CN115753699A - Visual detection method of tetracycline antibiotics in water - Google Patents
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- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A visual detection method of tetracycline antibiotics in water comprises the following steps: preparing fluorescent MOGs/SA composite spheres; measuring the working curve and the precision of the tetracycline antibiotics; and (4) visually detecting the tetracycline antibiotic wastewater. The invention has mild detection condition, high sensitivity and good tolerance, and can meet the detection requirements of different water samples and environmental conditions. The method can quickly and conveniently realize real-time quantitative analysis of the concentration of the tetracycline antibiotics in the water body, and is a very promising visual detection method for the tetracycline antibiotics in the water.
Description
Technical Field
The invention belongs to the technical field of chemical detection and analysis, and relates to a visual detection method for tetracycline antibiotics in water.
Background
Tetracycline antibiotics, such as tetracycline, chlortetracycline, oxytetracycline, doxycycline, and the like, are widely used for treating bacterial infections in humans and animals due to their advantages of broad-spectrum antibacterial activity, low cost, good oral absorption, and the like. However, abuse of tetracycline antibiotics by animal husbandry and aquaculture industry results in high residual tetracycline antibiotics in environmental media such as soil and water. Residual tetracycline antibiotics are considered to be an important organic contaminant in water. It is difficult to degrade in ambient water and remains active, thereby adversely affecting ecosystem and human health.
Metal-Organic gels (MOGs) are hybrid soft materials with hierarchical porous structures, rich active sites and stable physicochemical properties, which are constructed by non-covalent interactions of Metal ions or Metal clusters and Organic ligands; the lanthanide-based MOGs have abundant adsorption sites and unique optical characteristics, can effectively realize pollutant capture and reflect the pollutant concentration in the adsorption process through real-time and visible fluorescence change. In addition, sodium Alginate (SA), a natural, biocompatible and non-toxic polysaccharide, can be cross-linked with positive ions to form an insoluble egg-box structure and thus has potential as a formable carrier. By using powder form MOGs in combination with SA, its range of application in practice can be expanded.
At present, various methods are used for detecting tetracycline antibiotics, including high performance liquid chromatography, mass spectrometry, liquid chromatography-tandem mass spectrometry and the like, however, the methods have limitations, such as the defects of complicated detection means, high test cost and the like, so the invention provides a visual detection method for tetracycline antibiotics in water, and can rapidly, simply and conveniently realize real-time quantitative analysis of the concentration of the tetracycline antibiotics in water.
Disclosure of Invention
The invention aims to solve the problems in the background art and provides a visual detection method of tetracycline antibiotics in water.
In the present invention, TATB is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine; TEA is triethylamine; tb-MOG is terbium-based metal organogel; eu-MOG is europium-based metal organogel; SA is sodium alginate; tb-MOG/SA is terbium-based metal organogel/sodium alginate; eu-MOG/SA is europium-based metal organogel/sodium alginate; CTC is chlortetracycline hydrochloride; RSD is the Relative Standard Deviation (Relative Standard development).
A visual detection method of tetracycline antibiotics in water comprises the following steps:
step 1: preparation of fluorescent MOGs/SA complex spheres:
1.1. tb (NO) was added at a concentration of 0.1mol/L 3 ) 3 ·6H 2 O or Eu (NO) 3 ) 3 ·6H 2 Fully dissolving O in water, and mixing with 0.1mol/L TATB according to a volume ratio of 1;
1.2. uniformly dispersing the fluorescent Tb-MOG or Eu-MOG material obtained in step 1.1 in SA with the mass concentration of 1%, and respectively dropwise adding CaCl with the mass concentration of 2% 2 And curing the mixture in the solution for 2 hours to obtain Tb-MOG/SA composite balls or Eu-MOG/SA composite balls.
