CN113528121B - Application of lanthanide metal organic framework compound in detection of antibiotics and detection method - Google Patents

Application of lanthanide metal organic framework compound in detection of antibiotics and detection method Download PDF

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CN113528121B
CN113528121B CN202110161122.9A CN202110161122A CN113528121B CN 113528121 B CN113528121 B CN 113528121B CN 202110161122 A CN202110161122 A CN 202110161122A CN 113528121 B CN113528121 B CN 113528121B
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赵鹏
谢蕊蕊
陶佳
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Abstract

The invention discloses application of lanthanide metal organic framework compounds in detection of antibiotics and a detection method. Lanthanide metal organic framework compounds include Ln-MOF-1, ln-MOF-2, and Ln-MOF-3; ln-MOF-1 is doped with Eu 3+ And Tb 3+ Zr-BDC of (c); ln-MOF-2 is doped with Eu 3+ And Tb 3+ Zn-BTC- (4, 4' -bipyridine); ln-MOF-3 is doped with Eu 3+ And Tb 3+ Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid); eu (Eu) 3+ And Tb 3+ The total doping concentration of (2) is 20-50 mol%, eu 3+ And Tb 3+ The doping mole ratio of (0.5-2) to 1. Eight classes of antibiotics can be detected at the same excitation wavelength by preparing three lanthanide metal-organic framework compounds, and combining fluorescence analysis and principal component analysis methods.

Description

Application of lanthanide metal organic framework compound in detection of antibiotics and detection method
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to application of lanthanide metal organic framework compounds in detection of antibiotics and a detection method.
Background
At present, antibiotics are widely used for treating bacterial infectious diseases clinically, and clinically commonly used antibiotics comprise penicillin medicines, erythromycin medicines, cephalosporin medicines, quinolone medicines and the like. However, with the development of economic society and the improvement of the living standard of people, the abuse of antibiotics is increasing. Analytical detection of antibiotics is therefore becoming particularly important. In addition, since various drug residues or antibiotic accumulation do not involve only one antibiotic, it is of greater importance to analyze multiple antibiotics simultaneously.
To date, there have been many strategies for analysis of various antibiotic residues, including surface enhanced raman scattering, enzyme-linked immunosorbent, high performance liquid chromatography-mass spectrometry, and electrochemical methods. However, these methods have the non-negligible disadvantages of long sample pretreatment time, expensive instrumentation, trained technicians, etc. Fluorescence sensing technology has received much attention as an alternative to solving these problems due to its simplicity of operation and high sensitivity. However, the conventional fluorescent sensing mode requires a specific fluorescent probe to recognize one antibiotic, and it is difficult to simultaneously recognize a plurality of antibiotics in one method.
The Qiao et al (L.N.Qiao, S.H.Qian, Y.H.Wang, S.F.Yan, H.W.Lin, carbon Dots Based Lab-on-a-Nanoparticle Approach for theDetection and Differentiation of Antibiotics, chem. Eur. J.24 (2018) 4703-4709) study reported the analytical detection of multiple antibiotics using three carbon quantum dots, but the excitation emission of each quantum dot was different, which resulted in cumbersome operation steps, the lifetime of the quantum dot was generally nanosecond, and was subject to interference from other substances, and the strategy was able to detect only 20 antibiotics at most.
Chinese patent application CN112147117a discloses a method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material, which uses the competitive coordination of amino groups in water-unstable fluorescent metal organic framework Zn-TCPE and aminoglycoside antibiotics to metal ions, and determines the content of aminoglycoside antibiotics through signal change of fluorescence weakening before strengthening. However, this method can detect only aminoglycoside antibiotics, and the types of detection of antibiotics are very limited.
Therefore, there is a need to develop a method capable of detecting multiple antibiotics simultaneously.
Disclosure of Invention
In order to overcome the defect that a plurality of antibiotics cannot be detected simultaneously in the prior art, the invention provides application of three lanthanide metal organic framework compounds in detecting the antibiotics, and 25 antibiotics can be detected simultaneously under the same excitation wavelength by combining the luminescent characteristics of the lanthanide metal and the topological structure of the metal organic framework compounds and a fluorescence analysis technology.
