JP2019140044A - Ionizer - Google Patents

Abstract

To provide an ionizer having a structure suitable for mass spectrometry.SOLUTION: An ionizer 1 comprises: a cylindrical capillary 20 for spraying a solvent to supply to a base end from its leading end. The capillary 20 comprises spiral elongated strips 23 on its inner peripheral face, extending along and around an axial direction and providing a whirling motion to the solvent. The capillary 20 further comprises: an inside cylinder 21 shaped in a cylindrical form and allowing the solvent to circulate therein; and an outside cylinder 22 disposed outward in a radial direction of the inside cylinder 21 and allowing an ancillary fluid to circulate between the inner peripheral face and an outer peripheral face of the inside cylinder 21. The spiral elongated strips 23 are disposed along an inner peripheral face of the inside cylinder 21 in an axial direction, which may be further disposed on at least one of the outer peripheral face of the inside cylinder 21 and an inner peripheral face of the outside cylinder 22 along the axial direction.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an ionization apparatus.

  An electrospray ionization apparatus (hereinafter referred to as ESI) that includes a capillary and sprays droplets containing at least two kinds of solvents from the tip of the capillary is known. The ESI is a device that sprays ionized droplets from the tip of the capillary by applying a voltage to the capillary. As an example of such an apparatus, an apparatus used as a set with a mass spectrometer has been proposed (see, for example, Patent Document 1).

US Patent Publication No. 8203117

The apparatus described in Patent Document 1 mounts an object to be measured on a stage and sprays droplets (hereinafter referred to as primary droplets) from the capillary onto the object to be measured. As a result, a droplet including a fragment of the object to be measured (hereinafter referred to as a secondary droplet) is scattered. When the secondary droplet enters the entrance of the mass spectrometer, the mass of the molecules contained in the secondary droplet is analyzed by the mass spectrometer.
By the way, in the mass spectrometer, in order to detect the mass of the molecule contained in the secondary droplet more accurately, it is preferable that ESI has a structure more suitable for mass spectrometry.

  An object of this invention is to provide the ionization apparatus which has a structure more suitable for mass spectrometry.

  The present invention is an ionization apparatus including a cylindrical capillary that sprays a solvent supplied to a base end portion from the tip, and the capillary performs a swiveling motion on the inner circumferential surface along the axial direction. The present invention relates to an ionization apparatus including a turning slew.

  The capillary has a cylindrical shape, and is an inner cylinder capable of circulating a solvent therein, and an outer cylinder disposed radially outward of the inner cylinder, the inner circumferential surface and the outer circumferential surface of the inner cylinder. An outer cylinder through which auxiliary fluid can be circulated, and the spiral is disposed along the axial direction on the inner peripheral surface of the inner cylinder, and the outer peripheral surface of the inner cylinder and the outer cylinder It is preferable that it is further disposed along at least one of the inner peripheral surfaces of the outer cylinder along the axial direction.

  Moreover, it is preferable that a pitch becomes large as the said spiral goes to the front-end | tip part from the base end part of the said inner cylinder or the said outer cylinder.

  ADVANTAGE OF THE INVENTION According to this invention, the ionization apparatus which has a structure more suitable for mass spectrometry can be provided.

1 shows a schematic diagram of an ionization apparatus according to a first embodiment of the present invention. The fragmentary enlarged view of the axial cross section of the capillary of 1st Embodiment is shown. The top view of the outer peripheral surface of the inner cylinder of 1st Embodiment is shown. It is the schematic which shows the change of the state of the secondary droplet of 1st Embodiment. The schematic of the ionization apparatus which concerns on 2nd Embodiment of this invention is shown. The schematic of the ionization apparatus which concerns on 3rd Embodiment of this invention is shown. The block diagram of the control part of the ionization apparatus which concerns on 7th Embodiment of this invention is shown. It is the schematic which shows the moving direction of the stage of 7th Embodiment. It is a graph which shows the change of the mixing rate of the solvent changed by the supply part of 7th Embodiment. It is a graph which shows typically intensity information of a 7th embodiment.

  Hereinafter, an ionization apparatus 1 according to each embodiment of the present invention will be described with reference to FIGS.

[First Embodiment]
First, an ionization apparatus 1 and an analysis system according to a first embodiment of the present invention will be described with reference to FIGS.
The analysis system (not shown) is a system that analyzes the molecular mass (ionic strength) contained in the measurement object S (for example, a biological tissue impregnated with another molecule such as a drug). The analysis system includes a mass spectrometer 100 (see FIG. 8) and an ionizer 1.
The mass spectrometer 100 is an apparatus that can output the molecular mass (ion intensity) of ions contained in a fragment of the measurement object S introduced into the entrance E.

