CN113237944B - Membrane enrichment spray ionization device and method for real-time mass spectrometry analysis of organic amine in seawater - Google Patents
Membrane enrichment spray ionization device and method for real-time mass spectrometry analysis of organic amine in seawater Download PDFInfo
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Abstract
The invention relates to a film enrichment spray ionization device and method for realizing real-time mass spectrometry analysis of organic amine in seawater. Comprises a sample enriching and desorbing device and an electrospray ionization source. After a large-volume seawater sample flows through the tubular membrane, trace organic amine in seawater is adsorbed on the inner surface of the tubular membrane, a micro-volume solvent is injected into the tubular membrane, the organic amine adsorbed on the surface of the tubular membrane is eluted into the solvent by utilizing ultrasound, salt interference in the seawater is effectively removed in the adsorption and elution processes of the organic amine on the inner surface of the tubular membrane, and enrichment is realized. A plurality of polydimethylsiloxane tubular membranes are arranged in parallel; the spray ionization device is an electrospray ionization device or a paper spray ionization device, and the polydimethylsiloxane tubular film is connected with the spray ionization device. The device and the method realize online enrichment and electrospray rapid analysis of the trace organic amine in the seawater, and improve the analysis flux of an instrument.
Description
Technical Field
The invention belongs to the technical field of on-line continuous mass spectrometry, and particularly relates to a membrane enrichment spray ionization device and method for real-time mass spectrometry of organic amine in seawater.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Organic amine in the atmosphere is a main participant in the formation process of the aerosol, wherein trimethylamine and dimethylamine are used as common components of organic amine in the atmosphere, and have important influence on the nucleation and growth of aerosol particles. Ocean is the widest water body on earth and is the main source of two organic amines. Although organic amines are important nitrogen sources and can provide energy sources for marine organisms, too high a concentration of organic amines can affect the transcription of marine organism genetic materials and destroy the balance and stability of a marine organism circle. At present, the method for detecting organic amine in seawater at home and abroad is mainly gas chromatography or liquid chromatography, and the pretreatment such as filtration, impurity removal, headspace balance and the like needs to be carried out on a sample. Although the method has high analysis precision, the pretreatment steps are complicated, the cost is high, the rapid online analysis of a large amount of samples is difficult to realize, and the evaluation of the dynamic discharge amount of organic amine in the interface of seawater and sea and air is difficult to realize.
The mass spectrum, as a new method recognized by the existing qualitative analysis, has the advantages of high analysis speed, high resolution and sensitivity, strong qualitative ability and the like. Soft ionization techniques such as electrospray ionization, atmospheric pressure chemical ionization, vacuum ultraviolet photoionization, and the like are suitable for the rapid and efficient ionization of organic compounds. However, the high vacuum environment of mass spectrometry makes direct measurement of liquid samples impossible, and detection is usually performed after pretreatment by methods such as dynamic headspace, heating purge, gas-assisted desolvation, and the like. In addition, most of the methods can only realize the detection of fully substituted tertiary amine such as trimethylamine and the like, and can not detect organic amine containing H. Direct electrospray ionization is difficult to directly perform spray ionization analysis due to the salt effect in seawater.
In the existing literature, the separation of organic matters in water is carried out by liquid chromatography, the organic matters in water are conveyed to an extraction device according to separation time and then are changed into gas by two methods of spraying or gasification, and finally, a gas sample is conveyed to a mass spectrum for detection. However, in the invention, organic matters need to be gasified when being detected, and the proton affinities of different organic matters are different, so that a large amount of reagent ions such as H need to be introduced simultaneously 3 O + 、NH 4 + 、NO + 、O 2 + 、C 3 H 7 O + And the like, when the mass spectrum is analyzed continuously, the sample signal has serious attenuation effect in long-time analysis.
