JPWO2019049273A1 - Liquid chromatograph mass spectrometer - Google Patents

Abstract

An inverted L-shaped oven holder (3) is attached to the side surface of the housing (2a) of the mass spectrometer (2), and a column oven (11) is attached on the horizontal mounting table of the oven holder (3). . In the mass spectrometer (2), the straight tubular relay pipe (25) connected to the capillary (23) of the ESI probe (22) via a joint is taken out of the housing (2a). By adjusting the height of the mounting table of the oven holder (3), the central axis of the outlet side end portion (110a) of the column (110) and the central axis of the inlet side end portion of the relay pipe (25) are substantially reduced. The column oven 11 itself is shifted so as to be connected to each other with the openings at both ends being abutted so as to be positioned on a straight line. Thereby, the eluate containing the component separated by the column (110) can be sent to the capillary (23) via the very short relay pipe (25), and the analysis of the sensitivity can be performed while suppressing the diffusion of the component.

Description

  The present invention relates to a liquid chromatograph mass spectrometer that combines a liquid chromatograph and a mass spectrometer. As used herein, a mass spectrometer is an apparatus that performs mass analysis after dissociating ions derived from sample components in one or more stages, or performs mass analysis after ion separation by an ion mobility analysis (IMS) method. Device.

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

  In a mass spectrometer used for LC-MS, an atmospheric pressure ionization method such as an electrospray ionization (ESI) method or an atmospheric pressure chemical ionization (APCI) method is used to ionize components in a liquid sample. . Such a mass spectrometer may be used alone without being combined with a liquid chromatograph, or 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 performed. Therefore, in general LC-MS, the liquid chromatograph and the mass spectrometer are separated.

  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, etc.). The liquid chromatograph 1 includes one or a plurality of units 10 including a liquid feed pump and an injector, a column oven 11 in which a column is accommodated, and the like. The column oven 11 includes a heater and a cooler in order to control the temperature of the column with high accuracy. The column oven 11 and the ion source 20 of the mass spectrometer 2 are connected via a conduit 4 made of, for example, resin having flexibility and flexibility. The eluate eluted from the outlet of the column passes through this pipe 4 and is sent to the capillary of an ionization probe that sprays a liquid sample in the ionization chamber that is an atmospheric pressure atmosphere in the ion source 20. Since the conduit 4 is flexible to some extent, there is an advantage that the degree of freedom of arrangement of the liquid chromatograph 1 and the mass spectrometer 2 is relatively high.

  In recent years, especially in fields such as biochemistry, medicine, and drug development, there are often cases where a sample is a very small amount or a sample is valuable or expensive, and even if the sample is a small amount, analysis can be performed with high sensitivity and accuracy. There is a need to be able to do it. In order to meet these demands, liquid chromatographs employ a method of reducing the flow rate of the mobile phase that uses a thin column and suppresses the flow rate of the mobile phase supplied to the column. Correspondingly, in the ion source of the mass spectrometer, for example, a technique called nano-ESI or micro-ESI is used to efficiently ionize components in the eluate while suppressing the flow rate of the eluate introduced into the ionization probe. ing.

  In the general LC-MS as shown in FIG. 5, the longer the pipeline 4 is, the greater the diffusion (spreading in the time direction) of each component in the pipeline 4 is, and component detection in the mass spectrometer 2 is performed. The sensitivity of is reduced. Such a decrease in detection sensitivity due to the diffusion of components is particularly problematic when a very 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 to reduce its inner diameter. The most desirable configuration is that the outlet end of the column is directly connected to the inlet end of the capillary that is the sample flow path of the ionization probe (see Patent Document 1). Even when 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 diffusion of components is almost the same as when the column is connected directly. Can be suppressed.

