CN112951701B - In-situ thermal desorption ionization source for mass spectrometry - Google Patents
In-situ thermal desorption ionization source for mass spectrometry Download PDFInfo
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- CN112951701B CN112951701B CN201911258506.1A CN201911258506A CN112951701B CN 112951701 B CN112951701 B CN 112951701B CN 201911258506 A CN201911258506 A CN 201911258506A CN 112951701 B CN112951701 B CN 112951701B
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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
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
- H01J49/049—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample with means for applying heat to desorb the sample; Evaporation
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- 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
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Abstract
The invention relates to a mass spectrometer, in particular to an in-situ thermal desorption ionization source, which comprises a gas source, a flow stabilizing valve, a desorption cavity, an enrichment tube, an ion photon generating device, an ionization tube, an ion transmission cavity, an ion transmission electrode and a mass spectrometer. According to the invention, through reasonable design, the thermal desorption device and the ion photon generation device are tightly combined, so that the sample molecules which are pyrolyzed and sucked out are fully contacted with ions or photons generated by the ion photon generation device, and thus, high-efficiency ionization is obtained. The design structure is compact, the sample utilization rate is high, the detection sensitivity is high, and the detection capability of the mass spectrometer on trace analytes can be greatly improved.
Description
Technical Field
The invention relates to a mass spectrometry instrument, in particular to an in-situ thermal desorption photoionization source for mass spectrometry. This ionization source carries out the inseparable combination with thermal desorption device and ion photon generating device through reasonable design, and the sample utilization ratio is high, and detectivity is high, can greatly promote the detectability of mass spectrograph to trace analyte.
Background
The ionization source is the core part of the mass spectrometer and is used for converting neutral molecules into ions, and is the first link of mass spectrometry. Important indicators of ionization sources are sample utilization and detection sensitivity. High sample utilization and detection sensitivity may consume less sample and achieve lower sample detection limits. Therefore, how to improve the utilization rate and detection sensitivity of ionization source samples is a research focus of scientific researchers.
The Solid Phase Extraction (SPE) technology is to adsorb a target compound in a sample by using a solid adsorbent, separate the target compound from a matrix and an interfering compound of the sample, and then elute or heat-desorb the target compound by using a solvent so as to achieve the purpose of separating and enriching the target compound, thereby greatly enhancing the detection capability of trace analytes. On-line mass spectrometry generally uses an adsorption-thermal desorption system, when a sample passes through a selected adsorbent, a target object is adsorbed on the surface of the sample according to the similar phase dissolution principle, and a sample matrix directly flows through the adsorbent to complete the enrichment of the target object; after adsorption is completed, the adsorbent is heated to desorb the adsorbed target substance for detection.
Generally, an adsorption-thermal desorption system is connected with a mass spectrum by adopting an independent device, and the main defects of the connection mode are that the sample introduction dead volume is large, the sample diffusion is serious, and the utilization rate of the sample is low, so that the utilization efficiency of the sample after the thermal desorption enters a mass spectrum ionization source needs to be further improved by more effective design.
Through a search in patents and articles, relevant patents that were retrieved relating to thermal desorption and ionization sources are: 1. shimadzu analysis technology research & development (Shanghai) Co., ltd., ionization apparatus, mass spectrometer, ion mobility spectrometer, 2019-10-29; 2. vorte scientific, inc., using surface desorption ionization and rapid mass spectrometry, 2019-03-05. The patent 1 provides an ionization device, and a mass spectrometer and an ion mobility spectrometer with the ionization device, wherein a sampling device and a thermal desorption device are combined into a whole, and the important point is that the sampling device is more compact, the ionization part is not influenced, and better reproducibility and sensitivity can be obtained; patent 2 proposes a rapid identification method for surface desorption ionization mass spectrometry, and aims to provide an identification method suitable for a portable mass spectrometer and suitable for various desorption ionization sources. No report of in-situ thermal desorption ionization source capable of effectively improving the sample utilization rate and the instrument sensitivity is found.
Disclosure of Invention
The invention aims to combine the thermal desorption device and the ion photon generating device tightly through reasonable design, so that the sample utilization rate and the detection sensitivity are improved, and the method can greatly improve the detection capability of the mass spectrometer on trace analytes.
In order to realize the purpose, the invention adopts the technical scheme that:
an in-situ thermal desorption ionization source for mass spectrometry comprises an air source, a flow stabilizing valve, a desorption cavity, an enrichment tube, an ion photon generating device, an ion photon extraction tube, an ionization tube, an ion transmission cavity, an ion transmission electrode and a mass spectrometer, and is characterized in that:
a gas outlet of the gas source is connected with an inlet pipeline of the enrichment pipe through a flow stabilizing valve by a gas source pipeline, the enrichment pipe is arranged in the desorption cavity, and an outlet of the enrichment pipe is connected with an inlet of the ion transmission cavity through an ionization pipe;
ions generated by the ion photon generating device enter the ionization tube through the ion photon leading-out tube, the airflow is ionized in the ionization tube, and the ionized ions are transmitted to the mass spectrometer through the ion transmission electrode in the ion transmission cavity.
