CN117542720A - GC-IMS combined chromatographic column and ion migration tube connecting device and working method thereof - Google Patents
GC-IMS combined chromatographic column and ion migration tube connecting device and working method thereof Download PDFInfo
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- 230000005012 migration Effects 0.000 title claims abstract description 78
- 238000013508 migration Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 44
- 238000012546 transfer Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003480 eluent Substances 0.000 claims abstract description 19
- 239000012159 carrier gas Substances 0.000 claims abstract description 17
- 238000004458 analytical method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 139
- 238000010884 ion-beam technique Methods 0.000 claims description 6
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- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 description 24
- 238000001871 ion mobility spectroscopy Methods 0.000 description 20
- 230000035945 sensitivity Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 239000012898 sample dilution Substances 0.000 description 2
- 229910052695 Americium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- LXQXZNRPTYVCNG-UHFFFAOYSA-N americium atom Chemical compound [Am] LXQXZNRPTYVCNG-UHFFFAOYSA-N 0.000 description 1
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- 229910052722 tritium Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0031—Step by step routines describing the use of the apparatus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
-
- 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
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Abstract
The invention provides a GCIMS combined chromatographic column and ion migration tube connecting device and a working method thereof. The chromatographic column is used for pre-separating the detection sample; the ion migration tube is used for carrying out secondary analysis and detection on the chromatographic column eluate; the interface is used for vertically and hermetically connecting the chromatographic column with the ion transfer tube. According to the characteristics of different types of detection samples, the flow rate proportion of the floating gas and the carrier gas, the flow direction of the air flow and the heating temperature are regulated; inputting the detection sample into a chromatographic column for pre-separation to obtain a chromatographic column eluent; the chromatographic column eluate passes through the interface under the drive of carrier gas and enters the reaction zone of the ion migration tube; the drift gas blown in from the migration zone drives the chromatographic column eluent to enter the ionization source; when the ionization source adopts a cylindrical ionization source, the air outlet is sealed, and air flow flows out from the air outlet of the ionization source; when a sheet ionization source is adopted, air flows out from the air outlet; finally, the GCIMS spectrogram of the detection sample is obtained, and analysis and detection of the detection sample are realized.
Description
Technical Field
The invention relates to the technical field of GC-IMS (gas chromatography-ion mobility spectrometry) combination, in particular to a device for connecting a chromatographic column and an ion mobility tube in the GC-IMS combination and a working method thereof.
Background
Gas Chromatography (GC) is an efficient separation analysis technique and a gas chromatography detector is an important component of a gas chromatograph that senses and converts the component changes in the carrier gas into electrical signals. Common gas chromatograph detectors mainly include hydrogen Flame Ionization Detectors (FID), thermal Conductivity Detectors (TCD), and the like. Ion Mobility Spectrometry (IMS) is also a gas phase separation technique that characterizes various chemicals by gas phase ion mobility for the purpose of analytical detection of the various chemicals. When the ion mobility spectrometry is used as a detector of the gas chromatography, on one hand, the high sensitivity of the ion mobility spectrometry can provide high-sensitivity detection for the gas chromatography; on the other hand, the separation capacity of the ion mobility spectrometry can provide two-dimensional separation detection for gas chromatography and more information for accurate identification of complex mixtures; meanwhile, the two-dimensional separation capacity of the ion mobility spectrometry can realize the adjustable selective detection of the gas chromatography; in addition, the ion mobility spectrometry can work in a positive mode and a negative mode, and different detection modes can be selected according to different analytes, so that trace analysis and two-dimensional separation detection of complex samples are facilitated.
