CN117949421A - Alizarin/Al3+Application of base ratio fluorescent probe in ciprofloxacin detection - Google Patents
Alizarin/Al3+Application of base ratio fluorescent probe in ciprofloxacin detection Download PDFInfo
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- CN117949421A CN117949421A CN202410062441.8A CN202410062441A CN117949421A CN 117949421 A CN117949421 A CN 117949421A CN 202410062441 A CN202410062441 A CN 202410062441A CN 117949421 A CN117949421 A CN 117949421A
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 title claims abstract description 236
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229960003405 ciprofloxacin Drugs 0.000 title claims abstract description 117
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 66
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 58
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- 238000000034 method Methods 0.000 claims abstract description 15
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- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007995 HEPES buffer Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
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- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 208000021945 Tendon injury Diseases 0.000 description 1
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- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- KLOHDWPABZXLGI-YWUHCJSESA-M ampicillin sodium Chemical compound [Na+].C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C([O-])=O)(C)C)=CC=CC=C1 KLOHDWPABZXLGI-YWUHCJSESA-M 0.000 description 1
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- 235000014103 egg white Nutrition 0.000 description 1
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- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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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- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses an application of an alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection, wherein the alizarin/Al 3+ -based ratio fluorescent probe is formed by mixing an alizarin solution, an AlCl 3 solution and a HEPES buffer solution, under the condition that ciprofloxacin exists, excitation light with the wavelength of 355-365 nm is used for excitation, red fluorescence exists at 647-653nm, and blue fluorescence exists at 433-439 nm; the red fluorescence is used as a reference signal, the blue fluorescence is used as a response signal, and the ratio of the two fluorescence and the concentration of ciprofloxacin have a linear relationship, so that the method can be used for quantitative detection of ciprofloxacin; in addition, the alizarin/Al 3+ ratio fluorescent probe changes the color of the probe solution from red to purple to blue along with the increase of the concentration of the ciprofloxacin, so that semi-quantitative visual detection of the ciprofloxacin can be realized. The alizarin/Al 3+ -based ratio fluorescent probe has excellent selectivity and anti-interference capability, can realize visual detection and quantitative analysis of ciprofloxacin residues in eggs, and has good sensitivity and high accuracy.
Description
Technical Field
The invention belongs to the technical field of food safety detection, and particularly relates to application of an alizarin/Al 3+ -based ratio fluorescent probe in detecting ciprofloxacin.
Background
The dependence on antibiotics in the intensive breeding process of the laying hens greatly increases the risk of drug residues in eggs. Ciprofloxacin (CIP) belongs to fluoroquinolone antibiotics, has a simple structure, a broad antibacterial spectrum, strong antibacterial activity and low price, and is widely used for treating and preventing diseases such as bacterial infection in the poultry farming industry. However, CIP is highly residual and enters the human body through the food chain due to unreasonable use (e.g., performance of a drug holiday not in compliance with national regulations) and poor degradability. This may lead to antibiotic resistance in the body, causing tendon injury, hepatotoxicity, adverse effects on the central nervous system, and gastrointestinal dysfunction. Currently, many countries have banned the use of partial antibiotics in poultry farming and strictly specify residual limits for antibiotics. The national food safety standard GB 31650-2019 specifies the maximum residual limit of CIP in food products and explicitly disables during the poultry egg laying period. Therefore, an accurate and sensitive CIP residue detection method is established, and the method has important significance for guaranteeing the quality safety of eggs and promoting the healthy development of the poultry egg industry in China.
Currently developed analytical methods for detecting CIP residues mainly include High Performance Liquid Chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), capillary electrophoresis, enzyme-linked immunoassay (ELISA), electrochemical methods, and the like. These methods have the disadvantages of cumbersome sample pretreatment steps, expensive instruments, or high dependence on antibodies and high detection costs. In addition, the problems of poor reproducibility and stability, etc. have also limited the wide application of electrochemical detection methods.
