JP2007117850A - Sample spraying device for mass spectrometry - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To realize, without incompatibility, a combination of reduction of the temperature loss of the spray gas and enhancement of the degree of freedom of designing, enabling a reduction in power consumption of the electric heater for heating the spray gas to a predetermined temperature and stable and high-precision control of temperature, miniaturization of the whole body of the device and improvement of the maintenance characteristics, for a sample spray device for mass spectrometry which sprays an analyte sample at a predetermined temperature to ionize. <P>SOLUTION: The device has an insulated container 31 containing liquid nitrogen 32 for cooling, a heat exchanger 36 arranged close to a spray nozzle 51, insulation piping 35 guiding the liquid nitrogen 32 in the insulated container 31 to the cooling passage of the heat exchanger 36, a gas-supplying mechanism 21 supplying a spray gas to the cooling passage of the heat exchanger 36 and a variable heating mechanism 40 heating the gas having been cooled in the cooling passage to a predetermined temperature immediately before the spray nozzle 51. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sample spray apparatus for mass spectrometry used for subjecting a test sample to mass spectrometry, and particularly to an apparatus that is effective when applied to an electrospray ionization apparatus.

  The sample spray device for mass spectrometry is to spray and ionize the test sample introduced into the spray nozzle at a predetermined temperature by supplying the spray nozzle with a spray gas dried and temperature-controlled by cooling and heating. For example, it is used when mass spectrometry is performed without destroying a test sample such as a biopolymer such as protein and nucleic acid (see, for example, Patent Document 1).

  FIG. 5 schematically shows a conventional mass spectrometry sample spray apparatus 201. A device 201 shown in FIG. 1 includes a spray gas supply source 21, a vacuum heat insulating container (Dewar bin) 31, a heat exchanger 26, a temperature adjusting device 40, a spray nozzle 51, and the like.

  The spray gas supply source 21 generates high-pressure nitrogen gas as a spray gas (nebulizing gas). This spray gas is supplied to the cooling path of the heat exchanger 26 via the flow control valve 22.

  The vacuum heat insulating container 31 stores liquid nitrogen 32 as a cooling medium. The heat exchanger 26 is composed of a coiled conduit and is immersed in liquid nitrogen 32. The spray gas supplied from the spray gas supply source 21 is cooled to a very low temperature by being passed through the coiled conduit of the heat exchanger 26.

  The cooled spraying gas is conveyed to the temperature control device 40 through the gas conduit 261, where it is heated to a predetermined temperature and supplied to the spray nozzle 51. The temperature adjustment device 40 includes a temperature control device 41, an electric heater 42, and a temperature sensor 43, and heats the temperature while performing temperature feedback control so that the gas supplied to the spray nozzle 51 becomes a predetermined temperature.

  The high-pressure spraying gas is adjusted to a predetermined set temperature by the cooling means and the heating means described above, dried, and supplied to the spray nozzle 51. Although not shown, the spray nozzle 51 is supplied with a high-voltage electric field and a sample solution from a sample supply source 60. The sample solution is sprayed from the spray nozzle 51 together with the spray gas flow. During the spraying process, the sample is ionized and introduced into the mass spectrometer 10.

JP 2003-157793 A

It has been clarified by the present inventors that the above-described conventional apparatus has the following problems. That is,
(A) The spray gas is once cooled to a very low temperature by the heat exchanger 26 in the liquid nitrogen 32, but the cooled gas is warmed by the outside air (environment temperature) from the moment of leaving the heat insulating container 31. The magnitude of this temperature loss (cooling heat loss) increases as the gas transport distance between the heat insulating container 31 and the spray nozzle 51 increases. Therefore, in order to reduce the temperature loss, it is desirable to install the heat insulating container 31 as close to the spray nozzle 51 as possible.

  However, since the spray nozzle 51 is installed and used in a form attached to the mass spectrometer, the space around the spray nozzle 51 is severely limited, so that the liquid nitrogen 32 and the heat exchanger 26 are accommodated. There is almost no room to install a heat insulating container 31. For this reason, if the heat insulation container 31 is disposed close to the spray nozzle 51, the shape and size of the heat insulation container 31 are greatly restricted. That is, when trying to reduce the temperature loss of the spray gas, there arises a contradictory problem that the degree of freedom of design is significantly hindered.

