Ornidazole test paper based on fluorescent composite material and application of ornidazole test paper

Abstract

The invention discloses application of ornidazole test paper based on a fluorescent composite material. A stable yellow light emission fluorescent dye rhodamine 6G is introduced into a nano pore channel of a high-stability UIO-67 material to prepare the high-stability yellow light emission R6G-UIO-67 fluorescent composite material, and the fluorescent composite material can efficiently and rapidly detect ornidazole; meanwhile, the production cost is low, the operation is simple, and the luminous efficiency is good. Loading the composite material on filter paper to prepare ornidazole detection test paper; the sample to be detected is dropped on the test paper, whether ornidazole exists or not and the content of ornidazole can be visually judged according to the color change and color depth of the test paper under the condition of ultraviolet lamp irradiation, operation is efficient, and observation is convenient. Therefore, the method for detecting ornidazole by using the test paper is safe, energy-saving, short in detection time, accurate in detection result and visual, and can be popularized and applied on a large scale in ornidazole detection.

Description

Technical Field

[0001] The invention relates to the technical field of environmental detection, and in particular to a fluorescent composite material and a preparation method thereof, an ornidazole detection test paper and applications thereof. Background Art

[0002] With the rapid development of animal husbandry and aquaculture, veterinary antibiotics are not only widely used to prevent and treat livestock and poultry diseases, but are also used as feed additives to promote animal growth. In pursuit of economic benefits, some livestock practitioners add antibiotics such as ornidazole to feed as growth promoters in order to increase the growth rate and feed conversion rate of animals. Animals are often infected by various pathogens, such as bacteria, viruses and parasites. In order to prevent and treat these infections, the abuse of ornidazole leads to the emergence of drug residues and drug resistance problems. Due to the lack of effective supervision, a large number of veterinary antibiotics are ingested by animals, and residues are enriched in animal tissues, organs and edible products. The excretion of livestock and poultry and the discharge of aquaculture wastewater enter the environment, causing environmental pollution and having an important impact on human health.

[0003] Ornidazole was first successfully developed by Hoffer.M et al. in the United States, and this achievement was patented in the United States. In China, the research and development and production of ornidazole have also made significant progress. Ornidazole preparations are listed in my country as a Class IV new drug. It is an active drug that can resist most anaerobic bacteria and protozoa. With the continuous advancement of medical technology and the continuous increase in clinical needs, the position of ornidazole in the nitroimidazole drug market has gradually become prominent.

[0004] As a drug, the chemical components of ornidazole may exist and accumulate in the environment for a long time. If abused or improperly handled, the residues of ornidazole may enter the natural environment such as soil and water sources, causing environmental pollution. This pollution not only affects the environment itself, but may also threaten human health through the food chain. The abuse of ornidazole may destroy the balance of microbial communities in soil and water bodies. Drug residues may inhibit or kill certain microorganisms, thereby changing the structure and function of the ecosystem. This change may threaten the survival of other organisms in the ecosystem, even cause imbalance in the entire ecosystem, and even promote the production of drug-resistant bacteria. When the drug is overused, microorganisms such as bacteria may develop drug resistance through gene mutations, resulting in drug failure. These drug-resistant bacteria are not only difficult to kill by conventional drugs, but may also pose a serious threat to human health. At the same time, the spread of drug-resistant bacteria may further aggravate the problem of environmental pollution. If discharged into water bodies without proper treatment, it may cause harm to aquatic organisms. Aquatic organisms exposed to drug residues may cause abnormal growth, difficulty in reproduction, and even death. In addition, drug residues may also be transmitted to humans through the food chain, posing a potential risk to human health. Therefore, developing an efficient method for detecting ornidazole residues has extremely important practical significance for both environmental safety and human health.

[0005] Traditional methods for detecting antibiotics mainly include high performance liquid chromatography, ultra-high performance liquid chromatography-tandem mass spectrometry, enzyme-linked immunosorbent assay, microbial detection, etc. However, these methods are complex, time-consuming, and costly. Therefore, it is very important to develop an easy-to-operate, low-cost, simple and inexpensive method for detecting antibiotic residues for human health and environmental safety. Summary of the invention

[0006] The purpose of the present invention is to solve the above problems existing in the prior art and to provide an ornidazole detection test paper based on a fluorescent composite material and an application thereof.

