CN117238745A - Method for ion damage prevention in ion migration tube - Google Patents

Method for ion damage prevention in ion migration tube Download PDF

Info

Publication number
CN117238745A
CN117238745A CN202311154655.XA CN202311154655A CN117238745A CN 117238745 A CN117238745 A CN 117238745A CN 202311154655 A CN202311154655 A CN 202311154655A CN 117238745 A CN117238745 A CN 117238745A
Authority
CN
China
Prior art keywords
ion
air
migration
ions
tube
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
Application number
CN202311154655.XA
Other languages
Chinese (zh)
Inventor
谢斌
李国军
张军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHENZHEN SHENFEI ELECTRONIC TECHNOLOGY CO LTD
Original Assignee
SHENZHEN SHENFEI ELECTRONIC TECHNOLOGY CO LTD
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SHENZHEN SHENFEI ELECTRONIC TECHNOLOGY CO LTD filed Critical SHENZHEN SHENFEI ELECTRONIC TECHNOLOGY CO LTD
Priority to CN202311154655.XA priority Critical patent/CN117238745A/en
Publication of CN117238745A publication Critical patent/CN117238745A/en
Pending legal-status Critical Current

Links

Landscapes

  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The invention discloses a method for ion damage prevention in an ion migration tube, which relates to the technical field of ion migration, and the general solution of the existing migration tube is that a tail gas blowing mode is adopted, namely gas blowing is carried out from a terminal point to a starting point, but the gas quantity and the speed of the tail gas blowing are invariable, so that the effect is different for different ions, and the requirement of a high-sensitivity migration tube cannot be met.

