Laser-assisted electrospray ionization mass spectrometry ionization source device for detecting tetrabromobisphenol A and derivatives thereof and detection method of laser-assisted electrospray ionization mass spectrometry ionization source device

Abstract

The invention discloses a laser-assisted electrospray ionization mass spectrometry ionization source device for detecting tetrabromobisphenol A and derivatives thereof and a detection method of the laser-assisted electrospray ionization mass spectrometry ionization source device, and belongs to the technical field of mass spectrometry. The simple miniature laser probe is focused on the tip of the electrospray capillary tube, and laser and electrospray high voltage act on the solution to be measured at the same time, so that the ionization efficiency of the object to be measured is remarkably enhanced. Through reaction with silver ions, the established laser-assisted electrospray ionization mass spectrometry method can realize trace analysis of small-polarity and thermal-instability compounds tetrabromobisphenol A and derivatives thereof, and also has lower detection limit and higher sensitivity.

Description

Technical Field

[0001] The present invention belongs to the technical field of mass spectrometry analysis, and particularly relates to a laser-assisted electrospray ionization source device for detecting tetrabromobisphenol A and its derivatives and a detection method thereof. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and it is not necessarily regarded as an admission or an implication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] The ionization efficiency of mass spectrometry is a key factor affecting the sensitivity of mass spectrometry analysis. When analyzing some components with low volatility, poor thermal stability, and low polarity, existing commercial ionization sources often face the problem of difficult ionization. For example, the analysis of tetrabromobisphenol A diallyl ether (TBBPA-BAE), a derivative of tetrabromobisphenol A (TBBPA), which is a potential environmental persistent pollutant highly concerned in current environmental science, is often limited by ionization. Due to the low polarity of TBBPA-BAE molecules, conventional electrospray ionization (ESI) methods cannot achieve their ionization. In addition, as a new type of brominated flame retardant, TBBPA-BAE has poor thermal stability. When using ionization methods such as atmospheric pressure chemical ionization, electron impact ionization, or chemical ionization that require heating and vaporizing the components to be measured, high-energy bombardment and heating are likely to cause partial or complete dissociation of the molecules, thus significantly reducing the detection sensitivity. Except for silver ion reaction electrospray extraction ionization, common open-source ionization mass spectrometry, such as electrospray desorption ionization and direct analysis in real time ionization, cannot be used for the direct analysis of such components. However, the detection limit of TBBPA-BAE by silver ion reaction electrospray extraction ionization is 760 ng / L -1 , and it is still not suitable for analyzing low-content environmental samples.

[0004] Therefore, how to provide a detection method with simple method, low cost, and high sensitivity to achieve mass spectrometry analysis of trace TBBPA and TBBPA-BAE in environmental water samples is a technical problem that urgently needs to be solved. Summary of the Invention

[0005] To solve the deficiencies of the prior art, the objective of the present invention is to provide a laser-assisted electrospray ionization source device for detecting tetrabromobisphenol A and its derivatives and a detection method thereof, so as to solve the problem that existing ionization technologies are difficult to analyze TBBPA-BAE (low polarity, thermal instability). The device provided by the present invention combines laser with electrospray ionization, significantly enhancing the ionization efficiency of TBBPA and TBBPA-BAE. The method provided by the device is simple and has a low cost, can be used for mass spectrometry analysis of trace amounts of TBBPA and TBBPA-BAE in environmental water samples, can significantly improve the sensitivity of commercial electrospray ionization mass spectrometry analysis, and has good application prospects in environmental analysis.

[0006] The device of the present invention uses a low-cost and simple 450 nm, 500 mW micro laser probe to focus the laser on the electrospray nozzle. The laser and the electrospray high voltage act on the solution to be measured simultaneously, thereby significantly improving the ionization efficiency of the component to be measured. By reacting with silver ions, the established laser-assisted electrospray ionization mass spectrometry method can sensitively analyze the small-polarity, thermally unstable compound tetrabromobisphenol A diallyl ether (TBBPA-BAE). At the same time, this method can be directly applied to analyze tetrabromobisphenol A (TBBPA), with a low detection limit and high sensitivity. This method can analyze trace amounts of TBBPA and TBBPA-BAE in environmental samples and has good accuracy and practicability. The present invention provides an effective solution for analyzing difficult-to-ionize and thermally unstable components.

