CN110459459B - Ion-induced spray ionization method and device - Google Patents
Ion-induced spray ionization method and device Download PDFInfo
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- 239000007921 spray Substances 0.000 title claims abstract description 44
- 238000000752 ionisation method Methods 0.000 title claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 102
- 239000002904 solvent Substances 0.000 claims abstract description 96
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 22
- 238000002347 injection Methods 0.000 claims abstract description 18
- 239000007924 injection Substances 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011810 insulating material Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 238000006479 redox reaction Methods 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000004454 trace mineral analysis Methods 0.000 abstract description 4
- 230000003438 effect on compound Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 118
- 238000001819 mass spectrum Methods 0.000 description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 18
- 238000000132 electrospray ionisation Methods 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000012488 sample solution Substances 0.000 description 12
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 description 10
- 239000005630 Diquat Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000002798 polar solvent Substances 0.000 description 8
- 239000002027 dichloromethane extract Substances 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 4
- 239000000401 methanolic extract Substances 0.000 description 4
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- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- 239000012454 non-polar solvent Substances 0.000 description 2
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- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
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- 239000000443 aerosol Substances 0.000 description 1
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- 238000000889 atomisation Methods 0.000 description 1
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- 230000001939 inductive effect Effects 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
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- 239000002207 metabolite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
- H01J49/167—Capillaries and nozzles specially adapted therefor
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
本发明公开了一种离子诱导喷雾离子化方法和装置，所述离子诱导喷雾离子化方法是先通过高压使辅助溶剂产生带电的诱导离子，然后使诱导离子在毛细管中与样品进行电荷交换，使样品离子化。所述离子诱导喷雾离子化装置包括诱导离子产生装置、毛细管和质谱进样通道，诱导离子产生装置包括辅助溶剂通道，辅助溶剂通道连接有高压发生装置，辅助溶剂通道的出口端与毛细管的末端相通，毛细管的尖端位于质谱进样通道的轴线上，且毛细管不导电。本发明可有效解决传统ESI所存在的样品易发生源内氧化、离子化溶剂兼容性差的问题，对极性较低的化合物、易于发生氧化还原反应的化合物均具有良好的离子化效果，且对离子化溶剂兼容性好，且可用于痕量分析检测。
The present invention discloses an ion-induced spray ionization method and device, wherein the ion-induced spray ionization method first generates charged induced ions in an auxiliary solvent by high pressure, and then causes the induced ions to exchange charge with a sample in a capillary to ionize the sample. The ion-induced spray ionization device comprises an induced ion generating device, a capillary and a mass spectrometry injection channel, wherein the induced ion generating device comprises an auxiliary solvent channel, wherein the auxiliary solvent channel is connected to a high-voltage generating device, wherein the outlet end of the auxiliary solvent channel is connected to the end of the capillary, the tip of the capillary is located on the axis of the mass spectrometry injection channel, and the capillary is non-conductive. The present invention can effectively solve the problems of easy in-source oxidation and poor compatibility of ionized solvents in traditional ESI, and has good ionization effect on compounds with low polarity and compounds prone to redox reactions, and has good compatibility with ionized solvents, and can be used for trace analysis and detection.
Description
Technical Field
The invention relates to an ion-induced spray ionization method and device, and belongs to the technical field of mass spectrometry.
Background
Mass Spectrometry (MS) is an important analytical tool capable of analyzing complex mixtures, providing information about molecular weight, elemental composition, and chemical structure of the analyte, with a high degree of specificity and sensitivity. The basic principle of mass spectrometry is that each component in a sample is ionized in an ion source to generate positively charged ions with different charge-to-mass ratios, an ion beam is formed by the action of an accelerating electric field and enters a mass analyzer, and then opposite velocity dispersion is generated in the mass analyzer by utilizing the electric field and the magnetic field, and the ions are respectively focused to obtain a mass spectrogram, so that the mass of the mass analyzer is determined. Ionization techniques therefore have a significant impact on mass spectrometry results. In recent years, with the continuous innovation and improvement of compound desorption and ionization technology and mass analyzers, mass spectrometry is one of the most rapidly developed analysis technologies, and currently, mass spectrometry technology is increasingly used in the fields of chemistry and chemical industry, biology and life sciences, medicine, pharmacy, material science, environmental protection and the like.
