CN110746964A - Preparation method of fluorescence sensing material for trace detection of antibiotics in aqueous phase - Google Patents
Preparation method of fluorescence sensing material for trace detection of antibiotics in aqueous phase Download PDFInfo
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Abstract
The invention belongs to the technical field of antibiotic detection materials, and particularly relates to a preparation method of a fluorescence sensing material for trace detection of antibiotics in a water phase. Firstly, adding 2,2 ', 5' -terphenyl tetracid, m-benzylidene diimidazole, cadmium chloride and sodium hydroxide into a mixed solution of dimethyl amide and water, and uniformly stirring to obtain a mixed solution; putting the uniformly stirred mixed solution into an oven, heating to 130 ℃, and preserving heat for 3000 minutes; after the heat preservation is finished, the temperature is reduced to the room temperature at the cooling rate of 10 ℃/hour, and the obtained colorless blocky crystal is the fluorescence sensing material for trace detection of the antibiotics in the water phase. According to the invention, the aromatic polycarboxylic acid and the cadmium ion matched with the configuration are self-assembled under the hydrothermal condition, the advantages that the coordination bond has definite directionality and various valence bond structures in various patterns are fully exerted, and the fluorescent complex with a stable structure is constructed. Based on the fluorescence quenching effect caused by the host-guest interaction between the fluorescent complex and the antibiotic.
Description
Technical Field
The invention belongs to the technical field of antibiotic detection materials, and particularly relates to a preparation method of a fluorescence sensing material for trace detection of antibiotics in a water phase.
Background
Antibiotics (antibiotics) are chemical substances which are produced by microorganisms (including bacteria, fungi and actinomycetes) or higher animals and plants in the life process, have pathogen resistance or other activities, and can interfere with the development functions of other living cells.
In recent years, the information about antibiotics detected in water is reported to gradually enter the field of the public through media, and the attention is attracted. Antibiotics and resistance genes are detected in natural water, which is not a special phenomenon of a river but a general phenomenon. Antibiotics are currently used globally mainly for human treatment of diseases and for large-scale livestock breeding. Antibiotics, one of the most important discoveries in the scientific history of the last century, brought the medical level of mankind into an unprecedented era. The proper amount and reasonable and standard use of the antibiotics are for benefiting mankind. Antibiotic residues and resistance genes in the water body mainly come from human abuse of antibiotics.
The antibiotic can inhibit the growth of germs or even kill germs, but germs can generate drug resistance, the drug resistance refers to the characteristic that organisms (particularly pathogenic microorganisms) which are originally sensitive to certain antibiotic become highly resistant to the antibiotics after mutation, and the drug resistance of bacteria is also called drug resistance, which refers to that the sensitivity of the bacteria to the antibiotic is reduced or even disappears after the bacteria are contacted with the antibiotic for many times, so that the curative effect of the antibiotic to the drug-resistant bacteria is reduced or ineffective. The biggest concern with the problem of bacterial resistance is that once the "superbacteria" causing disease in the human body outbreak, the existing antibiotics are not able to cure. Worldwide, death cases due to lack of medicine are not uncommon after infection of humans by "superbacteria" carrying resistance genes.
Antibiotics are used as emerging pollutants in drinking water, are related to the healthy development of human society, and are increasingly concerned by people for detecting the antibiotics in water, and current methods for detecting trace amounts of antibiotics, such as high performance liquid chromatography, Raman spectroscopy, mass spectrometry and the like, generally have the defects of large equipment volume, high price, difficulty in carrying, more pretreatment and slow response time, and are not beneficial to the rapid trace amount detection of the antibiotics.
Disclosure of Invention
Aiming at the technical problems existing in the detection of the antibiotics in the water phase, the invention provides the preparation method of the fluorescence sensing material for detecting the trace antibiotics in the water phase, which is simple in method, low in cost, high in response speed and convenient to carry and use.
In order to achieve the purpose, the invention adopts the technical scheme that the invention provides a preparation method of a fluorescence sensing material for detecting trace antibiotics in an aqueous phase, which comprises the following effective steps:
a. firstly, adding 2,2 ', 5' -terphenyl tetracid, m-benzylidene diimidazole, cadmium chloride and sodium hydroxide into a mixed solution of dimethyl amide and water, and uniformly stirring to obtain a mixed solution;
b. putting the uniformly stirred mixed solution into an oven, heating to 130 ℃, and preserving heat for 3000 minutes;
c. after the heat preservation is finished, the temperature is reduced to the room temperature at the cooling rate of 10 ℃/hour, and the obtained colorless blocky crystal is the fluorescence sensing material for trace detection of the antibiotics in the water phase.
Preferably, the molar ratio of the 2,2 ', 5' -terphenyl tetracid to the m-benzylidene diimidazole to the cadmium chloride is 1:2: 2.
Preferably, the dimethyl amide and the water are mixed in a ratio of 1:1 by volume.