[0007] To achieve the above objective, the technical solution of the present invention is as follows:

[0008] In the first aspect, the present invention provides a laser-assisted electrospray ionization source device for detecting tetrabromobisphenol A and its derivatives, including a sample injection device, an electrospray device, a laser component, a support structure, and a mass spectrometry detection device;

[0009] The sample injection device is used to transport the solution to be measured;

[0010] The electrospray device includes a first pipeline for introducing the solution to be measured and a second pipeline for introducing gas. The first pipeline is connected to the injection needle in the sample injection device, and an electric high voltage is applied at the tip of the injection needle, so that the electrospray device forms charged droplets;

[0011] The laser component is arranged to focus the laser on the spray area of the electrospray device;

[0012] The support structure is used to adjust the relative position between the laser component and the electrospray device, so that the laser irradiation direction and the electrospray direction have a predetermined angle;

[0013] The mass spectrometry detection device is used to detect the ionized substance to be measured.

[0014] In one or more embodiments, the support structure is an ionization source platform, which has a three-dimensional adjustable function and can be used to fix the required electrospray device, laser assembly and mass spectrometry detection device.

[0015] Furthermore, the ionization source platform has an interface matching the mass spectrometry detection device, and interfaces for installing the electrospray device and the laser assembly.

[0016] Furthermore, the predetermined angle is 0 - 90°, and more preferably 90°. That is, the laser irradiation direction is perpendicular to the electrospray direction to obtain the best ionization effect.

[0017] In one or more embodiments, the sample introduction device includes an injection pump and a sample introduction needle, and the injection pump is connected to the sample introduction needle.

[0018] Furthermore, the volume of the sample introduction needle is 100 - 500 μL, preferably 250 μL.

[0019] Furthermore, the flow rate of the sample introduction needle is set to 1 - 3 μL / min -1 , preferably 1 - 2 μL / min -1 , more preferably 1 μL / min -1 .

[0020] In one or more embodiments, the first pipeline is a quartz capillary, and the second pipeline is a PEEK tube.

[0021] In one or more embodiments, the voltage of the high voltage electricity is ±(3 - 5) kV, preferably ±4 kV.

[0022] In one or more embodiments, the second pipeline is connected to a gas source, the gas source is nitrogen, and the flow rate of nitrogen is 300 - 700 mL / min -1 , preferably 400 - 500 mL / min -1 , preferably 400 mL / min -1 , to ensure the formation of a stable spray. The second pipeline in the electrospray device is connected to a nitrogen cylinder, and the sample in the quartz capillary is pneumatically atomized by high-flow nitrogen.

[0023] In one or more embodiments, the laser assembly includes a laser probe, and the power of the laser probe is 10 - 500 mW, preferably 400 - 500 mW, and more preferably 500 mW.

[0024] Furthermore, the laser wavelength is 450 - 650 nm, preferably 450 - 500 nm, and more preferably 450 nm.

[0025] In one or more embodiments, the distance between the laser probe and the nozzle of the electrospray device is 4 - 16 cm, preferably 8 - 12 cm, and more preferably 8 - 9 cm.

[0026] Furthermore, the distance between the nozzle of the electrospray device and the inlet of the mass spectrometry detection device is 4 - 16 mm, preferably 6 - 10 mm, and more preferably 6 - 8 mm.

[0027] In one or more embodiments, the mass spectrometry detection device uses a triple quadrupole mass spectrometer, an electrostatic field orbitrap mass spectrometer or a linear ion trap mass spectrometer (LTQ-XL), preferably a linear ion trap mass spectrometer. The mass spectrometry detection device uses collision-induced dissociation (CID) technology, and the collision gas is helium.

[0028] In one or more embodiments, the power supply voltage of the mass spectrometry detection device is set to ±(3 - 5) kV respectively in positive and negative ion modes, preferably ±4 kV; the temperature of the ion transfer tube is 250 - 300 °C, preferably 275 °C.

