WO2013122225A1 - 白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法 - Google Patents
白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法 Download PDFInfo
- Publication number
- WO2013122225A1 WO2013122225A1 PCT/JP2013/053743 JP2013053743W WO2013122225A1 WO 2013122225 A1 WO2013122225 A1 WO 2013122225A1 JP 2013053743 W JP2013053743 W JP 2013053743W WO 2013122225 A1 WO2013122225 A1 WO 2013122225A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sample
- mass spectrometry
- platinum
- imaging mass
- vapor deposition
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
- G01N27/623—Ion mobility spectrometry combined with mass spectrometry
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0004—Imaging particle spectrometry
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/2853—Shadowing samples
Definitions
- the present invention relates to an imaging mass spectrometry method using physical vapor deposition of platinum nanoparticles.
- the present invention relates to a sample preparation method in which platinum nanoparticles are physically vapor-deposited as an ionization support matrix on the surface of a sample subjected to imaging mass spectrometry, and an imaging mass spectrometry method using the sample.
- Mass spectrometry is one of the techniques for directly discovering and identifying target substances, but in recent years, imaging mass spectrometry (IMS) has been used to identify target substances in biological tissues and elucidate their localization.
- IMS imaging mass spectrometry
- ionization assistant matrix -free secondary ion mass spectrometry
- MALDI matrix-assisted laser desorption ionization method
- a chemically synthesized substance (organic matrix), a metal oxide or metal nanoparticle dispersed in a solvent (inorganic matrix) is known.
- the organic matrix includes 1,8-dihydroxy-9 (10H) -anthracenone (Dithranol), 2- (4-hydroxy phenylazo) benzoic acid (HABA), 2,5-dihydroxybenzoic acid (DHB), ⁇ -cyano
- HABA 1,8-dihydroxy-9
- HABA 2- (4-hydroxy phenylazo) benzoic acid
- DHB 2,5-dihydroxybenzoic acid
- ⁇ -cyano There are 4-hydroxycinnamic acid (CHCA), sinapinic acid (SA), etc., which are selected according to the analysis substance (protein, peptide, synthetic polymer, etc.).
- the matrix is dropped or sprayed in a liquid (solution) state and adheres to the sample, and the analysis target substance is taken in.
- crystal grains containing the substance to be analyzed are formed.
- the size of the crystal grains of the matrix is generally about 50 ⁇ m or more (Non-Patent Document 4). Since the substance to be analyzed is dispersed in the crystal grains of this matrix, even if the irradiation diameter of the laser beam for ionization is reduced, a spatial resolution higher than the crystal grain diameter of the matrix cannot be obtained.
- Non-Patent Document 5 IMS using gold vapor deposition has been proposed as a technique not using a liquid matrix. This method is characterized by depositing gold on the surface of the sample to support ionization. However, in this method, a special apparatus is required to deposit nanoparticulate gold, and the peak of the target substance is reduced or cannot be detected because the gold-derived ion peak appears strongly in the spectrum. There is room for further improvement.
- an imaging mass spectrometry method using a matrix for supporting ionization of a sample which has high ionization efficiency, suppresses migration and reduction of visual information, has no interference peak derived from the matrix, and analyzes with high spatial resolution.
- Patent Document 5 discloses an LDI plate for laser desorption ionization (LDI), which has platinum particles as ionization auxiliary particles for assisting ionization of a sample.
- LBI laser desorption ionization
- platinum particles are supported on a plate using a dispersion liquid in which platinum particles are dispersed, it is applied to physical vapor deposition of platinum on the surface of a sample or imaging mass spectrometry. There is no suggestion about that.
- the present invention is an imaging mass spectrometry method using a matrix for supporting ionization of a sample, which has high ionization efficiency, suppresses migration and reduction of visual information, has no interference peak derived from the matrix, and has high spatial resolution.
- the main object of the present invention is to provide an improved imaging mass spectrometry method which can be analyzed by the above method.
- the present inventors have found that the above object can be achieved when a sample is prepared by physical vapor deposition of platinum nanoparticles on the surface of a sample to be subjected to imaging mass spectrometry.
- the present invention has been completed.
- the present invention relates to the following imaging mass spectrometry method and sample preparation method for imaging mass spectrometry.
- An imaging mass spectrometry method comprising using a sample prepared by physical vapor deposition of platinum nanoparticles on the surface of a sample to be subjected to imaging mass spectrometry.
- the imaging mass spectrometry method according to Item 1 wherein the platinum nanoparticles have an average particle diameter of 2 to 20 nm.
- Item 3 The imaging mass spectrometry method according to Item 1 or 2, wherein the platinum nanoparticle layer formed by physical vapor deposition has a thickness of 2 to 50 nm. 4).
- Item 5. The imaging mass spectrometry method according to any one of Items 1 to 4, which uses a matrix-assisted laser desorption / ionization (MALDI) imaging mass spectrometer. 6).
- Item 7. The method for preparing a sample for imaging mass spectrometry according to Item 6, wherein the platinum nanoparticles have an average particle size of 2 to 20 nm. 8).
