CN109473336B - High-efficiency ionization probe electrospray mass spectrum ion source device and probe suitable for same - Google Patents
High-efficiency ionization probe electrospray mass spectrum ion source device and probe suitable for same Download PDFInfo
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Classifications
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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
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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
- H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
-
- 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
- H01J49/0472—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 pyrolysis
-
- 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
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- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
The invention relates to the technical field of detection and analysis, in particular to a high-efficiency ionization probe electrospray mass spectrometry ion source device and a probe suitable for the ion source device, which comprises the following components: the probe comprises a liquid phase capillary, a probe fixing base, a nitrogen gas gathering gas system, a gas heating device, a three-dimensional fine tuning control console and a probe. The ion source device can improve the ionization efficiency and the ion transmission efficiency of the detection sample, thereby expanding the detection range of the electrospray mass spectrum of the probe. The novel graphene oxide functionalized probe suitable for the high-efficiency ionization probe electrospray mass spectrometry ion source device can improve the enrichment capacity and the enrichment variety of the probe, and further expand the detection range of the probe electrospray mass spectrometry.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a high-efficiency ionization probe electrospray mass spectrometry ion source device and a probe suitable for the ion source device.
Background
Hiaroka proposed "probe electrospray ionization (PESI)", and ionization of sample molecules can be achieved by applying a certain voltage to the tip of a conductive probe to which a sample solution is adsorbed. Probes can be made using a variety of solid substrates, including paper, toothpicks, surface modified glass rods, and copper, tungsten, stainless steel, and the like.
The method successfully performs identification analysis on metabolites in onion cells at a single cell level based on analysis of epidermal cells inside and outside onion cells by combining porous metal probes obtained by corroding copper (Cu) wires with HCl and MALDI-TOF. Gong et al. Yu et al analyzed differences in metabolite composition in different plant cells using functionalized probes in combination with ESI-MS techniques. The surface of the probe is modified by acid corrosion, so that the probe is more easily soaked by liquid, and an auxiliary solvent is added to improve desorption capacity.
Compared with the traditional single-cell mass spectrometry method, the single-cell analysis technology based on the PESI has the following potential advantages: (1) direct live cell sampling; (2) The enrichment of the molecules to be detected is beneficial to the improvement of the detection sensitivity; (3) The miniaturized probe can realize the detection of subcellular structures; (4) less interference to cell protoplasts when sampling; the device of (5) is relatively simple and the probe is reusable. It follows that PESI-based single cell mass spectrometry techniques are likely to offer more opportunities for investigation of cell biology.
The existing PESI/MS (probe electrospray ionization mass spectrometry) detection technology is mainly applied to single-cell analysis, and a certain voltage is applied to the tip of a conductive probe adsorbed with a sample solution to realize ionization of sample molecules. However, in the sample ionization process, besides adding an auxiliary solvent to assist in sample desorption, no other auxiliary means is provided for assisting in sample desorption and focusing transmission to a mass spectrum detector, so that ionization efficiency and ion transmission efficiency are low, and the existing functionalized probe has limited enrichment capability (mostly fruit sugar and partial lipid) and limits the detection range.
In summary, how to improve ionization efficiency and ion transmission efficiency, improve probe enrichment capability, and expand probe electrospray mass spectrometry detection range is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a novel high-efficiency ionization probe electrospray mass spectrum ion source device and a probe suitable for the ion source device.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a high-efficiency ionization probe electrospray mass spectrometry ion source device, which comprises:
the three-dimensional fine tuning control console is used for fixing the probe fixing base, the nitrogen gas collecting system and the gas heating device;
a liquid capillary having a liquid inlet for ingress of an auxiliary solvent, the auxiliary solvent being capable of converting the auxiliary solvent at the liquid outlet of the liquid capillary into a spray for delivery between the ion source device and the ion sampling port of the mass spectrometer detector;
the probe fixing base is used for fixing a probe and is connected with high-voltage electricity, and ionization of a probe tip sample can be realized by applying the high-voltage electricity;
the nitrogen gas gathering system is used for focusing the ion beam and improving the ion transmission efficiency;
the nitrogen gathering gas system comprises a nitrogen conveying pipeline and a circular gas nozzle for conveying nitrogen gathering gas to the mass spectrum detector;
the gas heating device can heat the nitrogen gas gathering gas system to improve desorption and ionization efficiency.
