CN216133846U - Energy-adjustable in-situ ionization device - Google Patents
Energy-adjustable in-situ ionization device Download PDFInfo
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- CN216133846U CN216133846U CN202122576272.4U CN202122576272U CN216133846U CN 216133846 U CN216133846 U CN 216133846U CN 202122576272 U CN202122576272 U CN 202122576272U CN 216133846 U CN216133846 U CN 216133846U
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Abstract
The utility model discloses an energy-adjustable in-situ ionization device, which comprises a mass spectrum sample introduction channel, a sample introduction device and a pulse plasma generation device, wherein the pulse plasma generation device is used for generating pulse plasma serving as an ion source, the pulse plasma generated by the pulse plasma generation device is positioned in front of a port of the mass spectrum sample introduction channel, and an outlet end or a load sample end of the sample introduction device is positioned in or around the pulse plasma generated by the pulse plasma generation device. By using the pulse plasma as an ion source, the method can realize an ionization method with adjustable hardness and can realize the identification and analysis of isomers; but also can effectively avoid side reactions such as oxidation, degradation, polymerization and the like of the sample; moreover, the range of the measurable samples is wide, the forms are not limited, and the ionization efficiency on volatile small molecules is better; also, it can be used in combination with various sample introduction devices.
Description
Technical Field
The utility model relates to an energy-adjustable in-situ ionization device, and belongs to the technical field of mass spectrometry.
Background
Mass Spectrometry (MS) is an analytical tool for measuring ion mass-to-charge ratio (mass-to-charge ratio). The excellent sensitivity, detection limit, response speed and sample diversity of mass spectrometry make the mass spectrometry important in analytical methods. In recent decades, mass spectrometry has been developed rapidly, and is now widely used in the fields of chemistry and chemical engineering, biology and life science, medicine, pharmacy, material science, food science, environmental protection, atomic physics, etc.
The basic principle of mass spectrometry is to generate organic or inorganic ions by a suitable ionization method, and separate ions with different mass-to-charge ratios, thereby qualitatively or quantitatively detecting atoms or molecules. Therefore, ionization techniques are critical to the analytical results of mass spectrometry. In the beginning of the 20 th century, open mass spectrometry technologies represented by desorption electrospray ionization (DESI) and direct analysis in real time (DART) were developed, and these ion sources, which do not require complex sample preparation and achieve ionization in the original environment of the sample and under the open condition of the ion source, have brought the mass spectrometry technology into a new era.
The open ionization technology has been developed rapidly since the research group of cookies in 2004 developed desorption electrospray ionization (DESI) technology based on electrospray ionization (ESI) and the research group of robert.b. cody in 2005 developed real-time direct analysis ionization (DART) technology based on Atmospheric Pressure Chemical Ionization (APCI). The principle of DART ionization is that a discharge produces gas ions and metastable gas molecules, which react with an analyte to ionize it. However, such ionization techniques generally require the use of helium as the ionized gas, which increases the cost of the analytical test and also results in a complicated apparatus and inconvenient operation. Meanwhile, the ionization method is relatively soft, the obtained related information of the compound is less, and judgment needs to be carried out by combining with multi-stage mass spectrum data.
The plasma is the fourth state of matter except solid, liquid and gas, has been widely applied in daily life and production of people since the discovery of the nineteenth century, and the deep research of the basic principle and the application of the plasma is always a hotspot in the scientific research field.
The applicant discloses a mass spectrum source internal dissociation device based on a plasma principle in patent CN202020796592.3, which uses an arc plasma generating device, but is mainly used for fragmentation dissociation of a sample instead of ionization, and has the problems that the temperature of the used arc is too high, the dissociation degree of the measured compound is high, and the like.
SUMMERY OF THE UTILITY MODEL
In view of the above problems in the prior art, it is an object of the present invention to provide an in-situ ionization apparatus with adjustable energy.
In order to achieve the purpose, the utility model adopts the following technical scheme:
the utility model provides an energy adjustable normal position ionization device, includes mass spectrum sampling channel, sample introducing device and pulse plasma generating device, pulse plasma generating device is used for producing the pulse plasma as the ion source, the pulse plasma that pulse plasma generating device produced is located the port place ahead of mass spectrum sampling channel, the exit end or the load sample end of sample introducing device are arranged in the pulse plasma that pulse plasma generating device produced or around.
One embodiment, pulse plasma generating device includes adjustable voltage input module, impulse voltage generation module and two electrodes, all be connected with the wire between adjustable voltage input module and the impulse voltage generation module, between impulse voltage generation module and the electrode, the electrode is located the port place ahead of mass spectrum introduction passageway, the exit end or the load sample end of sample introducing device are located near the electrode.
According to a preferable scheme, the input voltage of the adjustable voltage input module is 3-30V, the output voltage of the pulse voltage generation module is 3-30 kV, and the distance between the two electrodes is 3-50 mm.
In a preferred embodiment, the shape of the electrode includes, but is not limited to, a rod, a needle, and a plate.
In a preferred embodiment, the material of the electrode includes, but is not limited to, metal, graphite, carbon fiber, and conductive polymer material.
