WO2021103429A1 - Method for analyzing and detecting four sulfonamide antibiotics in environmental water sample - Google Patents

Method for analyzing and detecting four sulfonamide antibiotics in environmental water sample Download PDF

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WO2021103429A1
WO2021103429A1 PCT/CN2020/089856 CN2020089856W WO2021103429A1 WO 2021103429 A1 WO2021103429 A1 WO 2021103429A1 CN 2020089856 W CN2020089856 W CN 2020089856W WO 2021103429 A1 WO2021103429 A1 WO 2021103429A1
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sulfonamide antibiotics
antibiotics
membrane
sulfonamide
analyzing
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PCT/CN2020/089856
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French (fr)
Chinese (zh)
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马继平
姜名珊
李爽
吴阁格
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青岛理工大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds

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  • the invention belongs to the field of antibiotic detection, and relates to an analysis and detection method of four sulfonamide antibiotics in environmental water samples.
  • SAs Sulfonamide antibiotics
  • SAs Sulfonamide antibiotics
  • p-aminobenzene sulfonamide Sulfonamide antibiotics
  • Extensive use of this antibiotic will not only increase the resistance of bacteria to antimicrobial agents, but also lead to accumulation of toxicity in organisms.
  • the content of sulfonamide antibiotics in water is low, and the water sample needs to be pretreated, and then it can be accurately determined after enrichment and concentration.
  • the pretreatment methods of sulfa antibiotics in water mainly include: solid-phase extraction, solid-phase micro-extraction, liquid-liquid extraction, microwave extraction, liquid-liquid micro-extraction, etc.
  • Solid-phase extraction has been widely used in the pretreatment of organic compounds in water samples due to its high recovery rate, short extraction time, high enrichment factor, low organic solvent consumption, easy automation and operation.
  • the chromatographic methods of sulfonamide antibiotics in water mainly include gas chromatography, gas chromatography-mass spectrometry, liquid chromatography, liquid chromatography mass spectrometry.
  • Gas chromatography is the earliest analytical method used to determine the residues of sulfonamide antibiotics in water, but requires derivatization; high-performance liquid chromatography does not require derivatization, and is a high-speed, high-sensitivity and high-automation separation and analysis technique.
  • Metal-organic frameworks are a class of nanoporous materials formed by organic-inorganic hybridization, and are currently one of the research hotspots and frontiers in the field of new materials.
  • the metal-organic framework material is mainly composed of a three-dimensional network structure crystal formed by the coordination bond between an aromatic acid or a base containing nitrogen and oxygen multidentate organic ligands and an inorganic metal center.
  • MOFs materials Compared with traditional porous materials, MOFs materials have many advantages, such as multiple types, large porosity and specific surface area, and strong pore size controllability, so they can be used in a variety of modern sample pretreatment technologies.
  • MOFs-based mixed matrix membrane method to prepare MOFs into membranes and apply them to membrane separation and membrane adsorption.
  • the MOFs in the mixed matrix membrane retains its highly crystalline porous structure and high specific surface area, and has higher permeability and selectivity.
  • it overcomes the poor mechanical strength and reproducibility, and the process Complicated drawbacks, with low energy consumption, low emissions, high separation, simple operation, easy recycling and other advantages.
  • the purpose of the present invention is to provide a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples.
  • the method has the characteristics of low toxicity, simple reaction conditions, and low equipment cost, and can be quickly and efficiently Analysis and detection of four sulfonamide antibiotics in environmental water samples.
  • the solid phase extraction membrane is a mixed matrix membrane formed of polyvinylidene fluoride and NH 2 -MIL-101 (Fe).
  • a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples is to perform suction filtration on a water sample containing sulfonamide antibiotics.
  • the suction filtration membrane used in the suction filtration is the above solid phase extraction membrane.
  • the deagent is to elute the sulfonamide antibiotics adsorbed on the filter membrane after suction filtration, and the sulfonamide antibiotics in the eluted solution are detected by high performance liquid chromatography; the eluent is a mixed solution of acetonitrile and ammonia; the sulfonamide Antibiotics are sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole.
  • the present invention uses the above solid phase extraction membrane to adsorb and enrich the four sulfonamide antibiotics in environmental water samples more quickly. If the enriched sulfonamide antibiotics cannot be eluted from the membrane, the detection cannot be achieved.
  • the invention found through experiments that the mixed solution of acetonitrile and ammonia water can better elute the enriched sulfonamide antibiotics, thereby realizing accurate detection of four sulfonamide antibiotics in environmental water samples by high performance liquid chromatography.
  • the present invention adopts metal organic framework material NH 2 -MIL-101 (Fe), which has good adsorption efficiency for four sulfonamide antibiotics; adopts metal organic framework material NH 2 -MIL-101 (Fe) as membrane solid phase extraction material , Using high performance liquid chromatography-ultraviolet fluorescence detector, the analysis method of four sulfonamide antibiotics in water samples was established. This method is easy to operate, greatly saves analysis time and cost, has good extraction effect, accurate analysis results, and reproducibility. Good; at the same time, the raw materials used in the present invention are cheap and easily available, the material preparation process is simple, the reaction conditions are mild, the application environment is friendly, and the market prospect is broad.
  • Figure 1 is a graph showing the influence of the amount of adsorbent involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: concentration of 10 ⁇ g/L, pH of 4; eluent: acetonitrile + 5% ammonia, salt The degree is 1%, the amount of eluent is 8ml ⁇ 2, and the elution time is 15min ⁇ 2.
  • Figure 2 is a graph of the influence of the pH of the water sample involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: the concentration is 10 ⁇ g/L, the amount of MOF is 60 mg, and the eluent is acetonitrile + 5% ammonia, The salinity is 1%, the amount of eluent is 8ml ⁇ 2, and the elution time is 15min ⁇ 2.
  • Figure 3 is a graph showing the influence of the types of eluents involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: concentration of 10 ⁇ g/L, dosage of MOF of 60mg, pH of 4, salinity of 1% , The amount of eluent is 8ml ⁇ 2, and the elution time is 15min ⁇ 2.
  • Figure 4 is a graph showing the influence of salinity on the extraction recovery rate of four sulfonamide antibiotics involved in the embodiment of the present invention; extraction conditions: concentration is 10 ⁇ g/L, MOF dosage is 60 mg, pH is 4, and eluent is acetonitrile +5 % Ammonia water, the amount of eluent is 8ml ⁇ 2, and the elution time is 15min ⁇ 2.
  • Figure 5 is a graph showing the influence of the amount of eluent involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: the concentration is 10 ⁇ g/L, the amount of MOF is 60 mg, the pH is 4, and the eluent is acetonitrile +5% ammonia water, salinity is 1%, elution time is 15min ⁇ 2.
  • Fig. 6 is a graph showing the influence of elution time on the extraction recovery rate of four sulfonamide antibiotics involved in the embodiment of the present invention; extraction conditions: concentration is 10 ⁇ g/L, MOF dosage is 60mg, pH is 4, eluent is acetonitrile+ 5% ammonia water, 1% salinity, and the eluent dosage is 8ml ⁇ 2.
  • Fig. 7 is an ultraviolet chromatogram of laboratory tap water without adding standard water sample 40 ⁇ g/L (a) and adding standard water sample (b) involved in the embodiment of the present invention; 1. Sulfadiazine, 2. Sulfamethazine, 3. . Sulfachloropyridazine, 4. Sulfamethoxazole.
  • Figure 8 is an ultraviolet chromatogram of the Laoshan Reservoir unspiked water sample 40 ⁇ g/L (a) and the spiked water sample (b) in an embodiment of the present invention; 1. Sulfadiazine, 2. Sulfamethazine, 3. Sulfamethazine Chlorpyridazine, 4. Sulfamethoxazole.
  • Figure 9 is an ultraviolet chromatogram of the seawater unspiked water sample 40 ⁇ g/L (a) and the spiked water sample (b) involved in the embodiment of the present invention; 1. sulfadiazine, 2. sulfamethazine, 3. sulfamethazine Chlorpyridazine, 4. Sulfamethoxazole.
  • the current solid-phase extraction method generally uses a solid-phase extraction column, and the use of a solid-phase extraction column requires steps such as packing and activation of the solid-phase extraction agent, which are complicated and costly in time.
  • the present invention intends to provide a simpler solid-phase extraction method, without filling a solid-phase extraction column and activation, and requiring one-step suction filtration to enrich sulfonamide antibiotics in water.
  • the problem of using suction filtration membrane for enrichment is how to selectively adsorb sulfonamide antibiotics, and at the same time ensure how to ensure the strength of the suction filtration membrane when the pressure difference is large during the suction filtration process.
  • the present invention proposes an analysis and detection method for four sulfonamide antibiotics in environmental water samples.
  • a typical embodiment of the present invention provides a solid-phase extraction membrane for sulfonamide antibiotics.
  • the solid-phase extraction membrane is a mixture of polyvinylidene fluoride and NH 2 -MIL-101 (Fe). Matrix membrane.
  • the solid-phase extraction membrane provided by the present invention can not only selectively adsorb the four sulfonamide antibiotics, but also ensures the strength of the suction filtration membrane, and at the same time, can avoid the poor binding strength that causes the solid-phase extraction membrane to absorb the four kinds of Changes in the selective adsorption of sulfa antibiotics.
