characterized in that: the specific detection method comprises the following steps: adding 2mg double-emission rare earth metal organic frame materials into different metal nitrate solutions or different medicines with the same concentration of 20ml, and measuring an emission spectrum when the excitation wavelength is 300nm after ultrasonic homogenization to obtain characteristic emission of rare earth metal europium and terbium; by terbium separationInternal fluorescence intensity ratio I of the seed 545 /I 490 On the abscissa, the internal fluorescence intensity ratio I of europium ion 615 /I 590 And drawing a two-dimensional decoding diagram for the ordinate, wherein each analyte corresponds to a unique decoding position, and effectively perceiving different analytes through two-dimensional reading to distinguish heavy metal lead ions from sulfonamides.
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