A multifunctional composite ion source apparatus and a method of using the same

Abstract

The application belongs to the technical field of mass spectrometry, and provides a multifunctional composite ion source device and a use method thereof.The multifunctional composite ion source device comprises a Y-shaped glass tube, a first capillary, a second capillary, an alternating current power supply, a direct current power supply and an outer electrode.The Y-shaped glass tube comprises a first inlet, a second inlet and an outlet.The first capillary and the second capillary are partially arranged in the Y-shaped glass tube in a penetrating manner, and the first capillary and the second capillary in the Y-shaped glass tube are arranged side by side.The first capillary and the second capillary in the Y-shaped glass tube are wrapped with copper wires in a side-by-side manner.The outer electrode is wrapped on the side surface of the Y-shaped glass tube close to the outlet.One end of the alternating current power supply is connected to the outer electrode, and the other end is connected to the first capillary.The direct current power supply is connected to the second capillary.The device can greatly expand the polarity range of the sample to be detected, and thus can realize comprehensive, real-time and accurate analysis of metabolites in a complex biological system.

Description

Technical Field

[0001] This invention relates to the field of mass spectrometry analysis technology, and in particular to a multifunctional composite ion source device and its usage method. Background Technology

[0002] Modern mass spectrometry, with its advantages of fast analysis speed, high resolution, and accurate results, has become an important tool in the field of chemical analysis. Its ultra-high sensitivity and diverse ionization methods have also greatly facilitated the study of volatile and non-volatile components. In recent years, leveraging the versatility and open-source nature of mass spectrometers, a series of atmospheric pressure ionization techniques have emerged, such as extraction electrospray ionization (EESI), dielectric barrier discharge ionization (DBDI), desorption electrospray ionization (DESI), direct real-time analysis (DART), and secondary electrospray ionization (SESI). These techniques not only inherit the technical advantages of traditional mass spectrometry but also overcome the limitations of cumbersome sample pretreatment in classical mass spectrometry methods, providing effective means for metabolomics and life science research.

[0003] The DBDI ionization technology developed by Professor Zhang Xinrong of Tsinghua University in 2007 utilizes high-voltage AC discharge under dielectric barrier conditions to excite inert gas to generate plasma, and achieves sample ionization through charge exchange reaction. This technology has advantages such as no need for auxiliary reagents, operation at normal pressure, inorganic selectivity, and easy miniaturization, and has attracted widespread attention. It performs well in the ionization of compounds with low proton affinity (such as explosives and pesticides) and weakly polar compounds, effectively making up for the shortcomings of electrospray ionization technology. On this basis, Wen Luhong et al. of Ningbo University carried out secondary innovations, including: (1) single-electrode discharge technology to make the external jet length of the ion beam exceed 4.5 cm, improving the applicability of on-site in-situ analysis; (2) vacuum-assisted ionization technology to reduce background noise and improve signal-to-noise ratio and detection sensitivity; (3) high temperature and high pressure safety protection technology to eliminate signal crosstalk and safety hazards, ensuring stable operation of the system. Based on these improvements, the detection limit of this technology when coupled with mass spectrometry reaches 10~100 ppb, and the overall performance is at an advanced level.

[0004] The EESI technology developed by Professor Chen Huanwen of Jiangxi University of Traditional Chinese Medicine achieves soft ionization through charge exchange between sample spray and charged solvent spray. This technology maintains compound stability when analyzing biological samples such as human aerosols, and requires no complex pretreatment. By selecting appropriate solvents, it allows for selective extraction, ionization, and detection of target molecules, making it highly suitable for in-situ analysis of biological samples and showing promising application prospects in the fields of aerosol and single-cell online analysis.

[0005] However, despite the significant progress made in the aforementioned open-source ion source technologies, many challenges remain in the detection of biological metabolites. First, biological systems contain a wide variety of metabolites with diverse polarities, making it difficult for a single ionization method to cover the analytical needs of all compounds with different polarities. Second, the complex composition of biological samples leads to severe matrix interference during detection, and the low ionization efficiency of weakly polar and non-polar compounds further hinders the comprehensive, real-time, and accurate analysis of metabolites using existing methods.

[0006] Therefore, it is of great significance to develop a multifunctional composite ion source device that can achieve comprehensive, real-time and accurate detection of compounds of different polarities in complex biological systems. Summary of the Invention

[0007] In view of this, the present invention provides a multifunctional composite ion source device and its usage method to solve the problem that the existing technology cannot achieve comprehensive, real-time and accurate analysis of metabolites in complex biological systems.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a multifunctional composite ion source device, comprising a Y-shaped glass tube, a first capillary, a second capillary, an AC power supply, a DC power supply, and an external electrode; The Y-shaped glass tube includes a first inlet, a second inlet, and an outlet; The first capillary and a portion of the second capillary are disposed inside the Y-shaped glass tube through the first inlet and outlet, and the first capillary and the second capillary are arranged side by side inside the Y-shaped glass tube. The Y-shaped glass tube is filled with copper wire and the first and second capillaries are arranged side by side. The second inlet is used to introduce gaseous samples and / or carrier gas into the interior of the Y-shaped glass tube; The external electrode is wrapped around the side surface of the Y-shaped glass tube near the outlet; One end of the AC power supply is connected to the external electrode, and the other end is connected to the first capillary tube; The DC power supply is connected to the second capillary.

[0009] The present invention also provides a method for using a multifunctional composite ion source device, comprising the following steps: When the sample to be tested is a nonpolar and / or weakly polar compound, the carrier gas is introduced into the interior of the Y-shaped glass tube through the second inlet. At the same time, the AC power supply is turned on, and the first and second capillaries covered with copper wires are used as internal electrodes. The AC power supply applies AC current between the internal and external electrodes, generating dielectric barrier discharge and low-temperature plasma inside the Y-shaped glass tube. Then, the sample to be tested is introduced into the interior of the Y-shaped glass tube, so that the low-temperature plasma interacts with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on DBDI ionization technology. When the sample to be tested is a polar compound, the carrier gas is introduced into the interior of the Y-shaped glass tube through the second inlet, the DC power supply is turned on at the same time, and the extraction solvent is introduced into the interior of the Y-shaped glass tube through the second capillary to form charged droplets. Then the sample to be tested is introduced into the interior of the Y-shaped glass tube, so that the charged droplets sequentially extract and exchange charge with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on EESI ionization technology.

