JP6061298B2 - Sample analyzer - Google Patents

Description

  The present invention relates to a sample analyzer for analyzing a sample such as a living tissue.

  As a technique in this type of field, for example, there is a sample analyzer described in Patent Document 1. This conventional sample analyzer is an apparatus for the purpose of identifying a pathological tissue during surgery, for example. In this apparatus, for example, tissue vapor containing ions generated when an affected part is incised with an electric knife or a laser knife is sucked with a polyethylene Teflon tube connected to a fluid pump and conveyed to the capillary inlet of the mass spectrometer. The mass spectrometer performs tissue identification based on the mass spectrum of the tissue vapor in real time. For example, during surgery, the identification of cancer cells and normal cells is performed for 1 second from the data of the phospholipid mass spectrum. By implementing to the extent, an index for determining the site to be excised can be quickly provided.

International Publication WO2010 / 136887 Pamphlet

  When the tissue of the trunk is evaporated with an electric knife or a laser knife, the ionization efficiency of the tissue is low, and most are neutral molecules. Therefore, in the above-described conventional sample analyzer, the tissue vapor sucked by the tube is further ionized (post-ionized) at the outlet of the venturi jet pump. Examples of the post-ionization method include an electron spray ionization method and a chemical ionization method. However, even when these methods are used, it is sometimes difficult to identify molecules that are difficult to ionize. In addition, in the electron spray ionization method, generation of multivalent ions may be a problem.

  There is also a photoionization method in the post ionization. The photoionization method is used, for example, for secondary ion mass spectrometry. Neutral molecules are subjected to multiphoton ionization by allowing a near-infrared femtosecond pulse laser to enter the plume of neutral molecules with high light intensity. Let However, even in the photoionization method, in order to obtain high light intensity, the laser light is collected by a lens and incident on the plume, so that it is possible to secure the interaction region and interaction time between the laser light and the neutral molecule plume. As a result, there is a problem that it is difficult to improve ionization efficiency.

  In addition, since the conventional sample analyzer described above uses an electric knife or a laser knife, there is no problem when there is a sufficient space above the affected area as in a surgical operation, but the depth of the ear is narrow. It is difficult to perform analysis when the affected area is targeted.

  Furthermore, the memory effect is also a problem in the conventional sample analyzer described above. The memory effect is a phenomenon in which a sample molecule is adsorbed inside a tube connected to a mass analyzer or a venturi jet pump, causing interference in the mass spectrum when the next analysis is performed. The memory effect is less likely to cause a problem when there are a large number of ions to be analyzed, but it is necessary to eliminate the influence as much as possible when a very small amount of a molecule that is difficult to ionize is to be analyzed.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a sample analyzer that can improve the ionization efficiency of a sample, reduce the memory effect, and enable analysis in a narrow space. And

  In order to solve the above problems, a sample analyzer according to the present invention includes a desorption / ionization laser for desorption / ionization of a sample, and vapor generated from the sample by the desorption / ionization laser connected to a suction means. A probe to be sucked, a post-ionization laser to post-ionize molecules contained in the vapor sucked by the probe, a mass analyzer to analyze a sample based on the mass spectrum of the vapor post-ionized by the post-ionization laser, The probe is constituted by a hollow optical fiber, and the light emitted from the desorption / ionization laser and the light emitted from the post ionization laser are guided to the hollow optical fiber.

  In this sample analyzer, the probe is constituted by a hollow optical fiber, and the outgoing light from the desorption / ionization laser and the outgoing light from the post ionization laser are guided to the hollow optical fiber. . As a result, a sufficient interaction region and interaction time between the vapor of the sample sucked in the hollow optical fiber and the emitted light of the post-ionization laser can be secured, so that the ionization efficiency of the sample can be improved. In addition, the light emitted from the desorption / ionization laser having a relatively high light intensity and the light emitted from the post-ionization laser are guided to the hollow optical fiber, so that the molecules adsorbed on the hollow optical fiber are desorbed. Is promoted and the memory effect is reduced. Furthermore, by using a hollow optical fiber as a probe, a handpiece such as an electric knife or a laser knife is not necessary, and the flexibility of the probe is ensured, and analysis in a narrow space is possible.

