JP2000208093A - Mass spectrometer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize analysis for a long time even if a migration compatible solvent containing non-volatile salt is used by having a vibrator for causing vibration to a needle electrode. SOLUTION: A needle electrode 22 is arranged in the vicinity of a first pore 8. A positive high voltage is applied in positive ion measurement and a negative high voltage of several kilovolt for instance is applied in negative ion measurement from power supply 53 of a high voltage. Thereby, a corona discharge is generated, and primary ions for chemical ionizing is generated. It is desirable that a needle electrode 22 is arranged in a needle electrode cover 26 to retard deposition of salt to the needle electrode 22. A supersonic wave vibrator 28 is attached on the needle electrode 22 or a needle electrode stand 25. When measurement is executed continuously for several hours, non-volatile salt is deposited in the vicinity of a front edge of the needle electrode 22. Then, vibration is applied to the needle electrode 22 with the supersonic wave vibrator 28 to peel sludge, which drops to remove. Since non-volatile salt is deposited on the needle electrode 22 is very fragile, it is possible to remove the salt by dynamics action such as vibration and the impact, etc., to cause acceleration in the needle electrode 22.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mass spectrometer, and in particular, to a liquid chromatograph / mass spectrometer combining a liquid chromatograph (hereinafter, referred to as LC) and a mass spectrometer (hereinafter, referred to as MS). Total (hereinafter, LC
/ MS).

[0002]

2. Description of the Related Art At present, in the field of analysis, it is required to establish a technique for analyzing a mixture. For example, when analyzing harmful substances in the environment, various substances are contained in a collected sample (for example, water of a lake). The same applies to the analysis of biologically relevant substances. For example, various substances are contained in biological samples such as blood and urine. Therefore, technology that can handle mixtures is indispensable for the analysis of environment-related substances and biological substances, but it is generally difficult to directly analyze a mixture.Therefore, it is necessary to detect each component after a process of separating the mixture. Means for identification are often used. Under these circumstances, LC / MS, which is an apparatus combining LC with excellent separation and MS with excellent substance identification,
Is very effective for the analysis of the above-mentioned environmental and biological substances.

Referring to FIG. 10, a basic configuration of a conventional LC / MS will be described. The liquid chromatograph 1 includes a mobile phase solvent tank 2, a liquid feed pump 3, a sample injector 4, a separation column 5, and a pipe 6 connecting them. The sample solution is injected from the sample injector 4 and is supplied by the liquid sending pump 3 together with the mobile phase solvent to the separation column
Sent to The separation column 5 is filled with a packing material. The sample solution is separated for each component in the separation column 5 by the interaction with the packing material.

[0004] The separated sample is sent to an ion source 7 and ionized. The ions generated by the ion source 7 are supplied to the first pore 8, the differential exhaust portion 10 exhausted by the exhaust system 9, and the second pore 1.
1, is introduced into the high vacuum section 13 evacuated by the exhaust system 12. In the high vacuum section 13, an ion optical system 14 for converging the ion orbit and a mass analyzer 15 for analyzing the mass of the ion (accurately, the value obtained by dividing the mass of the ion by the charge of the ion) are arranged. ing. The ions mass-analyzed by the mass analyzer 15 are detected by the detector 16,
The detected signal is sent to the data processing device 1 via the signal line 17.
8 for processing.

Although there are various types of ion sources, FIG. 10 shows an ion source based on the atmospheric pressure chemical ionization method as a typical example. The sample separated by the liquid chromatograph 1 is introduced into the spray capillary 19 together with the mobile phase solvent. The spray tube 19 is inserted into a heating block 20 heated to about 250 ° C., and the solution containing the sample is sprayed by heat. To vaporize the droplets generated by spraying, 4
A vaporization block 21 heated to about 00 ° C. is provided. In order to generate corona discharge, a needle electrode 22 is provided, and a high voltage of about 3 kV is applied. The gaseous sample generated by the vaporization of the droplets is ionized by a chemical reaction with primary ions generated by corona discharge. As a typical reaction example, a proton addition reaction from a hydronium ion is shown below.