[0010] Preferably, when the sample to be tested is in a liquid phase, the sample to be tested is introduced into the Y-shaped glass tube through the first capillary; the flow rate of the sample to be tested is 1~20 μL / min.

[0011] Preferably, when the sample to be tested is in the gas phase, the sample to be tested is introduced into the Y-shaped glass tube through the second inlet; the flow rate of the sample to be tested is 1~14 L / min.

[0012] Preferably, the carrier gas includes one or more of nitrogen, synthesis air and argon, and the flow rate of the carrier gas is 1~14 L / min.

[0013] Preferably, the AC power supply has a voltage of 4~8 kV and a frequency of 5~10 kHz.

[0014] Preferably, the extraction solvent is obtained by mixing methanol, formic acid and water; the volume ratio of methanol, formic acid and water is 1~10:0.05~0.3:50~100; and the flow rate of the extraction solvent is 1~50 μL / min.

[0015] Preferably, the voltage of the DC power supply is 3~6 kV.

[0016] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows: 1. The multifunctional composite ion source device of the present invention includes a Y-shaped glass tube, a first capillary, a second capillary, an AC power supply, a DC power supply, and an external electrode; the Y-shaped glass tube includes a first inlet, a second inlet, and an outlet; the first capillary and the second capillary are disposed inside the Y-shaped glass tube through the first inlet and the outlet, and the first capillary and the second capillary are arranged side by side inside the Y-shaped glass tube; the first capillary and the second capillary arranged side by side are covered with copper wire inside the Y-shaped glass tube; the second inlet is used to introduce gaseous sample and / or carrier gas into the interior of the Y-shaped glass tube; the external electrode is covered on the side surface of the Y-shaped glass tube near the outlet; one end of the AC power supply is connected to the external electrode, and the other end is connected to the first capillary; the DC power supply is connected to the second capillary. With the AC power on and the DC power off, this device can ionize nonpolar and / or weakly polar compounds using DBDI ionization technology, and with the DC power on and the AC power off, it can ionize polar compounds using EESI ionization technology. This greatly expands the polarity range of the samples to be tested, thus enabling comprehensive, real-time and accurate analysis of metabolites in complex biological systems.

[0017] 2. The device described in this invention can select the optimal ionization method according to the characteristics of the sample to be tested, such as the state of the compound, the ease of volatility, and the difference between polarity and weak polarity, so as to achieve high coverage and multifunctional detection of multipolar compounds.

[0018] 3. The multifunctional composite ion source device of the present invention retains the original performance of both DBDI and EESI ion sources, and the ion source mode of the device of the present invention can be quickly switched, which has the characteristics of quick and easy operation and has a very broad application prospect. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of the structure of the multifunctional composite ion source device described in this invention; Among them, 1. Y-shaped glass tube; 2. First capillary tube; 3. Second capillary tube; 4. AC power supply; 5. DC power supply; 6. External electrode; 7. First inlet; 8. Second inlet; 9. Outlet; 10. Copper wire; Figure 2The graph shows the effect of carrier gas type on signal-to-noise ratio during cyclohexanone ionization in Examples 1-4. Figure 3 The graph shows the effect of carrier gas flow rate on signal-to-noise ratio during cyclohexanone ionization in Examples 3, 5-8. Figure 4 This is a graph showing the effect of the mass spectrometer ion transmission tube temperature on the signal-to-noise ratio during cyclohexanone ionization in Example 3. Figure 5 The mass spectra of cyclohexanone, 2-pentanone, and acetone in Examples 3, 9, and 10 are shown below; Figure 5 In the image, 'a' represents the primary spectrum of cyclohexanone. Figure 5 b in the image represents the secondary spectrum of cyclohexanone. Figure 5 In the diagram, c represents the secondary spectrum of the cyclohexanone dimer. Figure 5 In the spectrum, d represents the primary spectrum of 2-pentanone. Figure 5 In the image, 'e' represents the secondary spectrum of 2-pentanone. Figure 5 f in the spectrum represents the secondary spectrum of the 2-pentanone dimer. Figure 5 In the spectrum, g represents the primary spectrum of acetone. Figure 5 In the image, 'h' represents the secondary spectrum of acetone. Figure 5 In the diagram, 'i' represents the secondary spectrum of acetone dimer; Figure 6 The mass spectra of 2,3,5,6-tetramethylpyrazine and triethylamine in Example 11 and Comparative Example 1 are shown below; Figure 6 In the spectrum, 'a' represents the primary spectrum of 2,3,5,6-tetramethylpyrazine. Figure 6 b in the spectrum represents the secondary spectrum of 2,3,5,6-tetramethylpyrazine. Figure 6 In the image, c represents the primary spectrum of triethylamine. Figure 6 In the spectrum, d represents the secondary spectrum of triethylamine; Figure 7 The chromatograms are those of 20 ppb cyclohexanone and 10 ppb tetramethylpyrazine in Examples 12-13; wherein, Figure 7 In the figure, 'a' represents the ion chromatogram for cyclohexanone extraction. Figure 7 In the figure, b represents the extraction ion chromatogram of tetramethylpyrazine; Figure 8 The calibration curve for cyclohexanone; Figure 9 The calibration curve for tetramethylpyrazine; Figure 10 The chromatograms are of 0.5 ppb cyclohexanone and 0.5 ppb tetramethylpyrazine from Examples 14-15; wherein, Figure 10 In the figure, 'a' represents the ion chromatogram for cyclohexanone extraction. Figure 10 In the figure, b represents the extraction ion chromatogram of tetramethylpyrazine; Figure 11 The graph shows the effect of carrier gas flow rate on signal-to-noise ratio during cyclohexanone ionization in Examples 16-21. Figure 12 The graph shows the effect of the amount of formic acid added during the ionization of cyclohexanone in Examples 22-26 and Comparative Example 2 on the signal-to-noise ratio. Figure 13 The graph shows the effect of DC voltage on signal-to-noise ratio during cyclohexanone ionization in Examples 27-31. Figure 14 The mass spectra of diethylamine and triethylamine in Examples 32-33 are shown below; Figure 14 In the image, 'a' represents the primary spectrum of diethylamine. Figure 14 In the image, b represents the secondary spectrum of diethylamine. Figure 14 In the image, c represents the primary spectrum of triethylamine. Figure 14 In the spectrum, d represents the secondary spectrum of triethylamine; Figure 15 The mass spectra of cyclohexanone, methanol, ethanol, isopropanol, acetone, and 2-pentanone in Examples 20 and 34-38 are shown below; Figure 15 In the image, 'a' represents the methanol mass spectrum. Figure 15 In the image, b represents the ethanol mass spectrum. Figure 15 In the image, 'c' represents the mass spectrum of isopropanol. Figure 15 In the image, 'd' represents the mass spectrum of acetone. Figure 15 In the image, 'e' represents the mass spectrum of 2-pentanone. Figure 15 f in the image represents the mass spectrum of cyclohexanone. Figure 16 The chromatograms are those of 30 ppb and 5 ppb triethylamine in Examples 39-40; wherein, Figure 16 In the figure, 'a' represents the extraction ion chromatogram of 30 ppb triethylamine. Figure 16 In the figure, b represents the extraction ion chromatogram of 5 ppb triethylamine; Figure 17 This is the calibration curve for triethylamine. Detailed Implementation