Step 2: working curve and precision for determination of tetracycline antibiotics
2.1. Selecting deionized water and river water, standing to separate solid from liquid, taking supernatant to prepare standard samples of tetracycline antibiotic solutions with different concentrations;
2.2. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in the supernatant obtained in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, wherein the detection equipment is in a dark state before being started, and detecting the value of a G channel or an R channel of a fluorescent photo of the fluorescent Tb-MOG/SA composite balls or the Eu-MOG/SA composite balls by using a cell phone software ColorMeter after the 365nm ultraviolet lamp is started, wherein the value is a blank value in a deionized water and river water system;
2.3. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in tetracycline antibiotic solutions with different concentrations in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, detecting the value of a G channel or an R channel of a fluorescent photo of the detection equipment by using mobile phone software ColorMeter after the 365nm ultraviolet lamp is started, and obtaining a linear equation of the concentration of the tetracycline antibiotic to be detected and the value of the G channel or the R channel after data processing;
2.4. for each concentration point in step 2.3, the G value or R value is measured three times to examine the precision of the detection method, which is measured by the recovery rate and Relative Standard Deviation (RSD); in addition, the detection limit of the detection method is examined by repeatedly detecting blank values of the fluorescent Tb-MOG/SA composite spheres or Eu-MOG/SA composite spheres in a deionized water and river water system and combining the fluorescence change ratio and the slope of a linear equation of the concentration of the tetracycline antibiotics.
And step 3: visual detection of tetracycline antibiotic wastewater
3.1. Selecting waste water polluted by different tetracycline antibiotics as samples to be detected, respectively soaking fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in the samples to be detected for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls or the Eu-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, enabling the detection equipment to be in a dark state before starting, and detecting the value of a G channel or an R channel of a fluorescent photo of the detection equipment by using mobile phone software ColorMeter after the 365nm ultraviolet lamp is started;
3.2. and (3) substituting the G value or the R value obtained in the step (3.1) into the working curve obtained in the step (2) to obtain the concentration of the tetracycline antibiotics in the sample to be detected.
The handset software ColorMeter is the prior art.
The invention has the following beneficial effects:
the method has mild detection conditions, high sensitivity and good tolerance, can meet the detection requirements of different water samples and environmental conditions, can quickly and conveniently realize real-time quantitative analysis of the concentration of the tetracycline antibiotics in the water body, and is a very promising visual detection method for the tetracycline antibiotics in the water.
Drawings
FIG. 1 is a fluorescent picture of fluorescent Tb-MOG/SA composite spheres and Eu-MOG/SA composite spheres of the present invention detecting CTC of different concentrations in deionized water;
FIG. 2 is a fluorescent picture of the fluorescent Tb-MOG/SA composite spheres and Eu-MOG/SA composite spheres of the invention detecting CTC with different concentrations under river water conditions;
FIG. 3 is a graph showing the working curve of the fluorescent Tb-MOG/SA composite spheres of the present invention for detecting CTC under the condition of deionized water;
FIG. 4 is a graph showing the operation of detecting CTC in deionized water by using the Eu-MOG/SA complex fluorescent beads according to the present invention;
FIG. 5 is a graph of the working curve of the fluorescent Tb-MOG/SA composite sphere of the invention for detecting CTC under river water conditions;
FIG. 6 is a graph showing the operation of the fluorescent Eu-MOG/SA complex beads according to the present invention for detecting CTC under river water conditions.
Detailed Description
Example 1:
the two methods for analyzing and detecting CTC in the environmental water sample and determining the working curve, which are related to the embodiment 1, specifically comprise the following steps:
step 1: preparation of fluorescent MOGs/SA composite spheres:
1.1. tb (NO) was added at a concentration of 0.1mol/L 3 ) 3 ·6H 2 O or Eu (NO) 3 ) 3 ·6H 2 O is fully dissolved in water and is mixed with 0.1mol/L TATB according to the volume ratio of 1; the Tb-MOG or the Eu-MOG is formed instantly at room temperature, and is frozen and dried after being centrifugally collected to obtain a fluorescent Tb-MOG or Eu-MOG material;
1.2. uniformly dispersing the fluorescent Tb-MOG or Eu-MOG material obtained in step 1.1 in SA with the mass concentration of 1%, and respectively dropwise adding CaCl with the mass concentration of 2% 2 And curing the solution for 2 hours to obtain the fluorescent Tb-MOG/SA or Eu-MOG/SA composite spheres.