  A condensing lens is preferably disposed on the tip side of the probe. The condensing lens is formed with a through-hole through which the emitted light from the desorption / ionization laser is condensed toward the sample and through which the vapor passes. Thereby, the analysis of the detail of a sample can be implemented suitably. Further, by forming a through hole in the condensing lens, it is possible to avoid obstructing suction of vapor generated from the sample.

  The probe is preferably constituted by a hollow optical fiber formed by forming a metal layer and a transparent dielectric layer on the inner surface of a hollow glass tube. In this case, the flexibility of the probe can be sufficiently secured.

  Moreover, it is preferable that the probe is comprised by the hollow optical fiber formed by forming a metal layer in a hollow metal tube. In this case, the heat resistance of the probe can be sufficiently secured, and the memory effect can be reduced by desorption of adsorbed molecules by heating.

  In addition, the probe includes a base end portion constituted by a hollow optical fiber formed by forming a metal layer and a transparent dielectric layer on the inner surface of a hollow glass tube, and a hollow formed by forming a metal layer on the hollow metal tube. It is preferable to include a tip portion made of an optical fiber. In this case, both heat resistance and flexibility of the probe can be ensured. The tip portion of the probe is more likely to adsorb molecules than the base end portion. Therefore, the memory effect can be sufficiently reduced by applying a hollow optical fiber formed by forming a metal layer on a hollow metal tube at the tip of the probe.

  Further, it is preferable that a guide laser indicating the direction of the tip of the probe is further provided, and emitted light from the guide laser is guided to the hollow optical fiber. Thereby, it becomes possible to visually recognize the irradiation position of the desorption / ionization laser on the sample, and the workability of the analysis can be improved.

  The suction means includes a vacuum cell connected to the proximal end of the probe, and a pump connected to the vacuum cell and sending vapor to the mass analyzer, and the emitted light from the post-ionization laser is a vacuum cell. It is preferable that light is also guided to a steam flow path from the pump to the pump. In this case, the interaction region and interaction time between the vapor of the sample and the emitted light of the post ionization laser can be further increased, and the ionization efficiency of the sample can be further improved.

  Moreover, it is preferable that a resonator that repeatedly reflects light emitted from the post-ionization laser in a direction substantially orthogonal to the flow of vapor is disposed in the vacuum cell or the pump. In this case, the interaction region and interaction time between the vapor of the sample and the emitted light of the post ionization laser can be further increased, and the ionization efficiency of the sample can be further improved.

  Moreover, it is preferable to further include a heating means for heating at least a part of a vapor flow path from the probe to the mass spectrometer. Thereby, the memory effect can be further reduced by desorption of adsorbed molecules by heating.

  Further, it is preferable that a potential gradient is formed from the distal end side to the proximal end side of the probe. Thereby, it is possible to increase the collection efficiency of ions flowing in the probe.

  According to the sample analyzer of the present invention, the ionization efficiency of the sample can be improved, the memory effect can be reduced, and analysis in a narrow space is possible.

