CN115254063A - Gel adsorption film, gradient diffusion device and application in artificial sweetener sampling - Google Patents
Gel adsorption film, gradient diffusion device and application in artificial sweetener sampling Download PDFInfo
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Abstract
The application discloses gel adsorption film, gradient diffusion device and application in artificial sweetener sampling. The gel adsorption film is prepared by the following method: adding an adsorption resin filler into a polymerization reaction system of polyacrylamide gel to obtain a mixture system; the polymerization reaction system of the polyacrylamide gel comprises an acrylamide monomer, an initiator and a catalyst; after the mixture system is subjected to polymerization reaction, cooling and forming the system after the polymerization reaction to form a gel adsorption film; the adsorbent resin filler is at least one of HLB filler, PWAX filler and WAX filler. The gel adsorption film is filled in the gradient diffusion device, so that the artificial sweetener in the environment to be detected can be quantitatively enriched in situ, the time-weighted average concentration of the artificial sweetener in a sampling time period is provided, and the sampling result is more representative; and the measurement result of the concentration of the artificial sweetener in the environment to be measured does not need to be calibrated, so that the concentration of the artificial sweetener in the environment to be measured can be estimated more accurately.
Description
Technical Field
The application belongs to the technical field of environmental science, and in particular relates to a gel adsorption film, a gradient diffusion device and application of the gel adsorption film in sampling of artificial sweeteners.
Background
Artificial Sweeteners (ASs) are synthetic or semi-synthetic organic compounds that replace sucrose and are widely used in food, beverage, pharmaceutical, personal care products because they generally have a sweetness that is much higher than sucrose. The earliest synthesized ASs were Saccharin (SAC), and the sweeteners synthesized hereafter were cyclamate (CYC) and Aspartame (ASP), in that order, which were mixed with saccharin and referred to as first generation sweeteners; acesulfame potassium (ACE) and Sucralose (SUC) were synthesized in 1967 and 1976, respectively, and are known as a new generation sweetener due to their poor biodegradability. As a non-nutritional food additive, ASs are hardly metabolized in human bodies, namely, only a little calorie is generated in human bodies, with the increasing importance on the problems of obesity, diabetes and the like, the ASs are used as a substitute product of cane sugar, the types and the application of the ASs are rapidly developed, and Asia, particularly China, is the largest production and consumption market of the ASs. Because of the wide application of ASs and the characteristic that ASs do not participate in human metabolic reactions basically, reports of detecting ASs in domestic sewage treatment systems and natural water bodies are rare, which also causes certain concerns. On the one hand, some studies have indicated that ingestion of ASs may cause some harm to humans, for example, french has indicated that obesity, cancer and other diseases in experimental populations may be associated with long-term consumption of ASs-containing foods. On the other hand, ASs may affect the growth of small animals, plants and microorganisms in natural water, and further affect the regional ecosystem. Therefore, the concentration and the pollution level of the ASs in the domestic sewage system and the natural water body are monitored and researched, and data support can be provided for better understanding of the source, distribution, migration, transformation and ecotoxicity effects of the ASs in the water body.
At present, the method for sampling the ASs in the water body mainly comprises active grabbing sampling and passive sampling by using a polar organic compound integration sampling technology (POCIS). The active grabbing sampling can only provide the instantaneous concentration of the target substance at a specific sampling time, and cannot reflect the fluctuation of the pollutant concentration along with the time, and the instantaneous concentration is not representative. However, the POCIS sampler must be calibrated in the field due to the difference between the field conditions and the laboratory calibration, and hydrodynamic conditions, such as flow rate, temperature and turbulence, may affect the sampling rate, resulting in uncertainty in the estimation of the concentration of the target in the water. The DGT technology is an efficient passive sampling technology based on Fick's first diffusion law, can quantitatively enrich pollutants to be detected in situ, and determines the Time Weighted Average (TWA) concentration of an object to be detected which penetrates through diffusion glue with a certain thickness in a sampling time period, so that the defect of active sampling is overcome. In addition, the DGT technology quantifies the diffusion process of the target object in the diffusion glue, so that the DGT technology is insensitive to hydrologic condition change, and measurement errors caused by field hydrologic condition change are avoided.