Ionization methods commonly used in mass spectrometry today mainly include electrospray ionization (Electrospray Ionization, ESI), and atmospheric pressure chemical ionization (Atmospheric Pressure Chemical Ionization, APCI) and Matrix assisted laser desorption ionization (Matrix ASSISTED LASER Desorption Ionization, MALDI). Among them, ESI is the most widely used one.
Electrospray ionization (ESI) is an ionization method proposed by the american scientist john, who has also acquired the nobel chemistry prize of 2002 because of its ability to ionize strongly polar, poorly volatile and thermally unstable compounds, and to preserve their integrity and the ability to obtain multi-charged ions. ESI is a soft ionization technology based on 'energy burst', and the process can be briefly described as introducing an object to be measured dissolved in a polar solvent into a capillary tube with a high voltage of 3-4kV, generating aerosol spray under the action of a high electric field and atomizing gas, generating charged liquid drops, and gradually forming ions in the desolvation process.
As mass spectrometry advances toward trace, trace detection, ESI techniques continue to advance. Novel ionization methods such as Nano-ESI, inductive ESI, etc. appear successively. These ionization methods are based mainly on ESI principle, using very fine capillaries to remove the atomizing gas so that it can analyze samples of nl and even pl levels.
However, the electrospray ionization technique has many defects, such as in ESI process, oxidation in the sample easily occurs, oxidation-reduction reaction of some samples easily occurs, and original ion signals of the samples are difficult to obtain, the compatible solvent range is very narrow, only a few polar solvents (such as methanol and acetonitrile) can be compatible, no signal is basically generated for compounds with lower polarity, and the ionization of compounds with lower polarity or poor solubility in polar solvents cannot be performed smoothly.
Disclosure of Invention
In view of the foregoing problems of the prior art, it is an object of the present invention to provide an ion-induced spray ionization method and apparatus.
In order to achieve the above purpose, the invention adopts the following technical scheme:
An ion-induced spray ionization method is to generate charged induced ions by high pressure in auxiliary solvent, and then to make the induced ions charge-exchanged with sample in capillary tube to ionize the sample.
Preferably, the ion-induced spray ionization method comprises the following steps:
a) Introducing the sample into a capillary;
b) Introducing an auxiliary solvent into the auxiliary solvent channel, and applying high pressure through a high-pressure generating device to enable the auxiliary solvent to generate charged induced ions;
c) The induced ions are transferred into the capillary to exchange charge with the sample, and ionize the sample.
More preferably, the high voltage applied by the high voltage generator is 1000 to 6000 v.
The ion-induced spray ionization device comprises an induced ion generation device, a capillary tube and a mass spectrum sample introduction channel, wherein the induced ion generation device comprises an auxiliary solvent channel for introducing an auxiliary solvent, the auxiliary solvent channel is connected with a high-pressure generation device, the outlet end of the auxiliary solvent channel is communicated with the tail end of the capillary tube, the tip end of the capillary tube is positioned on the axis of the mass spectrum sample introduction channel, and the capillary tube is non-conductive.
Preferably, the voltage provided by the high voltage generating device is 1000-6000 v.
As a further preferable mode, the high voltage generating device is an induced voltage generating device.
Preferably, a conductive metal foil is fixed outside the auxiliary solvent channel, and the high-voltage generating device is connected with the auxiliary solvent channel through the conductive metal foil.
Preferably, the auxiliary solvent in the auxiliary solvent channel is a polar solvent, including but not limited to methanol and acetonitrile, or a non-polar solvent, including but not limited to dichloromethane and toluene.
Preferably, the flow rate of the auxiliary solvent in the auxiliary solvent channel is 0.1-3 microliters/min.
Preferably, the auxiliary solvent channel is made of an insulating material, and the insulating material includes, but is not limited to, glass and peek.
Preferably, the axis of the capillary is on the same horizontal line as the axis of the mass spectrum sample injection channel.
Preferably, the axis of the auxiliary solvent channel is on the same level as the axis of the capillary tube.
Preferably, the distance between the tip outlet of the capillary tube and the port of the mass spectrum sample injection channel is 1-15 mm.
Preferably, the diameter of the tip outlet of the capillary tube is 1-20 microns.