  • the mixed matrix membrane is a new type of composite membrane material for preparing MOFs membrane material, which embeds MOFs crystal particles in a polymer substrate.
  • the preparation method is: dispersing polyvinylidene fluoride and NH 2 -MIL-101 (Fe) into a solvent and mixing uniformly, spreading the uniformly mixed liquid and removing the solvent to obtain solid phase extraction membrane.
  • the acetone and NH 2 -MIL-101 (Fe) obtained by dispersing NH 2 -MIL-101 (Fe) dispersion of polyvinylidene fluoride dissolved in N, N- two Methylformamide is used to obtain polyvinylidene fluoride solution.
  • the polyvinylidene fluoride solution and NH 2 -MIL-101 (Fe) dispersion are mixed uniformly, and the mixed solution is spread on the plate and heated to remove the solvent to obtain solid phase extraction. membrane.
  • the NH 2 -MIL-101 (Fe) of the present invention can be purchased commercially or obtained by self-synthesis.
  • the CAS number of NH 2 -MIL-101(Fe) is 1189182-85-1.
  • the present invention provides a method for preparing NH 2 -MIL-101 (Fe), which is obtained by solvothermal reaction between trivalent iron salt and aminoterephthalic acid.
  • the solvothermal reaction refers to heating the organic solvent system in a closed system to make the system in a high temperature and high pressure state for reaction.
  • the solvothermal reaction conditions are 100-130°C for 20-28 hours.
  • Another embodiment of the present invention provides a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples.
  • the water sample to be tested containing sulfonamide antibiotics is subjected to suction filtration, and the suction filtration membrane used for suction filtration is the above
  • the solid phase extraction membrane uses an eluent to elute the adsorbed sulfonamide antibiotics in the filter membrane after suction filtration, and the sulfonamide antibiotics in the eluted solution are detected by high performance liquid chromatography; the eluent is acetonitrile and ammonia
  • the sulfadiazine antibiotics are sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole.
  • the present invention uses the above solid phase extraction membrane to adsorb and enrich the four sulfonamide antibiotics in environmental water samples more quickly. If the enriched sulfonamide antibiotics cannot be eluted from the membrane, the detection cannot be achieved.
  • the invention found through experiments that the mixed solution of acetonitrile and ammonia water can better elute the enriched sulfonamide antibiotics, thereby realizing accurate detection of four sulfonamide antibiotics in environmental water samples by high performance liquid chromatography.
  • the pH of the water sample to be tested is adjusted to 2.5-3.5.
  • the pH of the water sample affects the adsorption effect of sulfonamide antibiotics.
  • the pH is 2.5-3.5, the adsorption effect of sulfonamide antibiotics is better.
  • the ammonia water is ammonia water with a concentration of 4 to 6%.
  • ammonia water with a concentration of 5% is the mass percentage.
  • sodium chloride is added to the water sample to be tested, so that the mass fraction of sodium chloride in the water sample to be tested after adjustment is 0.9-1.1%.
  • the salinity of sodium chloride in the water sample is 0.9-1.1%, the recovery rate of sulfonamide antibiotics is better.
  • the single use amount of the eluent is 7.5-8.5 mL.
  • the amount of eluent is related to the recovery rate of sulfa antibiotics.
  • the recovery rate of sulfa antibiotics is better.
  • the single elution time using the eluent is 14.5 to 15.5 min.
  • the recovery rate of sulfonamide antibiotics is better.
  • the eluent is removed after elution, and then dissolved in a mobile phase solution, and then subjected to high performance liquid chromatography detection.
  • the mobile phase solution is a mixture of acetonitrile and formic acid aqueous solution, and the pH of the formic acid aqueous solution is 2.5-3.5.
  • the volume ratio of acetonitrile to formic acid aqueous solution is 15-25:85-75.
  • the mobile phase detected by the high performance liquid chromatography includes acetonitrile and formic acid aqueous solution, and the pH of the formic acid aqueous solution is 2.5-3.5.
  • the elution procedure detected by high performance liquid chromatography is shown in the following table:
  • the Agilent ZORBAX SB-C18 HPLC column is used in the high performance liquid chromatography, with a length of 150 mm, an inner diameter of 4.6 mm, and a filler particle diameter of 5 ⁇ m;
  • the detector is a diode array ultraviolet detector ,
  • the measurement wavelength of the diode array ultraviolet detector is 270 nm, and the emission wavelength is 315 nm;
  • the sample is injected by the automatic sampler, and the sample volume is 10 ⁇ L.
  • the working curve-related parameters and method detection limits and precision calculation methods of the four sulfadiazine, sulfamethazine, sulfamethoxazole and sulfachloropyridazine sulfadiazine antibiotics are calculated as preparation four.
  • the working curve regression equation, linear range, correlation coefficient (R 2 ), method quantification limit and method detection limit of the four sulfonamide antibiotics are as follows:
  • the precision of the analytical method was verified by verifying the intra-day relative standard deviation of precision and the relative standard deviation of inter-day precision of the four sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole antibiotics, so
  • the calculation method of the intra-day relative standard deviation of precision and the relative standard deviation of inter-day precision of the four sulfonamide antibiotics is to first prepare four sulfonamide antibiotics with concentrations of 1 ⁇ g/L, 10 ⁇ g/L, 40 ⁇ g/L, low, medium, and 40 ⁇ g/L. A 200mL simulated water sample with three higher concentrations was measured in accordance with the membrane solid phase extraction procedure.
  • Each concentration point was measured in parallel three times within one day and the intra-day precision was expressed in terms of relative standard deviation.
  • the three concentrations were measured once a day for 3 days.
  • the inter-day precision is expressed by the relative standard deviation.
  • the result is that the intra-day relative standard deviation of the four sulfonamide antibiotics is in the range of 1.86% to 11.24%, and the inter-day relative standard deviation of the precision is in the range of 0.78% to 5.84%, which satisfies Analyze precision requirements.
  • Step 1 Preparation of metal organic framework material NH 2 -MIL-101(Fe) and NH 2 -MIL-101(Fe)-polyvinylidene fluoride mixed matrix film:
  • step (2) React the mixture prepared in step (1) at 100-130°C in the solvothermal reaction kettle for 24 hours, and wash the prepared mixture in the solvothermal reaction kettle with DMF to prepare NH 2 -MIL-101
  • the (Fe) mixed solution is vacuum dried at 100°C to prepare the metal organic framework material NH 2 -MIL-101 (Fe) for later use.
  • step (3) Coat the mixed solution obtained in step (3) evenly on a clean glass plate, and put it in an oven to dry to form a film;
  • Step 2 Using metal organic framework material NH 2 -MIL-101 (Fe) membrane solid phase extraction, combined with high performance liquid chromatography to analyze the four sulfonamide antibiotics in the water sample, the specific steps are as follows:
  • the detection conditions of high performance liquid chromatography are: use Agilent ZORBAX SB-C18 high performance liquid chromatography column, its specification is 150mm in length, 4.6mm in inner diameter, and diameter of filler particles is 5 ⁇ m; the detector is a diode array ultraviolet detector, the diode array The measurement wavelength of the UV detector is 270nm and the emission wavelength is 315nm; the autosampler injects samples, the sample volume is 10 ⁇ L, and the gradient elution procedures of 4 compounds are shown in the following table:
  • the main factors affecting the extraction recovery rate of the four sulfonamide antibiotics were investigated, and the optimal value of each factor when the extraction recovery rate was the highest was calculated, and then the four sulfonamide antibiotics were determined under the condition of the optimal value of each factor.
  • the working curve related parameters and method detection limit and precision, the specific process includes the following steps:
  • Step 1 Calculate the best value of each factor when the extraction recovery rate of the four sulfonamide antibiotics is the highest:
  • MOF membranes The concentration of each antibiotic is 0.01mg/L.
  • the extraction recovery rate increases with the increase of the adsorbent dosage, indicating that the metal organic framework material NH 2 -MIL-101 (Fe) 2 -MIL-101 (Fe) dosage increases, adsorption sites increase, and adsorption capacity increases; but when the amount of adsorbent is greater than 60mg, continue to increase the amount of metal organic framework material NH 2 -MIL-101 (Fe), four
  • the extraction recovery rate of the compound decreases or even hardly changes, so the amount of extractant used in this example is 60 mg.
  • This example examines the effect of the pH of the water sample on the surface adsorption site activity of the extraction material. This example examines the results of the extraction recovery rate under the conditions of pH 3, 4, 5.5, 7, and 8, respectively. The pH value is 3 The recovery rate increased in the range of ⁇ 4, and dropped sharply in the range of 4-8, indicating that the optimal pH of the material for the extraction of the four sulfonamide antibiotics was 4.
  • This example examines the influence of different eluents on the elution efficiency of the analyte adsorbed on the adsorbent.
  • This example examines the influence of four organic solvents: methanol, acetonitrile, acetone, and acetonitrile + 5% ammonia on the extraction recovery rate.
  • Acetonitrile + 5% ammonia water has the highest elution efficiency, so acetonitrile + 5% ammonia water is selected as the elution solvent in this embodiment.
  • This example examines the influence of salinity on the ionic strength and the diffusion rate of compounds in water.