Description

Method for ion damage prevention in ion migration tube
Technical Field
The invention relates to the technical field of ion migration, in particular to a method for ion damage prevention in an ion migration tube.
Background
Ion migration refers to the process of moving ions from one location or region to another. It is typically accomplished by ion transfer tubing or ion transfer apparatus, typically involving the steps of: ion generation, ion acceleration, ion control, ion transfer, ion detection, ion transfer have wide application in numerous fields such as mass spectrometry, ion implantation, gas chromatography, and ion separation and processing in certain industrial processes. Through reasonable design and control of ion migration processes, efficient, accurate and repeatable ion manipulation and separation can be achieved.
The ions move in an electric field at a non-uniform speed and acceleration, so that the calculation speed is inaccurate, and therefore, the difference of resolution and the error are generated, in a migration area, the ions move from a starting point to an end point, theoretically, the number of the ions at the starting point and the number of the ions at the end point are equal, but the ions are not in the actual situation, the ions are lossy, the conventional migration tube generally adopts a tail blowing mode, namely, the ions are blown from the end point to the starting point, firstly, the ions are enabled to run at the uniform speed as much as possible, secondly, the tail blowing plays a role of supporting the ions, but the air quantity and the speed of the tail blowing are invariable, so that the effect is different for different ions, and the requirement of the high-sensitivity migration tube cannot be met.
To solve the above problems, a method for ion migration tube ion damage free is proposed.
Disclosure of Invention
The invention aims to provide a method for ion loss prevention in an ion migration tube, which solves the problems of ion loss and non-uniform velocity in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for ion-damage-free in an ion transfer tube, characterized by: the device comprises a migration tube, a gas circuit control, a control center and a calculation unit;
the migration tube consists of a main pipeline, an inlet system, an outlet system, an airflow system and a control system;
the inlet system and the tail part of the migration tube are provided with air outflow ports for introducing ions into the main pipeline, the sample inlet, the ionization source and other components, and ions are generated and introduced into the migration tube;
an outlet system, wherein an air flow outlet supplies tail blowing air, and an ion detector and a mass spectrometer collect and detect ion flow after ion transmission is completed;
the main body pipeline is provided with a group of air hole matrixes along the length direction of the migration pipe, and air in the air holes is blown upwards and enters the migration pipe from the air hole matrixes;
the bottom of the ion transfer tube is provided with 8 stages of 3 bottom blowing openings respectively according to the left, middle and right sequence, the bottom blowing openings cover the bottom area of the whole ion transfer tube, the air outlet ends of the bottom blowing openings are in a horn shape, and the air can be uniformly dispersed;
the intensity of the gas is weakened from the end point to the starting point of the bottom blowing port, the gas intensity of the bottom blowing is gradually weakened, the gas injection speed and the gas quantity of each bottom blowing port are controlled, the pneumatic environment around the ions is changed from strong to weak, and the tail blowing and the bottom blowing are cooperated together to restrain the acceleration of the ions;
the gas path control controls the speed and the gas quantity of the gas, and adjusts and controls various parameters in the ion migration process;
the control center and the calculation unit are used for converging and calculating signal data and sending control instructions to all positions, the control center is used for adjusting the speed and the air quantity of air blown out of the air holes and controlling the pneumatic environment around ions, and control factors comprise parameters, detection types and levelness of instrument placement provided by the calculation unit;
the ion migration tube is internally provided with measuring sensors in two directions (X and Y), the sensors are used for measuring the levelness of the placement of the instrument, data are fed back to the control center, and the sensors are connected with the control center to ensure that the sensors can transmit the measuring data to the control center.
Preferably, the computing center stores the migration time and ionization capacity of various ions, and the actually sampled ion migration data is compared with the data in the database to identify the ions.
Preferably, the original signal data is obtained from the ion detector, and the original signal is amplified to enhance the amplitude and stability of the signal.
Preferably, the peak time and peak amplitude are analyzed, the amplified signal is analyzed, features are extracted by detecting the peak time and peak amplitude of the signal, and the peak time and amplitude are determined by using a peak detection algorithm technique.
Preferably, the time amplitude is compared, the peak time and the peak amplitude are compared with known reference data, and a corresponding detection report is generated according to the result of the time amplitude comparison.
Preferably, the ionization region is used for carrying out atomic ionization by ultraviolet irradiation, ionized ions can be absorbed by the flange plate to generate weak current signals, and the weak current signals are amplified and then sent to the calculation control center.
Preferably, the calculation control center is used for collecting and calculating the signal data and sending control instructions to each component, the air path control module is used for controlling the instrument air path, and the electric field control module is used for adjusting the intensity and the direction of the electric field in the migration tube. The ionization control module controls the ionization of the ultraviolet lamp.
