CN110850018A - Method for analyzing and detecting four sulfonamides antibiotics in environmental water sample - Google Patents
Method for analyzing and detecting four sulfonamides antibiotics in environmental water sample Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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Abstract
The invention belongs to the field of antibiotic detection, and relates to an analytical determination method for four sulfonamides antibiotics in a water sample, which utilizes a negative pressure suction filtration membrane solid phase extraction technology and adopts a metal organic framework material NH2-MIL-101(Fe) membrane solid phase extraction-high performance liquid chromatography to determine four antibiotics of sulfadiazine, sulfachlorpyridazine and sulfamethoxazole in an environmental water sample. The method is simple, convenient, rapid and sensitive to operate, and has the advantages of low detection limit, accuracy and good reproducibility; meanwhile, the raw materials used in the invention are cheap and easily available, the preparation process of the materials is simple, the reaction conditions are mild, the application environment is friendly, and the market prospect is wide.
Description
The technical field is as follows:
the invention belongs to the field of antibiotic detection, and relates to an analytical determination method for four sulfonamides antibiotics in a water sample, which utilizes a negative pressure suction filtration membrane solid phase extraction technology and adopts a metal organic framework material NH2-MIL-101(Fe) membrane solid phase extraction-high performance liquid chromatography to determine four antibiotics of sulfadiazine, sulfachlorpyridazine and sulfamethoxazole in an environmental water sample.
Background art:
sulfonamide Antibiotics (SAs) are a generic name for drugs having a sulfanilamide structure, and are widely used as broad-spectrum antibacterial agents for human medical treatment and livestock breeding. The use of such antibiotics in large quantities not only increases the resistance of bacteria to antibacterial agents, but also leads to toxic accumulation in organisms. The sulfonamide antibiotics in the environment mainly have two main sources: firstly, human and livestock urine and excrement; and secondly, the sewage is discharged from a town sewage treatment plant and enters an environmental water body. Not only causes serious pollution to the ecological environment, but also threatens the human health and the long-term development of the society, so that the detection of the sulfonamide antibiotics in the environmental water sample is more and more emphasized by people.
The content of the sulfonamide antibiotics in water is low, and the water sample needs to be pretreated, enriched and concentrated, and then can be accurately measured. At present, the pretreatment method of sulfonamide antibiotics in water mainly comprises the following steps: solid phase extraction, solid phase micro-extraction, liquid-liquid extraction, microwave extraction, liquid-liquid micro-extraction and the like. Solid phase extraction has been widely used for pretreatment of organic compounds in water samples due to high recovery rate, short extraction time, high enrichment factor, low organic solvent consumption, and easy automation and operation. The chromatographic method of the sulfonamide antibiotics in water mainly comprises gas chromatography, gas chromatography-mass spectrometry, liquid chromatography and liquid chromatography-mass spectrometry. Gas chromatography is the earliest analytical method for determining the residual quantity of sulfonamide antibiotics in water, but derivatization is needed; the high liquid chromatography does not need derivatization, and is a high-speed, high-sensitivity and high-automation separation analysis technology.
Metal-organic frameworks (MOFs) are a class of organic-inorganic hybrid nanoporous materials, and are one of the research hotspots and frontiers in the field of new materials. The metal-organic framework material is a three-dimensional network structure crystal formed by coordination bonding of aromatic acid or alkali containing nitrogen and oxygen multidentate organic ligand and an inorganic metal center. The MOFs material has many advantages compared with the traditional porous material, such as many kinds, large porosity and specific surface area, and strong pore size controllability, and thus can be applied to various modern sample pretreatment technologies. In recent years, researchers adopt an in-situ growth method, a seed crystal growth method, a post-synthesis modification method and a mixed matrix membrane method based on MOFs to prepare the MOFs into a membrane, and the MOFs are applied to the aspects of membrane separation, membrane adsorption and the like. Compared with the traditional process, on one hand, MOFs in the mixed matrix membrane keeps a highly-crystallized porous structure and a high specific surface area, and has high permeability and selectivity, and on the other hand, the MOFs overcomes the defects of poor mechanical strength and reproducibility and complex process, and has the advantages of low energy consumption, low emission, high separation degree, simplicity in operation, easiness in recycling and the like.