  (B) The temperature of the gas sprayed from the spray nozzle greatly affects the ionization efficiency of the test sample. The optimum temperature of the gas varies from sample to sample. For this reason, the temperature of the spray gas is adjusted to an optimum temperature according to the sample before the spray nozzle 51. This heating adjustment is performed using an electric heater 42 and a temperature sensor 43.

  In order to reliably perform this heating adjustment, it is necessary to cool the spray gas in consideration of the magnitude of temperature loss and temperature fluctuation during gas transportation. As described above, the cooling of the spray gas is performed in the liquid nitrogen 32. The amount of cooling is determined by the gas flow rate, the thermal conductivity of the pipe, the heat exchange efficiency, etc. Therefore, it is extremely difficult to control the cooling amount.

  For this reason, the temperature control of the spray gas can only be performed by adjusting the temperature before the spray nozzle 51. In order to ensure the warming adjustment, the spray gas before the warming adjustment must be cooled so that it is always lower than the set temperature.

  For this reason, the gas cooling in the heat exchanger 26 is performed so as to be always excessive in any case in anticipation of indeterminate temperature loss during gas transportation, a change in the set temperature, and the like. For this reason, there are cases where it is necessary to adjust the temperature of the gas that has been cooled excessively more than the set temperature. In this case, the heating load is remarkably increased, the power consumption of the electric heater is increased, and stable and highly accurate temperature control becomes difficult.

  (C) The heat exchanger 26 needs to have a sufficiently large cooling capacity in order to perform overcooling as described above. For this reason, there is a problem that the heat exchanger 26 is increased in size, and the heat insulating container 31 is increased in size, and the size of the entire apparatus is increased.

  (D) Nitrogen gas is normally used as the spray gas, but since a large amount is used, a nitrogen gas generator is generally used. In this case, the gas purity is about 99%, and when the open air is not sufficiently low, moisture condenses and freezes while passing through the pipe in the heat exchanger 26 in the liquid nitrogen 32 and accumulates in the pipe. Further, the gas flow is obstructed and stable operation becomes difficult. In this case, the frozen water must be removed.

  However, the removal operation cannot be performed unless all the piping including the heat exchanger 26 is taken out from the heat insulating container 31 containing the liquid nitrogen 32 or all the liquid nitrogen 32 in the heat insulating container 31 is removed. It was very troublesome and the operation of the apparatus had to be stopped for a long time for the work. That is, there is a problem that the maintainability of the heat exchanger 26 is poor.

  The present invention has been made in view of the above problems, and its purpose is to reduce both the temperature loss of the spray gas and increase the degree of freedom in design, and to improve the spray gas. Reduce power consumption and stable and highly accurate temperature control of the electric heater that adjusts the temperature to the set temperature, reduce the overall size of the device, improve maintainability, and contradict each other Not to achieve.

  Other objects and configurations of the present invention will become apparent from the description of the present specification and the accompanying drawings.

  Means provided by the present invention are as follows.

  (1) A sample spray for mass spectrometry in which a test gas introduced into the spray nozzle is sprayed and ionized at a predetermined temperature by supplying a spray gas dried and temperature-controlled by cooling and heating to the spray nozzle. In the apparatus, a heat insulating container for storing the cooling liquid nitrogen, a heat exchanger installed in the vicinity of the spray nozzle, and a heat insulating pipe for guiding the liquid nitrogen in the heat insulating container to the cooling flow path of the heat exchanger. A gas supplying means for supplying a gas for spraying to the channel to be cooled of the heat exchanger; and variable heating for heating the gas cooled in the channel to be cooled to an arbitrary set temperature just before the spray nozzle. And a sample spray apparatus for mass spectrometry.

  (2) In the above means (1), a sample spray apparatus for mass spectrometry, wherein the heat insulation pipe is constituted by using a vacuum heat insulation pipe in which a liquid nitrogen transport pipe is surrounded by a flexible outer tube.

  (3) The sample spray apparatus for mass spectrometry, wherein the heat exchanger and the variable heating means are structurally integrated in the means (1) or (2).

  (4) In any one of the means (1) to (3), the heat exchanger and the variable heating means are structurally integrated with the spray nozzle. .

  (5) The sample spray apparatus for mass spectrometry according to any one of the means (1) to (4), wherein a flow rate control valve for controlling a flow rate of liquid nitrogen in the heat exchanger is provided.