In a preferred embodiment, when the sample introduction device itself is electrically conductive, the sample introduction device can be electrically connected to a pulse voltage generation module in the pulsed plasma generation device for use as one of two electrodes of the pulsed plasma generation device.
In one embodiment, the distance between the pulse plasma region generated by the pulse plasma generating device and the port of the mass spectrum sample feeding channel is 5-50 mm.
In one embodiment, the sample introduction device is a sample loading device, an atmospheric pressure desorption device, or a sample introduction channel.
In a preferable scheme, the loaded sample end of the sample loading device is positioned in or around the pulse plasma generated by the pulse plasma generating device; the outlet end of the atmospheric pressure desorption device is positioned in or around the pulse plasma generated by the pulse plasma generating device; the outlet end of the sample introducing channel is positioned in or around the pulse plasma generated by the pulse plasma generating device.
In a preferred embodiment, the sample loading device includes, but is not limited to, a sample rod, a sample plate, a sampling probe, a capillary, and a forceps.
In a preferred embodiment, the atmospheric pressure desorption device includes, but is not limited to, a conductive heating plate, an ultrasonic atomization sheet, and an atomizer.
In a preferred embodiment, the sample introduction channel includes, but is not limited to, a carrier gas channel, and a spray needle.
Compared with the prior art, the utility model has the beneficial technical effects that:
1. the method uses the pulse plasma as an ion source, does not need to carry out complex pretreatment on the sample, is easy to realize and simple to operate, reduces the analysis cost, simplifies the sampling operation, shortens the analysis time, and can realize the in-situ rapid mass spectrometry of the sample;
2. the utility model creatively uses the pulse plasma to ionize the sample, not only thermal cracking is not easy to be caused, but also the ionization method with adjustable hardness can be realized by regulating and controlling the energy of the pulse plasma, and the identification and analysis of isomers can be realized;
3. compared with some existing open ionization technologies such as paper-based electrospray (PSI), the device has the advantages that the electrodes are not in direct contact with the sample, sample residues are hardly generated, and the device is very convenient to clean and recycle;
4. the device of the utility model simultaneously has a certain elimination effect on the matrix inhibition effect of the sample, and has better tolerance on high-salt solution;
5. as an atmospheric pressure ionization means, the device can be conveniently combined with common sample introduction technologies (such as ultrasonic atomization, atmospheric pressure solid analysis probes and the like) and mass spectrometers (such as triple quadrupole mass spectrometers, time-of-flight mass spectrometers, ion trap mass spectrometers and the like), is expected to have more applications in the aspect of mass spectrometry imaging, and has wide application prospects.
Drawings
FIG. 1 is a schematic diagram of a sample introduction device in an in situ ionization apparatus with adjustable energy according to the present invention as a sample loading device;
FIG. 2 is a schematic diagram of an atmospheric pressure desorption apparatus as a sample introduction apparatus in the energy-tunable in situ ionization apparatus provided by the present invention;
FIG. 3 is a schematic diagram of a sample introduction device in an in situ ionization apparatus with adjustable energy according to the present invention as a sample introduction channel;
FIG. 4 is a schematic diagram of the sample introduction device of the energy tunable in-situ ionization apparatus of the present invention being a conductive heating plate and serving as an electrode;
FIG. 5 is a diagram of mass spectrometry of triethylamine obtained in example 1 of the present invention;
FIG. 6 is a graph of mass spectrometry of octylamine obtained in example 1 of the present invention;
FIG. 7 is a graph of mass spectrometry of metandienone obtained in example 2 of the present invention;
FIG. 8 is a graph of mass spectrometry of citronellal obtained in example 3 of the present invention;
FIG. 9 is a diagram of mass spectrometry of methyl salicylate obtained in example 4 of the present invention (the electrode was a copper wire electrode);
FIG. 10 is a diagram of mass spectrometry of methyl salicylate obtained in example 4 of the present invention (the electrode is a carbon fiber electrode);
FIG. 11 is a graph showing mass spectrometry of methyl salicylate obtained in example 4 of the present invention (the electrode is a graphite electrode);
FIG. 12 is a graph of mass spectrometry of metronidazole obtained in example 5 of the present invention;
FIG. 13 is a graph of mass spectrometry of cholesterol obtained in example 6 of the present invention;
FIG. 14 is a graph of mass spectrometry of cinnamaldehyde obtained in example 7 of the present invention;
FIG. 15 is a graph of mass spectrometry of synthetic capsaicin obtained in example 8 of the present invention;
FIG. 16 is a graph showing mass spectrometry of diethyl maleate obtained in example 9 of the present invention (output voltage 9kV, distance between electrodes 15 mm);
FIG. 17 is a graph showing mass spectrometry of diethyl maleate obtained in example 9 of the present invention (output voltage 15kV, distance between electrodes 5 mm);
FIG. 18 is a graph of mass spectrometry of cinnamaldehyde, a perfume, obtained in example 10 of the present invention;
FIG. 19 is a graph of mass spectrometry of anthracene obtained in example 11 of the present invention;
FIG. 20 is a graph of mass spectrometry of caffeine obtained in example 11 of the present invention;
FIG. 21 is a graph of mass spectrometry of methyl salicylate obtained in example 12 of the present invention;
FIG. 22 is a graph of mass spectrometry of vanillin obtained in example 12 of the utility model;
FIG. 23 is a graph showing the relationship between the molecular ion peak signal intensity and the input voltage of N-N-butylaniline and 4-N-butylaniline obtained in example 13 of the present invention;
FIG. 24 is a graph showing the relationship between the molecular ion peak signal intensity and the input voltage of diethyl maleate obtained in example 14 of the present invention;
FIG. 25 is a graph showing the relationship between the molecular ion peak signal intensity and the input voltage of diethyl fumarate obtained in example 14 of the present invention;
the numbers in the figures are as follows: 1. a mass spectrometry sample introduction channel; 2. pulsed plasma (ion source); 3. a sample; 4. an adjustable voltage input module; 5. a pulse voltage generating module; 6. an electrode; 7. a wire; 8. a conductive heating plate; 9. a needle electrode; 10. a sample loading device; 11. an atmospheric pressure desorption device; 12. a sample introduction channel.
