CN110706997A - Soft x-ray ion source - Google Patents
Soft x-ray ion source Download PDFInfo
- Publication number
- CN110706997A CN110706997A CN201910908838.3A CN201910908838A CN110706997A CN 110706997 A CN110706997 A CN 110706997A CN 201910908838 A CN201910908838 A CN 201910908838A CN 110706997 A CN110706997 A CN 110706997A
- Authority
- CN
- China
- Prior art keywords
- ion source
- soft
- ionization
- protection device
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of ionization sources, and particularly relates to a soft x-ray ion source which comprises a radiation light source and a protection device, wherein the radiation light source is arranged on the protection device, the protection device is provided with a cavity used for coating short-wave radiation generated by the radiation light source, the protection device is provided with an opening, and the opening is communicated with the cavity and used for butting an ion source structure and an atmospheric pressure joint; the influence of insufficient ionization of the sample, addition of cluster ions and the like on analysis, which is caused by the ion inhibition effect, can be effectively solved; the sample which is difficult to ionize by ionization can obtain complete ionization products, the background interference is reduced, and meanwhile, a specific auxiliary sample radiation ionization auxiliary agent can be introduced to realize the ionization.
Description
Technical Field
The invention belongs to the technical field of ionization sources, and particularly relates to a soft x-ray ion source.
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, it is difficult to find an ion source with a general solution, and various ion sources have more or less limitations in analyzing the types of samples, mainly due to more or less problems in energy acquisition.
To solve the above problems, a soft x-ray ion source is proposed in the present application.
Disclosure of Invention
In order to solve the problems, the soft x-ray ion source provided by the invention forms a high-energy plasma atmosphere in the surrounding space environment through short-wave radiation in a specific waveband range, can directly and comprehensively ionize the surrounding air background and the sample, and ensures that discrimination-free complete ionization of complex sample components is completed under the condition of no pretreatment or matrix assistance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a soft x-ray ion source comprises a radiation light source and a protection device, wherein the radiation light source is arranged on the protection device, the protection device is provided with a cavity used for covering short-wave radiation generated by the radiation light source, the protection device is provided with an opening, and the opening is communicated with the cavity and used for butting an ion source structure and an atmospheric pressure interface;
short-wave radiation output by the radiation light source faces the inside of the protection device, and an excited high-energy state environment region is formed in the cavity;
and the protection device is provided with a sample leading and discharging mechanism for placing a sample in the excited high-energy state environment area.
In one embodiment of the present invention, the sample drawing mechanism employs a liquid introduction nozzle, and the liquid introduction nozzle is mounted on the protection device and is communicated with the cavity.
In one embodiment of the present invention, the sample drawing and placing mechanism employs a placing stage, and the placing stage is mounted on the protection device and located in the cavity.
As one scheme of the invention, the wave band of the short-wave radiation generated by the radiation light source is positioned between an ultraviolet wave band and a hard X-ray wave band on an 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.
As an aspect of the present invention, an ion condenser is disposed at the opening to focus ions generated inside the ion source.
As one scheme of the invention, the protection device is connected with a vacuum pump for pumping the cavity to form a low-pressure environment, and the pressure value of the low-pressure environment is 0.1Pa-1e4 Pa.
As one scheme of the invention, an auxiliary structure for introducing an auxiliary agent for assisting the radiation ionization of the sample is arranged on the protection device, and the auxiliary structure is communicated with the cavity.
In one embodiment of the present invention, the auxiliary agent includes at least one of methanol, ethanol, water vapor, hydrogen sulfide, methane, helium, and nitrogen.
As one scheme of the invention, the auxiliary structure is a pipeline, and the auxiliary agent is introduced into the cavity of the protection device through the pipeline.
As an aspect of the present invention, the auxiliary structure is a flange.
The technical scheme of the invention has the following beneficial technical effects:
1. the short-wave radiation source adopted in the invention has the advantages of small volume, simple structure, adjustable wave band, low stray light, high energy, sufficient sample ionization energy, no problems of desolvation and ion sampling efficiency, high sensitivity and good result reproducibility.
2. The soft X-ray ion source can effectively solve the problems of insufficient sample ionization caused by an ion suppression effect and the influence of adducted cluster ions and the like on analysis.
3. The soft X-ray ion source can ionize a sample (particularly biomacromolecules) which is difficult to ionize to obtain a complete ionization product, the structure can assist in vacuumizing, background interference is reduced, meanwhile, a specific auxiliary sample radiation ionization auxiliary agent can be introduced to achieve a, auxiliary ionization and the capability of richer fingerprint fragment 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 original characteristics, the achieved purposes and the effects of the invention easily understood, the invention is further described below with reference to the specific embodiments and the attached drawings, but the following embodiments are only the preferred embodiments of the invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts 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 are 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.