Preferably, the induced ion generating apparatus includes an auxiliary electrode provided in the auxiliary solvent passage.
As a further preferred embodiment, the auxiliary electrode is a conductor or a semiconductor.
As a further preferable aspect, the auxiliary electrode is detachable.
Preferably, the capillary tube is externally sleeved with a capillary tube fixing device.
Preferably, the sample introducing passage is further included, and the sample introducing passage communicates with the tip of the capillary.
As a further preferable mode, the flow rate of the liquid in the sample introduction channel is 50 nanoliters to 5 microliters/minute.
As a further preferable scheme, the device further comprises a three-way type fixing device, wherein the auxiliary solvent channel, the capillary tube and the sample introduction channel are respectively fixed in the three-way type fixing device.
Compared with the prior art, the invention has the beneficial technical effects that:
The invention creatively utilizes charged induced ions generated by the high-voltage ionization auxiliary solvent to exchange charges with the sample, so that the sample ionization is easy to realize, simple in operation and low in cost, the problems of easy in-source oxidation and poor ionization solvent compatibility of the sample existing in the traditional ESI can be effectively solved, the invention has good ionization effect on compounds with lower polarity and compounds easy to undergo oxidation-reduction reaction, and has good ionization solvent compatibility, the selectivity of the sample to be tested, the sample solvent and the auxiliary solvent is low, the sample object to be tested, the sample solvent and the auxiliary solvent can be tested in a wide range, and the invention can be used for trace analysis and detection, has strong applicability and obvious progress compared with the prior art.
Drawings
FIG. 1 is a schematic diagram of an ion-induced spray ionization apparatus according to the present invention;
FIG. 2 is a schematic view of the ionization apparatus of FIG. 1 with auxiliary electrodes;
FIG. 3 is a schematic view of the ionization device of FIG. 1 with a sample introduction channel and a three-way fixture;
FIG. 4 is a schematic view of the ionization device of FIG. 1 with auxiliary electrodes, sample introduction channels and a three-way fixture;
FIG. 5 is a mass spectrum analysis of a 100ppm diquat sample obtained in inventive example 1 using the ion-induced spray ionization apparatus of the present invention;
FIG. 6 is a mass spectrum analysis of a 100ppm diquat sample obtained using Nano-ESI in example 1 of the present invention;
FIG. 7 is a mass spectrum of a 100ppm diquat sample obtained using ESI in example 1 of the present invention;
FIG. 8 is a mass spectrum analysis chart of 10ppm anthracene sample obtained by using the ion-induced spray ionization device of the present invention in example 2 of the present invention;
FIG. 9 is a mass spectrum of a 10ppm anthracene sample obtained using Nano-ESI in example 2 of the present invention;
FIG. 10 is a mass spectrum analysis of 10ppm anthracene sample obtained by ESI in example 2 of the present invention;
FIG. 11 is a mass spectrum analysis chart of a methanol extract of pl-grade single Hela cells obtained by using the ion-induced spray ionization apparatus of the present invention in example 3 of the present invention;
FIG. 12 is a mass spectrum analysis chart of a single Hela cell dichloromethane extract obtained by using the ion-induced spray ionization apparatus of the present invention in example 4 of the present invention;
FIG. 13 is a mass spectrum of a single Hela cell dichloromethane extract obtained by employing Nano-ESI in example 4 of the present invention;
The mark in the figure is shown as a figure 1, an induced ion generating device, an auxiliary solvent channel, a 12, a high-voltage generating device, a 13, a conductive metal foil, a 14, an auxiliary electrode, a2, a capillary, a 3, a mass spectrum sample injection channel, a 4, a capillary fixing device, a 5, a sample introducing channel, a6, a tee joint, a 7, and a tee joint.
Detailed Description
The technical scheme of the invention is further and fully described below with reference to the accompanying drawings.
As shown in fig. 1 to 4, the ion-induced spray ionization device provided by the invention comprises an induced ion generating device 1, a capillary tube 2 and a mass spectrum sample injection channel 3, wherein the induced ion generating device 1 comprises an auxiliary solvent channel 11 for introducing an auxiliary solvent, the auxiliary solvent channel 11 is connected with a high-pressure generating device 12, the outlet end of the auxiliary solvent channel 11 is communicated with the tail end of the capillary tube 2, the tip end of the capillary tube 2 is positioned on the axis of the mass spectrum sample injection channel 3, and the capillary tube 2 is non-conductive.
