CN210778481U

CN210778481U - Mass spectrum ionization device

Info

Publication number: CN210778481U
Application number: CN201921600390.0U
Authority: CN
Inventors: 徐元宏; 乔金平
Original assignee: First Affiliated Hospital of Anhui Medical University
Current assignee: First Affiliated Hospital of Anhui Medical University
Priority date: 2019-09-25
Filing date: 2019-09-25
Publication date: 2020-06-16
Anticipated expiration: 2029-09-25

Abstract

The utility model belongs to the technical field of the ionization source, concretely relates to mass spectrum ionization device, including radiation light source and protecting sheathing, radiation light source installs in protecting sheathing, be equipped with mass spectrograph atmospheric pressure interface on the protecting sheathing, the protecting sheathing is located mass spectrograph atmospheric pressure interface side and is connected with mass spectrograph vacuum cavity, the position that corresponds mass spectrograph atmospheric pressure interface in the mass spectrograph vacuum cavity is equipped with ion guide, ion guide connects mass analyzer; the short wave radiation generated by the radiation light source faces the inside of the protective shell to form an excited high-energy state environment area. The protective shell is provided with a sample leading-out mechanism for placing a sample in an excited high-energy state environment area; the utility model discloses the shortwave radiation source of well adoption is small, simple structure, the wave band is adjustable, stray light is low, the energy is high, and sample ionization energy is abundant, and does not have the problem of desolvation and ion sampling efficiency, and sensitivity is high, and the reproducibility is good as a result.

Description

Mass spectrum ionization device

Technical Field

The utility model belongs to the technical field of the ionization source, concretely relates to mass spectrum ionization device.

Background

The ion source is a core component of a mass spectrometer, ionizes injected neutral substances into ions, is the first step for realizing mass spectrometry, and plays a very important role in the technical field of mass spectrometry. The ion source has many kinds, and mainly includes vacuum ionization sources and atmospheric pressure ionization sources. Vacuum ionization sources such as a fast atom bombardment electron ionization source (FAB), an electron bombardment ionization source (EI), a chemical ionization source (CI), and the like, all of which need to work under a certain vacuum condition, are ion sources capable of working in an atmospheric environment, and are a relatively representative electrospray ionization source (ESI), which is a relatively new ionization technology, and the electrospray ionization source has a unique advantage and a wide development prospect, and is paid much attention to.

Electrospray Ionization (also known as ESI) source is compatible with a variety of sample introduction methods, such as liquid chromatography, capillary electrophoresis, microfluidics, and the like. This ionization technique can not only analyze macromolecular compounds, but also generate multi-charged ions during ionization, and the types of compounds that can be analyzed are very large, including organic compounds, drugs and their metabolites, proteins, peptides, sugars, etc. Electrospray ionization sources are therefore of great interest for the development and application of the entire mass spectrometry technology, which has consequently gained the 2002 nobel prize for chemistry. Electrospray ionization sources operate with high flow rate requirements, generally with lower flow rates and higher sensitivity, mainly because high flow rates are not suitable for desolvation processes. The current ESI model mechanism is Coulomb explosion, if the flow rate is too high, the solvent can not be fully desolvated before entering a vacuum interface, and a normal ion signal can not be obtained. Therefore, under certain analysis conditions, nano-ESI is also required, and the flow rate can be reduced to nL level. ESI sources are generally limited by the rate of liquid phase flow, and low flow ESI sources tend to achieve higher degrees of desolvation, and thus higher ion transport efficiency and resolution. However, in liquid mass spectrometry, a faster sample liquid flow rate is typically required, and the radius of the droplet is proportional to the flow rate, which increases the time and distance required for desolvation, resulting in a low degree of desolvation, which results in inefficient sampling of the vacuum interface, thereby losing the high resolution of the low flow ESI source. Moreover, ESI has obvious ion suppression effect in working engineering (such as high salt condition is typical), and the added ions including water cluster can influence analysis. In order to solve the series of problems, an atmospheric pressure chemical ionization source APCI and an atmospheric pressure photoionization source APPI are derived, and the structures of the ion sources are similar and are effective supplements to an ESI source.