Another object of the present invention is to provide an antibiotic detection method based on the above lanthanide metal organic framework compound.
In order to solve the technical problems, the invention adopts the following technical scheme:
application of lanthanide metal organic framework compound in fluorescence analysis detection of antibiotics; the lanthanide metal organic framework compounds include Ln-MOF-1, ln-MOF-2, and Ln-MOF-3;
the Ln-MOF-1 is doped with Eu 3+ And Tb 3+ Zr-terephthalic acid (designated as Zr-BDC);
the Ln-MOF-2 is doped with Eu 3+ And Tb 3+ Zn-trimesic acid-4, 4 '-bipyridine (designated as Zn-BTC- (4, 4' -bipyridine));
the Ln-MOF-3 is doped with Eu 3+ And Tb 3+ Zn-2-methylimidazole-2, 2 '-bipyridine-3, 3' -dicarboxylic acid (noted as Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid));
eu in the Ln-MOF-1, ln-MOF-2 and Ln-MOF-3 3+ And Tb 3+ Is 20 to 50mol% and Eu 3+ And Tb 3+ The doping mole ratio of (0.5-2) to 1.
The application of the lanthanide metal organic framework compound in fluorescence analysis detection of antibiotics can detect various antibiotics at the same excitation wavelength.
Ln-MOF-1 is sphere-like, has an average particle size of 40nm and is negatively charged; ln-MOF-2 is spherical, has an average particle size of 2 mu m and has weak negative charge; ln-MOF-3 is nano-flake, has an average particle size of 200nm and has weak positive charge. Different antibiotics have different potentials, and the binding force is different between the various antibiotics and the three lanthanide metal organic framework compounds due to the action of static electricity, hydrophobic action and the like, and the binding force of the antibiotics and the metal organic framework compounds with different particle sizes and morphologies is also different, so that the corresponding fluorescence response is also different.
The three lanthanide metal organic framework compounds Ln-MOF-1, ln-MOF-2 and Ln-MOF-3 of the invention can be used for identifying various antibiotics due to different structural morphology, particle size and potential characteristics. If only a single lanthanide metal organic framework compound or two lanthanide metal organic framework compounds are used, fluorescence responses generated among different antibiotics are similar to each other, so that overlapping phenomena of part of the antibiotics in the scatter diagram can not be clearly distinguished.
Preferably, the Eu 3+ Is Eu (NO) 3 ) 3 The Tb is 3+ Is Tb (NO) 3 ) 3 。
Preferably, the molar ratio of Zr to BDC in the Ln-MOF-1 is (0.8-1.5) to 1.
More preferably, the molar ratio of Zr to BDC in the Ln-MOF-1 is 1:1.
Preferably, the mol ratio of Zn, BTC and 4, 4-dipyridine in Ln-MOF-2 is 2: (1-3): (0.5-1).
More preferably, the molar ratio of Zn, BTC and 4, 4-bipyridine in the Ln-MOF-2 is 2:2:1.
Preferably, the mol ratio of Zn, 2 '-bipyridine-3, 3' -dicarboxylic acid and 2-MIM in the Ln-MOF-3 is (1-4) to (2-4) to (1-2).
More preferably, the molar ratio of Zn, 2 '-bipyridine-3, 3' -dicarboxylic acid to 2-MIM in the n-MOF-3 is 2:2:1.
The invention also provides an antibiotic detection method based on the lanthanide metal organic framework compound, which comprises the following steps:
s1, fluorescence detection of antibiotics:
incubating antibiotics with Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, respectively, performing fluorescence analysis and detection, and reading Tb 3+ Fluorescence intensity value F at the peak of the emitted light 545 And Eu 3+ Fluorescence intensity value F at the peak of the emitted light 616 ；
S2, establishing an antibiotic scatter diagram:
according to F 545 /F 616 Performing principal component analysis by using SPSS to obtain a first discrimination factor, a second discrimination factor and a third discrimination factor, and establishing an antibiotic scatter diagram by taking the first discrimination factor, the second discrimination factor and the third discrimination factor as X, Y and Z axes respectively;
s3, detecting the antibiotics to be detected according to the S2 antibiotic scatter diagram.