In recent years, although research on CIP fluorescence detection has been advanced at home and abroad. For example, xia Hong et al discloses a method for detecting CIP using CdSe quantum dots by adding ciprofloxacin at different concentrations to a CdSe quantum dot solution, incubating with phosphate buffer at room temperature in darkness, exciting with light having a wavelength of 438nm, and recording the fluorescence intensity in the emission range of 450-650nm as CIP enhances CdSe quantum dot fluorescence by fluorescence resonance energy transfer, and the fluorescence intensity at 530nm increases gradually; then, suggesting a standard curve by taking CIP concentration as an abscissa and F 0/F as an ordinate, so that CIP detection is realized; wherein F 0 and F are the maximum emission intensities of the system in the absence and presence of ciprofloxacin, respectively. Liu Baoxia et al report a fluorescence method for detecting CIP using lanthanide coordination polymer nanoparticles (Eu/GMP NPs), which significantly enhances their fluorescence due to the strong coordination interaction between CIP and Eu 3+, measured the fluorescence intensity of Eu/GMP NPs in aqueous solution in the presence of different concentrations of CIP at 276nm as excitation wavelength, and then quantitatively analyzed the CIP by taking the fluorescence intensity of Eu/GMP NPs at 615nm and the CIP concentration as standard curves on the ordinate and abscissa, respectively. However, the above methods are all based on fluorescent probes with single signal detection, and the detection result is easily interfered by the probe concentration, excitation wavelength and environmental factors, so that the detection accuracy of the detected object is reduced.
Disclosure of Invention
The invention aims to solve the technical problems of providing the application of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection aiming at the defects of the prior art, wherein the probe has excellent selectivity and anti-interference capability, can realize visual detection and quantitative analysis of ciprofloxacin residues in eggs, and has good sensitivity and high accuracy.
The invention adopts the technical proposal for solving the problems that:
The application of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection is characterized in that the alizarin/Al 3+ -based ratio fluorescent probe is characterized in that the alizarin aggregation is induced to generate Aggregation Induction Effect (AIE) through the coordination of Al 3+ and-OH groups on the alizarin surface to cause the fluorescence intensity to be enhanced, so that stronger red fluorescence is generated at 647-653 nm; the coordination effect between Al 3+ and ciprofloxacin can cause the intrinsic fluorescence of ciprofloxacin to be obviously enhanced, and stronger blue fluorescence is generated at 433-439 nm; the red fluorescence is used as a reference signal, the blue fluorescence is used as a response signal, and the ratio of the two types of fluorescence (the ratio of red fluorescence intensity to blue fluorescence intensity or the ratio of blue fluorescence intensity to red fluorescence intensity) and the concentration of ciprofloxacin have a linear relationship within the range of 0.1 mu M-15 mu M, so that the detection of the ciprofloxacin content in the solution to be detected is realized.
According to the scheme, the alizarin/Al 3+ ratio fluorescent probe changes from red to purple to blue along with the increase of the concentration of ciprofloxacin, so that semi-quantitative visual detection of the concentration of ciprofloxacin in the solution to be detected can be realized.
The preparation method of the alizarin/Al 3+ -based ratio fluorescent probe comprises the following steps:
(1) Preparing alizarin solution with concentration of 0.4mg/mL-0.6mg/mL by taking water as a solvent;
(2) Preparing AlCl 3 solution with the concentration of 3mM-5mM by taking water as a solvent;
(3) Fully and uniformly mixing alizarin solution and AlCl 3 solution according to volume ratio (0.7-1) 1, and standing at room temperature to obtain mixed solution;
(4) Adding HEPES buffer solution into the mixed solution obtained in the step (3), and incubating for 10-20 minutes at 55-65 ℃ to obtain the alizarin/Al 3+ -based ratio fluorescent probe.
According to the scheme, in the step (4), the volume ratio of the mixed solution to the HEPES buffer solution is (0.6-0.9): 1.
According to the above scheme, HEPES buffer solution has a concentration of 0.005-0.015M and a pH of 4.8-5.2.
