CN111243936A - Pulse electrospray ion source, pulse sampling method and mass spectrum detection system - Google Patents
Pulse electrospray ion source, pulse sampling method and mass spectrum detection system Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
- H01J49/167—Capillaries and nozzles specially adapted therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
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Abstract
A pulse electrospray ion source, a pulse sampling method and a mass spectrum detection system are provided, the ion source comprises a sample supply device, a sampling capillary tube and an electrode, wherein a sample solution provided by the sample supply device enters from a sampling end of the sampling capillary tube and is output from an output end of the sampling capillary tube, the electrode charges the sample solution to provide a voltage required by electrospray formation, the ion source also comprises a moving device coupled to the sample supply device or the sampling capillary tube, and the sample supply device and the sampling capillary tube are subjected to intermittent relative movement according to a set pulse time sequence during sampling so that a sample in the sample supply device is intermittently contacted with the sampling end of the sampling capillary tube, thereby realizing pulse electrospray sampling. The invention realizes the synchronous operation of pulse sample introduction and ionization, and improves the utilization rate of the sample.
Description
Technical Field
The invention relates to the field of analytical instruments, in particular to a pulse electrospray ion source and a pulse sampling method.
Background
The mass spectrometer has been invented for over a hundred years, and is widely used due to the characteristics of high sensitivity, high accuracy, high analysis speed, strong qualitative capability and the like. The ion source is one of the core components of a mass spectrometer, and determines the detection range and sensitivity of the instrument. Among them, electrospray ion source is the most widely used ion source, and its technology has gained the Nobel prize.
The operation of electrospray can be described simply as: the sample solution is passed through the capillary at a low flow rate. The capillary is connected with a high voltage, and the positive and negative of the voltage depend on the property of the object to be detected. The voltage provides the electric field gradient required for charge separation of the liquid surface. Under the action of the electric field, the liquid forms a "taylor cone" at the capillary tip. Along with the evaporation of the solvent, the liquid drop shrinks, the repulsive force between charges in the liquid drop is increased, the liquid drop can generate coulomb explosion and is circulated in a reciprocating way, and finally gas-phase ions are obtained and are detected by the mass analyzer.
Traditional electrospray always produces gaseous phase ion, and the mass spectrometer pulse type advances a kind and detects ion, therefore only a part of ion that the ion source produced is detected by the mass spectrometer, causes the waste. Thus a pulsed electrospray ion source application results. Most of the existing pulse electrospray ion sources generate pulse electrospray by loading pulse high-voltage electricity and alternating-current high-voltage electricity, and the methods are based on improvement of an electricity-supplying mode. In the specific operation, auxiliary devices such as a pipette gun and a syringe pump are needed for sample injection, and then the sample injection and ionization are performed by pulse energization, namely the sample injection and ionization are asynchronous processes, and the utilization rate of the sample is not high.
Disclosure of Invention
The invention mainly aims to overcome the technical defects and provide a pulse electrospray ion source and a pulse sampling method, so that pulse sampling and ionization are synchronously performed, and the utilization rate of a sample is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pulse electrospray ion source comprises a sample supply device, a sample capillary and an electrode, wherein a sample solution provided by the sample supply device enters the sample capillary from a sample inlet end of the sample capillary, and is output from the output end of the sample injection capillary, the electrode is used for carrying out contact or non-contact electrification on the sample solution so as to provide the voltage required by the electrospray formation, wherein the pulsed electrospray ion source further comprises a moving device coupled to the sample supply device or the sample injection capillary, the moving device intermittently moves the sample supply device and the sample injection capillary according to a set pulse time sequence during sample injection, so that the sample in the sample supply appliance is intermittently contacted with the sample introduction end of the sample introduction capillary, thereby realizing pulse type electrospray sample introduction.
Further:
the sample supply means is a centrifuge tube or a sample plate, and the electrode is inserted into a sample solution in the centrifuge tube or placed under the sample plate.
The moving device comprises a moving table on which the sample supply apparatus is arranged, the sample supply apparatus is carried by the moving table for intermittent movement relative to the sample capillary during sample injection.