The antibiotic detection method of the invention is based on lanthanide metal organic framework compound, in particular Eu 3+ 、Tb 3+ The three doped metal organic framework compounds Ln-MOF-1, ln-MOF-2 and Ln-MOF-3 are combined with fluorescence analysis technology to detect the variety of antibiotics.
The Tb is 3+ The wavelength at the peak of the emitted light is 545nm, the Eu 3+ The wavelength at the peak of the emitted light is 616nm.
The incubation in step S1 is: mixing the antibiotics and the lanthanide metal organic framework compound, swirling for 5-10 min, and standing for 20-30 min at room temperature.
The fluorescence excitation wavelength detected by the fluorescence analysis in the step S1 is 330nm, and the scanning range is 500-750 nm.
The method for performing principal component analysis using SPSS in step S2 is as follows: for F 545 /F 616 The method comprises the steps of performing dimension reduction and factor analysis, selecting coefficient options in description, setting characteristic values in extraction options to be larger than 0, storing the characteristic values as variables in scores, displaying factor score matrixes, adding columns in the selected variables, setting the columns as category columns, setting the numerical value as 25, and obtaining the values of PC1, PC2 and PC3 in a data view.
The antibiotics may be beta-lactams, tetracyclines, quinolones, sulfonamides, aminoglycosides, macrolides, lincomycin, chloramphenicol antibiotics.
Alternatively, the antibiotic may be Ampicillin (AMP), amoxicillin (AMX), cefuroxime (CXM), cefalexin (CEL), azithromycin (AZM), clarithromycin (CLARY), roxithromycin (ROX), streptomycin (STR), spectinomycin (SPE), gentamycin (GN), tetracycline (TC), doxycycline (DOX), minocycline (MIN), aureomycin (CTE), chloramphenicol (CHL), thiamphenicol (TAP), florfenicol (FLO), norfloxacin (NFX), levofloxacin (LEV), lomefloxacin (LOM), ciprofloxacin (CIP), sulfadiazine (SD), sulfamethoxazole (cz), clindamycin (CLI), lincomycin (LIN).
When the antibiotics to be detected are more in variety, PC1, PC2 and PC3 can be selected to be taken as X, Y and Z axes respectively, and an antibiotic three-dimensional scatter diagram is established to identify the antibiotics; when the types of antibiotics to be detected are few, PC1 and PC2 can be selected as an X axis and a Y axis respectively, and an antibiotic two-dimensional scatter diagram is established to identify the antibiotics.
When the types of antibiotics to be detected are 1-10, the antibiotics can be completely identified and distinguished by establishing a two-dimensional scatter diagram, and the three-dimensional scatter diagram is required to be introduced into a Z axis, so that the antibiotics are relatively more complicated; when the types of antibiotics to be detected are more than 10, the antibiotics of all types cannot be clearly distinguished only by using the two-dimensional scatter diagram, the overlapping of the antibiotic scatter diagrams is easy to occur, a Z axis is required to be introduced, and a three-dimensional scatter diagram is established to identify the antibiotics.
Preferably, the preparation method of the Ln-MOF-1 comprises the following steps: to dissolve ZrOCl 2 ·8H 2 O and terephthalic acid (H) 2 Adding acetic acid solution into N, N-dimethylformamide solution of BDC), mixing uniformly to obtain mixed solution A, and mixing Eu 3+ And Tb 3+ Dripping into the mixed solution A, reacting for 12-15 h at 80-90 ℃, and obtaining Ln-MOF-1 after post-treatment.
Preferably, the preparation method of the Ln-MOF-2 comprises the following steps: zn (NO) 3 ) 2 ·6H 2 O, trimesic acid (H) 3 BTC), 4-dipyridine are dissolved in N, N-dimethylformamide solution, mixed evenly to obtain mixed solution B, eu is obtained 3+ And Tb 3+ Dripping the mixture into the mixed solution B, reacting for 45-48 h at the temperature of 110-120 ℃, and obtaining Ln-MOF-2 after post-treatment.
