CN111830117A - Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system - Google Patents
Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system Download PDFInfo
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- 238000001269 time-of-flight mass spectrometry Methods 0.000 title claims abstract description 24
- 239000007790 solid phase Substances 0.000 title claims abstract description 19
- 239000013307 optical fiber Substances 0.000 claims abstract description 56
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 238000004458 analytical method Methods 0.000 claims abstract description 21
- 238000001196 time-of-flight mass spectrum Methods 0.000 claims abstract description 20
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- 238000010168 coupling process Methods 0.000 claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 claims abstract description 19
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- 238000001514 detection method Methods 0.000 abstract description 16
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- G—PHYSICS
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- H—ELECTRICITY
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- 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
- H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
- H01J49/0463—Desorption by laser or particle beam, followed by ionisation as a separate step
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N2001/4038—Concentrating samples electric methods, e.g. electromigration, electrophoresis, ionisation
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Abstract
The invention relates to a laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system, which comprises a controller, a sample pretreatment platform, a solid phase microextraction handle, a laser generator, an optical coupling device and a time-of-flight mass spectrometry, wherein the controller is connected with the sample pretreatment platform; the extraction head of the solid phase microextraction handle is an optical fiber, one end of the optical fiber is coated with a solid phase microextraction coating, and the other end of the optical fiber is connected with an optical coupling device; the time-of-flight mass spectrum comprises a sample inlet part and an analysis part, and the optical fiber can extend into the sample inlet part. The sample pretreatment platform and the time-of-flight mass spectrum are electrically connected with the controller. The optical fiber is combined with the solid phase micro-extraction coating, so that not only can high enrichment capacity of target molecules be realized, but also high laser absorption capacity and photoelectric conversion efficiency are realized, and the laser ionization process of the target molecules is realized. And the solid phase extraction coating of the optical fiber has good stability and low damage rate in the laser ionization process, can not be excited by laser to separate, and obviously reduces the background interference during the detection of small molecules.
Description
Technical Field
The invention relates to the field of biological analysis and detection, in particular to a laser ionization solid phase microextraction-time-of-flight mass spectrometry combined system.
Background
Matrix-assisted laser desorption ionization (MALDI) is a soft ionization technique and is widely used in the analysis and detection of biomacromolecules. The working principle and the process are as follows: the target analyte to be detected is obtained by a proper sample pretreatment technology, is spotted on a suitable target plate together with the matrix in a proper mode, and is excited by proper laser energy after being dried and crystallized, and the matrix absorbs the laser energy and transfers the laser energy to the target analyte. The target analyte is ionized or protonated and then analyzed by a suitable detector. However, the method is limited in the analysis of small molecule compounds due to the interference of matrix molecules, and the detection accuracy of small molecule compounds is not high.
For matrix-assisted laser desorption, the sample pretreatment techniques are usually liquid phase extraction, solid phase extraction, or no extraction. The substrate solution needs to be prepared separately, and then the sample and the substrate solution are mixed to manually spot the plate, so that the automation cannot be performed. When the existing solid phase micro-extraction probe is combined with gas chromatography, the method comprises two processes, namely an extraction process and a desorption process; the extraction process is that the extraction fiber with adsorption coating is exposed in the sample for extraction, the desorption process is that the extraction device needle for completing the extraction process is inserted into the gasification chamber of the gas chromatography sample injection device, so that the extraction fiber is exposed in the high-temperature carrier gas, and the extract is continuously desorbed to enter the subsequent gas chromatography analysis, the analyte must have better thermal stability, the application range is limited, and the method is not suitable for the detection of the biological molecules.
The application number is CN201811356564.3, the method and the device for detecting the antibiotic substances by combining voltage-driven solid phase microextraction-Raman spectroscopy are also characterized in that the extraction head for fixing microextraction can quickly enrich the antibiotic substances and complete in-situ detection only by voltage and laser, but the analysis accuracy of the small molecular compounds cannot be improved.
Disclosure of Invention
The invention aims to solve the problems that the accuracy of small molecular compounds is low and the small molecular compounds cannot be automatically carried out in the prior matrix-assisted laser desorption ionization technology in the prior art, provides a system for combining laser ionization solid phase microextraction with flight time mass spectrometry, simplifies the pretreatment process of a sample and simultaneously improves the analysis accuracy of the small molecular compounds.