In the prior art, a dynamic purging bubbling device is proposed to convert volatile organic compounds in a liquid sample into a gaseous sample by a bubbling method, and the gaseous sample enters an atmospheric pressure photoionization source under the purging of a carrier gas. The atmospheric pressure photoionization source divides the ionization source into a reagent ion region and a sample region through an electrode with smaller inner diameter, reduces the loss of photons in the ion molecular region and improves the ionization efficiency. However, when detecting organic amine, the invention can only detect fully substituted tertiary amine such as trimethylamine, and can not detect organic amine containing H, for example, methylamine, dimethylamine, and the like can not be analyzed.
In the prior art, a solid phase extraction column is used for extracting a target substance, and then an eluent is used for collecting a sample. And drawing a standard curve of the target compound through ion chromatography, preprocessing a sample, finding out a corresponding target peak by combining a standard spectrogram, and calculating the concentration of the target compound according to the standard curve. However, the sample pretreatment of the technology needs a lot of time for detecting organic amine, and the sample pretreatment has high requirements on an extraction column and an elution solvent, so that online rapid analysis of a large number of samples cannot be performed, and the real-time organic amine emission flux cannot be evaluated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a film enrichment spray ionization device and a method for the real-time mass spectrometry of organic amine in seawater. The sample enrichment desorption device and the electrospray ionization source are utilized to realize the rapid and high-sensitivity detection of the organic amine in the liquid without sample pretreatment.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, a membrane enrichment spray ionization device for real-time mass spectrometry analysis of organic amine in seawater comprises,
the sample enrichment and desorption device comprises a plurality of polydimethylsiloxane tubular membranes, and the polydimethylsiloxane tubular membranes are arranged in parallel;
the spray ionization device is an electrospray ionization device or a paper spray ionization device, and the polydimethylsiloxane tubular film is connected with the spray ionization device.
The polydimethylsiloxane tubular membrane realizes the online treatment function, does not need complex pretreatment, and can be directly desalted after being enriched and desorbed by solvent extraction; meanwhile, the multi-path parallel enrichment device improves the flux of membrane enrichment, further improves the flux of on-line analysis, and can carry out rapid detection on multiple samples. And the spray ionization device realizes organic amine ionization, and ions enter a mass spectrum system for detection and analysis.
After a large-volume liquid sample flows through the tubular membrane, trace organic amine in seawater is adsorbed on the inner surface of the tubular membrane, a certain small-volume organic solvent is injected into the tubular membrane, the organic amine adsorbed on the tubular membrane is eluted into the solvent from the membrane surface by utilizing ultrasound, and the salt interference in the seawater is effectively removed in the adsorption and elution processes of the organic amine on the inner surface of the tubular membrane, so that the enrichment is realized. And (3) carrying out mass spectrometry on the organic amine subjected to enrichment extraction by adopting quartz capillary and high-voltage direct current spray ionization.
The rapid on-line enrichment analysis of the trace organic amine in the seawater is solved.
In a second aspect, the method for performing real-time mass spectrometry of organic amine by using the device comprises the following specific steps:
the liquid sample is adsorbed and enriched by a polydimethylsiloxane tubular membrane;
introducing an extractant into the polydimethylsiloxane tubular membrane enriched with organic amine to extract and desorb the organic amine;
the mixture after extraction is subjected to electrophoresis, solvent evaporation and liquid drop contraction under high pressure, the contracted liquid drops form charged liquid drops, the charged liquid drops form gas-phase ions, and the gas-phase ions enter a mass spectrum system.
The polydimethylsiloxane tubular membrane selectively adsorbs and enriches organic amine, then the organic amine enters an extracting agent, and the organic amine is subjected to spray ionization through separation from a solvent.