According to the scheme, in the step (4), after adding HEPES buffer solution, a certain amount of water can be added for dilution, and then incubation is carried out at 55-65 ℃ for 10-20 minutes, so as to obtain the alizarin/Al 3+ -based ratio fluorescent probe (solution). Wherein the volume ratio of the water to HEPES buffer is 1 (2-4).
On the basis of the above, the invention provides a method for detecting ciprofloxacin residues in eggs with high sensitivity based on alizarin/Al 3+ -based ratio fluorescent probes, which comprises the following steps:
1) Preparing CIP standard solutions with different concentrations by taking water as a solvent, wherein the concentration range is 0-15 mu M;
2) Respectively adding CIP standard solutions with different concentrations in the step 1) into the alizarin/Al 3+ ratio fluorescent probe (solution) in parallel, incubating for 10-20 minutes at 55-65 ℃, measuring the fluorescence intensity ratio at two places of 433-439nm and 647-653nm under the excitation wavelength of 355-365 nm, taking the fluorescence intensity ratio as an ordinate, taking the concentration of the CIP standard solution as an abscissa, and establishing a standard curve between the fluorescence intensity ratio and the CIP standard solution concentration;
3) And (3) measuring the fluorescence intensity ratio of 433-439nm and 647-653nm of the sample to be measured under the same condition as the step (2), and further obtaining the CIP concentration in the sample to be measured according to the standard curve obtained in the step (2).
According to the scheme, the sample to be detected is egg extract, and the preparation method comprises the following steps: weighing a certain amount of egg liquid sample (whole egg liquid, egg white or egg yolk liquid) of fresh eggs, and uniformly mixing by vortex; then, carrying out ultrasonic treatment by using a mixed solution of acetonitrile and water, and centrifugally collecting supernatant to obtain an egg extract which is used as a sample to be detected for detecting ciprofloxacin residues in eggs. Of course, dilution with buffer and/or water is also possible, HEPES buffer being preferred.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention constructs a novel alizarin/Al 3+ ratio fluorescent probe based on aggregation-induced emission effect (AIE) and coordination effect, and realizes the visual detection of ciprofloxacin residues. In the alizarin/Al 3+ -based ratio fluorescent probe, al 3+ triggers alizarin aggregation to cause fluorescence intensity enhancement, and red fluorescence is used as a reference signal; the coordination between Al 3+ and ciprofloxacin causes the intrinsic fluorescence of ciprofloxacin to be obviously enhanced, and the blue fluorescence is taken as a response signal; with increasing ciprofloxacin concentration, the probe (solution) changes from red to purple to blue, which provides the possibility for semi-quantitative visual analysis. Furthermore, the alizarin/Al 3+ -based ratio fluorescent probe exhibited good linear response to ciprofloxacin (R 2 =0.991) in the linear range of 0.01 to 10.00 μm, with a detection limit of 6.9nM. In addition, the alizarin/Al 3+ -based ratio fluorescent probe also has excellent selectivity and anti-interference capability, and satisfactory recovery rate and stability are shown in a labeled recovery experiment of ciprofloxacin residues in an egg sample.
2. The invention adopts the ratio fluorescence detection, improves the sensitivity and the accuracy through self calibration, is more accurate and stable than single signal detection, and is convenient for visual monitoring.
3. The invention has low cost, simple and convenient operation, accuracy and reliability, can complete detection within 15min, and has good application prospect.
Drawings
FIG. 1 shows the effect of Al 3+ on the fluorescence emission intensity of alizarin and the effect of CIP on the fluorescence emission intensity of alizarin/Al 3+ -based ratio fluorescent probe, including the fluorescence spectra of a, b, c, d four solutions and photographs under ultraviolet light; wherein a is alizarin solution with the concentration of 0.080mg/mL; b is the alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1, wherein the final concentration of alizarin is about 0.080mg/mL and the final concentration of Al 3+ is about 0.776mM; c is CIP solution with the concentration of 0.806 mu M; d is a mixed solution of alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1 and CIP solution, wherein the CIP final concentration is 0.806. Mu.M, the alizarin final concentration is 0.080mg/mL, and the Al 3+ final concentration is 0.776mM.