In order to solve the technical problems, the invention adopts the technical scheme that: a laser ionized solid phase microextraction-time-of-flight mass spectrometry combined system comprises a controller, a sample pretreatment platform, a solid phase microextraction handle arranged on the sample pretreatment platform, a laser generator, an optical coupling device and a time-of-flight mass spectrometry; the extraction head of the solid phase microextraction handle is an optical fiber, one end of the optical fiber is coated with a solid phase microextraction coating, and the other end of the optical fiber is connected with the optical coupling device; the laser emitted by the laser generator is coupled through the optical coupling device; the time-of-flight mass spectrum comprises a sample inlet part and an analysis part connected with the sample inlet part, and the optical fiber can extend into the sample inlet part; the sample pretreatment platform and the time-of-flight mass spectrum are both electrically connected with the controller.
The sample pretreatment platform is an existing experiment platform, and a plurality of mechanical arms capable of moving in three axes are arranged on the platform. The solid phase micro-extraction handle is arranged on the mechanical arm. The optical coupling device is an optical common instrument and mainly comprises a convex lens structure, a position adjusting base in the three-dimensional direction and an optical fiber connecting interface, wherein the controller is a computer control system and is provided with an operating system capable of controlling an experimental device; time-of-flight mass spectrometry is also an existing instrument. In the technical scheme, after the controller sets working parameters of the sample pretreatment platform and the flight time mass spectrum, the computer control system sends signals to the sample pretreatment platform and the flight time mass spectrum, the mechanical arm controls the extraction head of the solid phase extraction handle to be inserted into the sampling bottle, and a certain amount of target analytes in the sample bottle are adsorbed through the solid phase extraction coating on the optical fiber. Insert the extraction head to the introduction port portion through the arm in, laser generator produces laser to send to photosynthetic coupling device on, photosynthetic coupling device is with laser coupling to in the optic fibre, and transmit in the optic fibre. When high-energy laser is transmitted to the part coated with the solid-phase micro-extraction coating, the laser emitted from the fiber core of the optical fiber is coated on the surrounding extraction coating to be absorbed and transfers energy to target analytes, and protons are transferred to molecules or are obtained from the molecules in the ionization process, so that target molecules are ionized or protonated. The analysis part of the time-of-flight mass spectrum has negative pressure, and target molecules are ionized or protonated and then transmitted to the analysis part, so that detection and analysis are realized.
Preferably, the device further comprises a laser controller; the laser controller is electrically connected with the controller; the laser controller is also electrically connected with the laser generator and controls the laser wavelength of the laser generator. The laser controller is electrically connected with the computer control system, the computer control system sends out a starting signal of the laser generator, the computer control system is used for operating the laser controller to adjust the laser wavelength of the laser generator, the computer control system can also be used for receiving analysis data of the time-of-flight mass spectrum, and the computer control system is used for completing the integrated operation of the system.
According to the method, the photon energy is generated according to the formula E ═ hc/lambda, E is the generated photon energy, h is the Planck constant, c is the light speed, and lambda is the laser wavelength, and the laser controller adjusts the photon energy by adjusting the laser wavelength emitted by the laser generator. And the bond energy of different chemical bonds in different analytes is different, so the photon energy can be adjusted by adjusting the laser wavelength, and the selective breakage of the chemical bonds can be realized.
Preferably, the sample pretreatment platform is electrically connected with the time-of-flight mass spectrometer and the laser controller respectively. The sample pretreatment platform is electrically connected with the sample pretreatment platform through a signal converter. The method comprises the steps of electrically connecting all parts in a system, wherein a standard signal sample pretreatment platform of a laser controller is different from a flight time mass spectrum, so that all parts in the system are electrically connected by changing a signal working mode of the laser controller by using a signal converter, all instruments are in a linkage state, and the running time of each instrument is different, and after a computer sends a starting signal once, if each instrument moves independently, the cooperation between the instrument and the instrument is not coordinated, so that the starting signal needs to be sent to the instrument in advance, but the computer control system needs to be operated for many times, and the full automation of the experimental process is difficult to realize. After the instruments are linked, after the working parameters of each instrument are set through the computer control system, the instruments receive the starting signals, and the later started instruments can be started only after receiving the linked starting signals, so that after the computer control system can send the starting signals, each instrument of the system can automatically run according to the sequence.