The soft X-ray ion source described above:
example 1
As shown in FIG. 1, a radiation source 101; 102. a protection device; 103 liquid introduction connection; 104. exciting a high-energy state environment region; 105. and (4) opening.
The radiation light source 101 is used for generating X-rays to cover a high energy region, i.e. the excited high energy state environment region 104, the opening 105 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; 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 wave band of the short wave radiation generated by the radiation light source 101 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 light emitting process is in a continuous or discontinuous pulse form.
Example 2
As shown in fig. 2-3, in the figure: 101. a radiation source; 102. a protection device; 103 liquid introduction connection; 104. exciting a high-energy state environment region; 105. an opening; 106 an auxiliary structure; 107. a vacuum pump; 108. 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 106 is added, in this embodiment, the auxiliary structure 106 may be a pipeline for introducing an auxiliary sample radiation ionization auxiliary agent into the cavity, and what further needs to be described is: 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 106 may be any structure capable of guiding the auxiliary agent into the cavity, so as to achieve the function of improving the ionization efficiency or suppressing the interference of the background chemical noise.
In fig. 3, a vacuum pump 107 is added to pump the chamber to form a low-pressure environment, and the low-pressure environment has a pressure value of 0.1Pa to 1e4Pa, which can further assist in suppressing background chemical noise interference and helping the environment to be filled with the auxiliary sample radiation ionization auxiliary agent as much as possible.
In fig. 4, an ion condenser 108 is added, and in this embodiment, the ion condenser 108 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 as to improve the overall efficiency. 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 protection device; 203. a placing table; 204. exciting a high-energy state environment region; 205. and (4) opening.
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 wave band of the short wave radiation generated by the radiation light source 101 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 light emitting process is in a continuous or discontinuous pulse form.
Example 4
As shown in fig. 6-8, in the figures: 201. a radiation source; 202. a protection device; 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.
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 206 is added, in this embodiment, the auxiliary structure 206 may be a pipeline for introducing an auxiliary sample radiation ionization auxiliary agent into the cavity, and what further needs to be described is: 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 206 may be any structure capable of guiding the auxiliary agent into the cavity, so as to achieve the function of improving the ionization efficiency or suppressing the interference of the background chemical noise.
In fig. 7, a vacuum pump 207 is added for pumping the cavity to form a low-pressure environment, and the pressure value of the low-pressure environment is 0.1Pa-1e4Pa, which can further assist in suppressing the interference of background chemical noise 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 208 is added, and in this embodiment, the ion condenser 208 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 as to improve the overall efficiency.
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.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A soft x-ray ion source is characterized by comprising a radiation light source and a protection device, wherein the radiation light source is arranged on the protection device, the protection device is provided with a cavity used for covering short-wave radiation generated by the radiation light source, the protection device is provided with an opening, and the opening is communicated with the cavity and used for butt joint of an ion source structure and an atmospheric pressure joint;
short-wave radiation output by the radiation light source faces the inside of the protection device, and an excited high-energy state environment region is formed in the cavity;
and the protection device is provided with a sample leading and discharging mechanism for placing a sample in the excited high-energy state environment area.
2. The soft x-ray ion source of claim 1, wherein the sample placement mechanism employs a liquid introduction nozzle mounted to the protective device and in fluid communication with the chamber.
3. The soft x-ray ion source of claim 1, wherein the sample indexing mechanism employs a placement stage mounted to the protective device and positioned in the chamber.
4. A soft X-ray ion source according to claim 1, wherein the radiation source generates short wavelength radiation in a wavelength band between the ultraviolet and hard X-ray wavelength bands of the electromagnetic spectrum, and has a spectral range of 0.3mn-40nm, a photon energy of 29eV-9999eV, an intensity modulation, and a luminescence in the form of continuous or discontinuous pulses.
5. The soft x-ray ion source of claim 1, wherein the opening is provided with an ion condenser for focusing ions generated within the ion source.
6. The soft x-ray ion source of claim 1, wherein the protective device is coupled to a vacuum pump for evacuating the chamber to form a low pressure environment, the low pressure environment having a pressure value of 0.1Pa to 1e4 Pa.
7. The soft x-ray ion source of claim 1, wherein the protective device is provided with an auxiliary structure for introducing an auxiliary agent for assisting in ionizing radiation of the sample, the auxiliary structure being in communication with the chamber.