Preferably, the collected data is sent to a computing unit for processing, storing, displaying, and the man-machine and network center is responsible for displaying and storing the data of the computing control center, communicating with the network and interacting with the man-machine.
Preferably, proper smoothing and extreme point screening algorithms are used, so that accuracy of peak detection is improved, and errors are reduced.
Preferably, the calibration of the sensor ensures the accuracy and precision, the calibration comprises the steps of determining a reference value of the instrument placement relative to the horizontal position, comparing and adjusting the reading of the sensor with the actual levelness, feeding the measured levelness data back to the control center by the sensor, judging whether the levelness of the instrument placement meets the requirement or not by the control center according to the data, and adopting corresponding measures for adjustment.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for realizing ion nondestructive in the ion migration tube, an air hole matrix is arranged in the length direction of the migration tube, air in the air holes is blown upwards, the speed and the air quantity of each air are controlled by a control center, control factors come from a calculation unit, a detection type and instrument placement levelness, the aim is to achieve the purposes of lowest ion loss and maximum uniform motion in various modes and various environments, 24 bottom blowing air levels, 8 levels and 3 levels are added on the basis of the original migration tube, the bottom blowing air levels are respectively named as left, middle and right, the air strength of the bottom blowing air is from a terminal point to a starting point, the air strength is from strong to weak, ions cannot fall into a tube wall due to free falling, and meanwhile, the tail blowing air and the bottom blowing air are acted, so that the acceleration of the ions is inhibited, and the ions are enabled to better to move at uniform straight.
According to the method for ion damage prevention in the ion migration tube, when the instrument is placed in a non-horizontal state, the calculation center calculates according to the inclination angle, so that the ion running track is ensured to reach the end point from the starting point along the central axis of the migration tube, the ion loss is reduced, the instrument is placed in various angles through the adjustable bottom blowing intensity, and the method can be suitable for various complex use environments.
Drawings
FIG. 1 is a schematic view of an ion transfer tube according to the present invention;
FIG. 2 is a schematic view of an ion transfer tube according to the present invention;
FIG. 3 is a schematic view of an ion transfer tube according to the present invention;
FIG. 4 is a schematic view of the structure of the bottom blowing port of the present invention;
FIG. 5 is a schematic illustration of ion migration in accordance with the present invention;
FIG. 6 is a schematic diagram of ion migration of an ion transfer tube according to the present invention;
FIG. 7 is a schematic diagram of the operation flow of the present invention;
FIG. 8 is an ion mobility graph of the present invention.
In the figure: 1. an ion transfer tube; 2. a bottom air outlet;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only 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.
For a further understanding of the present invention, the present invention will be described in detail with reference to the drawings.
In a security inspection system, a core technology adopted generally is a substance ion migration technology, namely, the running speed of detecting substance ions so as to identify substances, and another technology is a fluorescence collection technology, which has the advantages of high detection sensitivity and picogram level, but has the disadvantages that the technology can only detect that the substance is an explosive, but cannot identify which explosive is, and cannot detect the drug, so that the use of a detection instrument realized by the fluorescence collection technology is not common;
in practical application, the ion transfer tube 1 comprises at least the following parts: the ionization region, the ion gate, the migration region and the collection region ionize the explosive molecules through ultraviolet irradiation, and the explosive is ionized into negative ions and the drug is ionized into positive ions according to the atomic characteristics of the substances. Ion gate: ions in the ionization region pass through the ion gate to the transport region, and the ion gate switch controls the timing and quantity of ions passing through. Migration zone: the migration zone is externally applied with an electric field, and ions move to the other side under the action of the electric field of the migration zone. Acquisition area: the ions move to the flange of the collecting area, the flange absorbs charges and forms an electron flow, and the electron flow is amplified and sent to the calculating unit, and the speed of ion migration is calculated in combination with the control of the ion gate.
The invention aims at the defect that the calculation speed is inaccurate and the resolution is unclear, and the optimization of the running track of the ions is realized by the adjustable bottom blowing intensity, the ions run from a starting point ion gate to an end point flange in a direction parallel to the central axis of a migration tube, the ions have almost no loss, the detection precision is improved, the arrangement of various angles of the instrument is realized by the adjustable bottom blowing intensity, the device can adapt to various complex use environments, and finally the bottom blowing is matched with the tail blowing, the running speed of the ions presents uniform speed property, and the ion mobility calculation is close to a theoretical value.
1-8, the method for ion damage prevention in the ion migration tube comprises a migration tube, a gas path control, a control center and a calculation unit, wherein the migration tube consists of a main pipeline, an inlet system, an outlet system, an airflow system and a control system;
the inlet system and the tail part of the migration tube are provided with air outflow ports for introducing ions into the main pipeline, the sample inlet, the ionization source and other components, and ions are generated and introduced into the migration tube;