Preferably, the preparation method of the Ln-MOF-3 comprises the following steps: zn (NO) 3 ) 2 ·6H 2 O, 2 '-bipyridine-3, 3' -dicarboxylic acid and 2-methylimidazole (2-MIM) are dissolved in N, N-dimethylformamide solution, and mixed evenly to obtain mixed solution C, eu is obtained 3+ And Tb 3+ Dripping the mixture into the mixed solution C, reacting for 72 to 80 hours at the temperature of between 110 and 120 ℃, and obtaining the Ln-MOF-3 through post-treatment.
Preferably, the post-treatment is filtration, washing, drying.
More preferably, the washing is washing with N, N-dimethylformamide.
More preferably, the drying is at 45-65 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides Eu doping 3+ And Tb 3+ Zr-BDC, eu-doped 3+ And Tb 3+ Zn-BTC- (4, 4' -bipyridine) and Eu doped 3+ And Tb 3+ The use of Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid) in the detection of antibiotics. By preparing three lanthanide metal organic framework compounds and combining fluorescence analysis and a principal component analysis method, eight antibiotics such as beta-lactams, tetracyclines, quinolones, sulfonamides, aminoglycosides, macrolides, lincomycin, chloramphenicol and the like can be detected simultaneously under the same excitation wavelength.
Drawings
FIG. 1 is an SEM image of Ln-MOF-1, ln-MOF-2, ln-MOF-3.
FIG. 2 is an X-ray diffraction pattern of Ln-MOF-1 and Zr-BDC.
FIG. 3 is an X-ray diffraction pattern of Ln-MOF-2 and Zn-BTC- (4, 4' -bipyridine).
FIG. 4 is an X-ray diffraction pattern of Ln-MOF-3 and Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid).
FIG. 5 is a fluorescence emission pattern of Ln-MOF-1, ln-MOF-2, ln-MOF-3.
FIG. 6 shows the principal component analysis spectra of 25 antibiotics.
Fig. 7 is a principal component analysis chart of a mixed antibiotic, wherein fig. 7A is a principal component analysis chart of a mixed antibiotic of norfloxacin and tetracycline in different proportions, and fig. 7B is a principal component analysis chart of a mixed antibiotic of norfloxacin and ciprofloxacin in different proportions.
Fig. 8A is a principal component analysis chart of minocycline, and fig. 8B is a principal component analysis chart of norfloxacin.
FIG. 9 is a bar graph of fluorescence response of minocycline.
Fig. 10 is a bar graph of fluorescence response of norfloxacin.
Fig. 11A is a standard curve of minocycline and fig. 11B is a standard curve of norfloxacin.
Detailed Description
The invention is further described below in connection with the following detailed description.
The starting materials in the examples are all commercially available, wherein:
zinc nitrate hexahydrate (Zn (NO 3) 2.6h2o) was purchased from western reagent company;
zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O), 2-methylimidazole, 4-bipyridine, 2 '-bipyridine-3, 3' -dicarboxylic acid from ala Ding Gongsi;
terephthalic acid (H) 2 BDC), trimesic acid (H) 3 BTC) purchased from rohn technologies limited;
25 antibiotics were purchased from Source leaf company;
norfloxacin tablets were purchased from Tianjin central pharmaceutical company, ltd;
norfloxacin capsules were purchased from south-Beijing Tongren Tang Huangshan extract pharmaceutical Co.
Norfloxacin eye drops were purchased from Anhui Shuangke pharmaceutical Co.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
Example 1 three lanthanide metal organic framework compounds Ln-MOF-1, ln-MOF-2, ln-MOF-3 were prepared:
at room temperature, 0.1mmol of ZrOCl was added 2 ·8H 2 O was dissolved in 4.8ml of N, N-dimethylformamide, and 0.1mmol of H was added 2 BDC is dissolved in 1.6mL of N, N-dimethylformamide, the two solutions are uniformly mixed after being respectively stirred for 5-10 min, and then 1.2mL of acetic acid solution is added to obtain a mixed solution A; to the mixture A, 0.1mmol of Eu (NO) was added dropwise 3 ) 3 And 0.1mmol of Tb (NO) 3 ) 3 Obtaining reaction liquid, transferring the reaction liquid into a 20mL stainless steel autoclave for reaction for 12-15 h at 80-90 ℃, filtering, washing and drying to obtain Ln-MOF-1.