In the technical scheme, the liquid phase outlet end of the liquid phase capillary tube is gradually reduced from one end far away from the ionization region to one end close to the ionization region, and the diameter of the ejection outlet of the liquid phase capillary tube is 0.8mm-1.2mm.
In the above technical scheme, the annular gas nozzle of the nitrogen gas collecting gas system is positioned at the front end of the gas heating device, and the inner side of the annular gas nozzle is provided with a gas outlet, so that the ionized sample can be transmitted to the mass spectrum detector.
In the above technical scheme, the nitrogen conveying pipeline of the nitrogen collecting gas system surrounds the outer side of the gas heating device, which is helpful for uniformly heating the gas.
In the technical scheme, the outer end of the probe fixing base is wrapped with insulating polytetrafluoroethylene, so that the safety of an experiment is ensured.
In the above technical scheme, a slide way is arranged on the three-dimensional fine tuning control console, pulleys suitable for the slide way are arranged on the probe fixing base, the nitrogen gas collecting and heating system and the gas heating device, and the probe fixing base, the nitrogen gas collecting and heating system and the gas heating device are fixed on the three-dimensional fine tuning control console through the pulleys.
In the above technical scheme, the three-dimensional fine adjustment console is provided with a first micrometer, a second micrometer and a third micrometer, the micrometer screw of the first micrometer is arranged along the X direction, the micrometer screw of the second micrometer is arranged along the Y direction, the micrometer screw of the third micrometer is arranged along the Z direction, the frame of the first micrometer is fixed on the micrometer screw of the second micrometer, the frame of the third micrometer is fixed on the micrometer screw of the second micrometer, and the annular gas nozzle of the gas heating device, the probe fixing base and the nitrogen gas collecting system is fixed on the micrometer screw of the third micrometer; wherein, X direction, Y direction, Z are two by two perpendicular.
In the above technical solution, the high-efficiency ionization probe electrospray mass spectrometry ion source device further includes: a control box for controlling the working voltage and temperature of the gas heating device; and the diaphragm valve is arranged on a nitrogen conveying pipeline of the nitrogen gathering gas system.
In the above technical scheme, the probe is a reduced graphene oxide functionalized probe.
The invention also provides a probe suitable for the high-efficiency ionization probe electrospray mass spectrometry ion source device, which is a reduced graphene oxide functionalized probe.
According to the technical scheme, the high-efficiency ionization probe electrospray mass spectrometry ion source device comprises a liquid phase capillary, a probe fixing base, a nitrogen gas collecting gas system and a gas heating device; the liquid capillary tube is provided with a liquid phase inlet for a liquid sample to enter, and converts a solvent at the liquid phase outlet into spray and conveys the spray to the position between the ion source and an ion sampling port of the mass spectrum detector;
a probe fixing base which can realize ionization of the needle tip sample by applying high voltage electricity; the nitrogen gas gathering system comprises a nitrogen gas conveying pipeline and a circular gas nozzle for conveying nitrogen gas gathering gas to the mass spectrum detector, and can focus ion beams to improve ion transmission efficiency; the gas heating device can heat the nitrogen gas gathering gas system to improve desorption and ionization efficiency.
When the method is applied, firstly, after the gas heating device is preheated to the experimental temperature, the probe enriched with the sample is fixed on the probe fixing base, and the positions of the probe, the liquid-phase capillary, the gas heating device and the circular nozzle of the nitrogen gas gathering gas system are adjusted by using three micrometers on the three-dimensional fine adjustment control console; then applying high-voltage electricity on the probe, simultaneously introducing an auxiliary solvent into the liquid-phase capillary from the liquid-phase inlet, converting the auxiliary solvent into spray at the liquid-phase outlet, and conveying the spray to the position between the ion source and the ion sampling port of the mass spectrum detector, so that the sample on the auxiliary probe is desorbed better; the nitrogen gas gathering gas system is opened (generally between 5 and 30 kPa), and the nitrogen gas gathering gas fully heated by the gas heating device can assist in desorption of the sample, improve ionization efficiency, and transmit the ionized sample to the mass spectrum detector, so that ion transmission efficiency is improved.
The beneficial effects of the invention are as follows:
the invention provides a high-efficiency ionization probe electrospray mass spectrum ion source device which comprises a nitrogen gas gathering gas system for focusing an ion beam and improving ion transmission efficiency, wherein the nitrogen gas gathering gas system comprises a nitrogen gas conveying pipeline, a circular gas nozzle for conveying nitrogen gas gathering gas to a mass spectrum detector, and a gas heating device for heating the nitrogen gas gathering gas system so as to improve desorption and ionization efficiency. The ion source device can improve the ionization efficiency and the ion transmission efficiency of the detection sample, thereby expanding the detection range of the electrospray mass spectrum of the probe.
