CN212967603U - Micro-spray ionization device - Google Patents

Abstract

The utility model discloses a trace spray ionization device, which comprises a sealed shell, a sample introducing mechanism, a spray needle, a high-voltage connecting mechanism and a reflection electron microscope; the sealed shell is hermetically connected with the inlet end of the mass spectrometer, a sealed cavity is formed in the sealed shell, the sample introducing mechanism is hermetically arranged in the sealed shell, and one end of the sample introducing mechanism is connected with the sample input pipeline; the spray needle is arranged on the sample introducing mechanism, an included angle between the spray needle and the central line of the inlet of the mass spectrometer is 0-90 degrees, the distance between the needle point of the spray needle and the inlet of the mass spectrometer is 2-30 mm, and the high-voltage connecting mechanism is electrically connected with the spray needle and the power supply respectively; the reflection electron microscope is arranged in the sealed cavity and is opposite to the inlet of the mass spectrometer, and the reflection electron microscope is electrically connected with an external adjustable power supply. The micro-spray ionization device has the advantages that the atomization efficiency is greatly improved, 100% of ions can be collected, the determination sensitivity is greatly improved, and the micro-spray ionization device is particularly suitable for micro-spray with the flow rate of less than 10 microliters/minute.

Description

Micro-spray ionization device

Technical Field

The utility model relates to a liquid mass spectrometry ion source technical field especially relates to a trace spraying ionization device.

Background

A mass spectrometer is an instrument for generating, separating and detecting charged particles, and is the most advanced instrument in the field of modern chemical analysis. In the process of mass spectrometry, a sample is firstly ionized in an ion source, generated ions and neutral molecules are mutually separated under the cross action of an electromagnetic field and a gravity field, ions with different masses enter a high vacuum cavity and are separated according to the mass under the action of the electromagnetic field, and the separated ions are finally detected by a charged particle detection device one by one.

At present, the ion source most commonly used in liquid phase mass spectrometry is an electrospray ion source, ionization reaction is performed under normal pressure, ion separation is performed in vacuum, and ions enter high vacuum from normal pressure and undergo a collection process, so that ionization efficiency and collection efficiency are two most critical indexes of the ion source and are the most main factors determining the sensitivity of a mass spectrometer.

The ionization efficiency of an electrospray ion source is directly related to the atomization efficiency, and under a given voltage condition, the smaller the volume of liquid atomized per unit time, the higher the atomization efficiency, and the higher the ionization efficiency. Therefore, from the viewpoint of improving the sensitivity of the mass spectrometer, the atomization efficiency is inevitably improved by the micro or ultra-micro spraying, and the sensitivity of the mass spectrometry is greatly improved. Based on this fact, many types of micro-spray ion sources are currently available, such as nano-spray ion sources, DART ion sources, in situ ionization ion sources, paper spray ion sources, glow discharge ion sources, and the like.

The nano-spray ion source is formed by using a capillary tube with an inner diameter of dozens of microns and a very fine tip to be close to and directly face an inlet of a mass spectrometer, spraying is carried out under the driving of 1-2 KV direct current voltage, and the nano-spray ion source is commonly used for analyzing biomacromolecules (such as protein). Because the spray is very close to the mass spectrum inlet, the spray voltage cannot be too high, otherwise, breakdown short circuit is easy to generate; the voltage is not high, and the optimal spraying efficiency is difficult to obtain; if the spray capillary is pulled away from the mass spectrometer inlet, the collection efficiency is again affected. There is also a nano-spray ion source on the market, in which a spray needle is directly inserted into an inlet capillary of a mass spectrometer for spraying, and the collection efficiency of the ion source reaches the limit, namely full collection, but the spray space is extremely small, and the atomization efficiency does not reach the ideal state. However, other various trace spray ion sources cannot achieve the effect of full collection no matter the spraying efficiency is.

Therefore, it is necessary to provide a micro-spray ionization device capable of achieving 100% collection efficiency while ensuring sufficient atomization, so as to solve the above problems.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide a can guarantee abundant atomizing, can realize 100% collection efficiency's trace spraying ionization device again.