  (6) In any one of the above means (1) to (5), the heat exchanger is a multiplex in which the inner cylinder and the outer cylinder are arranged coaxially and an annular cross-sectional flow path is formed between the two cylinders. The outer cylinder is formed so as to allow the spray gas to pass from one end to the other end of the annular cross-section flow path, and the inner cylinder is supplied through the heat insulating pipe with a heat radiating portion formed by bellows-like irregularities. A sample spray apparatus for mass spectrometry, characterized in that an introduction pipe and a lead-out pipe for circulating liquid nitrogen in the cylinder in the cylinder length direction are provided.

  Reducing the temperature loss of the spray gas and increasing the degree of freedom of design, reducing the power consumption of the electric heater that adjusts the temperature of the spray gas to the set temperature, and stable and highly accurate temperature control It can be achieved, the overall size of the apparatus can be reduced, the maintainability can be improved, and these can be achieved without contradicting each other.

  This makes it possible to perform mass analysis of a wide variety of test samples in an appropriate and efficient manner.For example, when a mass analyzer is used in combination with a chromatograph, it is optimal for the sample type that changes from moment to moment. It is also possible to variably set the spray conditions continuously.

 Operations / effects other than those described above will be apparent from the description of the present specification and the accompanying drawings.

  FIG. 1 is a schematic system diagram showing an embodiment of a sample spray apparatus for mass spectrometry according to the present invention.

  The mass spectrometric sample spray apparatus 20 shown in FIG. 1 supplies the spray nozzle 51 with a spray gas dried and temperature-controlled by cooling and warming, so that the test sample introduced into the spray nozzle 51 is heated to a predetermined temperature. And is used for mass spectrometry without destroying a test sample such as a biopolymer such as protein or nucleic acid.

The sample spray apparatus 20 for mass spectrometry of this embodiment is configured as an electrospray ionization apparatus, and includes a gas supply source 21 for spraying, a vacuum heat insulating container (Durbin) 31, a vacuum heat insulating pipe 35, a heat exchanger 36, a temperature control device 40, It consists of a spray nozzle 51 and the like.
A nitrogen gas generator is used as the spray gas supply source 21. High-pressure nitrogen gas is supplied as a spray gas (nebulizing gas) from the gas supply source 21 to the spray nozzle 51 through the flow control valve 22 and the heat exchanger 36.

  Liquid nitrogen 32 is accommodated in the vacuum heat insulation container 31, and a transport pipe 33 of a vacuum heat insulation pipe 35 is inserted into the liquid nitrogen 32. The vacuum heat insulating pipe 35 has a double pipe structure in which a transport pipe (flexible tube) 33 for liquid nitrogen 32 is surrounded by a flexible outer tube 34, and the two pipes 33 and 34 are vacuum insulated. The liquid nitrogen 32 in the container 31 is transported to the heat exchanger 36 by the vacuum insulation pipe 35.

  The heat exchanger 36 is installed on the same casing or base member as that of the temperature control device 40 and is structurally integrated, and is installed close to the spray nozzle 51. The heat exchanger 36 has a cooling channel and a channel to be cooled for performing heat exchange between the liquid nitrogen and the spray gas.

  The cooling channel of the heat exchanger 36 has an inflow side connected to the heat insulation pipe 35, and an outflow side connected to the suction pump 38 via the gas flow rate control valve 37, so that the liquid nitrogen 32 in the vacuum heat insulation container 31 is insulated from the heat insulation pipe 31. It flows through a predetermined flow rate through 35. Liquid nitrogen as a cooling medium is vaporized by heat exchange, and is sucked and exhausted by a suction pump 38 through a gas flow rate control valve 37. The flow rate of the liquid nitrogen, that is, the cooling amount can be variably controlled by adjusting the flow rate at the gas flow rate control valve 37.

  A spray gas (dry nitrogen gas) generated from the spray gas supply source 21 is introduced into the channel to be cooled of the heat exchanger 36 via the gas flow rate control valve 22. The introduced gas is cooled by exchanging heat with liquid nitrogen in the cooling channel. The cooled spray gas is immediately heated to the set temperature by the temperature adjusting device 40.

  The temperature adjusting device 40 constitutes a variable heating means, and includes a temperature control device 41, an electric heater 42, and a temperature sensor 43, and temperature feedback such that the gas supplied to the spray nozzle 51 becomes a set temperature. Warm while controlling.