  • the salinity of the water sample is added in this example to be 0%, 0.5%, 1%, 5%, 10% sodium chloride (NaCl), after adding NaCl, when the salt concentration is 0-1%, the recovery rate increases rapidly. As the salt concentration continues to increase, the recovery rate decreases and tends to stabilize. Therefore, the salt concentration is 1% in this embodiment.
  • This example examines the elution effect under the condition of eluting 4mL, 6mL, 8mL, 10mL, 12mL and eluting twice.
  • the single eluent dosage is 8mL
  • the recovery rate of the four sulfonamide antibiotics is the largest, and the dosage continues to increase.
  • the extraction recovery rate decreased, so in this example, the single eluent dosage was selected as 8 mL.
  • This example investigates the elution effect under the condition of elution 5min, 10min, 15min, 20min and 25min, and elution twice.
  • the recovery rate of the four sulfonamide antibiotics is the largest when the single elution time is 15min, so this example selects The single elution time is 15min.
  • Step 2 Determine the working curve related parameters of the four sulfonamide antibiotics and the detection limit and precision of the method:

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Abstract

A method for analyzing and detecting four sulfonamide antibiotics in an environmental water sample. The method comprises: performing suction filtration on a water sample to be tested containing sulfonamide antibiotics, a suction filtration membrane used for suction filtration being a solid phase extraction membrane; using an eluent to elute the sulfonamide antibiotics adsorbed in the filtration membrane after suction filtration; and performing high performance liquid chromatography detection on the eluted sulfonamide antibiotics that are in a solution. The eluent is a mixed solution of acetonitrile and ammonia solution; the sulfonamide antibiotics are sulfadiazine, sulfamerazine, sulfachloropyridazine, and sulfamethoxazole; and the solid phase extraction membrane is a mixed matrix membrane formed from polyvinylidene fluoride and NH2-MIL-101(Fe). The described method for analysis and detection has the features of having low toxicity, simple reaction conditions, and low device costs, and can rapidly and efficiently analyze and detect four sulfonamide antibiotics in an environmental water sample.

Description

一种环境水样中四种磺胺类抗生素的分析检测方法A method for analysis and detection of four sulfonamide antibiotics in environmental water samples 技术领域Technical field
本发明属于抗生素检测领域，涉及一种环境水样中四种磺胺类抗生素的分析检测方法。The invention belongs to the field of antibiotic detection, and relates to an analysis and detection method of four sulfonamide antibiotics in environmental water samples.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。Disclosure of the background information is only intended to increase the understanding of the overall background of the present invention, and is not necessarily regarded as an acknowledgement or any form of suggestion that the information constitutes the prior art known to those of ordinary skill in the art.
磺胺类抗生素(SAs)是一类具有对氨基苯磺酰胺结构药物的总称，被广泛应用于人类医疗和畜牧养殖的广谱抗菌剂。大量使用这种抗生素不仅会提高细菌对抗菌剂的耐药性，也会导致生物体内毒性蓄积。环境中磺胺类抗生素主要有两大来源：一是人类和畜禽尿液、粪便；二是城镇污水处理厂排放，进入环境水体。不仅对生态环境造成严重污染，还会威胁人类健康和社会的长远发展，因此对环境水样中磺胺类抗生素的检测越来越受到人们的重视。Sulfonamide antibiotics (SAs) are the general term for a class of drugs with the structure of p-aminobenzene sulfonamide, which are widely used in human medicine and animal husbandry as a broad-spectrum antimicrobial agent. Extensive use of this antibiotic will not only increase the resistance of bacteria to antimicrobial agents, but also lead to accumulation of toxicity in organisms. There are two main sources of sulfa antibiotics in the environment: one is human and livestock urine and feces; the other is discharged from urban sewage treatment plants and enters environmental water bodies. It not only causes serious pollution to the ecological environment, but also threatens human health and the long-term development of society. Therefore, the detection of sulfonamide antibiotics in environmental water samples has attracted more and more attention.
磺胺类抗生素在水中含量较低，需对水样进行预处理，富集浓缩后才可以准确测定。目前，磺胺类抗生素在水中的预处理方法主要有：固相萃取、固相微萃取、液液萃取、微波萃取、液液微萃取等。固相萃取由于回收率高，萃取时间短，富集因子高，有机溶剂消耗低，易于自动化和操作，已被广泛用于水样中的有机化合物前处理。水中磺胺类抗生素的色谱方法主要包括气相色谱法、气相色谱-质谱法、液相色谱法、液相色谱质谱法。气相色谱法是最早用来测定水中磺胺类抗生素残留量的分析方法，但需衍生化；高液相色谱法无需衍生化，是一种高速、高灵敏度和高自动化的分离分析技术。The content of sulfonamide antibiotics in water is low, and the water sample needs to be pretreated, and then it can be accurately determined after enrichment and concentration. At present, the pretreatment methods of sulfa antibiotics in water mainly include: solid-phase extraction, solid-phase micro-extraction, liquid-liquid extraction, microwave extraction, liquid-liquid micro-extraction, etc. Solid-phase extraction has been widely used in the pretreatment of organic compounds in water samples due to its high recovery rate, short extraction time, high enrichment factor, low organic solvent consumption, easy automation and operation. The chromatographic methods of sulfonamide antibiotics in water mainly include gas chromatography, gas chromatography-mass spectrometry, liquid chromatography, liquid chromatography mass spectrometry. Gas chromatography is the earliest analytical method used to determine the residues of sulfonamide antibiotics in water, but requires derivatization; high-performance liquid chromatography does not require derivatization, and is a high-speed, high-sensitivity and high-automation separation and analysis technique.
金属-有机骨架材料(metal-organic frameworks,MOFs)是一类有机-无机杂化形成的纳米多孔材料，目前是新材料领域的研究热点与前沿之一。金属-有机骨架材料主要由含有氮、氧多齿有机配体的芳香酸或碱与无机金属中心配位键合而形成的立体网络结构晶体。由于MOFs材料相较于传统多孔材料具有很多优点，如种类多、孔隙率和比表面积大、孔尺寸可调控性强，因此可被应用于多种现代化样品前处理技术中。近几年研究者们采用原位生长法、晶种生长法、合成后修饰法和基于MOFs的混合基质膜法，将MOFs制备成膜，应用于膜分离和膜吸附等方面。与传统工艺相比，一方面混合基质膜中的MOFs保留了其高度结晶的多孔结构和高比表面积，具有较高渗透性和选择性，另一方面又克服了机械强度和重现性差、工艺复杂的弊端，具有能耗低、排放低、分离度高、操作简单、易回收再利用等优势。Metal-organic frameworks (MOFs) are a class of nanoporous materials formed by organic-inorganic hybridization, and are currently one of the research hotspots and frontiers in the field of new materials. The metal-organic framework material is mainly composed of a three-dimensional network structure crystal formed by the coordination bond between an aromatic acid or a base containing nitrogen and oxygen multidentate organic ligands and an inorganic metal center. Compared with traditional porous materials, MOFs materials have many advantages, such as multiple types, large porosity and specific surface area, and strong pore size controllability, so they can be used in a variety of modern sample pretreatment technologies. In recent years, researchers have used in-situ growth method, seed growth method, post-synthesis modification method, and MOFs-based mixed matrix membrane method to prepare MOFs into membranes and apply them to membrane separation and membrane adsorption. Compared with the traditional process, on the one hand, the MOFs in the mixed matrix membrane retains its highly crystalline porous structure and high specific surface area, and has higher permeability and selectivity. On the other hand, it overcomes the poor mechanical strength and reproducibility, and the process Complicated drawbacks, with low energy consumption, low emissions, high separation, simple operation, easy recycling and other advantages.
发明内容Summary of the invention
为了解决现有技术的不足，本发明的目的是提供一种环境水样中四种磺胺类抗生素的分析检测方法，该方法具有毒性低、反应条件简单、设备成本低的特点，能够快速高效地对环境水样中四种磺胺类抗生素进行分析检测。In order to solve the deficiencies of the prior art, the purpose of the present invention is to provide a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples. The method has the characteristics of low toxicity, simple reaction conditions, and low equipment cost, and can be quickly and efficiently Analysis and detection of four sulfonamide antibiotics in environmental water samples.
为了实现上述目的，本发明的技术方案为：In order to achieve the above objective, the technical solution of the present invention is:
一方面，一种用于磺胺类抗生素的固相萃取膜，所述固相萃取膜是由聚偏二氟乙烯与NH 2-MIL-101(Fe)形成的混合基质膜。 On the one hand, a solid phase extraction membrane for sulfonamide antibiotics. The solid phase extraction membrane is a mixed matrix membrane formed of polyvinylidene fluoride and NH 2 -MIL-101 (Fe).
经过实验证实，当选择聚偏二氟乙烯与NH 2-MIL-101(Fe)形成的混合基质膜作为固相萃取膜，不仅能够对四种磺胺类抗生素进行选择性吸附，而且保证了抽滤膜的强度，更为重要是，能够保证NH 2-MIL-101(Fe)与聚偏二氟乙烯的结合强度，避免结合强度差导致固相萃取膜在抽滤过程中对四种磺胺类抗生素选择性吸附的变化。 Experiments have confirmed that when the mixed matrix membrane formed by polyvinylidene fluoride and NH 2 -MIL-101 (Fe) is selected as the solid phase extraction membrane, it can not only selectively adsorb the four sulfonamide antibiotics, but also ensure suction filtration The strength of the membrane, and more importantly, can ensure the binding strength of NH 2 -MIL-101(Fe) and polyvinylidene fluoride, and avoid the poor binding strength that causes the solid phase extraction membrane to resist the four sulfonamide antibiotics during the suction filtration process. Changes in selective adsorption.