  As shown in FIG. 1, the ionization apparatus 1 is an apparatus that sprays two or more types of solvents as primary droplets f toward the object S to be measured. The ionization apparatus 1 is an apparatus that obtains secondary droplets g including ionized fragments of the measurement object S by spraying the primary droplet f toward the measurement object S. And the ionization apparatus 1 is an apparatus which can miniaturize the droplet (especially secondary droplet g) to be sprayed. The ionization apparatus 1 is disposed adjacent to the inlet E (inlet) of the mass spectrometer 100 that analyzes the mass of the object S to be measured. Specifically, the ionization apparatus 1 includes a casing (not shown) that is set to a positive pressure from the inside of the mass spectrometer 100. The inlet E of the mass spectrometer 100 is disposed inside the casing. The ionization apparatus 1 includes a stage 10, a capillary 20, a supply unit 30, a power supply unit 40, a sound wave irradiation unit 50, and a control unit 60. In the following embodiments, when simply described as “droplet”, it indicates at least one of “primary droplet f” and “secondary droplet g”.

  The stage 10 is a mounting table on which the measurement object S is mounted. The stage 10 is formed in a plate shape, for example. The stage 10 is disposed in the vicinity of the inlet E of the mass spectrometer 100.

  The capillary 20 has a cylindrical shape, and is configured to be able to spray the solvent supplied to the proximal end portion from the distal end portion. The capillary 20 is formed of a conductive material. The capillary 20 is disposed with the tip portion directed toward the stage 10 (measurement object S) and is disposed at a predetermined distance from the stage 10. The tip of the capillary 20 is disposed opposite to the inlet E of the mass spectrometer 100. The axial direction of the capillary 20 is arranged so as to overlap a line connecting the inlet E of the mass spectrometer 100 and the object S to be measured. The capillary 20 is arranged to be inclined with respect to the stage 10 by an angle at which the secondary droplet g can be incident toward the inlet E of the mass spectrometer 100. In the present embodiment, the capillary 20 has a double structure in the radial direction. That is, the capillary 20 includes an inner cylinder 21 and an outer cylinder 22. Further, the capillary 20 includes a swirl 23.

  The inner cylinder 21 is disposed so that the tip thereof faces the stage 10. The inner cylinder 21 can distribute two types of mixed solvents therein.

  The outer cylinder 22 has a larger inner diameter than the inner cylinder 21. The outer cylinder 22 is disposed radially outward of the inner cylinder 21. That is, the outer cylinder 22 can circulate auxiliary fluid (for example, N2, other solvents, etc.) between the inner peripheral surface and the outer peripheral surface of the inner cylinder 21.

  As shown in FIGS. 2 and 3, the swirl 23 is disposed on the inner peripheral surface along the axial direction of the inner cylinder 21. The swirl 23 swirls the solvent flowing through the inner cylinder 21. Further, the spiral 23 is arranged along the axial direction on at least one of the outer peripheral surface of the inner cylinder 21 and the inner peripheral surface of the outer cylinder 22. In the present embodiment, the swirl 23 is disposed on both the outer peripheral surface of the inner cylinder 21 and the inner peripheral surface of the outer cylinder 22. The swirl 23 swirls the auxiliary fluid flowing between the outer peripheral surface of the inner cylinder 21 and the outer peripheral surface of the outer cylinder 22.

  According to the capillary 20 described above, two types of mixed solvents are supplied from the proximal end portion of the inner cylinder 21 toward the distal end portion. As a result, the two types of solvent are sprayed as primary droplets f from the tip of the inner cylinder 21 toward the measurement object S on the stage 10. At this time, the two types of solvent are sprayed from the tip of the inner cylinder 21 while making a swiveling motion by the swirl 23.

  In addition, the auxiliary fluid is supplied from the proximal end portion between the inner cylinder 21 and the outer cylinder 22 toward the distal end portion. At this time, the auxiliary fluid is discharged from between the inner cylinder 21 and the outer cylinder 22 while performing a swiveling motion by the spiral 23. The primary droplet f is sprayed on the measurement object S, thereby fragmenting the measurement object S. The fragmented measurement object S is included in the primary droplet f reflected by the measurement object S. Thereby, the primary droplet f reflected by the measurement object S becomes the secondary droplet g.