The novel reduced graphene oxide functionalized probe suitable for the high-efficiency ionization probe electrospray mass spectrometry ion source device can improve the enrichment capacity and the enrichment variety of the probe, and further expand the detection range of the probe electrospray mass spectrometry.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
Fig. 1 is a schematic diagram of a partial structure of an ion source device of an electrospray mass spectrometry of a high-efficiency ionization probe according to the present invention.
Reference numerals in the drawings denote:
the device comprises a 1-liquid phase capillary, a 2-probe fixing base, a 3-nitrogen gas collecting system, a 4-gas heating device, a 5-three-dimensional fine tuning console and a 6-probe.
Detailed Description
The invention provides a novel high-efficiency ionization probe electrospray mass spectrum ion source device which can improve ionization efficiency and ion transmission efficiency of a detection sample, so that the detection range of the probe electrospray mass spectrum is enlarged. The invention also provides a novel reduced graphene oxide functionalized probe suitable for the ion source device, which improves the enrichment capacity and the enrichment variety of the probe, and further expands the detection range of electrospray mass spectrometry of the probe.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The high-efficiency ionization probe electrospray mass spectrometry ion source device provided by the invention is described with reference to fig. 1, and comprises: the probe comprises a liquid phase capillary 1, a probe fixing base 2, a nitrogen gas collecting and gas system 3, a gas heating device 4, a three-dimensional fine tuning console 5 and a probe 6; the three-dimensional fine tuning control console 5 is used for fixing the probe fixing base 2, the nitrogen gas collecting and heating system 3 and the gas heating device 4; the liquid capillary 1 is provided with a liquid phase inlet for the auxiliary solvent to enter, and the auxiliary solvent at the liquid phase outlet of the liquid capillary 1 can be converted into spray to be conveyed between an ion source device and an ion sampling port of a mass spectrum detector, and the position of the auxiliary solvent is close to one side of an ionization region; the probe fixing base 2 is used for fixing the probe 6 and is connected with high-voltage electricity, and ionization of a probe 6 tip sample can be realized by applying the high-voltage electricity; the nitrogen gas gathering system 3 can focus ion beams and improve ion transmission efficiency; the nitrogen gathering gas system 3 comprises a nitrogen conveying pipeline and a circular gas nozzle for conveying nitrogen gathering gas to the mass spectrum detector; the gas heating device 4 is positioned at one side of the rear part of the circular ring-shaped gas nozzle, which is far away from the ionization region, and can heat the nitrogen gas collecting gas system 3 to improve the desorption and ionization efficiency. The annular gas nozzle of the nitrogen gas gathering system 3 is positioned at the front end of the gas heating device 4, and a gas outlet is arranged at the inner side of the annular gas nozzle at the outer side of the probe 6, so that ionized samples can be transmitted to the mass spectrum detector. The nitrogen conveying pipeline of the nitrogen gathering gas system 3 surrounds the outer side of the gas heating device 4, and is beneficial to uniformly heating the gas. The probe 6 is positioned in front of the gas heating device 4 and inside the circular gas nozzle.
When the method is applied, firstly, after the gas heating device 4 is preheated to the experimental temperature, the probe 6 enriched with the sample is fixed on the probe fixing base 2, and the positions of the probe 6, the liquid-phase capillary 1, the gas heating device 4 and the circular gas nozzle of the nitrogen gas gathering system 3 are adjusted by using three micrometer on the three-dimensional fine adjustment control console 5; then high-voltage electricity is applied to the probe 6, meanwhile, auxiliary solvent is led into the liquid-phase capillary 1 from the liquid-phase inlet of the liquid-phase capillary 1, the auxiliary solvent is converted into spray at the liquid-phase outlet and is conveyed between the ion source and the ion sampling port of the mass spectrum detector, and the sample on the auxiliary probe 6 is desorbed better; the nitrogen gas is opened (generally 5kPa to 30 kPa), and the nitrogen gas sufficiently heated by the gas heating device 4 can assist in desorption of the sample, improve ionization efficiency, and transfer the ionized sample to a mass spectrum detector, and improve ion transfer efficiency.
In summary, the high-efficiency ionization probe electrospray mass spectrometry ion source device can improve ionization efficiency and ion transmission efficiency of a detection sample, so that the detection range of the probe electrospray mass spectrometry is enlarged.