At room temperature, 0.3mmol of Zn (NO 3 ) 2 ·6H 2 O, 0.3mmol H 3 BTC and 0.15mmol of 4, 4-bipyridine were dissolved in 10mL of N, N-dimethylformamide to obtain a mixed solution B,to the mixture B, 0.1mmol of Eu (NO) was added dropwise 3 ) 3 And 0.1mmol of Tb (NO) 3 ) 3 Obtaining reaction liquid, placing the reaction liquid in a 20mL stainless steel autoclave, reacting for 45-48 hours at 110-120 ℃, filtering, washing and drying to obtain Ln-MOF-2.
At room temperature, 0.2mmol of Zn (NO 3 ) 2 ·6H 2 O, 0.1mmol of 2,2 '-bipyridine-3, 3' -dicarboxylic acid and 0.2mmol of 2-methylimidazole were dissolved in 5.5mL of N, N-dimethylformamide to obtain a mixed solution C, and 0.1mmol of Eu (NO) was added dropwise to the mixed solution C 3 ) 3 And 0.1mmol of Tb (NO) 3 ) 3 Obtaining reaction liquid, placing the reaction liquid into a 20mL stainless steel autoclave, reacting for 72-80 h at 110-120 ℃, filtering, washing and drying to obtain Ln-MOF-3.
Example 2
Example 2A number of antibiotics were analyzed, identified and tested using Ln-MOF-1, ln-MOF-2, ln-MOF-3.
Taking 100 mu M of each of 25 antibiotics, respectively incubating with 100 mu L of Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, blending the antibiotics with lanthanide metal organic framework compound, swirling for 5min, and standing for 20min at room temperature. Detecting by using a fluorescence spectrophotometer, setting excitation wavelength to be 330nm, emission wavelength to be 545nm and 616nm, scanning range to be 500-750 nm, measuring each antibiotic in parallel three times, and reading fluorescence intensity value F of 545nm 545 And a fluorescence intensity value F of 616nm 616 . According to F 545 /F 616 The method comprises the steps of (1) performing principal component analysis by using SPSS, selecting coefficient options in description, setting characteristic values greater than 0 in extraction options, storing the characteristic values as variables in scores, displaying a factor score matrix, adding columns in the selected variables, setting the columns as category columns, setting the numerical value as 25, obtaining values of PC1, PC2 and PC3 in a data view, taking the PC1, PC2 and PC3 as X, Y and Z axes respectively, and establishing an antibiotic three-bit scatter diagram for recognition analysis.
The 25 antibiotics of this example are respectively: AMP, AMX, CXM, CEL, AZM, CLARY, ROX, STR, SPE, GN, TC, DOX, MIN, CTE, CHL, TAP, FLO, NFX, left LEV, LOM, CIP, SD, SMZ, CLI, LIN.
Example 3
Example 3 analytical identification detection of mixed antibiotics was performed using Ln-MOF-1, ln-MOF-2, ln-MOF-3.
According to 0: 20. 2: 18. 4: 16. 6: 14. 10: 10. 12: 8. 16: 4. 18:2 and 20:0, preparing norfloxacin and tetracycline mixed antibiotic samples with different proportions according to the proportion of 20: 0. 6: 14. 8: 12. 10:10 and 0:20, preparing norfloxacin and ciprofloxacin mixed antibiotic samples with different proportions.
Taking 100 mu M of each of the above mixed antibiotic samples, respectively incubating with 100 mu L of Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, obtaining values of PC1, PC2 and PC3 according to the incubation, fluorescence analysis and principal component analysis methods of example 2, and establishing an antibiotic two-dimensional scatter diagram by taking the PC1 and the PC2 as X, Y axes respectively for identification analysis.
Example 4
Example 4 analysis, identification and detection of a single antibiotic was performed using Ln-MOF-1, ln-MOF-2, ln-MOF-3.
