Photochemical atomization system applied to selenium form analysis

Abstract

The utility model discloses a photochemical atomization system applied to selenium form analysis, and belongs to the technical field of mass spectrometry. The device comprises an atomizing chamber and an atomizer, an ultraviolet light source is arranged on the outer side of the top of the atomizing chamber, and the ultraviolet light source is used for irradiating a selenium-containing aerosol sample in the atomizing chamber to perform photochemical reaction and atomize selenium in various forms. According to the photochemical atomization system applied to selenium form analysis, provided by the utility model, selenium in various forms in a mobile phase is subjected to photochemical reaction to form atomic selenium under the irradiation of ultraviolet light, so that the atomization efficiency of a sample in ICP (Inductively Coupled Plasma) is improved, and a detection signal is enhanced. The ultraviolet light source of the photochemical atomization system is arranged at the outer top of the atomization chamber, peak broadening caused by re-condensation of an atomized sample is avoided, the atomization efficiency of selenium in various forms in an ICP flame torch is improved, the signal strength of selenium in various forms is enhanced, the detection lower limit of selenium in various forms is reduced, the detection sensitivity is improved, and the detection cost is reduced. The requirement on an instrument for selenium form analysis is reduced.

Description

Technical Field

[0001] The utility model relates to the technical field of mass spectrometry analysis, in particular to a photochemical atomization system applied to selenium form analysis. Background Art

[0002] Selenium (Se) is an important trace element for human anti-aging and anti-cancer, but it is also toxic. Its toxicity and bioavailability depend not only on its content, but also on its existence form. Inorganic selenium has low absorption and utilization rate and low toxicity threshold, while organic selenium has high absorption and utilization rate and high toxicity threshold, and is the main source of safe intake of selenium. In order to prevent merchants from adding inorganic selenium salts to make selenium-rich foods in pursuit of selenium-rich gimmicks, selenium morphology analysis and detection technology is of great significance.

[0003] At present, the main technical means of selenium speciation analysis technology include gas chromatography-mass spectrometry (GC-MS), capillary electrophoresis chromatography-inductively coupled plasma-mass spectrometry (CEC-ICP-MS), capillary electrophoresis-atomic fluorescence spectrometry (CEC-AFS), and high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). Among them, HPLC-ICP-MS has attracted the attention of scientific researchers because it can detect the most types of selenium and has the best stability.

[0004] Due to the low selenium content in food, the existing HPLC-ICP-MS cannot fully meet the detection sensitivity requirements. Utility Model Content

[0005] The purpose of the utility model is to provide a photochemical atomization system for selenium form analysis, so as to solve the problem of how to improve the signal intensity and sensitivity of various forms of selenium in the existing selenium-rich food detection process, so as to meet the inspection and detection needs of selenium-rich food.

[0006] The technical solution of the utility model to solve the above technical problems is as follows:

[0007] The utility model provides a photochemical atomization system for selenium morphology analysis, comprising an atomization chamber and an atomizer, wherein the atomization chamber is used for photochemical reaction;

[0008] The nebulizer is arranged on the nebulization chamber, and is used to nebulize the liquid sample containing selenium in different forms that continuously flows out from HPLC to form a selenium-containing aerosol;

[0009] The atomization chamber is made of quartz and an ultraviolet light source is arranged on the outer side of the top. The ultraviolet light source is used to irradiate the selenium-containing aerosol sample in the atomization chamber to carry out a photochemical reaction and atomize various forms of selenium.

[0010] Furthermore, the ultraviolet light source is annular, matched with the outer top wall of the atomization chamber, and perpendicular to the outer top wall of the atomization chamber.

[0011] Furthermore, the ultraviolet light source is a vacuum ultraviolet lamp or a krypton lamp.

[0012] Furthermore, an aerosol sample inlet is provided on the side wall of the atomization chamber, and the aerosol sample inlet is used to continuously transport the selenium-containing aerosol in the atomizer into the atomization chamber.

[0013] Furthermore, a waste liquid discharge port is provided at the bottom of the atomization chamber, and the waste liquid discharge port is used to discharge the liquid re-condensed from the aerosol in the atomization chamber.

[0014] Furthermore, an atomized sample discharge port is provided at the top of the atomization chamber for discharging the atomized sample after the photochemical reaction in the atomization chamber.

[0015] Furthermore, the atomizer is provided with a liquid inlet, and the liquid inlet is used to continuously deliver liquid samples containing selenium in different forms separated according to different retention times in HPLC to the atomizer.