Step 2: determining the working curve and the precision of CTC in different water samples:
2.1. selecting deionized water and river water, standing for solid-liquid separation, taking supernate to prepare aureomycin hydrochloride standard samples of 0, 10.0mg/L, 25.0mg/L, 50.0mg/L, 100.0mg/L, 150.0mg/L, 200.0mg/L, 250.0mg/L, 300.0mg/L, 350.0mg/L, 400.0mg/L and 450.0 mg/L;
2.2. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in the supernatant obtained in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, wherein the detection equipment is in a dark state before being started, and detecting the value of a G channel or an R channel of a fluorescent photo of the fluorescent Tb-MOG/SA composite balls or the Eu-MOG/SA composite balls by using a cell phone software ColorMeter after the 365nm ultraviolet lamp is started, wherein the value is a blank value in a deionized water and river water system;
2.3. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in two CTCs with different concentrations in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, enabling the detection equipment to be in a dark state before starting, and detecting the value of a G channel or an R channel of a fluorescent photo by using mobile phone software ColorMeter after the 365nm ultraviolet lamp is started;
2.4. the experimental result of the step 2.3 shows that the fluorescent Tb-MOG/SA composite spheres or Eu-MOG/SA composite spheres emit fluorescence with different intensities in two CTC solutions with different concentrations, as shown in FIG. 1 and FIG. 2, the higher the concentration of the added CTC is, the lower the fluorescence intensity is, and the lower the value of a G channel or an R channel is;
2.5. the data obtained in step 2.4 are processed to obtain a linear equation of the CTC concentration and the value of the G channel or the R channel as shown in fig. 3, 4, 5 and 6.
Example 2:
the accuracy and sensitivity of the working curve obtained in example 1 were tested in example 2:
and (2) respectively preparing two different CTC solutions with the concentrations of 100.0mg/L, 200.0mg/L and 300.0mg/L for deionized water and river water, measuring the G value or the R value of each concentration point, and substituting the G value or the R value of each concentration point into the linear equation of the CTC concentration and the G channel or the R channel value obtained in the embodiment 1 to further obtain the corresponding detection concentration. Repeating for three times, calculating the recovery rate and RSD, and inspecting the accuracy and sensitivity of the detection method; in addition, blank values of the fluorescent Tb-MOG/SA composite spheres or Eu-MOG/SA composite spheres in a deionized water and river water system are repeatedly detected, and the detection limit of the detection method is examined by combining the fluorescence change ratio and the slope of a linear equation of the concentration of the tetracycline antibiotics.
TABLE 1 accuracy and sensitivity of detection of CTC in deionized water using fluorescent Tb-MOG/SA or Eu-MOG/SA composite spheres
TABLE 2 accuracy and sensitivity of detection of CTC in river Water Using fluorescent Tb-MOG/SA Complex spheres or Eu-MOG/SA Complex spheres
TABLE 3 detection limits for detection of CTC in deionized water and river water using fluorescent Tb-MOG/SA composite spheres or Eu-MOG/SA composite spheres
The results of experiments show that the recovery rates of the fluorescent Tb-MOG/SA composite spheres and the Eu-MOG/SA composite spheres in the deionized water background for the visual detection of CTC are respectively 100.69-109.36% and 96.01-99.34%, and the RSD is respectively 2.00-5.29% and 1.92-5.01%; as shown in Table 2, the recovery rates of fluorescent Tb-MOG/SA and Eu-MOG/SA composite spheres in the river water background for visual detection of CTC are respectively 94.64% -100.40% and 91.50% -110.56%, and the RSD is respectively 2.40% -4.98% and 2.92% -4.83%, and the ranges meet the precision requirement; as shown in Table 3, the detection limits of fluorescent Tb-MOG/SA (Eu-MOG/SA) complex spheres against the background of deionized water and river water for visual detection of CTC were 8.24 μ M (5.54 μ M) and 29.27 μ M (33.41 μ M), respectively.