It is the schematic which shows the sample analyzer which concerns on 1st Embodiment of this invention. It is a perspective view which shows the probe used for the sample analyzer shown in FIG. It is sectional drawing of the base end part of a probe. It is sectional drawing of the front-end | tip part of a probe. It is a figure which shows the structure of the front end side of a probe. It is a figure which shows operation | movement of the sample analyzer shown in FIG. 1, (a) shows the timing of irradiation of the laser for desorption / ionization, (b) shows the neutral molecule density near a sample. FIG. 7 is a diagram illustrating the subsequent operation of FIG. 6, where (a) shows the neutral molecule density on the proximal end side of the probe, (b) shows the timing of post-ionization laser irradiation, and (c) shows CW The irradiation timing of the post ionization laser when using light is shown. It is the schematic which shows the attachment form of the heating means to a sample analyzer. It is the schematic which shows the formation form of the electric potential gradient to a sample analyzer. It is sectional drawing of the probe used for the sample analyzer shown in FIG. It is the schematic which shows the sample analyzer which concerns on 2nd Embodiment of this invention. It is the schematic which shows the sample analyzer which concerns on 3rd Embodiment of this invention. It is a figure which shows operation | movement of the sample analyzer shown in FIG. 12, (a) shows the neutral molecule density in the base end side of a probe, (b) shows the irradiation timing of the laser for post ionization. It is the schematic which shows the modification of the sample analyzer shown in FIG.

Hereinafter, preferred embodiments of a sample analyzer according to the present invention will be described in detail with reference to the drawings.
[First Embodiment]

FIG. 1 is a schematic diagram showing a sample analyzer according to the first embodiment of the present invention.
A sample analyzer 1 shown in FIG. 1 is configured as an apparatus that performs identification of a sample S such as a biological tissue including cells and the like based on a mass spectrum. For example, by analyzing the patient's sputum using this apparatus and identifying the bacteria contained in the sputum, it becomes possible to quickly select an appropriate antibiotic. Further, by combining this apparatus with an endoscope or the like, in addition to visual monitoring of the affected area, it is assumed that molecular information constituting the tissue of the affected area is used for diagnosis.

  As shown in FIG. 1, the sample analyzer 1 includes a probe 2, a desorption / ionization laser 3, a guide laser 4, a post ionization laser 5, a vacuum cell 6, and a venturi jet pump 7. And a mass analyzer 8.

  The probe 2 is made of, for example, a hollow optical fiber. The distal end side of the probe 2 is a free end toward the sample S. On the other hand, the proximal end side of the probe 2 is connected to a venturi jet pump 7 via a vacuum cell 6 and the inside of the probe 2 is evacuated. As shown in FIG. 2, the proximal end portion 2 a of the probe 2 is formed by a hollow optical fiber 11 made of quartz glass, and the distal end portion 2 b of the probe 2 is formed by a hollow optical fiber 12 made of metal. . The distal end side of the hollow optical fiber 11 and the proximal end side of the hollow optical fiber 12 are detachably connected by a connector 13.

  As shown in FIG. 3, the hollow optical fiber 11 has a hollow quartz glass tube 14. A metal layer 15 and a transparent dielectric layer 16 are formed on the inner surface of the quartz glass tube 14. The metal layer 15 is made of, for example, silver, and the transparent dielectric layer 16 is made of, for example, a cyclic olefin polymer. The metal layer 15 and the transparent dielectric layer 16 are designed so that the reflectance on the inner surface of the hollow optical fiber 11 is maximized with respect to, for example, an infrared laser having a wavelength of 2 μm or more. The diameter of the quartz glass tube 14 is, for example, 200 μm to 10 mm, and the inner diameter is, for example, 100 μm to 8 mm. These diameters are appropriately selected in consideration of the flexibility of the probe 2.

  On the other hand, the hollow optical fiber 12 has a hollow metal tube 17 as shown in FIG. The inner surface of the metal tube 17 is mirror-polished and a metal layer 18 is formed. As a material of the metal tube 17, for example, stainless steel, aluminum, iron or the like is used. The metal layer 18 is made of, for example, silver or aluminum. Such a hollow optical fiber 12 is less flexible than the hollow optical fiber 11, but has excellent heat resistance. Specifically, the hollow optical fiber 11 can be heated to about 150 ° C., which is the heating limit of the transparent dielectric layer 16, and the hollow optical fiber 12 can be heated to about 500 ° C., which is less than the melting point of the metal. Is possible. In these hollow optical fibers 11 and 12, even when molecules are adsorbed in the probe 2, the molecules can be desorbed by heating, and the memory effect is reduced (the heating means will be described later). .