[0006]

Embedded image H ₃ O ⁺ (H ₂ O) _n + M → (H ₂ O) _{n + 1} + MH ⁺ where M represents a sample molecule. By such a chemical reaction, a pseudo molecular ion in which a proton is added to the sample molecule is generated. Although the above reaction is a reaction that generates positive ions, a reaction that generates negative ions may be used according to the characteristics of the sample.

[0007]

In a separation operation in liquid chromatography using a detection method other than mass spectrometry (for example, ultraviolet absorption method), a mobile phase solvent containing a non-volatile salt (such as sodium phosphate) is selected. Often done. This is because the buffer capacity of the mobile phase solvent is high and the reproducibility of the separation is high.

However, in the above-mentioned conventional LC / MS, it is difficult to use a mobile phase solvent containing a hardly volatile salt. Since non-volatile salts are ionic compounds,
It is easily dissolved in a solvent and dissociated into positive and negative ions in a solution, but precipitates again as a salt when the solvent evaporates. Due to these characteristics, when a mobile phase solvent in which a non-volatile salt is dissolved is used in a mass spectrometer in which the solvent must be vaporized to generate gaseous ions, the non-volatile salt becomes an ion source or a pore. It easily precipitates in the vicinity. There are disadvantages such as precipitation of salt, instability of ionization, closure of pores, and inability to capture generated ions in a vacuum section.

Therefore, in the LC / MS analysis, a mobile phase solvent containing a volatile salt (such as ammonia acetate) which is not likely to precipitate is generally selected. That is, the measurer uses the detection method other than mass spectrometry and the LC / MS analysis,
The composition of the mobile phase solvent had to be changed.

As described above, when the composition of the mobile phase solvent changes, the separation in liquid chromatography is affected,
The retention time of each component changes. For this reason, there arises inconvenience that a database of retention times accumulated using a detection method other than mass spectrometry cannot be used for LC / MS analysis. For this reason, development of LC / MS that can use a mobile phase solvent containing a non-volatile salt has been strongly desired.

An LC / MS which can use a mobile phase solvent in which a hardly volatile salt is dissolved is disclosed in JP-A-61-952.
44 and Japanese Patent Application Laid-Open No. 8-145950 have been made, but still have the problem that the continuous operation time is limited to several hours. The cause is mainly that non-volatile salts precipitate near the tip of the needle electrode, and corona discharge becomes unstable. In recent years, in order to improve the efficiency of analysis work, use of an autosampler (automatic sample injector) connected to the LC / MS to operate continuously and unattended for a long time has been increasing. In such a situation,
It is not efficient to shut down the device every few hours to perform disassembly cleaning.

According to the present invention, even when a mobile phase solvent containing a hardly volatile salt is used, stable analysis can be performed over a long period of time.
It aims to provide C / MS.

[0013]

In the present invention, the above object is solved by an LC / MS having a mechanism for removing a salt deposited on a needle electrode.

More specifically, a sample supply tube for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply tube, and an atomizer for atomizing the sample solution. In a mass spectrometer comprising an ion source having a needle-shaped electrode for ionizing an atomized sample and a mass analyzer for analyzing ions generated by the ion source, vibration and rotation of the needle-shaped electrode, The object is attained by a mass spectrometer provided with means for giving an impact or the like, means for supplying an appropriate solvent to the tip of the needle electrode, or means for wiping the tip of the needle electrode.

[0015]

(Embodiment 1) FIG. 1 shows a mass spectrometer according to a first embodiment of the present invention, which removes non-volatile salts deposited by exerting a mechanical action on a needle electrode. FIG. Here, the mechanical action means an operation of causing acceleration of the needle electrode, such as vibration, impact, and rotation.

The solution from the liquid chromatograph is introduced into a spray capillary and sprayed. At this time, if heating and spraying are continued by the method shown in the prior art, the non-volatile salt may precipitate near the tip of the spray capillary and the spray may become unstable. In order to avoid this, it is desirable to use a spraying method such as electrostatic spraying or gas spraying that can generate fine mist without heating to a high temperature.