One or more technical schemes of the invention have the following beneficial effects:
according to the sample enrichment and desorption device provided by the invention, the polydimethylsiloxane tubular membrane is adopted for adsorption enrichment of organic amine, so that the organic amine can be selectively adsorbed, and substances such as inorganic salt and the like in the sample can not be adsorbed. Organic amine in the tubular membrane is extracted and then enters an electric spray ionization source, and the organic amine is ionized under high voltage and then enters mass spectrum detection. The designed electrospray ionization source is a soft ionization source, ionization is carried out under atmospheric pressure, and the vacuum requirement of a mass spectrum ionization region is reduced, so that the rapid and high-sensitivity detection of organic amine in seawater is realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a structural diagram of a membrane enrichment spray ionization device for real-time mass spectrometry analysis of organic amine in seawater;
FIG. 2 is a real-time mass spectrum of a sample in seawater, wherein a is a real-time mass spectrum of dimethylamine in a liquid, and b is a real-time mass spectrum of trimethylamine in a liquid;
wherein, 1, a sample enrichment and desorption device; 2. a spray ionization device; 3. a water pump; 4. ultrapure water; 5. a four-way valve; 6. a sampling pump; 7. a conical flask; 8. a liquid sample; 9. a microsyringe; 10. an extractant; 11. a polydimethylsiloxane tubular membrane; 12. an ultrasonic vibration motor; 13. a three-way valve; 14. a wastewater tank; 15. a pipeline; 16. a high voltage power supply; 17. a platinum wire; 18. a quartz capillary tube; 19. a metal capillary tube; 20. a mass spectrometry system; 21. fixing the disc; a Skimmer microwell.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, a membrane enrichment spray ionization device for real-time mass spectrometry analysis of organic amine in seawater comprises,
the sample enrichment and desorption device comprises a plurality of polydimethylsiloxane tubular membranes, and the polydimethylsiloxane tubular membranes are arranged in parallel;
the spray ionization device is an electrospray ionization device or a paper spray ionization device, and the polydimethylsiloxane tubular membrane is connected with the spray ionization device.
In some embodiments of the present invention, the electrospray ionization device includes a high voltage power supply, a first capillary, and a second capillary, wherein the polydimethylsiloxane tubular membrane is connected to the first capillary, the high voltage power supply is connected to a wire, the wire is fitted to extend into the inner side of the first capillary, and an outlet of the first capillary is disposed opposite to an inlet of the second capillary.
In the invention, the first capillary is used for electrospray ionization, and the ionized organic amine ions enter the mass spectrum through the second capillary vacuum differential system for mass-to-charge ratio separation.
In some embodiments of the invention, the first capillary and the second capillary are horizontally arranged, the outlet of the first capillary and the inlet of the second capillary are arranged at a distance, and the outlet end of the first capillary is a tip.
In some embodiments of the present invention, the sample enrichment and desorption apparatus further comprises a vibrating rod on which the polydimethylsiloxane tubular membrane is wound. Further, the vibrating rod is an ultrasonic vibration motor vibrating rod.
In some embodiments of the invention, the polydimethylsiloxane tubular membranes are arranged in a plurality of, side-by-side arrangements.
In some embodiments of the present invention, the sample enrichment and desorption device further comprises a sample injection device, and the sample injection device is connected with the polydimethylsiloxane tubular membrane. Furthermore, the sample injection device comprises a sample injection device, an extractant injection device and a water injection device which are respectively connected with the polydimethylsiloxane tubular membrane.
In some embodiments of the invention, the sample enrichment and desorption device further comprises a waste water device, and the polydimethylsiloxane tubular membrane outlet is connected with the waste water device.
In some embodiments of the invention, the second capillary is connected to a power source.
In some embodiments of the present invention, the first capillary and the second capillary are spaced apart by 10-15mm, the first capillary tip has an inner diameter of 5-10 μm, and the wire is spaced apart from the first capillary tip by 7-10 mm.
In some embodiments of the invention, the second capillary is spaced from the Skimmer microwells by 3 to 5 mm.
In some embodiments of the present invention, the first capillary is made of a non-metal material and is quartz or glass.
In some embodiments of the present invention, the second capillary is made of metal, such as stainless steel or copper.