The specific linkage mode is as follows: the computer control system opens the control software of each component and sets parameters according to requirements. Setting the wavelength and energy intensity of a laser controller, selecting an external excitation control mode, setting a laser generator in a preparation state, and automatically emitting laser once receiving an external electric signal; setting working methods of a sample pretreatment platform, such as incubator temperature (extraction temperature in the sample pretreatment process), extraction time, oscillation rate, sample bottle specification, sample bottle tray selection, three-dimensional position adjustment of mechanical arm work, sample introduction time, sample bottle and sample inlet insertion depth, coating exposure depth and other parameters; setting a working sequence of a sample pretreatment platform; setting the signal duration of the signal converter, namely the working time of the laser generator; setting the charge-to-mass ratio m/z detection range, the positive and negative ion working modes, the mass spectrum parameters and the like of the time-of-flight mass spectrum; and setting a working sequence of the time-of-flight mass spectrum.
After the computer control system generates a starting signal, operating a working sequence of the sample pretreatment platform, and starting a sample pretreatment process by the sample pretreatment platform; and operating a working sequence of the time-of-flight mass spectrum, wherein the time-of-flight mass spectrum ready is in a prerun state, and waiting for sample injection. The sample pretreatment platform starts to carry out a sample introduction process; after sample introduction, the sample pretreatment platform transmits an electric signal to the time-of-flight mass spectrum through a remote port data line, and the time-of-flight mass spectrum starts to work; after sample introduction, the sample pretreatment platform transmits an electric signal to the signal converter through a remote port data line, the signal converter transmits the electric signal to the laser controller, the laser controller controls the laser generator to generate laser, the laser is transmitted to the tail end optical fiber solid phase micro-extraction coating through the optical fiber, and a target analyte ionization process is started.
Preferably, the optical fiber is used for removing the coating layer and the outer cladding layer at one end of the solid phase micro-extraction coating. The optical fiber removes the coating layer and the outer cladding layer by using a hydrofluoric acid etching mode, so that laser can be emitted from the side surface of the optical fiber, and the optical fiber solid phase micro-extraction coating can absorb the energy of the laser more easily and transfer the energy to target analytes.
Preferably, the solid phase micro-extraction handle comprises an outer tube, an inner tube arranged in the outer tube and a pushing handle connected with the inner tube; the optical fiber is arranged in the inner tube, and one end of the optical fiber, which is coated with the solid-phase micro-extraction coating, extends out of the inner tube; the push handle pushes the inner tube to slide in the outer tube. The effect of outer tube is when optic fibre needs adsorb the target analyte and stretch into introduction port portion, because optic fibre is comparatively fragile, and the touching hard thing is damaged easily, can pierce through the outer tube earlier the dottle pin of sample bottle and introduction port portion, gets into one end distance back when the outer tube, and after promoting the handle and drive the inner tube and move one section distance through promoting, outside optic fibre stretches into the outer tube, the realization is to the absorption and the desorption of target analyte. Through the structure of solid phase microextraction handle, can stretch into sample bottle and introduction port portion with optic fibre smoothly, can directly use in different equipment, do benefit to the automatic process of system.
Preferably, the pushing handle is connected with a mechanical arm of the sample pretreatment platform. The motion of pushing the handle is operated through the mechanical arm of the sample pretreatment platform, and the sample pretreatment platform drives the pushing handle to move through the mechanical arm which is automatically controlled by an electric signal.
Preferably, the outer tube is connected with a sliding cylinder, and the pushing handle is connected with the sliding cylinder in a sliding manner. The pushing handle moves in the sliding cylinder, so that the moving direction of the pushing handle can be stabilized, and the pushing handle is prevented from deviating.
Preferably, the push handle is provided with a guide groove communicated to the inner tube, and the optical fiber extends to the inner cavity of the inner tube through the guide groove. The optical fiber is fixed in the inner tube through the guide groove, and the optical fiber can move along with the push handle, so that the optical fiber is conveniently connected with the optical coupling device.
