CN108335964A - Ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure - Google Patents

Ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure Download PDF

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Publication number
CN108335964A
CN108335964A CN201710052111.0A CN201710052111A CN108335964A CN 108335964 A CN108335964 A CN 108335964A CN 201710052111 A CN201710052111 A CN 201710052111A CN 108335964 A CN108335964 A CN 108335964A
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China
Prior art keywords
hole
internal diameter
flight time
mass spectrum
ion
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CN201710052111.0A
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Chinese (zh)
Inventor
洪义
谭国斌
高伟
乔佳
喻佳俊
苏海波
刘丹
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Gao Jilong
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Guangzhou Zhichun Scientific Instrument Co Ltd
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Priority to CN201710052111.0A priority Critical patent/CN108335964A/en
Publication of CN108335964A publication Critical patent/CN108335964A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/004Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • H01J49/0081Tandem in time, i.e. using a single spectrometer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/062Ion guides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/067Ion lenses, apertures, skimmers

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The present invention relates to a kind of ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure, drainage electrode piece can separate electric field and subsequent electrode.The second through-hole in conflux electrode slice is gradually reduced due to internal diameter, ion transmits under the guiding of air-flow, with larger effective ion receiving area, and due to the convergence effect to air-flow, the efficiency of transmission of ion can be effectively improved, because not having electric field in the second through-hole, the divergence field to be formed will not be gradually reduced because of internal diameter leads to losses of ions.It cools down rapidly in the ion channel that the ion come out from the second through-hole enters cooling focusing electrode, in the effect of the electric field of level Four rod structure and the collision process with background gas molecule, radial energy reduces, space divergence reduces, to form tiny ionic pump, it enters in time of-flight mass spectrometer, the sensitivity for being conducive to improve detection reduces detection limit, improves accuracy of detection.

Description

Ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure
Technical field
The present invention relates to chromatographies and mass spectrum detection field, more particularly, to a kind of ion mobility spectrometry and flight time matter Compose combined instrument and its connecting interface structure.
Background technology
Using the flight time as the mass spectrograph of representative, it is the technology that a kind of mass-to-charge ratio with ion carries out separation analysis, has The advantages such as high-resolution, high sensitivity, high-quality accuracy of measurement and quick analysis, are one kind that qualitative analysis is carried out to substance chemical composition Important means.But flight time mass spectrum cannot analyze the space conformation of isomer and complicated organic matter.Ion moves It is a kind of to carry out the skill of point analysis of variance according to analyte molecule quality, charge and collision cross-section (i.e. size and shape) to move spectrum Art can carry out preliminary separation to the molecule of isomer and tripe systems elephant.If in conjunction with the excellent of both analytical technologies Gesture detaches the mobility (or collision cross-section) of analyte using ion mobility spectrometry, then with flight time mass spectrum to analysis Object carries out mass spectrometry, realizes the separation of two different dimensions, and improves instrument peak capacity, can meet such as biological organic point The multicomponent sample analysis of son, complex matrices.
For ion mobility spectrometry when being combined with flight time mass spectrum, ion enters back into flight time mass spectrum through ion mobility spectrometry Instrument, there are ion transmission efficiency is low and the problems such as air pressure change could solve only by connecting suitable connecting interface The above problem.It is a kind of that the injection port of atmospheric pressure ionizationion time of-flight mass spectrometer, which is directly connected to ionic migration spectrum detection area, Feasible scheme.Common atmospheric pressure mass spectrometer interface is metal capillary interface, with simple in structure, to facilitate heating etc. excellent Point.But due in ion mobility spectrometry, ion is detached in a manner of " group ", is not only had in the axial direction of ion transmission Certain spatial dispersion equally has prodigious diverging radially.The ionic weight that metal capillary can be entered subtracts significantly It is few, and a large amount of gas ion transmission loss in pipe, it causes sensitivity inadequate, it is excellent that mass spectrographic detection limit cannot be given full play of Gesture.If directly aperture is used to be used as interface, it will appear that ionic weight is low, ion is by occurring supersonic expansion after aperture, sky Between dissipate the problems such as increasing again.
