CN111024804A - A chip-based sheath gas-assisted nano-electrospray mass spectrometry ion source system and method - Google Patents
A chip-based sheath gas-assisted nano-electrospray mass spectrometry ion source system and method Download PDFInfo
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- CN111024804A CN111024804A CN201911319854.5A CN201911319854A CN111024804A CN 111024804 A CN111024804 A CN 111024804A CN 201911319854 A CN201911319854 A CN 201911319854A CN 111024804 A CN111024804 A CN 111024804A
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- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
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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
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Abstract
一种基于芯片的鞘气辅助纳升电喷雾质谱离子源系统及方法，涉及检测分析技术领域，包括：弹性石英毛细管、鞘气辅助装置、等内径镀铬金导电喷针、有机玻璃芯片系统。将弹性石英毛细管尖端进行刻蚀制得等内径锥形尖端，采用低温磁控溅射的方法在其表面镀铬金导电层，制得可导电的等内径毛细管喷针，将喷针与有机玻璃芯片配合使用，且该芯片集成了鞘气辅助模块和高电压加电模块。本发明的装置除具有结构简单，容易搭建，不需要高流速的载气，无需加热且离子化过程可在大气压下实现等优点外，实现了微升及纳升流速下的灵敏度高信号稳定的质谱检测，从而弥补了传统大流速电喷雾与常规纳升级电喷雾技术的覆盖薄弱区，完善了电喷雾技术的应用范围。A chip-based sheath gas-assisted nanoliter electrospray mass spectrometry ion source system and method relates to the technical field of detection and analysis, including: elastic quartz capillary, sheath gas auxiliary device, equal inner diameter chrome-plated gold conductive spray needle, and plexiglass chip system. The tip of the elastic quartz capillary is etched to obtain a tapered tip of equal inner diameter, and a chrome-gold conductive layer is plated on its surface by low-temperature magnetron sputtering to obtain a conductive equal-inner diameter capillary spray needle. Used together, the chip integrates a sheath gas auxiliary module and a high-voltage power-on module. The device of the invention has the advantages of simple structure, easy construction, no need for a carrier gas with high flow rate, no need for heating, and the ionization process can be realized under atmospheric pressure, etc., and realizes high sensitivity and stable signal at microliter and nanoliter flow rates. Mass spectrometry detection, thus making up for the weak coverage of traditional high-flow electrospray and conventional nano-scale electrospray technology, and improving the application range of electrospray technology.
Description
Technical Field
The invention relates to a sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system and method based on a chip, and belongs to the field of micromachining and mass spectrometry.
Background
In the 60's of the 20 th century, Dole et al realized the use of electrospray coupled with mass spectrometry for the first time in a real sense. In the 90 s of the 20 th century, electrospray ionization (ESI) and mass spectrometry technologies were developed and widely used in the field of instrument manufacture and practical application, and commercial electrospray ion sources were widely deployed on mass spectrometers of various types.