[0029] In a second aspect, the present invention provides the application of the above-mentioned laser-assisted electrospray mass spectrometry ionization source device for detecting tetrabromobisphenol A and its derivatives in the detection of tetrabromobisphenol A and its derivatives.

[0030] In a third aspect, the present invention provides a method for detecting trace tetrabromobisphenol A and its derivatives in environmental water samples, which uses the above-mentioned laser-assisted electrospray mass spectrometry ionization source device for detecting tetrabromobisphenol A and its derivatives, and includes the following steps:

[0031] (1) Solution preparation: Prepare a solution of the analyte.

[0032] (2) Sample introduction: Deliver the solution of the analyte to the electrospray device through an injection device.

[0033] (3) Ionization: While forming an electrospray in the electrospray device, use the laser assembly to irradiate the spray area so that the laser energy and the electrospray high voltage act on the analyte synergistically.

[0034] (4) Ion detection: Select the positive ion mode and / or negative ion mode for detection according to the properties of the analyte, and select the primary ions of the analyte for collision-induced dissociation to perform fragment ion detection.

[0035] (5) Signal analysis: Collect and analyze the mass spectrometry signals.

[0036] In one or more embodiments, in step (1), the analyte includes tetrabromobisphenol A and its derivatives.

[0037] Further, when the analyte is tetrabromobisphenol A, the analyte solution is prepared by dissolving tetrabromobisphenol A in an organic solvent - water mixed solution. The concentration of the analyte solution containing tetrabromobisphenol A is 0.01 - 10 μg / L -1 .

[0038] Further, when the analyte is a tetrabromobisphenol A derivative, the analyte solution is prepared as follows: First, dissolve silver nitrate in an organic solvent - water mixed solution to obtain a silver nitrate solution; dissolve the tetrabromobisphenol A derivative in an organic solvent - water mixed solution to obtain a mother liquor of the tetrabromobisphenol A derivative, and then dilute the mother liquor of the tetrabromobisphenol A derivative with the silver nitrate solution to obtain an analyte solution containing the tetrabromobisphenol A derivative. Among them, the concentration of the silver nitrate solution is 5 - 15 mg / L -1 , preferably 10 mg / L -1 . The concentration of the analyte solution containing the tetrabromobisphenol A derivative is 0.1 - 10 μg / L -1 .

[0039] Further, the organic solvent includes methanol or ethanol, preferably methanol. Methanol has a higher polarity than ethanol and a higher evaporation rate than ethanol, which is more conducive to improving the stability of the spray and can more effectively promote the ionization of the analyte. Therefore, methanol is more suitable than other organic solvents

[0040] For the organic solvent - water mixed solution used in preparing the above analyte solution, the volume ratio of the organic solvent to water is (6 - 10):(0 - 4), preferably (7 - 9):(1 - 3), and further preferably 8:2

[0041] In one or more embodiments, in step (4), when the analyte is a tetrabromobisphenol A derivative, the positive ion mode is selected. In the positive ion mode, [TBBPA - BAE + Ag] is detected + ; when the analyte is tetrabromobisphenol A, the negative ion mode is selected. In the negative ion mode, [TBBPA - H] is detected - .

[0042] The above technical solution has the following advantages or beneficial effects:

[0043] (1) The present invention provides a laser-assisted electrospray mass spectrometry ionization source device and its detection method for detecting tetrabromobisphenol A and its derivatives. This method focuses a simple micro laser probe on the tip of the electrospray capillary, and uses the laser and the electrospray high voltage to act on the analyte solution simultaneously, thereby significantly enhancing the ionization efficiency of the analyte

[0044] (2) In the positive ion mode, this method combines with the silver ion reaction to achieve sensitive analysis of TBBPA - BAE, with a detection limit reaching 14 ng / L -1 and a linear range of 0.1 - 10 μg / L-1 (R 2 = 0.9917), the relative standard deviations within day and between days were 2.5% (n = 7) and 6.2% (d = 5, n = 3). In the negative ion mode, this method can directly enhance the ionization efficiency of TBBPA, and the detection limit reaches 3.3 ng L -1 , and the linear range is 0.01 - 10 μg L -1 (R 2 = 0.9902), the relative standard deviations within day and between days were 4.7% (n = 7) and 7.3% (d = 5, n = 3).