  The probe 2 may be composed of only the hollow optical fiber 11 or may be composed of only the hollow optical fiber 12. When it comprises only the hollow optical fiber 11, the flexibility of the probe 2 can be improved more. On the other hand, when it comprises only the hollow optical fiber 12, the heat resistance of the probe 2 can further be improved. Further, not only an infrared laser but also a short wavelength laser such as an ultraviolet excimer laser can be guided. When an ultraviolet laser is used, it is also preferable to further form a metal layer made of titanium oxide on the metal layer 18. In this case, titanium oxide is activated by irradiation with ultraviolet light, and molecular desorption can be promoted.

The desorption / ionization laser 3 is a laser that desorbs / ionizes a sample. As the desorption / ionization laser 3, for example, an infrared laser having a wavelength of 2 μm or more is used in consideration of an absorption rate of moisture in the tissue of the sample S. Examples of such an infrared laser include a Ho-YAG laser (wavelength 2.1 nm), an Er-YAG laser (wavelength 2.94 μm), a CO laser (wavelength 5.2 μm), and a CO ₂ laser (wavelength 10.6 μm). And an infrared wavelength tunable OPO laser.

  Depending on the type of sample S, it is preferable to use a titanium sapphire laser (wavelength 800 nm) having a pulse width as narrow as about 100 fs and a high peak intensity. In addition, an ultraviolet excimer laser such as an ArF laser (wavelength 193 nm), a KrF laser (wavelength 248 nm), or an XeCl laser (wavelength 308 nm), a third harmonic of a YAG laser (wavelength 355 nm), a nitrogen laser (wavelength 337 nm), or the like is used. You can also. The laser is mainly a pulse laser, but a CW laser may be used.

  As shown in FIG. 1, the emitted light 3 a from the desorption / ionization laser 3 is collected by the condenser lens 21, enters the vacuum cell 6 through the window 22, and is guided to the proximal end side of the probe 2. Is done. The outgoing light 3 a guided to the probe 2 propagates through the hollow optical fibers 11 and 12 while being totally reflected, and is emitted from the tip of the probe 2 toward the sample S.

  When the emitted light 3a is irradiated onto the sample S, the laser light is absorbed by moisture in the tissue of the sample S, heat is generated, and the tissue surface is ablated. As a result, molecules (neutral molecules) constituting the tissue and a few ions are vaporized and desorbed radially from the surface of the tissue. Vapor generated in the sample S is sucked by the probe 2 by the action of the venturi jet pump 7 and is transported from the probe 2 through the vacuum cell 6 to the mass analyzer 8. The ionization efficiency during desorption by the desorption / ionization laser 3 depends on conditions such as the composition of the sample S and the laser wavelength of the desorption / ionization laser 3.

  As shown in FIG. 5, a condensing lens 23 is disposed on the distal end side of the probe 2. Outgoing light 3 a emitted from the tip of the probe 2 is condensed to a diameter of about 100 μm on the surface of the sample S by the condenser lens 23. As a result, the sample S can be locally desorbed, and the spatial resolution of the analysis can be improved. In addition, a through hole 23a having a circular cross section, for example, is formed at a substantially central portion of the condenser lens 23. Therefore, the vapor generated in the sample S is sucked by the probe 2 through the through hole 23a.

  The guide laser 4 is a laser that indicates the direction of the tip of the probe 2. For the guide laser 4, for example, a visible light laser such as a He—Ne laser (wavelength 633 nm) is used. The emitted light 4 a from the guide laser 4 is reflected by the dichroic mirror 24 toward the window 22 of the vacuum cell 6 and is condensed by the condenser lens 21, and the emitted light 3 a of the desorption / ionization laser 3 The light is guided to the proximal end side of the probe 2 through the vacuum cell 6 in substantially the same optical path. The outgoing light 4 a guided to the probe 2 propagates through the hollow optical fibers 11 and 12 while being totally reflected, and exits from the tip of the probe 2 toward the sample S. Thereby, the emitted light 4a is irradiated onto the sample S at substantially the same position as the emitted light 3a, and the analysis position can be easily confirmed visually.