FIG. 1 shows an LC / MS equipped with a so-called sonic spray type spray device. The solution is introduced into a capillary 54 made of fused silica. The capillary 54 is inserted into a space partitioned by a partition 56 by a stainless steel tube 55 for holding the capillary 54. The partition 56 is provided with a gas outlet 57, and the end of the capillary 54 is held near the gas outlet 57. When a gas such as nitrogen is introduced into a space partitioned by the partition wall 56 and kept at a pressure of several atmospheres, a high-speed gas flow is generated via a gas ejection port. The solution that has reached the end of the capillary 54 is pulverized by the high-speed gas stream and sprayed as fine droplets. The vaporizing block 21 is provided with a collision plate 24, and the collision between the droplet and the collision plate 24 promotes the atomization of the droplet. The droplets are further vaporized as they pass through the heated vaporization block 21. The collision plate 24 also has the effect of precipitating some of the non-volatile salts contained in the droplets near the collision plate 24 and reducing the amount reaching the needle electrode 22 and the first pores 8.

A needle electrode 22 is disposed near the first pore 8, and a high voltage power supply 53 applies a high voltage of several kilovolts positive for positive ion measurement and negative for several kilovolts for negative ion measurement. As a result, corona discharge occurs, and primary ions for chemical ionization are generated. In order to delay the precipitation of salt on the needle electrode 22, the needle electrode 22 may be disposed in the needle electrode cover 26. The vibrator 28 is attached to the needle electrode 22 or the needle electrode base 25. As the vibrator 28, for example, an ultrasonic vibrator is used. When measurement is performed continuously for several hours, the needle electrode 22
The non-volatile salt precipitates near the tip. Therefore, the vibrator 28 applies vibration to the needle electrode 22 to exfoliate the precipitate and drop it to remove it.

The gaseous sample obtained by vaporizing the droplets is ionized by a chemical reaction with primary ions such as hydronium ions. The ions are in the first pore 8 and the differential exhaust section 1
0, introduced into the high vacuum section 13 through the second pores 11.
When the jet flows into the low pressure region through the first pores 8, the temperature of the jet decreases due to adiabatic expansion, and a so-called clustering reaction in which solvent molecules adhere to ions occurs. In order to prevent the clustering reaction, an electrode 31 with an intermediate pore, in which the intermediate
Is provided. The space between the first electrode with a fine hole 29 and the electrode with a medium fine hole 31 is exhausted through an exhaust port 32 provided in the electrode with a medium fine hole 31.

By adjusting the degree of vacuum in the space between the first electrode with a fine hole 29 and the electrode 31 with a medium fine hole, it flows into the electrode with a fine hole 31 through the first fine hole 8. This has the effect of reducing the adiabatic expansion area of the jet. It is desirable that the first electrode 29 with fine holes, the electrode 31 with intermediate fine holes, and the electrode 33 with second fine holes be heated. In order to improve the ion permeation efficiency, the power supply 34, 35, the fine pore first electrode 29, the intermediate fine electrode 31, and the second fine electrode 33 are respectively provided.
36 are connected, and a predetermined voltage is applied. High vacuum section 1
Reference numeral 3 denotes an ion optical system, a deflector, and a mass analyzer. Further, in order to prevent stray ions from reaching the detector 16, a partition plate 60 for separating the high vacuum section 13 is provided.
Is provided.

The ions converged by the Einzel lenses (37, 38, 39) constructed as the ion optical system enter the deflector case 40 and are deflected by the deflecting electrodes (41, 4).
The trajectory is deflected by the electric field generated in 2). In the deflector case 40, a so-called Q deflector composed of quadrupole electrodes may be arranged. The droplet serving as a noise source is discharged out of the deflector case 40 from the openings (43, 44).