[0045] (3) Compared with the conventional electrospray ionization technique, the analytical sensitivities of TBBPA and TBBPA - BAE are enhanced by 6.1 and 5.0 times respectively by the laser - assisted electrospray ionization technique. The structure of this device is simple and the cost is low, which is suitable for the ultrasensitive detection and trace analysis of TBBPA and TBBPA - BAE in environmental water samples. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The accompanying drawings forming a part of this invention are used to provide a further understanding of the invention. The schematic embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation to the invention.

[0047] Figure 1 FIG. is a diagram of the laser - assisted electrospray ionization source device for detecting tetrabromobisphenol A and its derivatives according to the present invention; wherein, 1, sampling device; 2, electrospray device; 3, laser assembly; 4, support structure; 5, mass spectrometry detection device;

[0048] Figure 2 FIG. shows the influence of the power and wavelength of the laser probe on the laser - assisted electrospray mass spectrometry;

[0049] Figure 3 FIG. shows the influence of the irradiation position of the laser probe on the laser - assisted electrospray mass spectrometry;

[0050] Figure 4 FIG. shows the influence of the distance between the laser probe and the electrospray nozzle on the laser - assisted electrospray mass spectrometry;

[0051] Figure 5 FIG. shows the influence of (A) sample flow rate, (B) nitrogen flow rate, (C) the ratio of methanol and water in the sample solvent, (D) the distance between the electrospray nozzle and the mass spectrometry inlet on the laser - assisted electrospray mass spectrometry;

[0052] Figure 6 FIG. is the standard curve diagrams obtained by detecting TBBPA and TBBPA - BAE based on laser - assisted electrospray ionization mass spectrometry (red) and electrospray ionization mass spectrometry (blue) respectively;

[0053] Figure 7 It is the selected ion chromatogram obtained by detecting TBBPA (0.1 μg / L -1 ) and TBBPA-BAE (1 μg / L -1 ) using laser-assisted electrospray ionization mass spectrometry (A) TBBPA (m / z 543) and TBBPA-BAE (m / z 731). Detailed implementation manners

[0054] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0055] Example 1:

[0056] Figure 1 It is a schematic diagram of the device for sensitive analysis of tetrabromobisphenol A and its derivatives by laser-assisted electrospray ionization mass spectrometry in the embodiment of the present invention, including:

[0057] 1 is a sampling device, including an injection pump and a sampling needle, and the volume of the sampling needle is 250 μL. The injection pump is used to uniformly transport the solution to be measured to the quartz capillary.

[0058] 2 is an electrospray device, including a first pipeline for introducing the solution to be measured and a second pipeline for introducing gas. The first pipeline is a quartz capillary, and the second pipeline is a PEEK tube. The quartz capillary and the PEEK tube are fixed by a PEEK screw. The PEEK tube is connected to a nitrogen cylinder, and the quartz capillary is connected to the sampling needle. An electric high voltage is applied at the tip of the sampling needle.

[0059] 3 is a laser assembly, configured to focus the laser on the spray area of the electrospray device; the laser assembly includes a laser probe.

[0060] 4 is a support structure, namely an ionization source platform. It is used to adjust the relative position between the laser assembly and the electrospray device so that the laser irradiation direction and the electrospray direction have a predetermined angle. The ionization source platform has an interface matching the mass spectrometry detection device and interfaces for installing the electrospray device and the laser assembly.

[0061] 5 is a mass spectrometry detection device, namely a mass spectrometer. It is used to detect the ionized substance to be measured. The mass spectrometry detection device uses a linear ion trap mass spectrometer (LTQ-XL, Thermo Fisher Scientific, USA).