Detailed Description
The technical scheme of the utility model is further described in detail and completely by combining the attached drawings.
As shown in fig. 1 to 4: the utility model provides an energy-adjustable in-situ ionization device which comprises a mass spectrum sample introduction channel 1, a sample introduction device and a pulse plasma generation device, wherein the pulse plasma generation device is used for generating a pulse plasma 2 serving as an ion source, the pulse plasma 2 generated by the pulse plasma generation device is positioned in front of a port of the mass spectrum sample introduction channel 1, and an outlet end or a load sample end of the sample introduction device is positioned in or around the pulse plasma 2 generated by the pulse plasma generation device.
The device can be compatible with common mass spectrometers (such as triple quadrupole mass spectrometers, time-of-flight mass spectrometers, ion trap mass spectrometers and the like), can also be popularized and applied to other mass spectrometry, can be used with the common mass spectrometers when being used for mass spectrometry, and has wide application range and strong practicability.
The method for realizing in-situ ionization by adopting the energy-adjustable in-situ ionization device comprises the steps of taking the pulse plasma 2 as an ion source, introducing the sample 3 into the region of the pulse plasma 2, and enabling the sample 3 to be in contact with the pulse plasma 2 for less than or equal to 1 second until the sample 3 is ionized (namely, the sample 3 is instantaneously ionized in the utility model). Specifically, referring to fig. 1 to 3, a sample 3 is introduced through a sample introduction device; starting a pulse plasma generating device to generate pulse plasma 2 (because the pulse plasma generating device is positioned in front of the port of the mass spectrum sample injection channel 1, namely, a pulse plasma region is generated in front of the port of the mass spectrum sample injection channel 1); when a sample 3 is introduced into the pulsed plasma region, the sample is ionized by the pulsed plasma 2. The generated sample ions enter the mass spectrometer through the mass spectrum sample introduction channel 1, and then mass spectrum analysis of the sample can be realized.
Referring to fig. 1 to 3 again, the pulsed plasma generating device includes an adjustable voltage input module 4, a pulsed voltage generating module 5 and two electrodes 6, wherein wires 7 are connected between the adjustable voltage input module 4 and the pulsed voltage generating module 5, and between the pulsed voltage generating module 5 and the electrodes, the electrodes 6 are located in front of a port of the mass spectrometry sample introduction channel 1, and an outlet end or a load sample end of the sample introduction device is located near the electrodes 6. The electrode 6 corresponds to a pulse plasma generating end of the pulse plasma generating apparatus, and the pulse plasma 2 is generated between the two electrodes 6. Correspondingly, the in-situ ionization method is realized as follows: introducing a sample 3 through a sample introduction device; setting adjustable voltage input module 4Input voltage and distance d between two electrodes 61(ii) a The power supply is switched on, the adjustable voltage input module 4 is started, the current enters the pulse voltage generation module 5 through the adjustable voltage input module 4, the pulse voltage generation module 5 generates high-voltage pulse voltage, and the generated high-voltage pulse voltage is transmitted to the electrode 6 to generate pulse plasma 2 (because the electrode 6 is positioned in front of the port of the mass spectrum sample introduction channel 1, namely, a pulse plasma region is generated in front of the port of the mass spectrum sample introduction channel 1); when a sample 3 is introduced into the pulsed plasma region, the sample is ionized by the pulsed plasma 2. The generated sample ions enter the mass spectrometer through the mass spectrum sample introduction channel 1, and then mass spectrum analysis of the sample can be realized.