另一方面，一种环境水样中四种磺胺类抗生素的分析检测方法，将含有磺胺类抗生素的待测水样进行抽滤，抽滤采用的抽滤膜为上述固相萃取膜，采用洗脱剂将抽滤后滤膜中吸附磺胺类抗生素进行洗脱，将洗脱后溶液中的磺胺类抗生素进行高效液相色谱检测；所述洗脱剂为乙腈与氨水的混合溶液；所述磺胺类抗生素为磺胺嘧啶、磺胺甲基嘧啶、磺胺氯哒嗪和磺胺甲恶唑。On the other hand, a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples is to perform suction filtration on a water sample containing sulfonamide antibiotics. The suction filtration membrane used in the suction filtration is the above solid phase extraction membrane. The deagent is to elute the sulfonamide antibiotics adsorbed on the filter membrane after suction filtration, and the sulfonamide antibiotics in the eluted solution are detected by high performance liquid chromatography; the eluent is a mixed solution of acetonitrile and ammonia; the sulfonamide Antibiotics are sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole.
本发明利用上述固相萃取膜能够更为快速的将环境水样中四种磺胺类抗生素进行吸附富集，若不能从膜中将富集的磺胺类抗生素洗脱，同样无法实现检测，因而本发明经过实验发现了乙腈与氨水的混合溶液能够更好的将富集的磺胺类抗生素洗脱，从而实现利用高效液相色谱对环境水样中四种磺胺类抗生素进行准确检测。The present invention uses the above solid phase extraction membrane to adsorb and enrich the four sulfonamide antibiotics in environmental water samples more quickly. If the enriched sulfonamide antibiotics cannot be eluted from the membrane, the detection cannot be achieved. The invention found through experiments that the mixed solution of acetonitrile and ammonia water can better elute the enriched sulfonamide antibiotics, thereby realizing accurate detection of four sulfonamide antibiotics in environmental water samples by high performance liquid chromatography.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明采用金属有机骨架材料NH 2-MIL-101(Fe)，对四种磺胺类抗生素具有较好的吸附效率；采用金属有机骨架材料NH 2-MIL-101(Fe)作为膜固相萃取材料，采用高效液相色谱-紫外线荧光检测器，建立了水样中的四种磺胺类抗生素的分析方法，该方法操作简便，大大节约分析时间和成本，萃取效果好，分析结果准确，重现性好；同时本发明所用原料廉价易得，材料制备过程简单，反应条件温和，应用环境友好，市场前景广阔。 The present invention adopts metal organic framework material NH 2 -MIL-101 (Fe), which has good adsorption efficiency for four sulfonamide antibiotics; adopts metal organic framework material NH 2 -MIL-101 (Fe) as membrane solid phase extraction material , Using high performance liquid chromatography-ultraviolet fluorescence detector, the analysis method of four sulfonamide antibiotics in water samples was established. This method is easy to operate, greatly saves analysis time and cost, has good extraction effect, accurate analysis results, and reproducibility. Good; at the same time, the raw materials used in the present invention are cheap and easily available, the material preparation process is simple, the reaction conditions are mild, the application environment is friendly, and the market prospect is broad.
附图说明Description of the drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为本发明实施例中涉及的吸附剂用量对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，pH为4；洗脱剂为乙腈+5％氨水，盐度为1％，洗脱剂用量8ml×2， 洗脱时间为15min×2。Figure 1 is a graph showing the influence of the amount of adsorbent involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: concentration of 10 μg/L, pH of 4; eluent: acetonitrile + 5% ammonia, salt The degree is 1%, the amount of eluent is 8ml×2, and the elution time is 15min×2.
图2为本发明实施例中涉及的水样pH对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，MOF用量为60mg，洗脱剂为乙腈+5％氨水，盐度为1％，洗脱剂用量8ml×2，洗脱时间为15min×2。Figure 2 is a graph of the influence of the pH of the water sample involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: the concentration is 10 μg/L, the amount of MOF is 60 mg, and the eluent is acetonitrile + 5% ammonia, The salinity is 1%, the amount of eluent is 8ml×2, and the elution time is 15min×2.
图3为本发明实施例中涉及的洗脱剂种类对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，MOF用量为60mg，pH为4，盐度为1％，洗脱剂用量8ml×2，洗脱时间为15min×2。Figure 3 is a graph showing the influence of the types of eluents involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: concentration of 10μg/L, dosage of MOF of 60mg, pH of 4, salinity of 1% , The amount of eluent is 8ml×2, and the elution time is 15min×2.
图4为本发明实施例中涉及的盐度对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，MOF用量为60mg，pH为4，洗脱剂为乙腈+5％氨水，洗脱剂用量8ml×2，洗脱时间为15min×2。Figure 4 is a graph showing the influence of salinity on the extraction recovery rate of four sulfonamide antibiotics involved in the embodiment of the present invention; extraction conditions: concentration is 10 μg/L, MOF dosage is 60 mg, pH is 4, and eluent is acetonitrile +5 % Ammonia water, the amount of eluent is 8ml×2, and the elution time is 15min×2.
图5为本发明实施例中涉及的洗脱剂用量对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，MOF用量为60mg，pH为4，洗脱剂为乙腈+5％氨水，盐度为1％，洗脱时间为15min×2。Figure 5 is a graph showing the influence of the amount of eluent involved in the embodiment of the present invention on the extraction recovery rate of four sulfonamide antibiotics; extraction conditions: the concentration is 10 μg/L, the amount of MOF is 60 mg, the pH is 4, and the eluent is acetonitrile +5% ammonia water, salinity is 1%, elution time is 15min×2.
图6为本发明实施例中涉及的洗脱时间对四种磺胺类抗生素萃取回收率的影响图；萃取条件：浓度为10μg/L，MOF用量为60mg，pH为4，洗脱剂为乙腈+5％氨水，盐度为1％，洗脱剂用量为8ml×2。Fig. 6 is a graph showing the influence of elution time on the extraction recovery rate of four sulfonamide antibiotics involved in the embodiment of the present invention; extraction conditions: concentration is 10μg/L, MOF dosage is 60mg, pH is 4, eluent is acetonitrile+ 5% ammonia water, 1% salinity, and the eluent dosage is 8ml×2.
图7为本发明实施例中涉及的实验室自来水不加标水样40μg/L(a)及加标水样(b)的紫外色谱图；1.磺胺嘧啶，2.磺胺甲基嘧啶，3.磺胺氯哒嗪，4.磺胺甲恶唑。Fig. 7 is an ultraviolet chromatogram of laboratory tap water without adding standard water sample 40μg/L (a) and adding standard water sample (b) involved in the embodiment of the present invention; 1. Sulfadiazine, 2. Sulfamethazine, 3. . Sulfachloropyridazine, 4. Sulfamethoxazole.
图8为本发明实施例中涉及崂山水库不加标水样40μg/L(a)及加标水样(b)的紫外色谱图；1.磺胺嘧啶，2.磺胺甲基嘧啶，3.磺胺氯哒嗪，4.磺胺甲恶唑。Figure 8 is an ultraviolet chromatogram of the Laoshan Reservoir unspiked water sample 40μg/L (a) and the spiked water sample (b) in an embodiment of the present invention; 1. Sulfadiazine, 2. Sulfamethazine, 3. Sulfamethazine Chlorpyridazine, 4. Sulfamethoxazole.
图9为本发明实施例中涉及的海水不加标水样40μg/L(a)及加标水样(b)的紫外色谱图；1.磺胺嘧啶，2.磺胺甲基嘧啶，3.磺胺氯哒嗪，4.磺胺甲恶唑。Figure 9 is an ultraviolet chromatogram of the seawater unspiked water sample 40μg/L (a) and the spiked water sample (b) involved in the embodiment of the present invention; 1. sulfadiazine, 2. sulfamethazine, 3. sulfamethazine Chlorpyridazine, 4. Sulfamethoxazole.
具体实施方式Detailed ways
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be pointed out that the following detailed descriptions are all exemplary and are intended to provide further description of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terms used here are only for describing specific embodiments, and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and/or "including" are used in this specification, they indicate There are features, steps, operations, devices, components, and/or combinations thereof.
据本发明的发明人所知，目前固相萃取的方法，一般采用固相萃取柱，而利用固相萃 取柱需要进行固相萃取剂的填充、活化等步骤，步骤繁琐，时间成本较高。本发明拟提供一种更为简便的固相萃取方法，无需填充固相萃取柱、活化，因需要一步抽滤即可将水中的磺胺类抗生素进行富集。利用抽滤膜进行富集，存在的问题是如何对磺胺类抗生素进行选择性吸附，同时保证抽滤过程中如何在压强差较大的情况下保证抽滤膜的强度。According to the inventors of the present invention, the current solid-phase extraction method generally uses a solid-phase extraction column, and the use of a solid-phase extraction column requires steps such as packing and activation of the solid-phase extraction agent, which are complicated and costly in time. The present invention intends to provide a simpler solid-phase extraction method, without filling a solid-phase extraction column and activation, and requiring one-step suction filtration to enrich sulfonamide antibiotics in water. The problem of using suction filtration membrane for enrichment is how to selectively adsorb sulfonamide antibiotics, and at the same time ensure how to ensure the strength of the suction filtration membrane when the pressure difference is large during the suction filtration process.