The ionization device disclosed by the invention can be compatible with common mass spectrometers (such as a triple quadrupole mass spectrometer, a time-of-flight mass spectrometer, an ion trap mass spectrometer, fourier transform ion cyclotron resonance and the like), can be popularized and applied to other mass spectrometry, can be used in combination with the common mass spectrometers when being used for mass spectrometry, and has wide application range and strong practicability.
The method for realizing ionization by adopting the ion-induced spray ionization device comprises the steps of firstly generating charged induced ions by an auxiliary solvent through high pressure, and then carrying out charge exchange on the induced ions and a sample in a capillary tube to ionize the sample. Specifically, the method comprises the following steps:
a) Introducing the sample into the capillary 2;
b) Introducing an auxiliary solvent into the auxiliary solvent channel 11, and applying high pressure through the high-pressure generating device 12 to enable the auxiliary solvent to generate charged induced ions;
c) The induced ions are transferred into the capillary 2 for charge exchange with the sample, and the sample is ionized.
As can be seen from the above, the ion-induced spray ionization device of the application adopts a non-contact high-pressure design, namely, the sample is separated from the high pressure, the sample is ionized by directly ionizing the sample by the high pressure, but the charged induced ions are generated by the high-pressure ionization auxiliary solvent, and then the sample is ionized by the charge exchange of the induced ions and the sample, so that the oxidation in a sample generating source can be effectively inhibited, the oxidation-reduction reaction of the sample to be detected can be furthest reduced, the ionization device also has good ionization effect on the sample which is easy to generate oxidation-reduction, in addition, the ionization device also has good compatibility with the ionization solvent because the sample is ionized by the induced ions, the selectivity of the ionization solvent is low, the compatible range of the sample and the sample solvent is larger, the sample can be a compound with lower polarity or larger polarity, the sample solvent can flexibly select a polar or nonpolar solvent, and further the ionization device has good ionization effect on the compound with lower polarity or poor solubility in the polar solvent, and the auxiliary solvent is not limited to the polar solvent but is more compatible with the acetonitrile (the high-polarity and the ionic solvent is not limited to the induction solvent with the polar solvent 2) and the compatible range of the ionic solvent is not transferred to the acetonitrile, therefore, the ionized sample can be sprayed out from the tip of the capillary tube 2 in an atomized state without auxiliary gases such as nitrogen and enter the subsequent mass spectrum sample injection channel 3 for mass spectrum analysis, the cost is low, the implementation is easy, the setting of the capillary tube 2 ensures that the ionization device consumes little sample, and the sample with a volume of only a few pl is required at the minimum, so that the ionization device is applicable to trace analysis and detection work.
In the present application, the voltage provided by the high voltage generator 12 is 1000 to 6000v. The high voltage generator 12 is an induced voltage generator, and generates an induced voltage of 1000 to 6000v. Compared with the conventional high voltage, the induced voltage can better reduce the occurrence of sample redox, and further enhance the ionization effect of the ionization device on unstable samples which are easy to generate redox.
Referring again to fig. 1-4:
The conductive metal foil 13 is fixed on the outside of the auxiliary solvent channel 11, and the high-voltage generating device 12 is connected with the auxiliary solvent channel 11 through the conductive metal foil 13, so that the conductivity of high voltage is enhanced, and the induction effect of the high voltage on the auxiliary solvent is further enhanced. Specifically, the conductive metal foil 13 is fixed outside the auxiliary solvent passage 11 by wrapping.
The flow rate of the auxiliary solvent in the auxiliary solvent channel 11 is 0.1 to 3 microliters/min.
The auxiliary solvent channel 11 may be made of insulating material or non-insulating material, and in the present application, the auxiliary solvent channel 11 is made of insulating material, which includes but is not limited to glass and peek, so as to further ensure the effect of non-contact high-voltage design.
The axis of the capillary 2 is on the same horizontal line as the axis of the mass spectrum sample injection channel 3, and the axis of the auxiliary solvent channel 11 is on the same horizontal line as the axis of the capillary 2, so that ions are induced to enter the capillary 2 to exchange charge with the sample, the sample is ionized, and the ionized sample enters the mass spectrum sample injection channel 3 for subsequent mass spectrum analysis.