Preferably, the end of the outer tube away from the push handle is a conical tip. The pointed end can be favorable for the outer tube to pierce through the sample bottle and the shock insulator of the sample injection port part.
Compared with the prior art, the invention has the beneficial effects that: the optical fiber is combined with the solid phase micro-extraction coating, so that not only can high enrichment capacity of target molecules be realized, but also high laser absorption capacity and photoelectric conversion efficiency are realized, and the laser ionization process of the target molecules is realized. The solid phase extraction coating of the optical fiber in the system has good stability in the laser ionization process, low damage rate, no separation by laser excitation, no interference of matrix molecules during the detection of small molecules, obvious reduction of background interference during the detection of small molecules and improvement of analysis accuracy.
The system simplifies the sample pretreatment process and the laser ionization process, can directly realize the sample pretreatment process by using the optical fiber outer coating, carries out enrichment, separation and transfer on target analytes, can directly carry out laser ionization, and can realize all automatic operations from the sample pretreatment to the detection process.
Drawings
FIG. 1 is a schematic diagram of a laser-ionized solid phase microextraction-time-of-flight mass spectrometry system in accordance with the present invention;
fig. 2 is an exploded view of a solid phase microextraction handle of the present invention.
Detailed Description
The drawings are for illustrative purposes only and are not to be construed as limiting the patent; for the purpose of better illustrating the embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted. The positional relationships depicted in the drawings are for illustrative purposes only and are not to be construed as limiting the present patent.
The technical scheme of the invention is further described in detail by the following specific embodiments in combination with the attached drawings:
example 1
Fig. 1 shows an embodiment of a laser-ionized solid phase microextraction-time-of-flight mass spectrometry system, which includes a sample pretreatment platform 1, a solid phase microextraction handle 2 mounted on the sample pretreatment platform 1, a laser generator 3, an optical coupling device 4, a time-of-flight mass spectrometry 5, a laser controller 6 and a controller 7; in this embodiment, the sample pre-processing platform 1 is a multifunctional sample pre-processing platform, specifically, the model is the MuitiPurpose Sampler MPSXT of gerstel, the model of the laser generator 3 is the radial tunable laser system of OPOTEK, the time-of-flight mass spectrum 5 is 6545-Q-TOF-LC/MS of agilent, the laser controller 6 is the radial tunable laser system ICE 760 of OPOTEK, and the controller 7 is a computer control system.
Specifically, the extraction head of the solid phase micro-extraction handle 2 is an optical fiber 8, one end of the optical fiber 8 is coated with a solid phase micro-extraction coating, and the other end is connected with the optical coupling device 4; laser emitted by the laser generator 3 is coupled through the optical coupling device 4; the time-of-flight mass spectrometer 5 comprises a sample inlet portion 501 and an analysis portion 502, the optical fiber 8 can extend into the sample inlet portion 501, and an outlet of the sample inlet portion 501 is connected with the analysis portion 502 through a capillary.
In the embodiment, the laser controller 6, the sample pretreatment platform 1 and the time-of-flight mass spectrum 5 are all electrically connected with the controller 7; the laser controller 6 is electrically connected with the laser generator 3; the sample pretreatment platform 1 is electrically connected with the laser controller 6 through the signal converter 9, and the sample pretreatment platform 1 is electrically connected with the flight time mass spectrum 5. The instrument and the instruments are electrically connected, so that all the instruments are in a linkage state, after working parameters of all the instruments are set, the computer control system only needs to send a starting signal to the instruments once, and the instruments are started according to the received linkage starting signal, so that the running time between the instruments is coordinated, meanwhile, the whole system can run automatically, and the computer control system does not need to be operated for many times to send signals.
Wherein, the optical fiber 8 is used for removing the coating layer and the outer cladding layer at one end of the solid phase micro-extraction coating. The optical fiber 8 removes the coating layer and the outer cladding layer by etching using hydrofluoric acid, so that laser light can be emitted from the side surface of the optical fiber 8, and the solid-phase microextraction coating of the optical fiber 8 can absorb the energy of the laser light more easily and transfer the energy to target analytes.