The post-ionization laser 5 is a laser for post-ionizing neutral molecules contained in vapor generated by desorption. As the post-ionization laser 5, when multiphoton ionization is performed, it is preferable to use a laser such as a titanium sapphire laser (wavelength 800 nm) or a YAG laser (wavelength 1064 nm) with a pulse width of nanoseconds to femtoseconds. On the other hand, in the case of performing one-photon ionization, a higher order generated by condensing the F ₂ excimer laser (wavelength 157 nm) or the third harmonic of the YAG laser (wavelength 355 nm) in a gas chamber containing Xe gas. It is preferable to use harmonics (wavelength 118 nm) with a pulse width of nanoseconds to femtoseconds. The repetition frequency of the post-ionization laser 5 is preferably matched with the repetition frequency of the desorption / ionization laser 3. The repetition frequency of the desorption / ionization laser 3 and the post-ionization laser 5 is ideally several kHz to several hundred kHz from the viewpoint of shortening the measurement time, but it depends on the capability of the signal processing system of the mass analyzer 8. To be determined as appropriate.

  The outgoing light 5a from the post-ionization laser 5 is condensed by the condenser lens 25, reflected by the dichroic mirror 26 toward the window 22 of the vacuum cell 6, and enters the vacuum cell 6 from the window 22. The light is guided to the proximal end side of the probe 2. The outgoing light 5a interacts with the vapor in the probe 2 or the vapor near the outlet on the proximal end side of the probe 2 and promotes ionization of neutral molecules in the vapor. When the length of the probe 2 is 1 m, the time for the outgoing light 5a to propagate through the hollow optical fibers 11 and 12 is about 3.3 ns, and the interaction time between the outgoing light 5a and the vapor generated by the desorption is sufficient. Can be secured.

Synchronization of the desorption / ionization laser 3 and the post-ionization laser 5 will be described with reference to FIGS. As shown in FIG. 6 (a), at time t _0, the emitted light 3a for laser 3 desorption ionization is irradiated onto the surface of the sample S, as shown in FIG. 6 (b), of the sample S At the surface, steam is generated over a time width t ₁ (for example, several tens of μs).

When this vapor is sucked by the probe 2, at the outlet on the proximal end side of the probe 2, as shown in FIG. 7A, the time width t ₂ longer than the time width t ₁ (for example, several tens μs to several hundreds). There is vapor over μs). Therefore, as shown in FIG. 7B, the irradiation with the post-ionization laser 5 is performed at the time t _{3 at} which the density of neutral molecules in the vapor becomes maximum at the outlet on the proximal end side of the probe 2. , Post ionization can be carried out efficiently.

  In addition to the pulse laser described above, a VW CW light source such as a deuterium lamp, an Ar excimer lamp (wavelength 126 nm), or a Kr excimer lamp (wavelength 147 nm) can also be used as the post-ionization laser 5. In this case, the interaction between the emitted light 5a and the vapor can be generated without synchronizing with the desorption / ionization laser 3 (see FIG. 7C).

  The vacuum cell 6 has, for example, a hollow rectangular parallelepiped shape, and is a window through which the outgoing light 3 a of the desorption / ionization laser 3, the outgoing light 4 a of the guide laser 4, and the outgoing light 5 a of the post-ionization laser 5 are incident. 22. Further, the base end side of the probe 2 is connected to the facing surface of the window 22, and a flow path 27 leading to the venturi jet pump 7 is provided on a surface orthogonal to the surface on which the window 22 is provided.