At present, the DGT sampling technology applied to the detection technology of polar organic compounds in natural water is relatively lacked, and particularly the DGT sampling technology aiming at artificial sweeteners is still blank.
Disclosure of Invention
The application aims to overcome the defects of at least one aspect of the prior art, and provides a gel adsorption film, a gradient diffusion device and application in artificial sweetener sampling, so as to solve the technical problems that the sampling concentration of the existing ASs sampling method is not representative, and the estimation of the concentration of the ASs in a water body is inaccurate.
In order to achieve the above object, according to a first aspect of the present application, there is provided a gel-adsorption film, which is prepared by:
adding an adsorption resin filler into a polymerization reaction system of polyacrylamide gel to obtain a mixture system; the polymerization reaction system of the polyacrylamide gel comprises an acrylamide monomer, an initiator and a catalyst;
after the mixture system is subjected to polymerization reaction, cooling and forming the system after the polymerization reaction to form the gel adsorption film;
the adsorption resin filler is at least one of HLB (hydrophilic lipophilic balance resin) filler, PWAX (weak anion inverse resin) filler and WAX (mixed weak anion resin) filler.
Further, the adsorption resin filler is subjected to cleaning and activation treatment by methanol and ultrapure water.
Further, the initiator is ammonium persulfate; and/or the catalyst is tetramethylethylenediamine.
Further, the temperature of the polymerization reaction is 45-47 ℃, and the time of the polymerization reaction is 40-45 min.
The second aspect of this application provides a gradient diffusion equipment, including above-mentioned any gel adsorption film, diffusion barrier, protection film and encapsulation shell, the protection film the diffusion barrier with the gel adsorption film stacks gradually the setting and is in the encapsulation shell, the protection film sets up encapsulation shell's opening end one side.
Further, the diffusion membrane is an agar gel membrane.
Further, the protective film is a PTFE hydrophilic filter membrane.
The third aspect of this application provides a gel adsorption film in the application of artificial sweetener sampling, will gel adsorption film arranges in the environment that awaits measuring that contains artificial sweetener in, makes gel adsorption film adsorbs the artificial sweetener in the environment that awaits measuring.
The fourth aspect of this application provides an application of gradient diffusion equipment in the sampling of artificial sweetener, will gradient diffusion equipment arranges in the environment that awaits measuring that contains artificial sweetener, makes gradient diffusion equipment adsorbs the artificial sweetener in the environment that awaits measuring.
Compared with the prior art, the method has the following technical effects:
the application discloses a gel adsorption film has excellent adsorptivity to the artificial sweetener in the environment that awaits measuring, but the artificial sweetener in the high-efficient absorption environment that awaits measuring.
The gel adsorption film capable of efficiently adsorbing the artificial sweetener in the environment to be detected is filled in the gradient diffusion device, so that the artificial sweetener in the environment to be detected can be quantitatively enriched in situ, the time-weighted average concentration of the artificial sweetener in a sampling time period is provided, and the sampling result is more representative; and the measurement result of the concentration of the artificial sweetener in the environment to be measured does not need to be calibrated, so that the concentration of the artificial sweetener in the environment to be measured can be estimated more accurately.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings needed to be used in the detailed description of the present application or the prior art description will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a gradient diffusion apparatus according to an embodiment of the present disclosure;
FIG. 2 is a graph showing the relationship between the adsorption quality and the adsorption time of the WAX-DGT apparatus for ASs, provided in example 2 of the present application;
fig. 3 is a graph showing a relationship between adsorption quality and adsorption time of a WAX-DGT apparatus for quantitatively measuring ASs in a natural water body, which is provided in embodiment 3 of the present application.