- the imaging mass spectrometry method of the present invention is characterized by using a sample prepared by physical vapor deposition of platinum nanoparticles on the surface of a sample to be subjected to imaging mass spectrometry.
- platinum nanoparticles act as a matrix for supporting ionization of a sample, and high ionization efficiency and spatial resolution can be obtained.
- sample migration is suppressed in that no liquid matrix is used, and physical vapor deposition of platinum nanoparticles does not reduce the visual information on the sample surface, so the sample surface can be observed with a CCD camera or microscope during analysis.
- the interference peak derived from platinum nanoparticles is not substantially observed, the peak derived from the sample can be analyzed with high accuracy. Such excellent effects are presumed to be based on the fact that platinum nanoparticles having a uniform particle diameter can be attached to the sample surface by physical vapor deposition.
- the imaging mass spectrometry method of the present invention can be widely used for imaging mass spectrometry in the fields of biochemistry, medicine, genomic drug discovery, and materials / nanotech.
- Samples to which the imaging mass spectrometry method of the present invention can be applied are not limited, and examples include biological specimens or biological specimens containing cells, and specifically, tissue slices derived from animals or plants, or adherent cultures on plates. And cultured cells of animals, plants and microorganisms. For example, if it is a plant, a tree, a plant, a flower, a fruit, a leaf, a root, a stem, etc. are mentioned.
- examples include organs, brain, tissue, skin, hair, cells and the like.
- the living tissue can be frozen as needed and then sliced thinly, and then vacuum-dried or used as it is as a tissue section.
- target substances contained in these biological specimens include biological substances such as proteins, peptides, nucleic acids, sugars and lipids, and synthetic low molecular compounds such as agricultural chemicals and pharmaceuticals administered to living bodies. , Synthetic polymers, and exogenous metabolites generated by the metabolism of these in living tissues.
- a sample in the material / nanotech field can be used as a sample.
- the sample include non-ferrous metals, ceramics, functional materials, battery materials, optical materials, carbon fibers, automobile materials, graphite, activated carbon, interlayer insulating films, organic semiconductor materials, polymer materials, low molecular materials, organic EL Examples include materials, additives, dyes, and inks.
- the imaging mass spectrometry method of the present invention uses a sample prepared by physical vapor deposition of platinum nanoparticles on the surface of the sample.
- physical vapor deposition PVD: Physical Vapor Deposition
- PVD Physical Vapor Deposition
- MBE ion plating, ion beam deposition, conventional sputtering, magnetron sputtering, ion beam sputtering, ECR sputtering, and the like.
- magnetron sputtering is preferred in the present invention.
- Magnetron sputtering has been used in the past as a pretreatment for high-resolution scanning electron microscope (HR-SEM) observations in order to provide conductivity to the surface of an insulating material.
- HR-SEM high-resolution scanning electron microscope
- the average particle diameter of platinum nanoparticles deposited on the sample surface by physical vapor deposition is preferably 2 to 20 nm, and more preferably 2 to 10 nm.
- the particle size distribution is preferably from 1 to 10, more preferably from 1 to 5.
- the thickness of the deposited layer (platinum nanoparticle layer) is preferably 2 to 50 nm, and more preferably 10 to 30 nm.
- the platinum nanoparticles deposited by physical vapor deposition are pure platinum nanoparticles in which a protective agent (organic molecule, polymer, etc.) is not attached to the particle surface, unlike commercially available platinum nanoparticles.
- the average particle diameter and particle size distribution of the platinum nanoparticles and the thickness of the body laminate in this specification are values measured by observation with an electron microscope.
- platinum nanoparticles having a uniform particle diameter can be deposited on the sample surface by using physical vapor deposition. If the deposition of nano-order fine particles in the above range is used, there is no risk of reducing visual information on the sample surface. Also, unlike the use of a liquid matrix, sample migration can be suppressed.
- the platinum nanoparticles act as a matrix to support ionization of the sample, but the platinum nanoparticles themselves can efficiently support ionization of the sample without being ionized by laser irradiation, so that high ionization efficiency is achieved. Spatial resolution can be obtained, and the occurrence of matrix-derived interference peaks can be avoided. Therefore, in the present invention, the S / N ratio and sensitivity of the detection signal are improved, and the peak derived from the sample can be analyzed with high accuracy.
- FIG. 1A is an SEM image when platinum is deposited on the carbon surface by physical vapor deposition
- FIG. 1B is an SEM image when gold is deposited on the magnetic tape surface by physical vapor deposition
- Fig. 5 is an SEM image when a conventional organic matrix for MALDI (the organic matrix is sinapinic acid) is attached by a spray method.
- a spray method When these SEM images are compared, it can be seen that nanoparticles having an extremely uniform particle diameter can be deposited uniformly when platinum is physically vapor-deposited.
- gold is physically vapor-deposited, the particle size is larger than when platinum is physically vapor-deposited, and the particle size is more varied.
- imaging mass spectrometry is performed using a sample prepared by the above technique, but the present invention includes not only an imaging mass spectrometry method but also a sample preparation method for imaging mass spectrometry by the above technique.
- the sample is irradiated with a laser to ionize the sample.
