WO2007097285A1

WO2007097285A1 - Quantization of mass spectrometric measurement employing total reflection laser irradiation method

Info

Publication number: WO2007097285A1
Application number: PCT/JP2007/052974
Authority: WO
Inventors: Takashi Korenaga; Masayoshi Ito; Kouhei Shibamoto; Hironobu Fukuzawa
Original assignee: Tokyo Metropolitan University
Priority date: 2006-02-22
Filing date: 2007-02-19
Publication date: 2007-08-30
Also published as: JP2007225395A

Abstract

The number of molecules of a sample is counted by irradiating the sample with evanescent light without employing a matrix in mass spectrometry. A laser beam is introduced in parallel with the bottom face of a trapezoidal prism and reflected totally off the inner surface of the bottom face of the prism to generate evanescent light on the outer surface of the bottom face, and quantitative analysis of the sample is carried out by evaporating the sample applied to the outer surface with the evanescent light.

Description

Specification

Quantification of mass spectrometry using total reflection laser irradiation

Technical field

[0001] The present invention is a quantitative analysis of laser desorption mass spectrometry represented by MALDI-MS (Matrix Assisted Laser Desorption / lonization-Mass Spectrometry). The present invention relates to a laser irradiation method that can be used as a method. Therefore, according to the present invention, it becomes possible to quantitatively analyze pollutants contained in a trace amount in the atmosphere and biomolecules present in a trace amount in the body, and can provide a very useful analysis method for all scientific fields.

Background art

[0002] Laser Desorption Mass Spectrometry (LD-MS) attracted attention in the 1980s and has been used mainly for surface analysis of metals and semiconductors. Because it uses a laser, it can be easily condensed using a lens, and analysis of a minute region is possible.

[0003] However, the ionic efficiency is low, and there are also drawbacks such as dissociating the target molecule, making it impossible to measure macromolecules.

[0004] Against this background, MALDI—TOF—MS (Matrix Support) was developed by Mr. Koichi Tanaka, who won the Nobel Prize in Chemistry in 2002, as one of the methods for analyzing macromolecules such as proteins. Laser desorption-time-of-flight-mass spectrometry) measuring devices are attracting attention.

[0005] The greatest feature of the MALDI method is to use a sample in which a compound collectively called a matrix is mixed in a large excess (hundred power thousand times) with a mixed crystal state. Matrix molecules mixed in large excess are converted to thermal energy (vibration energy at the mouth) by absorbing the laser energy, so the irradiation laser (MALDI method generally uses a pulse width of about several ns). Part of the matrix molecules contained in the reach region (depth: several μm, diameter: several hundred μm) are rapidly heated, vaporized or sublimated by irradiation with a short pulse laser with a pulse width of several ns. (See Figure 1).

[0006] At this time, the target molecules in the mixed crystal state are vaporized together with the matrix molecules. Since the irradiation laser energy is not received directly, the rate of the dissociation reaction is smaller than the vaporization reaction. In other words, it is possible to greatly reduce the fragment signal generated by dissociation of molecules, which is very effective for identification of huge molecules.

[0007] However, MALD and TOF-MS have major drawbacks. By using MALD and TOF-MS, the identification of substances can be applied to very large molecules, but it is impossible to quantify the substances.

[0008] This is because the sample forms a mixed crystal state after adding a large amount of matrix molecules to the target molecule, and therefore the abundance ratio of the target molecule in the sample changes depending on the position irradiated with the laser. In addition, since the penetration depth of light with a rough sample surface cannot be defined, it is not possible to estimate the laser energy reaching volume.

[0009] Therefore, in order to discuss quantitativeness, it is necessary to use a sample form that does not use matrix molecules and to control the arrival volume of the laser energy.

[0010] In addition, the purpose of local analysis (using the principle of a so-called near-field optical microscope) that uses laser light on the tip of a metal short needle or leaked light that has propagated through the fiber (Refer to Patent Document 1 below).

However, in the above method, since the surface plasmon induced at the tip of the metal short needle is used, the resolution depends on the radius of curvature of the tip, and the tip of the metal short needle can be created with good reproducibility. Because it is very difficult, it is not suitable for quantitative analysis. In addition, the method using the principle of the near-field optical microscope has not yet reached the practical level because the sensitivity is still insufficient. Furthermore, it is very difficult to detect the number of molecules induced at a time by the surface plasmon electric field induced at the tip of a metal short needle.