In the figure, 1, a gel adsorption film, 2, a diffusion film, 3, a protection film, 4 and a packaging shell.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
Compared with the actively-adopted technology, the gradient diffusion thin film (DGT) technology can quantitatively enrich pollutants to be detected in situ, and the Time Weighted Average (TWA) concentration of the object to be detected which penetrates through the diffusion film with a certain thickness in a sampling time period is measured, so that the defect of active sampling is overcome. And DGT technology is insensitive to hydrodynamic conditions because the thickness of the diffusion membrane is typically thicker than the thickness of the Diffusion Boundary Layer (DBL), and does not require field calibration in a matrix-like solution. Concentration value (C) of object to be measured in water body DGT ) The calculation formula (1) is as follows:
(1)
in the formula (1), M is the amount (ng) of the substance to be detected accumulated in the gel adsorption film; t is the exposure time(s); d is the diffusion coefficient (cm) of the object to be measured in the diffusion film layer 2 S); a represents the sample area (cm) of DGT 2 ) (ii) a Δ g is the thickness (cm) of the diffusion film layer through which the substance to be detected passes before being absorbed by the binding phase; delta is the thickness (cm) of the DBL, when the water flow rate is sufficiently fast (>0.2 cm/s), δ is negligible.
In a first aspect, embodiments of the present application provide a gel adsorption film, which is prepared by the following method:
(1) Adding an adsorption resin filler into a polymerization reaction system of polyacrylamide gel to obtain a mixture system; the polymerization reaction system of the polyacrylamide gel comprises an acrylamide monomer, an initiator and a catalyst;
(2) And after the mixture system is subjected to polymerization reaction, cooling the system subjected to polymerization reaction to form the gel adsorption film.
In the step (1), the adsorbent resin filler is at least one of an HLB filler, a PWAX filler, and a WAX filler. In the embodiment of the application, through experimental tests: the adsorption rate of WAX filler to ASs is 75.2% -89.7%, the adsorption rate of HLB filler to ASs is 69.8% -82.4%, and the adsorption rate of PWAX filler to ASs is 40.2% -86.5%, compared with HLB filler and PWAX filler, WAX filler has better adsorption to Artificial Sweeteners (ASs) in the environment to be tested, and the specific embodiment of the application takes WAX filler to prepare gel adsorption film as an example for illustration. In order to improve the adsorption performance of the adsorption resin filler on the ASs, the adsorption resin filler in the embodiment of the application can be cleaned and activated by methanol and ultrapure water which are three times the volume of the adsorption resin filler before being used.
In the step (1), ammonium persulfate may be used as an initiator and tetramethylethylenediamine may be used as a catalyst in the polymerization reaction system of polyacrylamide gel. It should be noted that the kind of the initiator and the catalyst is not limited thereto, and all initiators and catalysts that can promote the polymerization reaction of the acrylamide monomer to form the polyacrylamide gel may be used in the polymerization reaction system. In the specific embodiment of the application, the polymerization reaction system of the polyacrylamide gel comprises 14-16% of acrylamide solution by volume fraction, 9-11% of ammonium persulfate solution by mass fraction and tetramethylethylenediamine by volume ratio of 1000 (5.5-6.5) to 1.4-1.6. The polymerization reaction system can initiate polymerization reaction at 45-47 deg.c for 40-45 min.
The gel adsorption film of this application embodiment has excellent adsorptivity to the artificial sweetener in the environment that awaits measuring, but the artificial sweetener in the high-efficient absorption environment that awaits measuring. The environment to be detected can be water environment, sediment, sludge or soil and other environments.