The distance d between the tip outlet of the capillary 2 and the port of the mass spectrum sample introduction channel 3 is preferably 1-15 mm. Because the high-pressure generating device 12 is arranged in the auxiliary solvent channel 11, the distance between the high pressure and the mass spectrum sample introduction channel 3 is larger, the influence on the mass spectrometer is smaller, and the mass spectrum analysis effect is further ensured.
The diameter of the tip outlet of the capillary tube 2 is 1-20 microns. In the application, the front end of the capillary tube 2 is designed to be a tip, so that the atomization effect of the sample can be ensured, the sample spray can be conveniently generated, and the ionized sample can be sprayed out of the capillary tube 2 in an atomized state.
The capillary tube 2 is sleeved with a capillary tube fixing device 4 for fixing the capillary tube 2, so that the overall stability of the device is ensured.
Referring again to fig. 2 and 4, the ion generating device 1 includes an auxiliary electrode 14, and the auxiliary electrode 14 is disposed in the auxiliary solvent channel 11. The auxiliary electrode 14 can be matched with high-voltage auxiliary induction ion generation, so that the ionization effect is further improved. The auxiliary electrode 14 is a conductor or a semiconductor. The conductor may be a thin steel needle, and the semiconductor may be carbon fiber. In the present application, the auxiliary electrode 14 is detachable, removable from the auxiliary solvent passage 11, and whether or not the auxiliary electrode 14 is used can be selected as needed.
In the present application, the capillary 2 may be directly used to draw the sample solution, or the sample solution may be introduced into the capillary 2 (specifically, introduced into the tip of the capillary) by other means, and as shown in fig. 3 and fig. 4, the ionization device further includes a sample introduction channel 5, where the sample introduction channel 5 communicates with the end of the capillary 2, and the sample solution may be introduced into the capillary 2 through the sample introduction channel 5 when ionization is performed. The flow rate of the liquid (i.e., the sample solution) in the sample introduction channel 5 is 50 nanoliters to 5 microliters/minute. In practical use, the sample introduction channel 5 may be externally connected with a sample introduction device (not shown), and the sample introduction device includes, but is not limited to, continuous sample introduction devices such as liquid chromatography, gas chromatography, syringe pump, capillary electrophoresis, etc., so that the ionization device can continuously sample and the signal is stable. In the present application, the sample introduction channel 5 may be a peek tube. In order to make the ionization device have better balance and stability, the ionization device further comprises a three-way type fixing device, and the auxiliary solvent channel 11, the capillary tube 2 and the sample introduction channel 5 are respectively fixed in the three-way type fixing device. The three-way fixing device may be a general fixing device, for example, in the present application, the three-way fixing device includes a three-way 6 (which may be a liquid-phase three-way) and a three-way tight joint 7, the auxiliary solvent channel 11, the capillary tube 2, and the sample introducing channel 5 are respectively fixed in three different channels of the three-way 6, the three-way 6 is used for fixing and connecting the auxiliary solvent channel 11, the capillary tube 2, and the sample introducing channel 5, and the three-way tight joint 7 is used for ensuring the liquid tightness of the whole device. In the application, the tee joint 6 and the tee joint tightening joint 7 are made of peek.
The technical effects achieved by the present invention will be further described below with reference to specific application examples.
Example 1
The ion-induced spray ionization device and a mass spectrometer (the mass analyzer is a triple quadrupole rod) are adopted to generate unstable diquat (CAS. 2764-72-9) which is easy to generate oxidation-reduction reaction: Mass spectrometry was performed:
the experimental setup is shown in figure 3.