Patent Document 1: JP 2004-264043

Disclosure of the invention

Problems to be solved by the invention

[0012] An object of the present invention is to quantitatively count the number of molecules of a sample by irradiating the sample with evanescent light without using a matrix in mass spectrometry. Means for solving the problem

In the present invention, the above-described problem can be solved by the following means. (1) A quantitative analysis method or apparatus for a sample, in which laser light is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, whereby evanescent light is reflected on the outer surface of the bottom surface. A quantitative analysis method or apparatus for a sample characterized in that the sample applied to the outer surface is vaporized and ionized.

[0014] (2) A quantitative analysis method or apparatus for a sample, in which two laser beams having different wavelengths are introduced into a trapezoidal prism, and totally reflected on the inner surface of the bottom surface of the prism. A method or apparatus for quantitative analysis of a sample, characterized in that surface plasmon is induced on a metal coated on a bottom surface, and the sample coated on the metal is vaporized and ionized by the plasmon.

[0015] (3) A sample quantitative analysis method or apparatus, in which one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism. Thus, evanescent light is generated on the outer surface of the bottom surface, the sample applied to the outer surface is vaporized by the evanescent light, and the other laser light is outside the prism and close to the bottom surface of the prism. A sample quantitative analysis method or apparatus, wherein the sample is introduced in parallel to ionize the vaporized sample.

[0016] (4) A quantitative analysis method or apparatus for a sample, wherein one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism. The surface plasmon is induced on the metal coated on the bottom surface of the prism, the sample applied on the metal is vaporized by the plasmon, and the other laser beam is external to the prism, and the bottom surface of the prism A method or apparatus for quantitative analysis of a sample, characterized in that the sample is introduced in parallel in the vicinity of the sample and the vaporized sample is turned on.

[0017] (5) A quantitative analysis method or apparatus for a sample, in which laser light is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, so that it is formed outside the bottom surface of the prism. A quantitative analysis method or apparatus for a sample characterized by inducing surface plasmon on a coated metal and evaporating and ionizing the sample introduced on top of the metal. The invention's effect

[0018] The present invention relates to a laser desorption mass spectrometry in which a sample is mixed in a matrix. Therefore, the number of molecules present in the volume can be counted by estimating the spot area of the light and the reach distance of the evanescent light, thereby enabling a quantitative analysis.

Brief Description of Drawings

[0019] [FIG. 1] An explanatory diagram of an example in which two laser beams are totally reflected on the bottom surface of a trapezoidal prism, and a sample is vaporized by using evanescent light generated thereby.

[Fig.2] Explanatory drawing of an example of vaporizing and ionizing a sample on a metal thin film using surface plasmons generated by two laser beams

[Fig. 3] One laser beam is totally reflected in the prism, and the other laser beam is directly irradiated onto the sample to vaporize and ionize the sample.

[Fig.4] An illustration of an example of vaporizing and ionizing a sample by directly irradiating the sample with one laser beam on the metal thin film, and the other laser beam directly irradiating the sample.

[Fig.5] Illustration of an example of vaporizing a sample with a single laser beam

[Fig. 6] Example of measuring the strength ratio of various carbons in fullerene using the present invention

[Fig. 7] Correlation diagram of intensity and quantity in fullerene when using the present invention

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The best mode for carrying out the present invention will be described below.

Example 1

[0021] <Injection of two laser beams into the prism (no metal used)>

(1) Laser light irradiation method

As can be seen in Fig. 1, YAG laser was used as the light source, and two lights of 1064nm wavelength and 532nm, 355nm or 266nm light were used. Light with a wavelength of 1064 nm was converted into long-wavelength light through an OPO (optical parametric oscillation) crystal. The two lights were overlapped through a dichroic mirror, condensed through a long-focus lens, and reflected to a trapezoidal prism (Dove prism).

[0022] Long-wavelength infrared light is mainly used to induce vibrational excitation. The purpose of infrared light that has been wavelength-converted by OPO is to vaporize efficiently by exciting specific vibrations such as the OH stretching vibration of the target molecule. On the other hand, short wavelength ultraviolet light is mainly Irradiate for ionization of the converted molecules.