为了解决现有对磺胺类抗生素检测效率较低的问题，本发明提出了一种环境水样中四种磺胺类抗生素的分析检测方法。In order to solve the existing problem of low detection efficiency for sulfonamide antibiotics, the present invention proposes an analysis and detection method for four sulfonamide antibiotics in environmental water samples.
本发明的一种典型实施方式，提供了一种用于磺胺类抗生素的固相萃取膜，所述固相萃取膜是由聚偏二氟乙烯与NH 2-MIL-101(Fe)形成的混合基质膜。 A typical embodiment of the present invention provides a solid-phase extraction membrane for sulfonamide antibiotics. The solid-phase extraction membrane is a mixture of polyvinylidene fluoride and NH 2 -MIL-101 (Fe). Matrix membrane.
本发明提供的固相萃取膜，不仅能够对四种磺胺类抗生素进行选择性吸附，而且保证了抽滤膜的强度，同时能够避免结合强度差导致固相萃取膜在抽滤过程中对四种磺胺类抗生素选择性吸附的变化。The solid-phase extraction membrane provided by the present invention can not only selectively adsorb the four sulfonamide antibiotics, but also ensures the strength of the suction filtration membrane, and at the same time, can avoid the poor binding strength that causes the solid-phase extraction membrane to absorb the four kinds of Changes in the selective adsorption of sulfa antibiotics.
混合基质膜是制备MOFs膜材料的一种新型的复合膜材料，是将MOFs晶体微粒嵌入聚合物基底中。The mixed matrix membrane is a new type of composite membrane material for preparing MOFs membrane material, which embeds MOFs crystal particles in a polymer substrate.
该实施方式的一些实施例中，制备方法为：将聚偏二氟乙烯与NH 2-MIL-101(Fe)分散至溶剂中混合均匀，将混合均匀的液体平铺并去除溶剂获得固相萃取膜。 In some examples of this embodiment, the preparation method is: dispersing polyvinylidene fluoride and NH 2 -MIL-101 (Fe) into a solvent and mixing uniformly, spreading the uniformly mixed liquid and removing the solvent to obtain solid phase extraction membrane.
在一种或多种实施例中，将采用丙酮将NH 2-MIL-101(Fe)分散获得NH 2-MIL-101(Fe)分散液，将聚偏二氟乙烯溶解于N,N-二甲基甲酰胺获得聚偏二氟乙烯溶液，将聚偏二氟乙烯溶液与NH 2-MIL-101(Fe)分散液混合均匀，将混合溶液平铺在板上，加热去除溶剂获得固相萃取膜。 In one or more embodiments, the acetone and NH 2 -MIL-101 (Fe) obtained by dispersing NH 2 -MIL-101 (Fe) dispersion of polyvinylidene fluoride dissolved in N, N- two Methylformamide is used to obtain polyvinylidene fluoride solution. The polyvinylidene fluoride solution and NH 2 -MIL-101 (Fe) dispersion are mixed uniformly, and the mixed solution is spread on the plate and heated to remove the solvent to obtain solid phase extraction. membrane.
本发明所述的NH 2-MIL-101(Fe)可以通过市售购买获得，也可以通过自行合成获得。NH 2-MIL-101(Fe)的CAS号为1189182-85-1。 The NH 2 -MIL-101 (Fe) of the present invention can be purchased commercially or obtained by self-synthesis. The CAS number of NH 2 -MIL-101(Fe) is 1189182-85-1.
本发明提供了一种NH 2-MIL-101(Fe)的制备方法，将三价铁盐与氨基对苯二甲酸进行溶剂热反应获得。所述溶剂热反应是指在密闭体系中，对有机溶剂体系进行加热，使体系处于高温高压状态，进行反应。 The present invention provides a method for preparing NH 2 -MIL-101 (Fe), which is obtained by solvothermal reaction between trivalent iron salt and aminoterephthalic acid. The solvothermal reaction refers to heating the organic solvent system in a closed system to make the system in a high temperature and high pressure state for reaction.
在一种或多种实施例中，溶剂热反应的条件为100～130℃反应20～28h。In one or more embodiments, the solvothermal reaction conditions are 100-130°C for 20-28 hours.
本发明的另一种实施方式，提供了一种环境水样中四种磺胺类抗生素的分析检测方法，将含有磺胺类抗生素的待测水样进行抽滤，抽滤采用的抽滤膜为上述固相萃取膜，采用洗脱剂将抽滤后滤膜中吸附磺胺类抗生素进行洗脱，将洗脱后溶液中的磺胺类抗生素进行高效液相色谱检测；所述洗脱剂为乙腈与氨水的混合溶液；所述磺胺类抗生素为磺胺嘧啶、磺胺甲基嘧啶、磺胺氯哒嗪和磺胺甲恶唑。Another embodiment of the present invention provides a method for the analysis and detection of four sulfonamide antibiotics in environmental water samples. The water sample to be tested containing sulfonamide antibiotics is subjected to suction filtration, and the suction filtration membrane used for suction filtration is the above The solid phase extraction membrane uses an eluent to elute the adsorbed sulfonamide antibiotics in the filter membrane after suction filtration, and the sulfonamide antibiotics in the eluted solution are detected by high performance liquid chromatography; the eluent is acetonitrile and ammonia The mixed solution; the sulfadiazine antibiotics are sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole.
本发明利用上述固相萃取膜能够更为快速的将环境水样中四种磺胺类抗生素进行吸附 富集，若不能从膜中将富集的磺胺类抗生素洗脱，同样无法实现检测，因而本发明经过实验发现了乙腈与氨水的混合溶液能够更好的将富集的磺胺类抗生素洗脱，从而实现利用高效液相色谱对环境水样中四种磺胺类抗生素进行准确检测。The present invention uses the above solid phase extraction membrane to adsorb and enrich the four sulfonamide antibiotics in environmental water samples more quickly. If the enriched sulfonamide antibiotics cannot be eluted from the membrane, the detection cannot be achieved. The invention found through experiments that the mixed solution of acetonitrile and ammonia water can better elute the enriched sulfonamide antibiotics, thereby realizing accurate detection of four sulfonamide antibiotics in environmental water samples by high performance liquid chromatography.
该实施方式的一些实施例中，调节待测水样的pH为2.5～3.5。经过实验表明，水样的pH影响对磺胺类抗生素的吸附效果。当pH为2.5～3.5时，对磺胺类抗生素的吸附效果更好。In some examples of this embodiment, the pH of the water sample to be tested is adjusted to 2.5-3.5. Experiments show that the pH of the water sample affects the adsorption effect of sulfonamide antibiotics. When the pH is 2.5-3.5, the adsorption effect of sulfonamide antibiotics is better.
该实施方式的一些实施例中，所述氨水为浓度为4～6％的氨水。例如浓度为5％的氨水。氨水浓度为质量百分含量。In some examples of this embodiment, the ammonia water is ammonia water with a concentration of 4 to 6%. For example, ammonia water with a concentration of 5%. The concentration of ammonia is the mass percentage.
该实施方式的一些实施例中，向待测水样添加氯化钠，使调节后的待测水样中的氯化钠的质量分数为0.9～1.1％。经过实验表明，当水样中氯化钠的盐度为0.9～1.1％时，磺胺类抗生素的回收率更好。In some examples of this embodiment, sodium chloride is added to the water sample to be tested, so that the mass fraction of sodium chloride in the water sample to be tested after adjustment is 0.9-1.1%. Experiments show that when the salinity of sodium chloride in the water sample is 0.9-1.1%, the recovery rate of sulfonamide antibiotics is better.
该实施方式的一些实施例中，洗脱剂的单次使用量为7.5～8.5mL。经过实验表明，洗脱剂的用量与磺胺类抗生素的回收率有关，当洗脱剂的单次使用量为7.5～8.5mL时，磺胺类抗生素的回收率更好。In some examples of this embodiment, the single use amount of the eluent is 7.5-8.5 mL. Experiments show that the amount of eluent is related to the recovery rate of sulfa antibiotics. When the single use amount of eluent is 7.5 to 8.5 mL, the recovery rate of sulfa antibiotics is better.
该实施方式的一些实施例中，采用洗脱剂的单次洗脱时间为14.5～15.5min。当单次洗脱时间为14.5～15.5min时，磺胺类抗生素的回收率更好。In some examples of this embodiment, the single elution time using the eluent is 14.5 to 15.5 min. When the single elution time is 14.5～15.5min, the recovery rate of sulfonamide antibiotics is better.
该实施方式的一些实施例中，洗脱后将洗脱剂去除，再用流动相溶液溶解，然后进行高效液相色谱检测。In some examples of this embodiment, the eluent is removed after elution, and then dissolved in a mobile phase solution, and then subjected to high performance liquid chromatography detection.