In order to achieve the above purpose, the technical scheme of the utility model is that: the micro-spray ionization device is correspondingly connected with a mass spectrometer and comprises a sealed shell, a sample introducing mechanism, a spray needle, a high-voltage connecting mechanism and a reflection electron microscope; the sealed shell is hermetically connected with the inlet end of the mass spectrometer, a sealed cavity is formed inside the sealed shell, and the sealed cavity is communicated with the inlet of the mass spectrometer; the sample introducing mechanism is hermetically arranged in the sealed shell, and one end of the sample introducing mechanism is connected with the sample input pipeline; the spray needle is arranged on the sample introducing mechanism and is communicated with the sample pipeline, the spray needle extends into the sealed cavity, an included angle between the spray needle and the center line of the inlet of the mass spectrometer ranges from 0 degree to 90 degrees, the distance between the needle point of the spray needle and the inlet of the mass spectrometer ranges from 2 mm to 30mm, and the inner diameter of the spray needle ranges from 20mm to 200 mm; the high-voltage connecting mechanism is respectively and electrically connected with the spray needle and the power supply and is used for providing spray voltage for the spray needle; the reflection electron microscope is arranged in the sealed cavity and is opposite to the inlet of the mass spectrometer, and the reflection electron microscope is electrically connected with an external adjustable power supply.

Preferably, the reflective electron microscope is made of a metal material, the surface of the reflective electron microscope, which faces the inlet of the mass spectrometer, is of a smooth plane or spherical structure, the size of the reflective electron microscope is larger than that of an atomization cloud formed by the spray needle, and the reflective electron microscope pushes the ions of the object to be measured in the atomization cloud into the inlet of the mass spectrometer, so that the ions to be measured are all collected by the mass spectrometer, and the collection efficiency is improved.

Preferably, the sealing shell is made of metal, nonmetal or a combination of the metal and the nonmetal, which can endure the temperature of more than 300 ℃ for a long time, and the volume of the sealing cavity is larger than or equal to the volume of the atomization cloud formed by the atomizing needle.

Preferably, the volume of the sealed cavity is larger than or equal to the volume of an ellipsoidal atomized cloud formed by the spray needle, wherein the major axis of the ellipsoidal atomized cloud is 5-30 mm, and the minor axis of the ellipsoidal atomized cloud is 5-20 mm.

Preferably, the sample introducing mechanism is provided with a sealing slide way, the spray needle is slidably mounted in the sealing slide way, and the distance between the spray needle and the inlet of the mass spectrometer can be adjusted when the spray needle slides, so that the efficiency of collecting ions generated by spray ionization by the mass spectrometer is optimized.

Preferably, the high voltage connection mechanism comprises a high voltage lead and a connector connected with the high voltage lead, and the connector is arranged in the sealed shell in a penetrating mode and is in contact with the spray needle or the sample solution in the spray needle.

Preferably, trace spraying ionization device still includes ultrasonic vibration device, and it is including locating piezoelectric transducer in the sealed intracavity and locating sealed intracavity's supersonic generator, the spraying needle zonulae occludens in piezoelectric transducer, just the axial of spraying needle with piezoelectric transducer's vibration direction is mutually perpendicular, ultrasonic oscillation that supersonic generator produced is carried to piezoelectric transducer produces mechanical vibration in order to drive it and drive the spraying needle resonance, and then makes spraying needle itself become ultrasonic resonance pole, transmits ultrasonic vibration to the needle point of spraying needle to improve the efficiency of sample solution atomizing on the needle point by a wide margin.

Preferably, the trace spray ionization device further comprises a heating mechanism arranged in the sealing cavity, and the heating mechanism is arranged at the periphery of an atomization cloud formed by the spray needle to heat the atomization cloud so as to improve atomization and ionization efficiency.

Preferably, the heating mechanism comprises an infrared coating uniformly coated on the inner wall of the sealed cavity and two electrodes respectively contacted with the infrared coating, the electrodes are electrically connected to a power supply, when the infrared coating is electrified, infrared radiation is generated to heat an atomization cloud formed by the spray needle, as the temperature rises, a solvent of liquid beads in the atomization cloud is accelerated to volatilize, so that the liquid beads are rapidly reduced, the thinned fog beads are subjected to coulomb explosion to generate ions, the coulomb explosion is accelerated, the ionization efficiency of a substance to be detected can be improved, and the determination sensitivity is improved.

Preferably, the heating mechanism comprises an electromagnetic induction coil arranged in the sealed cavity and an electromagnetic wave generator connected with the electromagnetic induction coil, the electromagnetic induction coil is arranged outside the spray needle in a wrapping manner, and the electromagnetic wave generator is started to heat the atomization cloud formed by the spray needle by the electromagnetic induction coil so as to promote the liquid beads in the atomization cloud to be rapidly refined, so that the ionization efficiency is improved.

