CN112635292B - Thermal desorption ionization mechanism verification device and application thereof - Google Patents
Thermal desorption ionization mechanism verification device and application thereof Download PDFInfo
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- CN112635292B CN112635292B CN202011395404.7A CN202011395404A CN112635292B CN 112635292 B CN112635292 B CN 112635292B CN 202011395404 A CN202011395404 A CN 202011395404A CN 112635292 B CN112635292 B CN 112635292B
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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
- G01N27/626—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 heat to ionise a gas
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/4205—Device types
- H01J49/421—Mass filters, i.e. deviating unwanted ions without trapping
- H01J49/4215—Quadrupole mass filters
Abstract
The invention discloses a thermal desorption ionization mechanism verification device, which relates to the technical field of mass spectrometry, and comprises: the front end of the heat source is provided with conductive performance; the electronic generator is connected in series at the front end of the heat source; and the inlet of the mass spectrometer is positioned on the same horizontal line with the front end of the heat source. For compounds in low polarity solvents, the ionization analysis of the main components can be directly realized by using the device of the invention, and no other pretreatment or complicated instrument is needed. Compared with the conventional thermal desorption ionization technology, the device provided by the invention has a simple structure, the individuation of heat sources and electrons is radically clarified, and in-situ analysis of complex matrix samples such as cream, spray, eye drops and the like can be realized.
Description
Technical Field
The invention relates to the technical field of mass spectrometry, in particular to a thermal desorption ionization mechanism verification device and application thereof.
Background
The mass spectrum is an analysis method for realizing analysis by measuring the mass-to-charge ratio (m/z) of a sample to be detected, and has the characteristics of high analysis efficiency, high sensitivity, capability of being used for complex systems and the like. The basic principle of mass spectrometry is that a sample to be tested is ionized in an ion source to form gas-phase ions with different mass-to-charge ratios, an ion beam is formed by the action of an electric field and enters a mass analyzer, and the ions with different mass-to-charge ratios are separated by the action of the electric field or the magnetic field in the mass analyzer and are respectively focused on a mass detector to obtain a mass spectrogram. Mass spectrometry can be used to determine the molecular weight and structure of a compound and can be used to perform quantitative analysis.
Currently, conventional electrospray ion sources (ESI) and bombardment ion sources (EI) are capable of satisfying only certain polar compound analyses, and many mass spectrometry researchers are trying to invent an open ionization technique (AIMS) to satisfy a broader and more efficient ionization technique. The techniques currently in common use based on thermal desorption ionization are desorption electrospray ionization (DESI), matrix Assisted Laser Desorption Ionization (MALDI), electrospray assisted laser desorption ionization (ELDI), direct real-time analysis (DART), laser ablation electrospray ionization (LAESI), dielectric Barrier Discharge Ionization (DBDI), open flame ionization (AFI), carbon Fiber Ionization (CFI), rapid burst desorption ionization (FEDI), etc., which are characterized by real-time, high efficiency, high sensitivity, etc., and require no or only few sample preparation processes.
AIMS has been widely used in food safety monitoring, medical diagnosis, pharmaceutical analysis, biochemical analysis, environmental pollutant monitoring, polymer identification, molecular imaging, etc. While the AIMS ionization technology obtains relatively good detection effect, the defect of mechanism explanation is also present, most mechanisms focus on researching the application scene and mechanism of thermal desorption ionization, and the thermal desorption and ionization limits in the thermal desorption ionization are not clear, and deep research on related aspects is lacking, so that the elucidation of the thermal desorption ionization mechanism is fundamentally realized, the rapid construction of a thermal desorption ion source based on instruction is facilitated for a conventional laboratory, and theoretical guidance and research convenience are provided for a mass spectrometry laboratory.