[0021] like Figure 1 As shown, the present invention provides a multifunctional composite ion source device, including a Y-shaped glass tube 1, a first capillary tube 2, a second capillary tube 3, an AC power supply 4, a DC power supply 5, and an external electrode 6. The Y-shaped glass tube includes a first inlet 7, a second inlet 8, and an outlet 9; The first capillary 2 and the second capillary 3 are partially inserted through the first inlet 7 and the outlet 9 into the interior of the Y-shaped glass tube 1, and the first capillary 2 and the second capillary 3 inside the Y-shaped glass tube 1 are arranged side by side (without any gap between the first capillary 2 and the second capillary 3). The Y-shaped glass tube 1 is internally covered with copper wire 10 and the first capillary tube 2 and the second capillary tube 3 arranged side by side. The second inlet 8 is used to introduce gaseous samples and / or carrier gas into the interior of the Y-shaped glass tube 1; The external electrode 6 is wrapped around the side surface of the Y-shaped glass tube 1 near the outlet 9; One end of the AC power supply 4 is connected to the external electrode 6, and the other end is connected to the first capillary tube 2; The DC power supply 5 is connected to the second capillary tube 3 (the mass spectrometry electrospray ion source does not need to form a closed loop; it only needs to apply high voltage to the liquid).

[0022] In this invention, the first capillary 2 and the second capillary 3 are preferably made of quartz.

[0023] In this invention, the first capillary 2 and the second capillary 3 arranged side by side inside the Y-shaped glass tube 1 are wrapped together with copper wire 10, and the first capillary 2 and the second capillary 3 arranged side by side inside the Y-shaped glass tube 1 are closely arranged.

[0024] In this invention, the outlet 9 is directly opposite the mass spectrometer ion source; the temperature of the ion source is 250~300℃, preferably 255~285℃, more preferably 260~280℃, and even more preferably 270~275℃; the temperature of the ion source is preferably equal to the temperature of the ion transmission tube.

[0025] The present invention also provides a method for using a multifunctional composite ion source device, comprising the following steps: When the sample to be tested is a nonpolar and / or weakly polar compound, the carrier gas is introduced into the interior of the Y-shaped glass tube 1 through the second inlet 8. At the same time, the AC power supply 4 is turned on, and the first capillary 2 and the second capillary 3 covered with copper wire 10 are used as internal electrodes. The AC power supply 4 applies AC current between the internal electrode and the external electrode 6, generating dielectric barrier discharge and low-temperature plasma inside the Y-shaped glass tube 1. Then, the sample to be tested is introduced into the interior of the Y-shaped glass tube 1, so that the low-temperature plasma interacts with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on DBDI ionization technology. When the sample to be tested is a polar compound, the carrier gas is introduced into the Y-shaped glass tube 1 through the second inlet 8, the DC power supply 5 is turned on at the same time, and the extraction solvent is introduced into the Y-shaped glass tube 1 through the second capillary 3 to form charged droplets. Then the sample to be tested is introduced into the Y-shaped glass tube 1, so that the charged droplets sequentially extract and exchange charge with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on EESI ionization technology.

[0026] In this invention, the interaction preferably includes collision and / or charge exchange.

[0027] In this invention, when the AC power supply 4 is turned on and the DC power supply 5 is turned off, the copper wires 10 of the first capillary tube 2 and the second capillary tube 3 arranged side by side inside the Y-shaped glass tube 1 serve as internal electrodes. This can greatly save space while realizing the DBDI function, without affecting other functions.

[0028] In this invention, the external electrode 6 preferably comprises copper paper and / or tin foil.

[0029] In this invention, when the sample to be tested is in a liquid phase, the sample to be tested is introduced into the Y-shaped glass tube 1 through the first capillary tube 2; the flow rate of the sample to be tested is 1~20 μL / min, preferably 2~18 μL / min, more preferably 5~15 μL / min, and even more preferably 6~10 μL / min.

[0030] In this invention, when the sample to be tested is in the gas phase, the sample to be tested is introduced into the Y-shaped glass tube 1 through the second inlet 8; the flow rate of the sample to be tested is 1~14 L / min, preferably 2~13 L / min, more preferably 3~12 L / min, and even more preferably 5~10 L / min.