Compared with the prior art, the utility model discloses a trace spray ionization device, at first, its seal housing and mass spectrometer's entry end sealing connection, the sealed chamber that the inside sealed housing formed is linked together with the entry of mass spectrometer, therefore, the vacuum of mass spectrometer makes the sealed chamber of ion source form the vacuum state through its entry, is favorable to sample solution to atomize more effectively, and the sample after the atomizing can be all inhaled inside the mass spectrometer by the vacuum of mass spectrometer and be unlikely to destroy inside vacuum; secondly, the spray needle extends into the sealing cavity and forms an included angle with the central line of the inlet of the mass spectrometer, the included angle is 0-90 degrees, the distance between the needle point of the spray needle and the inlet of the mass spectrometer is 2-30 mm, the inner diameter of the spray needle is 20-200 mm, the flow of a sample is enabled to be not more than 10 microliter per minute by the spray needle, sufficient atomization can be guaranteed, the best spray effect is achieved, and ionization efficiency is improved; furthermore, by the action of the electron microscope, all ions generated in the ion source can be driven into the interior of the mass spectrometer. To sum up, the utility model discloses a trace spray ionization device 100, atomizing efficiency is 10 ~ 1000 times higher than the general liquid chromatography-mass spectrometry (LC/MS) electrospray ion source to can realize 100% ion collection, therefore make the detectivity improve by a wide margin, be particularly useful for the velocity of flow at the trace spray below 10 microlitres/minute.

Drawings

Fig. 1 is a schematic structural view of a first embodiment of the micro-spray ionization device of the present invention.

Fig. 2 is a schematic structural view of a second embodiment of the electrospray ionization device of the present invention.

Fig. 3 is a schematic structural view of a third embodiment of the micro-spray ionization device of the present invention.

Fig. 4 is a schematic structural view of a fourth embodiment of the electrospray ionization device of the present invention.

Detailed Description

Embodiments of the present invention will now be described with reference to the drawings, wherein like element numerals represent like elements throughout. The utility model provides a trace spray ionization device 100 mainly is applicable to the ionization of trace sample, is particularly useful for the trace spray that the sample velocity of flow is below 10 microlitres/minute, but does not use this as the limit.

Referring to fig. 1-4, the micro-spray ionization device 100 of the present invention includes a sealed housing 110, a sample introducing mechanism 120, a spray needle 130, a high voltage connecting mechanism 140, and a reflective electron microscope 150. The sealed housing 110 is hermetically connected to the end of the mass spectrometer 200 where the inlet 210 is located, a sealed cavity 111 is formed inside the sealed housing, the sealed cavity 111 is communicated with the inlet 210 of the mass spectrometer 200, and the volume of the sealed cavity 111 is greater than or equal to the volume of the aerosol cloud to be formed, preferably greater than the volume of the aerosol cloud to be formed. The sample introducing mechanism 120 is hermetically installed in the sealed housing 110 and has one end connected to the sample input line; the spray needle 130 is installed on the sample introducing mechanism 120 and communicated with the sample pipeline, the spray needle 130 extends into the sealed cavity 111, an included angle between the spray needle 130 and a central line P of an inlet 210 of the mass spectrometer 200 is 0-90 degrees, a distance L between a needle point of the spray needle 130 and the inlet 210 is 2-30 mm, and the inner diameter of the spray needle 130 is 20-200 mm; the high voltage connection mechanism 140 is electrically connected to the spray needle 130 and the power supply, respectively, for providing a spray voltage. The reflective electron microscope 150 is disposed in the sealed cavity 111 and faces the inlet 210 of the mass spectrometer 200, the reflective electron microscope 150 is electrically connected to an external adjustable power supply, and the reflective electron microscope 150 is used for pushing ions of an object to be measured into the inlet 210 of the mass spectrometer 200, so as to ensure that all ions to be measured are collected by the mass spectrometer 200, and improve the collection efficiency.

Referring to fig. 1 to 4, different embodiments of the micro-spray ionization device 100 of the present invention will be described in detail.