US9095791 specification

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

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

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

In order to solve the above problems, the present invention provides a liquid chromatograph mass spectrometer that introduces a liquid sample eluted from a column of a liquid chromatograph into a mass spectrometer and ionizes and analyzes components in the sample. ,
a) a column oven for controlling the temperature of the column accommodated therein;
b) An ionization probe that includes a capillary in which a flow channel through which the liquid sample introduced into the mass spectrometer flows is formed, and that ionizes components in the sample while spraying the liquid sample from the end of the capillary into the ionization chamber The inlet side end of the capillary or the inlet side end of the straight tubular relay pipe connected coaxially to the inlet side end of the capillary is taken out of the casing of the mass spectrometer. An ionization probe housed in the housing;
c) with respect to the casing of the mass spectrometer so that the central axis of the outlet side end of the column and the central axis of the capillary or the inlet side end of the relay pipe in the ionization probe are located on a straight line. An oven holding unit for holding the column oven;
It is characterized by having.

  In the liquid chromatograph / mass spectrometer according to the present invention, the ionization probe is typically an ionization in which the liquid sample is in a substantially atmospheric pressure atmosphere for 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 unit includes the central axis of the outlet side end of the column housed in the column oven and the ionization taken out of the mass spectrometer housing. The column oven is held with respect to the housing of the mass spectrometer so that the capillary of the probe or the central axis of the inlet side end of the relay pipe is positioned substantially in a straight line. Thereby, both can be connected in the state which faced | matched the opening of the exit side edge part of a column, and the opening of the capillary side of an ionization probe, or the inlet side edge part of relay piping. In such a connected state, the eluate (liquid sample) eluted from the outlet of the column travels straight and flows into the flow path of the capillary via the relay pipe. Since the distance from the liquid sample leaving the column outlet to the capillary tip is short and the flow is linear, diffusion of components in the liquid sample can be suppressed. In addition, 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 between the column and the capillary or the relay pipe.

  In the liquid chromatograph mass spectrometer according to the present invention, the oven holding part is a holder that is fixed to the casing of the mass spectrometer and to which the column oven is attached. Can do.

  According to this configuration, the column oven can be fixed to the housing of the mass spectrometer via the oven holding unit. As a result, the column oven and the mass spectrometer are substantially integrated. For example, even when vibration is applied to the apparatus from the outside, a large force is applied to the connection between the column and the capillary or the relay pipe. It can certainly be avoided.

  In the liquid chromatograph mass spectrometer according to the present invention, the oven holding unit moves the column oven relative to a housing of the mass spectrometer in a direction perpendicular to the central axis of the outlet side end of the column. It is good to have a configuration that can be held in a closed state.

  According to this configuration, the assembly accuracy of the apparatus and the mounting accuracy of the oven holding portion vary greatly. For this reason, the central axis of the column outlet side end portion and the central axis of the capillary or relay pipe inlet side end portion are separated. Even when the position is not on the straight line, the variation can be absorbed by adjusting the position of the column oven by the oven holding section. Thereby, 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 abutted with high dimensional accuracy.

  In the liquid chromatograph mass spectrometer according to the present invention, the column oven is placed on the mass spectrometer in accordance with the direction in which the outlet end of the column and the capillary of the ionization probe or the inlet end of the relay pipe face each other. In other words, it may be a stacked structure, but it is more convenient to place it horizontally from the viewpoint of maintainability of the apparatus.

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

  In this configuration, the column oven is disposed on the side of the mass spectrometer via the oven holding unit, and the column outlet side end of the column oven and the ionization probe capillary or relay pipe inlet end are directly connected. Can do.

  Moreover, in the liquid chromatograph mass spectrometer of the said aspect, the said oven holding | maintenance part is reverse L shape by a front view, and the upper part which is this reverse L shape can be fixed in the state which mounted the said column oven. A configuration that is a fixed base is preferable.

  According to this configuration, the column oven is held by the inverted L-shaped oven holding unit in a state of floating from the installation surface of the mass spectrometer, and a space is formed between the installation surface and the fixing base of the oven holding unit. Is 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, or a control circuit can be installed. Thereby, the installation space of the apparatus can be used effectively.