Taking 100 mu M of antibiotics norfloxacin and minocycline with different concentrations, respectively incubating with 100 mu L of Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, obtaining values of PC1, PC2 and PC3 according to the incubation, fluorescence analysis and principal component analysis methods of example 2, and establishing an antibiotic two-dimensional scatter diagram by taking the PC1 and the PC2 as X, Y axes respectively for identification analysis.
And respectively establishing a norfloxacin standard curve and a minocycline standard curve by taking the antibiotic concentration as an abscissa and taking the PC1 as an ordinate, and calculating the detection limit.
The concentration gradient of norfloxacin is: 0. Mu.M, 0.4. Mu.M, 1. Mu.M, 2. Mu.M, 4. Mu.M, 5. Mu.M, 6. Mu.M, 8. Mu.M, 15. Mu.M, 20. Mu.M, 40. Mu.M, 60. Mu.M, 80. Mu.M, 100. Mu.M, 200. Mu.M;
the annual gradient of minocycline was 0 μM, 2 μM, 4 μM, 6 μM, 8 μM, 10 μM, 20 μM, 40 μM, 60 μM, 80 μM, 100 μM, 200 μM, 300 μM.
Example 5
Example 5 analytical detection of antibiotics in pharmaceutical formulations using Ln-MOF-1, ln-MOF-2, ln-MOF-3.
(1) Norfloxacin formulations were tested using the antibiotic test method of the present invention:
the commercial preparation of norfloxacin (equivalent to 125mg of norfloxacin) was placed in a 500mL volumetric flask, and hydrochloric acid solution (10 mL,0.1 mol.L) was added -1 ) Dissolving, and diluting to the scale with deionized water; 1mL of the solution was diluted 10 times and filtered with a 0.22 μm microporous filter membrane to obtain a sample to be measured.
Taking 100 mu M of a sample to be detected, respectively incubating with 100 mu L of Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, and obtaining the values of PC1, PC2 and PC3 according to the incubation, fluorescence analysis and principal component analysis methods of the example 2. And carrying out calculation on the norfloxacin standard curve in the embodiment 4 to obtain the norfloxacin concentration in the sample to be detected.
(2) Detection of norfloxacin formulations using high performance liquid chromatography:
preparation of the solution to be tested: the commercial preparation of norfloxacin (equivalent to 125mg of norfloxacin) was placed in a 500mL volumetric flask, and hydrochloric acid solution (10 mL,0.1 mol.L) was added -1 ) Dissolving, and diluting to the scale with deionized water; 1mL of the solution was diluted 10 times and filtered with a 0.22 μm microporous filter membrane to obtain a sample to be measured.
Preparation of a control solution: taking about 25mg of norfloxacin reference substance, precisely weighing, placing into a 100ml measuring flask, adding 2ml of 0.1mol/L hydrochloric acid solution to dissolve, diluting with water to scale, shaking uniformly, precisely measuring 5ml, placing into a 50ml measuring flask, diluting with mobile phase to scale, and shaking uniformly.
Chromatographic conditions: octadecylsilane chemically bonded silica is used as a filler; 0.025mol/L phosphoric acid solution (the pH value is regulated to 3.0+/-0.1 by triethylamine) -acetonitrile (87:13) is taken as a mobile phase; the detection wavelength is 278nm; the sample volume was 20. Mu.l.
And detecting according to the conditions to obtain the peak area of the norfloxacin, and calculating the norfloxacin content according to the proportion of the peak area to the concentration.
The commercial formulations of norfloxacin in this example are norfloxacin tablets, norfloxacin capsules and norfloxacin eye drops, respectively.
Test results
(one) Ln-MOF-1, ln-MOF-2, ln-MOF-3 morphology and fluorescence Properties
As shown in FIG. 1, SEM images of Ln-MOF-1, ln-MOF-2 and Ln-MOF-3 show that Ln-MOF-1 is spherical, and the average particle size is 40nm; ln-MOF-2 is spherical and has an average particle diameter of 2 μm; ln-MOF-3 is in nano-sheet shape, and the average grain diameter is 200nm.