Referring initially to fig. 1, in a first embodiment of the present invention, a micro-spray ionization device 100 is sealingly connected to a mass spectrometer 200 having an inlet 210 formed in a side portion thereof. Specifically, the sealed housing 110 is sealingly connected to the side end of the mass spectrometer 200 having the inlet 210, i.e., the sealed housing 110 is located at the side of the mass spectrometer 200. The sample introducing mechanism 120 is mounted at the top of the sealed housing 110, the spray needle 130 is mounted at the sample introducing mechanism 120 and extends along the height direction of the sealed housing 110, so that the spray needle 130 and the center line P of the inlet 210 of the mass spectrometer 200 form an included angle of about 90 degrees, the distance L between the needle point of the spray needle 130 and the center line P of the inlet 210 is 2-30 mm, and the distance L between the two can be specifically optimized and adjusted according to the ionization property of the object to be measured; the sem 150 is disposed on an inner wall of the sealed chamber 111 in the width direction and faces the inlet 210 of the mass spectrometer 200.

In this embodiment, the external shape of the sealing housing 110 is not particularly limited, and may be a square circle or other shapes, so as to be good for aesthetic appearance and convenient for assembling and disassembling operations. The shape of the sealed cavity 111 of the sealed housing 110 is not limited in particular, and may be cylindrical, square, funnel-shaped or any other shape as long as it is enough to allow the spray needle 130 extending into the sealed cavity 111 to sufficiently spray the sample solution, that is, the formed atomized cloud does not touch the inner wall of the sealed cavity 111, and the volume of the sealed cavity 111 needs to be slightly larger than the volume of the atomized cloud. In this embodiment, the spray needle 130 is in the form of an ellipsoidal cloud, and the dimensions of the ellipsoidal cloud are generally 5-30 mm long axis and 5-20 mm short axis, so the volume of the sealed cavity 111 needs to be slightly larger than or equal to the volume of the ellipsoidal cloud with 5-30 mm long axis and 5-20 mm short axis.

The sealing case 110 is made of a material that can withstand a temperature of 300 ℃ or higher for a long period of time, for example, a metal, quartz, glass, polytetrafluoroethylene, PEEK, PTFE, or the like, but not limited thereto, and may be made of other metal, nonmetal, or a combination thereof that can withstand a temperature of 300 ℃ or higher for a long period of time.

With continued reference to fig. 1, at least one sample introducing mechanism 120 is provided, the connection between each sample introducing mechanism 120 and the sealed housing 110 needs to ensure air tightness, and each sample introducing mechanism 120 at least comprises an inner interface 121, the opening of the inner interface 121 faces to the inside of the sealed cavity 111, the inner interface 121 is used for connecting the spray needle 130 and communicating the spray needle 130 with the sample pipeline, and the inner interface 121 can be a perforation directly arranged on the sealed housing 110 and just allowing the spray needle 130 to penetrate, or can be a connector with a pipeline. Further, the sample introducing mechanism 120 may further comprise at least one external interface 122, wherein the external interface 122 is used for interfacing with the sample line and the auxiliary fluid line, and in this case, the sample introducing mechanism 120 may be, but is not limited to, a two-way, three-way, or multi-way connector.

In this embodiment, the sample introducing mechanism 120 includes an inner interface 121 and an outer interface 122, wherein the outer interface 122 is connected to the sample line, and the inner interface 121 is installed with the spray needle 130.

More preferably, the sample introduction mechanism 120 may further comprise a sealing slide in which the spray needle 130 is slidably mounted, wherein the distance between the spray needle 130 and the inlet 210 of the mass spectrometer 200 can be adjusted when the spray needle slides in the sealing slide, thereby optimizing the efficiency of collection of ions generated by spray ionization by the mass spectrometer 200.

With continued reference to fig. 1, the spray needle 130 of the present invention may be a hollow needle or a solid needle for transmitting a high voltage to the sample solution and transmitting the sample solution to the needle tip to be atomized under the high voltage. In this embodiment, the spray needle 130 is a metal capillary with an inner diameter of 20-200 μm, which is required to ensure smooth flow of the sample solution and the spraying effect.

As shown in fig. 1, in the present embodiment, the high voltage connection mechanism 140 includes a connector 141 and a high voltage wire 142 connected thereto, the connector 141 is disposed in a bore hole formed in the sealing housing 110 and contacts with the spray needle 130 or the sample solution in the spray needle 130, and the high voltage wire 142 is electrically connected to a power source. The voltage applied to the spray needle 130 by the high voltage connection mechanism 140 is between 1 kV and 8kV, preferably 2kV to 6 kV. It should be noted that, for the metal spray needle 130, the high voltage connection mechanism 140 may only include the high voltage wire 142, and be directly connected to any portion of the metal spray needle 130 except the needle tip through the high voltage wire 142, thereby simplifying the structure of the high voltage connection mechanism 140.