在一种或多种实施例中，流动相溶液为乙腈和甲酸水溶液的混合物，甲酸水溶液的pH为2.5～3.5。其中，乙腈与甲酸水溶液的体积比为15～25:85～75。In one or more embodiments, the mobile phase solution is a mixture of acetonitrile and formic acid aqueous solution, and the pH of the formic acid aqueous solution is 2.5-3.5. Wherein, the volume ratio of acetonitrile to formic acid aqueous solution is 15-25:85-75.
该实施方式的一些实施例中，所述高效液相色谱检测的流动相包括乙腈和甲酸水溶液，所述甲酸水溶液的pH为2.5～3.5。In some examples of this embodiment, the mobile phase detected by the high performance liquid chromatography includes acetonitrile and formic acid aqueous solution, and the pH of the formic acid aqueous solution is 2.5-3.5.
该实施方式的一些实施例中，高效液相色谱检测的洗脱程序如下表所示：In some examples of this embodiment, the elution procedure detected by high performance liquid chromatography is shown in the following table:
Figure PCTCN2020089856-appb-000001
Figure PCTCN2020089856-appb-000001
该实施方式的一些实施例中，高效液相色谱中，选用Agilent ZORBAX SB-C18高效液相色谱柱，长度为150mm，内径为4.6mm，填料颗粒直径为5μm；检测器为二极管阵列紫外检测器，所述二极管阵列紫外检测器的测定波长为270nm，发射波长315nm；自动进样器进样，进样量：10μL。In some examples of this embodiment, the Agilent ZORBAX SB-C18 HPLC column is used in the high performance liquid chromatography, with a length of 150 mm, an inner diameter of 4.6 mm, and a filler particle diameter of 5 μm; the detector is a diode array ultraviolet detector , The measurement wavelength of the diode array ultraviolet detector is 270 nm, and the emission wavelength is 315 nm; the sample is injected by the automatic sampler, and the sample volume is 10 μL.
该实施方式的一些实施例中，磺胺嘧啶、磺胺甲基嘧啶、磺胺甲恶唑和磺胺氯哒嗪四 种磺胺类抗生素的工作曲线相关参数和方法检出限和精密度的计算方法为配制四种磺胺类抗生素浓度为0.1μg/L、1μg/L、2μg/L、5μg/L、10μg/L、100μg/L的200mL水样，在优化的膜固相萃取条件下，进行高效液相色谱测定，四种磺胺类抗生素的工作曲线回归方程、线性范围、相关系数(R 2)、方法定量限和方法检出限如下表： In some examples of this embodiment, the working curve-related parameters and method detection limits and precision calculation methods of the four sulfadiazine, sulfamethazine, sulfamethoxazole and sulfachloropyridazine sulfadiazine antibiotics are calculated as preparation four. A 200mL water sample with a concentration of sulfa antibiotics of 0.1μg/L, 1μg/L, 2μg/L, 5μg/L, 10μg/L, 100μg/L, and HPLC under optimized membrane solid phase extraction conditions For the determination, the working curve regression equation, linear range, correlation coefficient (R 2 ), method quantification limit and method detection limit of the four sulfonamide antibiotics are as follows:
Figure PCTCN2020089856-appb-000002
Figure PCTCN2020089856-appb-000002
通过验证磺胺嘧啶、磺胺甲基嘧啶、磺胺氯哒嗪和磺胺甲恶唑四种磺胺类抗生素的日内精密度相对标准偏差和日间精密度相对标准偏差来验证所述分析方法的精密度，所述四种磺胺类抗生素的日内精密度相对标准偏差和日间精密度相对标准偏差的计算方法为先配制四种磺胺类抗生素浓度为1μg/L、10μg/L、40μg/L的低、中、高三个浓度的200mL模拟水样，再按照膜固相萃取步骤测定，每个浓度点一天内平行测定3次考察日内精密度并以相对标准偏差表示，三个浓度每天一次，测定3天考察日间精密度并以相对标准偏差表示，结果为四种磺胺类抗生素的日内精密度相对标准偏差在1.86％～11.24％范围内，日间精密度相对标准偏差在0.78％～5.84％范围内，满足分析精密度要求。The precision of the analytical method was verified by verifying the intra-day relative standard deviation of precision and the relative standard deviation of inter-day precision of the four sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole antibiotics, so The calculation method of the intra-day relative standard deviation of precision and the relative standard deviation of inter-day precision of the four sulfonamide antibiotics is to first prepare four sulfonamide antibiotics with concentrations of 1μg/L, 10μg/L, 40μg/L, low, medium, and 40μg/L. A 200mL simulated water sample with three higher concentrations was measured in accordance with the membrane solid phase extraction procedure. Each concentration point was measured in parallel three times within one day and the intra-day precision was expressed in terms of relative standard deviation. The three concentrations were measured once a day for 3 days. The inter-day precision is expressed by the relative standard deviation. The result is that the intra-day relative standard deviation of the four sulfonamide antibiotics is in the range of 1.86% to 11.24%, and the inter-day relative standard deviation of the precision is in the range of 0.78% to 5.84%, which satisfies Analyze precision requirements.
Figure PCTCN2020089856-appb-000003
Figure PCTCN2020089856-appb-000003
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below in conjunction with specific embodiments.
实施例1：Example 1:
实施例涉及的环境水样中四种磺胺类抗生素的分析检测方法具体包括以下步骤：The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples involved in the embodiment specifically includes the following steps:
步骤一：制备金属有机骨架材料NH 2-MIL-101(Fe)与NH 2-MIL-101(Fe)-聚偏二氟乙烯混合基质膜： Step 1: Preparation of metal organic framework material NH 2 -MIL-101(Fe) and NH 2 -MIL-101(Fe)-polyvinylidene fluoride mixed matrix film:
(1)将三氯化铁溶于N-N二甲基甲酰胺(DMF)中，再加入氨基对苯二甲酸，充分搅拌溶解；(1) Dissolve ferric chloride in N-N dimethylformamide (DMF), add aminoterephthalic acid, and stir to dissolve;
(2)将步骤(1)中制得的混合物在溶剂热反应釜内100-130℃条件下反应24h，将溶剂热反应釜内的制得的混合物用DMF洗涤制得NH 2-MIL-101(Fe)混合液，在100℃条件下真空干燥制得金属有机骨架材料NH 2-MIL-101(Fe)备用。 (2) React the mixture prepared in step (1) at 100-130°C in the solvothermal reaction kettle for 24 hours, and wash the prepared mixture in the solvothermal reaction kettle with DMF to prepare NH 2 -MIL-101 The (Fe) mixed solution is vacuum dried at 100°C to prepare the metal organic framework material NH 2 -MIL-101 (Fe) for later use.
(3)称取NH 2-MIL-101(Fe)粉末。向内加丙酮溶解。将聚偏二氟乙烯与DMF按照一定的比例配制成混合溶剂。向NH 2-MIL-101(Fe)溶液中加入1mL混合溶剂； (3) Weigh NH 2 -MIL-101 (Fe) powder. Add acetone to dissolve. The polyvinylidene fluoride and DMF are formulated into a mixed solvent in a certain ratio. Add 1 mL of mixed solvent to the NH 2 -MIL-101(Fe) solution;
(4)将步骤(3)中所得混合溶液均匀的涂在干净的玻璃板上，放入烘箱中干燥成膜；(4) Coat the mixed solution obtained in step (3) evenly on a clean glass plate, and put it in an oven to dry to form a film;
步骤二：利用金属有机骨架材料NH 2-MIL-101(Fe)膜固相萃取，结合高效液相色谱对水样中四种磺胺类抗生素进行分析，具体步骤如下： Step 2: Using metal organic framework material NH 2 -MIL-101 (Fe) membrane solid phase extraction, combined with high performance liquid chromatography to analyze the four sulfonamide antibiotics in the water sample, the specific steps are as follows:
(1)取金属有机骨架材料NH 2-MIL-101(Fe)膜于抽滤装置中，向烧杯中加入200mL水样(水样中四种磺胺类抗生素的浓度均为0.01mg/L)，使用抽滤装置进行抽滤； (1) Take the metal organic framework material NH 2 -MIL-101 (Fe) membrane in the suction filter device, and add 200 mL of water sample to the beaker (the concentration of the four sulfonamide antibiotics in the water sample is 0.01 mg/L), Use suction filtration device for suction filtration;
(2)用16mL乙腈+5％氨水分两次洗脱NH 2-MIL-101(Fe)膜，每次8mL，每次洗涤时间为15min，将洗脱液经过氮吹吹干，再用1mL流动相(20％乙腈+80％pH＝3甲酸水溶液)复溶，并进行高效液相色谱检测。 (2) Elute the NH 2 -MIL-101(Fe) membrane twice with 16mL of acetonitrile + 5% ammonia water, 8mL each time, and each wash time is 15min. Blow dry the eluate with nitrogen, and then use 1mL The mobile phase (20% acetonitrile + 80% pH=3 formic acid aqueous solution) was reconstituted and tested by high performance liquid chromatography.