[0016] Furthermore, the nebulizer is provided with an aerosol outlet, the aerosol outlet is connected to an atomizing nozzle, the atomizing nozzle is located in the atomizing chamber and faces the tangent direction of the outer edge of the atomizing chamber, and the atomizing nozzle is used to continuously spray the selenium-containing aerosol sample into the atomizing chamber.

[0017] Furthermore, the atomizer is provided with a carrier gas inlet, and the carrier gas inlet is connected to a carrier gas supply device through a conduit to provide gas that does not participate in the reaction for the atomization process.

[0018] The utility model has the following beneficial effects:

[0019] The photochemical atomization system for selenium morphology analysis provided by the utility model is a core component in the HPLC-ICP-MS coupling technology. Its function is to atomize liquid samples of various forms of selenium separated by HPLC. Under ultraviolet light irradiation, various forms of selenium in the mobile phase undergo photochemical reactions to form atomic selenium, which improves the atomization efficiency of the sample in ICP, thereby enhancing the detection signal. The ultraviolet light source of the photochemical atomization system is placed on the outer top of the atomization chamber, avoiding the peak broadening caused by the re-condensation of the atomized sample, improving the atomization efficiency of various forms of selenium in the ICP torch, enhancing the signal intensity of various forms of selenium, reducing the detection limit of various forms of selenium, improving the detection sensitivity, and reducing the instrument requirements for selenium morphology analysis.

[0020] The photochemical atomization system for selenium form analysis provided by the utility model introduces ultraviolet light before ICP detection, so that atomization reaction occurs in advance and the detection signal is improved; the ultraviolet light source of the photochemical atomization system is placed on the outer top of the atomization chamber, which is different from the design of a built-in ultraviolet light source or a bottom ultraviolet light source. The ultraviolet light source is placed on the outer upper part of the atomizer. Due to the obstruction of fog, the liquid sample re-condensed in the lower part of the atomization chamber cannot be illuminated by the ultraviolet light emitted by the ultraviolet light source, thereby avoiding the memory effect caused by the fog re-condensing into liquid and being irradiated with ultraviolet light. The chromatogram shows that there is no peak broadening, which reduces chromatographic interference and is conducive to the separate detection of selenium in various forms. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The drawings described herein are used to provide a further understanding of the embodiments of the present utility model, constitute a part of this application, and do not constitute a limitation of the embodiments of the present utility model. In the drawings:

[0022] Figure 1 This is a schematic diagram of the structure of the photochemical atomization system used for selenium form analysis provided by the utility model;

[0023] Figure 2 A schematic diagram of the structure of the atomization chamber in the photochemical atomization system for selenium form analysis provided by the utility model;

[0024] Figure 3 A schematic diagram of the structure of an atomizer in a photochemical atomization system for selenium form analysis provided by the utility model;

[0025] Figure 4 The test and analysis results of the experimental examples and control examples provided by the utility model.

[0026] Marks and corresponding parts names in the attached drawings:

[0027] In the figure: 10-atomization chamber, 11-aerosol sample inlet, 12-waste liquid outlet, 13-atomized sample outlet, 20-atomizer, 21-liquid inlet, 22-aerosol outlet, 23-atomization nozzle, 24-carrier gas inlet, 30-ultraviolet light source. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solution and advantages of the embodiment of the utility model clearer, the technical solution in the embodiment of the utility model will be clearly and completely described below in conjunction with the drawings in the embodiment of the utility model. Obviously, the described embodiment is a part of the embodiment of the utility model, not all of the embodiments. Generally, the components of the embodiment of the utility model described and shown in the drawings here can be arranged and designed in various different configurations.

[0029] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the present invention to be protected, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example

[0031] Please refer to Figure 1 As shown, a photochemical atomization system 20 for selenium form analysis provided by an embodiment of the utility model comprises an atomization chamber 10 and an atomizer 20, wherein the atomization chamber 10 is used for photochemical reaction;

[0032] The nebulizer 20 is disposed on the nebulization chamber 10, and is used to nebulize the liquid sample containing selenium in different forms that continuously flows out from the HPLC to form a selenium-containing aerosol;

[0033] The atomizing chamber 10 is made of quartz and an ultraviolet light source 30 is arranged on the outer side of the top. The ultraviolet light source 30 is used to irradiate the aerosol sample containing selenium in the atomizing chamber 10 to perform a photochemical reaction and atomize various forms of selenium.