In some embodiments of the present invention, the spray ionization device further comprises a skimmer micropore, the outlet of the second capillary is opposite to the skimmer micropore, the skimmer micropore is connected with a power supply, and the voltage of the power supply connected with the skimmer micropore is less than that of the second capillary.
In some embodiments of the invention, the spray ionization device further comprises a fixed disk, the fixed disk being fixedly connected with the second capillary.
In some embodiments of the invention, the spray ionization device further comprises a mass spectrometry system, and the outlet of the ski lmer microwell is connected to the mass spectrometry system.
In a second aspect, the method for performing real-time mass spectrometry of organic amine by using the device comprises the following specific steps:
the liquid sample is adsorbed and enriched by a polydimethylsiloxane tubular membrane;
introducing an extractant into the polydimethylsiloxane tubular membrane enriched with organic amine to extract the organic amine;
the mixture after extraction is subjected to electrophoresis, solvent evaporation and liquid drop contraction under high pressure, the contracted liquid drops form charged liquid drops, the charged liquid drops form gas-phase ions, and the gas-phase ions enter a mass spectrum system.
In one embodiment, the extractant is a methanol-water mixed solvent, and specifically, the volume ratio of methanol to water is 1: 1.
In one embodiment, the liquid sample may be domestic sewage, laboratory wastewater, chemical industry wastewater, river water, sea water, etc. after particulate matter filtration has been performed.
In one embodiment, the ultrasonic vibration time of the ultrasonic motor is 5-10 mins.
The invention relates to a membrane enrichment and spray ionization device for real-time continuous mass spectrometry analysis of organic amine in seawater, which comprises a sample enrichment and desorption device 1, a plurality of sample enrichment and desorption devices and a plurality of sample enrichment and desorption devices, wherein the sample enrichment and desorption devices comprise polydimethylsiloxane tubular membranes; the spray ionization device 2 is an electrospray ionization device or a paper spray ionization device, and the polydimethylsiloxane tubular membrane 11 is connected with the spray ionization device 2.
The method is used for analyzing and detecting trace organic amine in liquid samples such as seawater and the like. The method solves the problem of rapid online analysis of mass samples and the problem of evaluation of dynamic discharge of organic amine in seawater and sea-air interfaces. Can detect dimethylamine and trimethylamine in seawater.
The polydimethylsiloxane tubular membrane realizes the online treatment function, can be desalted without complex pretreatment, and can be directly detected after enrichment and extraction ionization; meanwhile, the multi-path parallel enrichment device improves the flux of membrane enrichment, further improves the flux of on-line analysis, and can carry out rapid detection on multiple samples. And then the ion sample is fed into a mass spectrum system through an electrospray ionization device or a paper spray ionization device.
The sample enrichment and desorption device comprises a polydimethylsiloxane tubular membrane, and the polydimethylsiloxane tubular membrane with larger transmission coefficient and diffusion coefficient is adopted for adsorption enrichment of organic amine, so that the organic amine can be selectively adsorbed, and inorganic salts and other substances in the sample cannot be adsorbed.
The enriched material is mixed with the extractant, separated from the polydimethylsiloxane tubular membrane and enters an electrospray ionization device.
The electrospray ionization device comprises a high-voltage power supply, a first capillary and a second capillary, wherein a sample is adsorbed and separated through a polydimethylsiloxane tubular membrane, the polydimethylsiloxane tubular membrane is connected with the first capillary, the first capillary and the second capillary are horizontally arranged, and an outlet of the first capillary is opposite to an inlet of the second capillary and is provided with a distance.
Organic amine and an extracting agent are mixed and then enter a first capillary, the organic amine is subjected to electrophoresis under high pressure in the first capillary, then the mixture is sprayed at the tip of the first capillary, a solvent is evaporated, liquid drops shrink, coulomb explosion is generated to generate smaller charged liquid drops, and the circulation is repeated to generate gas phase ions. And the generated gas-phase ions enter a flight time spectrometer for analysis through the metal capillary and the Skimmer micropores under the action of an electric field and a pressure difference.