The ions whose orbits are deflected are converged by the focusing electrode 45 and introduced into the mass analyzer. Although there are various types of mass analyzers, a configuration using a quadrupole ion trap mass analyzer will be described as a representative example. The quadrupole ion trap mass analyzer comprises a pair of end cap electrodes (46, 47) and a ring electrode.
The gate electrode 49 is provided for controlling the timing of the incidence of ions on the quadrupole ion trap mass analyzer. First, a high-frequency voltage is applied to the ring electrode 48 to generate an ion confinement potential inside the quadrupole ion trap mass analyzer. At this timing, the voltage applied to the gate electrode is adjusted so that ions can pass through the gate electrode. Helium gas supply (not shown) inside the quadrupole ion trap mass spectrometer
Helium is supplied from the reactor and maintained at a pressure of about 1 mTorr.

Ions that have entered the quadrupole ion trap mass analyzer lose energy by colliding with helium gas and are captured by the ion confinement potential. After accumulating the ions that have entered for a predetermined time (typically 50 milliseconds), the process proceeds to the stage of analyzing the mass of the ions. At this timing, the voltage applied to the gate electrode 49 is adjusted so that ions cannot pass through the gate electrode. Next, by gradually increasing the amplitude of the high-frequency voltage applied to the ring electrode 48, the orbit becomes unstable in ascending order of the value obtained by dividing the mass of the ion by the charge of the ion, and the end cap electrodes 46, 47 Is discharged out of the mass spectrometer through an opening provided in the mass spectrometer. The ejected ions are detected by the ion detector 16.

After the mass analysis is completed, the voltage applied to the ring electrode 48 is turned off to eliminate the ion confinement potential, thereby removing ions remaining inside the mass analyzer. By repeating such a series of operations, a mass spectrum of the sample substance is obtained. At the stage of analyzing the mass of the ions, a high frequency signal of a predetermined frequency may be applied between the end cap electrodes 46 and 47 to assist the ejection of the ions in order to improve the mass resolution and the like. Except for the step of analyzing the mass of ions, the ion stop electrode 5
0 to adjust the voltage applied to the detector 16
To avoid reaching.

In the sonic spray type spraying apparatus shown in FIG. 1, it is known that when the flow rate of the gas ejected from the gas ejection port 57 is increased, gaseous ions of the substance dissolved in the solution are generated. ing. It is also known that an electrostatic spray type spray device can convert a substance dissolved in a solution into gaseous ions. When a solution in which the refractory salt and the sample substance are dissolved is introduced into these spray devices, a large amount of ions derived from the refractory salt present in the solution are converted into gaseous ions. Since a voltage is applied to the needle electrode 22 and the first pored electrode 29, an electric field is formed, and the trajectory of the ions is bent under the influence of the electric field. For this reason, the amount of ions derived from the non-volatile salt reaching the vicinity of the first pores 8 is reduced.

Therefore, the use of a spraying device which is also used as an ion generator can reduce the problem that salts are deposited near the first pores 8 and block the first pores 8. Since the sample material is much less concentrated than the non-volatile salts, it is not ionized very efficiently by the atomizer. Accordingly, the gas is carried to the first pore 8 and the vicinity of the needle electrode 22 by a gas flow as an electrically neutral substance, and is ionized by a chemical reaction with primary ions.

The non-volatile salt deposited on the needle electrode is very brittle. For this reason, it can be removed by exerting a mechanical action such as vibration, impact, and rotation that causes acceleration to the needle electrode.

FIG. 2 shows a mass spectrometer which removes salt precipitated by applying an impact to a needle electrode, which is another method of this embodiment. A member 65 such as a ceramic rod is caused to collide with the needle electrode 22 by a driving device 66 to give an impact. Due to this impact, the salt deposited on the needle electrode 22 peels off and falls by gravity. Since the ionic strength changes when the tip position of the needle electrode 22 changes, it is desirable to suppress the impact force to such an extent that the needle electrode 22 is not deformed. In order to easily form the driving device 66, an elastic body such as rubber or a spring may be used.

FIG. 3 shows a mass spectrometer which removes the precipitated salt by rotating a needle electrode, which is still another method of this embodiment.
The needle electrode 22 or the needle electrode base 25 is connected to a motor 67 via a rotating shaft 68. When the measurement is performed for a long time and the non-volatile salt precipitates on the needle electrode 22, the needle electrode 22 is rotated by the motor 67 to remove the salt by centrifugal force.