  The high-pressure spraying gas is adjusted to a predetermined set temperature by the cooling means and the heating means described above, dried, and supplied to the spray nozzle 51. Although not shown, the spray nozzle 51 is supplied with a high-voltage electric field and a sample solution from a sample supply source 60. The sample solution is sprayed from the spray nozzle 51 together with the spray gas flow. During the spraying process, the solvent of the sample is vaporized and separated, and the sample is ionized and introduced into the mass spectrometer 10.

  In the apparatus 20 described above, the heat exchanger 36 is installed not in the heat insulating container 31 containing the liquid nitrogen 32 but in the vicinity of the spray nozzle 51, so that the spray gas cooled by the liquid nitrogen can be obtained. The temperature loss and temperature fluctuation caused by being heated by the outside air (environmental temperature) can be made much smaller than before.

  Since the liquid nitrogen 32 in the heat insulating container 31 is guided to the cooling flow path of the heat exchanger 36 by the vacuum heat insulating pipe 35, the heat insulating container 31 does not need to be disposed close to the heat exchanger 36 and is installed at an arbitrary position. can do. Thereby, there is no restriction on the shape and size of the heat insulating container 31, and it is possible to achieve both the reduction of the temperature loss of the spray gas and the increase in the degree of freedom of design.

  The spray gas is adjusted to a set temperature according to the test sample by heating the gas once cooled. However, as described above, the temperature loss and temperature fluctuation after cooling can be reduced in the present invention. Therefore, the amount of excessive cooling can be significantly reduced as compared with the conventional case. Thereby, the heating load is reduced, the power consumption of the electric heater can be reduced, and the temperature control can be performed stably and with high accuracy.

  As described above, the temperature range between the temperature before the temperature adjustment and the set temperature can be reduced, but this makes it possible to improve the control response until the temperature is adjusted to the set temperature. Furthermore, in the above embodiment, the flow control valve 37 for controlling the flow rate of liquid nitrogen in the heat exchanger 36 is provided. However, the control flow rate of the flow control valve 37 is variably controlled in conjunction with the temperature adjustment control. This makes it possible to variably control the cooling amount easily and quickly.

  As a result, the variable range (dynamic range) of the set temperature can be expanded, and the temperature can be adjusted smoothly and quickly at any set temperature. Therefore, for example, when a mass spectrometer is used in combination with a chromatograph, it is possible to obtain an effect that the optimum spray conditions can be continuously variably set according to the sample type that changes every moment.

  In addition, due to the above, the cooling capacity of the heat exchanger 36 can be significantly reduced as compared with the conventional case. As a result, the heat exchanger 36 can be downsized and the structure thereof can be simplified, and the overall size of the apparatus can be reduced.

  The moisture of the spray gas condenses and freezes in the heat exchanger 36. However, in the apparatus of the present invention, as described above, the heat exchanger 36 is miniaturized and the structure is simplified, thereby preventing the gas flow due to freezing. Can be made less frequent than before.

  Even when a gas flow failure occurs due to freezing, the removal operation can be performed easily and in a short time by stopping the supply of the liquid nitrogen 32. In other words, it has excellent maintainability.

  As described above, the sample spray device for mass spectrometry 20 according to the above-described embodiment includes the heat insulating container 31 that stores the cooling liquid nitrogen 32, the heat exchanger 36 that is installed in the vicinity of the spray nozzle 51, and the heat insulating container 31. In the heat insulating pipe 35 that leads the liquid nitrogen 32 to the cooling flow path of the heat exchanger 36, the gas supply source 21 that supplies the spray gas to the cooled flow path of the heat exchanger 36, and the cooled flow path of the heat exchanger 36. The temperature adjustment device 40 that heats the cooled gas to an arbitrary set temperature immediately before the spray nozzle 51 makes it possible to reduce both the temperature loss of the spray gas and increase the degree of design freedom. To reduce the power consumption and stable and highly accurate temperature control of the electric heater that adjusts the temperature of the working gas to the set temperature, to reduce the overall size of the device, to improve maintainability, Without contradictory Luo each other, it can be achieved.

  This makes it possible to perform mass analysis of a wide variety of test samples in an appropriate and efficient manner.For example, when a mass analyzer is used in combination with a chromatograph, it is optimal for the sample type that changes from moment to moment. Spray conditions can be continuously variably set.