[0062] Example 2:

[0063] The power and wavelength of the laser probe, the irradiation position of the laser probe, the distance between the laser probe and the electrospray nozzle, the sample flow rate, the nitrogen flow rate, the ratio of methanol and water in the sample solvent, and the distance from the electrospray nozzle to the mass spectrometry inlet all affect the ionization efficiency of laser-assisted electrospray. In this example, 0.1 μg L -1 of TBBPA and 1 μg L -1 of TBBPA-BAE standard solutions were selected for parameter optimization. The single-variable method was used to investigate the influence of different conditions on the ionization efficiency of the laser-assisted electrospray device. The specific process includes the following steps:

[0064] (1) Influence of the power and wavelength of the laser probe on laser-assisted electrospray mass spectrometry

[0065] First, the influence of laser probes with powers of 10, 50, 100, and 500 mW on the electrospray ionization efficiency at three wavelengths of 450, 520, and 650 nm was tested. As Figure 2 shown, the blue laser probe with a wavelength of 450 nm and a power of 500 mW achieved the highest ionization efficiency in the detection of both TBBPA and TBBPA-BAE. Although laser probes with powers exceeding 500 mW may provide greater ionization ability, higher laser powers also bring additional risks, such as an increased possibility of eye injury, increased equipment costs, and increased operational complexity. Therefore, a blue laser probe with 450 nm and 500 mW was selected for the experiment. (2) Influence of the irradiation position of the laser probe on laser-assisted electrospray mass spectrometry

[0066] The irradiation position of the laser probe is one of the key factors affecting the ionization efficiency. The laser irradiation positions are shown in Figure 3 BⅠ - BⅥ: laser off ( Figure 3 BⅠ), laser irradiating the electrospray nozzle ( Figure 3 BⅡ), the middle position between the electrospray nozzle and the mass spectrometry inlet ( Figure 3 BⅢ), the mass spectrometry inlet ( Figure 3 BⅣ), as well as the lower half of the spray ( Figure 3 BⅤ) and the upper half of the spray ( Figure 3 BⅥ). At the electrospray nozzle, the flying speed of the charged droplets is slower than that at other positions during the electrospray ionization process. When the laser beam irradiates the electrospray nozzle, the droplets can absorb more photons when passing through the laser beam. The laser probe is vertically fixed above the electrospray nozzle, and the laser beam is focused on the electrospray nozzle, forming a light spot with a diameter of 1 mm. Therefore, when the laser beam is irradiated on the electrospray nozzle, the highest ionization efficiency of both TBBPA and TBBPA-BAE is achieved.

[0067] (3) Influence of the distance between the laser probe and the electrospray nozzle on laser-assisted electrospray mass spectrometry

[0068] When the laser beam passes through the air, its intensity will decrease. Therefore, this experiment further explored the influence of the distance between the laser probe and the electrospray nozzle on laser-assisted electrospray mass spectrometry.

[0069] By adjusting the distance between the laser probe and the electrospray nozzle, it was found that when the laser probe was less than 90 mm away from the tip of the electrospray capillary, the intensity of the target ion signal gradually decreased ( Figure 4 ). The possible reason is that the laser is relatively close to the capillary nozzle, and the laser thermal effect is enhanced, resulting in the thermal decomposition of TBBPA and TBBPA-BAE. This result also indicates that using a laser probe with higher power will provide a stronger thermal effect, which may not be conducive to improving the ionization efficiency. When the laser probe is more than 90 mm away from the electrospray nozzle, the intensity of the target ion signal also gradually decreases, and the possible reason is the gradual attenuation of the laser energy. Therefore, the optimal condition is that the laser probe is 90 mm away from the electrospray nozzle.

[0070] (4) Influence of other relevant conditions of electrospray on laser-assisted electrospray mass spectrometry

[0071] For other key factors affecting the electrospray ionization efficiency, such as the sample flow rate, nitrogen flow rate, ratio of methanol and water in the sample solvent, and the distance from the tip of the electrospray capillary to the mass spectrometry inlet, the present invention optimized them (as Figure 5 shown in A-D). The results show that the optimal conditions are a sample flow rate of 1 μL min -1 , a nitrogen flow rate of 400 mL min -1 , a solvent composition of 80% methanol / 20% water, and a distance of 7 mm from the electrospray nozzle to the mass spectrometry inlet.