[0023] Since the focal length changes depending on the wavelength, it is necessary to match the focal point (condensing conditions on the sampler: fluence of laser intensity, spot diameter, etc.) before irradiating the prism. The focal length is adjusted using a lens. The irradiation delay time of the two lasers was 0 seconds.

[0024] The light source for LD uses a Spectra Fijik YAG laser (GCR11) with a pulse width of 8 ns and a repetition period of 1 to 30 Hz (variable). The laser intensity is set so as to sufficiently satisfy the vaporization or ionization conditions.

Laser light is incident in parallel from the side surface of the trapezoidal prism to the upper surface of FIG. 1 (which is a long side and is referred to as “bottom surface” in the present invention). In this case, the incident laser beam is totally reflected on the back side of the bottom surface of the trapezoidal prism (the inner surface of the prism), so that evanescent light (near-field light) is generated outside the bottom surface of the trapezoidal prism.

[0026] The intensity of the evanescent light attenuates exponentially with respect to the distance from the bottom of the trapezoidal prism, and the distance of 1 gives the incident wavelength, and the refractive index of the prism and air is n, n, and the incident angle.

twenty one

Where Θ is given by the following equation.

d = λ / 2 π (n sin _n

2 θ 1 1 Ϋ

[0027] Since evanescent light is derived from electric lines of force due to induced dipoles on the prism surface, it has the same energy as incident light, and its existence region depends on the wavelength.

[0028] On the other hand, compared to normal laser light, it exists very locally, so that light irradiation on a trapezoidal prism surface, which is optically smooth, is performed only in well-defined nanospaces. It becomes possible.

In other words, it is possible to realize quantitative analysis by indirectly estimating the number of sample molecules existing in the arrival area of evanescent light.

[0030] Matrix molecules are required when measuring molecules having a large molecular weight. In this case, since quantitative properties are greatly impaired, it is necessary to control the mixed crystal state of the sample well.

[0031] When Matrix molecules are not used, soft ionization is achieved by coaxially irradiating two laser beams: one infrared laser for vibration excitation of sample molecules and one ultraviolet laser light for electron excitation. (The International Journal of Mass Spectrometr y 241 (2005) 49-56 etc.).

[0032] Infrared laser light (wavelength range: 1 to 4 μm) is a laser beam obtained by passing through an OPO (Optical Parametric Oscillation) crystal, which is a type of nonlinear optical crystal. Using.

[0033] Further, the laser beam to be irradiated was condensed by a long focus lens in order to reduce the bias of the laser beam intensity on the irradiation surface in the prism. In this example, an aspherical lens having no spherical aberration was used in order to avoid the deformation of the laser light intensity profile depending on the distance of the lens force. By controlling the distance between the two lenses, it was used as a long focal length lens.

[0034] (2) Sample form

The sample to be applied on the trapezoidal prism should be a very thin film of sub / m order. The reason is that when the sample thickness is large, the sample molecules near the trapezoidal prism surface that is vaporized by light irradiation are capped with sample molecules in the area that is not irradiated with light, so the amount of molecules that are vaporized accurately is specified. This is because I can't.

[0035] As a method of creating a very thin film of sample molecules, a spin coating method, a reduction in wetting angle by modifying a prism surface, or the like is used.

[0036] The spin coating method is a method of rotating a substrate at a high speed and dropping a solution, and the film thickness can be controlled by the rotation speed.

[0037] Further, the reduction of the wetting angle is performed in order to modify the prism surface and greatly improve the wettability of the sample solvent to the prism surface. For example, if hydrophilicity is improved, it is a titanium oxide coating that is known for its antibacterial action and super hydrophilicity. As a result, the liquid film can be controlled to a submicrometer by applying a micrometer-order droplet onto the prism surface.

[0038] (3) Experimental results

As a sample, a benzene solution of fullerene was applied to the bottom surface of the Dove prism. The wavelength of one incident laser beam is 532 nm, the intensity is about 1 mj / pulse, and the repetition frequency is 10 Hz. The spectrum shown is an average of 1000 measurements. Figure 6 shows the measurement results. The vertical axis in Fig. 6 shows the strength ratio of various carbons in fullerene, and the horizontal axis shows these various carbons. The mass per unit charge is indicated.