Although it is different from the mass spectrometer which removes the salt deposited on the needle electrode, which is the main point of the present invention, the configuration for rotating the needle electrode as shown in FIG. 3 has another advantage.
When observing in detail how the non-volatile salt precipitates on the needle electrode, it can be seen that it does not precipitate on the entire surface of the needle electrode but precipitates more in a specific direction. This is presumably because the droplet containing the non-volatile salt is carried by the influence of the air current or the electric field and adheres to the needle electrode from a specific direction. Therefore, by rotating the needle electrode from time to time and changing the place where the salt precipitates,
The time until the discharge becomes unstable due to the effect of the precipitated salt can be greatly extended. In such a usage method, the motor 67 shown in FIG. 3 is not necessarily required. The needle electrode 22 may be fixed to a rotatable needle electrode table 25, and the measurer may rotate the needle electrode 22 every several hours. The operation of rotating the needle electrode may be performed automatically by providing a needle electrode rotation mechanism.

(Embodiment 2) FIG. 4 shows a mass spectrometer according to a second embodiment of the present invention which dissolves and removes a hardly volatile salt deposited by attaching a solvent to a needle electrode. The configuration using the electrostatic spraying type as the spraying device was shown.

The sample solution is introduced into the thin metal tube 61. When a voltage of several kilovolts is applied to the thin metal tube 61 by the atomizing power supply 62, a so-called electrostatic spray phenomenon in which the solution is sprayed from the end of the thin metal tube 61 occurs. In order to assist the spraying, a spraying gas introducing pipe 63 may be arranged on the outer periphery of the thin metal tube 61 to introduce a spraying gas such as nitrogen. The sprayed droplets are introduced into the vaporization block 21 to promote vaporization. A solvent introduction tube 64 is provided near the needle electrode 22 that generates corona discharge.

When the solvent flows at a low flow rate from the solvent inlet tube 64, the solvent first adheres to the needle electrode 22, and then moves along the needle electrode 22 by gravity, and stays as a droplet near the tip of the needle electrode 22. The non-volatile salt precipitated near the tip dissolves in the solvent droplets. As the solution continues to be fed, the diameter of the droplet increases, and eventually drops from the needle electrode 22. The component of the salt dissolved in the droplet is removed from the needle electrode 22 by dropping the droplet.

By repeating such a process several times, most of the precipitated salts can be removed. The gaseous sample obtained by vaporizing the droplets is ionized by a chemical reaction with primary ions such as hydronium ions generated by corona discharge. The ions are taken in through the first pore 8 and analyzed.

(Embodiment 3) FIG. 5 shows a mass spectrometer according to a third embodiment of the present invention, which removes hardly volatile salts deposited by spraying a solvent on a needle electrode. Solvent introduction tube 64
Is arranged with the tip of the needle electrode 22 facing the end. In order to remove the salt deposited on the needle electrode 22, a solvent is sprayed from the solvent introduction tube 64 toward the needle electrode 22. Since the salt precipitated on the needle electrode 22 is dissolved in the solvent, it can be removed by spraying the solvent for several tens of seconds.

Further, as shown in FIG.
Is arranged so as to also face the first pore 8, the needle electrode 2
At the same time as the removal of the salt precipitated in 2, the salt deposited near the pores 8 can be removed.

(Embodiment 4) FIG. 6 shows a fourth embodiment of the present invention, which has a needle electrode driving mechanism and dissolves and removes hard-to-evaporate salts precipitated by inserting a needle electrode into a solvent. 1 shows a mass spectrometer to perform. A cleaning solvent tank 71 is installed near the needle electrode 22. When the non-volatile salt precipitates on the needle electrode 22, the needle electrode 22 is moved by the needle electrode driving device 70,
The vicinity of the tip of the needle electrode 22 is settled in the washing solvent. Since the salt is dissolved in the solvent, it can be removed by immersing the needle electrode 22 in the solvent for a while.