  Moreover, even if the distance between the heat insulation container 31 and the heat exchanger 36 is separated by using a vacuum heat insulation pipe in which the liquid nitrogen transport pipe 33 is surrounded by a flexible outer tube 34 as the heat insulation pipe 35, the heat exchanger Liquid nitrogen required for cooling at 36 can be supplied without waste.

  By providing the flow rate control valve 37 for controlling the liquid nitrogen flow rate in the heat exchanger 36, variable control of the cooling amount can be performed smoothly and quickly. If the flow control valve 37 is linked to the control of the temperature control device 40, the amount of liquid nitrogen and the power consumption of the electric heater are both minimized by the optimization control of the cooling amount and the heating amount. The setting range can be greatly expanded.

  Furthermore, since the heat exchanger 36 and the temperature control device 40 are structurally integrated, the temperature loss at which the spray gas cooled by the heat exchanger 36 is heated by the outside air can be minimized. Thus, the above effect can be further enhanced.

  FIG. 2 shows an embodiment in which the heat exchanger 36, the temperature adjusting device 40, and the spray nozzle 51 are structurally integrated. As schematically shown in the figure, the heat exchanger 36, the temperature control device 40, and the spray nozzle 51 can be integrated into a single casing in a structural manner.

  According to the above configuration, the temperature loss of the spray gas can be further reduced, and the control accuracy and responsiveness of the temperature adjustment can be further improved.

  FIG. 3 shows a specific embodiment of the heat exchanger 36. The heat exchanger 36 shown in the figure is composed of an inner cylinder 362 and an outer cylinder 361. A small-diameter cylinder portion is extended in the axial direction at the tip of the outer cylinder 361, and an electric heater 42 is annularly formed outside the extension cylinder portion. It is provided in a surrounding form.

  The inner cylinder 362 and the outer cylinder 361 are arranged coaxially to form a multiple (double) cylinder. Between both the cylinders 362 and 361, a channel having an annular cross section is formed. The outer cylinder 361 is formed so as to allow the spray gas to pass from one end of the annular cross-section flow path to the other end. The inner cylinder 362 is provided with a heat radiating portion having bellows-like irregularities, and provided with an introduction pipe 363 and an outlet pipe 364 for circulating liquid nitrogen supplied through the heat insulating pipe 35 in the cylinder 362 in the cylinder length direction.

  In the heat exchanger 36 of this embodiment, the flow direction of the spray gas is substantially constant in the cylinder axis direction, so that the gas flow is smooth, and the heat radiation area (heat conduction area) is wide due to the bellows-like irregularities of the inner cylinder 362. Has the advantage that the heat exchange efficiency is also good. Furthermore, since the structure is simple, the gas flow is hardly inhibited by freezing of moisture, and even if it occurs, it can be easily removed. So-called maintainability is good.

  FIG. 4 shows another embodiment of the present invention. In this embodiment, two systems for gas cooling and heating are provided. In the first system, a spray gas having a set temperature is supplied to the spray nozzle 51, and in the second system, a necessary dry gas is supplied to the introduction port portion of the ion introduction tube 71. The ion introduction tube 71 is feedback-controlled to a predetermined temperature using an electric heater 72 and a temperature sensor 73. The sample sprayed from the spray nozzle 51 is introduced into the mass spectrometer 10 as a subsequent device via the ion introduction tube 71.

  As in the above-described embodiment, the first system includes a spray gas supply source 21, a gas flow rate control valve 22A, a vacuum heat insulation container (Duerbin) 31, a vacuum heat insulation pipe 35A, a heat exchanger 36A, a gas flow rate control valve 36A, It has a suction pump 38 and a temperature adjusting device 40A, and supplies the gas whose temperature is adjusted by cooling and heating to the spray nozzle 51.

  The second system uses the spray gas supply source 21, the vacuum insulation container 31 and the suction pump 38 in common with the first system, and includes a gas flow rate control valve 22B, a vacuum insulation pipe 35B, a heat exchanger 36B, By providing the gas flow rate control valve 36 </ b> B and the temperature adjustment device 40 </ b> B, a dry gas having a predetermined temperature is supplied to the introduction port portion of the ion introduction tube 71.

  Even in the above apparatus, highly stable temperature control is possible over a wide range from about −150 ° C. to about + 200 ° C. for both the spraying gas and the drying gas. In addition, after low temperature use such as cold spraying, impurities adsorbed near the ion introduction port can be removed by heating with a heater 72 attached to the ion introduction tube 71. After this heat treatment, the ion introduction tube 71 can be rapidly cooled by supplying a cryogenic drying gas, so that the next measurement can be performed quickly.