The working principle or working process of the embodiment is as follows: the controller 7 opens the control software of each instrument and sets parameters as required. Setting the wavelength and energy intensity of the laser controller 6, selecting an external excitation control mode, setting the laser generator 3 in a standby state, and automatically emitting laser once receiving an external electric signal; setting working methods of the sample pretreatment platform 1, such as incubator temperature (extraction temperature in the sample pretreatment process), extraction time, oscillation rate, sample bottle specification, sample bottle tray selection, three-dimensional position adjustment of mechanical arm work, sample introduction time, sample bottle and sample inlet insertion depth, coating exposure depth and other parameters; setting a working sequence of the sample pretreatment platform 1; setting the signal duration of the signal converter 9, namely the working time of the laser generator 3; setting the charge-to-mass ratio m/z detection range, the positive and negative ion working modes, the mass spectrum parameters and the like of the time-of-flight mass spectrum 5; the working sequence of the time-of-flight mass spectrum 5 is set.
After the controller 7 outputs a starting signal, the working sequence of the sample pretreatment platform 1 and the flight time mass spectrum 5 starts to run, the mechanical arm controls the extraction head of the solid-phase extraction handle to be inserted into the sampling bottle, and a certain amount of target analytes in the sample bottle are adsorbed through the solid-phase extraction coating on the optical fiber 8. Inserting an extraction head into the sample inlet part 501 through a mechanical arm, simultaneously transmitting an electric signal to the time-of-flight mass spectrum 5 through a remote port data line by the sample pretreatment platform 1 after sample introduction, and starting the time-of-flight mass spectrum 5; the sample pretreatment platform 1 after sample introduction transmits an electric signal to the signal converter 9 through a remote port data line, the signal converter transmits the electric signal to the laser controller 6, the laser controller 6 controls the laser generator 3 to generate laser and transmit the laser to the photosynthetic coupling device 4, and the photosynthetic coupling device 4 couples the laser to the optical fiber 8 and transmits the laser in the optical fiber 8. When high-energy laser is transmitted to the part coated with the solid-phase micro-extraction coating, the laser emitted from the fiber core of the optical fiber 8 is coated on the surrounding extraction coating to be absorbed and transfers energy to target analytes, and protons are transferred to molecules or are obtained from the molecules in the ionization process, so that target molecules are ionized or protonated. The analysis unit 502 of the time-of-flight mass spectrometer 5 has a negative pressure, the target molecules are ionized or protonated and then transmitted to the analysis unit 502, and the analysis unit 502 finally transmits the analysis result to the controller 7, thereby realizing automatic detection.
The beneficial effects of this embodiment: when the system is used in a laboratory, the specially-made solid-phase microextraction coating outside the optical fiber 8 not only can realize high enrichment capacity of target molecules, but also has high laser absorption capacity and photoelectric conversion efficiency, thereby realizing the laser ionization process of the target molecules. The solid phase extraction coating of the optical fiber in the system has good stability in the laser ionization process, low damage rate, no separation by laser excitation, no interference of matrix molecules during the detection of small molecules, obvious reduction of background interference during the detection of small molecules and improvement of analysis accuracy. The system simplifies the sample pretreatment process and the laser ionization process, can directly realize the sample pretreatment process by using the optical fiber 8 external coating, can enrich, separate and transfer target analytes, can directly carry out laser ionization, and can realize all automatic operations from the sample pretreatment to the detection process.
Example 2
Fig. 2 shows another embodiment of a laser-ionized solid phase microextraction-time of flight mass spectrometry 5 system, which differs from embodiment 1 in that the solid phase extraction handle is further defined.
The solid phase micro-extraction handle 2 comprises an outer tube 201, an inner tube 202 arranged in the outer tube 201 and a pushing handle 203 connected with the inner tube 202; the optical fiber 8 is arranged in the inner tube 202, and one end of the optical fiber 8 coated with the solid phase micro-extraction coating extends out of the inner tube 202; the push handle 203 pushes the inner tube 202 to slide within the outer tube 201. The effect of outer tube 201 is when optic fibre 8 need adsorb the target analyte and stretch into injection port portion 501, because optic fibre 8 is comparatively fragile, the touching hard thing is damaged easily, can pierce through the outer tube 201 earlier the spacer of sample bottle and injection port portion 501, after outer tube 201 got into one end distance, pushing handle 203 through the promotion and driving inner tube 202 and move a section distance, outside optic fibre 8 stretched into outer tube 201, the realization was to the absorption and the desorption of target analyte. Through the structure of solid phase micro-extraction handle 2, can stretch into sample bottle and introduction port part 501 with optic fibre 8 smoothly, can directly use in different equipment, do benefit to the automatic process of system.