In a specific embodiment, the high-efficiency ionization probe electrospray mass spectrometry ion source device provided by the invention applies 0- +/-5 kv high-voltage electric experiment sample ionization on the surface of the probe enriched with the sample, and the ionization sample is transmitted to a mass spectrometer for analysis through high-temperature nitrogen gas gathering gas, so that the high-efficiency ionization probe electrospray mass spectrometry ion source device is suitable for in-situ nondestructive sampling detection of cell, animal and plant samples.
In order to achieve a better spraying effect, in the high-efficiency ionization probe electrospray mass spectrometry ion source device provided by the embodiment, the liquid phase outlet end of the liquid phase capillary 1 is gradually reduced from one end far away from the ionization region to one end close to the ionization region, and the diameter of the ejection outlet of the liquid phase capillary 1 is 0.8mm-1.2mm, preferably 1mm; thus, the liquid phase outlet of the liquid phase capillary 1 has a small ejection port. It is understood that the liquid-phase capillary 1 may be a straight tube as long as the shape of the auxiliary liquid in the spray state can be achieved.
In order to facilitate the installation, a slide way is arranged on a three-dimensional fine adjustment control console 5 of the high-efficiency ionization probe electrospray mass spectrometry ion source device, pulleys suitable for the slide way are arranged at the lower parts of a probe fixing base 2, a gas heating device 4 and a nitrogen gas collecting gas system 3, and the probe fixing base 2, the gas heating device 4 and the nitrogen gas collecting gas system 3 are fixed on the three-dimensional fine adjustment control console 5 through the slide way and the pulleys; firstly, fixing a nitrogen gas collecting system 3 and a gas heating device 4, then fixing a probe fixing base 2, and adjusting the positions of a circular gas nozzle of the nitrogen gas collecting system 3 and a probe 6 to achieve the final ionization effect.
In order to further optimize the technical scheme, the three-dimensional fine adjustment console 5 is provided with a first micrometer, a second micrometer and a third micrometer, the micrometer screw of the first micrometer is arranged along the X direction, the micrometer screw of the second micrometer is arranged along the Y direction, the micrometer screw of the third micrometer is arranged along the Z direction, the frame of the first micrometer is fixed on the micrometer screw of the second micrometer, the frame of the third micrometer is fixed on the micrometer screw of the second micrometer, and the annular gas nozzles of the gas heating device 4, the probe fixing base 2 and the nitrogen gas collecting system 3 are fixedly arranged on the micrometer screw of the third micrometer; wherein, X direction, Y direction, Z are two by two perpendicular. According to the invention, the components can be three-dimensionally adjustable through the three micrometer arranged on the three-dimensional fine adjustment console 5, so that stable detection signals are obtained when the three-dimensional positions of different probes and nitrogen gathering gases are analyzed.
Of course, the present invention may also realize three-dimensional adjustability of the above components with respect to the three-dimensional fine adjustment console 5 by other means, such as X-directional, Y-directional, and Z-directional movement mechanisms each composed of a linear slide rail, a ball screw, and a servo motor.
Preferably, the high-efficiency ionization probe electrospray mass spectrometry ion source device further comprises a control box for controlling the working voltage and the temperature of the heating device 4; the nitrogen delivery pipeline of the nitrogen gathering gas system 3 is regulated to be delivered to the air pressure diaphragm valve of the mass spectrum detector, and the diaphragm valve is arranged on the nitrogen delivery pipeline of the nitrogen gathering gas system 3. In a specific working process, the working voltage of the heating device 4 is 24V, and the temperature is controlled by a temperature control meter of the control box. The pressure of the nitrogen gas accumulation gas can be regulated by a diaphragm valve according to the requirement. The device can also obtain stable detection signals by controlling parameters such as heating temperature, flow rate and the like of the nitrogen gathering gas when analyzing different components.
Further, the inner diameter of the liquid-phase capillary 1 is 75 μm to 150. Mu.m. The liquid phase capillary 1 is a metal capillary or a quartz capillary with polyimide coating on the surface layer, so that the liquid phase capillary 1 can be bent, the position of the liquid phase capillary is convenient to adjust, and meanwhile, the damage caused by bending in the working process is reduced. The polyimide has better high and low temperature resistance, electrical insulation, adhesion, radiation resistance, dielectric resistance, chemical stability and flame retardance, and prolongs the service life of the liquid capillary 1.