  The venturi jet pump 7 is a pump that performs evacuation, and evacuates the inside of the vacuum cell 6 and the hollow optical fibers 11 and 12 by flowing nitrogen or air from the nozzle 28 at about 5 atm. As a result, the vapor sucked by the probe 2 passes through the hollow optical fibers 11 and 12, reaches the inside of the vacuum cell 6, and is sent to the mass analyzer 8. The mass analyzer 8 performs tissue identification in real time based on the mass spectrum of the delivered vapor.

  As described above, in the sample analyzer 1, the probe 2 is constituted by the hollow optical fibers 11 and 12, and the outgoing light 3a from the desorption / ionization laser 3 and the outgoing light 5a from the post-ionization laser 5 are provided. Is guided to the hollow optical fibers 11 and 12. Thereby, since the interaction region and the interaction time between the vapor of the sample S sucked in the hollow optical fibers 11 and 12 and the emitted light 5a of the post-ionization laser 5 can be sufficiently secured, the ionization efficiency of the sample S Can be improved.

  Further, since the outgoing light 3a from the desorption / ionization laser 3 having a relatively high light intensity and the outgoing light 5a from the post ionization laser 5 are guided to the hollow optical fibers 11 and 12, respectively, the hollow optical fiber The desorption of the molecules adsorbed on 11 and 12 is promoted, and the memory effect is reduced. Furthermore, by using the hollow optical fibers 11 and 12 as the probe 2, a handpiece such as an electric knife or a laser knife is not required, and the flexibility of the probe 2 is ensured, so that analysis in a narrow space is possible.

  Further, in the sample analyzer 1, the proximal end portion 2a of the probe 2 is constituted by the hollow optical fiber 11 formed by forming the metal layer 15 and the transparent dielectric layer 16 on the inner surface of the hollow quartz glass tube 14, and the probe The two distal end portions 2 b are constituted by a hollow optical fiber 12 formed by forming a metal layer 18 on a hollow metal tube 17. With such a configuration, both heat resistance and flexibility of the probe 2 can be ensured.

  The tip portion 2b of the probe 2 is more likely to adsorb molecules than the base end portion 2a. Therefore, by applying the heat-resistant hollow optical fiber 12 to the tip portion 2b of the probe 2, the memory effect can be sufficiently reduced. Further, the tip portion 2b is detachable by the connector 13, and the tip portion 2b where the adsorption of the molecules has progressed can be easily replaced. In addition, when the adsorption | suction of a molecule | numerator arises in the probe 2, it is also suitable for the venturi jet pump 7 to close the exit by the side of the mass analyzer 8 and to circulate air or nitrogen in the probe 2.

  When the memory effect is reduced by heating, for example, as shown in FIG. 8, a hot wire (heating means) 31 may be wound around the outer surface of the probe 2, the vacuum cell 6, the flow path 27, and the venturi jet pump 7. preferable. The glass hollow optical fiber 11 is heated to about 150 ° C. from the viewpoint of heat resistance, but the metal hollow optical fiber 12, the vacuum cell 6, the flow path 27, and the venturi jet pump 7 are heated to 300 ° C. It is possible to heat above. Therefore, desorption of molecules adsorbed on the inner surface can be promoted, and the memory effect can be more reliably reduced. The hot wire 31 is not necessarily provided in all of the probe 2, the vacuum cell 6, the flow path 27, and the venturi / jet pump 7. By providing the hot wire 31 in at least one of them, a reduction in the memory effect can be expected.

  In the sample analyzer 1, it is preferable to form a potential gradient from the distal end side to the proximal end side of the probe 2. In this case, for example, as shown in FIG. 9, the probe 2 is divided into a plurality of sections, and these sections are electrically insulated by an insulating portion 32. Then, by applying a potential to the metal layers 15, 18, etc., and applying a potential gradient to the insulating portion 32, an electrostatic toward the mass analyzer 8 side with respect to ions generated in the sample S and ions in the probe 2. Attraction can be given. Thereby, the collection efficiency of ions can be increased.