The gas source is connected with the flow stabilizing valve through a gas source pipeline, and the other end of the flow stabilizing valve is connected to the enrichment pipe through an enrichment pipe inlet pipeline; the enrichment pipe is arranged in the desorption cavity, and the desorption cavity has a temperature control function and is a container capable of realizing heating desorption; the ion photon generating device can generate reagent ions for chemical ionization or photons for photo ionization; the ion photon leading-out tube is connected with the ion photon generating device and is used for leading out ions or photons; the ion photon eduction tube and the outlet of the enrichment tube are orthogonally connected, an ionization tube is formed at the joint, and chemical ionization or photo ionization is generated in the ionization tube; the other end of the ionization tube is connected with an ion transmission cavity, 2 or more ion transmission electrodes are arranged in the ion transmission cavity, the transmission electrodes are of flat plate structures with small holes in the middle, and the transmission electrodes are parallel to and coaxially arranged with the center hole of the ionization tube at intervals; the ion transmission cavity is connected with a mass spectrometer.
The gas source is one or more than two of inert gases such as clean nitrogen, helium, argon and the like; the flow stabilizing valve can stably regulate the gas flow to 1-300 mL.
An electric heating element and a temperature sensor are arranged in the desorption cavity, the temperature sensor is connected with a temperature controller, the electric heating element is connected with an external power supply through the temperature controller, the heating temperature of the desorption cavity is increased from room temperature to 400 ℃, the increment control is performed at 1 ℃, and the temperature control precision is 0.1 ℃; the enrichment pipe is made of metal or quartz glass; the desorption cavity can hold 1 or more enrichment tubes simultaneously.
The ion photon generating device can generate reagent ions for chemical ionization by one or more of discharge, radioactive source, photoionization and the like; photons can also be generated by one or more of a gas discharge lamp light source, a laser light source, a synchrotron radiation light source, and the like for photoionization.
The extracted ions are connected with a mass spectrometer, and a mass analyzer of the mass spectrometer is a time-of-flight mass analyzer, a quadrupole mass analyzer or an ion trap mass analyzer.
According to the invention, through reasonable design, the thermal desorption device and the ion photon generating device are tightly combined, so that the sample molecules which are pyrolyzed and sucked out are fully contacted with ions or photons generated by the ion photon generating device, and thus, high-efficiency ionization is obtained. The design structure is compact, the sample utilization rate is high, the detection sensitivity is high, the detection capability of the mass spectrometer on the trace analytes can be greatly improved, and the method has a wide application prospect in the aspect of high-sensitivity and rapid detection of the trace analytes.
Drawings
FIG. 1 is an in situ thermal desorption ionization source of the present invention.
FIG. 2 is an in-situ multi-channel thermal desorption ionization source derived from the present invention.
Detailed Description
Referring to fig. 1, the in-situ thermal desorption ionization source for mass spectrometry according to the present invention includes an air source 1, a flow stabilizer 2, a desorption chamber 6, an enrichment tube 5, an ion photon generating device 11, an ion photon extraction tube 9, an ionization tube 8, an ion transmission chamber 12, an ion transmission electrode 13, and a mass spectrometer 14, and is characterized in that:
a gas outlet of a gas source 1 is connected with an enrichment pipe inlet pipeline 4 through a flow stabilizing valve 3 by a gas source pipeline 2, an enrichment pipe 5 is arranged in a desorption cavity 6, and an outlet of the enrichment pipe 5 is connected with an inlet of an ion transmission cavity 12 through an ionization tube 8;
The gas source 1 is connected with the flow stabilizing valve 3 through a gas source pipeline 2, and the other end of the flow stabilizing valve 3 is connected to the enrichment pipe 5 through an inlet pipeline 4 of the enrichment pipe 5; the enrichment pipe 5 is arranged in the desorption cavity 6, and the desorption cavity 6 has a temperature control function and is a container capable of realizing heating desorption; the ion photon generating means 11 may generate reagent ions for chemical ionization or photons for photo ionization; the ion photon leading-out tube 9 is connected with the ion photon generating device 11 and is used for leading out ions or photons; the ion photon eduction tube 9 is orthogonally connected with the outlet of the enrichment tube 5, an ionization tube 8 is formed at the connection part, and chemical ionization or photo ionization is generated in the ionization tube 8; the other end of the ionization tube 8 is connected with an ion transmission cavity 12, 2 or more ion transmission electrodes 13 are arranged in the ion transmission cavity 12, the transmission electrodes 13 are flat plate structures with small holes in the middle, and are parallel to and coaxially arranged with the center hole of the ionization tube at intervals; the ion transport chamber 12 is connected to a mass spectrometer 14.
The gas source 1 is one or more than two of inert gases such as clean nitrogen, helium, argon and the like; the flow stabilizing valve 3 can stably regulate the gas flow to 1-300 mL.
An electric heating element and a temperature sensor are arranged in the desorption cavity 6, the temperature sensor is connected with a temperature controller, the electric heating element is connected with an external power supply through the temperature controller, the heating temperature of the desorption cavity 6 is increased from room temperature to 400 ℃, the increment control is performed at 1 ℃, and the temperature control precision is 0.1 ℃; the enrichment pipe 5 is made of metal or quartz glass; the desorption chamber 6 can simultaneously accommodate 1 or more (parallel) enrichment tubes 5.