  The supply unit 30 is connected to the proximal end portion of the capillary 20. Specifically, the supply unit 30 is connected to the proximal end portion of the inner cylinder 21. The supply unit 30 is configured to be able to dynamically change the mixing ratio of at least two types of solvents. In this embodiment, the supply part 30 is comprised so that the mixing rate of two types of solvents can be changed dynamically. The supply unit 30 includes two pump units 31 and a mixer 32.

  Each of the pump units 31 is, for example, a syringe pump, and is configured to be able to supply different solvents. Specifically, each of the pump units 31 is configured to be able to supply different solvents with a set supply amount.

  The mixer 32 is a device that mixes the solvents against the back pressure of the two solvents. The mixer 32 is connected to the two pump portions 31 and is connected to the proximal end portion of the inner cylinder 21. The mixer 32 mixes the solvent supplied from each of the two pump units 31. The mixer 32 supplies the mixed solvent to the proximal end portion of the inner cylinder 21.

  The power supply unit 40 is connected to the capillary 20 (inner cylinder 21). The power supply unit 40 applies a high voltage to the inner cylinder 21. Accordingly, the power supply unit 40 ionizes the mixed solvent that circulates inside the inner cylinder 21.

  The sound wave irradiation unit 50 irradiates the sprayed droplets with sound waves having a predetermined frequency. In the present embodiment, the sound wave irradiation unit 50 irradiates the secondary droplet g reflected by the measurement object S with a sound wave having a predetermined period. The sound wave irradiation unit 50 emits ultrasonic waves, for example. The sound wave irradiation unit 50 is arranged in front of the reflection position of the secondary droplet g (between the capillary 20 and the reflection position) in the direction along the reflection direction of the secondary droplet g. In other words, the sound wave irradiation unit 50 is disposed at a position where the entrance E of the mass spectrometer 100 is desired through the reflection position in the direction along the reflection direction of the secondary droplet g. The sound wave irradiation unit 50 irradiates sound waves in a direction toward the entrance E of the mass spectrometer 100 along the reflection direction of the secondary droplet g.

  The control unit 60 is connected to the two pump units 31 and the stage 10. The control unit 60 is configured to be able to dynamically change the operation amounts of the two pump units 31. That is, the control unit 60 is configured to be able to dynamically change the mixing ratio of the solvent by the two pump units 31. In the present specification, “dynamically changeable” is not limited to being able to be changed continuously (for example, linearly or curvedly), but also includes being able to be changed in a spot manner. The control unit 60 is configured to be able to instruct the operation of the stage 10 (for example, movement in the in-plane direction).

Next, operations of the ionization apparatus 1 and the analysis system according to the present embodiment will be described.
First, the control unit 60 determines the operation amounts of the two pump units 31 based on a preset mixing ratio. The control unit 60 operates the pump unit 31 with the determined operation amount. Thereby, the mixed solvent is supplied to the proximal end portion of the inner cylinder 21. An auxiliary fluid is supplied between the inner cylinder 21 and the outer cylinder 22.

  Next, the power supply unit 40 starts applying a voltage to the inner cylinder 21. Thereby, the solvent supplied to the base end part of the inner cylinder 21 is ionized. The ionized solvent is sprayed from the tip of the inner cylinder 21 toward the object to be measured S as primary droplets f. At this time, the solvent is sprayed on the measurement object S while being swung by the swirl 23 provided on the inner peripheral surface of the inner cylinder 21. In addition, the auxiliary fluid that has circulated between the inner cylinder 21 and the outer cylinder 22 is swung by the swirl 23 provided on the outer peripheral surface of the inner cylinder 21 and the inner peripheral surface of the outer cylinder 22, while the workpiece S is measured. Is released towards

  The object to be measured S is partially fragmented by spraying the ionized primary droplet f. Further, the primary droplet f hits the measurement object S and bounces back to become the secondary droplet g. The secondary droplet g includes the object to be measured S that has been fragmented, and moves toward the inlet E of the mass spectrometer 100.

  The sound wave irradiation unit 50 irradiates the secondary droplet g with a sound wave having a predetermined frequency. As shown in FIG. 4, the secondary droplet g vibrates when irradiated with sound waves. The oscillated secondary droplet g is split into a plurality of droplets. The total surface area of the secondary droplet g increases due to splitting. Thereby, the solvent contained in the secondary droplet g is easily evaporated. Therefore, the secondary droplet g is introduced into the inlet E of the mass spectrometer 100 with the amount of the solvent reduced.

