CN110618224B - [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof - Google Patents
[ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of materials, and discloses a [ H ]2Nmim][NTf2]A method for synthesizing a @ UiO-66-Br nanocomposite, said material comprising: bromine-functionalized Zr-MOFs (UiO-66-Br) and amino-functionalized imidazole ionic liquid ([ H ] H) loaded on same2Nmim][NTf2]). The invention also discloses application of the nano composite material in extraction and enrichment of sulfonamide antibiotics in a dispersed solid phase microextraction technology (DSPME) pretreatment water sample. The nano composite material disclosed by the invention is successfully applied to the extraction analysis of sulfonamide antibiotics, can be completed by using a small amount of adsorbent and sample in a short time, and has the characteristics of rapidness, sensitivity, high efficiency, economy and applicability. The invention can also screen, design and regulate and control the adsorbent according to the structure of the target analyte, provides a new idea for the analysis of other environmental pollutants, and has important significance for protecting the health and safety of the public and the environment.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof.
Background
The sulfonamide antibiotic, as an artificially synthesized antibacterial, plays an important role in the prevention and treatment of bacterial and protozoal infections. Some of them are also widely used in animal farms and fisheries to promote animal growth. Over 20,000 tons of sulfa antibiotics are introduced into the environment each year and are frequently detected in an aqueous environment. Studies have shown that sulfa antibiotics have a long life in the environment, are resistant to biodegradation, and accumulate in various organisms through the food chain. Some sulfonamides are carcinogenic and their residue in the environment increases bacterial resistance. In order to protect human health, the European Union and other countries including China have specified a maximum total residual amount of 100 μ g L in animal-derived foods-1. Therefore, it is very important to develop a sensitive detection method for sulfa antibiotics in environmental samples.
Metal Organic Frameworks (MOFs) are a class of novel porous materials consisting of metal ions or clusters and organic ligands. It has high specific surface area, controllable pore size, high heat stability and high chemical resistance. These structures and properties bring great potential for the application of MOFs in environmental analytical chemistry. To date, although some single-phase MOFs, including MIL-101, uo-67, ZIF-8 and other MOFs materials, have been used as adsorbents to extract enriched contaminants (e.g., pesticides, various endocrine disruptors and polycyclic aromatics, etc.). In order to further improve the adsorption performance and reduce the conditions of separation and collection, most of the existing researches tend to introduce some high-stability metal nano materials, metal oxides and the like (such as ferroferric oxide and silicon dioxide). However, these materials themselves do not have outstanding adsorption capacity, and even the introduction of some materials reduces the spatial volume and occupies effective adsorption sites of the MOFs.
Ionic Liquids (IL) have many unique physicochemical properties, for example: the composite adsorbing material is non-volatile and non-flammable, has good dissolving capacity for a plurality of pollutants, and is a good designable novel adsorbing material. It is receiving more and more attention and is used to separate and extract various pollutants from the environment. Thus, compared to a highly stable material that is not inherently outstanding in adsorption capacity. Some functionalized hydrophobic ionic liquids are packaged into MOFs materials with 3D pore structures, so that stable novel adsorption materials are prepared, and the method is an effective way for researching and developing novel solid phase extraction agents in water phases with great prospect.
Disclosure of Invention
The invention fills hydrophobic and amino-functionalized ionic liquid into Zr-MOFs materials for the first time to prepare the novel nano composite material which is used as a Dispersed Solid Phase Microextraction (DSPME) adsorbent, is applied to pre-enrichment treatment of sulfonamide antibiotics in a water phase for the first time, and has the characteristics of rapidness, sensitivity and high efficiency. The two novel materials adopted by the invention have excellent extraction and enrichment capacities, can be screened, designed and regulated to a certain extent according to the structure of a target analyte, and have important significance in the research of developing a specific high-performance adsorbent aiming at pollutants.
The invention provides a novel nano composite material based on metal organic framework loaded with ionic liquid and a preparation method thereof, wherein the ionic liquid is loaded into the metal organic framework material to prepare [ H ]2Nmim][NTf2]The @ UiO-66-Br nanocomposite is used as an adsorbent of a high-sensitivity dispersed solid phase microextraction technology (DSPME) for pretreating the sulfa antibiotic for the first time, and the sulfa antibiotic in an environmental water sample is pretreated. The application of the aspect has not been reported so far.