Invention content
Based on this, it is necessary to provide a kind of sensitivity and the higher ion mobility spectrometry of accuracy of detection and join with flight time mass spectrum With instrument and its connecting interface structure.
A kind of connecting interface structure of ion mobility spectrometry and flight time mass spectrum, including drainage electrode piece, conflux electrode slice And cooling focusing electrode, the drainage electrode piece, the conflux electrode slice and the cooling focusing electrode are set gradually;Wherein, The drainage electrode piece is equipped with first through hole;The conflux electrode slice is equipped with the second through-hole, the internal diameter of second through-hole from by One end of the nearly drainage electrode piece to one end far from the drainage electrode piece is gradually reduced, and the internal diameter of second through-hole The internal diameter of larger one end is consistent with the internal diameter of first through hole outlet end;The cooling focusing electrode is structure of quadrupole, The arrival end of the ion channel of cooling focusing electrode one end smaller with the internal diameter of second through-hole flushes, and the entrance The size at end is more than the internal diameter of described smaller one end of second through-hole internal diameter;The first through hole, second through-hole and described The coaxial setting of ion channel.
The internal diameter of the first through hole is consistent in one of the embodiments,.
The drainage electrode piece has main part and conduction part in one of the embodiments,;The conduction part projection exists The side surface far from the conflux electrode slice of the main part, and the outer wall of the conduction part and the angle of the side surface The number of degrees are not less than 90 °;The first through hole sequentially passes through the conduction part and the main part.
The internal diameter of the first through hole is 6~26mm in one of the embodiments,.
Second through-hole is the truncated cone-shaped hole of internal diameter even variation in one of the embodiments,.
The conflux electrode slice has interconnecting piece and conflux portion in one of the embodiments,;The interconnecting piece is close to institute The setting of drainage electrode piece is stated, conflux portion projection is in the side surface far from the drainage electrode piece of the interconnecting piece;Institute It states the second through-hole and sequentially passes through the interconnecting piece and the conflux portion.
In one of the embodiments, the internal diameter of larger one end of internal diameter of second through-hole be 6~26mm, internal diameter compared with The internal diameter of small one end is 0.1~0.3mm, and the distance of larger one end to the smaller one end of internal diameter of internal diameter is 2~5mm.
A diameter of 4~6mm of each electrode stem of the cooling focusing electrode in one of the embodiments, length 27 The size of~50mm, the arrival end of the ion channel of the cooling focusing electrode are 3.5~6mm.
A kind of ion mobility spectrometry and flight time mass spectrum combined instrument, including ion mobility spectrometry, flight time mass spectrum and above-mentioned The connecting interface structure of ion mobility spectrometry and flight time mass spectrum described in any embodiment, the ion mobility spectrometry fly with described It is connected by the connecting interface structure between row time mass spectrum.
The internal diameter of the drift tube of the ion mobility spectrometry is more than the interior of the first through hole in one of the embodiments, The end of diameter, drift tube setting coaxial with the first through hole, and the end of the drift tube and the first through hole it Between have interval.
Above-mentioned ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure, with traditional capillary or small The interface structures such as hole are compared, after can solving tube-like interface transmission efficiency is low and aperture interface holes ion space diverging increase again The problem of.Specifically, drainage electrode piece can separate electric field and subsequent electrode;The second through-hole in conflux electrode slice due to Internal diameter is gradually reduced, and ion transmits under the guiding of air-flow, has larger effective ion receiving area, and due to air-flow Convergence effect, the efficiency of transmission of ion can be effectively improved, in operation, conflux electrode slice is contacted with drainage electrode piece or Apply same voltage and form equipotential structure, thus there is no electric field in the second through-hole, will not be gradually reduced to be formed because of internal diameter Divergence field leads to losses of ions;It is cooled down rapidly in the ion channel that the ion come out from the second through-hole enters cooling focusing electrode Get off, in the effect of the electric field of level Four rod structure and the collision process with background gas molecule, radial energy reduction, space Diverging reduces, and to form tiny ionic pump, enters in time of-flight mass spectrometer, is conducive to the sensitivity for improving detection, Detection limit is reduced, accuracy of detection is improved.
