JP6780784B2 - Liquid chromatograph mass spectrometer - Google Patents

Description

The present invention relates to a liquid chromatograph mass spectrometer that combines a liquid chromatograph and a mass spectrometer. The mass spectrometer referred to here is a device that performs mass spectrometry after dissociating ions derived from a sample component in one step or a plurality of steps, or mass spectrometry after ion separation by an ion mobility analysis (IMS) method. Including the device.

In a liquid chromatograph mass spectrometer (hereinafter, may be abbreviated as "LC-MS" as appropriate), an eluent containing various components separated in the time direction by a column of a liquid chromatograph is introduced into the mass spectrometer and mass spectrometerd. After ionization with the ion source of the analyzer, ions derived from the sample component are separated and detected according to the mass-to-charge ratio m / z with a mass separator such as a quadrupole mass filter.

In the mass spectrometer used for LC-MS, atmospheric pressure ionization methods such as electrospray ionization (ESI) method and atmospheric pressure chemical ionization (APCI) method are used to ionize the components in the liquid sample. .. Such a mass spectrometer may be used alone without being combined with a liquid chromatograph, or an analysis in which the ion source is replaced with an ion source by another atmospheric pressure ionization method such as the DART (Direct Analysis in Real Time) method. May be done. Therefore, in general LC-MS, the liquid chromatograph and the mass spectrometer are separate bodies.

FIG. 5 is a schematic external front view of a general LC-MS in which the liquid chromatograph 1 and the mass spectrometer 2 are separate bodies (see Non-Patent Document 1 and the like). The liquid chromatograph 1 is composed of one or a plurality of units 10 including a liquid feeding pump, an injector, and a column oven 11 in which a column is housed. The column oven 11 includes a heater and a cooler for controlling the temperature of the column with high accuracy. The column oven 11 and the ion source 20 of the mass spectrometer 2 are connected to each other via a flexible and flexible pipe line 4, for example, made of resin. The eluate eluted from the outlet of the column passes through this conduit 4 and is sent to the capillary of the ionization probe that sprays the liquid sample at the ion source 20 into the ionization chamber in the atmosphere of atmospheric pressure. Since the pipeline 4 is flexible to some extent, there is an advantage that the degree of freedom of arrangement between the liquid chromatograph 1 and the mass spectrometer 2 is relatively high.

In recent years, especially in the fields of biochemistry, medical care, drug development, etc., there are many cases where the sample is very small or the sample is valuable or expensive, and even if the sample is very small, analysis can be performed with high sensitivity and accuracy. It is required to be able to do it. In order to meet such demands, in the liquid chromatograph, a method of reducing the flow rate by using a column having a small diameter and suppressing the flow rate of the mobile phase supplied to the column is adopted. Correspondingly, in the ion source of the mass spectrometer, for example, a method called nano ESI or micro ESI, which efficiently ionizes the components in the eluate while suppressing the flow rate of the eluate introduced into the ionization probe, is adopted. ing.

In a general LC-MS as shown in FIG. 5, the longer the pipeline 4, the greater the diffusion (spread in the time direction) of each component in the pipeline 4, and the component detection by the mass spectrometer 2. Sensitivity decreases. The decrease in detection sensitivity due to the diffusion of such components becomes a particular problem when a small amount of sample is measured at a low flow rate as described above. In order to suppress the diffusion of the components separated by the column, it is desirable to make the flow path of the eluate from the end of the column to the ionization probe as short as possible and reduce the inner diameter thereof. The most desirable configuration is such that the outlet end of the column is directly connected to the inlet end of the capillary, which is the sample flow path of the ionization probe (see Patent Document 1). Even if the outlet end of the column and the inlet end of the capillary are not directly connected, even if the column and the capillary are connected via a very short straight tubular relay pipe, the components are diffused to the same extent as if they were directly connected. It is possible to suppress.