The invention aims to load amino-functionalized imidazole ionic liquid to bromine-functionalized Zr-MOFs ([ H ] MOFs) through reasonable design according to the structure of sulfonamide antibiotics2Nmim][NTf2]@ UiO-66-Br) as DSPME adsorbent, and realizes sensitive and accurate enrichment detection of sulfonamide antibiotics in environmental water sample by combining high performance liquid chromatography.
The invention provides a [ H ]2Nmim][NTf2]@ UO-66-Br nanocomposites comprising bromine-functionalized Zr-MOFs (UO-66-Br) and amino-functional groups supported thereonIonic liquids of imidazole type ([ H ]2Nmim][NTf2])。
The amino-functionalized imidazole ionic liquid is synthesized by selecting hydrophobic bis (trifluoromethylsulfonyl) imide as an anion and selecting amino-functionalized imidazole as a cation.
The bromine-functionalized Zr-MOFs refers to UiO-66-Br, and is composed of Zr4+And organic ligand 2-bromoterephthalic acid are self-assembled through coordination bonds to form the metal organic framework material.
The ionic liquid is characterized in that: a significant feature of ionic liquids is that ionic liquids can be designed for different structures of the target analyte. Varying different combinations of cations, anions; different ionic liquids can be designed and synthesized by carrying out certain functionalized modification on cations and anions. SO in the structure of sulfonamide antibiotics2And (3) selecting hydrophobic bis (trifluoromethylsulfonyl) imide anions and imidazole cations with aromaticity for synthesizing the target ionic liquid according to the similar compatibility principle and potential pi-pi interaction. Four imidazole ionic liquids with different functions of hydroxyl, carboxyl, amino and benzyl are reasonably screened, designed and synthesized. Compared with the adsorbents loaded with the hydroxyl, carboxyl and benzyl functionalized ionic liquids and the unsupported ionic liquid, the UiO-66-Br material loaded with the amino functionalized ionic liquid shows the best adsorption performance.
Zr-MOFs characteristics: the Zr-MOFs material is made of Zr4+And a three-dimensional porous material formed by self-assembly of a terephthalic acid organic ligand through a coordination bond. It contains many potential pi-pi acting units. The charge property of the Zr-MOFs material is regulated and controlled by regulating and controlling functional groups on the Zr-MOFs organic ligand, so that the potential electrostatic interaction of the Zr-MOFs material can be regulated and controlled.
UiO-66-Br characteristics: UiO-66-Br is a group consisting of Zr4+And organic ligand 2-bromoterephthalic acid are self-assembled through coordination bonds to form a three-dimensional porous material. The material has a theoretical value of 900-1004m2High specific surface area per gram (chem. Commun.,2010,46, 7700-7702), and many potential roles such as pi-pi effect, electrostatic effect, etcThe force cell is a promising adsorption material and can be completely used as a solid carrier of the imidazole ionic liquid functionalized by amino.
[H2Nmim][NTf2]The characteristics of the @ UiO-66-Br nanocomposite material are as follows: [ H ]2Nmim][NTf2]@ UiO-66-Br is a type of encapsulation [ H ] in the cavity of UiO-66-Br2Nmim][NTf2]Ionic liquids are used to prepare novel nanocomposites. The material has a plurality of potential pi-pi acting force and electrostatic acting force units; and NH2、NO2Functionalized, Br-functionalized Zr-MOFs materials supporting [ H ] in comparison with unfunctionalized Zr-MOFs2Nmim][NTf2]The ionic liquid shows more excellent extraction performance on the sulfanilamide antibiotic. The amount of the nano composite material only needs 10-30mg, the time of adsorption extraction balance is 5-10min, and the extraction enrichment factor of the sulfa antibiotic can reach 270-300 times.
[ H ] proposed by the present invention2Nmim][NTf2]A preparation method of @ UiO-66-Br nanocomposite material, comprising the following steps:
(1) preparing an MOF material: the UiO-66-Br nano material is prepared according to the method reported in the literature (Commun, 2010,46, 7700-7702; J.ColloidInterface Sci, 2017,500, 88-95). In a 50mL Teflon lined autoclave charged with 20mL DMF, an equimolar amount of ZrCl was charged4And 2-bromoterephthalic acid (0.5 mmol). Then the mixture is sealed and placed in an oven at 120 ℃ for reaction for 12 hours. After cooling to room temperature, the solid product was collected by three washes with DMF and centrifugation at 8000g for 5 min. Subjecting the obtained product to CHCl3Soaking for 3 days, and replacing DMF molecules. And finally, drying the mixture in vacuum at the temperature of 80 ℃ to obtain a solid product, namely the UiO-66-Br nano material.