At present, a portable gas chromatography ion mobility spectrometry GC-IMS sample inlet (CN 202121343049.9; CN 202110669990.8) only discloses the buckle connection of a gas chromatography column, and an ion source device (CN 202222372181.3) for GC-IMS adopts discharge ionization and heats an interface, so that the gas flow of the gas chromatography column in the ionization source is not explicitly described; the gas chromatography ion mobility spectrometry GC-IMS interface (CN 201920282908.4) prolongs the irradiation time of a VUV lamp on gas chromatography eluate, but the ion introducing process is tortuous, and the ion utilization rate is extremely low. Patent nos. cn201310741366.X, CN201320878767.5, CN202111589494.8, CN99804923.9 all relate to GC-IMS interfaces, some use gas split (poor sensitivity), some use solenoid valves (poor time resolution), some use belt enrichment thermal analysis (poor time resolution, no flow rate matching), none relate to how gas chromatography eluate matches with ion mobility spectrometry ionization characteristics after entering the ionization source, sample dilution and flow rate matching, etc., which require innovative design of GC-IMS interfaces.
The usability of Ion Mobility Spectrometry (IMS) is significantly broadened after preseparation of complex mixtures by Gas Chromatography (GC). When compound analysis is performed, gas chromatography provides information for qualitative analysis as well as inhibits undesired compound interactions during ion mobility spectrometry ionization and detection, as well as Retention Index (RI) for compound separation. The advantages of GC-IMS combination are therefore:
(1) Eliminating cross sensitivity and charge competition problems between ions;
(2) The ion mobility spectrometry can further separate substances which have the same or similar retention time and cannot be separated, so that secondary analysis is realized, and the method has the characteristics of rapidness, sensitivity and portability.
The main challenge when combining gas chromatography with ion mobility spectrometry techniques is that the detection of chromatographic column eluting compounds by ion mobility spectrometry results in a signal profile that is generally poor. GC-IMS coupling is not simply connecting the outlet of a gas chromatography column to the ion mobility spectrometry sample inlet. Relates to a series of problems of matching of gas chromatography elution sample time and ion migration tube response time, matching of ion migration spectrum drift gas and gas chromatography carrier gas flow, large interface dead volume, low sensitivity and the like.
There are two ways to interface the GC-IMS coupling instrument column with the ion transfer tube: one is an axial connection and one is a vertical connection. Axial connection if a chromatographic column is inserted into an ion transfer tube, the chromatographic column occupies a certain space to affect the ionization zone flow field and ionization of the substance because the chromatographic column needs to pass through the ionization zone. Most importantly, as the chromatographic column is inserted too long, the chromatographic column is easy to be inserted and inclined, the coaxiality cannot be ensured, and the equipment vibration or the airflow sweeping chromatographic column outlet can continuously vibrate, so that the stability of the instrument is seriously affected.
Disclosure of Invention
According to the technical problems set forth above, a device for connecting a GC-IMS combined chromatographic column with an ion transfer tube and a working method thereof are provided. The invention mainly utilizes chromatographic columns, ion migration tubes and interfaces, solves the problem of GC-IMS interfaces, realizes the free replacement of different ionization sources at the same time, and does not need to change other parts of the ion migration tubes.
The invention adopts the following technical means:
a GCIMS combined chromatographic column and ion transfer tube connection device comprising: the chromatographic column is vertically connected to the ion migration tube through the interface; wherein:
the chromatographic column is used for pre-separating the detection sample and providing chromatographic column eluents for the ion migration tube;
the ion migration tube is used for carrying out secondary analysis and detection on chromatographic column eluents;
the interface is used for vertically and hermetically connecting the chromatographic column and the ion migration tube.
Further, the chromatographic column comprises a chromatographic column air outlet, the chromatographic column air outlet is vertically inserted into the ion migration tube, the part inserted into the ion migration tube is a nonmetallic chromatographic column, and the depth of the ion migration tube inserted into the chromatographic column is determined by the structure of the ion migration tube.