[0034] The photochemical atomization system for selenium morphology analysis provided by the utility model is a core component in the HPLC-ICP-MS coupling technology. Its function is to atomize liquid samples of various forms of selenium separated by HPLC. Under ultraviolet light irradiation, various forms of selenium in the mobile phase undergo photochemical reactions to form atomic selenium, which improves the atomization efficiency of the sample in ICP, thereby enhancing the detection signal. The ultraviolet light source 30 of the photochemical atomization system is placed on the outer top of the atomization chamber 10, avoiding the peak broadening caused by the re-condensation of the atomized sample, improving the atomization efficiency of various forms of selenium in the ICP torch, enhancing the signal strength of various forms of selenium, reducing the detection limit of various forms of selenium, improving the detection sensitivity, and reducing the instrument requirements for selenium morphology analysis.

[0035] The photochemical atomization system for selenium form analysis provided by the utility model introduces ultraviolet light before ICP detection, so that atomization reaction occurs in advance and the detection signal is improved. The ultraviolet light source 30 of the photochemical atomization system is placed on the outer top of the atomization chamber 10. Different from the design of built-in ultraviolet light source 30 or bottom ultraviolet light source 30, the ultraviolet light source 30 is placed on the outer upper part of the atomizer 20. Due to the obstruction of fog, the liquid sample re-condensed in the lower part of the atomization chamber 10 cannot be illuminated by the ultraviolet light emitted by the ultraviolet light source 30, thereby avoiding the memory effect caused by the fog re-condensing into liquid and being irradiated with ultraviolet light. The chromatogram shows that there is no peak broadening, which reduces chromatographic interference and is conducive to the separate detection of selenium in various forms.

[0036] The liquid chromatography successively separates the samples of selenium in different forms, which are atomized by the nebulizer 20 to form aerosol, and then undergo photochemical reaction with ultraviolet light in the nebulizer 20 to make the various forms of selenium successively undergo photochemical reaction to form atomic state, and then enter into the ICP-MS for detection; in this process, the liquid sample containing selenium in different forms is prevented from being excited by ultraviolet light due to the re-condensation of aerosol at the bottom of the nebulizer 20, thereby maintaining the separation degree of HPLC and enhancing the sensitivity of ICP-MS analysis.

[0037] The liquid separated by the liquid chromatograph generally includes the separated sample and the mobile phase. The atomized sample output after being processed by the photochemical atomization system provided in this embodiment enters the ICP-MS instrument for mass spectrometry analysis. Figure 1-3 As shown, in some feasible embodiments, the ultraviolet light source 30 is annular, the ultraviolet light source 30 is matched with the outer top wall of the atomization chamber 10 , and the ultraviolet light source 30 is perpendicular to the outer top wall of the atomization chamber 10 .

[0038] In some feasible embodiments, the ultraviolet light source 30 is a vacuum ultraviolet lamp or a krypton lamp.

[0039] In some feasible embodiments, an aerosol sample inlet 11 is disposed on the side wall of the atomization chamber 10 , and the aerosol sample inlet 11 is used to continuously deliver the selenium-containing aerosol in the atomizer 20 into the atomization chamber 10 .

[0040] In some feasible embodiments, a waste liquid outlet 12 is provided at the bottom of the atomizing chamber 10, and the waste liquid outlet 12 is used to discharge the liquid re-condensed from the aerosol in the atomizing chamber 10. Specifically, the waste liquid outlet 12 is connected to a waste liquid tank.

[0041] In some feasible embodiments, an atomized sample outlet 13 is provided at the top of the atomization chamber 10, for discharging the atomized sample after the photochemical reaction in the atomization chamber 10. Specifically, the atomized sample outlet 13 is connected to the ICP-MS. In some feasible embodiments, the atomizer 20 is provided with a liquid inlet 21, and the liquid inlet 21 is used to continuously deliver the liquid sample containing different forms of selenium separated by different retention times in HPLC to the atomizer 20.

[0042] In some feasible embodiments, the nebulizer 20 is provided with an aerosol outlet 22, and the aerosol outlet 22 is connected to an atomizing nozzle 23. The atomizing nozzle 23 is located in the atomizing chamber 10 and faces the tangential direction outside the atomizing chamber 10. The atomizing nozzle 23 is used to continuously spray the selenium-containing aerosol sample into the atomizing chamber 10.

[0043] In some feasible embodiments, the atomizer 20 is provided with a carrier gas inlet 24 , and the carrier gas inlet 24 is connected to a carrier gas supply device through a conduit to provide a gas that does not participate in the reaction for the atomization process.