Meanwhile, some substances with weak polarity are ionized by adopting a vacuum ultraviolet single photon dissociation (PI) technology, so that the analysis problem of a large amount of non-polar component complex systems is solved. A novel electrospray sample injection vacuum ultraviolet single photon ionization mass spectrometry device with Chinese patent publication No. CN101329299A and a method for preparing sample ions by adopting an electrospray technology to prepare compound ions, using a vacuum ultraviolet lamp or synchrotron radiation as a light source and irradiating the ions in a vacuum ultraviolet wavelength range smaller than 200 nm. Meanwhile, the Chinese patent publication No. CN103762150A discloses an ultrasonic atomization sample introduction volatile solvent auxiliary ionization low-pressure photoionization mass spectrum device, which combines the vacuum ultraviolet single photon ionization technology with the ultrasonic atomization volatile solvent technology. However, the light sources used in these technical disclosures are limited to the vacuum ultraviolet wavelength range (100-200nm), and the sample to be tested needs to be dissolved in a volatile organic solvent, so as to characterize the macromolecular segment and polypeptide which are not easy to dissolve and have complex structures, and have certain limitations. Although the vacuum ultraviolet single photon dissociation has high efficiency, the energy is low, the absorption edges of some important atoms cannot be covered, the dissociation does not have atom selectivity, and the directional dissociation of macromolecules has great difficulty. With the use of protons of hydration (H)₃O⁺) Method for transferring as ionization source proton transfer reaction source (PTR) the principle of this technology is that most VOCs have proton affinity higher than that of water and lower than that of highly polymerized water, and can be ionized by reacting with protons. If the n-butyl alcohol can not detect a molecular ion peak under normal test conditions, only a peak of butylene without hydroxyl can be detected, and great difficulty is brought to the test of the n-butyl alcohol.

In the existing atmospheric pressure ion source, an ion source of a general solution is not available, and various ion sources have limitations in the aspect of analyzing sample species, mainly because of problems in the aspect of energy acquisition.

In order to solve the above problems, a mass spectrometer ionization device is proposed in the present application.

SUMMERY OF THE UTILITY MODEL

In order to solve the above problem, the utility model provides a soft x-ray ion source passes through the short wave radiation of specific wave band scope, forms high energy plasma atmosphere at surrounding space environment, can be directly with the comprehensive ionization of surrounding air background and sample, guarantees to accomplish under the supplementary condition of no pretreatment or matrix and distinguishes complete ionization to the nothing of complicated sample composition.

The utility model provides a technical scheme that its technical problem adopted is:

a mass spectrum ionization device comprises a radiation light source and a protective shell, wherein the radiation light source is arranged on the protective shell, a mass spectrometer atmospheric pressure interface is arranged on the protective shell, a mass spectrometer vacuum cavity is connected to the side, located on the mass spectrometer atmospheric pressure interface, of the protective shell, an ion guide is arranged in the mass spectrometer vacuum cavity corresponding to the mass spectrometer atmospheric pressure interface, and the ion guide is connected with a mass analyzer;

the short wave radiation generated by the radiation light source faces the inside of the protective shell to form an excited high-energy state environment area.

And the protective shell is provided with a sample leading-out mechanism for placing the sample in an excited high-energy state environment area.

Further, the sample introducing mechanism adopts a liquid introducing connection pipe, and the liquid introducing connection pipe is arranged on the protective shell and used for introducing the liquid sample into the protective shell.

Furthermore, the sample introducing and placing mechanism adopts a placing table, the placing table is installed in the protective shell, and a groove is formed in the placing table and used for placing a sample.

Furthermore, the wave band of the short-wave radiation generated by the radiation light source is positioned between the ultraviolet wave band and the hard X-ray wave band on the electromagnetic spectrum, the spectral range is 0.3mn-40nm, the photon capacity is 29eV-9999eV, the intensity of the short-wave radiation is adjustable, and the luminescence process is in a continuous or discontinuous pulse form.

Furthermore, an ion condensing part is arranged at the opening and used for focusing ions generated in the ion source.

Further, the protective casing is connected with a vacuum pump through a pipeline so as to form a low-pressure environment in the protective casing, and the pressure value of the low-pressure environment is 0.1Pa-1e4 Pa.

Furthermore, an auxiliary structure for introducing an auxiliary agent for assisting the radiation ionization of the sample is arranged on the protective shell, and the auxiliary structure is communicated with the cavity.

Further, the auxiliary agent comprises at least one of methanol, ethanol, water vapor, hydrogen sulfide, methane, helium and nitrogen.

The above technical scheme of the utility model has following profitable technological effect:

1. the utility model discloses the shortwave radiation source of well adoption is small, simple structure, the wave band is adjustable, stray light is low, the energy is high, and sample ionization energy is abundant, and does not have the problem of desolvation and ion sampling efficiency, and sensitivity is high, and the reproducibility is good as a result.