Description of the drawings
Fig. 1 is the modular structure schematic diagram of the ion mobility spectrometry and flight time mass spectrum combined instrument of an embodiment;
Fig. 2 is the structural schematic diagram of the connecting interface structure of Fig. 1 intermediate ions migration spectrum and flight time mass spectrum, dotted line in figure Connector indicates the flow direction of drift gas;
Fig. 3 is using ion mobility spectrometry shown in Fig. 1 and flight time mass spectrum combined instrument to a concentration of 100pg/ μ L reserpines The mass spectrogram of sample;
Fig. 4 is with flight time mass spectrum combined instrument using the ion mobility spectrometry of traditional aperture interface to a concentration of 20ng/ μ The mass spectrogram of L reserpine samples.
Specific implementation mode
To facilitate the understanding of the present invention, below with reference to relevant drawings to invention is more fully described.In attached drawing Give presently preferred embodiments of the present invention.But the present invention can realize in many different forms, however it is not limited to this paper institutes The embodiment of description.Keep the understanding to the disclosure more thorough on the contrary, purpose of providing these embodiments is Comprehensively.
It should be noted that when element is referred to as " being fixed on " another element, it can be directly on another element Or there may also be elements placed in the middle.When an element is considered as " connection " another element, it can be directly connected to To another element or it may be simultaneously present centering elements.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the Listed Items of pass.
As shown in Figure 1, the ion mobility spectrometry of an embodiment and flight time mass spectrum combined instrument include ion mobility spectrometry 20, fly The connecting interface structure 10 of row time mass spectrum 30 and ion mobility spectrometry and flight time mass spectrum.Ion mobility spectrometry 20 and flight time It is connected by connecting interface structure 10 between mass spectrum 30.
Incorporated by reference to Fig. 2, the ion mobility spectrometry of the present embodiment and the connecting interface structure 10 of flight time mass spectrum include drainage Electrode slice 100, conflux electrode slice 200 and cooling focusing electrode 300.Drainage electrode piece 100, conflux electrode slice 200 and cooling are poly- Burnt electrode 300 is set gradually.
Wherein, drainage electrode piece 100 is equipped with first through hole 102.In the present embodiment, the internal diameter of first through hole 102 is uniform. The internal diameter of first through hole 102 is more smaller than the internal diameter of the drift tube 22 of ion mobility spectrometry 20.Preferably, the internal diameter of first through hole 102 For 6~26mm;Correspondingly, the internal diameter of drift tube 22 is preferably 8~30mm.The setting coaxial with drift tube 22 of first through hole 102 is (i.e. Central axes are conllinear).
In the present embodiment, drainage electrode piece 100 has main part 110 and conduction part 120.Main part 110 is in disc-shaped. 120 projection of conduction part is in a side surface of the separate conflux electrode slice 200 of main part 110, when mounted, by itself and drift tube 22 Relatively, and with drift tube 22 axially there is gap, such as the gap of 1~2mm.First through hole 102 sequentially passes through conduction part 120 And the middle part of main part 110.Preferably, main part 110 is integrally formed structures with conduction part 120.
Further, in the present embodiment, the number of degrees of the angle of the outer wall and side surface of conduction part 120 are excellent not less than 90 ° Choosing is arranged in 120 ° of angles, and because the internal diameter of first through hole 102 is consistent, the thickness of conduction part 120 is from one connect with main part 110 End to other end is gradually reduced.The conduction part 120 forms flow guiding structure, and guiding drift gas is towards moving in drift tube, such as Fig. 2 Shown in middle dotted arrow.
Conflux electrode slice 200 is equipped with the second through-hole 202.The internal diameter of second through-hole 202 is from close to the one of drainage electrode piece 100 It holds to one end far from drainage electrode piece 100 and is gradually reduced, and the internal diameter and first of larger one end of internal diameter of the second through-hole 202 The internal diameter of 102 outlet end of through-hole is consistent.Preferably, the second through-hole 202 is the truncated cone-shaped hole of internal diameter even variation.Second through-hole The internal diameter of 202 larger one end of internal diameter is 6~26mm, and the internal diameter of the smaller one end of internal diameter is 0.1~0.3mm, and internal diameter compared with The distance of big one end to smaller one end of internal diameter is 2~5mm.Aperture in the outlet end of the second through-hole 102 of truncated cone-shaped Under effect, air pressure can be reduced to 0.25~2Torr from 760Torr.