  Moreover, the liquid chromatograph mass spectrometer of the said aspect WHEREIN: The said oven holding part is good to set it as the structure provided with the adjustment mechanism which adjusts the height of the said fixed stand.

  In this configuration, the height of the fixed base is adjusted by the adjustment mechanism so that the height of the column outlet side end and the ionization probe capillary or relay pipe inlet side end are accurately matched and connected. can do.

  In this case, it is preferable that an operation element operated by a user to adjust the height of the fixed base in the adjustment mechanism is provided at a position on the front surface of the apparatus.

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

  Furthermore, in the liquid chromatograph mass spectrometer according to the aspect described above, the oven holding unit includes the fixing base on which the column oven is mounted, and a mass analyzer side fixing unit fixed to a housing of the mass analyzer. The fixing base may be configured to be detachable in a vertical direction with respect to the mass spectrometer side fixing portion.

  According to this configuration, when performing a mass spectrometer alone without using a liquid chromatograph, only the fixed base is removed upward while the mass spectrometer-side fixing unit is mounted on the mass spectrometer housing. Can do. When there is no fixed base, space for mounting various types of ionization units by other ionization methods is secured instead of ionization probes by, for example, ESI method or APCI method. Analysis using such ionization units Is possible. In addition, a fixed base can be easily attached as necessary, and analysis combining a liquid chromatograph and a mass spectrometer can be quickly performed.

  According to the liquid chromatograph mass spectrometer of the present invention, the liquid chromatograph column outlet and the ionizer probe of the mass spectrometer are stably held in the liquid chromatograph column oven with respect to the mass spectrometer. The inlet end of the capillary can be connected directly or via a short straight tubular relay pipe. Thereby, even when an external force such as vibration is applied to the apparatus, 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. In addition, 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 linear, diffusion of the sample components separated by the column can be suppressed. Thereby, the sample component can be detected with high sensitivity even in the measurement of the low flow rate.

BRIEF DESCRIPTION OF THE DRAWINGS The outline external appearance front view of LC-MS which is one Example of this invention. The front view (a) and side view (b), (c) of the oven holder in LC-MS of a present Example. The schematic block diagram of the state which looked at the column and mass spectrometer of LC in LC-MS of a present Example from the front. The schematic block diagram of the state which looked at the column and ion source of LC in LC-MS of a present Example from upper direction. The general | schematic external appearance front view of the conventional general LC-MS.

Hereinafter, an LC-MS according to 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 example. Fig.2 (a) is a front view of the oven holder in LC-MS of a present Example, FIG.2 (b), (c) is a side view of the oven holder. 3 is a schematic configuration diagram of the LC column and mass spectrometer in the LC-MS of the present embodiment as viewed from the front, and FIG. 4 is a schematic diagram of the LC column and the ion source as viewed from above. It is a block diagram. As shown in the figure, for the sake of convenience, the lateral direction of the apparatus 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 example includes a liquid chromatograph 1 and a mass spectrometer 2. The liquid chromatograph 1 includes one or a plurality of units 10 (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 includes a box-shaped casing 11a, and includes an oven chamber in which a heater and a cooler (not shown) are disposed and whose periphery is covered with a heat insulating material. A column 110 is accommodated in the oven chamber. The unit 10 and the end of the column 110 on the inlet side are connected via a flexible pipe 12, and the mobile phase into which the sample is injected in the injector is fed to the column 110 through the pipe 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 in a housing 2a that is long in the X-axis direction together with a vacuum pump (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 ESI probe 22 that sprays charged droplets in an ionization chamber 21 maintained in a substantially atmospheric pressure atmosphere. The ionization probe 22 has a capillary 23 through which a liquid sample with a low flow rate flows, and an end portion on the inlet side of the capillary 23 is connected to a straight tubular relay pipe 25 by a joint 24. The part is taken out 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 channel extending in the horizontal direction is formed in the capillary 23 and the relay pipe 25. The relay pipe 25 is made of, for example, a resin such as PEEK (polyether ether ketone) resin. Since the metal capillary 23 is not exposed to the outside of the ionization probe 22, 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 110 a thereof is positioned 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 is connected to the outlet side end 110 a of the column 110.