[0031] In this invention, the carrier gas preferably includes one or more of nitrogen, synthesis air and argon; the nitrogen preferably includes high-purity nitrogen (99.999%) and / or ordinary nitrogen (99.5%), and the flow rate of the carrier gas is 1~14 L / min, preferably 2~12 L / min, more preferably 3~10 L / min, and even more preferably 5~8 L / min.

[0032] In this invention, the voltage of the AC power supply 4 is 4~8 kV, preferably 4.5~7.5 kV, more preferably 5~7 kV, and even more preferably 5.5~6 kV; the frequency of the AC power supply 4 is 5~10 kHz, preferably 5.5~9.5 kHz, more preferably 6~9 kHz, and even more preferably 6.5~8 kHz.

[0033] In this invention, the extraction solvent is obtained by mixing methanol, formic acid and water; the volume ratio of methanol, formic acid and water is 1~10:0.05~0.3:50~100, preferably 2~8:0.08~0.25:60~98, more preferably 3~7:0.1~0.2:80~95, and even more preferably 4~6:0.12~0.15:85~90; the flow rate of the extraction solvent is 1~50 μL / min, preferably 5~30 μL / min, more preferably 8~20 μL / min, and even more preferably 10~15 μL / min.

[0034] In this invention, the voltage of the DC power supply 5 is 3~6 kV, preferably 3.5~5.5 kV, more preferably 4~5 kV, and even more preferably 4.5 kV.

[0035] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0036] Example 1

[0037] Adopting such Figure 1 The multifunctional composite ion source device shown introduces high-purity nitrogen gas (99.999%) into the Y-shaped glass tube 1 through the second inlet 8 at a flow rate of 12 L / min. Simultaneously, the AC power supply 4 (voltage +6.6 kV, frequency 8.6 kHz) is turned on, and the copper wire 10 covering the first capillary tube 2 and the second capillary tube 3 arranged side by side is used as the inner electrode. The AC power supply 4 applies AC current between the inner electrode and the outer electrode 6, generating dielectric barrier discharge and low-temperature plasma inside the Y-shaped glass tube 1. Then, a cyclohexanone sample with a volume concentration of 10 ppb is introduced into the Y-shaped glass tube 1 through the second inlet 8 at a flow rate of 10 L / min. The low-temperature plasma interacts with the cyclohexanone sample in the high-purity nitrogen gas phase through collisions and charge exchange, and the cyclohexanone is ionized based on DBDI.

[0038] Example 2

[0039] The only difference between Example 2 and Example 1 is that high-purity nitrogen (99.999%) is replaced with ordinary nitrogen (99.5%), while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0040] Example 3

[0041] The only difference between Example 3 and Example 1 is that high-purity nitrogen (99.999%) is replaced with synthetic air (nitrogen:oxygen = 79%:21%, Beijing Chengweixin Gas), while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0042] Example 4

[0043] The only difference between Example 4 and Example 1 is that high-purity nitrogen (99.999%) is replaced with argon, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0044] The ionized cyclohexanone from Examples 1-4 was transferred to a mass spectrometer via an ion transfer tube (at 275°C) for mass spectrometry analysis. The signal-to-noise ratio results are as follows: Figure 2 As shown. From Figure 2 The results show that the highest signal-to-noise ratio was achieved when synthesis air was used as the carrier gas, while the results for the other three carrier gas conditions were relatively similar. Compared to high-purity nitrogen, the oxygen component in synthesis air may promote the discharge and the generation of low-temperature plasma, thereby improving the ionization efficiency of cyclohexanone. Furthermore, significant background fluctuations were observed when using ordinary nitrogen, which may be related to the generation method of ordinary nitrogen. This also demonstrates that for the DBDI ion source mode, the uniformity and stability of the carrier gas composition have a significant impact on the detection results. It is worth noting that when rare gases are used as carrier gases, their low chemical reactivity and spectral interference make them suitable for generating dielectric barrier discharges; however, their high permeability can significantly affect the vacuum level of the mass spectrometry system, and long-term use may damage the mass spectrometer.

[0045] Example 5

[0046] The only difference between Example 5 and Example 3 is that the flow rate of the synthesis air is set to 6 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0047] Example 6

[0048] The only difference between Example 6 and Example 3 is that the flow rate of the synthesis air is set to 8 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0049] Example 7

[0050] The only difference between Example 7 and Example 3 is that the flow rate of the synthesis air is set to 10 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0051] Example 8

[0052] The only difference between Example 8 and Example 3 is that the flow rate of the synthesis air is set to 14 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0053] The ionized cyclohexanone from Examples 3, 5-8 was transferred to a mass spectrometer via an ion transfer tube (at 275°C) for mass spectrometry analysis. The signal-to-noise ratio results are as follows: Figure 3 As shown. From Figure 3 As can be seen, the carrier gas flow rate is also a major factor affecting the plasma generation efficiency in DBDI ion source mode. When the carrier gas flow rate is below 6 L / min, no discharge phenomenon was observed in the DBDI ion source, and no mass spectrometry signal was generated. When the carrier gas flow rate is gradually increased from 6 L / min to 12 L / min, the signal-to-noise ratio of the target analyte cyclohexanone increases accordingly, reaching a plateau region at 12 L / min. The high gas flow rate may promote the collision frequency between sample molecules and plasma active particles and promote the charge exchange process. Further increasing the gas flow rate to 14 L / min, the signal-to-noise ratio of the target analyte no longer increases, indicating that the ionization of the target analyte has reached equilibrium under this condition.