高效液相色谱检测条件为：选用Agilent ZORBAX SB-C18高效液相色谱柱，其规格为长度150mm，内径为4.6mm，填料颗粒直径为5μm；检测器为二极管阵列紫外检测器，所述二极管阵列紫外检测器的测定波长为270nm，发射波长315nm；自动进样器进样，进样量：10μL，4种化合物的梯度洗脱程序如下表所示：The detection conditions of high performance liquid chromatography are: use Agilent ZORBAX SB-C18 high performance liquid chromatography column, its specification is 150mm in length, 4.6mm in inner diameter, and diameter of filler particles is 5μm; the detector is a diode array ultraviolet detector, the diode array The measurement wavelength of the UV detector is 270nm and the emission wavelength is 315nm; the autosampler injects samples, the sample volume is 10μL, and the gradient elution procedures of 4 compounds are shown in the following table:
Figure PCTCN2020089856-appb-000004
Figure PCTCN2020089856-appb-000004
实施例2：Example 2:
本实施例对影响四种磺胺类抗生素萃取回收率的主要因素进行考察，计算出萃取回收率最高时各因素的最佳值，再在各因素最佳值的条件下测定四种磺胺类抗生素的工作曲线相关参数和方法检出限和精密度，具体工艺包括以下步骤：In this example, the main factors affecting the extraction recovery rate of the four sulfonamide antibiotics were investigated, and the optimal value of each factor when the extraction recovery rate was the highest was calculated, and then the four sulfonamide antibiotics were determined under the condition of the optimal value of each factor. The working curve related parameters and method detection limit and precision, the specific process includes the following steps:
步骤一：计算四种磺胺类抗生素萃取回收率最高时各因素的最佳值：Step 1: Calculate the best value of each factor when the extraction recovery rate of the four sulfonamide antibiotics is the highest:
(1)吸附剂用量对萃取回收率的考察(1) Investigation of the amount of adsorbent on the extraction recovery rate
本实施例考察MOF用量对萃取回收率的影响，分别称取40、50、60、70、80、90、 100mg金属有机骨架材料NH 2-MIL-101(Fe)制备MOF膜，水样中四种抗生素浓度均为0.01mg/L，当金属有机骨架材料NH 2-MIL-101(Fe)用量由40mg增加为60mg时，萃取回收率随吸附剂用量增加而增加，说明随金属有机骨架材料NH 2-MIL-101(Fe)用量增加，吸附位点增多、吸附量增加；但当吸附剂的用量大于60mg时，再继续增加金属有机骨架材料NH 2-MIL-101(Fe)用量，四种化合物萃取回收率下降甚至几乎不变，所以本实施例中萃取剂用量选取60mg。 In this example, the influence of the amount of MOF on the extraction recovery rate was investigated. Weigh 40, 50, 60, 70, 80, 90, 100 mg of metal organic framework material NH 2 -MIL-101 (Fe) to prepare MOF membranes. The concentration of each antibiotic is 0.01mg/L. When the dosage of the metal organic framework material NH 2 -MIL-101 (Fe) is increased from 40 mg to 60 mg, the extraction recovery rate increases with the increase of the adsorbent dosage, indicating that the metal organic framework material NH 2 -MIL-101 (Fe) 2 -MIL-101 (Fe) dosage increases, adsorption sites increase, and adsorption capacity increases; but when the amount of adsorbent is greater than 60mg, continue to increase the amount of metal organic framework material NH 2 -MIL-101 (Fe), four The extraction recovery rate of the compound decreases or even hardly changes, so the amount of extractant used in this example is 60 mg.
(2)水样pH对萃取回收率的考察(2) Investigation of pH of water sample on extraction recovery rate
本实施例考察水样pH对萃取材料的表面吸附位点活性的影响，本实施例分别考察了水样pH为3、4、5.5、7、8条件下的萃取回收率结果，pH值在3～4范围内的回收率上升，在4～8的范围内急剧下降，说明材料对四种磺胺类抗生素萃取最适的pH为4。This example examines the effect of the pH of the water sample on the surface adsorption site activity of the extraction material. This example examines the results of the extraction recovery rate under the conditions of pH 3, 4, 5.5, 7, and 8, respectively. The pH value is 3 The recovery rate increased in the range of ~4, and dropped sharply in the range of 4-8, indicating that the optimal pH of the material for the extraction of the four sulfonamide antibiotics was 4.
(3)洗脱剂种类对萃取回收率的考察(3) Investigation of the type of eluent on the extraction recovery rate
本实施例考察不同的洗脱剂对吸附于吸附剂的待测物洗脱效率的影响，本实施例考察了甲醇、乙腈、丙酮、乙腈+5％氨水四种有机溶剂对萃取回收率的影响，乙腈+5％氨水具有最高的洗脱效率，因此本实施例选取乙腈+5％氨水作为洗脱溶剂。This example examines the influence of different eluents on the elution efficiency of the analyte adsorbed on the adsorbent. This example examines the influence of four organic solvents: methanol, acetonitrile, acetone, and acetonitrile + 5% ammonia on the extraction recovery rate. Acetonitrile + 5% ammonia water has the highest elution efficiency, so acetonitrile + 5% ammonia water is selected as the elution solvent in this embodiment.
(4)盐度对萃取回收率的考察(4) Investigation of salinity on extraction recovery
本实施例考察盐度对水中离子强度和化合物的扩散速率的影响，为考察盐浓度对水样中四种磺胺类抗生素萃取回收率的影响，本实施例中加入使水样盐度分别为为0％、0.5％、1％、5％、10％的氯化钠(NaCl)，加入NaCl以后，当盐浓度为0-1％时，回收率迅速增加。随着盐浓度的持续增加，回收率降低，并且趋于稳定。因此本实施例选取盐浓度为1％。This example examines the influence of salinity on the ionic strength and the diffusion rate of compounds in water. In order to examine the influence of salt concentration on the extraction recovery rate of four sulfonamide antibiotics in a water sample, the salinity of the water sample is added in this example to be 0%, 0.5%, 1%, 5%, 10% sodium chloride (NaCl), after adding NaCl, when the salt concentration is 0-1%, the recovery rate increases rapidly. As the salt concentration continues to increase, the recovery rate decreases and tends to stabilize. Therefore, the salt concentration is 1% in this embodiment.
(5)洗脱剂用量对萃取回收率的考察(5) Investigation of the amount of eluent on the extraction recovery rate
本实施例考察洗脱4mL、6mL、8mL、10mL、12mL，洗脱两次条件下的洗脱效果，单次洗脱剂用量为8mL时四种磺胺类抗生素的回收率最大，用量继续增大后，萃取回收率下降，因此本实施例选取单次洗脱剂用量为8mL。This example examines the elution effect under the condition of eluting 4mL, 6mL, 8mL, 10mL, 12mL and eluting twice. When the single eluent dosage is 8mL, the recovery rate of the four sulfonamide antibiotics is the largest, and the dosage continues to increase. Afterwards, the extraction recovery rate decreased, so in this example, the single eluent dosage was selected as 8 mL.
(6)洗脱时间对萃取回收率的考察(6) Investigation of elution time on extraction recovery rate
本实施例考察洗脱5min、10min、15min、20min和25min，洗脱两次条件下的洗脱效果，单次洗脱时间为15min时四种磺胺类抗生素的回收率最大，因此本实施例选取单次洗脱时间为15min。This example investigates the elution effect under the condition of elution 5min, 10min, 15min, 20min and 25min, and elution twice. The recovery rate of the four sulfonamide antibiotics is the largest when the single elution time is 15min, so this example selects The single elution time is 15min.
步骤二：测定四种磺胺类抗生素的工作曲线相关参数和方法检出限及精密度：Step 2: Determine the working curve related parameters of the four sulfonamide antibiotics and the detection limit and precision of the method:
(1)配制四种抗生素浓度为0.1μg/L、1μg/L、2μg/L、5μg/L、10μg/L、100μg/L的200mL水样，在优化的膜固相萃取条件下，进行高效液相色谱测定，测定四种磺胺类抗生素的工作曲线回归方程、线性范围、相关系数(R 2)、方法定量限和方法检出限。 (1) Prepare 200mL water samples with four antibiotic concentrations of 0.1μg/L, 1μg/L, 2μg/L, 5μg/L, 10μg/L, 100μg/L, and perform high-efficiency under optimized membrane solid-phase extraction conditions. Liquid chromatography determination, determination of four sulfonamide antibiotics working curve regression equation, linear range, correlation coefficient (R 2 ), method quantification limit and method detection limit.
表1四种磺胺类抗生素的工作曲线回归方程、线性范围、相关系数(R 2)仪器检出限和方法检出限 Table 1 Working curve regression equation, linear range, correlation coefficient (R 2 ) of four sulfonamide antibiotics, instrument detection limit and method detection limit
Figure PCTCN2020089856-appb-000005
Figure PCTCN2020089856-appb-000005
(2)配制四种抗生素浓度为1μg/L、10μg/L、40μg/L的低、中、高三个浓度的200mL模拟水样，按照膜固相萃取步骤测定，每个浓度点一天内平行测定6次考察日内精密度(以相对标准偏差表示)，三个浓度每天一次，测定6天考察日间精密度(以相对标准偏差表示)，测得四种磺胺类抗生素的日内精密度相对标准偏差在1.86％～11.24％范围内，日间精密度相对标准偏差在0.78％～5.84％范围内，满足精密度要求。(2) Prepare four kinds of antibiotics with a concentration of 1μg/L, 10μg/L, 40μg/L, low, medium, and high three concentrations of 200mL simulated water samples, in accordance with the membrane solid phase extraction procedure, and each concentration point is measured in parallel within one day Intraday precision (expressed by relative standard deviation) was investigated for 6 times, three concentrations were measured once a day, and the interday precision (expressed by relative standard deviation) was measured for 6 days, and the relative standard deviation of intraday precision of four sulfonamide antibiotics was measured. In the range of 1.86% to 11.24%, the relative standard deviation of the daily precision is in the range of 0.78% to 5.84%, which meets the precision requirements.