Wherein, the pushing handle 203 is connected with the mechanical arm of the sample pretreatment platform 1. The motion of the pushing handle 203 is operated by a mechanical arm of the sample pretreatment platform 1, and the sample pretreatment platform 1 automatically controls the mechanical arm to drive the pushing handle 203 to move through an electric signal.
Specifically, the outer tube 201 is connected with a sliding cylinder 204, and the pushing handle 203 is located in the sliding cylinder 204 and is slidably connected with the sliding cylinder 204. The push handle 203 moves in the sliding cylinder 204, so that the moving direction of the push handle 203 can be stabilized, and the push handle 203 is prevented from deviating. The push handle 203 is provided with a guide groove 205 communicating to the inner tube 202, and the optical fiber 8 extends to the lumen of the inner tube 202 through the guide groove 205. The optical fiber 8 is fixed in the inner tube 202 via the guide groove 205, and the optical fiber 8 can move along with the push handle 203, which also facilitates the connection of the optical fiber 8 with the optical coupling device 4.
To facilitate the passage of the outer tube 201 through the septum, the end of the outer tube 201 distal to the push handle 203 is tapered at a tip 206. The spike 206 may facilitate the outer tube 201 to pierce the sample vial and the septum of the sample inlet portion 501.
This embodiment is consistent with the remaining features and operating principles of embodiment 1.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system comprises a controller (7), a sample pretreatment platform (1) and a solid phase microextraction handle (2) arranged on the sample pretreatment platform (1), and is characterized by further comprising a laser generator (3), an optical coupling device (4) and a time-of-flight mass spectrometry (5); the extraction head of the solid phase micro-extraction handle (2) is an optical fiber (8), one end of the optical fiber (8) is coated with a solid phase micro-extraction coating, and the other end of the optical fiber is connected with the optical coupling device (4); the laser emitted by the laser generator (3) is coupled through the optical coupling device (4); the time-of-flight mass spectrum (5) comprises a sample inlet part (501) and an analysis part (502) connected with the sample inlet part, and the optical fiber (8) can extend into the sample inlet part (501); the sample pretreatment platform (1) and the time-of-flight mass spectrum (5) are both electrically connected with the controller (7).
2. A laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 1 further comprising a laser controller (6) electrically connected to said controller (7); the laser controller (6) is also electrically connected with the laser generator (3) and controls the laser wavelength of the laser generator (3).
3. A laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 2, wherein said sample pretreatment platform (1) is electrically connected to said laser controller (6) and said time of flight mass spectrometry (5), respectively.
4. A laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 3, wherein said sample pretreatment platform (1) is electrically connected to said laser controller (6) through a signal converter (9).
5. A combined laser-ionized solid phase microextraction-time of flight mass spectrometry system according to any of claims 1-4, wherein said optical fiber is used to remove the coating and outer cladding at the end coated with the solid phase microextraction coating.
6. A combined solid phase microextraction-time of flight mass spectrometry system as claimed in claim 5, wherein said solid phase microextraction handle (2) comprises an outer tube (201), an inner tube (202) mounted within said outer tube (201), and a push handle (203) connected to said inner tube (202); the optical fiber (8) is arranged in the inner tube (202), and one end of the optical fiber (8) coated with the solid-phase micro-extraction coating extends out of the inner tube (202); the pushing handle (203) pushes the inner tube (202) to slide in the outer tube (201).
7. A combined laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 6, wherein said push handle (203) is connected to a robotic arm of said sample pretreatment platform (1).
8. A combined laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 7, wherein said outer tube (201) is connected with a slide cartridge (204), and said push handle (203) is slidably connected with said slide cartridge (204).
9. A combined laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 8, wherein said push handle (203) is provided with a guide slot (205) communicating with said inner tube (202), and said optical fiber (8) extends through said guide slot (205) to the lumen of said inner tube (202).