Referring again to fig. 1, the sem 150 is made of a metal material and may have a square, circular or other shape, the size of the sem 150 is large enough to cover the size of the cloud of atomized mist formed by the atomizing needle 130, in this embodiment, the size of the sem 150 is large enough to cover an ellipse with a major axis of 5-30 mm, the minimum allowable size is determined according to the amount of atomized mist (i.e., the size of the cloud of atomized mist), meanwhile, the surface of the sem 150 facing the inlet 210 of the mass spectrometer 200 is a smooth spherical structure, and the sem 150 is recessed away from the inlet 210; the sem 150 is connected to an adjustable voltage, the voltage is continuously adjustable, and the polarity (i.e., positive and negative) is consistent with the polarity of the ions to be detected, for example, by applying a dc voltage consistent with the polarity of the ions to be detected to the sem 150 and adjusting the voltage, the ions to be detected in the atomized cloud can be pushed into the inlet 210 of the mass spectrometer 200, so as to ensure that all the ions to be detected are collected by the mass spectrometer 200.

Understandably, the surface of the sem 150 facing the inlet 210 of the mass spectrometer 200 is not limited to a spherical surface, but may be provided as a plane or other structure.

Referring to fig. 1 again, in the micro spray ionization device 100 of the present invention, since the sealed cavity 111 forms a sealed butt joint with the inlet 210 of the mass spectrometer 200, the vacuum of the mass spectrometer 200 makes the inside of the sealed cavity 111 in a vacuum state and a negative pressure state through the inlet 210; when the spray needle 130 introduces the sample solution into the sealed cavity 111 at a flow rate lower than 10 microliters/minute, under the action of high voltage, the sample solution forms a charged atomized cloud at the needle tip of the spray needle 130, the substance to be detected in the sample solution is ionized along with continuous coulomb explosion of liquid beads in the charged atomized cloud, all generated ions are sucked into the mass spectrometer 200 by the vacuum of the mass spectrometer 200 without damaging the vacuum degree in the mass spectrometer 200, and in addition, under the action of the reflective electron microscope 150 facing the inlet 210, all ions generated in the ion source can be driven into the mass spectrometer 200, so that 100% ion collection is realized, and the measurement sensitivity is greatly improved.

Referring to fig. 2, in the second embodiment of the micro-spray ionization device 100 of the present invention, the difference from the first embodiment is only: the ultrasonic vibration device 160 is connected with the spray needle 130 in the sealed cavity 111, and has the characteristics of high frequency, short wavelength, no serious diffraction and good directionality, so that the motion path of ions is not easily influenced, and when sound is transmitted in the air, particles in the air are pushed to vibrate in a reciprocating manner to do work on the particles; and the ultrasonic frequency is high, the energy is big, can produce apparent heat effect when being absorbed by the medium, plays the effect of auxiliary heat simultaneously, consequently, makes spray needle 130 itself become ultrasonic resonance pole in this embodiment, transmits ultrasonic vibration to its needle point, can improve sample solution atomizing and the ionization's efficiency on the needle point by a wide margin.

More specifically, the ultrasonic vibration device 160 includes a piezoelectric transducer 161 disposed in the sealed cavity 111 and an ultrasonic generator 162 disposed outside the sealed cavity 111, the piezoelectric transducer 161 is connected to the inner wall of the sealed cavity 111, the spray needle 130 is tightly connected to the piezoelectric transducer 161, the axial direction of the spray needle 130 is perpendicular to the vibration direction of the piezoelectric transducer 161, a layer of hard insulating material (not numbered, as shown in fig. 2) is further disposed between the spray needle 130 and the piezoelectric transducer 161, an ultrasonic generator 162 is connected to the piezoelectric transducer 161, when the ultrasonic wave generated by the ultrasonic generator 162 is transmitted to the piezoelectric transducer 161, the piezoelectric transducer 161 can be driven to generate mechanical vibration to drive the spray needle 130 to resonate, further, the spray needle 130 itself is made to be an ultrasonic resonance rod, and ultrasonic vibration is transmitted to the needle tip of the spray needle 130, thereby greatly improving the efficiency of sample solution atomization on the needle tip.