  Thus, the apparatus 20 of the present invention can construct a plurality of gas supply systems by using the vacuum heat insulating container 31 containing the liquid nitrogen 32 and the suction pump 38 in common.

  As mentioned above, although this invention was demonstrated based on the typical Example, this invention can have various aspects other than having mentioned above. For example, the spray gas may be an inert gas other than nitrogen gas.

  In a sample spray apparatus for mass spectrometry that sprays and ionizes a test sample at a predetermined temperature, reducing both the temperature loss of the spray gas and increasing the degree of design freedom, and setting the spray gas to the set temperature Achieved reduction in power consumption and stable and highly accurate temperature control of the electric heater that controls heating, downsizing of the overall size of the device, improvement of maintainability, without contradicting each other can do.

  This makes it possible to perform mass analysis of a wide variety of test samples in an appropriate and efficient manner.For example, when a mass analyzer is used in combination with a chromatograph, it is optimal for the sample type that changes from moment to moment. It is also possible to variably set the spray conditions continuously.

1 is a schematic system diagram showing an embodiment of a sample spray apparatus for mass spectrometry according to the present invention. It is a schematic diagram which shows the structural example of the heat exchanger which concerns on this invention, a temperature regulator, and a spray nozzle. It is an abbreviated sectional view showing an example of composition of a heat exchanger concerning the present invention. 1 is a schematic system diagram showing an embodiment of a sample spray apparatus for mass spectrometry according to the present invention. It is a schematic system diagram which shows the structure of the conventional sample spray apparatus for mass spectrometry.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Mass spectrometer 20 Sample spray apparatus for mass spectrometry 21 Gas supply source for spray 22 Gas flow control valve 31 Vacuum insulated container (Durbin)
32 Liquid nitrogen 33 Transport pipe 34 Outer tube 35 Vacuum heat insulation pipe 36 Heat exchanger 361 Outer cylinder 362 Inner cylinder 363 Introduction pipe 364 Outlet pipe 37 Gas flow control valve 38 Suction pump 40 Temperature control device (variable heating means)
41 Temperature Controller 42 Electric Heater 43 Temperature Sensor 51 Electrospray 60 Sample Supply Source 71 Iontophoresis Tube 72 Electric Heater 73 Temperature Sensor

Claims (6)

  In the sample spray apparatus for mass spectrometry, spraying the test sample introduced into the spray nozzle at a predetermined temperature and ionizing the spray nozzle by supplying a spray gas dried and temperature-controlled by cooling and heating to the spray nozzle. A heat insulating container for storing liquid nitrogen for cooling; a heat exchanger installed close to the spray nozzle; a heat insulating pipe for guiding the liquid nitrogen in the heat insulating container to a cooling flow path of the heat exchanger; and the heat. A gas supply means for supplying a gas for spraying to the cooled flow path of the exchanger; and a variable heating means for heating the gas cooled in the cooled flow path to an arbitrary set temperature immediately before the spray nozzle. A sample spray device for mass spectrometry, comprising:   2. The sample spray apparatus for mass spectrometry according to claim 1, wherein the heat insulation pipe is configured using a vacuum heat insulation pipe in which a liquid nitrogen transport pipe is surrounded by a flexible outer tube.   3. The sample spray apparatus for mass spectrometry according to claim 1 or 2, wherein the heat exchanger and the variable heating means are structurally integrated.   The sample spray apparatus for mass spectrometry according to any one of claims 1 to 3, wherein the heat exchanger and the variable heating means are structurally integrated with the spray nozzle.   The sample spray apparatus for mass spectrometry according to any one of claims 1 to 4, further comprising a flow rate control valve for controlling a flow rate of liquid nitrogen in the heat exchanger.   5. The heat exchanger according to claim 1, wherein the heat exchanger is formed by a multiple cylinder in which an inner cylinder and an outer cylinder are arranged coaxially and an annular cross-sectional flow path is formed between the two cylinders. Is formed so as to allow the gas for spray to pass from one end to the other end of the annular cross-section flow path, and the inner cylinder is formed with a heat radiating portion by bellows-like irregularities and liquid nitrogen supplied through the heat insulating pipe is formed inside the cylinder. A sample spray device for mass spectrometry, characterized in that an introduction tube and a discharge tube that are circulated in a cylinder length direction are provided.

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