  When the analysis accuracy of the molecular mass by the mass spectrometer 100 is poor, it is conceivable that the mass of the fragment of the measurement object S contained in the secondary droplet g is small. Therefore, the control unit 60 dynamically changes the mixing ratio of the solvent. The controller 60 changes the operation amount of the pump unit 31 according to the changed mixing ratio. The control unit 60 changes the amount of operation of the pump unit 31 until the mixing ratio at which better analysis accuracy is obtained.

  According to the ionization apparatus 1 and the analysis system of the first embodiment described above, the following effects are obtained.

(1) The ionization apparatus 1 is a cylindrical capillary 20 that is connected to the proximal end portion of the capillary 20 and the capillary 20 that can spray the solvent supplied to the proximal end portion from the distal end portion. And a supply unit 30 capable of dynamically changing the mixing ratio of the solvent. Thereby, since the mixing amount of the solvent sprayed from the capillary 20 can be dynamically changed, a suitable mixing amount of the solvent can be easily generated. Therefore, the ionization apparatus 1 can be made into a structure more suitable for mass spectrometry.

(2) The supply unit 30 includes a plurality of pump units 31 that supply different solvents. Thereby, a mixing rate can be easily changed by changing the operation amount of the some pump part 31. FIG.

(3) The ionization apparatus 1 includes a capillary 20 that sprays droplets, and a sound wave irradiation unit 50 that irradiates the sprayed droplets with sound waves having a predetermined period. Thereby, the amount of evaporation of the solvent contained in the droplet can be increased by splitting the droplet and increasing the total surface area of the droplet. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

(4) The capillary 20 sprays the primary droplet f toward the object to be measured S, and the sound wave irradiation unit 50 irradiates the secondary droplet g reflected by the object to be measured S with a sound wave having a predetermined cycle. Thereby, the secondary droplet g can be split and the total surface area of the secondary droplet g can be increased. The secondary droplet g can increase the evaporation amount of the solvent by increasing the total surface area. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

(5) The sound wave irradiation unit 50 is disposed in front of the reflection position of the secondary droplet g in the direction along the reflection direction of the secondary droplet g. Thereby, the sound wave irradiation part 50 can irradiate a sound wave along the moving direction of the secondary droplet g, and the splitting efficiency of the secondary droplet g is improved. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

(6) The sound wave irradiation unit 50 emits ultrasonic waves. Thereby, since the secondary droplet g is irradiated with a sound wave having a relatively high frequency, the splitting efficiency of the secondary droplet g is improved. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

(7) The ionization apparatus 1 includes a cylindrical capillary 20 that sprays the solvent supplied to the base end portion from the tip, and the capillary 20 swirls with the solvent on the inner peripheral surface along the axial direction. It is equipped with a slewing 23 that gives motion. By giving a swirl motion to the solvent, the straightness of the primary droplet f increases. As a result, the amount of the primary droplet f reflected by the measured object S increases. Therefore, a larger number of objects to be measured S can be included in the secondary droplet g. Moreover, the path | route to the entrance E of the mass spectrometer 100 of the primary droplet f and the secondary droplet g becomes longer compared with the case where it only goes straight by turning motion. Thereby, there is little discharge of the primary droplet f and the secondary droplet g, and a solvent can be evaporated more efficiently. As described above, the structure of the ionization apparatus 1 can be made more suitable for mass spectrometry.

(8) The capillary 20 has a cylindrical shape, and is an inner cylinder 21 that can circulate the solvent therein, and an outer cylinder 22 that is disposed radially outward of the inner cylinder 21, and includes an inner peripheral surface and the inner cylinder. An outer cylinder 22 that can circulate auxiliary fluid between the outer cylinder 21 and the outer cylinder 22, and the spiral 23 is disposed on the inner circumference of the inner cylinder 21 along the axial direction. Is further disposed along the axial direction on at least one of the outer peripheral surface of the outer cylinder 22 and the inner peripheral surface of the outer cylinder 22. Thereby, a turning motion can be given also about an auxiliary fluid, and straight advanceability can be increased. Since the auxiliary fluid exists so as to cover the circumferential direction of the primary fluid, it is possible to suppress the diffusion of the primary fluid. Therefore, the structure of the ionization apparatus 1 can be made more suitable for mass spectrometry.

[Second Embodiment]
Next, an ionization apparatus 1 and an analysis apparatus according to a second embodiment of the present invention will be described with reference to FIG. In the description of the second embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
The ionization apparatus 1 and the analysis system according to the second embodiment differ from the first embodiment in that a plurality of capillaries 20 are provided. In the ionization apparatus 1 according to the second embodiment, the supply unit 30 can supply different solvents to the capillaries 20 and can dynamically change the supply amount of the solvent supplied to the capillaries 20. Thus, it is different from the first embodiment.