The piezoelectric transducer 161 may be a vibrator made of a piezoelectric ceramic sheet, a piezoelectric silicon sheet, a piezoelectric ceramic stack, or other piezoelectric materials, and is not particularly limited. In this embodiment, one or more piezoelectric ceramic stacks are used, the spray needle 130 is tightly connected to the piezoelectric ceramic stacks, the upper end of the spray needle 130 is isolated from the piezoelectric ceramic stacks by a layer of hard insulating material (see fig. 2) to be tightly combined, and the axial direction of the spray needle 130 is ensured to be perpendicular to the vibration direction of the piezoelectric ceramic stacks. Meanwhile, the piezoelectric ceramic stack is connected to an ultrasonic generator 162 with the frequency of 1.7MHz or more, after the ultrasonic vibration device 160 is started, ultrasonic vibration generated by the ultrasonic generator 162 is transmitted to the piezoelectric ceramic stack, the piezoelectric ceramic stack generates mechanical vibration, the vibration frequency of the piezoelectric ceramic stack is consistent with the output frequency of the ultrasonic generator 162, the piezoelectric ceramic stack drives the spray needle 130 to resonate, the tip part of the spray needle 130 has the maximum amplitude due to suspension, and a sample solution flowing out of the tip part is atomized by high-frequency ultrasonic vibration.

In the implementation, through the dual action of the piezoelectric transducer 161 and the high voltage on the spray needle 130, the sample solution forms the atomization cloud with charges at the needle tip of the spray needle 130, the substance to be detected in the sample solution is ionized along with the continuous coulomb explosion of the liquid beads in the atomization cloud with charges, so that the sample solution flowing to the needle tip is rapidly atomized, and the atomization efficiency is obviously improved compared with pure electrospray or other forms of atomization. It should be noted that, in the present embodiment, the case where the high voltage is directly connected to the spray needle 130 is equivalent to a composite ion source of electrospray and apci (atomic Pressure Chemical ionization).

In this embodiment, the structure, the arrangement mode, and the working principle of other parts are the same as those in the first embodiment, and are not described again.

Referring to fig. 3-4, the micro-spray ionization device 100 of the present invention may further include a heating mechanism, wherein the heating mechanism is disposed at the periphery of the atomization cloud formed by the spray needle 130 to heat the atomization cloud, so as to improve the atomization and ionization efficiencies.

Referring to fig. 3, in a third embodiment of the micro-spray ionization device 100 of the present invention, a heating mechanism 170 is further added to the second embodiment, and the heating mechanism 170 is preferably an infrared heating mechanism.

Specifically, the electrospray ionization device 100 in this embodiment is hermetically connected to the mass spectrometer 200 with the inlet 210 at the top, that is, the sealed housing 110 is hermetically connected to the top end of the mass spectrometer 200 with the inlet 210, and the sealed housing 110 is located above the mass spectrometer 200. The sample introducing mechanism 120 is mounted at the top of the sealed housing 110 and faces the inlet 210 of the mass spectrometer 200, the spray needle 130 is mounted at the sample introducing mechanism 120 and extends along the height direction of the sealed housing 110, the spray needle 130 faces the inlet 210 of the mass spectrometer 200, the axial direction of the spray needle 130 and the central line P of the inlet 210 of the mass spectrometer 200 are on the same straight line, that is, the two form an included angle of 0 °, the distance L between the tip of the spray needle 130 and the inlet 210 of the mass spectrometer 200 is 2-30 mm, in this embodiment, the distance L is specifically the distance between the tip and the end face of the inlet 210, as shown in fig. 3, of course, the distance L between the two can be specifically optimized and adjusted according to the ionization property; the reflective electron microscope 150 and the ultrasonic vibration device 160 are both installed at the top of the sealed cavity 111, and the ultrasonic vibration device 160 is located above the reflective electron microscope 150, so that the reflective electron microscope 150 faces the inlet 210 of the mass spectrometer 200, and the spray needle 130 sequentially passes through the ultrasonic vibration device 160 and the reflective electron microscope 150 and extends into the sealed cavity 111.

In this embodiment, the structure, arrangement and operation principle of the ultrasonic vibration device 160 are the same as those in the second embodiment, and the description thereof will not be repeated.

With reference to fig. 3, in this embodiment, the sealed housing 110 is made of quartz, the sealed cavity 111 is made into a cylindrical shape, the inner diameter of the sealed cavity 111 is about 45mm, the bottom end of the sealed housing 110 is hermetically and tightly connected to the inlet 210 of the mass spectrometer 200, a stainless steel disc with a diameter consistent with the inner diameter of the sealed cavity 111 is inserted into the top end of the sealed housing, the periphery of the stainless steel disc is firmly bonded to the inner wall of the sealed cavity 111 by vacuum glue, and the stainless steel is the sem 150.