Therefore, the invention seeks to design and provide a method for analyzing and detecting four sulfonamides antibiotics in an environmental water sample, wherein NH is adopted in the method2Preparation of NH from MIL-101(Fe) MOF Material2The MIL-101(Fe) -polyvinylidene fluoride mixed matrix membrane is used for realizing the rapid enrichment of four kinds of sulfanilamide antibiotics in water by a negative pressure suction filtration mode, and then the sulfanilamide antibiotics are quantitatively analyzed by a liquid chromatography.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and seeks to design an analysis and detection method for four sulfonamides antibiotics in an environmental water sample, wherein the method utilizes a membrane solid-phase extraction technology and simultaneously adopts a metal organic framework material NH2The MIL-101(Fe) membrane is used as a membrane solid phase extraction material, the method has the characteristics of low toxicity, simple reaction conditions and low equipment cost, and can be used for quickly and efficiently analyzing and detecting four sulfonamides antibiotics in an environmental water sample.
In order to achieve the purpose, the method for analyzing and detecting the four sulfonamides antibiotics in the environmental water sample, which is disclosed by the invention, specifically comprises the following steps of:
s1 preparation of metal organic framework material NH2MIL-101(Fe) with NH2MIL-101(Fe) -polyvinylidene fluoride mixed matrix membrane:
(1) dissolving ferric trichloride in N-N Dimethylformamide (DMF), adding amino terephthalic acid, and fully stirring and dissolving to obtain a mixture for later use;
(2) reacting the mixture prepared in the step (1) in a solvothermal reaction kettle at the temperature of 100 ℃ and 130 ℃ for 24 hours, and washing the mixture prepared in the solvothermal reaction kettle with DMF to prepare NH2-MIL-101(Fe) mixture, thenVacuum drying the mixed solution at 100 ℃ to obtain metal organic framework material NH2MIL-101(Fe) for future use；
(3) Weighing NH2-MIL-101(Fe) powder, and dissolving with acetone to obtain NH2Preparing a mixed solvent of polyvinylidene fluoride and DMF (dimethyl formamide) according to the proportion of 100mg:4mL into NH-101 (Fe) solution for later use2Adding 1mL of mixed solvent into the MIL-101(Fe) solution to prepare a mixed solution for later use;
(4) uniformly coating the mixed solution obtained in the step (3) on a clean glass plate, and drying the glass plate in an oven to obtain a metal organic framework material NH2-MIL-101(Fe) film;
s2, use of the metal organic framework material NH prepared in step S12MIL-101(Fe) membrane solid phase extraction, and analyzing four sulfanilamide antibiotics in a water sample by combining high performance liquid chromatography, wherein the method comprises the following specific steps:
(1) taking metal organic framework material NH2Putting the MIL-101(Fe) film into a suction filtration device, adding 200mL of water sample into a beaker, and performing suction filtration by using the suction filtration device;
(2) the NH was eluted twice with 16mL acetonitrile + 5% by volume aqueous ammonia28mL of MIL-101(Fe) membrane each time, washing for 15min each time, blowing the eluent by nitrogen for drying, redissolving by using 1mL of mobile phase (20% acetonitrile and 80% aqueous solution of 3 formic acid), wherein the volume ratio of the acetonitrile to the aqueous solution of formic acid is adopted, and carrying out high performance liquid chromatography detection;
further, the conditions of the high performance liquid chromatography in the invention are as follows: selecting an Agilent ZORBAX SB-C18 high performance liquid chromatography column with the specification of length of 150mm, inner diameter of 4.6mm and filler particle diameter of 5 μm; the detector is a diode array ultraviolet detector, the measuring wavelength of the diode array ultraviolet detector is 270nm, and the emission wavelength is 315 nm; sample introduction by an automatic sample injector, sample introduction amount: gradient elution procedure for 10 μ L, 4 compounds is shown in the following table:
the invention examines the main factors influencing the extraction recovery rate of the four sulfonamides antibiotics, calculates the optimal value of each factor when the extraction recovery rate is highest, and then determines the relevant parameters of the working curves of the four sulfonamides antibiotics and the detection limit and precision of the method under the condition of the optimal value of each factor, and the specific process comprises the following steps:
s1, calculating the optimal value of each factor when the extraction recovery rate of the four sulfonamides antibiotics is highest:
(1) investigation of adsorbent dosage on extraction recovery