Disclosure of Invention
The invention aims to provide a thermal desorption ionization mechanism verification device and application thereof, wherein an ion source is a hot electron ion source, so that a sample to be detected is ionized to generate fragment ions, and a strong proton addition peak and an addition peak of ammonium ions, sodium ions and potassium ions can be obtained through a mass analyzer of a mass spectrometer, so that the analysis of main components of low-polarity compounds, multi-type compounds and complex matrixes can be well satisfied; the method has the characteristics of low cost, simple and convenient operation, high ionization efficiency, no matrix interference, normal pressure operation and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a thermal desorption ionization mechanism verification apparatus, comprising:
the front end of the heat source is provided with conductive performance;
the electronic generator is connected in series at the front end of the heat source;
and the inlet of the mass spectrometer is positioned on the same horizontal line with the front end of the heat source.
The electron generator and the heat source are combined together to form a thermionic ion source, the thermionic ion source has relatively high ionization efficiency, and the operation is simple, and only one heat source and one electron generator in any form are needed; the applicability of the sample to be tested in the field of analysis science is proved by directly and conveniently analyzing the complex matrix sample of the actual sample without complex pretreatment before analysis, for example, ionization analysis is carried out by taking the main components in western medicines in different dosage forms such as spray, oral liquid, soft (cream) and the like and various types of compounds as objects.
The method has the advantages that the desorption and ionization of the sample to be detected are all the time an important scientific problem and research field of mass spectrometry, a mass spectrometry method based on thermal desorption has proven application value and is widely applied, the technology has no requirement on sample pretreatment, the sensitivity is high, and the quick detection of different types of organic molecules in different samples to be detected can be realized. However, the limits of thermal desorption and ionization are not obvious in most of the reported methods, and no research on the root-cause action mechanism is available at present.
Further, the distance between the front end of the heat source and the inlet of the mass analyzer is 0.5mm-20mm.
Further, the heat source comprises an electric soldering iron, a hot glue gun and an electric hair drier, and can also be a gas furnace, an oil furnace, a heat pump, solar energy, a lighter and plasma which are used as heat generating parts and are matched with a conductive conductor.
Further, the front end of the heat source is shaped like a horseshoe head, a pointed head, a bent pointed head, a flat head, a round head, a bent round head, a K-shaped tool bit, a round pointed head and a straight head.
Further, electrons generated by the electron generator are provided by alternating current or by direct current or by plasma contact. The plasma includes arc discharge, corona discharge, glow discharge, radio frequency discharge, dielectric barrier discharge, microwave induced discharge, and the like.
Further, the mass analyzer of the mass spectrometer is a single focus mass analyzer, a dual focus mass analyzer, a quadrupole mass analyzer, an ion trap mass analyzer, a fourier transform ion cyclotron resonance, or a time-of-flight mass analyzer.
Further, the distance between the serial connection position of the electron generator and the front end of the heat source and the front end head of the heat source is more than 2cm.
The invention also provides application of the thermal desorption ionization mechanism verification device, which comprises the following steps:
(1) Switching on a heat source power supply, and keeping stable when the temperature rises to a set value;
(2) Dipping a small amount of sample to be tested by using a sample applicator, placing the sample to be tested at the front end of a heat source, and starting an electronic generator;
(3) The sample to be tested is subjected to thermal desorption and is added with protons of water molecules in the air to form sample ions, and the sample ions sequentially enter a mass analyzer and a mass detector of the mass spectrometer.
The angle between the central axis of the sample applicator and the inlet centerline of the mass spectrometer may be any angle. The sample applicator is a high temperature resistant glass capillary, quartz capillary, microinjector, or the like. The sample applicator is solid, or may be hollow.
In the step (1), the set value of the temperature is 20-900 ℃.
In the step (2), the substance form of the sample to be measured is semisolid, liquid or solid (the melting point is lower than the temperature of the heat source). When the sample to be measured is semisolid or liquid, the sample volume is 0.01-1000 mu L.
Compared with the prior art, the invention has the following beneficial effects:
1. for compounds in low polarity solvents, the ionization analysis of the main components can be directly realized by using the device of the invention, and no other pretreatment or complicated instrument is needed.