In the present embodiment, conflux electrode slice 200 has interconnecting piece 210 and conflux portion 220.Interconnecting piece 210 is close to described Drainage electrode piece 100 is arranged.Interconnecting piece 210 is in disc-shaped.Separate drainage electrode piece of 220 projection of conflux portion in interconnecting piece 210 100 side surface.Second through-hole 202 sequentially passes through the middle part in interconnecting piece 210 and conflux portion 220.Further, in the present embodiment In, the thickness in conflux portion 220 is gradually reduced from the one end being connect with interconnecting piece 210 to the other end, and formation allows bit architecture, convenient for Subsequent cooling focusing electrode 300 docks.Preferably, interconnecting piece 210 is integrally formed structures with conflux portion 220.
The interconnecting piece 210 of conflux electrode slice 200 can be in direct contact with the main part 110 of drainage electrode piece 100, to poly- Equipotential between galvanic electricity pole piece 200 and drainage electrode piece 100;Or there is gap between interconnecting piece 210 and main part 110, In use, applying identical voltage respectively to conflux electrode slice 200 and drainage electrode piece 100, equipotential structure is formed, with by drawing Galvanic electricity pole piece 100 separates electric field and the conflux electrode slice 200 positioned at its rear, and electric field is not formed in the second through-hole 202.
Cooling focusing electrode 300 is structure of quadrupole, has four cylindrical electrode stems, is formed between four electrode stems Ion channel 302.The arrival end of the ion channel 302 of cooling focusing electrode 300 and the smaller one end of the internal diameter of the second through-hole 202 It flushes, and the size (the distance between two electrode stems for being located at diagonal position) of the arrival end is more than 202 internal diameter of the second through-hole The internal diameter of smaller one end.First through hole 102, second through-hole 202 and coaxial setting (the i.e. first through hole 102 of ion channel 302 The central axes of central axes, the central axes of the second through-hole 202 and ion channel 302 are conllinear).
In the present embodiment, a diameter of 4~6mm of each electrode stem of cooling focusing electrode 300, length are 27~50mm. The size of the arrival end of the ion channel 302 of cooling focusing electrode 300 is 3.5~6mm.
Mass spectrogram that Germicidal efficacy arrives is carried out such as using the ion mobility spectrometry and flight time mass spectrum combined instrument of the present embodiment Shown in Fig. 3.The signal strength that 100pg/ μ L reserpine samples are corresponded in Fig. 3 is 2812, and uses common small pore electrod observation To spectrogram as shown in figure 4, the signal strength of corresponding 20ng/ μ L reserpine samples is only 1020, and uses capillary interface Signal is not observed since the ion of gas phase almost loses in capillary in combined instrument.It can be with by the above experimental result Find out that the connecting interface structure using the present embodiment can substantially increase the efficiency of transmission of ion.