U.S. Pat. No. 9095791

"LCMS-8060 Ultra-high-speed triple quadrupole LC / MS / MS system", [online], Shimadzu Corporation, [Search on August 9, 2017], Internet <URL: http://www.an .shimadzu.co.jp/lcms/lcms8060/index.htm ＞

When the liquid chromatograph and the mass spectrometer are integrated, the outlet end of the column may be directly connected to the inlet end of the capillary, or the outlet end of the column and the inlet end of the capillary may be connected to a very short straight tubular relay pipe. It is easy to connect with. However, as described above, in order to increase the versatility of the device, in a configuration in which each unit of the liquid chromatograph and the mass spectrometer are separate bodies, the outlet end of the column may be directly connected to the inlet end of the capillary, or both. Is difficult to connect with a straight tubular relay pipe. This is because, for example, if vibration is applied to the entire device in such a connected state, an unreasonable load may be applied to the connection portion, the column, or the ionization probe, resulting in damage.

The present invention has been made to solve the above problems, and an object of the present invention is to exit a column of a liquid chromatograph even when the liquid chromatograph and the mass spectrometer are separate bodies. The end and the inlet end of the capillary of the ionization probe of the mass spectrometer are connected directly or via a short straight tubular relay pipe, and a large load is applied to the connection portion and the columns or the capillary on both sides thereof due to vibration or the like. It is to provide a liquid chromatograph mass spectrometer that can be avoided.

The present invention, which has been made to solve the above problems, is a liquid chromatograph mass spectrometer in which a liquid sample eluted from a liquid chromatograph column is introduced into a mass spectrometer, and components in the sample are ionized and analyzed. ,
a) A column oven that controls the temperature of the column housed inside,
b) An ionization probe that contains a capillary in which a flow path through which a liquid sample introduced into the mass spectrometer flows is formed, and ionizes the components in the sample while spraying the liquid sample into the ionization chamber from the end of the capillary. In a state where the inlet side end of the capillary or the inlet side end of the straight tubular relay pipe coaxially connected to the inlet side end of the capillary is taken out of the housing of the mass spectrometer. The ionization probe housed in the housing and
c) With respect to the housing of the mass spectrometer so that the central axis of the outlet side end of the column and the central axis of the capillary in the ionization probe or the inlet side end of the relay pipe are located on a straight line. And an oven holding part that holds the column oven
It is characterized by having.

In the liquid chromatograph mass spectrometer according to the present invention, the ionization probe typically ionizes a liquid sample in a substantially atmospheric pressure atmosphere in order to perform ionization by the ESI method, the APCI method, or the atmospheric pressure photoionization (APPI) method. It is sprayed indoors.

In the liquid chromatograph mass spectrometer according to the present invention, the oven holding portion is an ionization taken out from the central axis of the outlet side end of the column housed in the column oven and the outside of the housing of the mass spectrometer. Hold the column oven against the housing of the mass spectrometer so that the capillary of the probe or the central axis of the inlet end of the relay pipe is located approximately in line. As a result, both can be connected in a state where the opening at the outlet side end of the column and the opening at the inlet side end of the capillary of the ionization probe or the relay pipe are butted against each other. In such a connected state, the eluate (liquid sample) eluted from the outlet of the column goes straight and flows through the relay pipe or directly to the flow path of the capillary. Since the distance from the liquid sample exiting the column outlet to the tip of the capillary is short and the flow is linear, the diffusion of components in the liquid sample can be suppressed. Further, since the position of the column oven is determined with respect to the housing of the mass spectrometer, it is possible to avoid applying a large force to the connection portion between the column and the capillary or the relay pipe.

In the liquid chromatograph mass spectrometer according to the present invention, the oven holding portion itself is fixed to the housing of the mass spectrometer and is a holder to which the column oven is mounted. Can be done.

According to this configuration, the column oven can be fixed to the housing of the mass spectrometer via the oven holding portion. As a result, the column oven and the mass spectrometer are substantially integrated, so that even if vibration is applied to the device from the outside, a large force is applied to the connection between the column and the capillary or the relay pipe. You can definitely avoid it.