2. The utility model provides a soft X ray ion source can the effectual sample insufficient ionization that solution ion suppression effect brought and add the influence that cluster ion etc. brought to the analysis.

3. The utility model provides a sample (especially biological macromolecule) that soft X-ray ion source ionization is difficult to the ionization obtains complete ionization result, and the structure can assist evacuation, reduces background interference, can also let in specific supplementary sample radiation ionization auxiliary agent simultaneously and realize a, supplementary ionization, the ability of more abundant fingerprint piece information; b. and inhibiting background chemical noise interference and obtaining molecular parent ion information.

4. The application range is wide, the salt and buffer solution with certain degree can be tolerated, the requirement on sample treatment is not strict, and even untreated biological samples can be directly analyzed, thereby simplifying the complicated sample preparation process.

Drawings

Fig. 1 is a schematic structural diagram of the present invention in embodiment 1.

Fig. 2 is a schematic structural diagram of the present invention in embodiment 2.

Fig. 3 is a schematic structural diagram of the present invention in embodiment 2.

Fig. 4 is a schematic structural diagram of the present invention in embodiment 2.

Fig. 5 is a schematic structural diagram of the present invention in embodiment 3.

Fig. 6 is a schematic structural diagram of the present invention in embodiment 4.

Fig. 7 is a schematic structural diagram of the present invention in embodiment 4.

Fig. 8 is a schematic structural diagram of the present invention in embodiment 4.

Detailed Description

In order to make the technical means, the creation features, the achievement purposes and the functions of the present invention easy to understand, the present invention will be further explained below with reference to the following embodiments and the accompanying drawings, but the following embodiments are only the preferred embodiments of the present invention, and not all embodiments are included. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative work belong to the protection scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.

Specific embodiments of the present invention will be described below with reference to the accompanying drawings. The following several specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments.

A mass spectrometry ionization apparatus as described above:

example 1

As shown in FIG. 1, a radiation source 101; 102. a protective housing; 103 liquid introduction connection; 104. exciting a high-energy state environment region; 105. a mass spectrometer atmospheric pressure interface; 106. a mass spectrometer vacuum cavity; 107. ion guiding; 108. a mass analyzer.

The radiation light source 101 is used for generating X-rays to cover a high-energy region, namely the excited high-energy state environment region 104, and the rear end of the mass spectrometer atmospheric pressure interface 105 is in butt joint with a mass spectrometer vacuum chamber, specifically comprising necessary structures such as ion guides, mass analyzers, ion detectors and the like at all stages; the liquid sample enters the cavity from the liquid introduction connecting pipe 103 in a manual injection or peristaltic pump mode, a series of processes such as ionization, cluster removal and desolvation are completed in the excited high-energy state environment area 104, and the liquid sample enters the mass spectrometer through the mass spectrum atmospheric pressure interface negative pressure environment of the opening 105 to complete the whole process of ionization and entering the mass spectrum. It is further noted that: the band of the short-wave radiation generated by the radiation light source 101 is located between the ultraviolet band and the hard X-ray band on the electromagnetic spectrum, the spectral range is 0.3mn-40nm, the photon capacity is 29eV-9999eV, the intensity is adjustable, the luminescence process is in a continuous or discontinuous pulse form, and the mass analyzer 108 can be but is not limited to a quadrupole, an ion trap, a time-of-flight tube and the like.

Example 2

As shown in fig. 2-4, in the drawings: 101. a radiation source; 102. a protective housing; 103 liquid introduction connection; 104. exciting a high-energy state environment region; 105. a mass spectrometer atmospheric pressure interface; 106. a mass spectrometer vacuum cavity; 107. ion guiding; 108. a mass analyzer; 109. an auxiliary structure; 110. a vacuum pump; 111. an ion condenser.

The difference from example 1 is that: in order to improve the performance of the ion source, a part of supplementary structures are added.

In fig. 2, an auxiliary structure 109 is added, in this embodiment, the auxiliary structure 109 assists the introduction of the sample radiation ionization auxiliary agent, which may be a pipe, for introducing the auxiliary sample radiation ionization auxiliary agent into the protective housing 102, and it is further required to be described that: the auxiliary agent is at least one of methanol, ethanol, water vapor, hydrogen sulfide, methane, helium and nitrogen, and for example, the auxiliary agent is methanol and water vapor. The auxiliary structure 109 may be any structure capable of guiding the auxiliary agent into the protective housing, so as to achieve the functions of improving the ionization efficiency or suppressing the interference of the background chemical noise.