[0039] FIG. 7 is a plot of points where fullerene (C60) was diluted with acetone and applied to a plate, and the intensity of the desorbed and ionized fullerene was detected by TOF-MS using evanescent light. The vertical axis represents the intensity of fullerene (60), and the horizontal axis represents the amount of fullerene (C60).

Point A (upper right) in Figure 7 shows the intensity of deionized fullerene (C60) when 100 μg of fullerene (C60) is diluted with acetone and applied to the plate. Point B (middle) is Fullerene (C60) 100 μg diluted twice with acetone, ie, 50 μg fullerene (C60) strength, point C is 4 times diluted, ie 25 xg fullerene (C60) Point D is a plot of the fullerene (C60) strength of 12.

Fig. 7 shows that these four points are in a linear relationship. From the strength of various carbons in fullerene shown in Fig. 6, it can be quantified for each type of carbon, that is, the diameter of evanescent light and By estimating the volume of evanescent light reaching from the attenuation distance, it is shown that the molecules of the vaporized sample can be quantified.

Example 2

[0040] <In the case of <2 laser beams entering the prism (using metal)>

[0041] (1) Laser light irradiation method

As shown in FIG. 2, the laser light irradiation method is the same as in Example 1-1. However, the significance of laser light irradiation is different.

[0042] A metal thin film (such as gold or silver) is deposited on the bottom surface of the trapezoidal prism with a film thickness of about 50 degrees. When laser light is incident from the side surface of this trapezoidal prism, the incident laser light is totally reflected on the back side of the bottom surface of the trapezoidal prism, so that surface plasmons are excited by evanescent light on the metal thin film on the bottom surface of the trapezoidal prism.

[0043] It is difficult to estimate the attenuation constant of the surface plasmon electric field. The reason is that the fine structure such as surface irregularities is strongly influenced. However, if the average estimate

Since it is known to decay exponentially from the surface, a quantitative evaluation can be made by introducing a standard. However, since surface plasmon propagates only on the surface, there is an optimum incident angle for surface plasmon excitation due to the refractive index of the prism and the refractive index of the metal thin film. In addition, since the wavelength that resonates with surface plasmon excitation differs depending on the metal, a wavelength that depends on the metal species to be deposited is selected.

[0045] In this case, the enhanced photoelectric field induced on the metal surface is estimated to be about 10 times the incident photoelectric field. On the other hand, when the surface irregularity becomes a metal thin film of about several dozens, the law of conservation of wave number is broken, which makes it possible to excite surface plasmons that do not depend on the incident angle.

[0046] In this case, the enhanced photoelectric field reaches an average of 3 to 4 digits compared to the incident photoelectric field, and locally an enhancement of several orders of magnitude or more has been reported. It is possible to induce a vaporization reaction more efficiently by exciting a sample on a metal surface using an enhanced photoelectric field via surface plasmon excitation. In addition, because it is in contact with metal, it can be used as a matrix as soon as energy transfer to the metal surface occurs.

[0047] Since Matrix molecules are not mixed into the sample, the number of sample molecules existing in the volume can be defined by estimating the light arrival volume, so that quantitative discussion becomes possible. In this embodiment, since the metal thin film is used, the accuracy of estimating the light arrival volume is inferior to that of the method of the first embodiment.

[0048] (2) Sample form

The metal to be deposited on the prism surface is selected from metal species that can excite surface plasmons such as gold and silver with a single visible laser beam. Modification of the metal surface is not used because it affects surface plasmon excitation. The thickness of the deposited film is preferably about 50 mm. The sample is applied by dropping micrometer-order droplets.

Example 3

[0049] In the case of <laser beam passing through the surface of a single prism and incident inside a single prism (without using metal)> [0050] (1) Laser beam irradiation method

As shown in Fig. 3, the first laser beam is incident from the side of the trapezoidal prism. In this case, since the incident laser beam is totally reflected on the back side of the bottom surface of the trapezoidal prism, evanescent light is generated on the bottom surface of the trapezoidal prism.

[0051] The sample vaporized by the evanescent light becomes a punolem and exists in the region near the sample surface. The plume is ionized by the second laser beam. In this case, the wavelengths of the two laser beams are different.