The ion photon generating device 11 can generate reagent ions for chemical ionization by one or more of discharge, radioactive source, photoionization and the like; photons can also be generated by one or more of a gas discharge lamp light source, a laser light source, a synchrotron radiation light source, and the like for photoionization.
The extracted ions 15 are connected to a mass spectrometer 14, the mass analyser of which is a time-of-flight mass analyser, a quadrupole mass analyser or an ion trap mass analyser.
In specific implementation, as shown in fig. 1, firstly, the enrichment tube 5 is placed in the desorption cavity 6, and at this time, the gas source 1 is opened, and the flow of the gas source is adjusted through the flow stabilizing valve 3 to be matched with the mass spectrum sample injection quantity connected with the enrichment tube; carrying out temperature programming, starting to release the sample in the enrichment tube 5, and enabling the sample to be in contact with the ion photon generating device 11 to generate reagent ions or photons in the ionization tube 8 and to be efficiently ionized once the sample is desorbed; the ionized ions 15 enter the ion transmission cavity 12 and enter the mass spectrum 14 under the action of the ion transmission electrode 13, and finally an analysis result is obtained. Because the invention has compact design and the sample in the adsorption tube is ionized immediately after being desorbed, the sample has high utilization rate and high sensitivity, and the detection capability of the mass spectrometer on trace analytes can be greatly improved.
FIG. 2 shows an in-situ three-channel thermal desorption ionization source derived from the present invention, which has the advantage of having more sample size, thereby obtaining higher enrichment factor and detection sensitivity.
Claims (3)
1. An in-situ thermal desorption ionization source for mass spectrometry comprises an air source (1), a flow stabilizing valve (3), a desorption cavity (6), an enrichment tube (5), an ion photon generating device (11), an ion photon leading-out tube (9), an ionization tube (8), an ion transmission cavity (12), an ion transmission electrode (13) and a mass spectrometer (14), and is characterized in that:
a gas outlet of the gas source (1) is connected with an enrichment pipe inlet pipeline (4) through a flow stabilizing valve (3) by a gas source pipeline (2), an enrichment pipe (5) is arranged in a desorption cavity (6), and an outlet of the enrichment pipe (5) is connected with an inlet of an ion transmission cavity (12) through an ionization tube (8);
ions (10) generated by the ion photon generating device (11) enter the ionization tube (8) through the ion photon eduction tube (9), the airflow (7) is ionized in the ionization tube (8), and the ionized ions are transmitted to the mass spectrometer (14) through the ion transmission electrode (13) in the ion transmission cavity (12); the extracted ions (15) are connected with a mass spectrometer (14), and a mass analyzer of the mass spectrometer is a time-of-flight mass analyzer, a quadrupole mass analyzer or an ion trap mass analyzer;
the gas source (1) is connected with the flow stabilizing valve (3) through a gas source pipeline (2), and the other end of the flow stabilizing valve (3) is connected to the enrichment pipe (5) through an inlet pipeline (4) of the enrichment pipe (5); the enrichment pipe (5) is arranged in the desorption cavity (6), and the desorption cavity (6) has a temperature control function and is a container capable of realizing heating desorption; the ion photon generating device (11) can generate reagent ions for chemical ionization or photons for photo ionization; the ion photon leading-out tube (9) is connected with the ion photon generating device (11) and is used for leading out ions or photons; the ion photon eduction tube (9) is orthogonally connected with the outlet of the enrichment tube (5), an ionization tube (8) is formed at the connection part, and chemical ionization or photo ionization is generated in the ionization tube (8); the other end of the ionization tube (8) is connected with an ion transmission cavity (12), 2 or more ion transmission electrodes (13) are arranged in the ion transmission cavity (12), the ion transmission electrodes (13) are all flat plate structures with small holes in the middle, and are parallel to each other and coaxially arranged with the center hole of the ionization tube at intervals; the ion transmission cavity (12) is connected with a mass spectrometer (14); an electric heating element and a temperature sensor are arranged in the desorption cavity (6), the temperature sensor is connected with a temperature controller, the electric heating element is connected with an external power supply through the temperature controller, the heating temperature of the desorption cavity (6) is controlled from room temperature to 400 ℃, the increment is controlled at 1 ℃, and the temperature control precision is 0.1 ℃; the enrichment pipe (5) is made of metal or quartz glass; the desorption cavity (6) can simultaneously contain 1 or more enrichment pipes (5).
2. The in situ thermal desorption ionization source of claim 1 wherein:
the gas source (1) is one or more than two of clean nitrogen, helium and argon; the flow stabilizing valve (3) can stably regulate the gas flow to 1-300 mL.
3. The in situ thermal desorption ionization source of claim 1 wherein:
the ion photon generating device (11) generates reagent ions for chemical ionization through one or more of discharge, radioactive source and photoionization modes; or generating photons for photoionization by one or more of a gas discharge lamp light source, a laser light source or a synchrotron radiation light source.
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