Electrospray ionization is one of the ionization methods widely used in organic mass spectrometry instruments, and has been increasingly used for complicated biological sample analysis because of its good soft ionization performance and multi-charge ionization characteristics, and the development of electrospray technology is roughly divided into two directions: one direction is to combine with liquid phase, and seek to ensure good concentration response and stability of spraying system in large dynamic range of flow rate (several milliliters to tens of microliters), for which means of promoting ionization such as sheath gas auxiliary gas, heating, ultrasound, etc. are introduced in the spraying process, such electrospray process generally does not consider sample economy (in fact, sample supply is often excessive), sample consumption is large, ionization efficiency is limited and is not suitable for spraying process of microliter and nanoliter flow rate; the other direction is a liquid-phase-independent nano-liter electrospray technology, which focuses on the rapid analysis of precious samples, focuses more on the economy and detection sensitivity of the samples, and realizes an electrospray process with nano-liter or even pico-liter flow rate by further reducing the caliber of a mass spectrum spray needle, so that the problem of difficult solvent gasification does not exist at the small flow rate, and therefore, sheath gas and auxiliary gas are omitted from the spraying device. However, the self-contained sample delivery method and the 'pure' electrostatic spraying process without the assistance of sheath airflow are easily affected by the external environment, the stability of mass spectrum signals is greatly reduced, and the method cannot be applied to the electrospray process with micro-upgrading flow rate. In summary, neither the conventional electrospray by liquid mass spectrometry nor the nanoliter electrospray by direct sampling can simultaneously realize the electrospray mass spectrometry detection with high stability, high sample utilization rate and high sensitivity in the flow velocity range of a few microliters to a few tens of nanoliters, which becomes an application weak area of the electrospray technique. However, in the trend of precise and intensive analytical chemistry, especially in recent years driven by the development of microfluidic technology, many separation analysis and detection systems that originally operate at high flow rates are gradually moving into the weak area. Therefore, it is necessary to develop an electrospray system and method to overcome the shortcomings of conventional electrospray and nanoliter electrospray techniques at flow rates of several microliters to several tens of nanoliters and to improve the application range of electrospray techniques. The commercial electrospray ion source has a large volume and a high price, and the microfluidic chip has the advantages of miniaturization, integration, automation, portability and the like, has the functions of integrating a plurality of units such as a conventional ionization source, has the advantages of simple structure and low cost, and is more and more concerned by various circles.
The ion source system not only inherits the advantages of stable conventional electrospray signal and highly controllable ionization process, but also inherits the characteristics of simple structure, less sample consumption and high sensitivity of the traditional nano-liter electrospray, further improves the stability, controllability and intensive cheapness of the system by taking a chip as an integrated carrier of the system, and realizes high stability, high sample utilization rate and high sensitivity of the electrospray process at microliter to dozens of nano-liter flow rates, thereby further perfecting the electrospray technology, and having important significance for the development of the mass spectrum analysis field.
Disclosure of Invention
The invention constructs a sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system and method based on a chip, and realizes high stability, high sample utilization rate and high sensitivity of an electrospray process at a flow rate of microliter to dozens of nanoliters.
In order to realize the purpose, the invention adopts the technical scheme that: the utility model provides a sheath gas assists nanoliter electrospray mass spectrometry ion source system based on chip which characterized in that: comprises a conductive equal-inner-diameter capillary spray needle (2), an organic glass chip (4) and a sheath gas auxiliary device (5);
the conductive equal-inner-diameter capillary spray needle (2) is prepared by etching one end of an equal-inner-diameter elastic quartz capillary into a tip from the outer surface and then preparing a conductive layer on the surface of the end; the axial direction of the conductive equal-inner-diameter capillary spray needle (2) is recorded as the horizontal direction, a capillary spray needle micro-channel which is horizontally communicated from left to right is arranged in the organic glass chip (4), and a nitrogen gathering and conveying channel is also arranged at the same time, one end of the nitrogen gathering and conveying channel is communicated with the capillary spray needle micro-channel, and the other end of the nitrogen gathering and conveying channel is communicated with the outside of the organic glass chip (4); the tip end of the capillary spray needle (2) with the equal inner diameter penetrates through the organic glass chip (4) to reach a sample inlet of a mass spectrometer, the axis of the capillary spray needle (2) with the equal inner diameter and the axis of the sample inlet of the mass spectrometer are positioned on the same straight line, the inner diameter of a micro channel of the capillary spray needle is larger than the outer diameter of the capillary spray needle (2) with the equal inner diameter, and gaps are reserved around the capillary spray needle (2) with the equal inner diameter when the capillary spray needle (2) is in the micro channel of the capillary spray needle; the surface of the organic glass chip (4) through which the tip of the capillary spray needle (2) with the same inner diameter penetrates is marked as a front end surface, and the opposite surface is a rear end surface; a gasket (3) is arranged on the rear end face of the organic glass chip (4) and used for fixing the spray needle and a high-voltage power supply lead, the high-voltage power supply lead is connected with a conductive layer of the capillary spray needle (2) with the same inner diameter, and ionization of a sample at the needle point of the spray needle is realized by applying high voltage; the sheath gas auxiliary device (5) comprises a nitrogen conveying pipe, the nitrogen conveying pipe extends into the nitrogen gathering conveying channel, and the nitrogen gathering conveying channel and the outer surface of the nitrogen conveying pipe are sealed by a sealing material, so that nitrogen can be sprayed out from the periphery of the outer side surface of the tip of the capillary spray needle (2) with the same inner diameter as the front end surface of the organic glass chip (4), and the desolvation and ionization efficiency of a sample is improved; the other end of the capillary spray needle (2) with the same inner diameter is connected with a liquid chromatogram sample injection device (1) bearing a sample to be tested.