Further, the ion transfer tube includes: the device comprises an air outlet, an ionization source, a reaction zone, an ion gate and a migration zone; wherein:
the air outlet is arranged on the side surface of the first electrode of the ion transfer tube and is used for discharging air flow from the ion transfer tube;
the ionization source is arranged at the left end of the ion migration tube and comprises a cylindrical ionization source and a sheet ionization source, and is used for converting gas molecules or atoms into charged ions and enabling the ions to migrate and move under the action of an electric field;
the reaction zone is arranged between the ionization source and the ion gate and is used for carrying out ionization analysis on chromatographic column eluents under the drive of carrier gas;
the ion gate is arranged between the reaction zone and the migration zone and is used for controlling the ion beam;
the migration zone is arranged at the right end of the ion migration tube and used for blowing the floating gas into the ion migration tube to drive the ion beam to migrate.
Further, the interface includes: heating jacket, interface screw and interface nut; wherein:
the heating sleeve is wrapped outside the chromatographic column and the interface and is used for preventing eluent of the chromatographic column from condensing and remaining and blocking the interface;
the front end of the interface screw is of a conical structure, the rear end of the interface screw is of a cylindrical structure, and the interface screw is sleeved on the interface and used for fixing the interface;
the interface nut is of a cylindrical structure, the bottom conical structure is matched with the front end of the interface screw, and the interface nut is arranged below the reaction zone and is used for vertically and hermetically connecting the chromatographic column on the ion migration tube.
Further, the ionization source is a radioactive ionization source;
one end of the cylindrical ionization source is a closed end, the other end of the cylindrical ionization source is an open end, and the closed end is provided with an ionization source air outlet;
the on-chip ionization source comprises a VUV lamp ionization source, an air outlet is not arranged, and air flows out of the air outlet.
Further, the chromatographic column is a gas chromatographic column, including a capillary column, an MCC column and a preparation column.
Further, the ion gate is a BN type ion gate, a TP type ion gate or a field switching ion gate.
The invention also provides a working method of the GCIMS combined chromatographic column and ion migration tube connecting device, which comprises the following specific steps:
according to the characteristics of different types of detection samples, the flow rate proportion of the floating gas and the carrier gas, the flow direction of the air flow and the heating temperature are regulated;
inputting the detection sample into a chromatographic column for pre-separation to obtain a chromatographic column eluent;
the chromatographic column eluate passes through the interface under the drive of carrier gas and enters the reaction zone of the ion migration tube;
after the chromatographic column eluent enters the reaction zone, the drift gas blown in by the migration zone passes through the ion gate to drive the chromatographic column eluent to enter the ionization source;
when the ionization source adopts a cylindrical ionization source, the air outlet is sealed, and air flow flows out from the air outlet of the ionization source; when a sheet ionization source is adopted, air flows out from the air outlet;
and after the chromatographic column eluate is blown out of the ion migration tube, a GCIMS spectrogram of the detection sample is obtained, so that analysis and detection of the detection sample are realized.
Compared with the prior art, the invention has the following advantages:
1. according to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, the chromatographic column and the migration tube are vertically and hermetically connected, and the gas outlet of the chromatographic column is positioned in the reaction zone of the migration tube, so that substances eluted by chromatography directly enter the migration tube, and the GC-IMS combined zero-interface dead volume is truly realized.
2. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, when different ionization sources are replaced, other parts of the device are not required to be changed, the air outlet is automatically switched, the device is very convenient, and the GC-IMS combined use of the composite ionization sources is realized.
3. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, ionization substances of an ion migration spectrum are subjected to chemical ionization mainly by Reactant Ions (RIP), direct ionization exists, such as single photon ionization (SIP ionization) of a VUV lamp ionization source, so that substances eluted by chromatography are directly injected into the RIP, and the GC-IMS combined chromatographic column and ion migration tube connecting device is beneficial to improving the detection sensitivity of the GC-IMS.
4. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, under the purging of the drift gas, chromatographic column eluting substances flow out of the chromatographic column to blow out of the migration tube, pass through the reaction zone and the ionization zone in sequence, and are ionized into ions for a long time, so that high-sensitivity detection is realized.
5. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, unidirectional airflow is adopted in the ion migration spectrum, so that retention, vortex and residual time of a sample in the migration tube are reduced, matching of chromatographic elution time and ion migration tube response time is realized, and GC-IMS response time resolution is improved.
6. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, the problem of GC-IMS flow matching is solved by adjusting the flow rate proportion of the floating gas to the carrier gas, and the sample dilution is reduced.
7. According to the GC-IMS combined chromatographic column and ion migration tube connecting device and the working method thereof, before a sample enters the ion migration tube, the sample is heated and insulated by the heating sleeve in the whole process, so that the sample residue at the interface is reduced, and the elution speed is improved.
Based on the reasons, the method can be widely popularized in the fields of GC-IMS combination and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
Fig. 1 is a schematic structural diagram of a connection device of a GC-IMS combined chromatographic column and a cylindrical ionization source ion transfer tube in the present invention.
Fig. 2 is a schematic structural diagram of a connection device of a GC-IMS combined chromatographic column and a sheet ionization source ion transfer tube in the present invention.
Fig. 3 is a GC-IMS spectrum obtained by the connection device of the GC-IMS combined chromatographic column and the ion mobility tube of the cylindrical radioactive source in the present invention.
In the figure: 1. a chromatographic column; 2. a heating jacket; 3. an interface screw; 4. an interface nut; 5. an air outlet; 6. an ionization source gas outlet; 7. an ionization source; 7-1, a cylindrical ionization source; 7-1 to 1, a closed end; 7-1-2, an open end; 7-2, a chip ionization source; 8. an ion transfer tube; 9. a reaction zone; 10. a chromatographic column gas outlet; 11. an ion gate; 12. a migration zone; 13. an interface.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise. Meanwhile, it should be clear that the dimensions of the respective parts shown in the drawings are not drawn in actual scale for convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
In the description of the present invention, it should be understood that the azimuth or positional relationships indicated by the azimuth terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal", and "top, bottom", etc., are generally based on the azimuth or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and these azimuth terms do not indicate and imply that the apparatus or elements referred to must have a specific azimuth or be constructed and operated in a specific azimuth, and thus should not be construed as limiting the scope of protection of the present invention: the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "upper surface at … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial location relative to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "over" other devices or structures would then be oriented "below" or "beneath" the other devices or structures. Thus, the exemplary term "above … …" may include both orientations of "above … …" and "below … …". The device may also be positioned in other different ways (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
In addition, the terms "first", "second", etc. are used to define the components, and are only for convenience of distinguishing the corresponding components, and the terms have no special meaning unless otherwise stated, and therefore should not be construed as limiting the scope of the present invention.
As shown in fig. 1, the present invention provides a GC-IMS combined chromatographic column and ion mobility tube connection device, comprising: the chromatographic column 1, the ion migration tube 8 and the interface 13, wherein the chromatographic column 1 is vertically connected to the ion migration tube 8 through the interface 13; wherein:
the chromatographic column 1 is used for pre-separating a detection sample and providing a chromatographic column eluent for the ion transfer tube 8;
the ion migration tube 8 is used for carrying out secondary analysis and detection on chromatographic column eluents;
the interface 13 is used for vertically and hermetically connecting the chromatographic column 1 and the ion transfer tube 8.
In a specific implementation, as a preferred embodiment of the present invention, the chromatographic column 1 includes a chromatographic column air outlet 10, the chromatographic column air outlet 10 is vertically inserted into the ion transfer tube 8, the portion inserted into the ion transfer tube 8 is a nonmetallic chromatographic column, and the depth of inserting the ion transfer tube 8 is determined by the structure of the ion transfer tube 8.