(Embodiment 5) FIG. 7 shows a fifth embodiment of the present invention, in which a needle electrode driving mechanism is provided, and mass spectrometry for removing hard-volatile salts deposited by bringing the needle electrode into contact with a member. Show the total. A member 7 for removing salt near the needle electrode 22
2 is installed. When the non-volatile salt precipitates on the needle electrode 22, the needle electrode driving device 70 moves the needle electrode 22 to rub the vicinity of the tip of the needle electrode 22 against the member 72.
The precipitated salt is fragile, so it can be rubbed into the needle electrode 2
2 can be removed. In order to remove the salt more efficiently, the member 72 may be made of a material such as sponge or porous material having both moisture retention and elasticity, and a solvent may be introduced from the solvent introduction pipe 64 to wet the member 72. As shown in FIG. 7, the precipitated salt can be removed by bringing the needle electrode 22 into contact with the moistened member 72 (by piercing the needle electrode 22 into the member 72).

FIG. 8 shows a specific shape of the needle electrode cover 26 used in the present invention for reference. This needle electrode cover 2
Reference numeral 6 denotes a cylindrical shape surrounding the needle electrode 22, and the wall on the side of the spray device is made longer than the tip of the needle electrode 22 in order to prevent the airflow from the spray device from directly hitting the needle electrode 22.
When the needle electrode cover 26 is provided near the needle electrode 22, it is desirable that the needle electrode cover 26 be made of an insulating material so as not to affect the discharge.

In the present invention, the needle electrode cover 26 is not essential, but in order to reduce the amount of salt deposited on the needle electrode 22 per unit time, the air flow from the spray device is
Some ingenuity is desirable so as not to hit. As described above, the collision plate 24 shown in FIG. 1 also has the effect of reducing the amount of salt deposited on the needle electrode 22. Further, as shown in FIG. 9, a shield plate 73 may be used to isolate the needle electrode 22.
When the shielding plate 73 is made of metal or the like and a voltage is applied, an electric field is generated around the shielding plate 73. The generated ions relating to the salt are hardly approached to the needle electrode 22 under the influence of the electric field.

Even in the case of performing continuous analysis using an autosampler, a step of washing columns and pipes is required until the analysis of one sample is completed and the analysis of the next sample is started. Therefore, if the removal of the salt deposited on the needle electrode is performed in parallel with the washing process of the column and the piping, time can be saved.

For safety reasons, the voltage applied to the needle electrode should be turned off while removing the substance deposited on the needle electrode.

[0043]

According to the present invention, non-volatile salts deposited on the needle electrode can be easily removed. For this reason, it has become possible to stably generate ions for a long time even if a mobile phase solvent containing a hardly volatile salt is used.

[Brief description of the drawings]

FIG. 1 is a sectional view of a mass spectrometer according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view of a needle electrode section showing a modification of the first embodiment of the present invention.

FIG. 3 is a cross-sectional view of a needle electrode section showing a modification of the first embodiment of the present invention.

FIG. 4 is a sectional view of a main part of a mass spectrometer according to a second embodiment of the present invention.

FIG. 5 is a sectional view of a needle electrode section according to a third embodiment of the present invention.

FIG. 6 is a sectional view of a needle electrode section according to a fourth embodiment of the present invention.

FIG. 7 is a sectional view of a needle electrode section according to a fifth embodiment of the present invention.

FIG. 8 is a perspective view showing the shape of a needle electrode cover according to the embodiment of the present invention.

FIG. 9 is a cross-sectional view of a main part of a mass spectrometer showing an embodiment using a shielding plate instead of a needle electrode cover.