2. Compared with the conventional thermal desorption ionization technology, the device provided by the invention has a simple structure, the individuation of heat sources and electrons is radically clarified, and in-situ analysis of complex matrix samples such as cream, spray, eye drops and the like can be realized.
3. The device is compatible with common mass spectrometers such as a time-of-flight mass spectrometer, a triple quadrupole mass spectrometer, an ion trap mass spectrometer, a Fourier transform ion cyclotron resonance mass spectrometer, a magnetic mass spectrometer, an orbitrap mass spectrometer and the like, so that the device can be conveniently popularized to mass spectrometers of different types, and has wide application range and strong practicability.
Drawings
FIG. 1 is a schematic diagram of a thermal desorption ionization mechanism verification apparatus provided by the present invention;
FIG. 2 is a mass spectrum of the ferrocene methanol solution analyzed in example 1.
FIG. 3 is a mass spectrum of the analytical kaempferol methanol solution of example 2: (a) positive ion mode, (b) negative ion mode, and (c) secondary separation mass spectrum in positive ion mode.
Fig. 4 is a mass spectrum of the methanol solution of testosterone of methyl alcohol analyzed in example 3.
FIG. 5 is a mass spectrum of an acenaphthylene methanol solution analyzed in example 4.
FIG. 6 is a mass spectrum of example 5 for analysis of PEG 1000 in methanol.
FIG. 7 is a mass spectrum of the methanol solution of perfluorooctanoic acid analyzed in example 6.
Fig. 8 is a mass spectrum of the vitamin D3 methanol solution analyzed in example 7.
Fig. 9 is a mass spectrum of an analytical formestane methanol solution of example 8: (a) A mass spectrum in a positive ion mode, and (b) a secondary separation mass spectrum in the positive ion mode.
FIG. 10 is a mass spectrum of an analytical androsterone acetone solution of example 9.
FIG. 11 is a mass spectrum of an estradiol benzoate methanol solution analyzed in example 10.
Fig. 12 is a mass spectrum of example 11 for analysis of testosterone methanol solution.
FIG. 13 is a mass spectrum of an analytical 1-nitropyrene methanol solution of example 12.
FIG. 14 is a mass spectrum of an analytical levofloxacin eye drop of example 13.
The marks in the figure: 1-mass spectrometer, 2-electron generator, 3-heat source, 4-sample applicator.
Detailed Description
The present invention is further described below in conjunction with embodiments, which are merely some, but not all embodiments of the present invention. Based on the embodiments of the present invention, other embodiments that may be used by those of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
Example 1:
as shown in fig. 1, the thermal desorption ionization mechanism verification device provided by the present invention includes: a heat source 3, wherein the front end of the heat source 3 has electric conduction performance; an electron generator 2, wherein the electron generator 2 is connected in series at the front end of the heat source 3; the inlet of the mass spectrometer 1 is positioned on the same horizontal line with the front end of the heat source 3.
The sample applicator 4 is a high-temperature-resistant sample transfer probe such as a glass capillary, a microinjector and the like; the sample applicator 4 is solid or hollow and the sample applicator 4 is either blunt or sharp.
The distance between the electron generator 2 and the front end head of the heat source 3 is more than 2cm, so as to avoid the direct action and influence of an electric field and plasma on a sample; the distance d between the front end of the heat source 3 and the inlet of the mass spectrometer 1 is 0.5mm to 20mm.
A method for detecting organic ions by a thermal desorption ionization mechanism verification device, comprising the following steps:
(1) Switching on the power supply of the heat source 3, and keeping stable when the temperature rises to a set value;
(2) Dipping a small amount of sample to be tested by using a sample applicator 4, placing the sample to be tested at the front end of a heat source 3, and starting an electronic generator 2;
(3) The sample to be measured is thermally desorbed and adducted with protons of water molecules in the air to form sample ions, which sequentially enter a mass analyzer and a mass detector of the mass spectrometer 1.