8. The soft x-ray ion source of claim 7, wherein the auxiliary agent comprises at least one of methanol, ethanol, water vapor, hydrogen sulfide, methane, helium, and nitrogen.
9. The soft x-ray ion source of claim 7 or 8, wherein the auxiliary structure is a conduit through which the auxiliary agent passes into the cavity of the protective device.
10. The soft x-ray ion source of claim 7, wherein the auxiliary structure is a flange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910908838.3A CN110706997A (en) | 2019-09-25 | 2019-09-25 | Soft x-ray ion source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910908838.3A CN110706997A (en) | 2019-09-25 | 2019-09-25 | Soft x-ray ion source |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110706997A true CN110706997A (en) | 2020-01-17 |
Family
ID=69195152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910908838.3A Pending CN110706997A (en) | 2019-09-25 | 2019-09-25 | Soft x-ray ion source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110706997A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113643957A (en) * | 2021-06-03 | 2021-11-12 | 中山大学 | Soft X-ray chemical ionization source |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105247653A (en) * | 2013-03-22 | 2016-01-13 | 艾尔莫杜斯有限公司 | Method and device for ionizing particles of a sample gas flow |
| CN105308715A (en) * | 2013-06-20 | 2016-02-03 | 赫尔辛基大学 | Method and device for ionizing particles of a sample gas flow |
| CN108701579A (en) * | 2016-09-19 | 2018-10-23 | 卡尔萨公司 | Ionization device |
| CN109950127A (en) * | 2019-04-12 | 2019-06-28 | 江苏汭博医疗科技有限公司 | A kind of electric spray ion source auxiliary enhancement device |
-
2019
- 2019-09-25 CN CN201910908838.3A patent/CN110706997A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105247653A (en) * | 2013-03-22 | 2016-01-13 | 艾尔莫杜斯有限公司 | Method and device for ionizing particles of a sample gas flow |
| CN105308715A (en) * | 2013-06-20 | 2016-02-03 | 赫尔辛基大学 | Method and device for ionizing particles of a sample gas flow |
| CN108701579A (en) * | 2016-09-19 | 2018-10-23 | 卡尔萨公司 | Ionization device |
| CN109950127A (en) * | 2019-04-12 | 2019-06-28 | 江苏汭博医疗科技有限公司 | A kind of electric spray ion source auxiliary enhancement device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113643957A (en) * | 2021-06-03 | 2021-11-12 | 中山大学 | Soft X-ray chemical ionization source |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11017990B2 (en) | Compact mass spectrometer | |
| EP1476893B1 (en) | Internal introduction of lock masses in mass spectrometer systems | |
| US8648297B2 (en) | Coupling of liquid chromatography with mass spectrometry by liquid sample desorption electrospray ionization (DESI) | |
| US10424473B2 (en) | Compact mass spectrometer | |
| US10354847B2 (en) | Compact mass spectrometer | |
| GB2420007A (en) | Mass spectrometer protein profiles with atmospheric pressure ionisation | |
| Mallet et al. | Dictionary of mass spectrometry | |
| GB2348049A (en) | An ion source for mass spectrometry | |
| US20230207301A1 (en) | Multi-modal ionization for mass spectrometry | |
| WO2014191747A1 (en) | Compact mass spectrometer | |
| CN110706997A (en) | Soft x-ray ion source | |
| US10090144B2 (en) | Liquid extraction matrix assisted laser desorption ionisation ion source | |
| Verge et al. | Plasticizer contamination from vacuum system O-rings in a quadrupole ion trap mass spectrometer | |
| CN112185801B (en) | Novel photoelectric composite ion source | |
| CN210778481U (en) | Mass spectrum ionization device | |
| CN213366527U (en) | Mass spectrum ionization device | |
| CN107706081B (en) | The application method of mass spectrometer system, chromatography-mass spectroscopy system and the two | |
| CN111816544A (en) | Mass spectrum ionization device | |
| US20220037142A1 (en) | Desorption ion source with dopant-gas assisted ionization | |
| US20140374591A1 (en) | In situ generation of ozone for mass spectrometers | |
| CN209880539U (en) | Auxiliary enhancement device for electrospray ion source | |
| JP6607770B2 (en) | Ionization method, ionizer, and mass spectrometer | |
| CN212514440U (en) | Organic matter detection device of bipolar proton transfer reaction mass spectrum | |
| JP7435905B2 (en) | Mass spectrometer and mass spectrometry method | |
| Baykut et al. | Applying a dynamic method to the measurement of ion mobility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200117 |