The influence of the MOF dosage on the extraction recovery rate is considered, and 40mg, 50 mg, 60mg, 70 mg, 80 mg, 90 mg and 100mg of metal organic framework material NH are respectively weighed2Preparing an MOF membrane from MIL-101(Fe), wherein the concentrations of four antibiotics in a water sample are all 0.01mg/L, and when a metal organic framework material NH is adopted2When the dosage of MIL-101(Fe) is increased from 40mg to 60mg, the extraction recovery rate is increased along with the dosage of the adsorbent, which shows that the extraction recovery rate is increased along with the NH of the metal organic framework material2Increased MIL-101(Fe) usage, increased adsorption sites, increased adsorption capacity; when the dosage of the adsorbent is more than 60mg, the metal organic framework material NH is continuously increased2The extraction recovery rate of the four compounds is reduced or even almost unchanged due to the use of MIL-101(Fe), so that 60mg of the extraction agent is selected in the invention;
(2) investigation of water sample pH on extraction recovery rate
The influence of the pH of a water sample on the activity of the surface adsorption sites of the extraction material is inspected, the extraction recovery rate results of the water sample under the conditions that the pH is 3, 4, 5.5, 7 and 8 are respectively inspected, the recovery rate of the pH value is increased within the range of 3-4, and the recovery rate is sharply decreased within the range of 4-8, so that the optimum pH value of the material for extracting the four sulfonamide antibiotics is 4;
(3) investigation of eluent species on extraction recovery
The invention inspects the influence of different eluents on the elution efficiency of an object to be detected adsorbed on the adsorbent, inspects the influence of four organic solvents of methanol, acetonitrile, acetone, acetonitrile and 5% ammonia water on the extraction recovery rate, and has the highest elution efficiency of the acetonitrile and the ammonia water with the volume fraction of 5%, so the invention selects the acetonitrile and the 5% ammonia water as the elution solvent.
(4) Salinity investigation of extraction recovery
The influence of salinity on the ionic strength and the diffusion rate of compounds in water is inspected, in order to inspect the influence of salt concentration on the extraction recovery rate of four sulfonamide antibiotics in a water sample, sodium chloride (NaCl) which enables the salinity of the water sample to be 0%, 0.5%, 1%, 5% and 10% is added, after the NaCl is added, when the salt concentration is 0-1%, the recovery rate is rapidly increased, and along with the continuous increase of the salt concentration, the recovery rate is reduced and tends to be stable, so that the salt concentration selected by the method is 1%;
(5) investigation of eluent dosage on extraction recovery
According to the invention, the elution effects of 4mL, 6mL, 8mL, 10mL and 12mL of eluents are considered, the recovery rate of four sulfonamides antibiotics is the maximum when the single eluent dosage is 8mL, and the extraction recovery rate is reduced after the dosage is continuously increased, so that the single eluent dosage is 8 mL;
(6) examination of elution time on extraction recovery
According to the invention, the elution effect under the condition of two times of elution is considered for 5min, 10min, 15min, 20min and 25min, and the recovery rate of four sulfonamides antibiotics is maximum when the single elution time is 15min, so that the single elution time is selected to be 15 min;
s2, determining the relevant parameters of the working curves of the four sulfonamides antibiotics, and determining the detection limit and precision of the method:
(1) preparing 200mL water samples with the concentrations of four antibiotics of 0.1 mug/L, 1 mug/L, 2 mug/L, 5 mug/L, 10 mug/L and 100 mug/L, performing high performance liquid chromatography determination under the optimized membrane solid phase extraction condition, and determining the regression equation, the linear range and the correlation coefficient (R) of the working curves of the four sulfonamides antibiotics2) Method quantitation limit and method detection limit;
(2) preparing 200mL of simulated water samples with four antibiotics with concentrations of 1 mug/L, 10 mug/L and 40 mug/L, namely low, medium and high concentrations, measuring according to a membrane solid phase extraction step, parallelly measuring 3 times of in-day precision (expressed by relative standard deviation) of each concentration point within one day, measuring 3 days of in-day precision (expressed by relative standard deviation) of the three concentrations once per day, measuring the in-day precision of the four sulfonamides with the relative standard deviation of 1.86-11.24%, and measuring the in-day precision of the four sulfonamides with the relative standard deviation of 0.78-5.84%, so as to meet the analysis requirements.