(2) And (3) functionalized ionic liquid packaging: 0.01g of 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid ([ H ]2Nmim][NTf2]) And 0.09g of UiO-66-Br obtained in the above step (1) were mixed in 5mL of an aqueous solution. Stirring at room temperature for 5h, centrifuging at 8000g for 5min, and collecting the solid product at the bottom. Finally, drying in a vacuum oven at 80 ℃ overnight to obtain the [ H ]2Nmim][NTf2]@ UiO-66-Br nanocomposite.
The invention also provides a method for synthesizing the [ H ]2Nmim][NTf2]The @ UiO-66-Br nanocomposite is used as an adsorbent and is applied to detection and analysis of sulfonamide antibiotics in a pretreated water sample.
Wherein, the sulfanilamide antibiotics in the water sample comprise one or more of sulfadiazine, sulfamethazine, sulfamethoxazole, sulfalene, sulfamethoxazole and sulfamonomethoxine.
In the application of the invention, [ H ] is utilized2Nmim][NTf2]The @ UiO-66-Br nanocomposite is used as an adsorbent in a solid-phase microextraction technology to pretreat sulfonamide antibiotics in a water sample, and is combined with a high performance liquid chromatography-diode array detector to realize sensitive detection and analysis of the sulfonamide antibiotics in the water sample.
In the application of the invention, the method can complete the separation and detection analysis of various sulfonamides antibiotics by combining with high performance liquid chromatography and different detectors (such as an ultraviolet detector, a diode array detector, a mass spectrum detector and the like).
The invention also provides a [ H ]2Nmim][NTf2]A method for detecting and analyzing sulfonamide antibiotics in a water sample by using a @ UiO-66-Br nano composite material as an adsorbent. The method is based on [ H ]2Nmim][NTf2]A novel solid-phase microextraction technology for pretreating a water sample of a @ UiO-66-Br nanocomposite.
The method comprises the following steps:
a pretreatment step;
(II) a chromatographic detection analysis step;
and (III) analyzing and quantifying sulfonamide antibiotics.
Wherein the pretreatment step (one) comprises the following steps:
1) scale [ H ]2Nmim][NTf2]The @ UiO-66-Br nano composite material is dispersed in a water sample and treated by ultrasound for 5-10min to form a uniform suspension;
2) after 5-10min of adsorption equilibrium, centrifuging for 5-10minSeparate out the adsorbent i.e. [ H ]2Nmim][NTf2]@ UiO-66-Br nanocomposite; soaking the adsorbent with acidified methanol (containing 1-5% acetic acid, v/v), and performing desorption under ultrasonic wave;
3) after complete desorption, centrifuging at 8000-10000g for 5-10min to collect the eluent, and filtering the eluent by a 0.22 mu m organic filter head;
4) the eluent is purged and concentrated under the protection of nitrogen and then used for HPLC sample injection analysis.
And (II) the chromatographic detection and analysis step, namely, the detection and analysis of the sulfa antibiotic in the water sample are completed by utilizing a high performance liquid chromatography-diode array detector.
In the step of analyzing and quantifying the sulfa antibiotic, preparing standard water samples of the sulfa antibiotic with different concentration gradients, drawing a standard working curve by taking the peak area of the component to be measured in each standard solution as a vertical coordinate and the concentration of the component to be measured in each standard solution as a horizontal coordinate, and quantifying the sample by using the standard working curve. And replacing the added standard water sample with the environmental water sample with the same volume, and calculating the detection concentration of each sulfonamide antibiotic in the environmental water sample by using the standard working curve. The recovery of the sulfonamide antibiotics was calculated as follows (1):
wherein, CsedAnd C0Respectively representing the final concentration of the sulfa antibiotic in the concentrated and quantitative methanol and water samples; csedQuantitatively calculating the actual sample according to the standard working curve to obtain the standard working curve; vsedAnd V0Representing the volume of the quantified methanol and the initial volume of the water sample, respectively.
In the method, the antibiotics in the water sample can include but are not limited to sulfanilamide antibiotics: sulfadiazine (SD), Sulfamethazine (SM), Sulfamethazine (SMT), Sulfamethoxypyridazine (SMPD), Sulfalene (SMPZ), Sulfamethoxazole (SMX), Sulfamonomethoxine (SMM)), and the like.
In the method, sulfonamide antibioticsThe recovery efficiency of (A) is 94-109%; the linear range is 0.05-100 mu gL-1There may be slight deviations from detector to detector.