the outlet system, the air current outlet supplies tail blowing, the ion detector and mass spectrometer collect and detect ion flow after ion transmission is completed, the calculation center stores the migration time of various ions, and ionization capacity, the ion migration data actually sampled is compared with the data in the database, the ions are identified, the original signal data is obtained from the ion detector, the original signal is amplified to enhance the amplitude and stability of the signal, ion identification is to determine the process of the collected ion species by comparing the ion migration time actually sampled with the ion migration time stored in the database and the ionization capacity, the ion migration time actually sampled is compared with the ion migration time in the database, the ion species closest to the ion species is matched, the ionization capacity of the actually sampled ions is compared with the ion ionization capacity in the database, the ionization capacity is calculated through parameters such as ion quality and ion charge number, the signal amplification processing enhances the amplitude and stability of the output signal of the ion detector, the reliability and the detection of the signal, the signal is enhanced, the signal is accessed to the signal output of the ion detector, the signal is amplified to the amplifier to the low gain and the signal level, the signal is amplified to the amplifier, the signal is further amplified to the gain and the signal is amplified to the low-gain amplifier, the signal is further amplified and the gain is adjusted, the signal is amplified to the gain is further, the signal gain is amplified and the signal gain is further is amplified to be amplified and the gain is adjusted, the gain is amplified and the signal gain is further is amplified to the gain is amplified and the gain is amplified and amplified, the method is suitable for the requirements of different signal intensities and sampling systems, and can obtain enhanced ion signals for further subsequent data analysis and processing through ion identification and signal amplification;
the accuracy of wave crest detection is improved, errors are reduced, wave crest time and wave crest amplitude are analyzed by using proper smoothing processing and extreme point screening algorithm, amplified signals are analyzed, characteristics are extracted by detecting wave crest time and wave crest amplitude of the signals, the time and amplitude of wave crest are determined by using peak detection algorithm technology, the time and amplitude of wave crest are compared, the wave crest time and the wave crest amplitude are compared with known reference data, and corresponding detection reports are generated according to the comparison result of the time and amplitude
The main body pipeline is provided with a group of air hole matrixes along the length direction of the migration pipe, and air in the air holes is blown upwards and enters the migration pipe from the air hole matrixes;
the bottom of the ion transfer tube 1 is provided with 8 stages of 3 bottom blowing openings 2 respectively according to the left, middle and right sequence, the bottom blowing openings 2 cover the bottom area of the whole ion transfer tube 1, the air outlet ends of the bottom blowing openings 2 are in a horn shape, and the air can be uniformly dispersed;
the intensity of the gas is weakened from the end point to the starting point of the bottom blowing openings 2, the gas intensity of the bottom blowing is gradually weakened, the gas injection speed and the gas quantity of each bottom blowing opening 2 are controlled, the pneumatic environment around the ions is changed from strong to weak, and the acceleration of the ions is restrained by cooperation of tail blowing and bottom blowing;
the gas path control controls the speed and the gas quantity of the gas, and adjusts and controls various parameters in the ion migration process;
fig. 8 is an ion mobility diagram, with a sample containing three species, BP, TNT, RDX.
The horizontal axis represents the migration time, i.e., the time of the ions from the start point to the end point, and the migration tube is 60mm long, whereby the ion migration speed can be calculated;
the vertical axis represents the ion number, namely the content of BP, TNT, RDX in the sample, and the ion number is more when the content is more; in addition, the substances are different and have the same mass, and the ionized ion numbers are different, namely the ionization capacities are different;
the control center and the calculation unit are used for converging and calculating signal data and sending control instructions to all positions, the control center is used for adjusting the speed and the air quantity of air blown out of the air holes and controlling the pneumatic environment around ions, and control factors comprise parameters, detection types and levelness of instrument placement provided by the calculation unit;
the ion migration tube 1 is internally provided with measuring sensors in two directions (X and Y), the sensors are used for measuring the levelness of the instrument placement, data are fed back to the control center, the sensors are connected with the control center to ensure that the sensors can transmit the measured data to the control center, the calibration of the sensors is ensured, the accuracy and precision of the sensors are ensured, the calibration comprises the steps of determining a reference value of the instrument placement relative to the horizontal position, comparing and adjusting the reading of the sensors with the actual levelness, the sensors feed back the measured levelness data to the control center, and the control center judges whether the levelness of the instrument placement meets the requirement according to the data and adopts corresponding measures for adjustment;
the ionization region is used for carrying out atomic ionization by ultraviolet irradiation, ionized ions are absorbed by the flange plate to generate weak current signals, the weak current signals are amplified and then sent to the calculation control center, the calculation control center carries out signal data collection and calculation and sends control instructions to each component, the air circuit control module controls an instrument air circuit, and the electric field control module adjusts the electric field intensity and direction in the migration tube;