Compared with the prior art, the invention has the following beneficial effects: adopts metal organic framework material NH2MIL-101(Fe), has better adsorption efficiency on four sulfonamides antibiotics; adopts metal organic framework material NH2MIL-101(Fe) is used as a membrane solid phase extraction material, and a high performance liquid chromatography-ultraviolet fluorescence detector is adopted to establish an analysis method of four sulfonamides antibiotics in a water sample, wherein the method is simple, convenient, rapid and sensitive to operate and has the advantages of low detection limit, accuracy and good reproducibility; meanwhile, the raw materials used in the invention are cheap and easily available, the preparation process of the materials is simple, the reaction conditions are mild, the application environment is friendly, and the market prospect is wide.
Description of the drawings:
FIG. 1 is a graph showing the effect of the amount of adsorbent used in the present invention on the recovery rate of four sulfonamides.
FIG. 2 is a graph showing the influence of pH of a water sample on the extraction recovery rates of four sulfonamides.
FIG. 3 is a graph showing the influence of the eluent type on the extraction recovery rates of four sulfonamides.
FIG. 4 is a graph showing the effect of salinity on the extraction recovery of four sulfonamides according to the present invention.
FIG. 5 is a graph showing the effect of the amount of eluent used in the present invention on the recovery rate of four sulfonamides.
FIG. 6 is a graph showing the effect of elution time on the recovery of four sulfonamides.
FIG. 7 is the UV chromatogram of laboratory tap water without adding standard water sample 40 μ g/L (a) and standard water sample (b).
FIG. 8 is an ultraviolet chromatogram of Laoshan mountain reservoir without adding standard water sample 40 μ g/L (a) and standard water sample (b).
FIG. 9 is the ultraviolet chromatograms of the seawater sample without standard water sample 40 μ g/L (a) and the water sample with standard water (b).
The specific implementation mode is as follows:
the invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1:
the method for analyzing and detecting the four sulfonamides antibiotics in the environmental water sample comprises the following steps:
s1 preparation of metal organic framework material NH2MIL-101(Fe) with NH2MIL-101(Fe) -polyvinylidene fluoride mixed matrix membrane:
(1) dissolving ferric trichloride in N-N Dimethylformamide (DMF), adding amino terephthalic acid, and fully stirring and dissolving to obtain a mixture for later use;
(2) reacting the mixture prepared in the step (1) in a solvothermal reaction kettle at the temperature of 100 ℃ and 130 ℃ for 24 hours, and washing the mixture prepared in the solvothermal reaction kettle with DMF to prepare NH2Mixed liquid of-MIL-101 (Fe), and then the mixed liquid is dried in vacuum at 100 ℃ to prepare metal organic framework material NH2-MIL-101(Fe) for use;
(3) weighing NH2-MIL-101(Fe) powder, and dissolving with acetone to obtain NH2preparing-MIL-101 (Fe) solution for later use, preparing polyvinylidene fluoride and DMF into a mixed solvent according to a certain proportion, adding into NH2Adding 1mL of mixed solvent into the MIL-101(Fe) solution to prepare a mixed solution for later use;
(4) uniformly coating the mixed solution obtained in the step (3) on a clean glass plate, and drying the glass plate in an oven to obtain a metal organic framework material NH2-MIL-101(Fe) film;
s2, use of the metal organic framework material NH prepared in step S12MIL-101(Fe) membrane solid phase extraction, and analyzing four sulfanilamide antibiotics in a water sample by combining high performance liquid chromatography, wherein the method comprises the following specific steps:
(1) taking metal organic framework material NH2-MIL-101(Fe) film in suction filtration apparatusAdding 200mL of water sample (the concentration of four sulfonamides antibiotics in the water sample is 0.01mg/L) into the beaker, and performing suction filtration by using a suction filtration device;
(2) the NH was eluted twice with 16mL acetonitrile + 5% by volume aqueous ammonia28mL of MIL-101(Fe) membrane each time, washing for 15min each time, blowing the eluent by nitrogen for drying, redissolving by using 1mL of mobile phase (20% acetonitrile and 80% aqueous solution of 3 formic acid), wherein the volume ratio of the acetonitrile to the aqueous solution of formic acid is adopted, and carrying out high performance liquid chromatography detection;