Further, in the liquid chromatograph mass spectrometer according to the present invention, the oven holding portion moves the column oven with respect to the housing of the mass spectrometer in a direction orthogonal to the central axis of the outlet side end portion of the column. It is preferable to have a configuration that can be held in a state of being held.

According to this configuration, there are large variations in the assembly accuracy of the device and the mounting accuracy of the oven holding part, and therefore, the central axis of the outlet side end of the column and the central axis of the inlet side end of the capillary or the relay pipe are not aligned. Even if it is not located on a straight line, the variation can be absorbed by adjusting the position of the column oven by the oven holding portion. As a result, the opening at the outlet side end of the column and the opening at the inlet side end of the capillary of the ionization probe or the relay pipe can be connected with high dimensional accuracy.

In the liquid chromatograph mass spectrometer according to the present invention, the column oven is placed on the mass spectrometer according to the direction in which the outlet side end of the column and the capillary of the ionization probe or the inlet side end of the relay pipe face each other. That is, the structure may be stacked, but from the viewpoint of maintainability of the device, horizontal placement is more convenient.

Therefore, as a preferred embodiment of the liquid chromatograph mass spectrometer according to the present invention, the central axis of the outlet side end of the column in the column oven and the central axis of the inlet side end of the capillary or the relay pipe in the ionization probe. Are all in a horizontally stretched state, and the oven holding portion may be configured to hold the column oven against a substantially upright side wall surface of the housing of the mass spectrometer.

In this configuration, a column oven is placed on the side of the mass spectrometer via an oven holder, and the outlet side end of the column in the column oven is directly connected to the capillary of the ionization probe or the inlet side end of the relay pipe. Can be done.

Further, in the liquid chromatograph mass spectrometer of the above aspect, the oven holding portion has an inverted L shape in front view, and the upper portion of the inverted L shape can be fixed with the column oven mounted. The configuration should be a fixed base.

According to this configuration, the column oven is held in a floating state from the installation surface of the mass spectrometer by the inverted L-shaped oven holding portion, and a space is formed between the installation surface and the fixing base of the oven holding portion. Will be done. In this space, for example, a unit other than the column oven of the liquid chromatograph, for example, a unit including a liquid feed pump, an injector, a control circuit, or the like can be installed. As a result, the installation space of the device can be effectively used.

Further, in the liquid chromatograph mass spectrometer of the above aspect, the oven holding portion may be configured to include an adjusting mechanism for adjusting the height of the fixing base.

In this configuration, the height of the fixed base is adjusted by the adjustment mechanism to accurately match the height of the outlet side end of the column with the capillary of the ionization probe or the inlet side end of the relay pipe, and connect them. can do.

In this case, the adjusting mechanism may be configured to include an operator operated by the user to adjust the height of the fixed base at a position on the front surface of the device.

According to this configuration, for example, even when another unit is arranged in the space between the device installation surface and the fixed base of the oven holding portion as described above, the user can set the height of the fixed base from the front of the device. Can be adjusted. Therefore, the workability of height adjustment is good.

Furthermore, in the liquid chromatograph mass spectrometer of the above aspect, the oven holding portion includes the fixed base on which the column oven is mounted and the mass spectrometer side fixing portion fixed to the housing of the mass spectrometer. , And the fixed base may be configured to be detachable in the direction perpendicular to the fixed portion on the mass spectrometer side.

According to this configuration, when performing analysis by the mass spectrometer alone without using a liquid chromatograph, only the fixing base is removed upward while the fixed portion on the mass spectrometer side is attached to the housing of the mass spectrometer. Can be done. When the fixed base disappears, space is secured for mounting various types of ionization units by other ionization methods instead of the ionization probes by the ESI method or the APCI method, for example. Therefore, analysis using such ionization units is secured. Is possible. In addition, a fixed base can be easily attached as needed, and analysis by combining a liquid chromatograph and a mass spectrometer can be performed quickly.