[0072] Under the above selected experimental conditions, by separately testing the sample blank, and standard solutions of TBBPA at concentrations of 0.01, 0.1, 1, 4, 7, 10 μg L -1 and TBBPA-BAE at concentrations of 0.1, 1, 4, 7, 10 μg L -1 , the analytical performance of the developed device and method was evaluated, and the results are shown in Table 1. Figure 6 It is the standard curve for analyzing TBBPA and TBBPA-BAE by laser-assisted electrospray mass spectrometry (red) and the standard curve for analyzing TBBPA and TBBPA-BAE and their derivatives by electrospray mass spectrometry (black). The results show that the sensitivity of laser-assisted electrospray mass spectrometry for analyzing TBBPA and TBBPA-BAE is 6.1 and 5 times higher than that of electrospray mass spectrometry, respectively.

[0073] Table 1 Analytical performance of laser-assisted electrospray mass spectrometry

[0074]

[0075]

[0076] Example 3

[0077] Analysis of TBBPA (0.1 μg L -1 ) and TBBPA-BAE (1 μg L -1 ) by laser-assisted electrospray ionization mass spectrometry. When the laser was turned on and off in a periodic manner, as Figure 7 shown in the selected ion chromatograms of TBBPA (m / z 543) and TBBPA-BAE (m / z 731), it was found that the signals of both target analytes increased and decreased rapidly, indicating that laser-assisted electrospray ionization could rapidly and significantly enhance the electrospray ionization efficiency, thus improving the sensitivity of mass spectrometry analysis.

[0078] Example 4

[0079] Using the apparatus of Example 1, the concentrations of TBBPA and TBBPA-BAE in a river water sample 1, a river water sample 2, and a wastewater treatment plant effluent sample 3 were detected respectively. The analysis results are shown in Table 2. TBBPA was detected in all river water and wastewater treatment plant effluent samples, with the concentration range of 0.010 ± 0.004 μg L -1 –0.11 ± 0.02 μg L -1 . TBBPA-BAE was detected in river water samples 1, 2, 4 and wastewater treatment plant effluent samples, with the concentration range of 0.091 ± 0.016–0.19 ± 0.01 μg L -1 . When TBBPA and TBBPA-BAE with a concentration of 0.5 μg L -1 were spiked into the samples, the recoveries obtained were 88.0–106.0%, indicating that this method was accurate and reliable for analysis and had practical application prospects.

[0080] Table 2. Contents and recoveries of TBBPA and TBBPA-BAE in actual samples detected by laser-assisted electrospray ionization mass spectrometry

[0081]

[0082]

[0083] a Mean ± standard deviation (n = 3); Samples 1-4 are river water sample 1, sample 5 is river water sample 2, and sample 6 is wastewater treatment plant effluent sample 3;

[0084] The present invention introduces a laser-assisted electrospray ionization mass spectrometry method, which combines a simple laser probe, silver ion reaction with electrospray, and significantly improves the electrospray ionization efficiency. This method has been successfully applied to the environmental detection of trace TBBPA and TBBPA-BAE in the effluent of sewage treatment plants and river water samples, and helps mass spectrometry analyze components that are difficult to ionize and thermally unstable.

[0085] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A laser-assisted electrospray mass spectrometry ionization source device for detecting tetrabromobisphenol A and its derivatives, characterized in that: It includes a sample injection device, an electrospray device, a laser assembly, a supporting structure and a mass spectrometer detection device; The sample injection device is used to transport the solution to be tested; The electrospray device comprises a first pipeline for introducing a solution to be tested and a second pipeline for introducing a gas, wherein the first pipeline is connected to an injection needle in the injection device, and a high voltage is applied to the needle tip of the injection needle, so that the electrospray device forms charged droplets; The laser assembly is configured to focus the laser on the spray area of ​​the electrospray device; The support structure is used to adjust the relative position between the laser assembly and the electrospray device so that the laser irradiation direction and the electrospray direction have a predetermined angle; The mass spectrometer detection device is used to detect the ionized object to be detected.

2. The device according to claim 1, characterized in that The supporting structure is an ionization source platform, which has an interface matching with a mass spectrometer detection device and an interface for installing an electrospray device and a laser component; Preferably, the predetermined angle is 0-90°, and more preferably 90°.

3. The device according to claim 1, characterized in that The injection device comprises a syringe pump and an injection needle, and the volume of the injection needle is 100-500 μL, preferably 250 μL; Preferably, the flow rate of the injection needle is set to 1-3 μL min -1 , preferably 1-2 μL min -1 , more preferably 1 μL min -1 .