[0007] The technical solution adopted by the present invention is as follows: A method for preparing a fluorescent composite material comprises the following steps:

[0008] S1. Using a one-pot water bath reaction method, 67 mg of zirconium tetrachloride, 200 mg of rhodamine 6G, and 90 mg of 4,4'-biphenyldicarboxylic acid were mixed and placed in a reaction kettle, and then 15 mL of DMF and 3 mL of glacial acetic acid were added and ultrasonicated to obtain a mixture;

[0009] S2, placing the mixture in S1 into a vacuum drying oven for reaction and then cooling to room temperature;

[0010] S3. The cooled mixture was centrifuged, washed with DMF and methanol, and then dried to obtain the R6G@UIO-67 fluorescent composite material.

[0011] Preferably, the vacuum drying temperature in S2 is 120° C. and the reaction time is 24 h.

[0012] Preferably, the S3 is washed with DMF and methanol three times respectively and then dried at 85°C.

[0013] The invention also provides a fluorescent composite material prepared by the preparation method.

[0014] The present invention also provides an ornidazole detection test paper. The fluorescent composite material is dissolved by ultrasound, put into filter paper, ultrasound is repeated, and finally dried in a drying oven at 85° C. to obtain the ornidazole detection test paper.

[0015] Preferably, 50 mg of the fluorescent composite material is added to every 3 mL of solvent for dissolution; the solvent is water.

[0016] The present invention also provides the use of the ornidazole detection test paper in ornidazole detection, wherein a sample to be tested is dripped onto the ornidazole detection test paper, and whether the sample to be tested contains ornidazole is determined by observing the color change of the test paper under ultraviolet light irradiation.

[0017] The beneficial effects of the present invention are as follows: the R6G@UIO-67 fluorescent composite material synthesized in the present invention shows high selectivity for ornidazole, and can detect ornidazole in an aqueous solution containing a variety of antibiotics. By observing the color change of the test paper loaded with the R6G@UIO-67 fluorescent composite material under ultraviolet light irradiation, it can be judged whether the aqueous solution contains ornidazole, and the content of ornidazole can be judged according to the depth of the color change of the test paper, which has a high degree of visualization. In addition, the R6G@UIO-67 fluorescent composite material is also highly sensitive to ornidazole, and the test paper has a simple production process and can accurately detect ornidazole without the need for expensive instruments, thereby reducing the cost and time of detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 These are the characterization results of UIO-67 and R6G@UIO-67, including (a) XRD patterns of UIO-67 and R6G@UIO-67; (b) TAG patterns of UIO-67 and R6G@UIO-67; (c) structure diagram of R6G@UIO-67; and (d) SEM image of R6G@UIO-67.

[0019] Figure 2 The fluorescence of R6G@UIO-67 material under ultraviolet light.

[0020] Figure 3 The chemical structural formulas of eight common antibiotics.

[0021] Figure 4The loading conditions of different solvents under sunlight and ultraviolet light.

[0022] Figure 5 The fluorescence effect of the test paper loaded with different masses of R6G@UIO-67.

[0023] Figure 6 It is a control before and after adding different concentrations of antibiotics to the test paper under ultraviolet light.

[0024] Figure 7 The selectivity of R6G@UIO-67 for ornidazole. (a) Solid-state fluorescence emission spectrum of R6G@UIO-67. (b) Emission spectrum of R6G@UIO-67 with different concentrations of ODZ antibiotics. (c) Relative intensity of R6G@UIO-67 with different concentrations of different antibiotics. (d) Relative intensity of R6G@UIO-67 with selective induction of ODZ antibiotics. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0026] Example 1 Preparation of R6G@UIO-67 fluorescent composite material

[0027] Using a one-pot water bath method, a mixture of 4,4'-biphenyldicarboxylic acid (H2BPDC) (90 mg), zirconium chloride (ZrCl4) (67 mg) and rhodamine 6G (R6G) (200 mg) was added to a 50 mL polytetrafluoroethylene reaction vessel. Then, 15 mL of N,N'-dimethylformamide (DMF) and 3 mL of glacial acetic acid were added to the mixture, the mixture was ultrasonically treated for 15 min, and the reaction vessel was placed in an oven at 120 ° C for 24 h and then cooled to room temperature. The sample was collected by centrifugation, washed three times with DMF and methanol, respectively, and vacuum dried at 85 ° C to obtain a solid product of R6G@UIO-67 ( Figure 2 ).

