CN107445242B - Adsorption film for synchronously fixing multiple antibiotics under seawater condition - Google Patents
Adsorption film for synchronously fixing multiple antibiotics under seawater condition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the technical field of gradient diffusion films, and provides an adsorption film for fixing various antibiotics under the condition of seawater. An adsorption membrane for synchronously fixing a plurality of antibiotics under the condition of seawater comprises XDA-1 resin powder, agarose powder and ultrapure water, wherein the mass ratio of the XDA-1 resin powder to the agarose powder is 10: 1.5: 100, respectively; the diameter of the adsorption film is 25mm, and the thickness is 0.5 mm; the adsorption film for synchronously fixing various antibiotics under the condition of seawater is orange red. The XDA-1 resin had a specific surface area of 1279m2g‑1The pore diameter is 30 nm. The adsorption membrane for synchronously fixing various antibiotics under the condition of seawater has large adsorption capacity. The adsorption film prepared by the invention has large specific surface area and strong adsorption capacity to weak hydrophobic antibiotics, and has larger adsorption capacity and stronger adsorption capacity to antibiotics in seawater compared with other types of resin materials.
Description
Technical Field
The invention belongs to the technical field of gradient diffusion films, and relates to an adsorption film for fixing various antibiotics under the condition of seawater.
Background
The micro-pollutants in the seawater are important risk sources of ecology and human health, and have the characteristics of low environmental concentration, multiple and complex pollution conditions and large health risk. The pollution and ecological risks of antibiotics in seawater are particularly concerned, and the antibiotics can induce bacterial drug resistance to cause the emergence of resistance genes, so that not only can the ecological balance be influenced, but also the health of human bodies is greatly threatened. Therefore, the determination of the pollution level of antibiotics in seawater is of great significance for evaluating the ecological risk of the seawater.
The common antibiotic sampling mode is active sampling, and after sampling, the sample is moved to a laboratory for pretreatment and sample measurement. The active sampling is large in manpower and resource consumption, the sample transportation is inconvenient, and the pretreatment process is complicated. The passive sampling corresponding thereto is a hot spot of research in recent years. The passive sampling saves time and labor, the pretreatment steps such as filtration, enrichment and the like are completed simultaneously in the sampling process, and the time weighted average concentration of pollutants can be provided. The gradient diffusion in thin-films (DGT) is one of passive sampling, and the dynamic sampling is more accurate and convenient than other passive sampling techniques.
At present, DGT is applied to the determination of trace metals and organic matters in fresh water and the determination of trace metals in seawater, and the application of DGT to organic matters, particularly antibiotics, in seawater is not reported. The assembly of XAD-18 adsorption membranes into DGT in the document "Journal of environmental monitoring.2012,14(6): 1523" measures antibiotics in fresh water, but the adsorption membranes have reduced performance at high ionic strength and cannot be applied to seawater conditions. The seawater substrate condition is represented by alkaline pH (7.9-8.2) and high ionic strength (about 0.7M), most antibiotics are dissociated under the pH condition and are represented by coexistence of molecular state and ionic state, and due to factors such as competitive action, electrostatic repulsion, change of internal pores of the adsorption material under the high ionic strength condition and the like, the commonly used DGT adsorption layer cannot represent good adsorption performance on the antibiotics under the condition.
The XDA-1 macroporous adsorption resin is a nonpolar polymer adsorbent with high crosslinking degree and high specific surface area. Its high specific surface area and continuous pore structure give it excellent adsorption properties for antibiotics. Is widely applied to the separation and purification of antibiotics in the pharmaceutical field.
Disclosure of Invention
The invention aims to provide a DGT binding phase which is prepared by taking XDA-1 macroporous adsorption resin as an adsorbent and is suitable for detecting antibiotics and other weak hydrophobic organic pollutants in seawater, and can overcome the adverse effects of the alkaline pH and high ionic strength of the seawater on adsorption. The method is convenient to operate, easy to assemble into DGT and suitable for being applied to determination of antibiotics in seawater.
The technical scheme of the invention is as follows:
an adsorption membrane for synchronously fixing a plurality of antibiotics under the condition of seawater comprises XDA-1 resin powder and agarose powder, wherein the mass ratio of the XDA-1 resin powder to the agarose powder is 10: 1.5; the diameter of the adsorption film is 25mm, and the thickness is 0.5 mm; the adsorption film for synchronously fixing various antibiotics under the condition of seawater is orange red.