The method comprises the steps of taking methanol as a sample solvent, dissolving diquat into the methanol to prepare a 100ppm sample solution, introducing the sample solution into a capillary 2 through a sample introduction channel 5, wherein the flow rate of the sample solution in the sample introduction channel 5 is 5 microlitres/min, the distance d between the tip outlet of the capillary 2 and the port of a mass spectrum sample introduction channel 3 is 5mm, introducing the methanol into an auxiliary solvent channel 11 by taking the methanol as an auxiliary solvent, the flow rate of the methanol is 2 microlitres/min, switching on a high-voltage generating device 12, applying 2500V high voltage through the high-voltage generating device 12, ionizing the methanol to generate charged induced ions, transferring the induced ions into the capillary 2 to exchange charges with the sample, and ionizing the sample, wherein the sample ions enter a mass spectrum through the mass spectrum sample introduction channel 3 to perform subsequent mass spectrum analysis, and the analysis result is shown in figure 5. In addition, under the same conditions, the diquat was subjected to mass spectrometry by using conventional Nano-ESI and a mass spectrometer (the mass analyzer is a triple quadrupole rod), and the analysis results are shown in FIG. 6 and FIG. 7.
FIG. 5 is a mass spectrum analysis chart (positive ion mode) of a 100ppm diquat sample obtained by using the ion-induced spray ionization device of the present invention in this example, FIG. 6 is a mass spectrum analysis chart (positive ion mode) of a 100ppm diquat sample obtained by using Nano-ESI in this example, FIG. 7 is a mass spectrum analysis chart (positive ion mode) of a 100ppm diquat sample obtained by using ESI in this example, as can be seen from FIG. 5, the spectrum is easy to analyze without the interference of other impurity ion peaks except the ion peak (m/z 92) related to the compound, and the interference ion peaks (m/z is 157, 183) caused by the oxidation-reduction reaction of the sample in FIGS. 6 and 7 do not appear in the spectrum, which shows that the ion-induced spray ionization method and device of the present invention can effectively reduce the generation of the oxidation-reduction reaction of the compound and realize good ionization effect on the unstable compound which is easy to generate the oxidation-reduction reaction.
Example 2
The ion-induced spray ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole rod) are adopted to carry out anthracene with lower polarity: Mass spectrometry was performed:
the experimental setup is shown in fig. 4.
Toluene is used as a sample solvent, anthracene is dissolved in toluene to prepare 10ppm of sample solution, the sample solution is introduced into a capillary 2 through a sample introduction channel 5, the flow rate of the sample solution in the sample introduction channel 5 is 5 microliter/min, the distance d between the tip outlet of the capillary 2 and the port of a mass spectrum sample introduction channel 3 is 5mm, toluene is used as an auxiliary solvent, toluene is introduced into an auxiliary solvent channel 11, the flow rate of toluene is 2 microliter/min, a high-pressure generating device 12 is connected, 2500V high pressure is applied through the high-pressure generating device 12, meanwhile, an auxiliary electrode 14 (carbon fiber) is matched, so that charged induced ions are generated by the toluene, the induced ions are transferred into the capillary 2 to exchange charges with the sample, so that the sample is ionized, and the sample ions enter a mass spectrum through the mass spectrum sample introduction channel 3 to perform subsequent mass spectrum analysis, and the analysis result is shown in fig. 8. In addition, anthracene was subjected to mass spectrometry using conventional Nano-ESI and a mass spectrometer (a mass analyzer is a triple quadrupole) under the same conditions, and the analysis results are shown in fig. 9 and 10.
FIG. 8 is a mass spectrum analysis chart (positive ion mode) of a 10ppm anthracene sample obtained by using the ion-induced spray ionization device of the present invention in this example, FIG. 9 is a mass spectrum analysis chart (positive ion mode) of a 10ppm anthracene sample obtained by using Nano-ESI in this example, FIG. 10 is a mass spectrum analysis chart (positive ion mode) of a 10ppm anthracene sample obtained by using ESI in this example, as can be seen from FIG. 8, there is no interference of other impurity ion peaks except the ion peak (m/z 179) related to the compound in the spectrogram, and the spectrogram is easy to analyze, and no effective signal is detected in both FIG. 9 and FIG. 10, which shows that the ion-induced spray ionization method and device of the present invention can realize good ionization effect on the compound with lower polarity.
Example 3
The ion-induced spray ionization device and a mass spectrometer (the mass analyzer is Q-TOF) are adopted to carry out mass spectrometry on the single Hela cell methanol extract:
The experimental setup is shown in figure 1.