[0052] Further, the time delay between the first laser beam and the second laser beam is controlled. This is because the plume generated by the first laser beam can cope with the time required for the plume to reach the optical path of the second laser beam, and the plume state change (such as relaxation of the excited state).

[0053] (2) Sample form

The sample form in this example is the same as that in Example 11. Example 4

[0054] In the case of <Laser beam passing through the surface of one prism, incident inside a prism (using metal)>

[0055] (1) Laser light irradiation method

As shown in Fig. 4, the first laser beam is incident from the side of the trapezoidal prism. The irradiation method is the same as in Example 1-2.

[0056] Further, the time delay between the first laser beam and the second laser beam is controlled. This is because the plume generated by the first laser beam can cope with the time required for the plume to reach the optical path of the second laser beam, and the plume state change (such as relaxation of the excited state). The mechanism is the same as in Example 1-2, and the sample is vaporized using the enhanced photoelectric field generated by surface plasmons.

[0057] (2) Sample morphology

The sample form in this example is the same as in Example 12 Example 5

[0058] <Injection of laser light into one prism, sample surface spraying (using metal)>

[0059] (1) Laser light irradiation method

As shown in Fig. 5, a thin metal film (gold, silver, etc.) is deposited on the bottom of the trapezoidal prism with a film thickness of about 50 nm. When laser light is incident from the side of the trapezoid prism, the incident laser light is totally reflected from the back side of the bottom surface of the trapezoid prism. Surface plasmons are excited on the thin film by evanescent light.

However, since surface plasmon propagates only on the surface, there is an optimum incident angle for surface plasmon excitation due to the refractive index of the prism and the refractive index of the metal thin film. In addition, since the wavelength that resonates with surface plasmon excitation differs depending on the metal, a wavelength that depends on the metal species to be deposited is selected.

[0061] In this case, the enhanced photoelectric field induced on the metal surface is estimated to be about 10 times the incident photoelectric field. On the other hand, when the surface irregularity becomes a metal thin film of about several dozens, the law of conservation of wave number is broken, which makes it possible to excite surface plasmons that do not depend on the incident angle.

[0062] In this case, the ratio of the enhanced photoelectric field to the incident photoelectric field reaches an average of 3 to 4 digits, and an enhancement of several digits or more is reported locally. It is possible to induce a vaporization reaction more efficiently by exciting a sample on a metal surface using an enhanced photoelectric field via surface plasmon excitation. In addition, because it is in contact with metal, it can be used as a matrix as soon as energy transfer to the metal surface occurs.

[0063] Since Matrix molecules are not mixed into the sample, the number of sample molecules existing in the volume can be defined by estimating the light arrival volume, which makes it possible to discuss quantitativeness. In this embodiment, since the metal thin film is used, the accuracy of estimating the light arrival volume is inferior to that of the method of the first embodiment. The estimate is the optical reach X spot area.

[0064] (2) Sample form

The metal to be deposited on the prism surface is selected from metal species that can excite surface plasmons such as gold and silver with a single visible laser beam. Modification of the metal surface is not used because it affects surface plasmon excitation. The thickness of the deposited film is preferably about 50 mm. The liquid sample is introduced along the metal surface where the surface plasmon exists.

[0065] In the case of the present embodiment, the intensity of vaporizing the sample with only one laser is necessary.

Claims

The scope of the claims

[1] A quantitative analysis method for a sample, in which laser light is introduced in parallel to the bottom surface of a trapezoidal prism, and totally reflected on the inner surface of the bottom surface of the prism, so that And evanescent light is generated, and the sample coated on the outer surface is vaporized by the evanescent light.

[2] The quantitative analysis method according to claim 1, wherein the number of molecules in the vaporized sample is calculated by estimating the diameter of the evanescent light and the attenuation distance force. Quantitative analysis of samples.

[3] The quantitative analysis method according to claim 2, wherein the vaporized sample is ionized and subjected to mass spectrometry.

[4] A quantitative analysis method for a sample, in which two laser beams having different wavelengths are introduced into a trapezoid prism and totally reflected on the inner surface of the bottom surface of the prism. A method for quantitative analysis of a sample, characterized in that a sample coated on the outer surface is vaporized by evanescent light having a long wavelength and ionized by evanescent light having a short wavelength.