From the above, it can be seen that, in the present invention, the energy of the pulsed plasma 2 can be determined by the input voltage of the adjustable voltage input module 4 and the distance d between the two electrodes 61And (5) regulating and controlling. Specifically, the input voltage of the adjustable voltage input module 4 is 3-30V, the output voltage of the pulse voltage generation module 5 is 3-30 kV, and the distance d1 between the two electrodes 6 is 3-50 mm. When the input voltage of the adjustable voltage input module 4 is 10-30V, the output voltage of the pulse voltage generation module 5 is more than 10-30 kV, and the electrode distance d1When the thickness is 3-10 mm, pulse plasma is generated between the electrodes 6, more fragments are generated by ionizing the compound under the action of the pulse plasma, and the pulse plasma mode is adopted, or the mode is called as a hard ionization source; when the input voltage of the adjustable voltage input module 4 is 3-10V, the output voltage of the pulse voltage generation module 5 is 3-10 kV, and the electrode distance d1When the thickness is 10-50 mm, micro plasma is generated between the electrodes 6, and the fragments generated by the ionization of the compound under the action of the micro plasma are less, so that the micro plasma mode is adopted, or the mode is called as a soft ionization source mode. In the pulsed plasma mode, the input voltage of the adjustable voltage input module 4 is preferably 9V, the output voltage of the pulse voltage generation module 5 is preferably 9kV, and the distance d between the two electrodes 61Preferably 15 mm; in the microplasma mode, the input voltage of the adjustable voltage input module 4 is preferablyThe output voltage of the pulse voltage generation module 5 is preferably 15kV at 15V, and the distance d between the two electrodes 61Preferably 5 mm.
In the present invention, the electrode 6 may have a rod shape (as shown in fig. 1 to 3), a needle shape (as shown in fig. 4), or a plate shape. The material of the electrode 6 includes, but is not limited to, metal (e.g., tin-plated copper wire), graphite, carbon fiber, and conductive polymer material.
Further, when the sample-introducing device itself can conduct electricity, the sample-introducing device can be electrically connected to the pulse voltage generation module 5 in the pulsed plasma generation device, for use as one of the two electrodes of the pulsed plasma generation device. Specifically, referring to fig. 4, when the sample introducing device is a conductive heating plate 8, the conductive heating plate 8 is connected to the pulse voltage generating module 5 through a wire 7, and at this time, the conductive heating plate 8 is equivalent to a plate-shaped electrode and can be used as a pair of electrodes together with the needle-shaped electrode 9 in the figure. When in ionization, a solid sample can be firstly placed on the sample loading area on the conductive heating plate 8, or a liquid sample is directly dripped on the sample loading area on the conductive heating plate 8 through a liquid-transfering device, then the power supply is switched on, and pulse plasma 2 is generated between the conductive heating plate 8 and the needle electrode 9, so that the sample is ionized. The conductive heating plate 8 can be placed on a three-dimensional moving platform so that a plurality of samples can be tested. The temperature of the conductive heating plate 8 can be adjusted by a known means such as adjusting the power. In the utility model, the temperature of the conductive heating plate 8 is 20-250 ℃.
In the utility model, the distance d between the area of the pulse plasma 2 generated by the pulse plasma generating device and the port of the mass spectrum sample introduction channel 125-50 mm (preferably 10mm) to ensure the mass spectrometry effect.
In the present invention, the sample introducing means is a sample loading means 10 (shown in FIG. 1), an atmospheric pressure desorption means 11 (shown in FIG. 2) or a sample introducing passage 12 (shown in FIG. 3). Each sample introducing device is positioned near the plasma 2, and after the sample 3 is sent to the area of the plasma 2, the sample 3 is ionized under the action of the energy-adjustable pulse plasma 2.
Referring again to fig. 1, when the sample introduction device is a sample loading device 10, the sample loading end of the sample loading device 10 is located in or around the pulsed plasma 2 generated by the pulsed plasma generation device, and the sample loading device 10 includes, but is not limited to, a sample rod, a sample plate (which may be a conductive metal plate), a sampling probe, a capillary tube, and tweezers. When introducing the sample, for example: the liquid sample can be dipped by a sample rod and placed in or around the pulsed plasma; or directly putting the solid sample into the pulsed plasma; or the sample is placed directly on the conductive sample plate, and a pulsed plasma is generated between the electrode and the conductive sample plate.
Referring again to fig. 2, when the sample introducing device is an atmospheric pressure desorption device 11, the outlet end of the atmospheric pressure desorption device 11 is located in or around the pulsed plasma 2 generated by the pulsed plasma generating device, and the atmospheric pressure desorption device 11 includes, but is not limited to, a conductive heating plate, an ultrasonic atomization sheet, and an atomizer. When introducing the sample, for example: the liquid sample can be dropped on the conductive heating plate through the dropping device, and the pulsed plasma is generated through the conductive heating plate and the electrode, so that the sample is introduced into or around the pulsed plasma; or directly placing the solid sample on a conductive heating plate, and introducing the sample into or around the pulse plasma by generating the pulse plasma through the conductive heating plate and the electrode; or dropping the liquid sample on an ultrasonic atomization sheet, and introducing the atomized sample into or around the pulsed plasma through the atomization sheet.
Referring again to fig. 3, when the sample introducing device is a sample introducing channel 12, the outlet end of the sample introducing channel 12 is located in or around the pulsed plasma 2 generated by the pulsed plasma generating device, and the sample introducing channel 12 includes, but is not limited to, a carrier gas channel, and a spray needle. When introducing the sample, for example: a gaseous sample can be blown into or around the pulse plasma through the carrier gas channel; or introducing a sample spray into or around the pulsed plasma using a spray needle; or dissolving the solid sample into a solution, and introducing the solution into the pulsed plasma or around the pulsed plasma by a spraying or dripping device.