The high-voltage power supply is connected with a metal wire (which can be a platinum wire), the metal wire extends into the first capillary and keeps a certain distance with the tip of the first capillary, so that the extracted mixture is subjected to electrophoresis under the action of tip discharge and is sprayed out through the tip, and the speed of a substance is increased between one end of the metal wire and the tip of the first capillary.
The membrane enrichment spray ionization device for the real-time continuous mass spectrometry analysis of the organic amine in the seawater further comprises the following detailed structure:
as shown in FIG. 1, the sample enriching and desorbing apparatus further includes a vibrating rod on which a polydimethylsiloxane tubular membrane is wound. Further, the vibrating rod is an ultrasonic vibration motor vibrating rod. Organic amine in the liquid sample is adsorbed and enriched inside the polydimethylsiloxane tubular membrane, enters a certain amount of extractant after being enriched, and starts an ultrasonic vibration motor. The organic amine adsorbed inside the tubular membrane 11 is extracted into the extractant. The vibration is beneficial to the entry of the adsorbed organic amine into the extracting agent.
The tubular polydimethylsiloxane membrane is wound on the vibrating rod, the winding is mainly used for increasing the adsorption area of the tubular membrane, further increasing the adsorption capacity of substances, and finally accelerating the dissolution of the substances into the extracting agent through ultrasonic vibration.
The plurality of the polydimethylsiloxane tubular membranes are arranged in parallel. The parallel operation can be realized, the sample introduction is carried out simultaneously, the extraction efficiency is improved, and the sample detection time is shortened.
In one embodiment, the polydimethylsiloxane tubular membrane has a length of 10 to 20cm, an outer diameter of 0.6 to 1.2mm, and an inner diameter of 0.45 to 0.6 mm. Specifically, the tubular polydimethylsiloxane membrane 11 may have a length of 15cm, an outer diameter of 0.94mm and an inner diameter of 0.51 mm.
The sample introduction part has the following structure:
the sample enrichment and desorption device 1 also comprises a sample feeding device which is connected with the polydimethylsiloxane tubular membrane. Furthermore, the sample injection device comprises a sample injection device, an extractant injection device and a water injection device which are respectively connected with the polydimethylsiloxane tubular membrane. The sample enrichment and desorption device also comprises a waste water device, and the outlet of the polydimethylsiloxane tubular membrane is connected with the waste water device.
The sample injection device, the extractant injection device and the water injection device respectively adopt a micro-sampler for sample injection, and the sample injection amount and speed can be controlled. And in the process of enriching the sample, the waste liquid flowing out of the polydimethylsiloxane tubular membrane enters a waste water device.
The sample injection device is connected with the polydimethylsiloxane tubular membrane through a pipeline, and a valve is arranged on the pipeline. Specifically, sample sampling device and extractant sampling device are respectively through the pipe connection, and the connector sets up three-way valve 13, and water sampling device passes through the pipe connection with extractant sampling device, and the connector sets up three-way valve 13, and three sampling device's manifold is connected with a plurality of polydimethyl siloxane tubular membrane. The pipeline may be made of polytetrafluoroethylene.
The capillary portion is illustrated below:
in one embodiment, the second capillary has an outer diameter of 0.9 to 1.5mm and an inner diameter of 0.6 to 1mm, and the first capillary has an outer diameter of 1.2 to 1.8mm and an inner diameter of 0.7 to 1 mm.
The method specifically comprises the following steps: the second capillary 19 is a stainless steel metal capillary with an outer diameter of 1.2mm and an inner diameter of 0.8mm, and the two capillaries are arranged coaxially with a distance of 4 mm; the first capillary tube 18 and the second capillary tube 19 are coaxially arranged with a distance of 10-15mm, the outer diameter of the quartz capillary tube is 1.5mm, the inner diameter of the quartz capillary tube is 0.86mm, and the inner diameter of the tip end of the quartz capillary tube is 5-10 mu m; the platinum wire 17 is arranged in the quartz capillary and is 7-10mm away from the tip of the capillary.