Compared with the prior art, the invention has the advantages and positive effects that,
1. according to the invention, the aromatic polycarboxylic acid and the cadmium ion matched with the configuration are self-assembled under the hydrothermal condition, the advantages that the coordination bond has definite directionality and various valence bond structures in various patterns are fully exerted, and the fluorescent complex with a stable structure is constructed. Based on fluorescence quenching effect caused by host-guest action between the fluorescent complex and the antibiotic, the prepared fluorescent complex can realize trace detection of the antibiotic in the water phase, and the detection Limit (LOD) can reach ppb order of magnitude.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive labor.
FIG. 1 is an atomic structural diagram of a fluorescence sensing material provided in example 1;
FIG. 2 is the structural formula of the antibiotic to be detected provided in example 1;
FIG. 3 is the effect of different antibiotics, NFZ (a), NFT (b), DND (c), MND (d), RND (e), OND (f), on the fluorescence intensity of the fluorescence sensing material in the aqueous phase, provided in example 1, at varying concentrations of 0-25 μ M;
FIG. 4 shows Stern-volume equation of the effect of concentration on fluorescence intensity of the system in aqueous phase for different antibiotics NFZ (a), NFT (b), DND (c), MND (d), RND (e), OND (f);
FIG. 5 is a diagram showing the repeatability of detection of fluorescent sensing materials in different antibiotics NFZ (a), NFT (b), DND (c), MND (d), RND (e) and OND (f).
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the accompanying drawings and examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1, this example provides a method for preparing a fluorescence sensing material for trace detection of antibiotics in aqueous phase
2,2 ', 5' -terphenyltetracid (p-tert-phenyl-2, 2 ', 5' -tetracarboxylate acid (H4tptc)) (1.6mg, 0.004mmol), m-terphenyltetracid (p-tert-phenyl-2, 2 ', 5' -tetracarboxylate acid) (m-terphenylacrylate, m-terpBenzylidene-bis (imidozol-1-ylmethyl) bezene (bimb) (1.9mg, 0.008mmol), CdCl2·2.5H2A mixture of O (1.8mg, 0.008mmol) and 0.2mmol of NaOH was dissolved in 1mL DMF/H2And (3) O (v/v, 1/1), stirring uniformly, putting into a hard glass tube, heating the mixed solution to 130 ℃ in an oven, keeping the temperature for 3000 minutes, and cooling to room temperature at a cooling rate of 10 ℃/hour. The obtained colorless bulk crystal was the prepared compound (fluorescent sensor material), filtered, washed with mother liquor and pure water three times, dried naturally and weighed, and the yield was 47%.
Elemental analysis: c25H19CdN4O4The structure is shown in figure 1. Theoretical value C, 54.41; h, 3.47; n, 10.15; test values C, 54.36; h, 3.87; 10.13. infrared (KBr pellet, cm-1) 3451(m),1566(vs),1521(m),1425(vs),1390(s),1348(s),1241(s),1109(s),1087(s),1022(w),897(w),859(s),778(s),727(s),618(m),589 (w).
Specific experiments are as follows:
0.2mg of a newly prepared fluorescence sensing material is ground, placed in 2mL of water and ultrasonically vibrated for 30 minutes, and then antibiotic solutions with different volume (microliter) and concentration of 0.1mM are dropwise added into the aqueous solution, so that the fluorescence intensity of the antibiotic solutions with different concentrations can be changed. According to Stern-Volmer equation I0/I＝Ksv[Q]The Ksv parameter can be calculated from the relationship between the antibiotic concentration and the ratio of the fluorescence intensity. Then using the detection limit LOD of 3 sigma/KsvAnd calculating the detection limit. And corresponding concentration calculation is carried out according to the antibiotic solution with unknown concentration and the fluorescence intensity of the prepared fluorescence sensing material, so that trace detection of the antibiotic is realized.
As shown in figure 2, four nitroimidazole antibiotics (1,2-dimethyl-5-nitroimidazole (DND), CAS No. 551-92-8, nitroimidazole (MND), CAS No. 443-48-1, nitroimidazole (RND), CAS No. 7681-76-7, Ornidazole (OND), CAS No. 16773-42-5) and two nitrofuran antibiotics (nitrofuran (NFZ), CAS No. 59-87-0, Nitrofuratin (NFT) and CAS No. 67-20-9) are selected as the target antibiotics of our research, because the antibiotics have a broad spectrum and low price and are often overdosed in livestock breeding, which causes great risk to food safety. In the experimental process, the fluorescence intensity of the prepared fluorescent sensing material in the water phase is rapidly reduced along with the dropwise addition of the six antibiotics, so that the phenomenon of fluorescence quenching is caused. To further understand the relationship between the antibiotic dropping amount (i.e. concentration) and the fluorescence intensity, we tested the fluorescence intensity of the fluorescence sensing material in the water phase at different concentrations of different kinds of antibiotics, and the results are shown in fig. 3.