表2四种磺胺类抗生素的日间精密度与日内精密度Table 2 Inter-day precision and intra-day precision of four sulfonamide antibiotics
Figure PCTCN2020089856-appb-000006
Figure PCTCN2020089856-appb-000006
实施例3：Example 3:
测定实验室自来水、青岛市崂山水库、海水中四种磺胺类抗生素的残留量，采集3种水样后先用孔径为80～120μm的快速定性滤纸过滤，再用0.45μm滤膜过滤；将过滤后的水样采用实施例1所述方法进行测定，并用实施例2所述方法进行准确度测试，分别配制四种抗生素浓度为1μg/L、10μg/L、40μg/L的低、中、高三个浓度的实际水样进行加标回收率试验，每个浓度点测定3次，计算3次测定的平均值、相对标准偏差和加标回收率；其中， 三种水样空白中均未检出四种磺胺类抗生素；结果见表3；实际水样空白和加标色谱图分别见图8-9；从表中能够看出，本实施例的加标回收率为33.9％-80.3％，相对标准偏差为0.63％-5.79％，因此，本实施例的萃取效果好，分析结果准确，重现性好。Determine the residues of four sulfonamide antibiotics in tap water in the laboratory, Laoshan Reservoir in Qingdao City, and seawater. After collecting 3 kinds of water samples, filter with a fast qualitative filter paper with a pore size of 80～120μm, and then filter with a 0.45μm filter membrane; The latter water samples were measured using the method described in Example 1, and the accuracy test was performed using the method described in Example 2. The four antibiotics were prepared with low, medium, and high concentrations of 1μg/L, 10μg/L, and 40μg/L. The actual water samples with different concentrations were tested for the standard addition recovery rate, and each concentration point was measured three times, and the average value, relative standard deviation and standard addition recovery rate of the three determinations were calculated; among them, none of the three water sample blanks were detected Four sulfonamide antibiotics; the results are shown in Table 3; the actual blank and spiked chromatograms of the actual water sample are shown in Figs. 8-9, respectively; as can be seen from the table, the spiked recovery rate of this example is 33.9%-80.3%, relative The standard deviation is 0.63%-5.79%. Therefore, the extraction effect of this example is good, the analysis result is accurate, and the reproducibility is good.
表3自来水、地表水、海水加标回收率(n＝3，μg/L)Table 3 Standard recovery rate of tap water, surface water and sea water (n=3, μg/L)
Figure PCTCN2020089856-appb-000007
Figure PCTCN2020089856-appb-000007
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种用于磺胺类抗生素的固相萃取膜，其特征是，所述固相萃取膜是由聚偏二氟乙烯与NH 2-MIL-101(Fe)形成的混合基质膜。 A solid phase extraction membrane for sulfa antibiotics is characterized in that the solid phase extraction membrane is a mixed matrix membrane formed by polyvinylidene fluoride and NH 2 -MIL-101 (Fe).
  2. 如权利要求1所述的用于磺胺类抗生素的固相萃取膜，其特征是，制备方法为：将聚偏二氟乙烯与NH 2-MIL-101(Fe)分散至溶剂中混合均匀，将混合均匀的液体平铺并去除溶剂获得固相萃取膜。 The solid-phase extraction membrane for sulfa antibiotics according to claim 1, wherein the preparation method is: dispersing polyvinylidene fluoride and NH 2 -MIL-101 (Fe) into a solvent and mixing uniformly. Mix the well-mixed liquid flat and remove the solvent to obtain a solid phase extraction membrane.
  3. 一种环境水样中四种磺胺类抗生素的分析检测方法，其特征是，将含有磺胺类抗生素的待测水样进行抽滤，抽滤采用的抽滤膜为权利要求1或2所述的固相萃取膜，采用洗脱剂将抽滤后滤膜中吸附磺胺类抗生素进行洗脱，将洗脱后溶液中的磺胺类抗生素进行高效液相色谱检测；所述洗脱剂为乙腈与氨水的混合溶液；所述磺胺类抗生素为磺胺嘧啶、磺胺甲基嘧啶、磺胺氯哒嗪和磺胺甲恶唑。A method for analyzing and detecting four sulfonamide antibiotics in environmental water samples, which is characterized in that the water sample to be tested containing sulfonamide antibiotics is suction filtered, and the suction filtration membrane used for suction filtration is the one described in claim 1 or 2. The solid phase extraction membrane uses an eluent to elute the adsorbed sulfonamide antibiotics in the filter membrane after suction filtration, and the sulfonamide antibiotics in the eluted solution are detected by high performance liquid chromatography; the eluent is acetonitrile and ammonia The mixed solution; the sulfadiazine antibiotics are sulfadiazine, sulfamethazine, sulfachloropyridazine and sulfamethoxazole.
  4. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，调节待测水样的pH为2.5～3.5。The method for analyzing and detecting four sulfonamide antibiotics in an environmental water sample according to claim 3, wherein the pH of the water sample to be tested is adjusted to 2.5-3.5.
  5. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，向待测水样添加氯化钠，使调节后的待测水样中的氯化钠的质量分数为0.9～1.1％；The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples according to claim 3, characterized in that sodium chloride is added to the water sample to be tested so that the quality of the sodium chloride in the water sample to be tested is adjusted The score is 0.9～1.1%;
    或，洗脱剂的单次使用量为7.5～8.5mL；Or, the single use amount of the eluent is 7.5～8.5mL;
    或，采用洗脱剂的单次洗脱时间为14.5～15.5min。Or, the single elution time using eluent is 14.5~15.5min.
  6. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，洗脱后将洗脱剂去除，再用流动相溶液溶解，然后进行高效液相色谱检测。The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples according to claim 3, characterized in that the eluent is removed after elution, and then dissolved in a mobile phase solution, and then detected by high performance liquid chromatography.
  7. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，所述高效液相色谱检测的流动相包括乙腈和甲酸水溶液，所述甲酸水溶液的pH为2.5～3.5。The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples according to claim 3, characterized in that the mobile phase detected by the high performance liquid chromatography includes acetonitrile and formic acid aqueous solution, and the pH of the formic acid aqueous solution is 2.5~ 3.5.
  8. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，高效液相色谱检测的洗脱程序如下表所示：The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples according to claim 3, characterized in that the elution procedure of high performance liquid chromatography detection is shown in the following table:
    Figure PCTCN2020089856-appb-100001
    Figure PCTCN2020089856-appb-100001
  9. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，高效液相色谱中，选用Agilent ZORBAX SB-C18高效液相色谱柱，长度为150mm，内径为4.6mm，填料颗粒直径为5μm；检测器为二极管阵列紫外检测器，所述二极管阵列紫外检测器的测定波长为270nm，发射波长315nm；自动进样器进样，进样量：10μL。The method for analyzing and detecting four sulfonamide antibiotics in environmental water samples according to claim 3, characterized in that, in the high performance liquid chromatography, an Agilent ZORBAX SB-C18 high performance liquid chromatography column with a length of 150 mm and an inner diameter of 4.6 is selected. mm, the diameter of the filler particles is 5 μm; the detector is a diode array ultraviolet detector, the measurement wavelength of the diode array ultraviolet detector is 270 nm, and the emission wavelength is 315 nm; the sample is injected by the autosampler, and the sample volume is 10 μL.
  10. 如权利要求3所述的环境水样中四种磺胺类抗生素的分析检测方法，其特征是，磺胺嘧啶、磺胺甲基嘧啶、磺胺甲恶唑和磺胺氯哒嗪四种磺胺类抗生素的工作曲线相关参数和方法检出限和精密度的计算方法为配制四种磺胺类抗生素浓度为0.1μg/L、1μg/L、2μg/L、5μg/L、10μg/L、100μg/L的200mL水样，在优化的膜固相萃取条件下，进行高效液相色谱测定，四种磺胺类抗生素的工作曲线回归方程、线性范围、相关系数、方法定量限和方法检出限如下表：The method for analyzing and detecting four sulfa antibiotics in environmental water samples according to claim 3, which is characterized in that the working curves of sulfadiazine, sulfamethazine, sulfamethoxazole and sulfachloropyridazine are four sulfa antibiotics The calculation method of detection limit and precision of related parameters and methods is to prepare 200mL water samples with four sulfonamide antibiotics at concentrations of 0.1μg/L, 1μg/L, 2μg/L, 5μg/L, 10μg/L, 100μg/L , Under optimized membrane solid phase extraction conditions, high performance liquid chromatography determination, the working curve regression equation, linear range, correlation coefficient, method quantification limit and method detection limit of the four sulfonamide antibiotics are as follows:
    Figure PCTCN2020089856-appb-100002
    Figure PCTCN2020089856-appb-100002
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