The sample to be measured is liquid or semisolid, can be directly dipped, and can also be quantitatively loaded with a certain volume of sample.
When the sample to be measured is solid, the sample can be directly dipped and melted at high temperature, so that ionization analysis of the compounds in the solid sample is realized.
As a preferable scheme, the concentration of the sample solution is 0.05-100 mug/mL; the volume of the quantitatively loaded sample solution is 0.01-1000 mu L.
Example 1
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of Ferrocene (Ferrocene), a sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (flat head) of the electric soldering iron heat source 3 and a mass spectrum inlet is 4mm,5A current is applied to a position with a distance of 2cm from the front end of the heat source 3, the temperature of the heat source 3 is 400 ℃, the voltage of the capillary is 30V, the temperature of the capillary is 300 ℃, the voltage of a tube lens is 100V, and data are collected in a positive ion mode.
In this example, the selected test compound was ferrocene, and the reagent was methanol at a concentration of 15. Mu.g/mL. FIG. 3 is a mass spectrum of the ferrocene methanol solution (0.5. Mu.L) of the present example obtained using the apparatus of the present invention. The mass spectrum result shows that the addition peak [ M+H ] of ferrocene and proton] + The m/z is 187. This is different from the conventional desorption ionization results, which tend to be molecular ion peaks, due to the lower ionization energy of ferrocene.
Example 2
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of Kaempferol (Kaempferol), a sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (round head) of the electric soldering iron heat source 3 and a mass spectrum inlet is 5mm,4A current is applied to a position 3cm away from the front end of the heat source 3, the temperature of the heat source 3 is 350 ℃, the voltage of the capillary is 30V, the temperature of the capillary is 300 ℃, the voltage of a tube lens is 100V, and data are collected under the conditions of a positive ion mode and a negative ion mode respectively.
In this example, the selected test compound was kaempferol in methanol (0.1. Mu.L) and the solvent was methanol at a concentration of 10. Mu.g/mL, and FIG. 2 is a mass spectrum of kaempferol in methanol (0.1. Mu.L) obtained by the method of the present invention. Wherein FIG. 3a is a mass spectrum in positive ion mode with m/z 287; FIG. 3b is a mass spectrum in negative ion mode, m/z being 285; fig. 3c is a secondary mass spectrum in positive ion mode with major fragment peaks 269, 258, 241, 231, 213, 165 and 153, which according to prior art reports are consistent with their fragmentation characteristics and coincide with the primary spectrum in the mass spectrum of fig. 3a, indicating that the thermionic ion source has not only soft ionization but also a degree of hard ionization characteristics.
Example 3
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of the testosterone (Mesterlon), a sample applicator 4 is a 0.5 mu L microinjector, the distance between the front end (bent tip) of the electric soldering iron heat source 3 and a mass spectrum inlet is 3mm,6A current is applied to a position 3.5cm away from the front end of the heat source 3, the temperature of the heat source 3 is 450 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and positive ion mode data acquisition is carried out.
In this example, the selected test compound was a solution of testosterone in hexane, the solvent was n-hexane, and the concentration was 20. Mu.g/mL, and FIG. 4 is a mass spectrum of the solution of testosterone in hexane (0.5. Mu.L) obtained by the method of the present invention. The mass spectrum analysis result shows that the addition peak [ M+H ] of the testosterone and the proton] + The m/z is 305.
Example 4
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electron generator 2 to realize ionization analysis of Acenaphthylene (Acenaphthylene), and the sample applicator 4 is a 10 mu L Hamilton microinjector. The distance between the front (tip) of the electric iron heat source 3 and the inlet of the mass spectrum is 6mm, the arc plasma is applied to the position 4cm away from the front end of the heat source 3, the temperature of the heat source 3 is 200 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and the positive ion mode acquires data.