Fluorescence analysis shows that when the concentration of the antibiotics reaches 25 mu M, the quenching rates of the six antibiotics on the fluorescence of the system exceed 85 percent. By analyzing the relationship between the antibiotic concentration and the fluorescence intensity of the system, we obtained the Stern-Volumer linear equation shown in FIG. 4. Quenching constant KsvI.e. the pre-concentration coefficient in the equation. Reuse limit LOD of 3 sigma/KsvThe detection limits of the fluorescent sensing material we prepared on the above NFZ, NFT, DND, MND, RND, and OND antibiotics in the aqueous phase were calculated to be 42ppb,71ppb,24ppb,48ppb,86ppb, and 42ppb, respectively. As can be seen from fig. 5, the fluorescence sensing material provided in this embodiment has good repeatability in the detection processes of different antibiotics nfz (a), nft (b), dnd (c), mnd (d), rnd (e), ond (f).
In addition, after three repeated detections, the prepared fluorescent sensing material can still keep the recognition efficiency of more than 98%, and shows good repeatable performance. After detection, powder diffraction analysis shows that the prepared fluorescent sensing material still has a stable structure and shows excellent stability.
In summary, it is easy to find that the trace amount detection of the antibiotic by using the fluorescent sensing material prepared in the present application has the following advantages compared with the current technology:
1. the organic-inorganic hybrid complex fluorescent sensing material in the scheme is simple to prepare and does not need complex instruments; 2. in the detection process, the method is rapid and convenient, the detection time is not more than 3 minutes generally, and the reliability of the detection result is high; 3. has lower detection limit on antibioticsPpb levels, i.e. 10-9The mol/L can realize the rapid detection of trace antibiotics in the water phase, and 4, the preliminary judgment of naked-light naked eyes on the concentration of a detected sample can be realized by means of a handheld ultraviolet lamp, so that the further detection is convenient; 5. the organic-inorganic hybrid complex fluorescent sensing material prepared in the scheme has the characteristic of recycling, so that the cost is greatly reduced; 6. the organic-inorganic hybrid complex fluorescent sensing material prepared in the scheme can exist stably, so that the application range of the material is expanded, and the loss and pollution of early-stage sample preparation are reduced.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (3)
1. A preparation method of a fluorescence sensing material for trace detection of antibiotics in an aqueous phase is characterized by comprising the following effective steps:
a. firstly, adding 2,2 ', 5' -terphenyl tetracid, m-benzylidene diimidazole, cadmium chloride and sodium hydroxide into a mixed solution of dimethyl amide and water, and uniformly stirring to obtain a mixed solution;
b. putting the uniformly stirred mixed solution into an oven, heating to 130 ℃, and preserving heat for 3000 minutes;
c. after the heat preservation is finished, the temperature is reduced to the room temperature at the cooling rate of 10 ℃/hour, and the obtained colorless blocky crystal is the fluorescence sensing material for trace detection of the antibiotics in the water phase.
2. The method for preparing a fluorescence sensing material for trace detection of antibiotics in an aqueous phase according to claim 1, wherein the molar ratio of 2,2 ", 5" -terphenyltetracarboxylic acid, m-benzylidene diimidazole and cadmium chloride is 1:2: 2.
3. The method for preparing the fluorescence sensing material for trace detection of antibiotics in aqueous phase according to claim 1, wherein the ratio of the dimethyl amide to the water is mixed according to the volume ratio of 1: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150306A (en) * | 2021-05-08 | 2021-07-23 | 聊城大学 | FMOF material with high water stability, preparation thereof and application thereof in sensing detection of fleroxacin in water |
Citations (2)
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| CN105713024A (en) * | 2016-01-22 | 2016-06-29 | 辽宁大学 | Zn<II>-based metal-organic framework and preparation method and application thereof |
| CN106496024A (en) * | 2016-08-31 | 2017-03-15 | 哈尔滨理工大学 | For efficient detection Hg2+The super molecular complex with fluorescent functional based on aromatic carboxylic acids part and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713024A (en) * | 2016-01-22 | 2016-06-29 | 辽宁大学 | Zn<II>-based metal-organic framework and preparation method and application thereof |
| CN106496024A (en) * | 2016-08-31 | 2017-03-15 | 哈尔滨理工大学 | For efficient detection Hg2+The super molecular complex with fluorescent functional based on aromatic carboxylic acids part and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| YUJUAN ZHANG ET AL.: "Two cadmium(II)) coordination polymers as luminescent sensors for the detection of nitrofuran/nitroimidazole antibiotics", 《CRYSTENGCOMM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150306A (en) * | 2021-05-08 | 2021-07-23 | 聊城大学 | FMOF material with high water stability, preparation thereof and application thereof in sensing detection of fleroxacin in water |
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Application publication date: 20200204 |