According to the liquid chromatograph mass spectrometer according to the present invention, the outlet end of the column of the liquid chromatograph and the ionization probe of the mass spectrometer are held in a state where the column oven of the liquid chromatograph is stably held with respect to the mass spectrometer. It can be connected to the inlet end of the capillary directly or via a short straight tubular relay pipe. As a result, even when an external force such as vibration is applied to the device, it is possible to avoid applying a large load to the connection portion between the column and the capillary or the relay pipe, the column itself, or the capillary itself. Further, since the distance of the flow path from the outlet of the column to the tip of the capillary of the ionization probe can be shortened and linearized, the diffusion of the sample component separated by the column can be suppressed. As a result, the sample component can be detected with high sensitivity even in the measurement of a particularly low flow rate.

The schematic external front view of LC-MS which is one Example of this invention. Front view (a) and side view (b), (c) of the oven holder in LC-MS of this embodiment. The schematic block diagram of the LC column and the mass spectrometer of the LC-MS of this Example seen from the front. The schematic block diagram of the LC column and the ion source in LC-MS of this Example seen from above. Schematic external front view of a conventional general LC-MS.

Hereinafter, LC-MS, which is an embodiment of the present invention, will be described with reference to the accompanying drawings.
FIG. 1 is a schematic external front view of the LC-MS of this embodiment. FIG. 2A is a front view of the oven holder in the LC-MS of this embodiment, and FIGS. 2B and 2C are side views of the oven holder. Further, FIG. 3 is a schematic configuration diagram of the LC column and the mass spectrometer in the LC-MS of this embodiment as viewed from the front, and FIG. 4 is a schematic configuration of the LC column and the ion source as viewed from above. It is a block diagram. As shown in the figure, for convenience, the lateral direction of the device is defined as the X-axis direction, the height direction is defined as the Z-axis direction, and the depth direction is defined as the Y-axis direction.

As shown in FIG. 1, the LC-MS of this embodiment comprises a liquid chromatograph 1 and a mass spectrometer 2. The liquid chromatograph 1 includes one or more units (two units in the example of FIG. 1, but the number may be one or three or more) including a liquid feed pump, an injector, a control circuit, and the like, and a column oven. 11 and. The column oven 11 has a box-shaped housing 11a, and includes an oven chamber in which a heater and a cooler (not shown) are arranged and the periphery thereof is covered with a heat insulating material. The column 110 is housed in the oven chamber. The unit 10 and the inlet side end of the column 110 are connected via a flexible pipeline 12, and the mobile phase in which the sample is injected in the injector is fed to the column 110 through the conduit 12.

The mass spectrometer 2 includes an ion source 20 and an analysis unit 200. The ion source 20 and the analysis unit 200 are housed inside a housing 2a long in the X-axis direction together with a vacuum pump and the like (not shown). As shown in FIG. 3, the mass spectrometer 2 is a triple quadrupole mass spectrometer. The ion source 20 is an ESI ion source and includes an ionization probe 22 that sprays charged droplets into an ionization chamber 21 maintained in a substantially atmospheric pressure atmosphere. The ionization probe 22 has a capillary 23 through which a low-flow liquid sample flows, and the inlet-side end of the capillary 23 is connected to a straight tubular relay pipe 25 by a joint 24, and the inlet-side end of the relay pipe 25 is connected. The portion is taken out to the outside of the housing 2a substantially horizontally. That is, the capillary 23 and the relay pipe 25 are substantially integrated by the joint 24, and a linear liquid sample flow path extending in the horizontal direction is formed inside the capillary 23 and the relay pipe 25. The relay pipe 25 is made of a resin such as PEEK (polyetheretherketone) resin, and the metal capillary 23 is not exposed to the outside of the ionization probe 22, so that high safety can be ensured.