[0044] Experimental example

[0045] This experimental example provides a HPLC-photochemical atomization system-ICP / MS combined technology to simultaneously determine six selenium forms in selenium-rich salts with high sensitivity and accuracy. The experimental conditions are as follows:

[0046] Sample treatment: Weigh a quantitative sample (1g-2g), add 20mg of pepsin, add 15-20mL of hydrochloric acid solution with a pH of 1.5, incubate at a constant temperature of 40℃ for 2h, take the supernatant after centrifugation and filter it through a 0.2um filter membrane for analysis and testing.

[0047] Chromatographic conditions: Hamilton PRP-X100 (10 μm, 4.1×250 mm) column, 25 mM citric acid-2% methanol (pH=4.0) as mobile phase A, 25 mM citric acid-10% methanol (pH=4.0) as mobile phase B, at 1 mL min -1 Gradient elution at a flow rate of .

[0048] ICP-MS conditions: 80 Se 16 O was detected as a quantitative isotope.

[0049] The experimental example is to start the photochemical atomization system provided in this embodiment, and the control example is not to start the photochemical atomization system provided in this embodiment. The analysis results are shown in Figure 4 shown.

[0050] This experiment is suitable for the analysis and determination of various selenium forms in selenium-rich salts. The detection limits of each form are: selenocystine 0.02ng mL -1 ,Se(Ⅳ)0.02ng mL -1 , methylselenocysteine ​​0.03ng mL -1 ,Se(VI)0.04ng mL -1 , selenomethionine 0.05ng mL -1 , selenoethionine 0.15ng mL -1 The sample spike recovery rate was 99.15-105.0%, and the relative standard deviation of multiple measurements was less than 5%.

[0051] The specific implementation methods described above further illustrate the purpose, technical solutions and beneficial effects of the utility model in detail. It should be understood that the above description is only the specific implementation method of the utility model and is not used to limit the protection scope of the utility model. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the utility model should be included in the protection scope of the utility model.

Claims

1. A photochemical atomization system for selenium speciation analysis, characterized in that: include: A spray chamber, an atomizer and an ultraviolet light source, wherein the spray chamber is used for photochemical reaction; The nebulizer is arranged on the nebulization chamber, and is used to nebulize the liquid sample containing selenium in different forms that continuously flows out from HPLC to form a selenium-containing aerosol; The atomization chamber is made of quartz and an ultraviolet light source is arranged on the outer side of the top. The ultraviolet light source is used to irradiate the selenium-containing aerosol sample in the atomization chamber to carry out a photochemical reaction and atomize various forms of selenium.

2. A photochemical atomization system for selenium speciation analysis according to claim 1, characterized in that: The ultraviolet light source is annular, matched with the outer top wall of the atomization chamber, and perpendicular to the outer top wall of the atomization chamber.

3. The photochemical atomization system for selenium form analysis according to claim 1, characterized in that: The ultraviolet light source is a vacuum ultraviolet lamp or a krypton lamp.

4. The photochemical atomization system for selenium form analysis according to claim 1, characterized in that: The side wall of the atomization chamber is provided with an aerosol sample inlet, and the aerosol sample inlet is used to continuously transport the selenium-containing aerosol in the atomizer into the atomization chamber.

5. The photochemical atomization system for selenium form analysis according to claim 4, characterized in that: A waste liquid discharge port is arranged at the bottom of the atomization chamber, and the waste liquid discharge port is used to discharge the liquid re-condensed from the aerosol in the atomization chamber.

6. The photochemical atomization system for selenium form analysis according to claim 4, characterized in that: An atomized sample discharge port is arranged on the top of the atomization chamber, which is used to discharge the atomized sample after the photochemical reaction in the atomization chamber.

7. The photochemical atomization system for selenium form analysis according to claim 4, characterized in that: The atomizer is provided with a liquid inlet, and the liquid inlet is used to continuously deliver liquid samples containing selenium in different forms separated according to different retention times in HPLC to the atomizer.

8. The photochemical atomization system for selenium speciation analysis according to claim 4, characterized in that: The atomizer is provided with an aerosol outlet, and the aerosol outlet is connected to an atomizing nozzle. The atomizing nozzle is located in the atomizing chamber and faces the tangent direction of the outer edge of the atomizing chamber. The atomizing nozzle is used to continuously spray the selenium-containing aerosol sample into the atomizing chamber.

9. The photochemical atomization system for selenium speciation analysis according to claim 4, characterized in that: The atomizer is provided with a carrier gas inlet, and the carrier gas inlet is connected to a carrier gas supply device through a conduit to provide gas that does not participate in the reaction for the atomization process.

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