In a second aspect of the embodiments of the present application, a gradient diffusion device is provided, the structure is shown in fig. 1, and includes the above-mentioned gel adsorption film 1, diffusion film 2, protection film 3 and package shell 4, protection film 3, diffusion film 2 and gel adsorption film 1 are stacked in sequence and set in package shell 4, and protection film 3 is set on one side of the opening end of package shell 4, that is, on one side of water sample infiltration in the environment to be tested is allowed in contact with the environment to be tested.
The diffusion membrane 2 in the embodiment of the application can be selected as an agar gel membrane or a polyacrylamide gel membrane, and the adsorption rates of the agar gel membrane and the polyacrylamide gel membrane to ASs in the environment to be tested are both lower and are below 10%, so that the agar gel membrane and the polyacrylamide gel membrane can be used as diffusion membranes of gradient diffusion devices. The specific examples of the present application use agar gel membranes as diffusion membranes because of their ease of preparation. The agar gel film can be prepared by the following method:
adding agar with the mass ratio of 1.4-1.6% into ultrapure water, heating the solution at 83-87 ℃ and continuously stirring, and simultaneously placing a glass mold into an oven to be heated to 73-75 ℃. And when the agar is completely dissolved and no suspended particles are visible in the solution, injecting the solution into a glass mold. And naturally and vertically placing the mould, and obtaining the agar gel membrane after the solution is cooled to room temperature and condensed.
The protective film 3 of the embodiment of the present application may be selected from a PTFE hydrophilic filter film, i.e., a hydrophilic polytetrafluoroethylene filter film. The PTFE hydrophilic filter membrane has extremely low adsorption rate to ASs in the environment to be measured, the adsorption rate is 1.10% -7.49%, and the influence of the gradient diffusion device on the measurement and calculation of the concentration of the ASs in the environment to be measured can be reduced by taking the PTFE hydrophilic filter membrane as a protective membrane.
The packaging shell 4 of the embodiment of the application is made of polytetrafluoroethylene materials, and the adsorption rate of the packaging shell 4 to ASs in the environment to be tested is less than 5%.
The gel adsorption film 1 capable of efficiently adsorbing the artificial sweetener in the environment to be detected is filled in the gradient diffusion device, the diffusion film 2 and the protection film 3 which have lower adsorption rate on the ASs in the environment to be detected are used in a matched mode, the ASs in the environment to be detected can be quantitatively enriched in an in-situ mode, the time-weighted average concentration of the ASs in a sampling time period is provided, and a sampling result is more representative; and the measurement result of the concentration of the ASs in the environment to be measured does not need to be calibrated, and the concentration of the ASs in the environment to be measured is more accurately estimated.
The third aspect of the embodiment of this application provides an application of gel adsorption film in the sampling of artificial sweetener, will gel adsorption film arranges in the environment that awaits measuring that contains artificial sweetener in, makes gel adsorption film adsorbs the artificial sweetener in the environment that awaits measuring.
In a fourth aspect of the embodiments of the present application, an application of a gradient diffusion device in sampling of an artificial sweetener is provided, and the gradient diffusion device is placed in an environment to be tested containing the artificial sweetener, so that the gradient diffusion device adsorbs the artificial sweetener in the environment to be tested.
The gel adsorption film, the gradient diffusion device and the application thereof in sampling artificial sweeteners of the embodiments of the present application are illustrated by a plurality of specific examples.
Example 1
The application embodiment 1 provides a gel adsorption film, a gradient diffusion device and a preparation method of the gel adsorption film. The method specifically comprises the following steps:
(1) Preparation of agar gel membrane (diffusion membrane): agar in a mass proportion of 1.5% was added to ultrapure water, and the solution was heated at 90 ℃ with constant stirring, while the glass mold was placed in an oven and heated to 75 ℃. When the agar was completely dissolved and no suspended particles were visible in the solution, the solution was poured into a glass mold with a spacer of 0.8mm thickness. The mold was naturally placed upright, after the solution cooled to room temperature and coagulated, the glass mold was opened, the gel was cut into disks of 2.5cm in diameter to give agar gel membranes, which were stored in 0.01M NaCl solution at 4 ℃.