[0054] The ionized cyclohexanone from Example 3 was transmitted to a mass spectrometer via ion transfer tubes at different temperatures (225°C, 250°C, 275°C, 300°C, 325°C, and 350°C) for mass spectrometry analysis. The signal-to-noise ratio results are as follows: Figure 4 As shown. From Figure 4 As can be seen, the signal-to-noise ratio of the target analyte cyclohexanone rapidly increases as the temperature of the ion transmission tube rises from 225℃ to 275℃, reaching a peak at 275℃. Increasing the temperature of the ion transmission tube (ion source temperature) is beneficial for the effective desorption and ion transmission of the analyte, but it is also important to avoid analyte decomposition due to excessively high temperatures.

[0055] Example 9

[0056] The difference between Example 9 and Example 3 is that the cyclohexanone sample with a volume concentration of 10 ppb is replaced with a 2-pentanone sample with a volume concentration of 10 ppb, and the 2-pentanone sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and finally, cyclohexanone is ionized based on DBDI.

[0057] Example 10

[0058] The only difference between Example 10 and Example 1 is that the cyclohexanone sample is replaced with an acetone sample with a volume concentration of 20 ppb, while other conditions remain unchanged. Finally, the acetone is ionized based on DBDI.

[0059] The ionized cyclohexanone, ionized 2-pentanone, and ionized acetone from Examples 3, 9, and 10 above were transferred to a mass spectrometer via ion transfer tubes (temperature 275°C) for mass spectrometry analysis. The mass spectrum results are shown below. Figure 5 As shown; where, Figure 5In the image, 'a' represents the primary spectrum of cyclohexanone. Figure 5 b in the image represents the secondary spectrum of cyclohexanone. Figure 5 In the diagram, c represents the secondary spectrum of the cyclohexanone dimer. Figure 5 In the spectrum, d represents the primary spectrum of 2-pentanone. Figure 5 In the image, 'e' represents the secondary spectrum of 2-pentanone. Figure 5 f in the spectrum represents the secondary spectrum of the 2-pentanone dimer. Figure 5 In the spectrum, g represents the primary spectrum of acetone. Figure 5 In the image, 'h' represents the secondary spectrum of acetone. Figure 5 In the diagram, 'i' represents the secondary spectrum of acetone dimer. From... Figure 5 As can be seen from a~i in the diagram, the [M+H] of the three ketones (cyclohexanone, 2-pentanone, and acetone) is... + The signal, and its results, can be verified by collision-induced dissociation (CID). Monomeric ketones undergo enol isomerization during ionization, thus losing a neutral water molecule after CID. Furthermore, protonated dimer peaks [2M+H] were observed in the results for cyclohexanone and 2-pentanone. + After fragmentation, it generates protonated monomers. Although acetone could not be verified by CID due to its small molecular weight, its high-resolution mass spectrometry analysis results were in good agreement with the theoretical value (theoretical value 59.0497; measured value 59.0498; Δm = 1.7 ppm, where Δm is the error).

[0060] Example 11

[0061] The only difference between Example 11 and Example 9 is that the 2-pentanone sample was replaced with 2,3,5,6-tetramethylpyrazine at a volume concentration of 10 ppb, while other conditions remained unchanged. Finally, 2,3,5,6-tetramethylpyrazine was ionized based on DBDI.

[0062] Comparative Example 1

[0063] The only difference between Comparative Example 1 and Example 9 is that the 2-pentanone sample was replaced with triethylamine at a volume concentration of 10 ppb, while other conditions remained unchanged. Finally, the triethylamine was ionized based on DBDI.

[0064] The ionized 2,3,5,6-tetramethylpyrazine and ionized triethylamine from Example 11 and Comparative Example 1 were transferred to a mass spectrometer via ion transfer tubes (temperature 275°C) for mass spectrometry analysis. The mass spectrum results are shown below. Figure 6 As shown; where, Figure 6 In the spectrum, 'a' represents the primary spectrum of 2,3,5,6-tetramethylpyrazine. Figure 6 b in the spectrum represents the secondary spectrum of 2,3,5,6-tetramethylpyrazine. Figure 6 In the image, c represents the primary spectrum of triethylamine. Figure 6 In the image, 'd' represents the secondary spectrum of triethylamine. From... Figure 6 In the expression 'a', we can observe [M+H] with m / z = 137. + Signal peak, from Figure 6 The observed fragment ion (b) is 96, suggesting that it underwent ring-opening and lost a neutral acetonitrile molecule during the CID process. This result strongly demonstrates the application potential of the DBDI mode of the device described in this invention in the detection of the nonpolar compound 2,3,5,6-tetramethylpyrazine. Figure 6 In c, besides [M+H] where m / z = 102, we also observed... + In addition to the peak, a strong oxidation product [M+O+H] was also produced. + The structure of this oxidation product can be determined by... Figure 6 Further verification was performed using the second-order spectrum of d. This indicates that the oxidation product [M+O+H] is produced. + The reason may be that the low-temperature plasma generated by DBDI contains Oxidizing species such as OH radicals and O3 cause triethylamine to be oxidized.

[0065] In summary, the mass spectrometry results of Examples 3, 9-11, and Comparative Example 1 demonstrate that the DBDI mode of the device described in this invention can achieve the analysis of various polar compounds such as ketones, pyrazines, and amines. However, during the ionization process, a significant amount of the target compound, triethylamine, may be oxidized by the low-temperature plasma, which adversely affects the detection of related compounds. In other words, the DBDI mode of the device described in this invention is effective for detecting weakly polar and non-polar compounds, but its detection performance for polar compounds is relatively poor.

[0066] Example 12

[0067] The only difference between Example 12 and Example 3 is that the cyclohexanone sample with a volume concentration of 10 ppb is replaced with a cyclohexanone sample with a volume concentration of 20 ppb, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0068] Example 13

[0069] The only difference between Example 13 and Example 3 is that the cyclohexanone sample with a volume concentration of 10 ppb is replaced with a tetramethylpyrazine sample with a volume concentration of 10 ppb, and the sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and the tetramethylpyrazine is finally ionized based on DBDI.