X-ray diffraction pattern spectra of Ln-MOF-1, ln-MOF-2, ln-MOF-3, and standard XRD patterns of undoped lanthanide metals of the three materials, as shown in FIGS. 2-4. It can be seen that Eu in three lanthanide metal organic framework compounds 3+ And Tb 3+ Does not affect its own crystal structure.
FIG. 5 shows fluorescence emission patterns of Ln-MOF-1, ln-MOF-2, ln-MOF-3 at an excitation wavelength of 330nm, and it can be seen that three lanthanide metal-organic framework compounds each have Eu 3+ (616 nm) and Tb 3+ (545 nm) characteristic fluorescence emission.
(II) identification analysis and detection of 25 antibiotics
FIG. 6 is a principal component analysis chart of 25 antibiotics, as can be seen: each antibiotic has a specific fluorescent response pattern, and 25 antibiotics can be distinguished from each other. Meanwhile, the short distance between the three parallel measurement points also shows that the method has good precision and reproducibility. Furthermore, interfering substances such as metal ions and amino acids can also be distinguished from antibiotics. These results demonstrate the ability of the antibiotic detection methods of the present invention to simultaneously identify multiple antibiotics.
(III) analysis, identification and detection of two mixed antibiotics
According to the figure 7, for the norfloxacin and tetracycline mixed antibiotic sample and the norfloxacin and ciprofloxacin mixed antibiotic sample with different concentrations, different antibiotics can be completely distinguished according to the principal component analysis spectrum. These results indicate that the antibiotic detection method of the present invention is sensitive not only to different classes of antibiotics, but also to the same class of antibiotics, different classes of antibiotics.
(IV) analysis, identification and detection of a single antibiotic
According to the method of the present invention, it is possible to effectively distinguish between different concentrations of a single antibiotic, as shown in FIG. 8. FIG. 9 is a bar graph of the fluorescence response of minocycline, FIG. 10 is a bar graph of the fluorescence response of norfloxacin showing that F increases with increasing antibiotic concentration 545 /F 616 The values also exhibit a certain regularity. When PC1 exceeds 60%, it can be used to quantify antibiotic concentrations. According to the standard curve of minocycline of fig. 11A, the PC1 value (y) and the minocycline (x) concentration have the following relationship: y=0.018 x-1.077 (R 2 = 0.9760), the linear range is 2 to 200 μm, and the detection limit is 1.23 μm. According to the standard curve of norfloxacin of fig. 11B, the linear equation of the PC1 value (y) and norfloxacin (x) is y= 2.4677 × lgx-1.9150 (R 2 = 0.9836), the linear range is 0.4 to 20 μm, and the detection limit is 0.06 μm.
The above results demonstrate that the method of the present invention also has good detection accuracy for a single antibiotic.
Fifth, analysis and detection of antibiotics in pharmaceutical preparations
The norfloxacin agents were detected using conventional high performance liquid chromatography and the detection method of the present invention, and the detection data were compared, and the results are shown in table 1. Percentage (%) of the indicated amount=actual detected amount/standard amount x 100%.
It can be seen that the method and the high performance liquid chromatography of the invention have consistency in the results of analyzing three norfloxacin preparations, and the standard deviation is in a normal range (90.0% -110.0%), which shows the accuracy of the method.
TABLE 1 detection of norfloxacin in pharmaceutical formulations
Figure SMS_1
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (9)

1. Application of lanthanide metal organic framework compound in fluorescence analysis detection of antibiotics; the lanthanide metal organic framework compounds are Ln-MOF-1, ln-MOF-2 and Ln-MOF-3;
the Ln-MOF-1 is doped with Eu 3+ And Tb 3+ Zr-BDC of (c);
the Ln-MOF-2 is doped with Eu 3+ And Tb 3+ Zn-BTC- (4, 4' -bipyridine);
the Ln-MOF-3 is doped with Eu 3+ And Tb 3+ Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid);
eu in said Ln-MOF-1, ln-MOF-2 or Ln-MOF-3 3+ And Tb 3+ The total doping concentration of (a) is 20-50 mol%, and Eu 3+ And Tb 3+ The doping mole ratio of the two is (0.5-2) to 1;
the antibiotics are beta-lactams, tetracyclines, quinolones, sulfonamides, aminoglycosides, macrolides, lincomycin and chloramphenicol antibiotics.