In this example, the selected test compound was acenaphthylene methanol solution, the solvent was methanol solution, the concentration was 10. Mu.g/mL, and FIG. 5 is a mass spectrum of the acenaphthylene methanol solution (3. Mu.L) of this example obtained by the method of the present invention. The mass spectrum analysis result shows that the addition peak [ M+H ] of acenaphthylene and proton] + The m/z is 153, which shows that the method can be used for ionization analysis of low-polarity compounds such as polycyclic aromatic hydrocarbon and the like, and has stronger proton addition capability.
Example 5
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of PEG 1000, a sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (bent round head) of the electric soldering iron heat source 3 and a mass spectrum inlet is 5mm, dielectric barrier discharge plasma is added at the position 4cm away from the front end of the heat source 3, the temperature of the heat source 3 is 250 ℃, the voltage of the capillary is 30V, the temperature of the capillary is 300 ℃, the voltage of a tube lens is 100V, and data are collected in a positive ion mode.
In this example, the selected test compound was PEG 1000 polymer, methanol in a concentration of 5. Mu.g/mL, and FIG. 6 is a mass spectrum of a methanol solution (1.0. Mu.L) of PEG 1000 obtained by the method of the present invention. The mass spectrometry results show a typical mass spectrum of the polymer PEG 1000.
Example 6
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of perfluoro caprylic acid (Pentadecafluorooctanoic acid), a sample applicator 4 is a 2.0 mu L injector, the distance between the electric soldering iron heat source 3 and a mass spectrum inlet is 5mm, arc plasma is applied to a position 5cm away from the front end of the heat source 3, the temperature of the heat source 3 is 60 ℃, the temperature of a quadrupole mass analyzer, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and data are collected in an anion mode.
In this example, the selected test compound was a methanol solution of perfluorooctanoic acid, the solvent was methanol, and the concentration was 10. Mu.g/mL, and FIG. 7 is a mass spectrum of the methanol solution of perfluorooctanoic acid (1.0. Mu.L) of this example obtained by the method of the present invention. Mass spectrometry analysis results showed that perfluoro caprylic acid [ M-H ]] – The m/z is 413, which indicates that the device can realize ionization analysis of perfluorinated pollutants.
Example 7
The thermal desorption ionization mechanism verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of vitamin D3 (vitamin D3), a sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (flat head) of the electric soldering iron heat source 3 and a mass spectrum inlet is 4mm,6A current is applied to the position 8cm away from the front end of the heat source 3, the temperature of the heat source 3 is 150 ℃, the temperature of an ion trap mass analyzer, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and positive ion mode data acquisition is carried out.
In this example, the test compound selected was vitamin D3, the reagent was methanol, and the concentration was 30. Mu.g/mL, FIG. 8 was obtained using the method of the present inventionMass spectrum of vitamin D3 methanol solution (1 μl) was described in this example. The mass spectrum analysis result shows that the addition peak [ M+H ] of the vitamin D3 and the proton] + The m/z was 385, and no dehydration peak was found, further verifying the soft ionization characteristics of the thermionic ionization source.
Example 8
The thermal desorption ionization verification apparatus combines a heat source 3 and an electron generator 2 to perform ionization analysis of Formestane (Formestane), and the sample applicator 4 is a 0.5 μl syringe. The distance between the front end of the electric hair drier heat source 3 and the mass spectrum inlet is 2mm,80mA current is applied to the position 6cm away from the front end of the heat source 3, the temperature of the heat source 3 is 400 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and the positive ion mode collects data.
In this example, the selected test compound was a solution of formestane in ethyl acetate, the solvent was ethyl acetate, and the concentration was 50. Mu.g/mL, FIG. 9 is a mass spectrum of the formestane ethyl acetate solution (2. Mu.L) obtained using the method of the present invention, FIG. 9a is a mass spectrum in positive ion mode, m/z was 303, FIG. 9b is a secondary mass spectrum in positive ion mode, m/z 303, and fragments thereof were 285, 267, 249 and 173, which were reported in the prior art to be consistent with their cleavage characteristics.