Claims (1)
1. A visual detection method of tetracycline antibiotics in water is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparation of fluorescent MOGs/SA complex spheres:
1.1. tb (NO) was added at a concentration of 0.1mol/L 3 ) 3 ·6H 2 O or Eu (NO) 3 ) 3 ·6H 2 O was sufficiently dissolved in water and mixed with 0.1mol/L of TATB at a volume ratio of 1Promoting the dissolution of TATB in water; the Tb-MOG or the Eu-MOG is formed instantly at room temperature, and is subjected to freeze drying after centrifugal collection to obtain a fluorescent Tb-MOG or Eu-MOG material;
1.2. uniformly dispersing the fluorescent Tb-MOG material or Eu-MOG material obtained in the step 1.1 in SA with the mass concentration of 1%, and respectively dropwise adding the fluorescent Tb-MOG material or Eu-MOG material into CaCl with the mass concentration of 2% 2 In the solution, fluorescent Tb-MOG/SA or Eu-MOG/SA composite balls are obtained after curing for 2 hours;
and 2, step: the working curve and the precision of the tetracycline antibiotics are measured:
2.1. selecting deionized water and river water, standing to separate solid from liquid, taking supernatant to prepare standard samples of tetracycline antibiotic solutions with different concentrations;
2.2. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in the supernatant obtained in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, wherein the detection equipment is in a dark state before being started, and detecting the value of a G channel or an R channel of a fluorescent photo of the fluorescent Tb-MOG/SA composite balls or the Eu-MOG/SA composite balls by using a cell phone software ColorMeter after the 365nm ultraviolet lamp is started, wherein the value is a blank value in a deionized water and river water system;
2.3. respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in tetracycline antibiotic solutions with different concentrations in the step 2.1 for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, detecting the value of a G channel or an R channel of a fluorescent photo of the detection equipment by using mobile phone software ColorMeter after the 365nm ultraviolet lamp is started, and obtaining a linear equation of the concentration of the tetracycline antibiotic to be detected and the value of the G channel or the R channel after data processing;
2.4. measuring the G value or the R value of each concentration point in the step 2.3 for three times to examine the precision of the detection method, wherein the precision is measured by RSD); in addition, the detection limit of the detection method is inspected by repeatedly detecting blank values of the fluorescent Tb-MOG/SA composite spheres or Eu-MOG/SA composite spheres in a deionized water and river water system and combining the fluorescence change ratio and the slope of a linear equation of the concentration of the tetracycline antibiotics;
and step 3: visual detection of tetracycline antibiotic wastewater:
3.1. selecting waste water polluted by different tetracycline antibiotics as samples to be detected, respectively soaking the fluorescent Tb-MOG/SA composite balls or Eu-MOG/SA composite balls obtained in the step 1 in the samples to be detected for 10 minutes, taking out the fluorescent Tb-MOG/SA composite balls and placing the fluorescent Tb-MOG/SA composite balls in a fixed position of detection equipment with a built-in 365nm ultraviolet lamp, wherein the detection equipment is in a dark state before being started, and detecting the value of a G channel or an R channel of a fluorescent photo by using mobile phone software ColorMeter after the 365nm ultraviolet lamp is started;
3.2. and (3) substituting the G value or the R value obtained in the step (3.1) into the working curve obtained in the step (2) to obtain the concentration of the tetracycline antibiotics in the sample to be detected.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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