In the present invention, the water samples include, but are not limited to: clean water samples such as river water, surface water, well water, tap water, and other water samples suitable for use in the present invention.
The invention has the advantages and beneficial effects that:
the method encapsulates hydrophobic imidazole ionic liquid into UiO-66-Br to successfully prepare [ H ]2Nmim][NTf2]@ UiO-66-Br nanocomposite.
The method of the invention fully utilizes the outstanding performances of the ionic liquid and the metal organic framework material, and applies the composite material to the detection and analysis of the sulfa antibiotic in the environmental actual water sample for the first time. Compared with the pure UiO-66-Br nano material as the adsorbent, the adsorbent loaded with the ionic liquid has obviously better extraction and enrichment effects on the sulfa antibiotics when a water sample is pretreated.
According to the structure of the sulfonamide antibiotics, the amino functionalized ionic liquid is screened, designed and synthesized, and introduced into the UiO-66-Br material, so that the extraction and enrichment capacity of the amino functionalized ionic liquid in a water phase is enhanced. The novel nano composite material combines the dual advantages of the functionalized imidazole ionic liquid and the functionalized Zr-MOFs, and is used as an adsorbent in dispersed solid-phase microextraction for the first time and used for pretreating sulfonamide antibiotics in a water phase. The electrostatic interaction of the nano composite material and the pi-pi interaction play an important role in the extraction and enrichment of sulfonamide antibiotics.
The nano composite material provided by the method has high recovery efficiency and strong extraction and enrichment capacity on the sulfonamide antibiotics. The method has the advantages of high sensitivity, simple operation and small dosage of the sample and the extracting agent, and is a fast, efficient, economic and applicable technology for detecting and analyzing the sulfonamide antibiotics. The method of the invention is successfully applied to the extraction analysis of sulfonamide antibiotics, and can be completed in a short time by using a small amount of adsorbent and sample. The method can also screen, design and regulate the ionic liquid and the MOFs material in the adsorbent according to the structure of the target analyte, provides a new idea for analyzing other environmental pollutants, and has important significance for protecting the health and safety of the public and the environment.
Drawings
FIG. 1 shows a composite material [ H ] synthesized in example 12Nmim][NTf2]XRD characterization (A), FTIR characterization (B), N of @ UiO-66-Br2Adsorption-desorption isotherms (C).
Fig. 2A and 2B show seven kinds of sulfa antibiotics and the structural formulas of four kinds of ionic liquids, respectively, and fig. 2C shows the influence of different kinds of ionic liquids on the extraction effect of the sulfa antibiotics.
FIG. 3A is an organic ligand of four MOFs; 3B is Zeta potential of four MOFs at pH 6.5; 3C is the Zeta potential of UiO-66-Br at different pH values; 3D, 3E and 3F are different MOFs respectively, and the pH value and the ionic liquid ratio influence the extraction effect of the sulfa antibiotic.
FIG. 4 is a chromatogram of seven sulfa antibiotics; chromatographic peak: corresponding to SD, SM, SMT, SMPD, SMPZ, SMX and SMM, respectively.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
EXAMPLE 1 Synthesis of [ H2Nmim][NTf2]@ UiO-66-Br nanocomposite
(1) Preparing an MOF material: the UiO-66-Br nano material is prepared according to the method reported in the literature (Commun, 2010,46, 7700-7702; J.ColloidInterface Sci, 2017,500, 88-95). In a 50mL Teflon lined autoclave charged with 20mL DMF, an equimolar amount of ZrCl was charged4And 2-bromoterephthalic acid (0.5 mmol). Then the mixture is sealed and placed in an oven at 120 ℃ for reaction for 12 hours. After cooling to room temperature, the solid product was collected by three washes with DMF and centrifugation at 8000g for 5 min. Subjecting the obtained product to CHCl3Soaking for 3 days, and replacing DMF molecules. And finally, drying the mixture in vacuum at the temperature of 80 ℃ to obtain a solid product, namely the UiO-66-Br nano material.
(2) And (3) functionalized ionic liquid packaging: 0.01g of 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid ([ H ]2Nmim][NTf2]) And 0.09g of UiO-66-Br obtained in the above step (1) were mixed in 5mL of an aqueous solution. Stirring at room temperature for 5h, centrifuging at 8000g for 5min, and collecting the solid product at the bottom. Finally, the mixture is dried in a vacuum oven at 80 ℃ overnight, thus obtaining the invention [ H2Nmim][NTf2]@ UiO-66-Br nanocomposite.