FIG. 10 is a sectional view showing a conventional liquid chromatograph / mass spectrometer.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Liquid chromatograph, 2 ... Mobile phase solvent tank, 3 ... Liquid sending pump, 4 ... Sample injector, 5 ... Separation column,
6 piping, 7 ion source, 8 first pore, 9 exhaust system,
Reference numeral 10: differential exhaust portion, 11: second pore, 12: exhaust system, 1
3 ... High vacuum section, 14 ... Ion optical system, 15 ... Mass analyzer, 16 ... Detector, 17 ... Signal line, 18 ... Data processing device, 19 ... Spray tube, 20 ... Heating block, 21 ... Evaporation block, 22 ... needle electrode, 23 ... heating block holder,
24: collision plate, 25: needle electrode base, 26: needle electrode cover,
27: needle electrode holder, 28: ultrasonic transducer, 29: first
Electrodes with pores, 30 ... mesopores, 31 ... electrodes with mesopores,
32: exhaust port, 33: electrode with second pore, 34, 35, 3
6 power supply, 37, 38, 39 Einzel lens electrode, 40 deflector case, 41, 42 deflector electrode, 4
3, 44: opening, 45: focusing electrode, 46, 47: end cap electrode, 48: ring electrode, 49: gate electrode, 50: ion stop electrode, 51: connector, 52
... Insulation material, 53 ... High voltage power supply, 54 ... Capillary, 55
... Stainless steel tube, 56 ... Partition wall, 57 ... Gas outlet, 58
... Atomizer holder, 59 ... Insulation ring, 60 ... Partition plate,
Reference numeral 61 denotes a thin metal tube, 62 denotes a power supply for spraying, 63 denotes a spray gas introducing pipe, 64 denotes a solvent introducing pipe, 65 denotes a member, 66 denotes a driving device, 67 denotes a motor, 68 denotes a rotating shaft, and 69 denotes a terminal for voltage application. ... needle electrode driving device, 71 ... washing solvent tank, 72
... moisturizer, 73 ... shielding plate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Hirabayashi, Inventor 1-280 Higashi Koikekubo, Kokubunji-shi, Tokyo Inside the Central Research Laboratory of Hitachi, Ltd. Within Central Research Laboratory (72) Inventor Minoru Sakairi 1-280 Higashi Koigakubo, Kokubunji-shi, Tokyo F-term within Central Research Laboratory, Hitachi, Ltd. 5C038 EE02 EF04 EF33 GG08 GH02 GH11

Claims (7)

[Claims] A sample supply pipe for supplying a sample solution containing a measurement sample; an atomizer for atomizing the sample solution supplied from the sample supply pipe; and an atomizer for atomizing the sample solution. An ion source comprising a needle electrode for ionizing the sample,
A mass spectrometer comprising a mass spectrometer for analyzing ions generated by the ion source, wherein the mass spectrometer includes a vibrator for vibrating the needle electrode. 2. A sample supply pipe for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply pipe, and an atomizer atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
A mass spectrometer comprising a mass spectrometer for analyzing ions generated by the ion source, wherein the mass spectrometer includes a member for impacting the needle electrode. 3. A sample supply pipe for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply pipe, and an atomizer atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
A mass spectrometer comprising a mass spectrometer for analyzing ions generated by the ion source, further comprising a motor for rotating the needle electrode. 4. A sample supply pipe for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply pipe, and an atomizer atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
What is claimed is: 1. A mass spectrometer comprising a mass spectrometer for analyzing ions generated by said ion source, characterized in that said mass spectrometer has a solvent introduction tube for attaching a solvent to said needle-shaped electrode. 5. A sample supply pipe for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply pipe, and an atomizer atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
What is claimed is: 1. A mass spectrometer comprising a mass spectrometer for analyzing ions generated by said ion source, wherein said mass spectrometer has a solvent introduction tube for spraying a solvent onto said needle-shaped electrode. 6. A sample supply pipe for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply pipe, and atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
A mass spectrometer comprising a mass spectrometer for analyzing ions generated by the ion source, wherein the mass spectrometer further comprises a washing solvent tank for washing the needle electrode. 7. A sample supply tube for supplying a sample solution containing a measurement sample, an atomizer for atomizing the sample solution supplied from the sample supply tube, and an atomizer atomized by the atomizer. An ion source comprising a needle electrode for ionizing the sample,
A mass spectrometer comprising a mass spectrometer for analyzing ions generated by the ion source, the mass spectrometer having a member for rubbing the needle electrode.