Preferably, the outer end of the probe fixing base 2 is wrapped with insulating polytetrafluoroethylene, so that the safety of an experiment is ensured.
Preferably, the probe 6 is a reduced graphene oxide functionalized probe.
The invention also provides a probe suitable for the high-efficiency ionization probe electrospray mass spectrometry ion source device, which is a reduced graphene oxide functionalized probe.
The preparation process of the reduced graphene oxide functionalized probe is as follows:
(1) Copper probe preparation
A gold coil with a diameter of 2mm was used as a cathode, a copper wire with a length of 5cm and a thickness of 1mm was placed on the surface of the cathode in a KOH solution containing 30% (wt/wt), and the copper wire was placed on the center of the cathode coil, and immersed in an etching solution for about 1 mm. A DC voltage is applied between the two, the voltage is set to be 5.0V, and the stopping current is 2.2mA. The whole etching process lasts for about 5 minutes.
(2) Preparation of functional reduced graphene oxide probe
And fixing a platinum wire counter electrode, taking Ag/AgCl (saturated KCl) as a reference electrode, taking an etched copper needle as a working electrode, and scanning a cyclic voltammogram (Cyclic Voltammetry, CY) in the GO solution. The potential window is-1.5-0.5V, the initial scanning potential is-1.5V, the scanning speed is 0.2V/s, and the scanning cycle period is 20. And after the scanning is finished, the probe is taken out of the GO solution and is fully cleaned by ultrapure water, so that the reduced graphene oxide functionalized probe is obtained.
In one embodiment of the specific practice:
high-efficiency ionization probe electrospray mass spectrometry ion source device: the heating temperature of the gas is 230 ℃, the pressure of nitrogen gathering gas is 150kPa, the distance between the probe 6 and the mass spectrum detector is-1 mm, the vacuum degree of an external vacuum pump is 0.25kPa, and the distance between the liquid phase ejection port and the mass spectrum detector is 3mm above the connecting line of the probe 6 and the mass spectrum detector.
The liquid sample to be measured is tetrahydroberberine with the concentration of 1 mug/mL, and is dissolved in PBS aqueous solution. The probe 6 was concentrated in the sample for 30 seconds using the probe 6, and the probe 6 was fixed on the probe fixing base 2, and a +3kv voltage was applied to the probe 6 through the probe fixing base 2, whereby a good ionization effect was obtained.
In another embodiment of the specific practice:
high-efficiency ionization probe electrospray mass spectrometry ion source device: the gas heating temperature is 230 ℃, the nitrogen gas gathering gas pressure is 150kPa, the distance between the reduced graphene oxide functional probe and the mass spectrum detector is-1 mm, the vacuum degree of an external vacuum pump is 0.25kPa, and the liquid phase ejection port is positioned above the connecting line of the reduced graphene oxide functional probe and the mass spectrum detector and is 3mm away from the mass spectrum detector.
The liquid sample to be measured is gamma-aminobutyric acid with the concentration of 1 mug/mL, and is dissolved in PBS aqueous solution. The reduced graphene oxide functionalized probe is enriched in the sample for 30 seconds, the reduced graphene oxide functionalized probe is fixed on the probe fixing base 2, and a voltage of-2.5 kv is applied to the reduced graphene oxide functionalized probe through the probe fixing base 2, so that a good ionization effect is obtained.
The invention realizes in-situ nondestructive sampling detection of biological samples such as cells, animals, plants and the like. The qualitative and quantitative analysis of the compounds with different properties is realized by optimizing the types of auxiliary solvents, the positions of the auxiliary solvents and the mass spectrum inlet, the positions of the probes, the nitrogen gathering gas flow rate, the temperature and the like, and an in-situ nondestructive sampling detection analysis method suitable for biological samples such as cells, animals, plants and the like can be established according to research results. The invention greatly expands the application of the probe electrospray ion source in the related fields.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A high efficiency ionization probe electrospray mass spectrometry ion source device, comprising:
the three-dimensional fine tuning control console (5) is used for fixing the probe fixing base (2), the nitrogen gas collecting and gas system (3) and the gas heating device (4);
a liquid capillary (1) having a liquid inlet for the ingress of an auxiliary solvent, the auxiliary solvent being capable of converting the auxiliary solvent at the liquid outlet of the liquid capillary (1) into a spray for delivery between an ion source device and an ion sampling port of a mass spectrometer detector;
the probe fixing base (2) is used for fixing the probe (6) and is connected with high-voltage electricity, and ionization of a probe (6) needle point sample can be realized by applying the high-voltage electricity;
the nitrogen gas gathering system (3) is used for focusing the ion beam and improving the ion transmission efficiency;
the nitrogen gathering gas system (3) comprises a nitrogen conveying pipeline and a circular gas nozzle for conveying nitrogen gathering gas to the mass spectrum detector;
the gas heating device (4) can heat the nitrogen gas gathering gas system (3) to improve the desorption and ionization efficiency.