For the product [ H ] synthesized in example 1 above2Nmim][NTf2]The @ UiO-66-Br nanocomposite material is characterized, such as the MOFs material UiO-66-Br and the composite material [ H ] shown in FIG. 1A2Nmim][NTf2]The XRD characterization pattern of @ UiO-66-Br shows that the crystal structure of UiO-66-Br remains stable, but the relative intensity of the peaks decreases. This indicates [ H2Nmim][NTf2]Have been encapsulated into the cavities of Zr-MOFs material. According to FTIR characterization (FIG. 1B), the product composite [ H ] was synthesized2Nmim][NTf2]No characteristic peak of ionic liquid was observed in @ UiO-66-Br, which may be influenced by the pore shielding effect of the UiO-66-Br material. As shown in FIG. 1C, N is compared with UiO-66-Br2Adsorption-desorption isotherm display [ H2Nmim][NTf2]Adsorption of N by @ UiO-66-Br nanocomposite (adsorbent)2The amount of (c) is significantly reduced. Can be seen, [ H ]2Nmim][NTf2]Ionic liquids have been successfully encapsulated in UiO-66-Br Material and example 1 successfully synthesized [ H2Nmim][NTf2]@ UiO-66-Br nanocomposite.
Example 2 invention [ H2Nmim][NTf2]Application of @ UiO-66-Br nano composite material as adsorbent
[ H ] prepared in example 12Nmim][NTf2]The @ UiO-66-Br nanocomposite is used as a DSPME adsorbent and combined with a high performance liquid chromatography-diode array detector (HPLC-DAD) to realize the adsorption of seven kinds of sulfaantibiotics (comprising Sulfadiazine (SD), Sulfamethylpyridine (SM), sulfadimethy pyrimidine (SMT), Sulfatrimethoprim (SMPD), Sulfalene (SMPZ) and sulfamethoxazole in an environmental water sample(SMX), and Sulfamonomethoxine (SMM)) in a sample. Comprises a pretreatment step, a chromatographic detection and analysis step, and an analysis and quantification step of the sulfa antibiotic.
The pretreatment step comprises the following steps:
1) weigh 10.0mg of [ H ]2Nmim][NTf2]The @ UiO-66-Br nanocomposite is dispersed in a 30.0mL water sample and is subjected to ultrasonic treatment for 10min to form a uniform suspension;
2) after adsorption equilibrium, centrifuging for 5min at 8000g to separate out adsorbent; soaking the adsorbent with 5.0mL of methanol (containing 1% acetic acid, v/v), and desorbing under ultrasound for 10 min;
3) after complete desorption, the eluate was collected by centrifugation at 8000g for 5min and filtered through a 0.22 μm organic filter;
4) the eluate was concentrated to 100. mu.L under nitrogen purge and analyzed by HPLC-DAD injection.
The chromatographic detection and analysis step comprises the following steps:
the detection and analysis of the sulfa antibiotic in the water sample is completed by using a high performance liquid chromatography-diode array detector, as shown in figure 2.
Wherein, the liquid chromatogram detection conditions are as follows:
a chromatographic column: InertSustanin C18 column, 5.0 μm,4.6mmid × 250 mm;
flow rate: 0.8mLmin-1；
Sample introduction amount: 10 mu L of the solution;
column temperature: 40 ℃;
mobile phase: is prepared from 32% methanol and 68% 0.01mol L-1Oxalic acid aqueous solution.
The (III) sulfanilamide antibiotic analysis and quantification steps comprise the following steps:
1) preparing standard water samples of the sulfa antibiotics with different concentration gradients, and preferably preparing the standard water samples on the same day; by using [ H ]2Nmim][NTf2]The @ UiO-66-Br nanocomposite completed the pretreatment step and the chromatographic detection analysis step above. Drawing standard work by taking the peak area of the component to be measured in each standard solution as the ordinate and the concentration of the component to be measured in each standard solution as the abscissaCurve, sample quantification with standard working curve.
2) And (3) replacing the added standard water sample with the environmental water sample with the same volume to finish the pretreatment step and the chromatographic detection analysis step, and calculating the detection concentration of each sulfa antibiotic in the environmental water sample (namely the actual sample) by using the standard working curve.
3) The recovery of the sulfonamide antibiotics was calculated as follows (1):
wherein, CsedAnd C0Respectively representing the final concentration of the sulfa antibiotic in the concentrated and quantitative methanol and water samples; csedCarrying out quantitative calculation on an environmental water sample according to a standard working curve to obtain the environmental water sample; vsedAnd V0Representing the volume of the quantified methanol and the initial volume of the water sample, respectively.