[0028] The structure, stability and morphology of the target R6G@UIO-67 fluorescent composite material were characterized by thermogravimetric analysis (TGA), X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). Figure 1 As shown, R6G@UIO-67 has a thermal stability up to 550°C, emits bright yellow light at 580nm, and has a quantum yield of 44.66%, which can selectively detect ornidazole among seven antibiotics. Figure 3) were selected from the R6G@UIO-67 fluorescent composite material to select the most significant antibiotics for fluorescence quenching, of which the most obvious one was ornidazole (ODZ), which was mixed with the other seven antibiotics (metronidazole (DTZ), nitrofurantoin (NFT), nitrofurantoin (NFZ), furazolidone (FZD), metronidazole (MDZ), ronidazole (RDZ), and chloramphenicol (CAP)) in sequence to detect the selectivity of R6G@UIO-67 fluorescent composite material for antibiotics. Figure 7 Analysis showed that the R6G@UIO-67 fluorescent composite material had good selectivity for ornidazole, and test paper for detecting ornidazole was then prepared.

[0029] Example 2 Preparation of Ornidazole Test Paper

[0030] 50 mg of R6G@UIO-67 material (prepared in Example 1) was weighed and dissolved in 3 mL of water. The sample was ultrasonically dissolved for 20 min, then placed in filter paper, ultrasonicated for another 10 min, and dried at 85° C. to obtain an ornidazole antibiotic detection test paper.

[0031] According to the method in Example 2, DMF, acetic acid, and methanol were used as solvents for R6G@UIO-67 materials to prepare the test paper of the control group. By observing the fluorescence intensity effect of the filter paper obtained in Example 2 and the control group under ultraviolet light environment, it was found that the filter paper prepared with water as the solvent had the best effect ( Figure 4 ).

[0032] According to the method in Example 2, 10 mg, 20 mg, and 50 mg of the material were weighed and added to 3 mL of water to obtain filter paper. It was found that the test paper with 50 mg had the best effect ( Figure 5 ).

[0033] Example 3 Detection of ornidazole antibiotics using the developed test paper

[0034] (1) Prepare ornidazole solutions of different concentrations: dilute the high concentration (1000 μg / mL) ornidazole antibiotic solution to prepare a low concentration of metronidazole antibiotic, and prepare ornidazole antibiotic solutions of different concentrations (10 μg / mL, 20 μg / mL, 50 μg / mL, 100 μg / mL, 200 μg / mL, 500 μg / mL).

[0035] (2) 50 μL of the above-mentioned different concentrations of ornidazole antibiotics were added to the ornidazole test paper (prepared in Example 2) and the fluorescence quenching effect was observed under ultraviolet light ( Figure 6 ).

[0036] (3) Conclusion: Through comparative analysis and observation under ultraviolet light environment, it was found that different concentrations of ornidazole solution can cause fluorescence quenching of the metronidazole antibiotic detection test paper, among which 10μg / mL ornidazole solution has a very significant fluorescence quenching effect on the test paper. Therefore, the ornidazole antibiotic detection test paper also performs well in the application of trace detection of ornidazole.

[0037] The specification and drawings of the present invention are considered to be illustrative rather than restrictive. On the basis of the present invention, those skilled in the art can make some substitutions and modifications to some of the technical features according to the disclosed technical content without creative labor, all of which are within the protection scope of the present invention.

Claims

1. A method for preparing a fluorescent composite material, characterized in that: The following steps are involved: S1. Using a one-pot water bath reaction method, 67 mg of zirconium tetrachloride, 200 mg of rhodamine 6G, and 90 mg of 4,4'-biphenyldicarboxylic acid were mixed and placed in a reaction kettle, and then 15 mL of DMF and 3 mL of glacial acetic acid were added and ultrasonicated to obtain a mixture; S2, placing the mixture in S1 into a vacuum drying oven for reaction and then cooling to room temperature; S3. The cooled mixture was centrifuged, washed with DMF and methanol, and then dried to obtain the R6G@UIO-67 fluorescent composite material.

2. The preparation method according to claim 1, characterized in that: The vacuum drying temperature in S2 is 120° C. and the reaction time is 24 h.

3. The preparation method according to claim 1, characterized in that: The S3 was washed three times with DMF and methanol respectively, and then dried at 85°C.

4. A fluorescent composite material obtained by the preparation method according to any one of claims 1 to 3.

5. An ornidazole test paper, characterized in that, The fluorescent composite material according to claim 4 is added to a solvent, dissolved by ultrasound, put into filter paper, ultrasound is performed again, and finally dried in a drying oven at 85° C. to obtain an ornidazole test paper.

6. A test strip for ornidazole according to claim 5, characterized in that, 50 mg of the fluorescent composite material was added into every 3 mL of solvent to dissolve; the solvent was water.

7. Use of the ornidazole test paper as claimed in claim 5 in ornidazole detection, characterized in that, The sample to be tested is dropped onto the ornidazole test paper, and the color change of the test paper is observed under ultraviolet light to determine whether the sample to be tested contains ornidazole.

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