10. A laser-ionized solid phase microextraction-time of flight mass spectrometry system according to claim 6, wherein the end of said outer tube (201) distal from said push handle (203) is a tapered tip (206).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010699861.9A CN111830117A (en) | 2020-07-20 | 2020-07-20 | Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system |
| PCT/CN2020/114178 WO2022016683A1 (en) | 2020-07-20 | 2020-09-09 | Laser ionization system for combined use of solid-phase microextraction and time of flight mass spectrometry |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010699861.9A CN111830117A (en) | 2020-07-20 | 2020-07-20 | Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system |
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| WO (1) | WO2022016683A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113192818A (en) * | 2021-03-26 | 2021-07-30 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030003596A1 (en) * | 1990-04-02 | 2003-01-02 | Pawliszyn Janusz B. | Method and device for solid phase microextraction and desorption |
| US20050011831A1 (en) * | 2002-08-28 | 2005-01-20 | Pawliszyn Janusz B. | Method and device for solid phase microextraction and desorption |
| CN101637668A (en) * | 2009-01-14 | 2010-02-03 | 中山大学 | Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof |
| CN203379635U (en) * | 2013-07-05 | 2014-01-08 | 上海新拓分析仪器科技有限公司 | Solid-phase microextraction device |
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
| CN110887891A (en) * | 2019-11-07 | 2020-03-17 | 广东省测试分析研究所（中国广州分析测试中心） | Micro-extraction-nano-liter electrospray ion source system in capillary and application |
| US20200191705A1 (en) * | 2018-12-17 | 2020-06-18 | Thermo Finnigan Llc | Apparatus and Methods for Handling and Spectrophotometry of Small Liquid Samples |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100565776C (en) * | 2007-12-03 | 2009-12-02 | 厦门大学 | Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer |
| CN202267612U (en) * | 2011-10-25 | 2012-06-06 | 中国地质大学（武汉） | Simple solid phase microextraction sampling device |
| CN103018370A (en) * | 2012-12-21 | 2013-04-03 | 江苏今世缘酒业股份有限公司 | Method for judging important flavor substance of liquor |
| CN105363426B (en) * | 2015-12-08 | 2018-10-16 | 复旦大学 | A kind of method of meso-porous titanium dioxide silicon composite connexus spectrum identification peptide fragment |
| WO2017147707A1 (en) * | 2016-03-02 | 2017-09-08 | Jp Scientific Limited | Solid phase microextraction coating |
| CN107870194B (en) * | 2016-09-27 | 2020-08-28 | 中国科学院生态环境研究中心 | Matrix-assisted laser desorption-gas phase polarization-induced proton transfer mass spectrometry |
| CN109374766B (en) * | 2018-11-02 | 2021-07-06 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation and application of fatty alcohol-polyoxyethylene ether and alkylphenol polyoxyethylene ether high-enrichment solid-phase microextraction probe |
-
2020
- 2020-07-20 CN CN202010699861.9A patent/CN111830117A/en active Pending
- 2020-09-09 WO PCT/CN2020/114178 patent/WO2022016683A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030003596A1 (en) * | 1990-04-02 | 2003-01-02 | Pawliszyn Janusz B. | Method and device for solid phase microextraction and desorption |
| US20050011831A1 (en) * | 2002-08-28 | 2005-01-20 | Pawliszyn Janusz B. | Method and device for solid phase microextraction and desorption |
| CN101637668A (en) * | 2009-01-14 | 2010-02-03 | 中山大学 | Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof |
| CN203379635U (en) * | 2013-07-05 | 2014-01-08 | 上海新拓分析仪器科技有限公司 | Solid-phase microextraction device |
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
| US20200191705A1 (en) * | 2018-12-17 | 2020-06-18 | Thermo Finnigan Llc | Apparatus and Methods for Handling and Spectrophotometry of Small Liquid Samples |
| CN110887891A (en) * | 2019-11-07 | 2020-03-17 | 广东省测试分析研究所（中国广州分析测试中心） | Micro-extraction-nano-liter electrospray ion source system in capillary and application |
Non-Patent Citations (1)
| Title |
|---|
| 刘昌孝: "《实用药物动力学》", 31 October 2003, 中国医药科技出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113192818A (en) * | 2021-03-26 | 2021-07-30 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
| CN113192818B (en) * | 2021-03-26 | 2022-07-08 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
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|---|---|
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