The technical effects achieved by the present invention will be further described below with reference to specific application examples.
Example 1
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to react with amine compound triethylamine
(MW 101) and octylamine
(MW 129) mass spectrometry was performed:
a sample is introduced using a sample loading device 10, the sample loading device 10 being a glass rod.
Preparing triethylamine and octylamine into 1mg/mL sample solutions by using an acetonitrile solvent respectively; introducing a sample by dipping a glass rod; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is set to be 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, the volatilized sample is ionized under the effects of the energy, the chemical reactivity and the like of the pulse plasma 2, the generated proton ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is enabled to be in a collecting state all the time.
FIG. 5 is a mass spectrum of triethylamine obtained in the present example, FIG. 6 is a mass spectrum of octylamine obtained in the present example, as shown in FIGS. 5 and 6: the pattern is shown except for [ M + H ] related to the compound]+And outside the peak, the interference of other impurity ion peaks is little, which shows that the in-situ ionization device has good detection capability on small molecular amine compounds.
Example 2
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to remove the steroid compoundsMethanetestosterone hydrate
(MW 301) mass spectrometry was performed:
a sample is introduced using a sample loading device 10, the sample loading device 10 being a glass rod.
Preparing metandienone into a sample solution of 0.1mg/mL by using an acetonitrile solvent; introducing a sample by dipping a glass rod; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, the sample is desorbed and ionized under the action of the energy, chemical reactivity and the like of the pulse plasma 2, the generated proton-added ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in a collection state.
Fig. 7 is a mass spectrum of metandienone obtained in this example, as shown in fig. 7: the spectrum is shown except for [ M + H ] related to the compound]+The interference of other impurity ion peaks except the peak (m/z 301) is little, which indicates that the in-situ ionization device has good ionization efficiency on the steroid compounds.
Example 3
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to carry out ionization on aldehyde compound citronellal
(MW 154) mass spectrometry was performed:
introducing a sample by using a sample loading device 10, wherein the sample loading device 10 is a glass rod;
preparing citronellal into a sample solution of 0.1mg/mL by using an acetonitrile solvent; introducing a sample by dipping a glass rod; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, the sample is desorbed and ionized under the action of the energy, chemical reactivity and the like of the pulse plasma, the generated proton-added ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in a collection state.
FIG. 8 is a mass spectrum of citronellal obtained in this example, as shown in FIG. 8: the interference of other impurity ion peaks except the [ M + H ] + peak (M/z 155) related to the compound in a spectrogram is little, which shows that the in-situ ionization device has good ionization efficiency on the small-molecular aldehyde compound.
Example 4
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to carry out the reaction on the compound methyl salicylate
Mass spectrometry was performed (MW 152):
introducing a sample by using a sample loading device 10, wherein the sample loading device 10 is a glass rod; the electrode 6 is a copper wire electrode, a graphite electrode and a carbon fiber electrode;
preparing methyl salicylate into a sample solution of 0.1mg/mL by using an acetonitrile solvent; introducing a sample by dipping a glass rod; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, the sample is desorbed and ionized under the action of the energy, chemical reactivity and the like of the pulse plasma, the generated proton-added ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in a collection state.
FIG. 9 is a mass spectrum of methyl salicylate obtained using a copper wire electrode according to the present example; FIG. 10 is a mass spectrum of methyl salicylate obtained using a carbon fiber electrode in the present example; FIG. 11 is a mass spectrum of methyl salicylate obtained using a graphite electrode in the present example; as can be seen from fig. 9 to 11: the spectrum is shown except for [ M + H ] related to the compound]+The interference of other impurity ion peaks outside the peak (m/z153) is little, which shows that the in-situ ionization device provided by the utility model can be suitable for electrodes made of various conductive materials.
Example 5
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted for carrying out metronidazole treatment on solid tablets
Mass spectrometry was performed (MW 171):
introducing a sample by using a sample loading device 10, wherein the sample loading device 10 is a pair of tweezers;
putting metronidazole tablets in the middle of the electrode 6 by using tweezers; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, the sample is desorbed and ionized under the action of the energy, chemical reactivity and the like of the pulse plasma, the generated proton-added ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in a collection state.
FIG. 12 is a mass spectrum of metronidazole obtained in this example, as shown in FIG. 12: the spectrum is shown except for [ M + H ] related to the compound]+The peak (m/z 172) is not interfered by other impurity ion peaks, which shows that the in-situ ionization device has good ionization efficiency on solid samples.