the ionization control module controls the ionization of the ultraviolet lamp, the collected data are sent to the calculation unit for processing, storage, display, man-machine and network center are responsible for displaying and storing the data of the calculation control center, and the data are communicated with the network, and meanwhile interaction with man-machine is performed.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. A method for ion-damage-free in an ion transfer tube, characterized by: the device comprises a migration tube, a gas circuit control, a control center and a calculation unit;
the migration tube consists of a main pipeline, an inlet system, an outlet system, an airflow system and a control system;
the inlet system and the tail part of the migration tube are provided with air outflow ports for introducing ions into the main pipeline, the sample inlet, the ionization source and other components, and ions are generated and introduced into the migration tube;
an outlet system, wherein an air flow outlet supplies tail blowing air, and an ion detector and a mass spectrometer collect and detect ion flow after ion transmission is completed;
the main body pipeline is provided with a group of air hole matrixes along the length direction of the migration pipe, and air in the air holes is blown upwards and enters the migration pipe from the air hole matrixes;
the bottom of the ion transfer tube (1) is provided with 8 stages of 3 bottom air blowing openings (2) respectively according to the left, middle and right sequence, the bottom air blowing openings (2) cover the bottom area of the whole ion transfer tube (1), the air outlet ends of the bottom air blowing openings (2) are in a horn shape, and the air can be uniformly dispersed;
the intensity of the gas is weakened from the end point to the starting point of the bottom blowing openings (2), the gas intensity of the bottom blowing is gradually weakened, the gas injection speed and the gas quantity of each bottom blowing opening (2) are controlled, the pneumatic environment around ions is changed from strong to weak, and the tail blowing and the bottom blowing are cooperated together to restrain the acceleration of the ions;
the gas path control controls the speed and the gas quantity of the gas, and adjusts and controls various parameters in the ion migration process;
the control center and the calculation unit are used for converging and calculating signal data and sending control instructions to all positions, the control center is used for adjusting the speed and the air quantity of air blown out of the air holes and controlling the pneumatic environment around ions, and control factors comprise parameters, detection types and levelness of instrument placement provided by the calculation unit;
the ion migration tube (1) is internally provided with measuring sensors in two directions (X and Y), the sensors are used for measuring the levelness of the placement of the instrument, data are fed back to the control center, and the sensors are connected with the control center to ensure that the sensors can transmit the measuring data to the control center.
2. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: the calculation center stores the migration time and ionization capacity of various ions, and the actually sampled ion migration data is compared with the data in the database to identify the ions.
3. A method of ion-damage-free ion transfer of ion-transfer tubing as claimed in claim 2, wherein: raw signal data is obtained from the ion detector, and the raw signal is amplified to enhance the amplitude and stability of the signal.
4. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: analyzing the time and amplitude of the wave crest, analyzing the amplified signal, extracting the characteristics by detecting the time and amplitude of the wave crest of the signal, and determining the time and amplitude of the wave crest by using a peak detection algorithm technology.
5. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: and comparing the time amplitude, the peak time and the peak amplitude with known reference data, and generating a corresponding detection report according to the result of the time amplitude comparison.
6. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: and the ionization region is used for carrying out atomic ionization by ultraviolet irradiation, ionized ions can be absorbed by the flange plate to generate weak current signals, and the weak current signals are amplified and then sent to the calculation control center.
7. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: the calculation control center is used for collecting and calculating the signal data and sending control instructions to each component, the air channel control module is used for controlling the instrument air channel, and the electric field control module is used for adjusting the intensity and the direction of the electric field in the migration tube. The ionization control module controls the ionization of the ultraviolet lamp.
8. The method of ion-damage-free ion transfer of claim 7, wherein: the collected data are sent to a computing unit for processing, storing, displaying, man-machine interaction and network center for displaying and storing the data of the computing control center, communicating with the network and interacting with man-machine interaction.
9. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: proper smoothing and extreme point screening algorithm are used, so that accuracy of wave crest detection is improved, and errors are reduced.
10. The method of ion-transport tube ion-damage-free as claimed in claim 1, wherein: and the sensor is used for calibrating, ensuring the accuracy and precision of the sensor, determining a reference value of the instrument placement relative to the horizontal position, comparing and adjusting the sensor reading with the actual levelness, feeding back measured levelness data to the control center, judging whether the levelness of the instrument placement meets the requirement or not according to the data by the control center, and taking corresponding measures for adjustment.
CN202311154655.XA 2023-09-08 2023-09-08 Method for ion damage prevention in ion migration tube Pending CN117238745A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311154655.XA CN117238745A (en) 2023-09-08 2023-09-08 Method for ion damage prevention in ion migration tube