Above-mentioned ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure 10, with traditional capillary or The interface structures such as aperture are compared, after can solving tube-like interface transmission efficiency is low and aperture interface holes ion space diverging increase again Big problem.Specifically, drainage electrode piece 100 can separate electric field and subsequent electrode, and can guide drift gas into Enter drift tube 22.Since internal diameter is gradually reduced, ion passes under the guiding of air-flow for the second through-hole 202 in conflux electrode slice 200 It is defeated, there is larger effective ion receiving area, and due to the convergence effect to air-flow, the transmission of ion can be effectively improved Conflux electrode slice 200 is contacted with drainage electrode piece 100 or is applied same voltage formation equipotential knot by efficiency in operation Structure, thus there is no electric field in the second through-hole 202, the divergence field to be formed will not be gradually reduced because of internal diameter leads to losses of ions.From The ion that two through-holes 202 come out is entered in the ion channel 302 of cooling focusing electrode 300 and is cooled down rapidly, in level four bars The effect of the electric field of structure and in the collision process of background gas molecule, radial energy reduce, space divergence reduce, to Tiny ionic pump is formed, is entered in time of-flight mass spectrometer 30, the sensitivity for improving detection is conducive to, reduces detection limit, Improve accuracy of detection.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. the connecting interface structure of a kind of ion mobility spectrometry and flight time mass spectrum, which is characterized in that including drainage electrode piece, gather Galvanic electricity pole piece and cooling focusing electrode, the drainage electrode piece, the conflux electrode slice and the cooling focusing electrode are set successively It sets;Wherein, the drainage electrode piece is equipped with first through hole;The conflux electrode slice is equipped with the second through-hole, second through-hole The one end of internal diameter from close to one end of the drainage electrode piece to far from the drainage electrode piece is gradually reduced, and described second is logical The internal diameter of the larger one end of internal diameter in hole is consistent with the internal diameter of first through hole outlet end;The cooling focusing electrode is quadrupole Rod structure, the arrival end of the ion channel of cooling focusing electrode one end smaller with the internal diameter of second through-hole flush, And the size of the arrival end is more than the internal diameter of described smaller one end of second through-hole internal diameter;The first through hole, described second are led to Hole and the coaxial setting of the ion channel.
2. the connecting interface structure of ion mobility spectrometry as described in claim 1 and flight time mass spectrum, which is characterized in that described The internal diameter of first through hole is consistent.
3. the connecting interface structure of ion mobility spectrometry as claimed in claim 2 and flight time mass spectrum, which is characterized in that described Drainage electrode piece has main part and conduction part;The conduction part projection is in the main part far from the conflux electrode slice One side surface, and the outer wall of the conduction part and the number of degrees of the angle of the side surface are not less than 90 °;The first through hole is passed through successively Wear the conduction part and the main part.
4. the connecting interface structure of ion mobility spectrometry as claimed in claim 3 and flight time mass spectrum, which is characterized in that described The internal diameter of first through hole is 6~26mm.
5. the connecting interface structure of ion mobility spectrometry as described in any one of claims 1 to 4 and flight time mass spectrum, special Sign is that second through-hole is the truncated cone-shaped hole of internal diameter even variation.
6. the connecting interface structure of ion mobility spectrometry as claimed in claim 5 and flight time mass spectrum, which is characterized in that described Conflux electrode slice has interconnecting piece and conflux portion;The interconnecting piece is arranged close to the drainage electrode piece, conflux portion projection In the side surface far from the drainage electrode piece of the interconnecting piece;Second through-hole sequentially passes through the interconnecting piece and institute State conflux portion.
7. the connecting interface structure of ion mobility spectrometry as claimed in claim 6 and flight time mass spectrum, which is characterized in that described The internal diameter of larger one end of internal diameter of the second through-hole is 6~26mm, and the internal diameter of the smaller one end of internal diameter is 0.1~0.3mm, and interior The distance of the larger one end of diameter to smaller one end of internal diameter is 2~5mm.
8. the connecting interface structure of ion mobility spectrometry as claimed in claim 7 and flight time mass spectrum, which is characterized in that described A diameter of 4~6mm of each electrode stem of cooling focusing electrode, length are 27~50mm, and the ion of the cooling focusing electrode is logical The size of the arrival end in road is 3.5~6mm.
9. a kind of ion mobility spectrometry and flight time mass spectrum combined instrument, which is characterized in that including ion mobility spectrometry, flight time matter Spectrum and as ion mobility spectrometry according to any one of claims 1 to 8 and flight time mass spectrum connecting interface structure, it is described from It is connected by the connecting interface structure between sub- migration spectrum and the flight time mass spectrum.
10. example migration spectrum as claimed in claim 9 and flight time mass spectrum combined instrument, which is characterized in that the ion moves Move spectrum drift tube internal diameter be more than the first through hole internal diameter, drift tube setting coaxial with the first through hole, and There is interval between the end of the drift tube and the end of the first through hole.
CN201710052111.0A 2017-01-20 2017-01-20 Ion mobility spectrometry and flight time mass spectrum combined instrument and its connecting interface structure Pending CN108335964A (en)

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