Example 6
By adopting the utility modelThe energy-adjustable in-situ ionization device and the mass spectrometer (the mass analyzer is a triple quadrupole) are used for cholesterol
(MW 386) mass spectrometry:
introducing a sample by adopting an atmospheric pressure desorption device 11, wherein the atmospheric pressure desorption device 11 is an ultrasonic atomization sheet;
preparing cholesterol into a sample solution of 0.1mg/mL by using a dichloromethane solvent; dropwise adding the sample solution on an ultrasonic atomization device; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, and the distance between the two electrodes 6 is 5 mm; and opening the ultrasonic atomization device to enable the atomized sample to enter the middle or periphery of the pulse plasma, desorbing and ionizing the sample under the action of the energy, chemical reactivity and the like of the pulse plasma, enabling the generated proton-added ions to enter a mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and enabling the mass analyzer to be in an acquisition state all the time.
FIG. 13 is a mass spectrum of cholesterol obtained in this example, as shown in FIG. 13: the spectrum is not related to [ M-H ] of the compound2O+H]+The interference of other impurity ion peaks outside the peak (m/z 369) is little, which shows that the combination of the in-situ ionization device and the ultrasonic atomizer of the atmospheric pressure desorption device has good ionization effect.
Example 7
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted for the cinnamaldehyde
Mass spectrometry was performed (MW 132):
introducing a sample by using a sample introduction channel 12, wherein the sample introduction channel 12 is a spray needle;
preparing cinnamaldehyde into a sample solution of 0.1mg/mL by using an acetonitrile solvent; introducing the sample solution into a spray needle through a sample tube, and spraying the sample solution out of the spray needle in a spray mode under the action of auxiliary gas; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, and the distance between the two electrodes 6 is 5 mm; under the action of the energy, chemical reactivity and the like of the pulse plasma, the sample spray is subjected to desorption ionization, the generated proton ions enter a mass spectrometer through a mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in an acquisition state.
FIG. 14 is a mass spectrum of cinnamaldehyde obtained in this example, as shown in FIG. 14: the spectrum is shown except for [ M + H ] related to the compound]+The peak (m/z 133) is not interfered by other impurity ion peaks, which shows that the in-situ ionization device and the spray needle of the sample introducing device have good ionization effect when being used together.
Example 8
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to synthesize the capsaicin
(MW 293) mass spectrometry:
introducing a sample by adopting an atmospheric pressure desorption device 11, wherein the atmospheric pressure desorption device 11 is a conductive heating plate;
preparing the synthesized capsaicin into a sample solution of 0.1mg/mL by using an acetonitrile solvent; dropping 20 μ L of the sample solution on a conductive heating plate by a dropping device; opening the conductive heating plate to raise the temperature to 100 ℃; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, and the distance between the two electrodes 6 is 5 mm; the sample is desorbed from the conductive heating plate, under the action of the energy, chemical reactivity and the like of the pulse plasma, the sample is ionized, the generated proton ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in an acquisition state.
FIG. 15 is a spectrum of the synthetic capsaicin obtained in this example, as shown in FIG. 15: the spectrum is shown except for [ M + H ] related to the compound]+The peaks (m/z is 294) and other impurity ion peaks have little interference, which shows that the in-situ ionization device and the atmospheric pressure desorption device (conductive heating plate) have good ionization effect.
Example 9
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted for the diethyl maleate
(MW 172) mass spectrometry was performed at different voltages and discharge modes:
introducing a sample by using a sample loading device 10, wherein the sample loading device 10 is a glass rod;
preparing diethyl maleate into a sample solution of 0.1mg/mL by using an acetonitrile solvent; introducing a sample by dipping a glass rod; opening an adjustable voltage input module 4 of the pulse plasma generating device, adjusting the input voltage to be 8V direct current under a micro plasma discharge mode, enabling the distance between two electrodes 6 to be 15mm, enabling the current to generate pulse voltage through a pulse voltage generating module 5, enabling the output voltage to be 9kV, and generating micro plasma (namely micro pulse plasma) between the electrodes 6; in addition, under a pulse plasma discharge mode, the input voltage can be adjusted to be 15V direct current, the distance between the two electrodes 6 is 5mm, the current generates pulse voltage through the pulse voltage generation module 5, the output voltage is 15kV, and pulse plasma is generated between the electrodes 6; the sample is continuously contacted with the pulse plasma 2 for 1 second, under the action of the energy, the chemical reactivity and the like of the pulse plasma, the sample is ionized, the generated proton ions and fragment ions enter a mass spectrometer through a mass spectrum sample inlet to realize detection, and the mass analyzer is always in an acquisition state.
FIG. 16 is a mass spectrum of diethyl maleate obtained in the microplasma discharge mode (soft ionization source mode, output voltage of 9kV, distance between electrodes 6 of 15mm) of the present example, and FIG. 17 is a mass spectrum of diethyl maleate obtained in the pulsed plasma mode (hard ionization source mode, output voltage of 15kV, distance between electrodes 6 of 5mm) of the present example; as shown in FIG. 16, the molecular fragmentation is significantly reduced at low voltage, and as shown in FIG. 16, more fragment signals are generated at high voltage, indicating that the present invention can selectively generate molecular fragmentation information according to the plasma energy.