In one embodiment, the voltage of the high voltage power supply is 2-3 kV.
The second capillary is connected with a power supply. In one embodiment, a DC voltage of 0-100V is applied to the second capillary 19; the Skimmer micro-pores 22 are applied with a DC voltage of 0-100V, which is lower than the second capillary 19.
The diameter sizes of the first capillary and the second capillary affect the normal flow of the gas phase ions formed by the organic amine.
The applied voltage of the first capillary and the second capillary influences the process that the organic amine enters the second capillary from the first capillary and then enters the micropores of the sketch, and therefore continuity is guaranteed.
The distance between the first capillary and the second capillary, the distance between the metal wire and the tip, and the inner diameter of the tip of the first capillary influence the rapid formation of gas phase ions by organic amine.
The other parts of the structure of the spray ionization device are explained as follows:
the spray ionization device further comprises a skimmer micropore and a mass spectrum system, wherein the outlet of the second capillary tube is opposite to the skimmer micropore, the skimmer micropore is connected with a power supply, and the voltage of the power supply connected with the skimmer micropore is smaller than that of the second capillary tube. The outlet of the Skimmer microwell is connected with a mass spectrometry system. And the gas phase ions pass through the Skimmer micropores and then enter a mass spectrum system for detection. Further, the Skimmer pores 22 are circular stainless steel electrodes. The mass spectrometry system comprises a time-of-flight spectrometer.
The electrospray ionization device further comprises a fixed disc 21, and the fixed disc 21 is fixedly connected with the second capillary tube. The fixed disk 21 is made of polyetheretherketone. For the fixation of the second capillary, remaining coaxially opposite to the first capillary.
A method for analyzing organic amine by using a membrane enrichment spray ionization device for real-time continuous mass spectrometry analysis of organic amine in liquid.
The method for carrying out real-time continuous mass spectrometry analysis on the organic amine by using the device comprises the following specific steps:
100mL of seawater sample 8 is measured into a conical flask 7, and a sampling pump 6 is started to perform sampling at 10mLmin -1 Is injected at a flow rate and is discharged into a wastewater tank 14 after passing through a polydimethylsiloxane tubular membrane 11. The four-way valve 5 and the three-way valve 13 were adjusted, 15 μ l of an extractant 10 (methanol: water volume ratio 1:1) was injected into the polydimethylsiloxane tubular membrane 11 using the microsyringe 9, the four-way valve 5 and the three-way valve 13 were closed, the ultrasonic vibration motor 12 was turned on, and the resulting extract was injected into the silicate quartz capillary 18 through the line 15 after 5 min. The high voltage power supply 16 is turned on and the voltage is set to 2500V, and simultaneously, the mass spectrometry system 20 starts to collect the mass spectra for 60 s. The quartz capillary 18 is at a distance of 12mm from the metal capillary 19. The sample forms gas phase between the silicate quartz capillary 18 and the metal capillary 19 under the action of the electric fieldThe ions then enter the mass spectrometry system 20 through the skinner pores 22 under the action of an electric field and a pressure difference for detection. The total time of single sample detection is about 10mins, wherein the time of membrane enrichment extraction is 8min, the mass spectrometry detection needs 2min, when multiple samples are continuously detected, 3 paths of parallel enrichment and extraction devices run in a time sequence, one sample can be detected every 2min after 8 minutes of enrichment extraction time, and the 3 paths of parallel devices or multiple paths of parallel devices greatly improve the flux of sample on-line analysis.
And after the detection is finished, starting the water pump 3 and cleaning the sample injection system by using ultrapure water 4.