further, in this embodiment, the conditions of the hplc method are as follows: selecting an Agilent ZORBAX SB-C18 high performance liquid chromatography column with the specification of length of 150mm, inner diameter of 4.6mm and filler particle diameter of 5 μm; the detector is a diode array ultraviolet detector, the measuring wavelength of the diode array ultraviolet detector is 270nm, and the emission wavelength is 315 nm; sample introduction of an automatic sample injector, sample introduction amount: gradient elution procedure for 10 μ L, 4 compounds is shown in the following table:
example 2:
in this embodiment, the main factors affecting the extraction recovery rates of the four sulfonamides antibiotics are examined, the optimal values of the factors when the extraction recovery rate is the highest are calculated, and the parameters related to the working curves of the four sulfonamides antibiotics and the detection limits and precision of the method are determined under the condition of the optimal values of the factors, and the specific process comprises the following steps:
s1, calculating the optimal value of each factor when the extraction recovery rate of the four sulfonamides antibiotics is highest:
(1) investigation of adsorbent dosage on extraction recovery
The influence of the MOF dosage on the extraction recovery rate is considered, and 40mg, 50 mg, 60mg, 70 mg, 80 mg, 90 mg and 100mg of metal organic framework material NH are respectively weighed2Preparing an MOF membrane from MIL-101(Fe), wherein the concentrations of four antibiotics in a water sample are all 0.01mg/L, and when a metal organic framework material NH is adopted2When the dosage of MIL-101(Fe) is increased from 40mg to 60mg, the extraction recovery rate is increased along with the dosage of the adsorbent, which shows that the extraction recovery rate is increased along with the NH of the metal organic framework material2Increased MIL-101(Fe) usage, increased adsorption sites, increased adsorption capacity; when the dosage of the adsorbent is more than 60mg, the metal organic framework material NH is continuously increased2The extraction recovery rate of the four compounds is reduced or even almost unchanged due to the use of MIL-101(Fe), so that 60mg of the extraction agent is selected in the invention;
(2) investigation of water sample pH on extraction recovery rate
The influence of the pH of a water sample on the activity of the surface adsorption sites of the extraction material is inspected, the extraction recovery rate results of the water sample under the conditions that the pH is 3, 4, 5.5, 7 and 8 are respectively inspected, the recovery rate of the pH value is increased within the range of 3-4, and the recovery rate is sharply decreased within the range of 4-8, so that the optimum pH value of the material for extracting the four sulfonamide antibiotics is 4;
(3) investigation of eluent species on extraction recovery
The invention inspects the influence of different eluents on the elution efficiency of an object to be detected adsorbed on an adsorbent, and inspects the influence of four organic solvents of methanol, acetonitrile, acetone and acetonitrile + ammonia water with the volume fraction of 5% on the extraction recovery rate, wherein the acetonitrile + 5% ammonia water has the highest elution efficiency, so the invention selects the acetonitrile + 5% ammonia water as an elution solvent;
(4) salinity investigation of extraction recovery
The invention inspects the influence of salinity on the ionic strength and the diffusion rate of compounds in water, and in order to inspect the influence of salt concentration on the extraction recovery rate of four sulfonamide antibiotics in a water sample, sodium chloride (NaCl) is added to ensure that the salinity of the water sample is respectively 0%, 0.5%, 1%, 5% and 10%, and after the NaCl is added, the recovery rate is rapidly increased when the salt concentration is 0-1%. Along with the continuous increase of the salt concentration, the recovery rate is reduced and tends to be stable, so that the salt concentration selected by the method is 1%;
(5) investigation of eluent dosage on extraction recovery
According to the invention, the elution effects of 4mL, 6mL, 8mL, 10mL and 12mL of eluents are considered, the recovery rate of four sulfonamides antibiotics is the maximum when the single eluent dosage is 8mL, and the extraction recovery rate is reduced after the dosage is continuously increased, so that the single eluent dosage is 8 mL;
(6) examination of elution time on extraction recovery
According to the invention, the elution effect under the condition of two times of elution is considered for 5min, 10min, 15min, 20min and 25min, and the recovery rate of four sulfonamides antibiotics is maximum when the single elution time is 15min, so that the single elution time is selected to be 15 min;