Example 3 comparison and optimization of adsorption Properties of ILs @ Zr-MOFs nanocomposites
(1) Design synthesis and performance comparison of the Zr-MOFs material:
the Sulfa Antibiotic (SAs) is an amphoteric adsorbate, and can be used as SA according to different pH values of water samples±Or SA0Has a pKa value of 6.3 to 7.4. By regulating and controlling the difference of functional groups on the Zr-MOFs organic ligand, the Zr-MOFs material can show the difference of the charge performance. The four Zr-MOFs materials were prepared according to the literature reported method (Commun, 2010,46, 7700-7702; J. colloid interface Sci, 2017,500,88-95), the basic procedure being the same as in example 1. Except that 0.5mmol of terephthalic acid, 2-amino terephthalic acid and 2-nitro terephthalic acid as precursors are respectively used to replace 2-bromoterephthalic acid in example 1 to prepare UiO-66, UiO-66-NH2And UiO-66-NO2The materials are synthesized. Changing the types of Zr-MOFs materials, respectively using 0.09g of UiO-66 and UiO-66-NH2And UiO-66-NO2The material replaces UiO-66-Br in the functionalized ionic liquid encapsulation in the embodiment 1, and then the [ H ] can be correspondingly prepared2Nmim][NTf2]@UiO-66，[H2Nmim][NTf2]@UiO-66-NH2And [ H2Nmim][NTf2]@UiO-66-NO2A nanocomposite material.
The ILs @ Zr-MOFs nano composite materials are respectively used as DSPME adsorbents, and are combined with a high performance liquid chromatography-diode array detector to pretreat sulfonamide antibiotics in an environmental water sample, and the specific steps are the same as those in example 2. The extraction efficiency of the adsorbent (ILs @ MOFs nano composite material) is measured by the chromatographic peak area of the extracted and recovered sulfanilamide antibiotics.
As the ionic liquids all show electric neutrality, the electric charge of the ILs @ Zr-MOFs nano composite material is determined by the Zr-MOFs material. UiO-66-Br showed electropositivity in the pH range of 3.5-6.5 and electronegativity in the range greater than 6.5 (FIG. 3C). Br and NO2The functionalized adsorbent showed a heterogeneous charge with the sulfonamide antibiotic at pH 6.5, indicating that electrostatic interactions play an important role in the adsorption of SAs. As shown in FIGS. 3D-E, with NH2And NO2[ H ] compared to the non-functionalized Zr-MOFs materials2Nmim][NTf2]The @ UiO-66-Br nanocomposite exhibited the best extraction recovery performance at pH 6.5. Wherein NO2The chromatographic peak area of each sulfonamide antibiotic of the functionalized adsorbent is small, probably due to NO2Greater steric hindrance effect.
(2) Design synthesis and performance comparison of ionic liquid:
SO in the structure of sulfonamide antibiotics2NH group and aromatic ring (figure 2A), according to the principle of similarity and compatibility and potential pi-pi interaction, hydrophobic bis (trifluoromethylsulfonyl) imide anion and imidazole cation with aromaticity are selected for synthesizing the target ionic liquid. Four imidazole ionic liquids with different functionalized hydroxyl, carboxyl, amino and benzyl groups are reasonably screened, designed and synthesized and respectively correspond to [ HOmim ]][NTf2]、[HOOCmim][NTf2]、[H2Nmim][NTf2]And [ Bzmim][NTf2]Four ionic liquids (fig. 2B). Changing the kind of the ionic liquid, and respectively using 0.01g of the ionic liquid 1-hydroxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imideAmine ([ HOmim ]][NTf2]) 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([ HOOCmim)][NTf2]) And 1-benzyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([ Bzmim [)][NTf2]) Replacement of [ H ] in functionalized Ionic liquid packages of example 12Nmim][NTf2]Then [ HOmim ] can be prepared correspondingly][NTf2]@UiO-66-Br， [HOOCmim][NTf2]@ UiO-66-Br and [ Bzmim @][NTf2]@ UiO-66-Br nanocomposite.
The ILs @ Zr-MOFs nano composite materials are respectively used as DSPME adsorbents, and are combined with a high performance liquid chromatography-diode array detector to pretreat sulfonamide antibiotics in an environmental water sample, and the specific steps are the same as those in example 2. The extraction efficiency of the adsorbent (ILs @ MOFs nano composite material) is measured by the chromatographic peak area of the extracted and recovered sulfanilamide antibiotics.