Example 10
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted for common spice cinnamaldehyde
Mass spectrometry was performed (MW 132):
introducing a sample by adopting an atmospheric pressure desorption device 11, wherein the atmospheric pressure desorption device 11 is a conductive heating plate 8, and the conductive heating plate 8 and the needle-shaped electrode 9 jointly form a pair of electrodes;
preparing cinnamaldehyde into a sample solution of 0.1mg/mL by using an acetonitrile solvent; dropping 20 μ L of the sample solution to the sample loading area on the conductive heating plate 9 by a dropping device; the conductive heating plate 9 is opened to raise the temperature to 100 ℃; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, pulse plasma 2 is generated between the needle electrode 9 and the conductive heating plate 8, the distance between the needle electrode 9 and the conductive heating plate 8 is 8mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, under the action of the energy, the chemical reactivity and the like of the pulse plasma, the sample is ionized, the generated proton ions enter the mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in a collection state.
Fig. 18 is a cinnamaldehyde mass spectrum obtained in this example (the electrode is a needle electrode consisting of a needle electrode 9 and a conductive heating plate 8), and it can be seen from fig. 18: the peaks of other impurity ions except the [ M + H ] + peak (M/z ═ 132) related to the compound in the spectrogram are less interfered, and the needle plate electrode pulse plasma adopted by the utility model has good ionization efficiency on volatile small molecules.
Example 11
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to process anthracene of different samples on the same electrode plate
(MW 178) and caffeine
(MW 194) mass spectrometry was performed:
a sample is introduced by adopting a sample loading device 10, the sample loading device 10 is a sample plate, the sample plate is a metal plate (the metal plate is similar to the unheated conductive heating plate 8 in the figure 4), and the metal plate and the needle-shaped electrode 9 jointly form a pair of electrodes;
preparing anthracene into a sample solution of 0.1mg/mL by using a dichloromethane solvent; preparing caffeine into a sample solution of 0.1mg/mL by using a methanol solvent; respectively dripping 20 mu L of two sample solutions on a metal plate by a dripping device, wherein the distance between the two samples is 1 mm; the metal plate is not heated and is used as a common sample loading device, and the metal plate is placed on a three-dimensional moving platform; meanwhile, the metal plate is connected with the pulse voltage generation module 5 through a lead 7, so that the metal plate is used as one electrode of the electrodes, and the other electrode of the electrodes is a needle electrode 9, thus the metal plate and the needle electrode 9 jointly form a pair of electrodes; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, pulse plasma is generated between the needle electrode 9 and the metal plate, the distance between the needle electrode 9 and the metal plate is 8mm, the three-dimensional moving platform is adjusted, two samples on the metal plate are respectively and continuously contacted with the pulse plasma 2 for 1 second, under the action of the energy, the chemical reactivity and the like of the pulse plasma, the samples are ionized, the generated proton ions enter the mass spectrometer through the mass spectrum sampling channel 1 to realize detection, and the mass analyzer is always in a collecting state.
Fig. 19 is a mass spectrum of anthracene obtained in this example (electrode is needle electrode 9 and metal plate composed of needle electrode), fig. 20 is a mass spectrum of caffeine obtained in this example (electrode is needle electrode 9 and metal plate composed of needle electrode), and it can be seen from fig. 19 and 20: the two spectra clearly show the spatial resolution of two different compounds, which shows that the in-situ ionization device can realize the spatial resolution of the compounds, is expected to have more applications in the aspect of mass spectrum imaging, and has wide application prospect.
Example 12
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to carry out the pair of common isomer methyl salicylate
(MW 152) with vanillin
Mass spectrometry was performed (MW 152):
introducing a sample by using a sample introduction channel 12, wherein the sample introduction channel 12 is a zero-pressure spray needle;
preparing methyl salicylate and vanillin into a sample solution of 0.1mg/mL by using an acetonitrile solvent; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is 15V direct current, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 15kV, the pulse plasma 2 is generated between the two electrodes 6, the distance between the two electrodes 6 is 5mm, a sample is continuously contacted with the pulse plasma 2 for 1 second, under the action of energy, chemical reactivity and the like of the pulse plasma, the sample is sprayed out of the spray needle and ionized by the pulse plasma and dissociated in the source, the generated proton ions and fragment ions enter the mass spectrometer through the mass spectrum sampling channel 1 to be detected, and the mass analyzer is enabled to be in a collecting state all the time.
FIG. 21 is a mass spectrum of the molecular ion peak and its fragment peak signals of methyl salicylate obtained in this example, and FIG. 22 is a mass spectrum of the molecular ion peak and its fragment peak signals of vanillin obtained in this example; as can be seen from fig. 21 and 22: the energy-adjustable in-situ ionization device can realize the detection and identification of isomers.
Example 13
The energy-adjustable in-situ ionization device and a mass spectrometer (a mass analyzer is a triple quadrupole) are adopted to carry out the pair of common isomer N-N-butylaniline
(MW 149) with 4-n-butylaniline
(MW 149) mass spectrometry was performed to analyze the trend of the mass response signal as a function of energy:
introducing a sample by using a sample loading device 10, wherein the sample loading device 10 is a glass rod;
preparing N-N-butylaniline and 4-N-butylaniline into a sample solution of 0.1mg/mL by using a solvent B; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is direct current of 7.5V-12.5V, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 7.5kV-12.5kV, the pulse plasma 2 is generated between the two electrodes 6, and the distance between the two electrodes 6 is 5 mm; the sample is continuously contacted with the pulse plasma 2 for 1 second, the sample is desorbed and ionized under the action of the pulse plasmas with different energies, the generated proton ions enter a mass spectrometer through the mass spectrum sample introduction channel 1 to realize detection, and the mass analyzer is always in an acquisition state.