According to the conductive equal-inner-diameter capillary spray needle (2) prepared in the invention, the taper length of the tip of the spray needle is 1-10 mm, the outer diameter of the taper tip is 5-360 microns, the inner diameter is 1-50 microns, the thickness of the conductive layer is 1-10 microns, the length of the covered section of the conductive layer is 4-8 cm, the length of an organic glass chip is 2-4 cm, the width of the organic glass chip is 1-1.5 cm, and the thickness of the organic glass chip is 0.5-1.1 cm, wherein the diameter of a micro-channel of the capillary spray needle is 0.1-0.3 cm, the length of the micro-channel is 0.5-1 cm (consistent with the thickness direction), the diameter of a nitrogen gathering and conveying channel is 0.1-0.3 cm, and the length.
The method comprises the steps of etching the elastic quartz capillary tip by hydrofluoric acid to form an equal-inner-diameter conical tip, performing chrome plating on the surface of the elastic quartz capillary tip by adopting a low-temperature magnetron sputtering method, forming a conductive equal-inner-diameter capillary spray needle (2), matching the spray needle with an organic glass chip for use, namely preparing a penetrating capillary spray needle micro-channel in the organic glass chip (4) in a punching mode, avoiding direct contact between a sample and the organic glass surface by unique structural design, reducing sample pollution, integrating a sheath gas auxiliary module and a high-voltage power-up module on the chip, and realizing integration and miniaturization of an ion source device.
The preparation method comprises the following steps:
s1, preparation of equal-diameter capillary (2): intercepting a section of elastic quartz capillary tube with the length of about 30-60 cm and the inner diameter of 1-50 mu m, and preparing a tip with the same inner diameter by using a hydrofluoric acid etching method;
s2, plating a conductive gold layer on the surface of the tip: after the surface treatment of the plasma cleaning instrument, the equal-inner-diameter tip obtained in the step S1 is placed in a film plating machine, chromium plating and gold particles are plated on the surface of the equal-inner-diameter tip by adopting a low-temperature magnetron sputtering method to form a conductive layer, and a conductive equal-inner-diameter nano-scale spray needle is prepared;
s3, preparing an organic glass chip: intercepting an organic glass with the length of 2-4 cm, the width of 1-1.5 cm and the thickness of 0.5-1 cm, and preparing two micro channels by utilizing a drilling mode of a drill bit, wherein the two micro channels respectively correspond to a capillary needle micro channel and a nitrogen gathering and conveying channel; inserting the front end of a nitrogen conveying pipe connected with a nitrogen bottle into a nitrogen gathering channel on a chip in a length of 0.3-0.4 cm, sealing an interface by using epoxy glue, inserting the tip end of a capillary into a capillary needle micro-channel, connecting a lead and fixing the position by using a gasket.
And S2, performing surface treatment on the prepared equal-inner-diameter tip by using a plasma cleaner, wherein the surface treatment is mainly used for performing surface treatment on the tip of the capillary tube to enhance the adhesion of the chromium layer on the surface.
The rear end of the conductive equal-inner-diameter capillary needle (2) is connected with the liquid chromatogram (1), so that a direct sample introduction mode under constant-current hydraulic drive is realized, and volume and flow rate controllable operation is realized on a sample to be introduced through regulation and control of a driving force.