FIG. 2 is a mass spectrum of seawater detection, which shows clear peak pattern and almost no impurities.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The membrane enrichment and spray ionization device for the real-time mass spectrometry analysis of organic amine in seawater is characterized in that: the device comprises a plurality of sample enrichment and desorption devices, a plurality of sample enrichment and desorption devices and a plurality of sample enrichment and desorption devices, wherein the sample enrichment and desorption devices comprise polydimethylsiloxane tubular membranes which are arranged in parallel;
the spray ionization device is an electrospray ionization device or a paper spray ionization device, and the polydimethylsiloxane tubular film is connected with the spray ionization device;
the sample enrichment and desorption device also comprises a sample injection device which is connected with the polydimethylsiloxane tubular membrane;
the sample enrichment and desorption device also comprises a wastewater device, and the outlet of the polydimethylsiloxane tubular membrane is connected with the wastewater device;
the sample enrichment and desorption device also comprises a vibrating rod, and the polydimethylsiloxane tubular membrane is wound on the vibrating rod; the vibrating rod is an ultrasonic vibration motor vibrating rod;
the electrospray ionization device comprises a high-voltage power supply, a first capillary and a second capillary, wherein a polydimethylsiloxane tubular membrane is connected with the first capillary, the high-voltage power supply is connected with a metal wire, the metal wire is matched and extends into the inner side of the first capillary, and the outlet of the first capillary is opposite to the inlet of the second capillary;
the first capillary tube and the second capillary tube are horizontally arranged, a space is arranged between the outlet of the first capillary tube and the inlet of the second capillary tube, and the outlet end of the first capillary tube is a tip end;
the distance between the first capillary tube and the second capillary tube is 10-15mm, the inner diameter of the tip of the first capillary tube is 5-10 mu m, and the distance between the metal wire and the tip of the first capillary tube is 7-10 mm;
the spray ionization device further comprises a skimmer micropore and a mass spectrum system, wherein the outlet of the second capillary tube is opposite to the skimmer micropore, the skimmer micropore is connected with a power supply, and the voltage of the power supply connected with the skimmer micropore is smaller than that of the second capillary tube; the outlet of the Skimmer micropore is connected with a mass spectrum system; gas phase ions enter a mass spectrum system for detection after passing through the Skimmer micropores; the Skimmer micropores are round stainless steel electrodes; the mass spectrometry system comprises a time-of-flight spectrometer;
the distance between the second capillary and the Skimmer micropore is 3-5 mm.
2. The membrane-enriched spray ionization device for the real-time mass spectrometry analysis of organic amine in seawater according to claim 1, characterized in that: the extractant is methanol-water mixed solvent.
3. The membrane-enriched spray ionization device for the real-time mass spectrometry of organic amines in seawater according to claim 2, characterized in that: the volume ratio of methanol to water was 1: 1.
4. The membrane-enriched spray ionization device for the real-time mass spectrometry analysis of organic amine in seawater according to claim 1, characterized in that: the liquid sample is domestic sewage, experimental wastewater, chemical industry enterprise drainage, river water and seawater.
5. The membrane-enriched spray ionization device for the real-time mass spectrometry analysis of organic amine in seawater according to claim 4, characterized in that: the liquid sample is seawater.
6. The method for performing the real-time mass spectrometry of the organic amine in the seawater by using the membrane enrichment spray ionization device for the real-time mass spectrometry of the organic amine in the seawater according to any one of claims 1 to 5, which is characterized by comprising the following steps:
the seawater sample is adsorbed and enriched by a polydimethylsiloxane tubular membrane;
introducing an extractant into the polydimethylsiloxane tubular membrane enriched with organic amine to extract the organic amine;
the mixture after extraction is subjected to electrophoresis under high pressure, solvent evaporation is sprayed, liquid drops shrink, the shrunk liquid drops form charged liquid drops, the charged liquid drops form gas-phase ions, and the gas-phase ions enter a detection device.
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