2. The use according to claim 1, wherein the molar ratio of Zr to BDC in the Ln-MOF-1 is (0.8-1.5) to 1.
3. The use according to claim 1, wherein the molar ratio of Zn, BTC to 4, 4-bipyridine in the Ln-MOF-2 is 2:1-3:0.5-1.
4. The use according to claim 1, wherein the molar ratio of Zn, 2 '-bipyridine-3, 3' -dicarboxylic acid to 2-MIM in Ln-MOF-3 is (1-4): (2-4): (1-2).
5. The use according to claim 1, wherein the preparation method of Ln-MOF-1 comprises the steps of:
to dissolve ZrOCl 2 ·8H 2 Adding acetic acid solution into N, N-dimethylformamide solution of O and terephthalic acid, mixing uniformly to obtain mixed solution A, and mixing Eu 3+ And Tb 3+ Dripping into the mixed solution A, reacting for 12-15 h at 80-90 ℃, and obtaining Ln-MOF-1 after post-treatment.
6. The use according to claim 1, wherein the preparation method of Ln-MOF-2 comprises the following steps:
zn (NO) 3 ) 2 ·6H 2 O, trimesic acid and 4, 4-dipyridine are dissolved in N, N-dimethylformamide solution, mixed evenly to obtain mixed solution B, eu is obtained 3+ And Tb 3+ Dripping the mixture into the mixed solution B, reacting for 45-48 h at the temperature of 110-120 ℃, and obtaining Ln-MOF-2 after post-treatment.
7. The use according to claim 1, wherein the preparation method of Ln-MOF-3 comprises the following steps:
zn (NO) 3 ) 2 ·6H 2 O, 2 '-bipyridine-3, 3' -dicarboxylic acid and 2-methylimidazole are dissolved in N, N-dimethylformamide solution, and mixed evenly to obtain mixed solution C, eu is obtained 3+ And Tb 3+ Dripping the mixture into the mixed solution C, reacting for 72 to 80 hours at the temperature of between 110 and 120 ℃, and obtaining the Ln-MOF-3 through post-treatment.
8. An antibiotic detection method based on lanthanide metal organic framework compound, which is characterized by comprising the following steps:
s1, fluorescence detection of antibiotics:
after the antibiotics are respectively incubated with Ln-MOF-1, ln-MOF-2 and Ln-MOF-3, fluorescence analysis detection is carried out, and Tb is read 3+ Fluorescence intensity value F at the peak of the emitted light 545 And Eu 3+ Fluorescence intensity value F at the peak of the emitted light 616 ；
S2, establishing an antibiotic scatter diagram:
according to F 545 /F 616 Is performed using SPSSComponent analysis is carried out to obtain a first discrimination factor, a second discrimination factor and a third discrimination factor, and an antibiotic scatter diagram is established by taking the first discrimination factor, the second discrimination factor and the third discrimination factor as X, Y and a Z axis respectively;
s3, detecting antibiotics to be detected according to the S2 antibiotic scatter diagram;
the Ln-MOF-1 is doped with Eu 3+ And Tb 3+ Zr-BDC of (c);
the Ln-MOF-2 is doped with Eu 3+ And Tb 3+ Zn-BTC- (4, 4' -bipyridine);
the Ln-MOF-3 is doped with Eu 3+ And Tb 3+ Zn- (2-MIM) - (2, 2 '-bipyridine-3, 3' -dicarboxylic acid);
eu in said Ln-MOF-1, ln-MOF-2 or Ln-MOF-3 3+ And Tb 3+ The total doping concentration of (a) is 20-50 mol%, and Eu 3+ And Tb 3+ The doping mole ratio of the two is (0.5-2) to 1;
the antibiotics are beta-lactams, tetracyclines, quinolones, sulfonamides, aminoglycosides, macrolides, lincomycin and chloramphenicol antibiotics.
9. The method for detecting antibiotics according to claim 8, wherein the fluorescence excitation wavelength for the fluorescence analysis detection is 330nm and the scanning range is 500 to 750nm.
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