2. The electrospray mass spectrometry ion source device according to claim 1, wherein the liquid phase outlet end of the liquid phase capillary (1) tapers from one end far from the ionization region to one end near the ionization region, and the diameter of the ejection outlet of the liquid phase capillary (1) is 0.8mm-1.2mm.
3. The electrospray mass spectrometry ion source device according to claim 1, wherein the annular gas nozzle of the nitrogen gas collecting system (3) is positioned at the front end of the gas heating device, and a gas outlet is arranged at the inner side of the annular gas nozzle, so that ionized samples can be transmitted to the mass spectrometer detector.
4. The high-efficiency ionization probe electrospray mass spectrometry ion source device according to claim 1, wherein a nitrogen delivery pipeline of the nitrogen concentration gas system (3) surrounds the outer side of the gas heating device (4) to facilitate uniform heating of gas.
5. The high-efficiency ionization probe electrospray mass spectrometry ion source device according to claim 1, wherein the outer end of the probe fixing base (2) is wrapped with insulated polytetrafluoroethylene, so that the safety of an experiment is ensured.
6. The high-efficiency ionization probe electrospray mass spectrometry ion source device according to claim 1, wherein a slide way is arranged on the three-dimensional fine tuning control console (5), pulleys suitable for the slide way are arranged on the probe fixing base (2), the nitrogen gas collecting gas system (3) and the gas heating device (4), and the probe fixing base (2), the nitrogen gas collecting gas system (3) and the gas heating device (4) are fixed on the three-dimensional fine tuning control console (5) through the pulleys.
7. The high-efficiency ionization probe electrospray mass spectrometry ion source device according to claim 1, wherein a first micrometer, a second micrometer and a third micrometer are arranged on the three-dimensional fine adjustment control console (5), micrometer screws of the first micrometer are arranged along an X direction, micrometer screws of the second micrometer are arranged along a Y direction, micrometer screws of the third micrometer are arranged along a Z direction, a frame of the first micrometer is fixed on the micrometer screws of the second micrometer, a frame of the third micrometer is fixed on the micrometer screws of the second micrometer, and circular gas nozzles of the gas heating device (4), the probe fixing base (2) and the nitrogen gas collecting system (3) are fixedly arranged on the micrometer screws of the third micrometer; wherein, X direction, Y direction, Z are two by two perpendicular.
8. The high efficiency ionization probe electrospray mass spectrometry ion source apparatus of claim 1, further comprising: a control box for controlling the operating voltage and temperature of the gas heating device (4); and a diaphragm valve for adjusting the pressure of the nitrogen gas gathering system (3), wherein the diaphragm valve is arranged on a nitrogen gas conveying pipeline of the nitrogen gas gathering system (3).
9. The high-efficiency ionization probe electrospray mass spectrometry ion source device according to any one of claims 1 to 8, wherein the probe (6) is a reduced graphene oxide functionalized probe.
10. A probe suitable for use in a high efficiency ionization probe electrospray mass spectrometry ion source apparatus according to any one of claims 1 to 8, characterized in that it is a reduced graphene oxide functionalized probe.
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| CN110455972B (en) * | 2019-08-21 | 2022-01-14 | 哈尔滨阿斯顿仪器有限公司 | Liquid chromatography-mass spectrometry combined analysis method and interface device used by same |
| CN111243937B (en) * | 2020-03-11 | 2024-05-24 | 知健生物分子研究院(南京)有限公司 | Capillary electrophoresis mass spectrometry equipment and biochemical analysis system |
| CN111627794B (en) * | 2020-04-17 | 2023-04-25 | 宁波大学 | Thermal analysis electrospray ion source with enrichment function |
| CN112051341A (en) * | 2020-09-08 | 2020-12-08 | 广东联捷生物科技有限公司 | Liquid phase mass spectrum sampling and electrospray combined device |
| CN112858452B (en) * | 2021-01-19 | 2023-10-03 | 岛津企业管理（中国）有限公司 | Living body analysis system combining probe electrospray ionization and mass spectrum |
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