(2) Preparing a gel adsorption film: selecting an Oasis-WAX solid phase extraction cartridge with the grain diameter of 30-40 mu m, taking out WAX filler in the cartridge, filling the WAX filler into a hollow column with only a lower layer of spacer, and cleaning and activating the WAX filler by using methanol and ultrapure water with the volume of three times of the WAX filler at the flow rate of 1 mL/min. Taking the wet WAX filler, adding an acrylamide solution with the volume fraction of 15%, and uniformly mixing. Adding 10 mass percent of ammonium persulfate solution and tetramethylethylenediamine into the mixed solution. The volume ratio of the three solutions was 1000.5, using 2.6mL acrylamide solution per 1g of filler. The above solutions were mixed well and poured into a glass mold with a 0.25mm thick PTFE gasket. Horizontally placing the mould in an oven, heating for 45 minutes at 45-47 ℃, taking out the mould after the solution in the mould is solidified into a film, taking out the gel adsorption film, and soaking in a sodium chloride solution with the concentration of 0.01M. And replacing the solution soaked with the gel adsorption film once every 2 hours, and taking out the solution after the pH value of the solution is detected to be lower than 7.0 after 24 hours to obtain the WAX-polyacrylamide gel adsorption film.
(3) Assembly of gradient diffusion device (WAX-DGT device): the DGT housing base was placed horizontally on a table top and the WAX-gel adsorption membrane, agar gel membrane and PTFE hydrophilic filter membrane were laid flat on top of each other using clean forceps. And buckling a DGT shell cover to ensure that no air bubbles exist between the films, and finishing the assembly of the WAX-DGT device.
Example 2
Experimental tests are carried out on the deployment time of the WAX-DGT prepared in the embodiment 1 of the application, and the specific process is as follows:
the WAX-DGT device was exposed to a solution having an ASs concentration of 200 μ g/L (IS (ionic strength) =0.01m, ph =6 ± 0.2, t =22 ± 1 ℃,350 rpm), the container was covered with aluminum foil, and the WAX-DGT device was removed at 10, 20, 30, 40, and 50 hours. After the WAX-DGT device is taken out, the WAX-DGT shell is washed by ultrapure water, then the WAX-DGT is disassembled, a diffusion glue layer, namely an agar gel film layer, is peeled, the gel adsorption film is placed in a brown bottle, 5mL of methanol is used for extracting the gel adsorption film, ultrasonic treatment is carried out twice for 30min each time, the concentration of ASs in eluent is measured, the quantity of the ASs adsorbed by the gel adsorption film is calculated, the quantity of the ASs is substituted into a formula (1), the measured concentration of the WAX-DGT is obtained through calculation, and the measurement result is shown in figure 2.
From FIG. 2, see at C DGT That is, under the condition that the concentration of the target substance ASs in the solution is basically stable, the adsorption mass M of the target substance ASs on the gel adsorption film is in direct proportion to the adsorption time t. In the experiment, the adsorption quality and the adsorption time of the gel adsorption film on the ASs are increased linearly, and the theoretical calculation requirement is met.
Example 3
The WAX-DGT prepared by the gradient diffusion device in the embodiment 1 is applied to sampling of a field water sample environment, and the specific process is as follows:
selecting two natural water body sampling points, placing three groups of WAX-DGT devices on each sampling point, keeping the WAX-DGT devices at a position which is about 15cm below the water surface during placement, and placing the WAX-DGT devices with upward windows. Three sets of WAX-DGT devices were recovered 7 days, 14 days, and 21 days after standing, and the concentration of ASs was measured by eluting within 24 hours after each recovery, as shown in FIG. 3.