  The entire analysis unit 200 is accommodated 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 close to the ionization chamber 21. Each of the chambers 202 to 204 is evacuated by a vacuum pump, and has a differential evacuation system configuration in which the degree of vacuum increases stepwise 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. Within the first intermediate vacuum chamber 202, a plurality of electrode plates arranged so as to surround the ion optical axis C are used. An ion guide 205 is provided. 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 includes a plurality of rod electrodes that surround the ion optical axis C. An ion guide 207 is installed. In the high vacuum chamber 204, a front quadrupole mass filter 208 and a rear quadrupole mass filter 211 are disposed with a collision cell 209 having an ion guide 210 disposed therein, and an ion detector 212 is further provided. Is provided.

  As described above, the eluate containing the components separated in the column 110 in a state where the outlet side end portion 110a of the column 110 and the inlet side end portion 23a of the capillary 23 of the ESI probe 22 are connected via the relay pipe 25. Is supplied to the capillary 23 via the relay pipe 25, charged droplets derived from the eluate are sprayed into the ionization chamber 21 from the end of the capillary 23. The charged droplet collides with the atmosphere and is refined, and the sample component becomes gas ions in the process of evaporation of the solvent. The generated ions are sucked into the desolvation tube 26 by the gas flow formed by the differential pressure across the desolvation tube 26 and 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 ESI probe 22 and the ion introduction direction into the desolvation tube 26 are both substantially in a straight line in the horizontal direction. However, when the apparatus is viewed from above as shown in FIG. 4, the central axis of the charged droplet spray flow and the central axis of the inlet end of the desolvation pipe 26 are not in a straight line but predetermined. The crossing has an angle of. This is to reduce the fact that neutral particles such as large charged droplets, solvent gas, or component molecules that are not ionized, which are not vaporized, enter the desolvation tube 26 as they are. 4, when the apparatus is viewed from above as shown in FIG. 4, the extending direction of the capillary 23 of the ESI probe 22 is slightly shifted 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 on a substantially 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 front quadrupole mass filter 208. Of the ions derived from the sample components introduced, only ions having a specific mass-to-charge ratio corresponding to the voltage applied to the front-stage quadrupole mass filter 208 pass through the front-stage quadrupole mass filter 208, and the precursor ions The collision cell 209 is entered. A CID (collision-induced dissociation) gas is introduced into the collision cell 209 continuously or intermittently, and the precursor ions are dissociated in contact with the CID gas to generate various product ions. This product ion is introduced into the post-stage quadrupole mass filter 211, and only product ions having a specific mass-to-charge ratio corresponding to the voltage applied to the post-stage quadrupole mass filter 211 pass through the post-stage quadrupole mass filter 211. It passes through and reaches the ion detector 212. The ion detector 212 generates a detection signal corresponding to the amount of ions that have reached.

In the LC-MS of the present embodiment, the outlet side end portion 110a of the column 110 and the inlet side end portion 23a of the capillary 23 are connected via a very short straight tubular relay pipe 25. Is adopted.
On the side surface (left side surface) on the side where the ion source 20 is located in the housing 2a of the mass spectrometer 2, an inverted L-shaped oven holder 3 is attached with screws or the like in front view. The oven holder 3 includes a fixing base 30 to which the column oven 11 is attached, and a mass analyzer-side fixing portion 31 that is fixed to the housing 2a of the mass analyzer 2.