The mobile station is provided with a table top arranged along the horizontal direction and is arranged to move along the vertical direction, the sample supply device is arranged on the horizontal table top of the mobile station, and the sample injection capillary is positioned above the mobile station along the vertical direction.
The moving device comprises a capillary moving device, the sample injection capillary is fixed on the capillary moving device, and the capillary moving device drives the capillary to move intermittently relative to the sample supplier during sample injection.
The capillary moving device is a capillary lifting device, the sample supply appliance is horizontally arranged, and the capillary lifting device controls the sample injection capillary to move up and down relative to the sample supply appliance.
The output of advance kind capillary connects low pressure cavity, low pressure cavity is the low pressure cavity of mass spectrograph, or for additionally setting up advance kind capillary's output with sealed low pressure cavity between the introduction port of mass spectrograph, preferably, the atmospheric pressure of low pressure cavity is at 10-4-105Pa。
The sampling capillary is arranged in the cavity, the sampling capillary penetrates through the carrier gas passage, and an outlet of the carrier gas passage extends to the output end of the sampling capillary. The carrier gas is preferably controlled to have consistent pulse timing with the sample injection.
The inner diameter of the sample capillary is 10-150 mu m, and the outer surface of the sample capillary is coated with a polyamide coating.
A method of pulsed electrospray injection using the pulsed electrospray ion source, the method comprising: when advancing the appearance, according to the pulse sequence of setting for, through the mobile device makes sample supply utensil with advance the appearance capillary and take place intermittent type nature relative movement, make sample in the sample supply utensil intermittently with advance the appearance end contact of appearance capillary, sample solution passes through advance the appearance end entering of appearance capillary advance the appearance capillary, and follow advance the output of appearance capillary, simultaneously, through the electrode pair sample solution carries out contact or non-contact's power-up, makes sample solution be in advance the output of appearance capillary and form the electrospray, realize pulsed electrospray and advance the appearance from this.
A mass spectrometry detection system comprising an electrospray ion source and a mass spectrometer, wherein the electrospray ion source is the pulsed electrospray ion source.
The invention has the following beneficial effects:
the pulse electrospray ion source provided by the invention realizes the synchronous sampling and ionization in the pulse electrospray process, improves the utilization rate of samples compared with the traditional pulse sampling mode, simplifies the structure of an instrument, and has the remarkable advantages of small sample consumption and short response time.
In a preferred embodiment, the ion source of the invention does not need an auxiliary sample feeding device, utilizes self-suction sample feeding and adopts non-contact electrification to avoid dead volume and sample pollution generated by a sample feeding channel.
Drawings
FIG. 1 is a schematic diagram of a pulsed electrospray ion source according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a pulsed electrospray ion source and a compact mass spectrometry detection system according to another embodiment of the invention.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element. In addition, the connection may be for either a fixed or coupled or communicating function.
It is to be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing the embodiments of the present invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be in any way limiting of the present invention.
Fig. 1 is a schematic structural diagram of a pulsed electrospray ion source according to an embodiment of the present invention. Fig. 2 is a schematic structural diagram of a pulsed electrospray ion source and a mass spectrometry detection system according to another embodiment of the present invention. Referring to fig. 1 and 2, an embodiment of the present invention provides a pulsed electrospray ion source, which includes a sample supply device (e.g. a centrifuge tube 3 or a sample plate 3'), a sample capillary 4, and an electrode 2, wherein a sample solution provided by the sample supply device enters the sample capillary 4 from a sample inlet end of the sample capillary 4 and is output from an output end of the sample capillary 4, the electrode 2 is used for performing contact or non-contact energization on the sample solution to provide a voltage required for electrospray formation, wherein the pulsed electrospray ion source further includes a moving device (e.g. a lifting table 1) coupled to the sample supply device or the sample capillary 4, and the moving device intermittently moves the sample supply device and the sample capillary 4 relative to each other based on a preset pulse timing sequence during sample injection, so that the sample in the sample supply appliance intermittently contacts with the sample inlet end of the sample capillary 4, thereby realizing pulse type electrospray sample injection.