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311154655.XA CN117238745A (en) 2023-09-08 2023-09-08 Method for ion damage prevention in ion migration tube

Publications (1)

Publication Number Publication Date
CN117238745A true CN117238745A (en) 2023-12-15

Family

ID=89092306

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311154655.XA Pending CN117238745A (en) 2023-09-08 2023-09-08 Method for ion damage prevention in ion migration tube

Country Status (1)

Country Link
CN (1) CN117238745A (en)

Similar Documents

Publication Publication Date Title
CN103299183B (en) Device for preparing sample supplied to ion mobility sensor and controlling method of device
CN108072690B (en) Ion mobility spectrometry and ion trap mass spectrometry combined device and analysis method
JP5738997B2 (en) Method and apparatus for gas detection and identification using an ion mobility spectrometer
US20080149823A1 (en) Cell structure, device and method for gas analysis
CN102262039A (en) Method and device for detecting indoor heavy metal pollution by using single particle aerosol mass spectrometer (SPAMS)
US6297501B1 (en) Simultaneous detection isotopic ratio mass spectrometer
US5281915A (en) Sensor for detecting a high molecular weight substance using ionization effects
Nomizu et al. Determination of zinc in individual airborne particles by inductively coupled plasma mass spectrometry with digital signal processing
CN105717065A (en) Continuous monitoring device for non-methane total hydrocarbon and working method of continuous monitoring device
CN102253112B (en) Method for identifying substance by relative ion mobility spectrum
US7956323B2 (en) Ion mobility spectrometer and method for determining an analyte substance or an analyte substance mixture in the presence of a dopant mixture by means of an ion mobility spectrometer
CN117238745A (en) Method for ion damage prevention in ion migration tube
WO2021140178A9 (en) Calibration of mass spectrometry systems
JP3509424B2 (en) Quadrupole mass spectrometer
US3974380A (en) Mass spectrometer
WO2019144923A1 (en) Gas path flow monitoring apparatus and method for ion mobility spectrometer
CN114280005A (en) Device and method for rapidly analyzing and detecting hydrogen and hydrogen isotopes
US7131343B2 (en) Method of measuring density properties of a particle distribution
CN112098502B (en) Detection method for calibrating ion mobility spectrometer by utilizing multiple ion peaks
US3596088A (en) Time-of-flight mass separator having a flowing gas stream perpendicular to an ion drift field for increased resolution
CN113869632B (en) Method and device for evaluating performance of ionization device
CN109155230B (en) Measurement and verification of open-type ionization spots
US3009096A (en) Method and apparatus for testing gases
CN112924521A (en) Real-time online ion mobility spectrometry quantification method
FI83706C (en) Method and apparatus for measuring paper formation

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