As shown in fig. 2C, compared with the hydroxyl-, carboxyl-and benzyl-functionalized ionic liquids, the adsorbent loaded with the amino-functionalized ionic liquid has the largest chromatographic peak area of each sulfonamide antibiotic recovered by extraction, and shows the best extraction recovery performance.
(3) The proportioning optimization and performance comparison of the ionic liquid are as follows:
encapsulation of example 1 functionalized Ionic liquids [ H2Nmim][NTf2]The mass ratio to UiO-66-Br was changed from 10 wt.% (1:9) to 5 wt.%, 15 wt.% and 20 wt.%. The correspondingly prepared nanocomposites are each [ H ]2Nmim][NTf2]@ UiO-66-Br-5，[H2Nmim][NTf2]@ UiO-66-Br-15 and [ H2Nmim][NTf2]@UiO-66-Br-20。
The ILs @ Zr-MOFs nano composite materials are respectively used as DSPME adsorbents, and are combined with a high performance liquid chromatography-diode array detector to pretreat sulfonamide antibiotics in an environmental water sample, and the specific steps are the same as those in example 2. The extraction efficiency of the adsorbent (ILs @ MOFs nano composite material) is measured by the chromatographic peak area of the extracted and recovered sulfanilamide antibiotics.
As can be seen from FIG. 3F, compared with pure UiO-66-Br material, the sulfonamide antibiotics after loading ionic liquidThe respective peak areas of the elements are significantly increased, at a loading of 10 wt.% of ionic liquid, i.e. using [ H ]2Nmim][NTf2]When the @ UiO-66-Br-10 nanocomposite is used as an adsorbent, the chromatographic peak area of each sulfonamide antibiotic obtained by extraction and recovery is the largest, namely, 10 wt.% of [ H ] is loaded2Nmim][NTf2]The ionic liquid has the best extraction recovery efficiency on UiO-66-Br.
Example 4 alignment of the Linear analysis of the method of the invention with literature
[ H ] prepared in example 12Nmim][NTf2]The @ UiO-66-Br nanocomposite is used as a DSPME adsorbent and is combined with a high performance liquid chromatography-diode array detector (HPLC-DAD) to realize sensitive and accurate enrichment detection analysis on seven kinds of sulfaantibiotics (comprising Sulfadiazine (SD), Sulfamethylpyridine (SM), sulfadimethy pyrimidine (SMT), sulfamethoxy pyridazine (SMPD), Sulfalene (SMPZ), Sulfamethoxazole (SMX) and Sulfamonomethoxine (SMM)) in an environmental water sample. The specific procedure was the same as in example 2.
In this example, the data results of the linear analysis of sulfa antibiotics in the DSPME pretreated water sample are shown in table 1 below; the data of the standard recovery rate of the sulfa antibiotic in the DSPME pre-treated water sample are shown in Table 2; the ratio of the DSPME method to the methods in other documents is shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
aHollow fiber supported liquid phase micro-extraction;bliquid-liquid microextraction of the polyion liquid-based dispersion;cadsorbing and extracting by a molecularly imprinted polymer rod;dperforming magnetic mixed semi-fiber solid phase extraction;emagnetic solid phase extraction
And (3) comparing the documents: 1, j.chromatogr.a,2017,1500, 24-31; 2, j.chromatogr.a,2009,1216, 6259-6266; chromatogr.a,2018,1571, 47-54; 4, j.pharmaceut.biomed.anal, 2016,129, 593-; 5, Methods,2014,6, 9725-; 6, Talanta,2013,116, 695-; 7, J.Chromatogr.A, 2010,1217, 5602-; chromatogr.a,2006,1131, 1-10; 9, Chinese JAnal Chem,2012,40, 1002-1010; 10, Talanta,2011,85, 97-103.
The partially developed methods ( references 1, 3, 5, 7) showed strong enrichment capacity (250-1000) and highly sensitive detection limit (0.01-0.09 μ g L)-1). They are obtained mainly by using a large amount of adsorbent or sample. Extraction techniques based on adsorption bars/fibers ( references 2,4, 9, 10) generally require a series of complicated pretreatment processes, and their extraction time is too long (45-960min), adsorption equilibrium is difficult to achieve in a short time, and recovery efficiency is unstable. Other methods (references 6 and 8) can achieve rapid extraction analysis with small sample volumes, but their sensitivity and enrichment factor are not satisfactory. In the method, the sensitive analysis of the sulfa antibiotic with high enrichment factor and stable recovery rate can be realized only by using a small amount of adsorbent and sample. The adsorption equilibrium can be realized in a short extraction time. All comparison results show that the DSPME method developed by the invention is a rapid, sensitive, efficient, economical and applicable detection and analysis method for the sulfa antibiotic in the water sample.