In a preferred embodiment, the pulsed electrospray ion source further comprises a carrier gas passage 5, the sample capillary 4 passes through the carrier gas passage 5, and an outlet of the carrier gas passage 5 extends to an output end of the sample capillary 4. More preferably, the carrier gas and the sample introduction are controlled to have a consistent pulse time sequence, and the pulse carrier gas is generated at the output end of the sample introduction capillary 4 immediately after the sample introduction, so that the electrospray desolventizing process is promoted, and the sample utilization rate is improved.
In some embodiments, the pulsed power-up may be performed at a timing that coincides with the pulse timing. However, the present invention is not limited to applying power in a pulse manner, as long as the voltage required for generating electrospray is ensured to exist when the sample solution is injected into the injection capillary 4.
In another embodiment, a pulsed electrospray ionization method for pulsed electrospray ionization using the pulsed electrospray ionization source of any of the preceding embodiments comprises: when advancing the appearance, according to the pulse sequence of setting for, through the mobile device makes sample supply utensil with advance kind capillary 4 and take place intermittent type nature relative movement, make sample in the sample supply utensil intermittent type ground with advance kind capillary 4's introduction end contact, sample solution passes through advance kind capillary 4's introduction end gets into advance kind capillary 4, and follow advance kind capillary 4's output, simultaneously, it is right through electrode 2 the sample solution carries out contact or non-contact's power-up, makes the sample solution be in advance kind capillary 4's output and form the electrospray, realizes the pulsed electrospray and advances the appearance from this.
In a further embodiment, a mass spectrometry detection system comprises an electrospray ion source and a mass spectrometer, wherein the electrospray ion source is the pulsed electrospray ion source of any preceding embodiment.
The pulse electrospray ion source provided by the embodiment of the invention realizes synchronous sample introduction and ionization in the pulse electrospray process, improves the sample utilization rate compared with the traditional pulse sample introduction mode, simplifies the structure of an instrument, and has the remarkable advantages of small sample consumption and short response time.
Features and advantages of particular embodiments of the present invention are described further below in conjunction with the following figures.
The utility model provides a pulse electric spray ion source of embodiment, including advance kind capillary 4, carrier gas passageway 5, elevating platform 1, electrode 2, centrifuging tube 3 or sample board 3', low pressure cavity 6, advance kind capillary 4 one end as advancing kind end, the other end is arranged in low pressure cavity 6, 6 atmospheric pressure of low pressure cavity is at 10-4-105Pa; the sample introduction capillary 4 passes through the carrier gas passage 5; the electrode 2 is arranged below the sample plate 3' or inserted into a sample solution in a centrifuge tube 3; the electrode 2 and the centrifuge tube 3 or the sample plate 3' can be arranged on the lifting platform 1 together, and the lifting platform 1 can move up and down or move in a three-dimensional direction; the other end of the low-pressure cavity 6 is connected with a sample inlet of the mass spectrometer. In addition, the sample injection capillary 4 can be installed on the lifting platform 1, and the intermittent movement of the sample injection end of the capillary relative to the centrifuge tube 3 or the sample plate 3' can be realized. All realize advancing the sample capillary 4 intermittent type nature contact sample above, realize the pulsed advance kind. The lifting table 1 can be replaced by other types of moving tables, and the relative moving direction is not limited to vertical movement.
Preferably, the inner diameter of the sample injection capillary 4 is 10-150 μm, and the material is a capillary coated with a polyamide coating.
Preferably, the air pressure 10 in the low pressure chamber 6-4-105Pa, the air pressure can be reduced by utilizing the suction force of a sample inlet of the mass spectrometer or the air suction can be realized by connecting an air suction pump for air suction.
In some embodiments, the low-pressure cavity 6 may be a low-pressure cavity 6 of the mass spectrometer itself, or may be a separately provided sealed low-pressure cavity 6.
In some embodiments, the carrier gas passage 5 may be continuously filled with gas, or intermittently filled with gas. The gas introduced into the carrier gas passage 5 may be air, nitrogen, hydrogen, helium, or the like.
In some embodiments, the electrode 2 is loaded with a dc high voltage, and the electrode 2 is non-contact powered with the sample of the centrifuge tube 3 or the sample plate 3'. Alternatively, the electrode 2 is loaded with direct current high voltage electricity, and the electrode 2 is in contact with the sample of the centrifuge tube 3 or the sample plate 3' to realize contact electrification.