The XDA-1 resin had a specific surface area of 1279m2g-1The pore diameter is 30 nm.
The invention has the beneficial effects that:
the adsorption film for synchronously fixing multiple antibiotics under the condition of seawater has high specific surface area and strong adsorption capacity on weak-hydrophobicity antibiotics. Compared with other types of resin materials, the resin material has larger adsorption capacity and stronger adsorption capacity to antibiotics in seawater.
The adsorption membrane for synchronously fixing various antibiotics under the condition of seawater can overcome the influence of pH and ionic strength on the adsorption of the antibiotics by the adsorption membrane, is suitable for being applied to DGT (denaturing gradient transistor) and is used for determining the antibiotic pollution in the seawater.
The preparation method and the preparation process of the adsorption film for synchronously fixing multiple antibiotics under the seawater condition are easy to control, and the adsorption films prepared in different batches have stable performance and higher strength.
Drawings
FIG. 1 is a comparison of total antibiotic adsorption amounts of the adsorption film prepared by the present invention and other types of resin adsorption films in simulated seawater;
FIG. 2 is a schematic structural diagram of a DGT device assembled with an adsorption membrane for synchronously fixing multiple antibiotics under seawater conditions prepared by the present invention;
FIG. 3(1) is a graph showing the change of the amount of sulfamethoxazole adsorbed by a DGT device incorporating the adsorption film prepared by the present invention with respect to the standing time.
FIG. 3(2) is a graph showing the change of the amount of enrofloxacin adsorbed by a DGT device incorporating an adsorption film prepared according to the present invention with respect to the standing time.
FIG. 3(3) is a graph showing the change of the amount of chloramphenicol adsorbed by a DGT apparatus incorporating an adsorption film prepared according to the present invention with respect to the standing time.
In the figure: 1, a plastic shell; 2, adsorbing the film; 3, a diffusion film; 4, filtering the membrane.
Detailed Description
In order to better understand the contents of the present invention, the following examples are given to further illustrate the present invention, but the scope of the present invention is not limited by the examples.
Example 1
The preparation process comprises the following steps:
step one, preparing XDA-1 functionalized resin powder
(1) Drying XDA-1 macroporous resin, and grinding with a grinder;
(2) sieving the ground resin powder twice, and reserving the middle part;
step two, activating the XDA-1 resin powder screened in the step one by using methanol, and then leaching by using ultrapure water;
step three, mixing the resin, agarose powder and ultrapure water which are activated and washed in the step two according to the mass ratio of 10: 1.5 (mass): 100 (volume) to obtain a glue making solution;
and step four, placing the mixed solution obtained in the step three on a magnetic stirrer, heating and stirring until the mixed solution is clear and transparent, pouring the mixed solution into a glass mold which is preheated in advance (at 50 ℃) and has the internal space thickness of 0.5mm while the mixed solution is hot, flatly placing the mixed solution in the glass mold, and cooling the mixed solution to the room temperature after about 30-40 min.
And step five, cutting the cooled gel film obtained in the step four into a disc with the diameter of 25mm to obtain the required adsorption film.
Preferably, the two-pass screen sizes described in step one are 200 mesh and 400 mesh, with screen sizes of 38 and 75 microns.
Preferably, the activation and washing in the second step are performed by sequentially using methanol and ultrapure water, and the volume ratio of the resin, the methanol and the ultrapure water is about 1: 8: 8.
example 2
The adsorption membrane prepared by the invention is placed in 10mL antibiotic simulated seawater solutions with different concentrations, the concentration gradients are set to be 10, 20, 50, 100, 150 and 200 mug/L, and the shaking table is vibrated for adsorption for 24 hours. And (3) determining the antibiotic concentration in the solution before and after adsorption by using ultra performance liquid chromatography tandem mass spectrometry to calculate the adsorption ratio (%) of the adsorption film to the antibiotic. As can be seen from Table 1, for most antibiotics, the adsorption proportion of the adsorption film prepared by the invention is higher than 90%, and the adsorption effect is excellent, which shows that the adsorption film is feasible to be applied to the determination of antibiotics in seawater by DGT.