FIG. 2 shows a schematic diagram of the coordination of alizarin with Al 3+.
FIG. 3 shows the hydrodynamic diameter distribution of the Al 3+ solution before and after alizarin addition in example 2; alizarin in the figure represents alizarin solution at a concentration of 0.080mg/mL; alizarin+Al 3+ represents the alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1, wherein the final concentration of alizarin is 0.080mg/mL and the final concentration of Al 3+ is 0.776mM.
Fig. 4 shows a model of the binding of Al 3+ to CIP.
FIG. 5 shows hydrodynamic diameter profiles of CIP solution of example 2 before and after the addition of alizarin/Al 3+ -based ratio fluorescent probe; wherein alizarin+Al 3+ represents the alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1, wherein the final concentration of alizarin is 0.080mg/mL and the final concentration of Al 3+ is 0.776mM; alizarin+Al 3+ +CIP represents the mixed solution of alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1 and CIP solution, wherein the CIP final concentration is 0.806. Mu.M, the alizarin final concentration is 0.080mg/mL, and the Al 3+ final concentration is 0.776mM.
FIG. 6 shows the fluorescence emission pattern of the alizarin/Al 3+ -based ratio fluorescent probe of example 2 after addition of CIP.
FIG. 7 shows a linear correlation of CIP concentration to fluorescence intensity ratio (I 436/I650) in example 2.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
In the following examples, reagents and instrumentation were used:
Aluminum trichloride hexahydrate (AlCl 3. 6H 2O), ciprofloxacin (CIP), chloramphenicol (CHL), roxithromycin (ROX), sodium Ampicillin (AMP), lincomycin hydrochloride (LIN), streptomycin (STR), azithromycin (AZI), kanamycin sulfate (KAN), gentamicin sulfate (GEN), furacilin (FRZ), sodium sulfate, sodium sulfite, magnesium chloride, zinc chloride, glucose, L-histidine (L-His), acetonitrile all supplied by Shanghai Micheline Biochemical Co., ltd; alizarin is provided by the company of the sciences of the ridge (Guangdong, inc.); 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES), dimethyl sulfoxide was purchased from Shanghai Ala Ding Huaxue reagent Co., ltd; the water used for solution preparation in the experiment is ultrapure water; HEPES buffer was: 0.01m hepes, ph=5.0. The chemical reagents are all analytically pure and have no special description and are not further purified.
FL 6500 fluorescence spectrophotometer (perkin elmer instruments ltd., usa); ML-3002T/02 precision electronic balance (precision 0.0001g, metrele-Tolyduo national Co., ltd.); zeta potentiometers (Zeta, ZSU3100, uk); DF-101S thermostatic water bath (Gongyi, china Instrument Limited liability company); KQ-250DE ultrasonic multifrequency washer (Kunshan ultrasonic instruments Co., ltd.); high-speed cryocentrifuge (JW-3021 HR).
Example 1 construction and characterization of alizarin/Al 3+ -based ratio fluorescent probes
Alizarin solution (500. Mu.L, 0.5 mg/mL) and AlCl 3 solution (600. Mu.L, 4.0 mM) were thoroughly mixed, and then allowed to stand at room temperature (24 ℃) for 5min to obtain a mixed solution. Subsequently, 1500 μl of HEPES buffer (0.01 m, ph=5.0) was added to the above mixed solution, incubated at 60 ℃ for 15 minutes, and 500 μl of water was added to obtain alizarin/Al 3+ -based ratio fluorescent probe (solution).