In some embodiments, when the carrier gas passage 5 is intermittently filled with gas, the timing sequence and the pulse injection timing sequence are synchronized.
In various embodiments of the present invention, the liquid sample may be powered by contacting the electrode 2 with the sample; or the high-voltage electrode 2 is not contacted with the sample, the positive and negative charges in the sample are separated by utilizing the induction of a high-voltage electric field, the solution is polarized, and the sample pollution caused by the contact of the solution and the electrode 2 is avoided. The sample self-suction type sample introduction can be realized by utilizing the air pressure difference at the two ends of the capillary tube without an auxiliary device. The sample liquid provided by the sample introduction capillary 4 and the centrifuge tube 3 or the sample plate 3' intermittently contacts, so that impulse type sample introduction charged liquid drops are realized, the transmission speed of the liquid in the centrifuge tube 3 can be effectively improved, and the response time is prolonged. Further preferably, the pulse carrier gas and the sample injection time sequence are controlled, and the pulse carrier gas is generated at the tail end of the sample injection capillary 4 immediately after sample injection, so that the electrospray desolventizing process is promoted, and the sample utilization rate is improved. Fourthly, the synchronous sampling and ionization can be realized, and the real-time monitoring of the chemical reaction can be realized.
Example 1
Fig. 1 is a schematic structural diagram of a pulsed electrospray ion source in this embodiment. Comprises a sample injection capillary 4, a carrier gas passage 5, a lifting platform 1, an electrode 2, a centrifuge tube 3 and a low-pressure cavity 6.
One end of the sample injection capillary 4 is used as a sample injection end, and the other end of the sample injection capillary is arranged in the low-pressure cavity 6; the sample introduction capillary 4 passes through the carrier gas passage 5; the electrode 2 is inserted into the solution in the centrifuge tube 3; the electrode 2 and the centrifuge tube 3 are arranged on the lifting platform 1 together; the lifting platform 1 can move up and down or in a three-dimensional direction; the other end of the low-pressure cavity 6 is connected with a sample inlet of the mass spectrometer. The capillary 4 is in pulse contact with a sample to be detected, self-suction sample introduction is performed, pulse electrospray can be generated in the low-pressure cavity 6, and therefore a sample ion signal is detected by the mass spectrometer.
Example 2
As shown in fig. 2, the device comprises a sample injection capillary 4, a carrier gas passage 5, a gas passage valve 7, a lifting platform 1, an electrode 2, a sample plate 3 'and a mass spectrometer cavity 6'.
One end of the sample injection capillary 4 is used as a sample injection end, the other end of the sample injection capillary 4 is arranged in a cavity 6' of the mass spectrometer, and the sample injection capillary 4 passes through the carrier gas passage 5; the electrode 2 is arranged below the sample plate 3, and the liquid drop 8 to be detected is arranged on the sample plate 3'; the electrode 2 and the sample plate 3' are arranged on the lifting platform 1 together; the lifting platform 1 can move up and down or in a three-dimensional direction; the air path valve 7 is intermittently opened, the capillary 4 is in pulse contact with a sample to be detected, when liquid drops to be detected are transmitted to the tail end of the capillary 4, the air path valve 7 is instantly opened, the dissolution removing process of electrospray is promoted, and finally a sample ion signal is detected by the mass spectrometer.
The background of the present invention may contain background information related to the problem or environment of the present invention and does not necessarily describe the prior art. Accordingly, the inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention. In the description herein, references to the description of the term "one embodiment," "some embodiments," "preferred embodiments," "an example," "a specific example," or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the claims.
Claims (10)
1. A pulse electrospray ion source comprises a sample supply device, a sample capillary and an electrode, wherein the sample solution provided by the sample supply device enters the sample capillary from the sample inlet end of the sample capillary and is output from the output end of the sample capillary, the electrode is used for carrying out contact or non-contact power-up on the sample solution so as to provide the voltage required for forming electrospray, and the pulse electrospray ionization device is characterized by further comprising a moving device coupled to the sample supply device or the sample capillary, and the moving device enables the sample supply device and the sample capillary to intermittently move relatively according to the set pulse timing sequence during sample injection so that the sample in the sample supply device intermittently contacts with the sample inlet end of the sample capillary, thereby realizing pulse electrospray injection.