4. The device according to claim 1, characterized in that The first pipeline is a quartz capillary tube, and the second pipeline is a PEEK tube; Preferably, the voltage of the high voltage is ±(3-5) kV, preferably ±4 kV; Preferably, the second pipeline is connected to a gas source, the gas source is nitrogen, and the flow rate of nitrogen is 300-700 mL min -1 , preferably 400-500mL min -1 , more preferably 400 mL min -1 .

5. The device according to claim 1, characterized in that The laser assembly includes a laser probe, the power of the laser probe is 10-500mW, preferably 400-500mW, and more preferably 500mW; Preferably, the laser wavelength is 450-650nm, preferably 450-500nm, and more preferably 450nm; Preferably, the distance between the laser probe and the nozzle of the electrospray device is 4-16 cm, preferably 8-12 cm, and more preferably 8-9 cm; Preferably, the distance between the nozzle of the electrospray device and the inlet of the mass spectrometry detection device is 4-16 mm, preferably 6-10 mm, and more preferably 6-8 mm.

6. The device according to claim 1, characterized in that The mass spectrometry detection device adopts a triple quadrupole mass spectrometer, an electrostatic field orbital trap mass spectrometer or a linear ion trap mass spectrometer, preferably a linear ion trap mass spectrometer; Preferably, the mass spectrometry detection device adopts collision induced dissociation technology, and the collision gas is helium; Preferably, the power supply voltage of the mass spectrometer detection device is set to ±(3-5) kV in the positive and negative ion modes, respectively, preferably ±4 kV; Preferably, the ion transfer tube temperature is 250-300°C, preferably 275°C.

7. Use of the laser-assisted electrospray mass spectrometry ionization source device for detecting tetrabromobisphenol A and its derivatives as claimed in any one of claims 1 to 6 in detecting tetrabromobisphenol A and its derivatives.

8. A method for detecting trace amounts of tetrabromobisphenol A and its derivatives in environmental water samples, using the laser-assisted electrospray mass spectrometry ionization source device for detecting tetrabromobisphenol A and its derivatives according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Solution preparation: Prepare the test solution; (2) Sample introduction: transporting the sample solution to the electrospray device through a sample injection device; (3) Ionization: While the electrospray device is forming the electrospray, a laser assembly is used to irradiate the spray area, so that the laser energy and the electrospray high voltage act synergistically on the analyte; (4) Ion detection: Select positive ion mode and / or negative ion mode for detection according to the properties of the analyte, and select the primary ions of the analyte for collision-induced dissociation and fragment ion detection; (5) Signal analysis: Collect and analyze mass spectrometry signals.

9. The detection method according to claim 8, characterized in that: In step (1), the analyte includes tetrabromobisphenol A and its derivatives; Preferably, when the analyte is tetrabromobisphenol A, the analyte solution is tetrabromobisphenol A dissolved in an organic solvent-water mixed solution; wherein the concentration of the analyte solution containing tetrabromobisphenol A is 0.01-10 μg L -1 ; Preferably, when the analyte is a tetrabromobisphenol A derivative, the analyte solution is prepared by first dissolving silver nitrate in an organic solvent-water mixed solution to obtain a silver nitrate solution; then dissolving the tetrabromobisphenol A derivative in an organic solvent-water mixed solution to obtain a tetrabromobisphenol A derivative mother liquor; and then diluting the tetrabromobisphenol A derivative mother liquor with a silver nitrate solution to obtain a analyte solution containing the tetrabromobisphenol A derivative; wherein the concentration of the silver nitrate solution is 5-15 mg L -1 , preferably 10 mg L -1 ; The concentration of the test solution containing tetrabromobisphenol A derivatives is 0.1-10 μg L -1 ; Preferably, the organic solvent comprises methanol or ethanol, wherein the volume ratio of the organic solvent to water in the organic solvent-water mixed solution is (6-10):(0-4), preferably (7-9):(1-3), and further preferably 8:

2.

10. The detection method according to claim 8, characterized in that: In step (4), when the analyte is a tetrabromobisphenol A derivative, a positive ion mode is selected; when the analyte is tetrabromobisphenol A, a negative ion mode is selected.

Images