As can be seen from FIG. 1, alizarin solution shows a weak fluorescence signal at 650nm at an excitation wavelength of 360 nm. With the addition of Al 3+, the fluorescence signal of the alizarin solution at 650nm is significantly enhanced, namely the alizarin/Al 3+ -based ratio fluorescent probe (solution) has significant red fluorescence at 650nm, and also exhibits significant red fluorescence under an ultraviolet lamp. This is probably due to the fact that Al 3+ induces alizarin aggregation by coordination with the-OH groups on the alizarin surface, resulting in an aggregation-induced effect (AIE), thus generating stronger fluorescence. The CIP solution exhibited intrinsic fluorescence at 436nm, and Al 3+ significantly enhanced the fluorescence signal of CIP when added to the alizarin/Al 3+ -based ratiometric fluorescent probe solution, while the 650nm fluorescence emission peak from alizarin remained essentially unchanged, which provides the possibility for ratiometric fluorescence detection of CIP. Accordingly, photographs of the solution under 365nm ultraviolet light also further demonstrate this color transition.
FIG. 3 shows the hydrodynamic diameter of alizarin alone and that after introduction of Al 3+, it can be seen that the introduction of Al 3+ induces aggregation of alizarin solution, changing its average diameter from 25.95nm to 48.99nm. Therefore, a fluorescent probe can be constructed by adding Al 3+ to alizarin solution, and CIP can be detected by calculating the ratio of fluorescent signals at 436nm and 650 nm.
Example 2 method for detecting ciprofloxacin with alizarin/Al 3+ -based ratio fluorescent probe
500. Mu.L of CIP standard solutions (0, 0.1, 0.5, 1, 2.5, 5, 7, 10, 13, 15. Mu.M) of different concentrations were added to the alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1, and after incubation at 60℃for 15 minutes, fluorescence spectra were recorded at room temperature at excitation wavelengths of 360nm, and fluorescence intensities at 436nm and 650nm (labeled I 436 and I 650) were measured, with slits of excitation and emission wavelengths of 5nm.
As can be seen from fig. 4, al 3+ inhibits excited intramolecular proton transfer (esit) of CIP molecules by complexing with carboxyl groups and pyridone in CIP, thereby enhancing fluorescence signal of CIP. It can be inferred that the response mechanism of the alizarin/Al 3+ based ratio fluorescent probe to CIP is probably due to the fact that Al 3+ forms a complex with CIP further after binding alizarin, suppressing the esit of CIP, resulting in an enhancement of fluorescence signal. To verify this hypothesis, the hydrodynamic diameter was also measured, and as shown in FIG. 5, the addition of CIP increased the average diameter of the alizarin/Al 3+ -based ratio fluorescent probe from 48.99nm to 88.26nm, indicating that CIP can bind to the alizarin/Al 3+ -based ratio fluorescent probe by electrostatic interactions.
The fluorescence intensity (I 436/I650) ratio of two fluorescence signals is taken as an ordinate, the CIP concentration is taken as an abscissa to fit a standard curve, the linear fitting result is shown in figure 7, the fitting equation is y= 1.760x-0.137 (R 2 =0.991, S/N=3), the linear range is between 0.01 and 10.00 mu M, and the detection limit is 6.9nM, so that the fluorescence signal of the alizarin/Al 3+ -based ratio fluorescent probe has a good linear relation with the CIP concentration, and can be used for detecting the concentration of ciprofloxacin in a sample to be detected.
Example 3 method for detecting ciprofloxacin residue in egg by applying alizarin/Al 3+ -based ratio fluorescent probe to egg sample
In order to evaluate the application potential and feasibility of the alizarin/Al 3+ -based ratio fluorescent probe in actual detection, a labeled recovery method is adopted to analyze the residual quantity of fluoroquinolone in eggs. 1.0g of whole egg liquid sample of fresh egg is weighed and mixed uniformly by vortex, then 2mL of CIP solution (the CIP solution concentration is 0, 0.5, 1.5 and 2.5 mu M respectively) is added for 3 times, then 5mL of acetonitrile solution (acetonitrile: water, 9:1, v/v) is added, after vortex mixing uniformly again, ultrasonic treatment is carried out for 10min, centrifugation is carried out for 10min (12000 rpm) at 4 ℃, and supernatant is collected. Repeating the above operation for 3 times, collecting the supernatant to obtain an egg extract, and using the egg extract as a sample to be detected for detecting ciprofloxacin residues in eggs for later use.