In specific implementation, as a preferred embodiment of the present invention, the ion transfer tube 8 includes: an air outlet 5, an ionization source 7, a reaction zone 9, an ion gate 11 and a migration zone 12; wherein:
the air outlet 5 is arranged on the side surface of the first electrode of the ion transfer tube 8 and is used for discharging air flow from the ion transfer tube 8;
the ionization source 7 is arranged at the left end of the ion migration tube 8 and comprises a cylindrical ionization source 7-1 and a sheet ionization source 7-2, and is used for converting gas molecules or atoms into charged ions and enabling the ions to migrate and move under the action of an electric field;
the reaction zone 9 is arranged between the ionization source 7 and the ion gate 11 and is used for carrying out ionization analysis on chromatographic column eluents under the drive of carrier gas;
the ion gate 11 is arranged between the reaction zone 9 and the migration zone 12 and is used for controlling the ion beam;
the migration zone 12 is disposed at the right end of the ion migration tube 8, and is used for blowing a bleaching gas into the ion migration tube 8 to drive the ion beam to migrate.
In particular, as a preferred embodiment of the present invention, the interface 13 includes: a heating sleeve 2, an interface screw 3 and an interface nut 4; wherein:
the heating sleeve 2 is wrapped outside the chromatographic column 1 and the interface 13 and is used for preventing chromatographic column eluate from condensing and remaining and blocking the interface 13;
the front end of the interface screw 3 is of a conical structure, the rear end of the interface screw is of a cylindrical structure, and the interface screw is sleeved on the interface 13 and used for fixing the interface 13;
the interface nut 4 is in a cylindrical structure, the bottom conical structure is matched with the front end of the interface screw 3, and the interface nut is arranged below the reaction zone 9 and is used for vertically and hermetically connecting the chromatographic column 1 on the ion migration tube 8.
In specific implementation, as a preferred embodiment of the present invention, the ionization source 7 is a radioactive ionization source; such as tritium, nickel or americium sources, or vacuum ultraviolet lamps VUV lamps, corona discharge, laser pulse ionization sources.
One end of the cylindrical ionization source 7-1 is a closed end 7-1-1, the other end of the cylindrical ionization source is an open end 7-1-2, and the closed end 7-1-1 is provided with an ionization source air outlet 6;
the on-chip ionization source 7-2 comprises a VUV lamp ionization source, an air outlet is not arranged, and air flows out from the air outlet 5.
In specific implementation, as a preferred embodiment of the present invention, the chromatographic column 1 is a gas chromatographic column, including a capillary column, an MCC column and a preparation column.
In specific implementation, as a preferred embodiment of the present invention, the ion gate 11 is a BN-type ion gate, a TP-type ion gate, or a field switching ion gate.
The invention also provides a working method of the GC-IMS combined chromatographic column and ion migration tube connecting device, which comprises the following specific steps:
s1, according to the characteristics of different types of detection samples, adjusting the flow rate ratio of the floating gas to the carrier gas, the flow direction of the air flow and the heating temperature;
s2, inputting a detection sample into the chromatographic column 1 for pre-separation to obtain a chromatographic column eluent;
s3, enabling the chromatographic column eluate to enter a reaction zone 9 of the ion migration tube through an interface 13 under the drive of carrier gas;
s4, after the chromatographic column eluate enters the reaction zone 9, the drift gas blown in by the migration zone 12 passes through the ion gate 11 to drive the chromatographic column eluate to enter the ionization source 7;
s5, when the ionization source 7 adopts the cylindrical ionization source 7-1, the air outlet 5 is sealed, and air flows out from the ionization source air outlet 6; when the sheet-like ionization source 7-2 is adopted, the air flow flows out from the air outlet 5;
s6, after the chromatographic column eluate is blown out from the ion transfer tube 8, a GC-IMS spectrogram of the detection sample is obtained, and analysis and detection of the detection sample are realized.
Example 1
As shown in fig. 1, the present embodiment provides a schematic structure of a connection device between a chromatographic column and an ion transfer tube of a cylindrical ionization source, wherein the cylindrical ionization source 7-1 and the ion transfer tube 8 are coaxially arranged, an opening is formed at one end of the cylindrical ionization source 7-1, one end is sealed, and an ionization source air outlet 6 is formed in the center of the sealed end. The cylindrical ionization source 7-1 is inserted into the first electrode of the ion transfer tube to seal the gas outlet 5. Through a GC-IMS interface, the chromatographic column 1 passes through the reaction zone 9, after the insertion depth is optimized, a sample flowing out of the gas outlet 10 of the chromatographic column flows out of the gas outlet 6 of the ionization source through the reaction zone 9 and the ionization source 7 under the purging of the floating gas, so that the detection sensitivity is improved; due to the adoption of the unidirectional airflow mode, the residues of the sample in the reaction area 9 and the ionization source 7 can be effectively prevented, and the time resolution of sample detection is improved. The structure realizes zero interface dead volume.