In fig. 3, a vacuum pump 110 is added to draw vacuum, and the internal air pressure value is controlled to be 0.1Pa-1e4Pa, which can further assist in suppressing background chemical noise interference and helping the interior of the environment to be filled with the auxiliary sample radiation ionization auxiliary agent as much as possible.

In fig. 4, an ion condenser 111 is added, and in this embodiment, the ion condenser 111 is an ion lens, and is used to better focus ions generated inside the ion source, and more ions are introduced into an atmospheric pressure interface of the later-stage mass spectrometer, so that the overall efficiency is improved. Of course, in some embodiments, the ion condenser 108 may be other ion condensing devices. The whole ionization process is the same as that of the embodiment 1, and the added auxiliary structures improve the ionization efficiency and reduce the background interference in the environment, thereby being beneficial to improving the ionization efficiency and the sensitivity of the ion source.

Example 3

As shown in fig. 5, in the figure: 201. a radiation source; 202. a protective housing; 203. a placing table; 204. exciting a high-energy state environment region; 205. a mass spectrometer atmospheric pressure interface; 206. a mass spectrometer vacuum cavity; 207. ion guiding; 208. a mass analyzer.

The radiation light source 201 is used for generating X-rays to cover a high energy region, i.e. the excited high energy state environment region 204, the opening 205 is a butt joint position of an ion source structure and an atmospheric pressure interface, and the rear end is butted with a mass spectrometer vacuum chamber, specifically including necessary structures such as ion guides, mass analyzers, ion detectors and the like at all stages; a liquid or a fixed sample is placed in a sample groove on a placing table 203, a series of processes such as ionization, cluster removal and desolvation are completed in an excited high-energy state environment area 204, and the liquid or the fixed sample enters a mass spectrometer through a mass spectrum atmospheric pressure interface negative pressure environment of an opening 205 to complete the whole process of ionization and entering the mass spectrum. It is further noted that: the band of the short-wave radiation generated by the radiation source 201 is located between the ultraviolet band and the hard X-ray band on the electromagnetic spectrum, the spectral range is 0.3mn-40nm, the photon capacity is 29eV-9999eV, the intensity is adjustable, the luminescence process is in a continuous or discontinuous pulse form, and the mass analyzer 208 can be but not limited to a quadrupole, an ion trap, a time-of-flight tube and the like.

Example 4

As shown in fig. 6-8, in the figures: 201. a radiation source; 202. a protective housing; 203. a placing table; 204. exciting a high-energy state environment region; 205. an opening; 206. an auxiliary structure; 207. a vacuum pump; 208. an ion condenser; 209 an auxiliary structure; 210. a vacuum pump; 211. an ion condenser.

Unlike embodiment 3, in order to improve the performance of the ion source, a part of a supplementary structure is added.

In fig. 6, an auxiliary structure 209 is added, in this embodiment, the auxiliary structure 209 may be a pipeline (a pipe) for introducing an auxiliary sample radiation ionization auxiliary agent into the protective housing, and it is further to be noted that: the auxiliary agent is at least one of methanol, ethanol, water vapor, hydrogen sulfide, methane, helium and nitrogen, and for example, the auxiliary agent is methanol and water vapor. The auxiliary structure 209 may be any structure capable of guiding the above-mentioned additives into the cavity, so as to achieve the functions of improving the ionization efficiency or suppressing the interference of the background chemical noise.

In fig. 7, a vacuum pump 210 is added to draw vacuum, and the internal air pressure value is controlled to be 0.1Pa-1e4Pa, which can further assist in suppressing background chemical noise interference and helping the interior of the environment to be filled with the auxiliary sample radiation ionization auxiliary agent as much as possible.

In fig. 8, an ion condenser 211 is added, and in this embodiment, the ion condenser 211 is an ion lens, and is used to better focus ions generated inside the ion source, and more ions are introduced into an atmospheric pressure interface of the later-stage mass spectrometer, so that the overall efficiency is improved.

Of course, in some embodiments, the ion condenser 208 may also be other ion condensing devices. The whole ionization process is the same as that of the embodiment 3, and the added auxiliary structures improve the ionization efficiency and reduce the background interference in the environment, thereby being beneficial to improving the ionization efficiency and the sensitivity of the ion source.