As shown in FIG. 3, the column 110 is arranged so that the central axis of the outlet side end portion 110a is located substantially in line with the central axis of the relay pipe 25 (which is also the central axis of the capillary 23). The inlet side end of the relay pipe 25 is inserted into the column oven 11 of the liquid chromatograph 1 and connected to the outlet side end 110a of the column 110.

The entire analysis unit 200 is housed in the vacuum chamber 201. The inside of the vacuum chamber 201 is partitioned into a first intermediate vacuum chamber 202, a second intermediate vacuum chamber 203, and a high vacuum chamber 204 from the side closer to the ionization chamber 21. Each of the chambers 202 to 204 is evacuated by a vacuum pump, and has a differential exhaust system in which the degree of vacuum gradually increases from the ionization chamber 21 toward the high vacuum chamber 204.

The ionization chamber 21 and the first intermediate vacuum chamber 202 communicate with each other through a small-diameter desolvation tube 26, and from a plurality of electrode plates arranged so as to surround the ion optical axis C in the first intermediate vacuum chamber 202. An ion guide 205 is installed. The first intermediate vacuum chamber 202 and the second intermediate vacuum chamber 203 communicate with each other through a small hole at the top of the skimmer 206, and the second intermediate vacuum chamber 203 is composed of a plurality of rod electrodes surrounding the ion optical axis C. The ion guide 207 is installed. In the high vacuum chamber 204, a front-stage quadrupole mass filter 208 and a rear-stage quadrupole mass filter 211 are arranged with a collision cell 209 in which an ion guide 210 is arranged, and an ion detector 212 is further arranged. It is provided.

As described above, the eluate containing the components separated in the column 110 in a state where the outlet side end 110a of the column 110 and the inlet side end 23a of the capillary 23 of the ionization probe 22 are connected via the relay pipe 25. Is supplied to the capillary 23 via the relay pipe 25, and charged droplets derived from the eluate are sprayed into the ionization chamber 21 from the end of the capillary 23. The charged droplets collide with the atmosphere and become finer, and the sample component becomes gas ions in the process of further evaporating the solvent. The generated ions are sucked into the desolvation tube 26 by the gas flow formed by the differential pressure at both ends of the desolvation tube 26, and are introduced into the first intermediate vacuum chamber 202.

As shown in FIG. 3, when the apparatus is viewed from the front, the spraying direction of the charged droplets from the ionization probe 22 and the introduction direction of the ions into the desolvation tube 26 are both horizontally aligned. However, as shown in FIG. 4, when the device is viewed from above, the central axis of the spray flow of charged droplets and the central axis of the inlet end of the desolvation tube 26 are not in a straight line but are predetermined. It intersects diagonally with an angle of. This is to reduce the possibility that large charged droplets or solvent gas whose solvent has not been vaporized, or neutral particles such as non-ionized component molecules enter the solvent removal tube 26 as they are. Due to such a configuration, when the device is viewed from above as shown in FIG. 4, the extension direction of the capillary 23 of the ionization probe 22 is slightly deviated from the X-axis direction, but the relay connected to the capillary 23 is connected. The inlet side end of the pipe 25 and the outlet side end 110a of the column 110 are located substantially in a straight line.

As described above, the ions derived from the sample components introduced into the first intermediate vacuum chamber 202 are converged by the ion guide 205 and sent to the second intermediate vacuum chamber 203 through the small holes of the skimmer 206. These ions are converged by the ion guide 207, sent to the high vacuum chamber 204, and introduced into the pre-stage quadrupole mass filter 208. Among the ions derived from the introduced sample components, only the ions having a specific mass-to-charge ratio corresponding to the voltage applied to the pre-stage quadrupole mass filter 208 pass through the pre-stage quadrupole mass filter 208 and are precursor ions. Enter the collision cell 209 as. A CID (collision-induced dissociation) gas is continuously or intermittently introduced into the collision cell 209, and the precursor ions come into contact with the CID gas and dissociate to generate various product ions. This product ion is introduced into the rear quadrupole mass filter 211, and only the product ion having a specific mass-to-charge ratio corresponding to the voltage applied to the rear quadrupole mass filter 211 can use the rear quadrupole mass filter 211. It passes through and reaches the ion detector 212. The ion detector 212 generates a detection signal according to the amount of ions reached.