As can be seen from FIG. 3, the amount of ASs absorbed by the WAX-DGT unit into the natural water increases with time (correlation coefficient R) over a three-week period 2 Greater than 0.82) but the adsorption rate for the majority of the ASs in the third week sample decreased. The results show that the WAX-DGT device can quantitatively measure the ASs in the natural water body, but the standing time is not longer than two weeks.
The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these are all within the scope of protection of the present application. Therefore, the temperature of the molten metal is controlled, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The gel adsorption film is characterized by being prepared by the following method:
adding an adsorption resin filler into a polymerization reaction system of polyacrylamide gel to obtain a mixture system; the polymerization reaction system of the polyacrylamide gel comprises an acrylamide monomer, an initiator and a catalyst;
after the mixture system is subjected to polymerization reaction, cooling and forming the system after polymerization reaction to form the gel adsorption film;
the adsorption resin filler is at least one of HLB filler, PWAX filler and WAX filler.
2. The gel adsorbent film according to claim 1, wherein said adsorbent resin filler is washed and activated with methanol and ultrapure water.
3. The gel-adsorption film of claim 1, wherein the initiator is ammonium persulfate; and/or the catalyst is tetramethylethylenediamine.
4. A gel-adsorption film according to any one of claims 1 to 3, wherein the polymerization temperature is 45 to 47 ℃ and the polymerization time is 40 to 45min.
5. A gradient diffusion device, comprising the gel adsorption film, the diffusion film, the protection film and the package housing of any one of claims 1 to 4, wherein the protection film, the diffusion film and the gel adsorption film are sequentially stacked in the package housing, and the protection film is arranged on one side of an open end of the package housing.
6. A gradient diffusion device according to claim 5, wherein said diffusion membrane is an agar gel membrane.
7. The gradient diffusion device of claim 5, wherein the protective membrane is a PTFE hydrophilic filter membrane.
8. The use of a gel adsorbent film according to any one of claims 1 to 4 in sampling an artificial sweetener, wherein the gel adsorbent film is placed in an environment to be tested containing an artificial sweetener, such that the gel adsorbent film adsorbs the artificial sweetener in the environment to be tested.
9. Use of a gradient diffuser according to any one of claims 5 to 7 in sampling an artificial sweetener, wherein the gradient diffuser is placed in an environment to be tested containing the artificial sweetener such that the gradient diffuser adsorbs the artificial sweetener in the environment to be tested.
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| CN202211031202.3A CN115254063B (en) | 2022-08-26 | 2022-08-26 | Gel adsorption film, gradient diffusion device and application thereof in artificial sweetener sampling |
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| CN116251571A (en) * | 2023-03-29 | 2023-06-13 | 南京大学 | Method and device for measuring antiviral drugs |
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| CN105381781A (en) * | 2015-11-13 | 2016-03-09 | 南京大学 | Adsorption film mixing three metallic oxides and preparation method thereof and method for measuring fluorinion based on gradient diffusion thin film technology |
| CN108107123A (en) * | 2017-12-12 | 2018-06-01 | 江汉大学 | The method that liquid chromatogram-triple quadrupole rods tandem mass spectrometries detect 7 kinds of artificial sweetening agents in environment water simultaneously |
| CN111659358A (en) * | 2020-06-11 | 2020-09-15 | 南京大学 | DGT adsorption membrane, preparation method thereof and method for monitoring perfluoro and polyfluoro compounds based on DGT technology |
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| CN105381781A (en) * | 2015-11-13 | 2016-03-09 | 南京大学 | Adsorption film mixing three metallic oxides and preparation method thereof and method for measuring fluorinion based on gradient diffusion thin film technology |
| CN108107123A (en) * | 2017-12-12 | 2018-06-01 | 江汉大学 | The method that liquid chromatogram-triple quadrupole rods tandem mass spectrometries detect 7 kinds of artificial sweetening agents in environment water simultaneously |
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| CN116251571A (en) * | 2023-03-29 | 2023-06-13 | 南京大学 | Method and device for measuring antiviral drugs |
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