The method comprises the steps of plating a nanoscale metal chromium layer on the surface of the quartz capillary tube by using a low-temperature magnetron sputtering method, plating a micron gold conductive layer on the surface of the quartz capillary tube, wherein the chromium layer serves as a connecting layer of the quartz capillary tube and the gold layer, so that the mechanical strength and the adhesive force of the plating layer are improved, and the service life of a spray needle is prolonged.
The gasket (3) is made of polytetrafluoroethylene, and the safety of the experiment is guaranteed while the probe and the high-voltage power supply lead are fixed.
And a nitrogen gathering and gas conveying channel of the sheath gas auxiliary device (5) surrounds the periphery of the spray needle, so that the desolvation efficiency of the sample is improved.
A penetrating capillary needle-spraying micro-channel is prepared in the organic glass chip (4) in a punching mode, so that direct contact between a sample and the surface of organic glass is avoided, and sample pollution is reduced.
The organic glass chip (4) realizes the integration of a capillary spray needle, a sheath gas auxiliary module and a high-voltage power-up module.
The method for ionizing by using the chip-based sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system comprises the following steps of: (1) inserting the conductive equal-inner-diameter capillary spray needle (2) into a capillary spray needle micro-channel, and enabling the tip of the conductive equal-inner-diameter capillary spray needle (2) and a sample inlet of a mass spectrometer to be positioned on the same straight line; (2) placing a solution to be detected into a liquid chromatogram sample introduction device (1), and introducing the solution to the tip of a conductive equal-inner-diameter capillary needle (2) through a capillary under the hydraulic drive; (3) and applying direct current voltage to the surface of the conductive equal-inner-diameter capillary spray needle (2) through a lead to ionize the sample to be tested, forming an ion beam to enter a mass spectrometer, namely completing the ionization process of the sample to be tested in one nanoliter electrospray spray needle, and continuously providing nitrogen gas by a sheath gas auxiliary device (5) in the process.
Due to the adoption of the technical scheme, the invention has the following advantages:
(1) the injection end of the prepared equal-inner-diameter mass spectrum spray needle has the same inner diameter with the tip of the spray needle, so that the blockage condition of the tip of the spray needle can be effectively reduced, and the service life of the spray needle is prolonged;
(2) the tail end of the capillary spray needle with the equal inner diameter is connected with a liquid chromatogram, a direct sample introduction mode under constant-current hydraulic drive is realized, and volume and flow rate controllable operation is realized on a sample to be introduced through regulating and controlling a driving force;
(3) by preparing the micro-channel on the organic glass chip, the spray needle is matched with the organic glass chip for use, and the penetrating capillary spray needle micro-channel is prepared in a punching mode, the unique structural design avoids direct contact between a sample and the surface of the organic glass, and the sample pollution is reduced;
(4) the organic glass chip integrates the sheath gas auxiliary module and the high-voltage power-up module, so that the miniaturization and simplification of the ion source device are realized;
(5) the prepared sheath gas-assisted nano-spraying system can realize ionization under atmospheric pressure, does not need high-flow-rate carrier gas and does not need heating.
Drawings
FIG. 1 is a schematic diagram of a chip-based sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system of the present invention;
the device comprises a liquid chromatogram sample injection device 1, a conductive equal-inner-diameter capillary needle 2, a gasket 3, an organic glass chip 4 and a sheath gas auxiliary device 5.