In the LC-MS of this embodiment, in order to connect the outlet side end 110a of the column 110 and the inlet side end 23a of the capillary 23 via a very short straight tubular relay pipe 25, the following characteristics are characteristic. The configuration is adopted.
An inverted L-shaped oven holder 3 is attached to the side surface (left side surface) of the housing 2a of the mass spectrometer 2 on the side where the ion source 20 is located by screws or the like. The oven holder 3 includes a fixing base portion 30 to which the column oven 11 is attached, and a mass spectrometer side fixing portion 31 fixed to the housing 2a of the mass spectrometer 2.

The fixed base portion 30 has a mounting base portion 300 having a substantially horizontal holding plate on which the column oven 11 is placed in an inverted L-shaped bent shape, and an extension piece extending vertically downward integrally with the mounting base portion 300. It is composed of a part 301. On the other hand, the mass spectrometer side fixing portion 31 has a substantially U-shaped top view having a pair of guide walls 310 on both sides thereof, and the distance between the pair of guide walls 310 is slightly larger than the width of the extending piece portion 301. ing. A plurality of claw portions 311 are formed from the pair of guide walls 310 inwardly, and the extending piece portion 301 is slidably held up and down with respect to the guide wall 310 by the claw portions 311.

A height adjustment knob 312 is provided on the outer surface of the guide wall 310 in the same direction as the front surface of the device, and the height adjustment knob 312 is connected to a feed screw 313 extending in the Y-axis direction. A slider 314 is screwed on the feed screw 313, and a rotary bearing portion 315 that is rotatable about an axis in the X-axis direction is provided on the slider 314. A triangular inclined guide piece 302 inclined with respect to the Y-axis direction is provided on the lower surface of the extending piece portion 301 of the fixed base portion 30, and the rotary bearing portion 315 is in contact with the inclined guide piece 302 to be in contact with the fixed base portion. It supports the entire 30.

As shown in FIG. 1, the column oven 11 is fixed on the mounting table portion 300 of the oven holder 3 fixed to the left side surface of the housing 2a of the mass spectrometer 2. This fixing may be fixed with screws or fixed with another metal fitting or the like. With the column oven 11 fixed on the mounting table 300 in this way, the column 110 in the column oven 11 is horizontal. On the other hand, the inlet-side end of the relay pipe 25 connected to the capillary 23 of the ionization probe 22 in the mass spectrometer 2 projects substantially horizontally from the housing 2a. At this time, if there is a discrepancy between the height of the outlet side end 110a of the column 110 and the height of the capillary 23 and the relay pipe 25 of the ionization probe 22, the height may be adjusted as follows.

When the user rotates the height adjustment knob 312, the feed screw 313 rotates in conjunction with the rotation, and the slider 314 moves in the axial direction (Y-axis direction) of the feed screw 313. FIG. 2B shows a state in which the slider 314 has moved to the rearmost position, and FIG. 2C shows a state in which the slider 314 has moved to the most forward position. When the rotary support portion 315 moves together with the slider 314, the position of the tilt guide piece 302 in contact with the upper end of the rotary support portion 315 changes. Therefore, when the user rotates the height adjustment knob 312, the entire fixed base portion 30 moves up and down in response to the movement of the slider 314. The height adjustment range of the upper surface of the mounting base portion 300 of the fixed base portion 30 is d shown in FIG.