Example 2
As shown in fig. 2, the present embodiment provides a schematic structure of a connection device between a chromatographic column and an ion transfer tube of a sheet ionization source, wherein the sheet ionization source 7-2 is located at one end of the ion transfer tube 8 and is placed coaxially with the ion transfer tube 8. At this time, the gas outlet 5 of the migration tube is smooth, the chromatographic column 1 is inserted into the reaction zone 9 through the GC-IMS interface, the sample flowing out of the gas outlet 10 of the chromatographic column flows out of the ion migration tube 8 under the purging of the drift gas, so that the residue of the sample in the reaction zone 9 and the ionization zone 13 is effectively prevented, the time resolution of sample detection is improved, the zero dead volume of the interface is realized by directly injecting the sample into the ion migration tube 8, and the detection sensitivity is improved. And adjusting the flow ratio of the floating gas and the carrier gas to realize the flow matching of the GC-IMS combination.
Example 3
As shown in fig. 3, the embodiment provides a GC-IMS spectrum obtained by a chromatographic column and a cylindrical radioactive source ionization source ion transfer tube connection device, and the detection conditions are: the ionization source is nickel source, the air bleaching gas flow rate is 400ml/min, and the air carrier gas flow rate is20ml/min, the temperature of the GC and interface heating jacket is 60 ℃, the temperature of the ion transfer tube 8 is 100 ℃, and the expired air is directly injected. As can be seen from the 2-dimensional heat map, the chromatographic column and ionization source interface structure, NH in exhaled breath 3 And compounds such as acetone and the like are effectively separated and are rapidly eluted from the ion transfer tube 8, so that the tailing phenomenon is avoided, and high sensitivity and time resolution are realized. The problems of matching of GC sample elution and ion mobility spectrometry response time, matching of IMS drift gas and GC carrier gas flow, large dead volume of an interface, low sensitivity and the like are solved, and meanwhile, ionization detection of compounds by various ionization sources can be realized by replacing the ionization sources.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. A GC-IMS combined chromatographic column and ion transfer tube connection device, comprising: the chromatographic column (1), the ion migration tube (8) and the interface (13), wherein the chromatographic column (1) is vertically connected to the ion migration tube (8) through the interface (13); wherein:
the chromatographic column (1) is used for pre-separating a detection sample and providing chromatographic column eluents for the ion migration tube (8);
the ion migration tube (8) is used for carrying out secondary analysis and detection on chromatographic column eluents;
the interface (13) is used for vertically and hermetically connecting the chromatographic column (1) and the ion migration tube (8).
2. The device for connecting a GC-IMS combined chromatographic column with an ion transfer tube according to claim 1, wherein the chromatographic column (1) comprises a chromatographic column outlet (10), the chromatographic column outlet (10) is vertically inserted into the ion transfer tube (8), the portion inserted into the ion transfer tube (8) is a nonmetallic chromatographic column, and the depth of insertion into the ion transfer tube (8) is determined by the structure of the ion transfer tube (8).