  The fixed base part 30 includes a mounting base part 300 having a substantially horizontal holding plate on which the column oven 11 is placed in a shape bent in an inverted L shape, and an extending piece extending vertically downward integrally with the mounting base part 300. Part 301. On the other hand, the mass spectrometer-side fixing part 31 has a substantially U-shape when viewed from above with 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 extended piece part 301. ing. A plurality of claw portions 311 are formed inwardly from the pair of guide walls 310, and the extended piece portion 301 is held by the claw portions 311 so as to be slidable up and down with respect to the guide wall 310.

  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 apparatus, 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 rotation support portion 315 that is rotatable around an axis in the X-axis direction is provided on the slider 314. A triangular inclined guide piece 302 that is inclined with respect to the Y-axis direction is provided on the lower surface of the extended piece 301 of the fixed base 30, and the rotary support 315 is in contact with the inclined guide piece 302, Supports the entire 30.

  As shown in FIG. 1, the column oven 11 is fixed on the mounting table 300 of the oven holder 3 fixed to the left side surface of the housing 2 a of the mass spectrometer 2. This fixing may be a screw fixing or a fixing using another metal fitting. 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 end portion on the inlet side of the relay pipe 25 connected to the capillary 23 of the ESI probe 22 in the mass spectrometer 2 projects substantially horizontally from the housing 2a. At this time, if there is a deviation 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 ESI 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 height adjustment knob 312, 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 farthest rear, and FIG. 2C shows a state in which the slider 314 has moved to the farthest forward. When the rotation support part 315 moves together with the slider 314, the position of the inclined guide piece 302 in contact with the upper end of the rotation support part 315 changes. Therefore, when the user rotates the height adjustment knob 312, the entire fixed base 30 moves up and down according to the movement of the slider 314. The height adjustment range of the upper surface of the mounting table 300 of the fixed table 30 is d shown in FIG.

  That is, in the height direction (Z-axis direction), the difference 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 ESI probe 22 is absorbed by the distance d shown in FIG. It is possible. Thereby, for example, even if there is a dimensional error in assembly of the apparatus or an installation 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 ESI probe 22 The height can be aligned. Note that 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 ESI probe 22 is the position when the column oven 11 is placed on (mounted on) the mounting table 300. Can be absorbed by adjustment. Accordingly, after the opening of the outlet side end portion 110a of the column 110 and the opening of the inlet side end portion of the relay pipe 25 are accurately matched in a straight line, the column oven 11 itself is shifted in a direction approaching 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 is connected to the outlet side end 110 a of the column 110. As a result, the column 110 and the capillary 23 are connected 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 apparatus from the outside or a force that moves the column oven 11 is applied. Even in this case, a large force is not applied to the connection portion between the column 110 and the relay pipe 25, and it is possible to avoid disconnection or damage to the column 110, the relay pipe 25, or the capillary 23.

  Further, since the oven holder 3 has an inverted L shape when viewed from the front, a space is formed between the mounting table 300 and the installation surface of the apparatus as shown in FIG. Therefore, liquid chromatograph units other than the column oven 11 can be accommodated in this space, and the installation space can be used effectively. In addition, since the height of the mounting table 300 can be adjusted from the front, even if another unit is placed in the space below the mounting table 300 as described above, such a thing becomes an obstacle to the height adjustment. Never become.

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

  The above-described embodiment is merely an example of the present invention, and it is obvious that modifications, corrections, and additions may be made as appropriate within the scope of the present invention.

  For example, in the LC-MS of the above embodiment, the column 110 and the capillary 23 are 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. The structure connected to the part 110a may be sufficient. The capillary 23 is made of glass or other non-conductive material, 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 disposed so as to surround the tip of the capillary 23 in the vicinity thereof. In such a configuration, even if the inlet side end of the capillary 23 is pulled out of the housing 2a, the safety problem is small. Further, the relay pipe 25 may not necessarily be a single pipe but may be a plurality of connected pipes.