To the alizarin/Al 3+ -based ratio fluorescent probe (solution) prepared in example 1, 500. Mu.L of the above egg extract (CIP concentrations of 0, 0.5, 1.5, 2.5. Mu.M, respectively) was added, and after incubation at 60℃for 15min, the fluorescence intensities at 436nm and 650nm were measured at an excitation wavelength of 360nm, and the concentration of ciprofloxacin in the egg extract was calculated by substituting the standard curve in example 2. The test was run in 3 replicates and averaged.
The inspection results are shown in table 1, the recovery rate of CIP in an actual egg sample is 82.00-102.00%, the relative standard deviation range is 0.06% -0.17%, and good recovery rate and relative standard deviation are shown, so that the method for detecting ciprofloxacin residues in eggs based on alizarin/Al 3+ -based ratio fluorescent probe provided by the invention has good performance in FQs detection, can be used for sensitive and accurate detection of CIP, and has wide application prospect.
TABLE 1 determination of CIP in egg samples
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (10)
1. The application of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection is characterized in that the alizarin/Al 3+ -based ratio fluorescent probe is formed by mixing an alizarin solution, an AlCl 3 solution and a buffer solution, and water is used as a solvent; the alizarin/Al 3+ -based ratio fluorescent probe is excited by excitation light with the wavelength of 355-365 nm under the condition that ciprofloxacin exists, red fluorescence exists at 647-653nm, and blue fluorescence exists at 433-439 nm; the ratio of the fluorescence intensities of the red fluorescence and the blue fluorescence has a linear relation with the concentration of ciprofloxacin, and is used for realizing quantitative detection of the ciprofloxacin.
2. The application of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection is characterized in that the alizarin/Al 3+ -based ratio fluorescent probe is formed by mixing an alizarin solution, an AlCl 3 solution and a buffer solution, and water is used as a solvent; the alizarin/Al 3+ -based ratio fluorescent probe is excited by excitation light with the wavelength of 355-365 nm under the condition that ciprofloxacin exists, red fluorescence exists at 647-653nm, and blue fluorescence exists at 433-439 nm; the alizarin/Al 3+ ratio fluorescent probe changes the color of a probe solution from red to blue along with the increase of the concentration of ciprofloxacin, and is used for realizing semi-quantitative visual detection of the ciprofloxacin.
3. The use of the alizarin/Al 3+ -based ratio fluorescent probe according to claim 1 or 2 in ciprofloxacin detection, wherein the preparation method of the alizarin/Al 3+ -based ratio fluorescent probe comprises the following steps:
(1) Preparing alizarin solution with concentration of 0.4mg/mL-0.6mg/mL by taking water as a solvent;
(2) Preparing AlCl 3 solution with the concentration of 3mM-5mM by taking water as a solvent;
(3) Fully and uniformly mixing alizarin solution and AlCl 3 solution according to volume ratio (0.7-1) 1, and standing at room temperature to obtain mixed solution;
(4) Adding buffer solution or buffer solution and water into the mixed solution obtained in the step (3), and incubating for 10-20 minutes at 55-65 ℃ to obtain the alizarin/Al 3+ -based ratio fluorescent probe; the alizarin/Al 3+ -based ratio fluorescent probe is a solution, wherein the final concentration of alizarin is in the range of 0.05-0.10mg/mL, and the final concentration of Al 3+ is in the range of 0.5-1.0 mM.
4. The use of alizarin/Al 3+ -based ratio fluorescent probe according to claim 3 for ciprofloxacin detection, wherein the buffer is HEPES buffer with a concentration of 0.005-0.015m and a ph of 4.8-5.2.