2. The pulsed electrospray ion source of claim 1, wherein the sample supply instrument is a centrifuge tube or a sample plate, the electrode is inserted into a sample solution in the centrifuge tube, or the electrode is placed under the sample plate.
3. The pulsed electrospray ion source of claim 1 or claim 2, wherein the movement means comprises a moving stage on which the sample supply is mounted, the sample supply being carried by the moving stage for intermittent movement relative to the sample capillary during sample introduction.
4. The pulsed electrospray ion source of claim 3, wherein the moving stage has a horizontally disposed mesa and is configured to move in a vertical direction, the sample supply instrument is disposed on the horizontal mesa of the moving stage, and the sample capillary is positioned vertically above the moving stage.
5. A pulsed electrospray ion source according to claim 1 or claim 2, wherein the movement means comprises a capillary movement means, the sample injection capillary being fixed to the capillary movement means, the capillary being moved by the capillary movement means during sample injection to move intermittently relative to the sample supply.
6. The pulsed electrospray ion source of claim 5, wherein said capillary movement device is a capillary elevation device, said sample supply means is horizontally disposed, said capillary elevation device controls elevation movement of said sample introduction capillary relative to said sample supply means.
7. The pulsed electrospray ion source according to any of claims 1 to 6, characterized in that the output end of the sample capillary is connected to a low pressure chamber, the low pressure chamber being a low pressure chamber of a mass spectrometer or a sealed low pressure chamber additionally arranged between the output end of the sample capillary and the sample inlet of the mass spectrometer, preferably the low pressure chamber has a gas pressure of 10-4-105Pa。
8. The pulsed electrospray ion source according to any of claims 1 to 7, preferably further comprising a carrier gas passage through which the sample capillary passes, an outlet of the carrier gas passage extending to an output end of the sample capillary, more preferably controlling carrier gas to have consistent pulse timing with sample injection; preferably, the inner diameter of the sample capillary is 10-150 μm, and the outer surface is coated with a polyamide coating.
9. A pulsed electrospray injection method using the pulsed electrospray ion source of any of claims 1 to 8, the method comprising: when advancing the appearance, according to the pulse time sequence of setting for, through the mobile device makes sample supply utensil with advance the relative movement of the intermittent type nature that the kind capillary takes place, make sample in the sample supply utensil intermittently with advance the kind end contact of kind capillary, sample solution passes through advance the kind end entering of kind capillary advance kind capillary, and follow advance the output of kind capillary, simultaneously, through the electrode pair sample solution carries out contact or non-contact's power-up, makes sample solution be in advance the output of kind capillary and form the electrospray, realizes pulsed electrospray and advances the appearance from this.
10. A mass spectrometry detection system comprising an electrospray ion source and a mass spectrometer, wherein the electrospray ion source is a pulsed electrospray ion source according to any of claims 1 to 8.
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CN112420482A (en) * | 2020-11-12 | 2021-02-26 | 清华大学深圳国际研究生院 | Pulse sample introduction device and method |
WO2021143078A1 (en) * | 2020-01-17 | 2021-07-22 | 清华大学深圳国际研究生院 | Pulse electrospray ion source, pulse sample injection method, and mass spectrum detection system |
CN113421815A (en) * | 2021-06-18 | 2021-09-21 | 广东联捷生物科技有限公司 | Vacuum electrospray ion source assembly and electrospray method |
CN114792620A (en) * | 2022-04-11 | 2022-07-26 | 中国科学院化学研究所 | Electrospray mass spectrometry device and electrospray method |
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WO2021143078A1 (en) * | 2020-01-17 | 2021-07-22 | 清华大学深圳国际研究生院 | Pulse electrospray ion source, pulse sample injection method, and mass spectrum detection system |
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CN112420482B (en) * | 2020-11-12 | 2022-05-17 | 清华大学深圳国际研究生院 | Pulse sample introduction device and method |
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