s2, determining the relevant parameters of the working curves of the four sulfonamides antibiotics, and determining the detection limit and precision of the method:
(1) preparing 200mL water samples with the concentrations of four antibiotics of 0.1 mug/L, 1 mug/L, 2 mug/L, 5 mug/L, 10 mug/L and 100 mug/L, performing high performance liquid chromatography determination under the optimized membrane solid phase extraction condition, and determining the regression equation, the linear range and the correlation coefficient (R) of the working curves of the four sulfonamides antibiotics2) Method quantification limit and method detection limit:
TABLE 1 regression equation, linear range, and correlation coefficient (R) of working curves for four sulfonamides antibiotics2) Instrument detection limit and method detection limit
(2) 200mL of simulated water samples with the four antibiotics with the concentrations of 1 mug/L, 10 mug/L and 40 mug/L and with the concentrations of low, medium and high are prepared, the measurement is carried out according to the membrane solid phase extraction step, the precision within 6 investigation days (expressed by relative standard deviation) is parallelly measured at each concentration point within one day, the precision within 6 investigation days (expressed by relative standard deviation) is measured once per day at three concentrations, the precision within 6 investigation days (expressed by relative standard deviation) is measured, the relative standard deviation of the precision within four sulfonamides within 1.86-11.24% within the day is measured, and the relative standard deviation of the precision within 0.78-5.84% within the day is measured, so that the precision requirement is met.
TABLE 2 interday and intraday precision of four sulfonamides
Example 3:
measuring the residual amounts of four sulfonamides antibiotics in tap water in a laboratory, Laoshan reservoirs in Qingdao city and seawater, collecting 3 water samples, filtering with rapid qualitative filter paper with the pore diameter of 80-120 μm, and filtering with a 0.45 μm filter membrane; measuring the filtered water sample by the method described in example 1, performing accuracy test by the method described in example 2, preparing four practical water samples with the antibiotic concentrations of 1 mug/L, 10 mug/L and 40 mug/L and with the low, medium and high concentrations respectively, performing a standard recovery rate test, measuring each concentration point for 3 times, and calculating the average value, the relative standard deviation and the standard recovery rate of the 3 measurements; wherein, four kinds of sulfanilamide antibiotics are not detected in the blank of the three water samples; the results are shown in Table 3; the blank and the standard chromatogram of the actual water sample are respectively shown in FIGS. 8-9; as can be seen from the table, the recovery rate of the added standard in this example is 33.9% -80.3%, and the relative standard deviation is 0.63% -5.79%, so the extraction effect of this example is good, the analysis result is accurate, and the reproducibility is good.
Table 3 recovery rate of tap water, surface water and seawater (n ═ 3, ug/L)
Claims (7)
1. The method for analyzing and detecting the four sulfanilamide antibiotics in the environmental water sample is characterized in that the four sulfanilamide antibiotics comprise sulfadiazine, sulfamethazine, sulfamethoxazole and sulfachlorpyridazine, and the specific process operation steps are as follows:
s1 preparation of metal organic framework material NH2MIL-101(Fe) with NH2MIL-101(Fe) -polyvinylidene fluoride mixed matrix membrane:
(1) dissolving ferric trichloride in N-N Dimethylformamide (DMF), adding amino terephthalic acid, and fully stirring and dissolving to obtain a mixture for later use;
(2) reacting the mixture prepared in the step (1) in a solvothermal reaction kettle at the temperature of 100 ℃ and 130 ℃ for 24 hours, and washing the mixture prepared in the solvothermal reaction kettle with DMF to prepare NH2-MIL-101(Fe) mixed solution, and then the mixed solution is dried in vacuum at 100 ℃ to prepare metal organic framework material NH2-MIL-101(Fe) for use;
(3) weighing NH2-MIL-101(Fe) powder, and dissolving with acetone to obtain NH2Preparing a mixed solvent of polyvinylidene fluoride and DMF (dimethyl formamide) according to the proportion of 100mg:4mL into NH-101 (Fe) solution for later use2Adding 1mL of mixed solvent into the MIL-101(Fe) solution to prepare a mixed solution for later use;
(4) uniformly coating the mixed solution obtained in the step (3) on a clean glass plate, and drying the glass plate in an oven to obtain a metal organic framework material NH2-MIL-101(Fe) film;