In conclusion, the amino functionalized imidazolyl ionic liquid is packaged into the Zr-MOF material with the 3D pore structure, and the novel Zr-MOF material is preparedOf (a) a nanocomposite ([ H ]2Nmim][NTf2]@ UiO-66-Br) which can be used as adsorbent in dispersed solid phase microextraction. The invention firstly provides the application of the composite material in the pretreatment of the sulfonamide antibiotics in the water phase. The invention [ H ]2Nmim][NTf2]The @ UiO-66-Br composite material shows strong extraction and enrichment capacity in an actual water sample. The invention combines the high performance liquid chromatography to successfully develop a method for detecting the sulfa antibiotic in the actual water sample, which is rapid, sensitive, efficient, economical and applicable. The method has the advantages of small amount of adsorbent and sample, and short adsorption extraction equilibrium time. In addition, the adsorbent can be screened, designed and regulated according to the structure of the target analyte, and a new platform is provided for the analysis of other environmental pollutants. The invention has extremely important application value in the fields of health safety, environmental protection and the like.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (9)
1. [ H ]2Nmim][NTf2]@ UiO-66-Br nanocomposite, characterized in that said material comprises: bromine-functionalized UiO-66-Br and amino-functionalized imidazole ionic liquid [ H ] loaded on same2Nmim][NTf2]；
Said [ H ]2Nmim][NTf2]The preparation method of the @ UiO-66-Br nanocomposite comprises the following steps: 1-aminopropyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid [ H ]2Nmim][NTf2]Mixing with UiO-66-Br in water solution, stirring, centrifuging, collecting, and drying; said [ H ]2Nmim][NTf2]In @ UiO-66-Br nanocomposite [ H @2Nmim][NTf2]Is 5%, 10% or 15% by mass.
2. The nanocomposite of claim 1, wherein the UiO-66-Br specific surface area900-2The structure of the stable three-dimensional cavity and a unit containing pi-pi action and electrostatic action force.
3. The [ H ] of claim 1 or 22Nmim][NTf2]The application of the @ UiO-66-Br nano composite material in the detection and analysis of sulfonamide antibiotics in a water sample.
4. The use of claim 3, wherein the sulfa antibiotic in the aqueous sample comprises any one or more of sulfadiazine, sulfamethazine, sulfamethoxypyridazine, sulfalene, sulfamethoxazole, sulfamonomethoxine.
5. [ H ] according to claim 1 or 22Nmim][NTf2]The method for detecting and analyzing the sulfonamide antibiotics in the water sample by using the @ UiO-66-Br nanocomposite as the adsorbent is characterized by comprising the following steps of:
a pretreatment step;
(II) a chromatographic detection analysis step;
and (III) analyzing and quantifying sulfonamide antibiotics.
6. The method of claim 5, wherein the pre-processing step comprises the following:
1) subjecting said [ H ] to2Nmim][NTf2]The @ UiO-66-Br nano composite material is dispersed in a water sample and treated by ultrasound for 5-10min to form a uniform suspension;
2) after 5-10min of adsorption equilibrium, centrifuging for 5-10min to obtain the [ H ]2Nmim][NTf2]The @ UiO-66-Br nano composite material is soaked in 5-10mL of acidified methanol, and desorption is completed under the condition of ultrasonic treatment for 5-10 min;
3) after complete desorption, centrifuging at 8000-10000g for 5-10min, collecting eluate, and filtering with 0.22 μm organic filter head;
4) and (4) purging and concentrating the eluent obtained after filtration under the protection of nitrogen, and then using the eluent for HPLC sample injection analysis.
7. The method of claim 6, wherein the sulfa antibiotic in the aqueous sample comprises any one or more of sulfadiazine, sulfamethazine, sulfamethoxypyridazine, sulfalene, sulfamethoxazole, and sulfamonomethoxine.
8. The process according to claim 6, wherein the process has a recovery efficiency of 94-109% for sulfonamide antibiotics; the linear range is 0.05 to 100 mu g L-1。
9. The method of claim 6, wherein [ H ] is used2Nmim][NTf2]The time of absorbing and extracting equilibrium is 5-10min with @ UiO-66-Br adsorbent.
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