FIG. 23 is a graph showing the relationship between the molecular ion peak signal intensity and the input voltage of N-N-butylaniline and 4-N-butylaniline obtained in this example, as shown in FIG. 23: for a pair of isomers, the relationship curve between the molecular ion peak intensity and the input voltage is different, so that the in-situ ionization device can detect and identify the isomers.
Example 14
The in-situ ionization device adopting the pulse plasma principle and the mass spectrometer (the mass analyzer is a triple quadrupole) are used for pairing common one pair of isomer diethyl maleate
(MW 172) with diethyl fumarate
(MW 172) mass spectrometry was performed to analyze the trend of the mass spectrum signal as a function of energy:
introducing a sample by using a sample introduction channel 12, wherein the sample introduction channel 12 is a zero-pressure spray needle;
respectively preparing N-N-butylaniline and 4-N-butylaniline into 0.1mg/mL sample solutions by using an acetonitrile solvent; the adjustable voltage input module 4 of the pulse plasma generating device is opened, the input voltage is direct current of 7.5V-12.5V, the current generates pulse voltage through the pulse voltage generating module 5, the output voltage is 7.5kV-12.5kV, the pulse plasma 2 is generated between the two electrodes 6, and the distance between the two electrodes 6 is 5 mm; the two samples are respectively and continuously contacted with the pulse plasma 2 for 1 second, the samples are desorbed and ionized under the action of the pulse plasmas with different energies, the generated proton ions enter a mass spectrometer through a mass spectrum sample introduction channel to realize detection, and the mass analyzer is always in an acquisition state.
FIG. 24 is a graph showing the relationship between the molecular ion peak signal intensity of N-N-butylaniline obtained in this example and the input voltage, and FIG. 25 is a graph showing the relationship between the molecular ion peak signal intensity of 4-N-butylaniline obtained in this example and the input voltage, as shown in FIGS. 24 and 25: for a pair of isomers, the relationship curve between the molecular ion peak signal intensity and the input voltage is different, so that the in-situ ionization device can detect and identify the isomers.
It is finally necessary to point out here: the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. An energy-adjustable in-situ ionization device is characterized in that: including mass spectrum introduction channel, sample introducing device and pulse plasma generating device, pulse plasma generating device is used for producing the pulse plasma as the ion source, the pulse plasma that pulse plasma generating device produced is located mass spectrum introduction channel's port place ahead, the exit end of sample introducing device or load sample end are located pulse plasma that pulse plasma generating device produced or around.
2. The energy tunable in-situ ionization device of claim 1, wherein: the pulse plasma generating device comprises an adjustable voltage input module, a pulse voltage generating module and two electrodes, wherein wires are connected between the adjustable voltage input module and the pulse voltage generating module and between the pulse voltage generating module and the electrodes, the electrodes are positioned in front of a port of a mass spectrum sample introduction channel, and the outlet end or the load sample end of the sample introducing device is positioned near the electrodes.
3. The energy tunable in-situ ionization device of claim 2, wherein: the input voltage of the adjustable voltage input module is 3-30V, the output voltage of the pulse voltage generation module is 3-30 kV, and the distance between the two electrodes is 3-50 mm.
4. The energy tunable in-situ ionization device of claim 2, wherein: the morphology of the electrode includes, but is not limited to, rod-like, needle-like, plate-like.
5. The energy tunable in-situ ionization device of claim 1, wherein: the distance between a pulse plasma region generated by the pulse plasma generating device and the port of the mass spectrum sample feeding channel is 5-50 mm.
6. The energy tunable in-situ ionization device of claim 1, wherein: the sample introducing device is a sample loading device, an atmospheric pressure desorption device or a sample introducing channel.
7. The energy tunable in-situ ionization device of claim 6, wherein: the load sample end of the sample loading device is positioned in or around the pulse plasma generated by the pulse plasma generating device; the outlet end of the atmospheric pressure desorption device is positioned in or around the pulse plasma generated by the pulse plasma generating device; the outlet end of the sample introducing channel is positioned in or around the pulse plasma generated by the pulse plasma generating device.
8. The energy tunable in-situ ionization device of claim 6 or 7, wherein: the sample loading device includes but is not limited to a sample rod, a sample plate, a sampling probe, a capillary tube and a tweezers.
9. The energy tunable in-situ ionization device of claim 6 or 7, wherein: the atmospheric pressure desorption device comprises but is not limited to a conductive heating plate, an ultrasonic atomization sheet and an atomizer.
10. The energy tunable in-situ ionization device of claim 6 or 7, wherein: the sample introducing channel includes but is not limited to a carrier gas channel and a spray needle.
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