FIG. 2 is a comparison graph of the intensity of detection signals of glucose solutions with gradient concentrations measured by three ion source devices (ESI, Nano-ESI are commercial ion sources, and Nano-ESI-onchip is the device of the present invention) according to an embodiment of the present invention
FIG. 3 is a graph showing the comparison of signal stability when the same amount of glucose solution is measured by using three ion source devices according to the embodiment of the present invention at 100. mu.M.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The embodiment of the invention provides a sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system and a method based on a chip, and the method is described in detail by taking an elastic quartz capillary tube with the outer diameter of 360 micrometers and the inner diameter of 25 micrometers as raw materials to prepare a conductive nanometer upgrading spray needle with the equal inner diameter and an organic glass chip with the length of 3cm, the width of 1cm and the thickness of 0.5cm as examples, and comprises the following specific implementation steps:
s1, preparation of equal-diameter capillary (2): intercepting a section of elastic quartz capillary tube with the length of about 30cm and the diameter of 25 mu m, and preparing a tip with the same inner diameter by utilizing a hydrofluoric acid etching method;
s2, plating a conductive gold layer on the surface of the tip: placing the tip with the equal inner diameter obtained in the step S1 after the surface treatment of the plasma cleaning instrument into a film plating machine, and plating a gold conducting layer on the surface of the tip by adopting a low-temperature magnetron sputtering method to prepare a conductive nano-scale spray needle;
s3, preparing an organic glass chip: intercepting a piece of organic glass with the length of 3cm, the width of 1cm and the thickness of 0.5cm, and preparing two micro-channels by utilizing a drilling mode of a drill, wherein the diameter of the micro-channel of the capillary spray needle is 0.1cm, the length of the micro-channel is 0.5cm, and the diameter of the nitrogen gathering and conveying channel is 0.1cm, and the length of the nitrogen gathering and conveying channel is 0.5 cm. Inserting the front end of a nitrogen conveying pipe connected with a nitrogen bottle into a nitrogen gathering channel on a chip in a length of 0.3-0.4 cm, sealing an interface by using epoxy glue, inserting the tip end of a capillary into a capillary needle micro-channel, connecting a lead and fixing the position by using a gasket.
The chip-based sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system prepared according to the method of the embodiment is used for detecting signals of glucose solution with gradient concentration.
S1, preparing a glucose solution with gradient concentrations of 0nM, 10nM, 100. mu.M, 10. mu.M and 1. mu.M;
s2, building a chip-based sheath gas-assisted nanoliter electrospray ionization mass spectrometry ion source system;
s3, adopting three different mass spectrum ion source devices for sample injection analysis to obtain a detection signal intensity comparison result of the glucose solution with the same sample injection amount and gradient concentration;
and S4, adopting three different mass spectrum ion source devices for sample injection analysis, and obtaining a signal stability comparison result during mass spectrum detection of 100 mu M glucose solution under the same sample injection amount.
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Cited By (6)
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| CN112863995A (en) * | 2021-01-17 | 2021-05-28 | 复旦大学 | Method for manufacturing nano-spray needle of electrospray ion source |
| CN113764255A (en) * | 2021-05-28 | 2021-12-07 | 昆山聂尔精密仪器有限公司 | An electrospray ion source device without auxiliary gas cylinder |
| CN114242541A (en) * | 2021-12-14 | 2022-03-25 | 厦门大学 | Preparation method of nano-liter electrospray spray needle |
| CN114464521A (en) * | 2022-02-17 | 2022-05-10 | 河北医科大学 | A kind of capillary needle and preparation method thereof |
| CN115360082A (en) * | 2022-09-02 | 2022-11-18 | 中国石油大学(北京) | Device for carrying out nanoliter electrospray ionization on organic inclusion and application thereof |
| CN120356819A (en) * | 2025-06-24 | 2025-07-22 | 北京理工大学 | Digital micro-fluidic-mass spectrometry online coupling ion source and online analysis method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112863995A (en) * | 2021-01-17 | 2021-05-28 | 复旦大学 | Method for manufacturing nano-spray needle of electrospray ion source |
| CN112863995B (en) * | 2021-01-17 | 2022-05-20 | 复旦大学 | Manufacturing method of nano-spray needle of electrospray ion source |
| CN113764255A (en) * | 2021-05-28 | 2021-12-07 | 昆山聂尔精密仪器有限公司 | An electrospray ion source device without auxiliary gas cylinder |
| CN114242541A (en) * | 2021-12-14 | 2022-03-25 | 厦门大学 | Preparation method of nano-liter electrospray spray needle |
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