  One of the plurality of capillaries 20 is arranged similarly to the capillary 20 in the first embodiment. The other of the plurality of capillaries 20 is arranged with the tip portion directed toward the stage 10 (measurement object S). In the present embodiment, the other capillary 20 is disposed above the object to be measured S.

According to the ionization apparatus 1 and the analysis apparatus of the second embodiment described above, the following effects are produced in addition to the above (1) to (8).
(9) A plurality of capillaries 20 are provided. The supply unit 30 can supply different solvents to the capillaries 20 and can dynamically change the supply amount of the solvent supplied to the capillaries 20. Thereby, while being able to mix a solvent above to-be-measured object S, a mixing amount can be changed dynamically. Since the supply amount of the solvent supplied to each capillary 20 can be changed independently, both the mixing rate and the supply amount can be changed. Therefore, the flexibility when mixing the solvent can be improved.

[Third Embodiment]
Next, an ionization apparatus 1 and an analysis system according to a third embodiment of the present invention will be described with reference to FIG. In the description of the third embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
In the ionization apparatus 1 and the analysis system according to the third embodiment, as shown in FIG. 6, the sound wave irradiation unit 50 is located in the vicinity of the inlet E of the mass spectrometer 100 that is disposed ahead of the reflection direction of the secondary droplet g. It differs from the first and second embodiments in that it is arranged.

According to the ionization apparatus 1 and the analysis system of the third embodiment described above, the following effects are produced in addition to the above (1) to (9).
(10) The sound wave irradiation unit 50 is disposed in the vicinity of the entrance E of the mass spectrometer 100 that is disposed ahead of the reflection direction of the secondary droplet g. Even with such a configuration, the splitting efficiency of the secondary droplet g can be increased. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

[Fourth Embodiment]
Next, an ionization apparatus 1 and an analysis system according to the fourth embodiment of the present invention will be described. In the description of the fourth embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
The ionization apparatus 1 and the analysis system according to the fourth embodiment differ from the first to third embodiments in that the sound wave irradiation unit 50 irradiates a sound wave having a predetermined cycle toward the primary droplet f.

According to the ionization apparatus 1 and the analysis system of the fourth embodiment described above, the following effects are produced in addition to the above (1) to (10).
(11) The capillary 20 sprays the primary droplet f toward the object to be measured S, and the sound wave irradiation unit 50 irradiates the primary droplet f with a sound wave having a predetermined cycle. Thereby, it can reduce in size from the primary droplet f. By reducing the size of the primary droplet f, it is considered that the amount of the measurement object S contained in the secondary droplet g can be increased.

[Fifth Embodiment]
Next, an ionization apparatus 1 and an analysis system according to a fifth embodiment of the present invention will be described. In the description of the fifth embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
The ionization apparatus 1 and the analysis system according to the fifth embodiment are different from the first to fourth embodiments in that the capillary 20 sprays the secondary droplet g containing the measurement object S. Moreover, in the ionization apparatus 1 which concerns on 5th Embodiment, the sound wave irradiation part 50 differs from 1st-4th embodiment by the point which irradiates the sound wave of a predetermined frequency to the secondary droplet g.

  According to the ionization apparatus 1 and the analysis system according to the fifth embodiment described above, the following effects are obtained in addition to the above (1) to (11).

(12) The capillary 20 sprays the secondary droplet g containing the object to be measured S, and the sound wave irradiation unit 50 irradiates the secondary droplet g with a sound wave having a predetermined frequency. Thereby, the splitting efficiency of the secondary droplet g sprayed by the capillary 20 is improved. Therefore, the amount of the solvent contained in the secondary droplet g entering the inlet E of the mass spectrometer 100 can be reduced, and the structure of the ionizer 1 can be made more suitable for mass analysis.

[Sixth Embodiment]
Next, an ionization apparatus 1 and an analysis system according to a sixth embodiment of the present invention will be described. In the description of the sixth embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
In the ionization apparatus 1 and the analysis system according to the sixth embodiment, the first to fifth points are such that the pitch increases from the proximal end of the inner cylinder 21 or the outer cylinder 22 toward the distal end. Different from the embodiment.

  According to the ionization apparatus 1 and the analysis system according to the sixth embodiment described above, the following effects are obtained in addition to the above (1) to (12).