Example 9
The thermal desorption ionization verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of Androsterone (Androsterone), a sample applicator 4 is a 10 mu L Hamilton microinjector, the distance between the front end (tip) of the electric soldering iron heat source 3 and a mass spectrum inlet is 5mm,5A current is applied to the distance from the front end of the heat source 3 is 4cm, the temperature of the heat source 3 is 350 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and data are collected in a positive ion mode.
In this example, the selected test compound was androsterone, the solvent was acetone, and the concentration was 20. Mu.g/mL, and FIG. 10 is a mass spectrum of an androsterone acetone solution (0.5. Mu.L) of this example obtained by the method of the present invention, and the m/z was 291 as a result of mass spectrometry. This is a significant difference from conventional analysis of sterols, and other thermal desorption ionization techniques often detect androgens[M–2H 2 O+H] + As a result, the mass spectrum of the thermionic ion source has no dehydration peak, which shows that the soft ionization characteristic of the thermionic ion source is superior to that of the conventional thermal desorption ionization source.
Example 10
The thermal desorption ionization verification device combines a heat source 3 and an electronic generator 2 to realize ionization analysis of the diethylstilbestrol benzoate, a sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (round head) of the electric soldering iron heat source 3 and a mass spectrum inlet is 3mm,1A direct current (lithium battery) is applied to a position 2cm away from the front end of the heat source 3, the temperature of the heat source 3 is 550 ℃, the temperature of an ion trap mass analyzer, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and data are collected under the positive ion mode.
In this example, the test compound selected was dihydroxybenzoate, water as the solvent, and 20. Mu.g/mL, and FIG. 11 is a mass spectrum of an aqueous solution (2.5. Mu.L) of dihydroxybenzoate as described in this example obtained using the method of the present invention. The mass spectrum analysis result shows that the addition peak [ M+H ] of the dihydroxybenzoic acid and the proton] + The m/z is 377.
Example 11
The thermal desorption ionization verification apparatus was combined with a heat source 3 and an electron generator 2 to perform ionization analysis of Testosterone (Testosterone), and the sample applicator 4 was a 10 μl Hamilton microinjector. The distance between the front end (bent tip) of the electric soldering iron heat source 3 and the mass spectrum inlet is 4mm, the distance between the electron generator 2 and the front end of the heat source 3 is 3cm, the temperature of the heat source 3 is 450 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and the positive ion mode collects data.
In this example, the selected test compound was an acetone solution of testosterone in acetone at a concentration of 15 μg/mL, and FIG. 12 is a mass spectrum of the testosterone acetone solution (0.4 μl) of this example obtained using the method of the present invention. The mass spectrum analysis result shows that the addition peak [ M+H ] of testosterone and proton] + Its m/z is 289.
Example 12
The thermal desorption ionization verification apparatus combines a heat source 3 and an electron generator 2 to perform ionization analysis of 1-Nitropyrene (1-Nitropyrene), and a sample applicator 4 is a 10. Mu.L Hamilton microinjector. The distance between the front end (horseshoe head) of the electric soldering iron heat source 3 and the mass spectrum inlet is 2mm,3A current is applied to the position 2cm away from the front end of the heat source 3, the temperature of the heat source 3 is 400 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and the positive ion mode acquires data.
In this example, the selected methanol solution of 1-nitropyrene as the test compound was methanol at a concentration of 15. Mu.g/mL, and FIG. 13 is a mass spectrum of 1-nitropyrene (1. Mu.L) as described in this example obtained by the method of the present invention. The mass spectrum analysis result shows that the addition peak [ M+H ] of the 1-nitropyrene and the proton] + The m/z is 248, and the conventional thermal desorption ionization result is molecular ion peak.
Example 13
The thermal desorption ionization verification device combines the heat source 3 and the electronic generator 2 to realize ionization analysis of the main component Levofloxacin (Levofloxacin) in the Levofloxacin eye drops. The sample applicator 4 is a glass sample application capillary with an inner diameter of 1.2mm, the distance between the front end (horseshoe head) of the electric soldering iron heat source 3 and the mass spectrum inlet is 5mm, the distance between the electron generator 2 and the front end of the heat source 3 is 2cm, the temperature of the heat source 3 is 400 ℃, the capillary voltage is 30V, the capillary temperature is 300 ℃, the tube lens voltage is 100V, and the positive ion mode acquires data.