For electrical insulation of the probe 2, for example, as shown in FIG. 10, a configuration in which the divided portions 33, 33 of the probe 2 are connected by an insulating ring 34 can be adopted. Similarly, electrical insulation may be performed between the vacuum cell 6 and the venturi jet pump 7 and between the venturi jet pump 7 and the mass analyzer 8. In this case, the memory effect can be further reduced.
[Second Embodiment]

  A second embodiment of the present invention will be described. FIG. 11 is a schematic diagram showing a sample analyzer according to the second embodiment of the present invention. As shown in the figure, in the sample analyzer 41 according to the second embodiment, the emitted light 5a from the post-ionization laser 5 is used for the flow of vapor in the vacuum cell 6 and from the vacuum cell 6 to the venturi jet pump 7. This is different from the above embodiment in that light is also guided to the path 27.

  More specifically, in the sample analyzer 41, a half mirror 42 and a total reflection mirror 43 are further arranged in the optical system of the post-ionization laser 5, and the outgoing light 5 a branched by the half mirror 42 is reflected by the condenser lens 44. The light enters the vacuum cell 6 through the window 45 facing the flow path 27 while being condensed. The outgoing light 5 a that has entered the vacuum cell 6 passes through the vicinity of the outlet on the proximal end side of the probe 2 and is guided into the flow path 27.

With such a configuration, it becomes possible to cause the vapor of the sample S and the emitted light 5a of the post-ionization laser 5 to interact over the path from the outlet on the proximal end side of the probe 2 to the flow path 27. The interaction time can be further increased. Therefore, the ionization efficiency of the sample S can be further improved.
[Third Embodiment]

  A third embodiment of the present invention will be described. FIG. 12 is a schematic diagram showing a sample analyzer according to the third embodiment of the present invention. As shown in the figure, the sample analyzer 51 according to the third embodiment is such that a resonator 52 that repeatedly reflects the emitted light 5a from the post-ionization laser 5 is disposed in the vacuum cell 6. This is different from the above embodiment.

More specifically, in the sample analyzer 51, as in the second embodiment, the half mirror 42 and the total reflection mirror 43 are further arranged in the optical system of the post-ionization laser 5, and the emitted light branched by the half mirror 42. 5 a enters the vacuum cell 6 through the window 45 facing the flow path 27 while being condensed by the condenser lens 44. Further, in the vacuum cell 6, for example, a resonator 52 including a pair of mirrors having a reflectance of 99.99% or more at the wavelength of the post-ionization laser 5 is disposed corresponding to the position of the window 45. The output light 5a is repeatedly reflected by the device 52 in a direction substantially perpendicular to the flow of steam. In the sample analyzer 51, for example, as shown in FIG. 13, irradiation is carried out post-ionization laser 5 in accordance with the time t ₄ when the neutral molecule begins to be released in the steam at the outlet of the base end side of the probe 12.

With such a configuration, the emitted light 5 a from the post-ionization laser 5 can be present in the resonator 52 over the entire time t ₂ during which neutral molecules are present in the vacuum cell 6. Therefore, the vapor of the sample S and the emitted light 5a of the post-ionization laser 5 can be more reliably interacted in the vacuum cell 6, and the interaction region and the interaction time can be further increased. The ionization efficiency of the sample S can be further improved.

  The resonator 52 is not limited to being disposed in the vacuum cell 6, and may be disposed in the venturi jet pump 7 as in the sample analyzer 61 shown in FIG. 14, for example. In the example of FIG. 14, a vacuum cell 62 is arranged in front of the mass analyzer 8 in the venturi jet pump 7, and the emitted light 5 a branched by the half mirror 42 is vacuumed from the window 63 while being condensed by the condenser lens 44. The light enters the cell 62. In the vacuum cell 62, a resonator 52 is disposed corresponding to the position of the window 63, and the resonator 52 repeatedly reflects the emitted light 5a in a direction substantially perpendicular to the flow of vapor. .