s2, use of the metal organic framework material NH prepared in step S12Solid-phase extraction with an MIL-101(Fe) membrane, and analysis of four sulfonamides antibiotics in a water sample by combining high performance liquid chromatography, which comprises the following steps:
(1) taking metal organic framework material NH2Putting the MIL-101(Fe) film into a suction filtration device, adding 200mL of water sample into a beaker, and performing suction filtration by using the suction filtration device;
(2) the NH was eluted twice with 16mL acetonitrile + 5% by volume aqueous ammonia28mL of MIL-101(Fe) membrane per wash time of 15min, blowing the eluate through nitrogen and then blowing it through a 1mL streamRe-dissolving the mobile phase (20% acetonitrile and 80% pH (pH) 3 formic acid aqueous solution), wherein the acetonitrile and the formic acid aqueous solution are in a volume ratio, and performing high performance liquid chromatography detection;
2. the method for analyzing and detecting four sulfonamides antibiotics in the environmental water sample according to claim 1, wherein the conditions of high performance liquid chromatography are as follows: selecting an Agilent ZORBAXSB-C18 high performance liquid chromatography column with the specification of length of 150mm, inner diameter of 4.6mm and filler particle diameter of 5 μm; the detector is a diode array ultraviolet detector, the measuring wavelength of the diode array ultraviolet detector is 270nm, and the emission wavelength is 315 nm; sample introduction by an automatic sample injector, sample introduction amount: gradient elution procedure for 10 μ L, 4 compounds is shown in the following table:
3. the method for analyzing and detecting four sulfonamides antibiotics in an environmental water sample according to claim 1, wherein the pH value of the water sample used in the detection method is 4 to ensure the accuracy of the detection result.
4. The method for analyzing and detecting four sulfonamides antibiotics in an environmental water sample according to claim 1, wherein the elution solvent used in the detection method is acetonitrile + 5% ammonia water, and the amount of single eluent is 8 mL.
5. The method for analyzing and detecting four antibiotics in an environmental water sample according to claim 1, wherein the relative standard deviation of precision in day of the four antibiotics measured by the analyzing and detecting method is 1.86% -11.24%, and the relative standard deviation of precision in day is 0.78% -5.84%.
6. The method for analyzing and detecting four sulfonamides (antibiotics) in an environmental water sample according to claim 1The calculation method is characterized in that the working curve related parameters, the method detection limits and the precision of the four sulfa antibiotics such as sulfadiazine, sulfamethazine, sulfamethoxazole and sulfachlorpyridazine are calculated by preparing 200mL water samples with the concentrations of the four sulfa antibiotics of 0.1 mu g/L, 1 mu g/L, 2 mu g/L, 5 mu g/L, 10 mu g/L and 100 mu g/L, and performing high performance liquid chromatography determination under the optimized membrane solid phase extraction condition, and the regression equation, the linear range and the correlation coefficient (R) of the working curves of the four sulfa antibiotics2) Method quantitation limits and method detection limits are as follows:
7. the method for analyzing and detecting four sulfanilamide antibiotics in an environmental water sample according to claim 1, wherein the precision of the analyzing method is verified by verifying the relative standard deviation of the daily precision and the relative standard deviation of the daytime precision of the four sulfanilamide antibiotics, such as sulfadiazine, sulfamethazine, sulfachlorpyridazine and sulfamethoxazole, the calculating method of the relative standard deviation of the daily precision and the relative standard deviation of the daily precision of the four sulfanilamide antibiotics comprises the steps of preparing 200mL of simulated water samples with the four sulfanilamide antibiotics with the concentrations of 1 ug/L, 10 ug/L and 40 ug/L and with the concentrations of low, medium and high, determining according to the membrane solid phase extraction step, parallelly determining 3 times of the daily precision of each concentration point in one day and expressing the relative standard deviation once a day, the precision in the day of 3 days is measured and expressed by relative standard deviation, and the result shows that the relative standard deviation of the precision in the day of the four sulfonamides antibiotics is within 1.86-11.24%, the relative standard deviation of the precision in the day is within 0.78-5.84%, and the requirement of analysis precision is met.
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