In this example, selected is levofloxacin, which is a main component of levofloxacin eye drops containing phosphate buffer salt, and fig. 14 is a mass spectrum of direct ionization of the levofloxacin eye drops obtained in this example obtained by the method of the present invention. The mass spectrum analysis result shows that the addition peak of the levofloxacin and the proton [ M+H ]] + The m/z is 362, which demonstrates that the ion source of the present invention has good complex matrix tolerance and salt tolerance.
The above examples show that, because the heat source 3 and the electron generator 2 employed in the present invention are various in form, the thermal desorption ionization mechanism verification apparatus greatly improves ionization efficiency, and can ionize compounds dissolved in various solvents of different polarities and realize ionization analysis of main components in complex matrix samples. The device can be compatible with common mass analyzers (such as an orbit ion trap, a triple quadrupole rod, flight time, magnetic mass spectrum, fourier ion cyclotron resonance, an orbit trap and the like), and is popularized to other mass spectrum analysis, and has wide application range and strong practicability. In addition, the device fully clarifies the individuation of the heat source 3 and electrons in thermal desorption ionization, and provides theoretical guidance for each laboratory in the aspect of constructing a novel ion source.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A thermal desorption ionization mechanism verification apparatus, comprising:
the front end of the heat source is provided with conductive performance;
the electronic generator is connected in series at the front end of the heat source;
and the inlet of the mass spectrometer is positioned on the same horizontal line with the front end of the heat source.
2. The thermal desorption ionization mechanism verification device according to claim 1, wherein the distance between the front end of the heat source and the inlet of the mass analyzer is 0.5mm-20mm.
3. The thermal desorption ionization mechanism verification device according to claim 1, wherein the heat source comprises an electric soldering iron, a hot glue gun, and an electric hair dryer.
4. A thermal desorption ionization mechanism verification apparatus according to claim 3, wherein the front end of the heat source is shaped as a horseshoe, a pointed tip, a bent pointed tip, a flat head, a rounded head, a bent rounded head, a K-bit, a rounded pointed tip, and a straight head.
5. The thermal desorption ionization mechanism verification apparatus according to claim 1, wherein the electrons generated by the electron generator are provided by alternating current or by direct current or by plasma contact.
6. The thermal desorption ionization mechanism verification apparatus according to claim 1, wherein the mass analyzer of the mass spectrometer is a single focus mass analyzer, a dual focus mass analyzer, a quadrupole mass analyzer, an ion trap mass analyzer, fourier transform ion cyclotron resonance, or a time-of-flight mass analyzer.
7. The thermal desorption ionization mechanism verification apparatus according to claim 1, wherein the distance between the serial connection position of the electron generator and the front end of the heat source and the front end head of the heat source is greater than 2cm.
8. Use of a thermal desorption ionization mechanism verification apparatus based on the thermal desorption ionization mechanism verification apparatus of claim 1, comprising the steps of:
(1) Switching on a heat source power supply, and keeping stable when the temperature rises to a set value;
(2) Dipping a small amount of sample to be tested by using a sample applicator, placing the sample to be tested at the front end of a heat source, and starting an electronic generator;
(3) The sample to be tested is subjected to thermal desorption and is added with protons of water molecules in the air to form sample ions, and the sample ions sequentially enter a mass analyzer and a mass detector of the mass spectrometer.
9. The use of a thermal desorption ionization mechanism verification apparatus according to claim 8, wherein in the step (1), the set value of the temperature is 20 ℃ to 900 ℃.
10. The use of a thermal desorption ionization mechanism verification apparatus according to claim 8, wherein in the step (2), when the sample to be tested is a semisolid or a liquid, the sample volume is 0.01 to 1000 μl.
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