[0070] The 20 ppb cyclohexanone and 10 ppb tetramethylpyrazine from Examples 12-13 above were transferred to a mass spectrometer via ion transfer tubes (temperature 275°C) for analysis. The extracted ion chromatogram results are as follows: Figure 7 As shown; where, Figure 7In the figure, 'a' represents the ion chromatogram for cyclohexanone extraction. Figure 7 In the figure, b represents the extraction ion chromatogram of tetramethylpyrazine. Figure 7 As can be seen from a~b, even at low concentrations (10~20 ppb), the DBDI mode of the device described in this invention can achieve sensitive detection of weakly polar and non-polar compounds.

[0071] A calibration curve for cyclohexanone was obtained by plotting the volume concentration of cyclohexanone on the x-axis and the signal intensity of cyclohexanone on the y-axis. Figure 8 As shown. A calibration curve for tetramethylpyrazine is obtained by plotting the volume concentration of tetramethylpyrazine on the x-axis and the signal intensity of tetramethylpyrazine on the y-axis, as shown. Figure 9 As shown. From Figures 8-9 As can be seen, within a volume concentration range of 1–20 ppb, the DBDI mode of the device described in this invention exhibits good linearity (R0) for the detection of both cyclohexanone and tetramethylpyrazine. 2 = 0.999), which further demonstrates the feasibility of the device described in this invention for detecting weakly polar and non-polar compounds and its good quantitative analysis performance.

[0072] Example 14

[0073] The only difference between Example 14 and Example 12 is that the cyclohexanone sample with a volume concentration of 20 ppb is replaced with a cyclohexanone sample with a volume concentration of 0.5 ppb, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on DBDI.

[0074] Example 15

[0075] The only difference between Example 15 and Example 13 is that the tetramethylpyrazine with a volume concentration of 10 ppb is replaced with tetramethylpyrazine with a volume concentration of 0.5 ppb, while other conditions remain unchanged. Finally, the tetramethylpyrazine is ionized based on DBDI.

[0076] The 0.5 ppb cyclohexanone and 0.5 ppb tetramethylpyrazine from Examples 14-15 above were transferred to a mass spectrometer via ion transfer tubes (temperature 275°C) for analysis. The extracted ion chromatogram results are as follows: Figure 10 As shown; where, Figure 10 In the figure, 'a' represents the ion chromatogram for cyclohexanone extraction. Figure 10 In the figure, b represents the extraction ion chromatogram of tetramethylpyrazine. Figure 10 As shown in figures a-b, the signal-to-noise ratios (SNRs) of cyclohexanone and tetramethylpyrazine are 38 and 26, respectively, demonstrating the effective detection of these two compounds at a concentration of 0.5 ppb (S / N 3:1 is the limit of detection). This detection result meets the DBDI limit of detection criteria (1-10 ppb).

[0077] Example 16

[0078] Adopting such Figure 1 The multifunctional composite ion source device shown introduces synthesis air (same as in Example 3) into the Y-shaped glass tube 1 through the second inlet 8 at a flow rate of 2 L / min. At the same time, the DC power supply 5 (voltage of 3.0 kV) is turned on, and the extraction solvent (volume ratio of methanol, formic acid and water of 4.8:0.2:95, i.e., the amount of formic acid added is 0.2%) is introduced into the Y-shaped glass tube 1 through the second capillary 3 at a flow rate of 10 μL / min to form charged droplets. Then, a cyclohexanone sample with a volume concentration of 10 ppb (same as in Example 1) is introduced into the Y-shaped glass tube 1 through the second inlet 8 at a flow rate of 10 L / min. The charged droplets sequentially extract and exchange charge with cyclohexanone in the synthesis air gas phase, and ionize cyclohexanone based on EESI.

[0079] Example 17

[0080] The only difference between Example 17 and Example 16 is that the flow rate of the synthesis air is set to 4 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0081] Example 18

[0082] The only difference between Example 18 and Example 16 is that the flow rate of the synthesis air is set to 6 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0083] Example 19

[0084] The only difference between Example 19 and Example 16 is that the flow rate of the synthesis air is set to 8 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0085] Example 20

[0086] The only difference between Example 20 and Example 16 is that the flow rate of the synthesis air is set to 10 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0087] Example 21

[0088] The only difference between Example 21 and Example 16 is that the flow rate of the synthesis air is set to 12 L / min, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0089] The ionized cyclohexanone from Examples 16-21 above was transferred to a mass spectrometer via an ion transfer tube (at 275°C) for mass spectrometry analysis. The signal-to-noise ratio results are as follows: Figure 11As shown. From Figure 11 As can be seen, as the carrier gas flow rate gradually increases from 2 L / min to 10 L / min, the signal-to-noise ratio of the target peak increases from 2.0 × 10⁻⁶. 3 Gradually increased to 1.1×10 4 This indicates that increasing the carrier gas flow rate is beneficial for the extraction of the target analyte at the gas-liquid interface and the subsequent solvent evaporation process, thereby improving the overall ionization efficiency and detection sensitivity. Further increasing the carrier gas flow rate to 12 L / min did not increase the signal-to-noise ratio of the target analyte further; at this point, the system's gas flow rate already met the analytical requirements of the EESI mode in the device described in this invention.

[0090] Example 22

[0091] The only difference between Example 22 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 0.05%, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0092] Example 23

[0093] The only difference between Example 23 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 0.1%, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0094] Example 24

[0095] The only difference between Example 24 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 0.5%, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0096] Example 25

[0097] The only difference between Example 25 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 1%, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0098] Example 26

[0099] The only difference between Example 26 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 2%, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0100] Comparative Example 2

[0101] The only difference between Comparative Example 2 and Example 20 is that the amount of formic acid added to the extraction solvent is set to 0%, while other conditions remain unchanged, and cyclohexanone is ultimately ionized based on EESI.