More specifically, the heating mechanism 170 in this embodiment includes an infrared coating 171 uniformly coated on the inner wall of the sealed cavity 111, and two electrodes 172 contacting the infrared coating 171, the infrared coating 171 is formed by an infrared coating and has a thickness of about 0.1-0.5 mm, the electrodes 172 are externally connected to two output terminals of a 0-100V continuously adjustable ac or dc power source, 2-50V voltage is applied to the infrared coating 171 through the two electrodes 172, alternating current and direct current are not limited, infrared radiation is generated when the infrared coating 171 is electrified so as to heat atomization cloud enclosed in the infrared coating 171, the atomization cloud is radiated and heated to 50-400 ℃, as the temperature rises, a solvent of liquid beads in the atomization cloud is accelerated to volatilize, the liquid beads are rapidly reduced, the thinned liquid beads are subjected to coulomb explosion to generate ions, the coulomb explosion is accelerated, the ionization efficiency of a substance to be detected can be improved, and therefore the determination sensitivity is improved.

Referring to fig. 3 again, when the micro-spray ionization device 100 of the present embodiment works, the voltage is adjusted to 5V, at this time, the temperature in the sealed cavity 111 is about 100 ℃, the sample solution is input into the spray needle 130 from the sample pipeline above the sealed housing 110, the sample solution forms a charged atomized cloud at the needle point of the spray needle 130 under the action of high voltage, the substance to be detected in the sample solution is ionized as coulomb explosion continuously occurs to the liquid beads in the charged atomized cloud, the generated ions are not only attracted by the high voltage and the vacuum of the mass spectrometer 200, but also under the action of the reflective electron microscope 150, so as to be collected more completely, and after the infrared coating 171 is electrified, the infrared coating generates infrared radiation to heat the atomized cloud, the heating temperature can be controlled by adjusting the power supply voltage, which can reach as high as 400 ℃, so as to further improve the atomization and ionization efficiency (obtain thorough atomization and finer atomized beads), the atomization efficiency is 10-1000 times higher than that of a common Liquid chromatography Mass Spectrometer (LC/MS) electrospray ion source, so that the measurement sensitivity is greatly improved.

Referring to fig. 4, in a fourth embodiment of the micro-spray ionization device 100 of the present invention, it is different from the third embodiment only in that: the heating mechanism 170 is different, and the other parts are the same, and the description of the same parts is omitted.

In this embodiment, the heating mechanism 170 is heated by electromagnetic radiation, and includes an electromagnetic induction coil 173, two connectors 174 connected to the electromagnetic induction coil 173, and an electromagnetic wave generator electrically connected to the connectors 174, the electromagnetic induction coil 173 is disposed in the sealed cavity 111 and is spiral, the electromagnetic induction coil 173 is wrapped outside the spray needle 130, so that the electromagnetic induction coil 173 can surround the atomized cloud, the electromagnetic wave generator can generate electromagnetic waves with a frequency higher than 100kHz, the electromagnetic wave generator starts to heat the atomized cloud formed by the spray needle 130, so that the atomized cloud generates strong heat due to induction, the temperature rises rapidly, the liquid beads in the atomized cloud are refined rapidly, and coulomb explosion occurs, thereby greatly improving the ionization efficiency of the substance to be detected and improving the detection sensitivity thereof.

With the above description, in the micro spray ionization device 100 of the present invention, firstly, the sealing housing 110 is hermetically connected to the inlet 210 of the mass spectrometer 200, and the sealing cavity 111 formed inside the sealing housing 110 is communicated with the inlet 210 of the mass spectrometer 200, so that the vacuum of the mass spectrometer 200 enables the sealing cavity 111 of the ion source to form a vacuum state through the inlet 210, which is beneficial to more effectively atomizing the sample solution, and the atomized sample can be completely sucked into the mass spectrometer 200 by the vacuum of the mass spectrometer 200 without damaging the internal vacuum degree; secondly, the spray needle 130 extends into the sealing cavity 111, the included angle between the spray needle 130 and the central line P of the inlet 210 of the mass spectrometer 200 is 0-90 degrees, the distance L between the needle point of the spray needle 130 and the inlet 210 of the mass spectrometer 200 is 2-30 mm, the inner diameter of the spray needle 130 is 20-200 mm, the flow rate of a sample is enabled to be not more than 10 microlitres per minute by the spray needle 130, sufficient atomization can be guaranteed, the best spray effect is achieved, and ionization efficiency is further improved; furthermore, by the action of the electron mirror 150, all of the ions generated within the ion source may be driven into the interior of the mass spectrometer 200. To sum up, the utility model discloses a trace spray ionization device 100, atomizing efficiency is 10 ~ 1000 times higher than the Liquid chromatography Mass Spectrometer (LC/MS) electrospray ion source usually to can realize 100% ion collection, therefore make the measuring sensitivity improve greatly, be particularly useful for the flow rate at the trace spray below 10 microlitre/minute.