5. The use of the alizarin/Al 3+ -based ratio fluorescent probe according to claim 3 in ciprofloxacin detection, wherein in step (4), the volume ratio of the mixed solution to the buffer is (0.6-0.9): 1 range; the volume ratio of the mixed solution to water is (1.8-2.7): 1.
6. The use of the alizarin/Al 3+ -based ratio fluorescent probe according to claim 1 or 2 in ciprofloxacin detection, characterized in that the specific application method comprises the following steps:
1) Preparing ciprofloxacin standard solutions with different concentrations by taking water as a solvent, wherein the concentration range is 0-15 mu M;
2) Respectively adding the ciprofloxacin standard solutions with different concentrations in the step 1) into the alizarin/Al 3+ ratio fluorescent probe, incubating for 10-20 minutes at 55-65 ℃, measuring the fluorescence intensity ratio at two places of 433-439nm and 647-653nm under the excitation wavelength of 355-365 nm, taking the fluorescence intensity ratio as an ordinate, taking the concentration of the ciprofloxacin standard solution as an abscissa, and establishing a standard curve between the fluorescence intensity ratio and the concentration of the ciprofloxacin standard solution;
3) And (3) measuring the fluorescence intensity ratio of 433-439nm and 647-653nm of the sample to be measured under the same condition as the step (2), and further obtaining the ciprofloxacin concentration in the sample to be measured according to the standard curve obtained in the step (2).
7. The application of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection, wherein the sample to be detected is egg extract, and the preparation method is as follows: and (3) uniformly mixing fresh egg liquid by vortex, then carrying out ultrasonic treatment by using a mixed solution of acetonitrile and water, and centrifuging to collect supernatant, namely an egg extract, wherein the supernatant is used as a sample to be detected for detecting ciprofloxacin residues in eggs.
8. The use of the alizarin/Al 3+ -based ratio fluorescent probe in ciprofloxacin detection according to claim 7, wherein the egg extract is diluted with HEPES buffer as a sample to be tested for detecting ciprofloxacin residues in eggs.
9. The method for detecting ciprofloxacin residues in eggs based on alizarin/Al 3+ -based ratio fluorescent probe is characterized by comprising the following specific steps:
S1, preparing an alizarin/Al 3+ -based ratio fluorescent probe: uniformly mixing alizarin aqueous solution with concentration of 0.4mg/mL-0.6mg/mL and AlCl 3 aqueous solution with concentration of 3mM-5mM according to volume ratio (0.7-1) 1 to obtain mixed solution; mixing the obtained mixed solution with a buffer solution, or mixing the obtained mixed solution with the buffer solution and water, and then incubating for 10-20 minutes at 55-65 ℃ to obtain the alizarin/Al 3+ -based ratio fluorescent probe, wherein the final concentration of alizarin is in the range of 0.05-0.10mg/mL and the final concentration of Al 3+ is in the range of 0.5-1.0 mM;
s2, respectively adding ciprofloxacin standard solutions with different concentrations into the alizarin/Al 3+ ratio fluorescent probe obtained in the step S1 in parallel, incubating at 55-65 ℃ for 10-20 minutes, measuring the fluorescence intensity ratio of 433-439nm and 647-653nm at the excitation wavelength of 355-365 nm, taking the fluorescence intensity ratio as an ordinate, taking the concentration of the ciprofloxacin standard solution as an abscissa, and establishing a standard curve between the fluorescence intensity ratio and the concentration of the ciprofloxacin standard solution;
s3, taking an egg extract of fresh eggs as a sample to be detected for detecting ciprofloxacin residues in the eggs, measuring the fluorescence intensity ratio of 433-439nm and 647-653nm of the sample to be detected under the same condition as that of the step S2, and further obtaining the ciprofloxacin concentration in the sample to be detected according to a standard curve obtained in the step S2.
10. The method for detecting ciprofloxacin residues in eggs based on alizarin/Al 3+ -based ratio fluorescent probes according to claim 9, wherein the linear range of the standard curve is in the range of ciprofloxacin concentration of 0.1 μm to 15 μm.
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