It is further noted that the wavelength band of the short wave radiation generated by the radiation source 201 is preferably in the extreme ultraviolet region and the soft x-ray region. Light in the extreme ultraviolet and soft x-ray spectral regionsThe molecules can be basically matched with main resonance lines of all elements, so that short-wave radiation under the frequency band has very high energy, introduced gas and liquid samples or chemical components to be analyzed of solid and liquid samples placed in an ion source can be fully ionized, air components in the surrounding environment can be ionized into a high-energy plasma state, the sample can be protected under a high-energy atmosphere before the ionized components enter a vacuum interface, the loss is reduced, and the sensitivity is effectively improved; while some hydrated proton morphology (H) may be present₃O⁺) In the occurrence of proton transfer reaction, the high-energy plasma can further alleviate the following adverse effects due to the high-energy radiation phenomenon: 1) the phenomenon of sufficient ionization of the sample is weakened due to factors such as an ion suppression effect and the like; 2) ion clusters, hydrated ion clusters and the like in the solution to be analyzed affect the result analysis.

The auxiliary agent is mainly used in the analysis process of the components difficult to ionize, the auxiliary gases are easy to accept soft x-ray energy and are converted into high-energy plasmas, the high-energy radiation effect of the high-energy plasmas can generate a large number of hot electrons due to the photoelectron effect, and the components difficult to ionize can be completely ionized in a small space by carrying out various processes including chemical ionization, self chemical ionization, electron ionization and the like. For analysis of some easily ionized components, interference of background chemical noise can be inhibited by auxiliary extraction of low air pressure or introduction of inert gases such as helium, argon, nitrogen and the like, and the information of the molecular parent ions can be obtained only by the action of soft x-ray radiation on the ionization process of a sample.

Furthermore, the continuous working mode of the short-wave radiation light source can not only adapt to the continuous large-flow-rate liquid sampling process, but also can be matched according to different flow rate optimization, selection of auxiliary sample radiation ionization auxiliary agents and the like, and further can realize control over the environmental excitation degree by adjusting a proper energy range in the application process of complex systems such as biological tissue blood and the like, so that the supplementary analysis of substances with weak response to traditional ESI, APCI, APPI and other plasma source sources can be controlled, such as ultrahigh sensitive response to halogen-containing organic matters in a soft X-ray mode.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the above embodiments, and the description in the above embodiments and the description is only preferred examples of the present invention, and is not intended to limit the present invention, and that the present invention can have various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications all fall into the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. The mass spectrum ionization device is characterized by comprising a radiation light source and a protective shell, wherein the radiation light source is arranged on the protective shell, a mass spectrometer atmospheric pressure interface is arranged on the protective shell, a mass spectrometer vacuum cavity is connected to the side, located on the mass spectrometer atmospheric pressure interface, of the protective shell, an ion guide is arranged in the mass spectrometer vacuum cavity corresponding to the mass spectrometer atmospheric pressure interface, and the ion guide is connected with a mass analyzer;

short-wave radiation generated by the radiation light source faces the inside of the protective shell to form an excited high-energy state environment region;

2. A mass spectrometry ionization apparatus according to claim 1 wherein the sample introduction mechanism employs a liquid introduction nozzle mounted to the protective housing for introducing the liquid sample into the protective housing.

3. The mass spectrum ionization device as claimed in claim 1, wherein the sample introducing mechanism employs a placing table, the placing table is installed in the protective housing, and the placing table is provided with a groove for placing the sample.

4. A mass spectrometer ionization device according to claim 1, wherein the radiation source generates short-wave radiation in a wavelength range between the ultraviolet and hard X-ray wavelength ranges of the electromagnetic spectrum, and has a spectral range of 0.3mn-40nm, a photon energy of 29eV-9999eV, a tunable intensity, and a luminescence in the form of continuous or discontinuous pulses.

5. The mass spectrometer ionization apparatus of claim 1, wherein the opening is provided with an ion condenser for focusing ions generated within the ion source.

6. The mass spectrum ionization apparatus of claim 1, wherein the protective enclosure is connected to a vacuum pump via a conduit to form a low pressure environment within the protective enclosure, wherein the low pressure environment has a pressure value of 0.1Pa to 1e4 Pa.

7. The mass spectrum ionization device of claim 1, wherein an auxiliary structure for introducing an auxiliary agent for assisting the ionization of the sample by radiation is provided on the protective housing, and the auxiliary structure is in communication with the chamber.

8. A mass spectrometry ionization apparatus according to claim 7 wherein the auxiliary agent comprises methanol or ethanol.