(13) The pitch of the spiral 23 increases from the proximal end of the inner cylinder 21 or the outer cylinder 22 toward the distal end. As a result, the angular acceleration applied to the droplet at the proximal end is small, and the angular acceleration applied to the droplet at the distal end is increased. As the droplet moves from the base end portion toward the tip end portion, the flow velocity increases due to the application of voltage. When the flow velocity is low, the generation of turbulent flow at the base end can be suppressed by reducing the angular acceleration. On the other hand, turning motion can be made faster by increasing the angular acceleration at the tip portion where the flow velocity is fast. Therefore, the swirl motion can be efficiently given to the primary droplet f.

[Seventh Embodiment]
Next, an ionization apparatus 1, an ionization method, a program, and an analysis system according to a seventh embodiment of the present invention will be described with reference to FIGS. In the description of the sixth embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.

  The ionization apparatus 1, ionization method, program, and analysis system according to the seventh embodiment have a mass of a solution (hereinafter referred to as a standard solution P) in which the types and mixing ratios of molecules included in advance are known on the stage 10. The analysis is performed by the analysis apparatus 100. This analysis is a preliminary analysis performed in advance when analyzing the measurement object S. The ionization apparatus 1, ionization method, program, and analysis system according to the present embodiment can analyze the measurement object S by including in the standard solution P molecules that are equivalent to the molecules impregnated in the measurement object S. Optimize the mixing ratio of the optimal solvent. As shown in FIG. 7, the control unit 60 according to the seventh embodiment includes an operation instruction unit 61, a mixing ratio specifying unit 62, an intensity information acquisition unit 63, a timing detection unit 64, and an optimum value determination unit 65. .

  The operation instruction unit 61 transmits an operation signal to the supply unit 30 and the stage 10. Thereby, the operation instruction unit 61 dynamically changes the mixing ratio of at least two kinds of solvents (primary droplets f) in the supply unit 30. For example, the operation instruction unit 61 dynamically changes the mixing ratio of the two types of solvents by linearly changing the mixing ratio of one of the two types of solvents from 0% to 100%. Further, the operation instruction unit 61 moves the stage 10. Specifically, the operation instructing unit 61 moves the stage 10 in one of the in-plane directions so that the solvent whose mixing ratio is dynamically changed can be sprayed to different positions of the measurement object S. For example, the operation instruction unit 61 moves the stage 10 from the point C to the point D in FIG. For example, as illustrated in FIG. 9, the operation instruction unit 61 dynamically changes the mixing rate (the amount of one solvent relative to the entire solvent) from 0% to 100% according to the moving speed from the point C to the point D. Change. The operation instruction unit 61 causes the supply unit 30 to supply the solvent to the capillary 20.

  The mixing rate specifying unit 62 specifies the mixing rate of the solvent. For example, the mixing ratio specifying unit 62 acquires the operation speed of the pump unit 31 included in the operation signal transmitted to the supply unit 30 by the operation instruction unit 61, thereby mixing the solvent instructed by the operation instruction unit 61. Identify rates.

  The intensity information acquisition unit 63 acquires the ion intensity obtained from the mass spectrometer 100 as intensity information. Specifically, the intensity information acquisition unit 63 acquires the ion intensity obtained by the mass spectrometer 100 as the intensity information as a result of spraying on the measurement object S. For example, as shown in FIG. 10, the intensity information acquisition unit 63 acquires the ion intensity at each position in the result of moving the stage 10 from the point C to the point D as intensity information.

  The timing detection unit 64 refers to the intensity information acquired by the intensity information acquisition unit 63. The timing detection unit 64 detects the timing (for example, time) when the ion intensity indicated by the intensity information is equal to or greater than a predetermined value. The timing detection unit 64 detects, for example, the timing when the ion intensity indicated by the intensity information becomes a predetermined value or more. In the present embodiment, the timing detection unit 64 detects the timing at which the ion intensity has the highest intensity as the ion intensity timing at which the predetermined value or more is reached. The timing detection unit 64 outputs the detected timing.

  The optimum value determination unit 65 determines the mixing ratio at the detected timing as the optimum value optimal for ionization. Specifically, the optimum value determining unit 65 acquires the output timing, and acquires the solvent mixing rate at the acquired timing from the mixing rate specifying unit 62. The mixing ratio specifying unit 62 determines the acquired mixing ratio of the solvent to an optimum value.

Next, operations related to the ionization apparatus 1, ionization method, program, and analysis system according to the present embodiment will be described.
First, as shown in FIG. 8, the standard solution P is placed on the stage 10.