Table 1 adsorption ratio (%)% of antibiotics in solutions of various concentrations for adsorption membranes prepared according to the present invention
Example 3
The DGT containing the adsorption film prepared by the invention is applied to the determination of the antibiotics in the actual seawater. Immersing DGT in seawater for 8 hours, taking out the adsorption membrane, eluting the adsorption membrane twice by using 5mL of methanol containing 0.1% formic acid, then blowing the elution liquid nitrogen to be nearly dry, redissolving by using an initial mobile phase, and finally carrying out quantitative analysis by using ultra performance liquid chromatography-tandem mass spectrometry. In the passive sampling process, active sampling is simultaneously carried out as comparison. The results show that the antibiotic levels measured by passive sampling and the traditional active sampling mode have better consistency.
Table 2 contains the DGT of the adsorption film prepared by the invention and the antibiotic determination result of active sampling in actual seawater
Claims (1)
1. An adsorption film for synchronously fixing multiple antibiotics under the condition of seawater is characterized in thatThe adsorption membrane comprises XDA-1 resin powder and agarose powder, and the mass ratio of the XDA-1 resin powder to the agarose powder is 10: 1.5; the diameter of the adsorption film is 25mm, and the thickness of the adsorption film is 0.5 mm; the adsorption film is orange red; the XDA-1 resin had a specific surface area of 1279m2(ii)/g, pore diameter of 30 nm;
the preparation method of the adsorption film for synchronously fixing various antibiotics under the condition of seawater comprises the following steps:
step one, preparing XDA-1 functionalized resin powder;
(1) drying XDA-1 macroporous resin, and grinding with a grinder;
(2) sieving the ground resin powder twice, and reserving the middle part;
the two-time sieving sizes are 200 meshes and 400 meshes, and the sieving particle sizes are 38 microns and 75 microns;
step two, activating the XDA-1 resin powder screened in the step one by using methanol, and then leaching by using ultrapure water;
step three, mixing the resin, the agarose powder and the ultrapure water which are activated and washed in the step two according to the mass ratio: quality: the volume is 10: 1.5: uniformly mixing the raw materials according to the proportion of 100 to obtain a glue making solution;
step four, placing the mixed solution obtained in the step three on a magnetic stirrer, heating and stirring until the mixed solution is clear and transparent, pouring the mixed solution into a glass mold which is preheated to 50 ℃ in advance and has an internal space thickness of 0.5mm, horizontally placing the glass mold in advance, and cooling to room temperature after 30-40 min;
and step five, cutting the cooled gel film obtained in the step four into a disc with the diameter of 25mm to obtain the required adsorption film.
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| CN110108809B (en) * | 2019-04-29 | 2021-09-28 | 南京大学 | Method for measuring fine sesame drugs |
| CN110327903A (en) * | 2019-07-19 | 2019-10-15 | 大连理工大学 | A kind of preparation method and application of antibiotics molecular engram adsorbed film |
| CN110702802A (en) * | 2019-10-24 | 2020-01-17 | 上海海洋大学 | Method for passively monitoring antibiotic content in aquaculture water in situ |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS598176B2 (en) * | 1977-12-02 | 1984-02-23 | ベイラ−・カレツジ・オブ・メデイシン | Resin for selectively removing antibiotics from bacterially infected body fluid samples and method of using the same |
| CN101058068A (en) * | 2007-05-31 | 2007-10-24 | 浙江工商大学 | Macroporous adsorption resin special used for separating antibiotic and its preparation method |
| CN104492376A (en) * | 2014-12-19 | 2015-04-08 | 南京大学 | Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique |
| CN107037193A (en) * | 2017-06-22 | 2017-08-11 | 泉州师范学院 | A kind of water body free state pollutant passive sampling apparatus and the method for sampling |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS598176B2 (en) * | 1977-12-02 | 1984-02-23 | ベイラ−・カレツジ・オブ・メデイシン | Resin for selectively removing antibiotics from bacterially infected body fluid samples and method of using the same |
| CN101058068A (en) * | 2007-05-31 | 2007-10-24 | 浙江工商大学 | Macroporous adsorption resin special used for separating antibiotic and its preparation method |
| CN104492376A (en) * | 2014-12-19 | 2015-04-08 | 南京大学 | Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique |
| CN107037193A (en) * | 2017-06-22 | 2017-08-11 | 泉州师范学院 | A kind of water body free state pollutant passive sampling apparatus and the method for sampling |
Non-Patent Citations (1)
| Title |
|---|
| "A novel passive water sampler for in situ sampling of antibiotics";Chang-Er Chen等;《J. Environ. Monit.》;20120630;第14卷;第1523-1530页 * |
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