That is, in the height direction (Z-axis direction), the deviation between the height of the outlet side end 110a of the column 110 and the height of the capillary 23 of the ionization probe 22 and the height of the relay pipe 25 is absorbed by the distance d shown in FIG. It is possible. As a result, even if there is a dimensional error in assembling the device or a mounting error of the oven holder 3 itself, the outlet side end 110a of the column 110 and the inlet side end of the relay pipe 25 of the ionization probe 22 The height can be made uniform. The displacement in the depth direction (Y-axis direction) between the outlet side end 110a of the column 110 and the relay pipe 25 of the ionization probe 22 is the position when the column oven 11 is placed (mounted) on the mounting table 300. It can be absorbed by adjustment. As a result, the opening of the outlet side end 110a of the column 110 and the opening of the inlet side end of the relay pipe 25 are accurately aligned with each other, and then the column oven 11 itself is shifted in the direction closer to the ionization probe 22. The inlet side end of the relay pipe 25 is inserted into the column oven 11, and the inlet side end thereof is connected to the outlet side end 110a of the column 110. As a result, the column 110 and the capillary 23 are connected to each other via the relay pipe 25.

At this time, since the mass spectrometer 2 and the column oven 11 are integrated via the oven holder 3, for example, vibration is applied to the entire device or a force for moving the column oven 11 is applied from the outside. Even in this case, a large force is not applied to the connecting portion between the column 110 and the relay pipe 25, and it is possible to prevent the connection from being disconnected or the column 110, the relay pipe 25, or the capillary 23 from being damaged.

Further, since the oven holder 3 has an inverted L shape when viewed from the front, a space is formed between the mounting base 300 and the installation surface of the device as shown in FIG. Therefore, a liquid chromatograph unit other than the column oven 11 can be stored in this space, and the installation space can be effectively utilized. Further, since the height of the mounting base 300 can be adjusted from the front, even if another unit is placed in the space below the mounting base 300 in this way, such a unit becomes an obstacle to the height adjustment. It never becomes.

Further, the fixing base portion 30 in the oven holder 3 can be pulled out upward from the fixing portion 31 on the mass spectrometer side. That is, the fixing base portion 30 can be removed while the mass spectrometer-side fixing portion 31 of the oven holder 3 is attached to the housing 2a of the mass spectrometer 2. When the mass spectrometer 2 is used alone, instead of using the ESI method or the APCI method as the ion source 20, when it is desired to attach an ionization unit for ionization such as the DART method or the PESI method, or to replace it with such a unit. There is. By temporarily removing the fixed base portion 30, it becomes easy to attach such an ionization unit. Further, when it is desired to perform LC / MS analysis, the fixed base portion 30 can be easily attached to return to the original state (that is, the state shown in FIG. 1).

The above-mentioned embodiment is merely an example of the present invention, and it is natural that even if it is appropriately changed, modified or added within the scope of the gist of the present invention, it is included in the claims of the present application.

For example, in the LC-MS of the above embodiment, the column 110 and the capillary 23 were connected via the non-conductive relay pipe 25, but the inlet side end of the capillary 23 is directly connected to the outlet side end of the column 110. It may be configured to be connected to the unit 110a. The capillary 23 is non-conductive, such as made of glass, and an electric field is applied to the liquid sample reaching the tip of the capillary 23 by applying a high voltage to a metal cylinder arranged so as to surround the tip of the capillary 23. In such a configuration, even if the entrance side end of the capillary 23 is pulled out to the outside of the housing 2a, the problem of safety is small. Further, the relay pipe 25 is not necessarily one pipe, but may be a pipe in which a plurality of pipes are connected.

Further, for example, in the LC-MS of the above embodiment, the column oven is arranged on the side of the mass spectrometer by using an oven holder, but the outlet side end of the column and the inlet side end of the capillary are separated. If both are stretched in the vertical direction, place the column oven above the mass spectrometer, that is, on the top surface of the housing of the mass spectrometer, and fix it with the oven holder. May be good. In any case, fix the column oven to the mass spectrometer so that the outlet side end of the column and the inlet side end of the capillary are aligned and the openings at both ends can be abutted. Just do it.

Further, the shape of the oven holder is not limited to that described in the above embodiment. Further, the height adjusting mechanism of the mounting base is not limited to that described in the above embodiment.