  Next, the operation instruction unit 61 moves the stage 10 from the position of the point C to the position of the point D. Further, the operation instruction unit 61 dynamically changes the mixing ratio of at least two kinds of solvents to the supply unit 30 while the stage 10 moves from the position of the point C to the position of the point D, and the mixed solvent. Is supplied to the capillary. Thereby, as shown in FIG. 9, the capillary sprays the solvent having different mixing ratios at different positions from the point C to the point D. The sprayed solvent is taken into the inlet of the mass spectrometer 100 and subjected to mass analysis.

  Here, the mixing rate specifying unit 62 specifies the mixing rate of the solvent instructed by the operation instruction unit 61. For example, the mixing rate specifying unit 62 specifies the mixing rate of the solvent based on the operation speed of the pump unit 31 instructed by the operation instruction unit 61.

  The intensity information acquisition unit 63 acquires ion intensity obtained as a result of being taken into the inlet E of the mass spectrometer 100 as intensity information. The intensity information acquisition unit 63 acquires intensity information as illustrated in FIG. 9 from the mass spectrometer 100, for example. The intensity information acquisition unit 63 sends the acquired intensity information to the timing detection unit 64.

  The timing detection unit 64 detects the timing at which the ion intensity included in the intensity information becomes a predetermined value or more. For example, as illustrated in FIG. 9, the timing detection unit 64 outputs the time t to the optimum value determination unit 65 as the detected timing.

  The optimum value determination unit 65 acquires the timing from the timing detection unit 64 and acquires the mixing rate at the time t from the mixing rate specifying unit 62. Thereby, the optimum value determining unit 65 determines the optimum mixing ratio in the standard solution P.

According to the ionization apparatus 1, the ionization method, the program, and the analysis system according to the seventh embodiment described above, the following effects are obtained in addition to the effects (1) to (13).
(14) The ionization apparatus 1 further includes a control unit 60 that optimizes the mixing rate of the solvent in the supply unit 30, and the control unit 60 dynamically changes the mixing rate of at least two kinds of solvents in the supply unit 30. And an operation instructing unit 61 for supplying the solvent to the capillary, a mixing rate specifying unit 62 for specifying the mixing rate of the solvent, and an intensity information acquiring unit 63 for acquiring the ion intensity obtained from the mass spectrometer 100 as intensity information, A timing detection unit 64 that detects a timing at which the ion intensity indicated by the intensity information is equal to or greater than a predetermined value, and an optimal value determination unit 65 that determines the mixing ratio at the detected timing as an optimal value optimal for ionization. . In the mass spectrometer 100, the mixing ratio can be optimized in advance for the standard solution P containing the molecules to be analyzed. As a result, the mixing rate can be optimized for molecules that are considered to be included in the object to be measured S to be actually analyzed, so that the analysis accuracy of the object to be measured S can be improved. The same applies to the ionization method, the program, and the analysis system.

  The preferred embodiments of the ionization apparatus, ionization method, program, and analysis system of the present invention have been described above, but the present invention is not limited to the above-described embodiments, and can be modified as appropriate.

  For example, in the above-described embodiment, two types of solvents are mixed, but more solvents may be mixed. In this case, you may increase the number of the pump parts 31 in 1st Embodiment. In the second embodiment, the number of capillaries 20 and pump units 31 may be increased.

  Moreover, in the said embodiment, although the pump part 31 demonstrated the form provided with two or more syringe pumps, it replaced with this and the pump part 31 may be provided with two or more plunger pumps.

  In the above embodiment, the capillary 20 may be single. In this case, the spiral 23 is disposed on the inner peripheral surface along the axial direction. Thereby, a turning motion can be given to the solvent.

  Moreover, in the said 2nd Embodiment, although the other capillary 20 shall be arrange | positioned above the to-be-measured object S, it is not restrict | limited to this. The other capillary 20 may be arranged in any way as long as the tip portion is arranged toward the measurement object S as long as the solvent can be sprayed on the measurement object S.

  Moreover, in the said 7th Embodiment, the example in which the standard solution P was analyzed was shown. In addition to this, the homogenate of the measurement object S may be analyzed with respect to the standard solution P added. That is, analysis may be performed on the liquefied measurement object S to which the standard solution P is added. Thus, the mixing ratio may be further optimized based on a preliminary analysis in accordance with the actual analysis.

  Moreover, in the said 7th Embodiment, although the mixing rate specific | specification part 62 specified the mixing rate based on the operating speed of the pump part 31, it is not restrict | limited to this. For example, the mixing rate specifying unit 62 may specify the mixing rate based on the pressure ratio of the pump unit 31. In addition, the mixing rate specialty unit may be provided in the mixer 32 and may specify the mixing rate based on the opening degree of a valve (not shown) disposed in the flow path of each pump unit 31.