The structure, arrangement, operation principle, etc. of the mass spectrometer 200 according to the present invention are conventional arrangements well known to those skilled in the art, and will not be described in detail herein.

The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, therefore, the invention is not limited thereto.

Claims (10)

1. A kind of trace spray ionization device, correspond to the mass spectrometer and connect, characterized by that, comprising:

the sealed shell is hermetically connected with the inlet end of the mass spectrometer, and a sealed cavity is formed inside the sealed shell and communicated with the inlet of the mass spectrometer;

the sample introducing mechanism is hermetically arranged on the sealed shell, and one end of the sample introducing mechanism is connected with the sample input pipeline;

the spray needle is arranged on the sample introducing mechanism and is communicated with the sample pipeline, the spray needle extends into the sealing cavity, an included angle between the spray needle and the center line of the inlet of the mass spectrometer ranges from 0 degree to 90 degrees, the distance between the needle point of the spray needle and the inlet of the mass spectrometer ranges from 2 mm to 30mm, and the inner diameter of the spray needle ranges from 20mm to 200 mm;

a high voltage connection mechanism electrically connected to the spray needle and a power supply, respectively, for supplying a spray voltage to the spray needle;

and the reflection electron microscope is arranged in the sealed cavity and is opposite to the inlet of the mass spectrometer, and the reflection electron microscope is electrically connected with an external adjustable power supply.

2. The electrospray ionization device according to claim 1, wherein said sem is made of a metallic material and has a smooth planar or spherical surface facing the inlet of said mass spectrometer, said sem having a size greater than the size of the cloud of atomized mist formed by said spray needle.

3. The electrospray ionization device of claim 1, wherein said sealed housing is made of a metallic, non-metallic or combination thereof material that withstands temperatures above 300 degrees celsius for long periods of time and said sealed chamber has a volume greater than or equal to the volume of the atomized cloud formed by said spray needle.

4. The micro-spray ionization device according to claim 3, wherein the volume of the sealed chamber is larger than or equal to the volume of the ellipsoidal atomized cloud having a major axis of 5 to 30mm and a minor axis of 5 to 20mm formed by the spray needle.

5. The electrospray ionization device according to claim 1, wherein said sample introduction mechanism is provided with a sealing slide, said spray needle being slidably mounted in said sealing slide, said spray needle being slidable to adjust the distance between its inlet relative to said mass spectrometer.

6. The electrospray ionization device according to claim 1, wherein said high voltage connection means comprises a high voltage wire and a connector connected thereto, said connector being inserted into said sealed housing and contacting said spray needle or the sample solution therein.

7. The micro-spray ionization device as claimed in claim 1, further comprising an ultrasonic vibration device including a piezoelectric transducer disposed in the sealing chamber and an ultrasonic generator disposed outside the sealing chamber, wherein the spray needle is closely connected to the piezoelectric transducer, and the axial direction of the spray needle is perpendicular to the vibration direction of the piezoelectric transducer, and the ultrasonic oscillation generated by the ultrasonic generator is transmitted to the piezoelectric transducer to drive the piezoelectric transducer to generate mechanical vibration to drive the spray needle to resonate.

8. The electrospray ionization device according to claim 1 or 7, further comprising a heating mechanism disposed within said sealed chamber, said heating mechanism surrounding the periphery of the cloud formed by said spray needles to heat said cloud.

9. The electrospray ionization device according to claim 8, wherein said heating mechanism comprises an infrared coating uniformly applied to the inner wall of said sealed chamber and two electrodes in contact with said infrared coating, respectively, said electrodes being electrically connected to a power supply, said infrared coating generating infrared radiation when energized to heat the atomized cloud formed by said spray needle.

10. The electrospray ionization device according to claim 8, wherein said heating mechanism comprises an electromagnetic coil disposed in said sealed chamber and an electromagnetic wave generator connected to said electromagnetic coil, said electromagnetic coil is disposed outside said spray needle, and said electromagnetic wave generator is activated to heat the atomized cloud formed by said spray needle by said electromagnetic coil.

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