  Further, for example, in the LC-MS of the above example, the column oven was arranged on the side of the mass spectrometer using the oven holder, but the outlet side end of the column and the inlet side end of the capillary were If both extend vertically, fix the column oven with the oven holder above the mass spectrometer, that is, on the top of the mass spectrometer housing. Also good. In any case, the column oven should be fixed to the mass spectrometer so that the outlet end of the column and the inlet end of the capillary are aligned and the openings at both ends can be abutted. That's fine.

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

DESCRIPTION OF SYMBOLS 1 ... Liquid chromatograph 10 ... Unit 11 ... Column oven 11a ... Case 110 ... Column 110a ... Outlet side end 12 ... Pipe line ... Mass spectrometer 2a ... Case 20 ... Ion source 21 ... Ionization chamber 22 ... ESI probe 23 ... Capillary 24 ... Joint 25 ... Relay pipe 26 ... Solvent removal 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 ... First-stage quadrupole mass filter 209 ... Collision cell 211 ... Second-stage quadrupole mass filter 212 ... Ion detector 3 ... Oven holder 30 ... Fixing base part 300 ... Mounting base part 301 ... Extension piece part 302 ... Inclined guide piece 31 ... Mass spectrometer side fixing part 310 ... Guide wall 311 ... Claw part 312 ... Height adjustment knob 313 ... Feed 314 ... sliders 315 ... rotary bearing C ... ion optical axis

Claims (8)

In a liquid chromatograph mass spectrometer that introduces a liquid sample eluted from a liquid chromatograph column into a mass spectrometer and ionizes and analyzes components in the sample,
a) a column oven for controlling the temperature of the column accommodated therein;
b) An ionization probe that includes a capillary in which a flow channel through which the liquid sample introduced into the mass spectrometer flows is formed, and that ionizes components in the sample while spraying the liquid sample from the end of the capillary into the ionization chamber The inlet side end of the capillary or the inlet side end of the straight tubular relay pipe connected coaxially to the inlet side end of the capillary is taken out of the casing of the mass spectrometer. An ionization probe housed in the housing;
c) with respect to the casing of the mass spectrometer so that the central axis of the outlet side end of the column and the central axis of the capillary or the inlet side end of the relay pipe in the ionization probe are located on a straight line. An oven holding unit for holding the column oven;
A liquid chromatograph mass spectrometer comprising: The liquid chromatograph mass spectrometer according to claim 1,
The liquid chromatograph mass spectrometer according to claim 1, wherein the oven holder is a holder to which the column oven is mounted while being fixed to the casing of the mass spectrometer. The liquid chromatograph mass spectrometer according to claim 1,
The oven holding unit can hold the column oven in a state where the column oven is moved in a direction perpendicular to the central axis of the outlet side end 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 column outlet side end of the column oven and the central axis of the capillary or relay pipe inlet side end of the ionization probe are both horizontally extended, and the oven holding unit is A liquid chromatograph mass spectrometer characterized in that the column oven is held against a substantially upright side wall surface of a housing of the mass spectrometer. The liquid chromatograph mass spectrometer according to claim 4,
The oven holding part has an inverted L shape when viewed from the front, and the upper part of the inverted L shape is a fixed base that can be fixed with the column oven mounted thereon. Analysis equipment. The liquid chromatograph mass spectrometer according to claim 5,
The liquid chromatograph mass spectrometer according to claim 1, wherein the oven holding unit includes an adjustment mechanism for adjusting a height of the fixed base. The liquid chromatograph mass spectrometer according to claim 6,
A liquid chromatograph mass spectrometer comprising an operation element operated by a user to adjust the height of the fixed base in the adjustment mechanism at a position on the front surface of the apparatus. The liquid chromatograph mass spectrometer according to claim 5,
The oven holding unit includes the fixing base on which the column oven is mounted, and a mass spectrometer side fixing part fixed to a housing of the mass spectrometer, and the fixing base is fixed on the mass analyzer side A liquid chromatograph mass spectrometer, which is detachable in a vertical direction with respect to the unit.

Images