[0102] The ionized cyclohexanone from Examples 22-26 and Comparative Example 2 was transferred to a mass spectrometer via an ion transfer tube (temperature 275°C) for mass spectrometry analysis. The mass spectrum results are as follows: Figure 12 As shown. From Figure 12 As can be seen, the signal-to-noise ratio (SNR) of the target analyte improved by 5 times when 0.05% formic acid was added, indicating that the formic acid additive significantly promoted the protonation of the target analyte and improved the SNR. Within the range of 0.05% to 2% formic acid, the ionization efficiency of EESI reached its optimum at a formic acid ratio of 0.2%; however, when the formic acid ratio exceeded 0.2%, the SNR of the detection signal showed a decreasing trend. This may be because excessive formic acid leads to over-acidification of the solution, thereby forming multi-charged ions and reducing the signal intensity of the target analyte. Furthermore, excessive formic acid may introduce some matrix components, thus increasing background noise. Therefore, the optimal formic acid addition ratio in the EESI mode extraction solution using the device described in this invention is 0.2%.

[0103] Example 27

[0104] The only difference between Example 27 and Example 20 is that the voltage of the DC power supply 5 is set to 1.5 kV, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0105] Example 28

[0106] The only difference between Example 28 and Example 20 is that the voltage of the DC power supply 5 is set to 2.0 kV, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0107] Example 29

[0108] The only difference between Example 29 and Example 20 is that the voltage of the DC power supply 5 is set to 2.5 kV, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0109] Example 30

[0110] The only difference between Example 30 and Example 20 is that the voltage of the DC power supply 5 is set to 3.5 kV, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0111] Example 31

[0112] The only difference between Example 31 and Example 20 is that the voltage of the DC power supply 5 is set to 4.0 kV, while other conditions remain unchanged. Finally, cyclohexanone is ionized based on EESI.

[0113] The ionized cyclohexanone from Examples 27-31 above was transferred to a mass spectrometer via an ion transfer tube (at 275°C) for mass spectrometry analysis. The mass spectrum results are as follows: Figure 13 As shown. From Figure 13 As can be seen, the signal-to-noise ratio (SNR) of the target gradually increases as the voltage rises from 1.5 kV to 2.5 kV, but remains at a relatively low level overall, indicating that the target has not yet been fully ionized. The SNR of the target reaches its peak at 3.0 kV and then shows a downward trend. The decline may be related to corona discharge caused by excessively high voltage and the increase in background signal.

[0114] Example 32

[0115] The only difference between Example 32 and Example 20 is that cyclohexanone is replaced with a diethylamine sample with a volume concentration of 10 ppb, and the diethylamine sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and the diethylamine is finally ionized based on EESI.

[0116] Example 33

[0117] The only difference between Example 33 and Example 20 is that cyclohexanone is replaced with a triethylamine sample with a volume concentration of 10 ppb, and the triethylamine sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and the triethylamine is finally ionized based on EESI.

[0118] The ionized diethylamine and triethylamine from Examples 32-33 were respectively transmitted to a mass spectrometer via ion transfer tubes (temperature 275°C) for mass spectrometry analysis. The mass spectrum results are as follows: Figure 14 As shown; where, Figure 14 In the image, 'a' represents the primary spectrum of diethylamine. Figure 14 In the image, b represents the secondary spectrum of diethylamine. Figure 14 In the image, c represents the primary spectrum of triethylamine. Figure 14 In the image, 'd' represents the secondary spectrum of triethylamine. From... Figure 14 [M+H] can be observed in both a and c. + Ions, but without oxidation signal [M+O+H] + .from Figure 14 As can be seen from b and d, the target peaks at m / z of 74 and 102 both lose a neutral ethylene molecule, which is consistent with their structural prediction.

[0119] Example 34

[0120] The only difference between Example 34 and Example 20 is that cyclohexanone is replaced with a methanol sample with a volume concentration of 10 ppb, while other conditions remain unchanged. Finally, methanol is ionized based on EESI.

[0121] Example 35

[0122] The only difference between Example 35 and Example 20 is that cyclohexanone is replaced with an ethanol sample with a volume concentration of 10 ppb, while other conditions remain unchanged. Finally, the ethanol is ionized based on EESI.

[0123] Example 36

[0124] The only difference between Example 36 and Example 20 is that cyclohexanone is replaced with an isopropanol sample with a volume concentration of 10 ppb, while other conditions remain unchanged. Finally, isopropanol is ionized based on EESI.

[0125] Example 37

[0126] The only difference between Example 37 and Example 20 is that cyclohexanone is replaced with an acetone sample with a volume concentration of 10 ppb, while other conditions remain unchanged. Finally, acetone is ionized based on EESI.

[0127] Example 38

[0128] The only difference between Example 38 and Example 20 is that cyclohexanone is replaced with a 2-pentanone sample with a volume concentration of 10 ppb, and the 2-pentanone sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and 2-pentanone is finally ionized based on EESI.

[0129] The ionized cyclohexanone, ionized methanol, ionized ethanol, ionized isopropanol, ionized acetone, and ionized 2-pentanone from Examples 20 and 34-38 were transferred to a mass spectrometer via ion transfer tubes (at 275°C) for mass spectrometry analysis. The mass spectrum results are as follows: Figure 15 As shown; where, Figure 15 In the image, 'a' represents the methanol mass spectrum. Figure 15 In the image, b represents the ethanol mass spectrum. Figure 15 In the image, 'c' represents the mass spectrum of isopropanol. Figure 15 In the image, 'd' represents the mass spectrum of acetone. Figure 15 In the image, 'e' represents the mass spectrum of 2-pentanone. Figure 15 f in the image represents the mass spectrum of cyclohexanone. From... Figure 15 As can be seen from a~c, small molecule alcohols readily generate [M+H]. + and its dimer [2M+H] + Signal. Alcohol molecules possess a polar hydroxyl group (-OH), where the oxygen atom is highly electronegative, while the hydrogen atom carries a partially positive charge. This allows the hydrogen atom of one alcohol molecule to form a strong intermolecular hydrogen bond (OH···O) with the oxygen atom of another alcohol molecule. Furthermore, proton transfer, particularly common in soft ionization techniques, allows the protonated alcohol molecule to continue acting as a proton donor, forming a stable "proton-sharing dimer" with another alcohol molecule via hydrogen bonds, ultimately appearing as [2M+H] in the mass spectrum.+ Ions. From Figure 15 As can be seen from d~f, the EESI detection results for ketone compounds are similar to those of DBDI, with cyclohexanone and 2-pentanone both producing strong [M+H] reactions. + and its dimer [2M+H] + Acetone, on the other hand, only showed [M+H] activity. + Signal. The results show that such compounds can be detected well using either the DBDI or EESI mode of the device described in this invention.