3. The GC-IMS combined chromatographic column and ion transfer tube connection device according to claim 1, wherein the ion transfer tube (8) comprises: an air outlet (5), an ionization source (7), a reaction zone (9), an ion gate (11) and a migration zone (12); wherein:
the air outlet (5) is arranged on the side surface of the first electrode of the ion transfer tube (8) and is used for discharging air flow from the ion transfer tube (8);
the ionization source (7) is arranged at the left end of the ion migration tube (8) and comprises a cylindrical ionization source (7-1) and a sheet ionization source (7-2) which are used for converting gas molecules or atoms into charged ions and enabling the ions to migrate and move under the action of an electric field;
the reaction zone (9) is arranged between the ionization source (7) and the ion gate (11) and is used for carrying out ionization analysis on chromatographic column eluents under the drive of carrier gas;
the ion gate (11) is arranged between the reaction zone (9) and the migration zone (12) and is used for controlling the ion beam;
the migration zone (12) is arranged at the right end of the ion migration tube (8) and is used for blowing the floating gas into the ion migration tube (8) to drive the ion beam to migrate.
4. The GC-IMS combined chromatographic column and ion transfer tube connection device according to claim 1, wherein the interface (13) comprises: the heating device comprises a heating sleeve (2), an interface screw (3) and an interface nut (4); wherein:
the heating sleeve (2) is wrapped outside the chromatographic column (1) and the interface (13) and is used for preventing eluent of the chromatographic column from condensing and remaining and blocking the interface (13);
the front end of the interface screw (3) is of a conical structure, the rear end of the interface screw is of a cylindrical structure, and the interface screw is sleeved on the interface (13) and used for fixing the interface (13);
the interface nut (4), the cylindricality structure, bottom toper structure and interface screw (3) front end phase-match sets up in reaction zone (9) below for with chromatographic column (1) perpendicular sealing connection on ion migration pipe (8).
5. A GC-IMS combined chromatographic column and ion transfer tube connection according to claim 3, characterized in that the ionization source (7) is a radioactive ionization source;
one end of the cylindrical ionization source (7-1) is a closed end (7-1-1), the other end of the cylindrical ionization source is an open end (7-1-2), and the closed end (7-1-1) is provided with an ionization source air outlet (6);
the on-chip ionization source (7-2) comprises a VUV lamp ionization source, an air outlet is not arranged, and air flows out of the air outlet (5).
6. The GC-IMS combined chromatographic column and ion transfer tube connection device according to claim 1, wherein the chromatographic column (1) is a gas chromatographic column including a capillary column, an MCC column and a preparation column.
7. The GC-IMS combined column and ion transfer tube connection device according to claim 1, wherein the ion gate (11) is a BN-type ion gate, a TP-type ion gate or a field switching ion gate.
8. A method of operating a GC-IMS combination chromatographic column and ion mobility tube connection device according to any of claims 1 to 7, comprising the specific steps of:
according to the characteristics of different types of detection samples, the flow rate proportion of the floating gas and the carrier gas, the flow direction of the air flow and the heating temperature are regulated;
inputting the detection sample into a chromatographic column (1) for pre-separation to obtain chromatographic column eluate;
the chromatographic column eluate is driven by carrier gas to enter a reaction zone (9) of the ion migration tube through an interface (13);
after the chromatographic column eluent enters the reaction zone (9), the drift gas blown in by the migration zone (12) passes through the ion gate (11) to drive the chromatographic column eluent to enter the ionization source (7);
when the ionization source (7) adopts a cylindrical ionization source (7-1), the air outlet (5) is sealed, and air flow flows out from the ionization source air outlet (6); when the sheet ionization source (7-2) is adopted, the air flow flows out from the air outlet (5);
after the chromatographic column eluate is blown out from the ion migration tube (8), a GC-IMS spectrogram of a detection sample is obtained, and analysis and detection of the detection sample are realized.
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|---|---|---|---|
| CN202311714070.9A CN117542720A (en) | 2023-12-12 | 2023-12-12 | GC-IMS combined chromatographic column and ion migration tube connecting device and working method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311714070.9A CN117542720A (en) | 2023-12-12 | 2023-12-12 | GC-IMS combined chromatographic column and ion migration tube connecting device and working method thereof |
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| CN202311714070.9A Pending CN117542720A (en) | 2023-12-12 | 2023-12-12 | GC-IMS combined chromatographic column and ion migration tube connecting device and working method thereof |
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| CN (1) | CN117542720A (en) |
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