1 ... Liquid chromatograph 10 ... Unit 11 ... Column oven 11a ... Housing 110 ... Column 110a ... Outlet side end 12 ... Pipe line 2 ... Mass spectrometer 2a ... Housing 20 ... Ion source 21 ... Ionization chamber 22 ... Ionization probe 23 ... Capillary 24 ... Joint 25 ... Relay pipe 26 ... Desolving pipe 200 ... Analytical unit 201 ... Vacuum chamber 202 ... First intermediate vacuum chamber 203 ... Second intermediate vacuum chamber 204 ... High vacuum chamber 205, 207, 210 ... Ion guide 206 ... Skimmer 208 ... Front quadrupole mass filter 209 ... Collision cell 211 ... Rear quadrupole mass filter 212 ... Ion detector 3 ... Oven holder 30 ... Fixed base 300 ... Mounting base 301 ... Extension piece 302 ... Inclination guide piece 31 ... Mass spectrometer side fixing part 310 ... Guide wall 311 ... Claw part 312 ... Height adjustment knob 313 ... Feed screw 314 ... Slider 315 ... Rotation support part C ... Ion optical axis

Claims (8)

In a liquid chromatograph mass spectrometer in which a liquid sample eluted from a liquid chromatograph column is introduced into a mass spectrometer and the components in the sample are ionized and analyzed.
a) A column oven that controls the temperature of the column housed inside,
b) An ionization probe that contains a capillary in which a flow path through which a liquid sample introduced into the mass spectrometer flows is formed, and ionizes the components in the sample while spraying the liquid sample into the ionization chamber from the end of the capillary. In a state where the inlet side end of the capillary or the inlet side end of the straight tubular relay pipe coaxially connected to the inlet side end of the capillary is taken out of the housing of the mass spectrometer. The ionization probe housed in the housing and
c) With respect to the housing of the mass spectrometer so that the central axis of the outlet side end of the column and the central axis of the capillary in the ionization probe or the inlet side end of the relay pipe are located on a straight line. And an oven holding part that holds the column oven
A liquid chromatograph mass spectrometer characterized by the present invention. The liquid chromatograph mass spectrometer according to claim 1.
A liquid chromatograph mass spectrometer, wherein the oven holder is a holder that is fixed to the housing of the mass spectrometer and to which the column oven is mounted. The liquid chromatograph mass spectrometer according to claim 1.
The oven holding portion is characterized in that the column oven can be held in a state of being moved in a direction orthogonal to the central axis of the outlet side end portion of the column with respect to the housing of the mass spectrometer. Chromatograph mass spectrometer. The liquid chromatograph mass spectrometer according to claim 1.
The central axis of the outlet side end of the column in the column oven and the central axis of the inlet side end of the capillary or relay pipe in the ionization probe are both in a horizontally extended state, and the oven holding portion is in a state of being horizontally extended. A liquid chromatograph mass spectrometer characterized by holding the column oven against a substantially upright side wall surface of the housing of the mass spectrometer. The liquid chromatograph mass spectrometer according to claim 4.
The oven holding portion has an inverted L-shape when viewed from the front, and the upper portion of the inverted L-shape is a fixed base that can be fixed with the column oven mounted on the liquid chromatograph mass. Analysis equipment. The liquid chromatograph mass spectrometer according to claim 5.
The oven holding portion is a liquid chromatograph mass spectrometer including an adjusting mechanism for adjusting the height of the fixing base. The liquid chromatograph mass spectrometer according to claim 6.
A liquid chromatograph mass spectrometer comprising an operator operated by a user to adjust the height of the fixed base in the adjusting mechanism at a position on the front surface of the apparatus. The liquid chromatograph mass spectrometer according to claim 5.
The oven holding portion includes the fixing base on which the column oven is mounted and the mass spectrometer side fixing portion fixed to the housing of the mass spectrometer, and the fixing base is fixed on the mass spectrometer side. A liquid chromatograph mass spectrometer characterized by being removable in the direction perpendicular to the unit.

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