[0130] In summary, the EESI mode of the device described in this invention can achieve the analysis of various polar and weakly polar compounds such as amines, alcohols, and ketones. The "soft ionization" and high chemical stability of EESI make it particularly promising for the detection of thermally unstable and highly reactive compounds.

[0131] Example 39

[0132] The only difference between Example 39 and Example 20 is that cyclohexanone is replaced with a triethylamine sample with a volume concentration of 30 ppb, and the triethylamine sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and the triethylamine is finally ionized based on EESI.

[0133] Example 40

[0134] The only difference between Example 40 and Example 20 is that cyclohexanone is replaced with a triethylamine sample with a volume concentration of 5 ppb, and the triethylamine sample is introduced into the Y-shaped glass tube 1 through the first capillary 2. Other conditions remain unchanged, and the triethylamine is finally ionized based on EESI.

[0135] The ionized triethylamine from Examples 39-40 above was transferred to a mass spectrometer via an ion transfer tube (at 275°C) for mass spectrometry analysis. The mass spectrum results are as follows: Figure 16 As shown; where, Figure 16 In the figure, 'a' represents the extraction ion chromatogram of 30 ppb triethylamine. Figure 16 In the figure, b represents the extraction ion chromatogram of 5 ppb triethylamine. From... Figure 16 As shown in figures a-b, the S / N ratio of triethylamine at a concentration of 30 ppb is 889. As the triethylamine concentration further decreases to 5 ppb, the S / N ratio of the chromatographic peak decreases to 56 (S / N 3:1 is the detection limit). This detection result meets the mid-term evaluation index for the EESI mode detection limit (1-10 ppb). Furthermore, we evaluated the quantitative detection performance of this ion source device. A calibration curve for triethylamine was obtained by plotting the triethylamine volume concentration on the x-axis and the triethylamine signal intensity on the y-axis, as shown below. Figure 17 As shown. From Figure 17As can be seen, within a concentration range of 10–50 ppb, the EESI mode of the device described in this invention exhibits good linearity (R0) for the detection of triethylamine. 2 =0.995), which demonstrates the sensitive detection and good quantitative analysis performance of the EESI mode of the device described in this invention for polar compounds.

[0136] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multifunctional composite ion source device, characterized in that, It includes a Y-shaped glass tube, a first capillary tube, a second capillary tube, an AC power supply, a DC power supply, and an external electrode; The Y-shaped glass tube includes a first inlet, a second inlet, and an outlet; The first capillary and a portion of the second capillary are disposed inside the Y-shaped glass tube through the first inlet and outlet, and the first capillary and the second capillary are arranged side by side inside the Y-shaped glass tube. The Y-shaped glass tube is filled with copper wire and the first and second capillaries are arranged side by side. The second inlet is used to introduce gaseous samples and / or carrier gas into the interior of the Y-shaped glass tube; The external electrode is wrapped around the side surface of the Y-shaped glass tube near the outlet; One end of the AC power supply is connected to the external electrode, and the other end is connected to the first capillary tube; The DC power supply is connected to the second capillary.

2. The method of using the multifunctional composite ion source device according to claim 1, characterized in that, Includes the following steps: When the sample to be tested is a nonpolar and / or weakly polar compound, the carrier gas is introduced into the interior of the Y-shaped glass tube through the second inlet. At the same time, the AC power supply is turned on, and the first and second capillaries covered with copper wires are used as internal electrodes. The AC power supply applies AC current between the internal and external electrodes, generating dielectric barrier discharge and low-temperature plasma inside the Y-shaped glass tube. Then, the sample to be tested is introduced into the interior of the Y-shaped glass tube, so that the low-temperature plasma interacts with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on DBDI ionization technology. When the sample to be tested is a polar compound, the carrier gas is introduced into the interior of the Y-shaped glass tube through the second inlet, the DC power supply is turned on at the same time, and the extraction solvent is introduced into the interior of the Y-shaped glass tube through the second capillary to form charged droplets. Then the sample to be tested is introduced into the interior of the Y-shaped glass tube, so that the charged droplets sequentially extract and exchange charge with the sample to be tested in the carrier gas phase, and the sample to be tested is ionized based on EESI ionization technology.

3. The method of using the multifunctional composite ion source device according to claim 2, characterized in that, When the sample to be tested is in a liquid phase, the sample to be tested is introduced into the Y-shaped glass tube through the first capillary tube; the flow rate of the sample to be tested is 1~20 μL / min. When the sample to be tested is in the gas phase, the sample to be tested is introduced into the Y-shaped glass tube through the second inlet; the flow rate of the sample to be tested is 1~14 L / min.

4. The method of using the multifunctional composite ion source device according to claim 3, characterized in that, The carrier gas includes one or more of nitrogen, synthesis air and argon, and the flow rate of the carrier gas is 1~14 L / min.

5. The method of using the multifunctional composite ion source device according to claim 4, characterized in that, The AC power supply has a voltage of 4~8 kV and a frequency of 5~10 kHz.

6. The method of using the multifunctional composite ion source device according to claim 4, characterized in that, The extraction solvent is obtained by mixing methanol, formic acid and water; the volume ratio of methanol, formic acid and water is 1~10:0.05~0.3:50~100; The flow rate of the extraction solvent is 1~50 μL / min.

7. The method of using the multifunctional composite ion source device according to claim 6, characterized in that, The voltage of the DC power supply is 3~6 kV.

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