  Moreover, in the said 7th Embodiment, although the timing detection part 64 detected the timing when the ion intensity contained in intensity | strength information becomes more than predetermined value, it is not restrict | limited to this. The timing detection unit 64 may use the time from the time when the solvent is supplied from the capillary 20 until the mass analysis is performed in the mass spectrometer 100 as the delay time. In this case, the timing detection unit 64 may output a timing obtained by subtracting the delay time from the timing at which the ion intensity of a predetermined value or more is obtained. Thereby, the mixing time can be further optimized by correcting the time when the solvent is sprayed from the tip of the capillary 20 and the time when the solvent reaches the mass spectrometer 100.

  Moreover, in the said 7th Embodiment, although the intensity | strength information acquisition part 63 acquired the intensity | strength information in which ion intensity is shown with respect to time as shown in FIG. 10, it is not restrict | limited to this. The intensity information acquisition unit 63 may acquire instantaneous ion intensity as intensity information. In this case, the timing detection unit 64 may detect the timing after accumulating the intensity information.

  Moreover, in the said 7th Embodiment, although the operation instruction | indication part 61 showed the example which changes the mixing rate to the supply part 30 linearly, it is not restrict | limited to this. The operation instruction unit 61 may cause the supply unit 30 to change the mixing rate in a spot manner or intermittently change the mixing rate.

  In the seventh embodiment, the control unit 60 can be realized by hardware, software, or a combination thereof. Here, “realized by software” means realized by a computer reading and executing a program. When configured by hardware, a part or all of the control unit 60 is integrated with an integrated circuit (LSI (Large Scale Integrated circuit), ASIC (Application Specific Integrated Circuit), gate array, FPGA (Field Programmable Gate Array)), for example. IC).

  When all or some of the functions of the control unit 60 included in the present invention are configured by software, a hard disk, ROM, or the like that stores a program describing all or part of the operation of the control unit 60 included in the present invention This is realized by storing information necessary for computation in DRAM and operating the program on the CPU in a computer composed of a storage unit, a DRAM that stores data necessary for computation, a CPU, and a bus connecting each unit can do.

  Moreover, it is good also as a structure which performs each function with which the control part 60 included in this invention is provided on one or several server suitably. Moreover, you may implement | achieve each function with which the control part 60 included in this invention is utilized using a virtual server function etc. on a cloud.

  The program can be stored using various types of computer readable media and provided to a computer. Computer readable media include various types of tangible storage media. Examples of the computer-readable medium include a magnetic recording medium (for example, a flexible disk, a magnetic tape, a hard disk drive), a magneto-optical recording medium (for example, a magneto-optical disk), a CD-ROM (Read Only Memory), a CD-R, a CD- R / W, semiconductor memory (for example, mask ROM, PROM (Programmable ROM), EPROM (Erasable PROM), flash ROM, RAM (random access memory)).

DESCRIPTION OF SYMBOLS 1 Ionizer 10 Stage 20 Capillary 21 Inner cylinder 22 Outer cylinder 23 Turning 30 Supply part 31 Pump part 32 Mixer 40 Electric power supply part 50 Sound wave irradiation part 60 Control part 61 Operation instruction part 62 Mixing rate specific | specification part 63 Strength information acquisition part 64 Timing detection unit 65 Optimum value determination unit 100 Mass spectrometer E Inlet f Primary droplet g Secondary droplet S Object to be measured

Claims (3)

An ionization apparatus including a cylindrical capillary that sprays a solvent supplied to a base end from a tip,
The said capillary is an ionization apparatus provided with the spiral which gives a rotational motion to a solvent on the internal peripheral surface along an axial direction. The capillary is
An inner cylinder that is cylindrical and can circulate the solvent inside;
An outer cylinder disposed radially outward of the inner cylinder, and an outer cylinder capable of circulating auxiliary fluid between the inner peripheral surface and the outer peripheral surface of the inner cylinder;
Further comprising
The spiral is disposed along the axial direction on the inner circumferential surface of the inner cylinder, and further disposed along the axial direction on at least one of the outer circumferential surface of the inner cylinder and the inner circumferential surface of the outer cylinder. The ionization apparatus of Claim 1 to be performed.   The ionization apparatus according to claim 2, wherein the pitch of the spiral increases from a proximal end portion to a distal end portion of the inner cylinder or the outer cylinder.

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