  Even in such a configuration, the vapor of the sample S and the emitted light 5a of the post-ionization laser 5 can be more reliably interacted in the vacuum cell 6, and the interaction region and the interaction time are further increased. be able to. Therefore, the ionization efficiency of the sample S can be further improved.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the vacuum cell 6 and the mass analyzer 8 are connected via the venturi jet pump 7, but when the mass analyzer 8 includes an exhaust pump, the venturi jet pump 7 is omitted. The vacuum cell 6 and the mass analyzer 8 may be directly connected. In this case, the device can be further reduced in size.

  DESCRIPTION OF SYMBOLS 1,41,51,61 ... Sample analyzer, 2 ... Probe, 2a ... Base end part, 2b ... Tip part, 3 ... Desorption / ionization laser, 3a ... Emission light, 4 ... Guide laser, 4a ... Emission light DESCRIPTION OF SYMBOLS 5 ... Post ionization laser, 5a ... Output light, 6 ... Vacuum cell, 7 ... Venturi jet pump (suction means), 8 ... Mass spectrometer, 11, 12 ... Hollow optical fiber, 14 ... Quartz glass tube, 15 ... Metal layer, 16 ... Transparent dielectric layer, 17 ... Metal tube, 18 ... Metal layer, 23 ... Condensing lens, 23a ... Through-hole, 27 ... Channel, 31 ... Heat ray (heating means), 52 ... Resonator, S …sample.

Claims (10)

A desorption / ionization laser that desorbs / ionizes the sample;
A probe connected to suction means for sucking vapor generated from the sample by the desorption / ionization laser;
A post-ionization laser for post-ionization of molecules contained in the vapor sucked by the probe;
A mass analyzer for analyzing the sample based on a mass spectrum of the vapor post-ionized by the post-ionization laser;
The probe is constituted by a hollow optical fiber,
A sample analyzer, wherein light emitted from the desorption / ionization laser and light emitted from the post-ionization laser are guided to the hollow optical fiber.   A condensing lens having a through-hole through which the vapor passes and the light emitted from the desorption / ionization laser is condensed toward the sample is disposed on the tip side of the probe. The sample analyzer according to claim 1.   3. The sample analyzer according to claim 1, wherein the probe is constituted by a hollow optical fiber formed by forming a metal layer and a transparent dielectric layer on an inner surface of a hollow glass tube.   3. The sample analyzer according to claim 1, wherein the probe is configured by a hollow optical fiber formed by forming a metal layer on a hollow metal tube.   The probe includes a proximal end portion formed by a hollow optical fiber formed by forming a metal layer and a transparent dielectric layer on the inner surface of a hollow glass tube, and hollow light formed by forming a metal layer on the hollow metal tube. The sample analyzer according to claim 1, further comprising a tip portion made of a fiber. A guide laser indicating the direction of the tip of the probe;
The sample analyzer according to claim 1, wherein emitted light from the guide laser is guided to the hollow optical fiber. The suction means is
A vacuum cell connected to the proximal end of the probe;
A pump connected to the vacuum cell and delivering the vapor to the mass analyzer;
The sample analyzer according to claim 1, wherein the emitted light from the post-ionization laser is also guided to the vapor flow path from the vacuum cell to the pump. .   8. The resonator according to claim 7, wherein a resonator that repeatedly emits light emitted from the post-ionization laser in a direction substantially perpendicular to the flow of the vapor is disposed in the vacuum cell or the pump. Sample analyzer.   The sample analyzer according to any one of claims 1 to 8, further comprising heating means for heating at least a part of the flow path of the vapor from the probe to the mass analyzer.   The sample analyzer according to claim 1, wherein a potential gradient is formed from the distal end side to the proximal end side of the probe.

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