[5] Quantitative analysis of a sample, in which two laser beams with different wavelengths are introduced into a trapezoid prism and totally reflected on the inner surface of the bottom surface of the prism, thereby evanescent on the outer surface of the bottom surface. Quantitative analysis of a sample characterized by generating light, inducing surface plasmon on a metal covering the bottom surface of the prism by the evanescent light, and vaporizing and ionizing the sample coated on the metal by the plasmon Analytical method.

[6] Quantitative analysis of a sample, wherein one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, whereby the outer surface of the bottom surface The evanescent light is caused to evaporate the sample coated on the outer surface by the evanescent light, and the other laser light is introduced outside the prism in parallel to the bottom surface of the prism, and the vaporization is performed. A method for quantitative analysis of a sample, characterized in that the sample is ionized by irradiating the irradiated sample.

[7] A quantitative analysis method for a sample, in which one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, Evanescent light is generated on the outer surface of the bottom surface, surface plasmon is induced on the metal coated on the bottom surface of the prism by the evanescent light, the sample coated on the metal is vaporized by the plasmon, and the other laser light is emitted. A method for quantitative analysis of a sample, characterized in that the sample is ionized by irradiating the vaporized sample outside and in parallel with the prism bottom surface.

[8] A quantitative analysis method for a sample, in which laser light is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, thereby generating evanescent light on the outer surface of the bottom surface. A method for quantitative analysis of a sample, characterized in that surface plasmon is induced on a metal coated on the outside of the bottom surface of the prism by the evanescent light, and the sample introduced into the upper part of the metal is vaporized and ionized by the plasmon.

[9] A sample vaporization and ionization apparatus, which introduces laser light parallel to the bottom surface of the trapezoidal prism and totally reflects it on the inner surface of the bottom surface of the prism, thereby generating evanescent light on the outer surface of the bottom surface. A sample vaporizing and ionizing apparatus, characterized by vaporizing and ionizing the sample coated on the outer surface by the evanescent light.

[10] A sample vaporization and ionization apparatus, which introduces two laser beams having different wavelengths into a trapezoidal prism and totally reflects them on the inner surface of the bottom surface of the prism, thereby evanescent on the outer surface of the bottom surface. A sample vaporization and ionization apparatus characterized by causing light to vaporize and ionize a sample applied to the outer surface.

[11] An apparatus for vaporizing and ionizing a sample, in which two laser beams having different wavelengths are introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, whereby evanescent light is reflected on the outer surface of the bottom surface. Vaporization and ionization of a sample characterized by inducing surface plasmon on a metal coated on the bottom surface of the prism by the evanescent light, and vaporizing and ionizing the sample coated on the metal by the plasmon apparatus.

[12] An apparatus for vaporizing and ionizing a sample, wherein one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, thereby Evanescent light is generated on the outer surface, and the evanescent light is The sample coated on the outer surface is vaporized, and the other laser beam is introduced in parallel to the outside of the prism, close to the bottom surface of the prism, and irradiated to the vaporized sample. An apparatus for vaporizing and ionizing a sample, characterized by ionizing the sample.

[13] An apparatus for vaporizing and ionizing a sample, wherein one of two laser beams having different wavelengths is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, thereby Evanescent light is generated on the outer surface, surface plasmon is induced on the metal coated on the bottom surface of the prism by the evanescent light, the sample applied on the metal is vaporized by the plasmon, and the other laser light is A sample vaporization and ionization apparatus, wherein the sample is ionized by irradiating the vaporized sample, which is outside the prism and introduced in parallel near the bottom surface of the prism.

[14] An apparatus for vaporizing and ionizing a sample, wherein laser light is introduced into a trapezoidal prism and totally reflected on the inner surface of the bottom surface of the prism, thereby generating evanescent light on the outer surface of the bottom surface. An apparatus for vaporizing and ionizing a sample, characterized in that surface plasmon is induced on a metal coated on a bottom surface of the prism by evanescent light, and the sample introduced into the upper part of the metal is vaporized and ionized by the surface plasmon.

[15] In the sample quantitative analysis device, the vaporized sample is estimated by estimating the aperture and attenuation distance of the evanescent light using the sample vaporization and ionization device according to any one of claims 9 to 14. Quantitative sample analyzer characterized by calculating the number of molecules in the sample and performing mass spectrometry.