Methanol is used as a sample solvent, hela cells are cultured in a standard cell culture dish with the thickness of 60mm according to a conventional cell biological culture flow, 15pl of methanol is filled in advance in a capillary tube 2, the Hela cells are penetrated into the Hela cells under the control of a three-dimensional moving platform, the Hela cells are extracted to obtain single Hela cell methanol extract (sample solution), then the capillary tube 2 is fixed, the distance d between the tip outlet of the capillary tube 2 and the port of a mass spectrum sample injection channel 3 is 3mm, methanol is used as an auxiliary solvent, the methanol is introduced into the auxiliary solvent channel 11, the flow rate of the methanol is 0.5 microliter/min, a high-pressure generating device 12 is connected, 2000V of high-pressure is applied through the high-pressure generating device 12, high-pressure ionized methanol is generated, the induced ions are transferred into the capillary tube 2 to exchange charges with the sample, the sample is ionized, and the sample ions enter the mass spectrum sample injection channel 3 for mass spectrum analysis, and the subsequent mass spectrum analysis results are shown in figure 11.
FIG. 11 is a mass spectrum analysis chart (positive ion mode) of a pl-stage single Hela cell methanol extract obtained by using the ion-induced spray ionization device of the present invention in the example, and as can be seen from FIG. 11, peaks of a plurality of cell metabolites appear in the spectrum, particularly, a high signal appears in m/z 600-900, mainly phospholipid components in Hela cells, which illustrates that trace samples can be monitored and analyzed by using the ion-induced spray ionization method and device of the present invention.
Example 4
The ion-induced spray ionization device and a mass spectrometer (the mass analyzer is Q-TOF) are adopted to carry out mass spectrometry on the dichloromethane extract liquid of the single Hela cells:
the experimental setup is shown in figure 2.
Culturing Hela cells in a standard cell culture dish with 60mm according to a conventional cell biology culture flow by taking methylene dichloride as a sample solvent, filling the capillary with 15pl of methylene dichloride in advance, penetrating the Hela cells under the control of a three-dimensional moving platform, extracting the Hela cells to obtain single Hela cell methylene dichloride extract (sample solution), fixing the capillary 2, wherein the distance d between the tip outlet of the capillary 2 and the port of a mass spectrum sample injection channel 3 is 3mm, introducing the methylene dichloride into the auxiliary solvent channel 11 by taking the methylene dichloride as an auxiliary solvent, introducing the methylene dichloride with the flow rate of 0.5 microliter/min, switching on a high-pressure generating device 12, applying 2000V high pressure by the high-pressure generating device 12, simultaneously matching with an auxiliary electrode 14 (carbon fiber) to enable the methylene dichloride to generate charged induced ions, transferring the induced ions into the capillary 2 to exchange charges with the sample, and ionizing the sample, and enabling the sample ions to enter the mass spectrum through the sample injection channel 3 to enter a mass spectrum for subsequent mass spectrum analysis, wherein the analysis results are shown in figure 12. In addition, single Hela cell dichloromethane extract was subjected to mass spectrometry using a conventional Nano-ESI and mass spectrometer (Q-TOF as mass analyzer) under the same conditions, and the analysis results are shown in FIG. 13.
FIG. 12 is a mass spectrum analysis chart (positive ion mode) of a single Hela cell dichloromethane extract obtained by using the ion-induced spray ionization device of the invention in the example, FIG. 13 is a mass spectrum analysis chart (positive ion mode) of a single Hela cell dichloromethane extract obtained by using Nano-ESI in the example, and as can be seen from FIG. 12, a very high signal of phospholipids in Hela cells appears in m/z 600-900 in the spectrogram, a signal peak of cholesterol (m/z 369) which is not detected in FIG. 13 appears, and the effective signal peak obtained in FIG. 13 is less and the spectrogram is more complex, which shows that the polarity range of solvents which can be compatible by using the ion-induced spray ionization method and device of the invention is wider.
In summary, the ion-induced spray ionization method and device can effectively solve the problems of low in-source oxidation and poor ionization solvent compatibility of the samples in the traditional ESI, have good ionization effects on compounds with lower polarity and compounds with easy oxidation-reduction reaction, have good ionization solvent compatibility, therefore, have low selectivity on samples to be tested, sample solvents and auxiliary solvents, can test sample objects, sample solvents and auxiliary solvents, have wide ranges, can be used for conventional analysis and detection, can be used for trace analysis and detection, have strong applicability, and have significant progress and practical value compared with the prior art.
It should be noted that the foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that may be easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
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