- the wavelength of the laser is preferably about 250 to 600 nm, and is preferably adjusted by a condensing optical system so that the irradiation diameter on the sample is 50 ⁇ m or less.
- the sample to be analyzed is a cell, it is desirable to reduce the laser beam irradiation diameter to 10 ⁇ m or less (about several ⁇ m).
- the platinum nanoparticle absorbs the laser, and the sample molecule is ionized by the interaction (energy transfer) between the platinum nanoparticle and the sample.
- the ionization, detection and imaging can be performed by one imaging mass spectrometer (for example, MALDI imaging mass spectrometer: apparatus name “AutoFlex III” manufactured by Bruker), but is not limited to this apparatus.
- MALDI imaging mass spectrometer apparatus name “AutoFlex III” manufactured by Bruker
- a commercially available MALDI and an imaging apparatus can also be used in combination.
- imaging (two-dimensional) mass spectrometry of a target substance can be performed by performing mass spectrometry and analysis at an arbitrary position of a sample.
- platinum nanoparticles are physically vapor-deposited on the sample surface, migration of the sample and loss of visual information are avoided, so that the sample surface can be observed with a CCD camera or a microscope during analysis. .
- CCD cameras and microscopes used for observation can be used according to conventional methods.
- platinum nanoparticles act as a matrix for supporting ionization of a sample, and high ionization efficiency and spatial resolution can be obtained.
- sample migration is suppressed in that no liquid matrix is used, and physical vapor deposition of platinum nanoparticles does not reduce the visual information on the sample surface, so the sample surface can be observed with a CCD camera or microscope during analysis.
- the interference peak derived from platinum nanoparticles is not substantially observed, the peak derived from the sample can be analyzed with high accuracy. Such excellent effects are presumed to be based on the fact that platinum nanoparticles having a uniform particle diameter can be attached to the sample surface by physical vapor deposition.
- the imaging mass spectrometry method of the present invention can be widely used for imaging mass spectrometry in the fields of biochemistry, medicine, genomic drug discovery, and materials / nanotech.
- Example 1 is an SEM image when platinum is physically vapor-deposited on the carbon surface, (b) is an SEM image when gold is physically vapor-deposited on the surface of the magnetic tape, and (c) is a conventional organic matrix for MALDI ( It is a SEM image when the organic matrix is sinapinic acid) attached by a spray method.
- MALDI It is a SEM image when the organic matrix is sinapinic acid
- Example 1 imaging is performed on a substance having a mass-to-charge ratio (m / z) of 1000 or more in the fingerprint region.
- A) is a figure which shows the area
- B) is a figure which shows the state (sample) after carrying out physical vapor deposition of the platinum nanoparticle.
- Example 2 it is a figure which shows the mass spectrum (m / z) in each area
- Example 2 it is imaging of the substance distributed in the paper area
- (A) is a figure which shows the state which developed three types of dye on TLC in Example 3.
- Example 4 is a figure which shows the state (sample) after carrying out physical vapor deposition of the platinum nanoparticle.
- Example 3 it is a mass spectrum (m / z) which shows that all three types of dyes are detected by mass spectrometry.
- Example 3 it is the imaging of three types of dyes analyzed.
- A) is a figure which shows the state which developed three types of sugar on TLC in Example 4.
- FIG. (B) is an imaging of the three sugars analyzed.
- C), (d) and (e) are mass spectra showing the results of detection of all three types of sugars by mass spectrometry.
- Example 4 it is the imaging which developed three types of sugar on TLC and the chemical structure of three types of analyzed sugar.
- Example 5 platinum vapor deposition
- the comparative example 1 gold vapor deposition
- platinum vapor deposition platinum vapor deposition
- comparative example 1 gold vapor deposition
- Example 6 it is a figure which shows the state which dripped the methylene blue solution of various density
- Example 6 it is the imaging which imaged the ion peak distribution of the substance whose mass to charge ratio (m / z) is 372.
- concentration is 372.
- FIG. (A) is IMS imaging of a sample obtained in Example 7 by applying a methanol dispersion of platinum nanoparticles (average particle size 5 nm) onto an ink spot.
- (B) is an IMS imaging of a sample obtained by depositing platinum on an ink spot. It is a figure which shows the mass spectrum obtained in Example 8 and Comparative Example 2. It is a figure which shows the mass spectrum obtained in Example 9 and Comparative Example 3.
- Example 10 and Comparative Example 4 is a graph comparing mass spectrum intensities in Examples 8 to 10 and Comparative Examples 2 to 4.
- the distribution of acephate in Example 8 and Comparative Example 2 is visualized.
- a dotted circle indicates a dripped region.
- FIG. It is a visualization of the distribution of acetamiprid in Example 12.
- a peak of m / z 245 derived from acetamiprid was adopted.
- a dotted circle indicates a dripped region. It is a figure which shows the mass spectrum obtained in Example 13. 2 is a visualization of the distribution of the two types of acetamiprid and thiophanate methyl of Example 13.
- 14 is a visualization of the leaf acephate distribution in Example 14.
- FIG. 17 is a visualization of the distribution of stem acephate in Example 14.
- FIG. The peak of m / z 206 derived from acephate was adopted.
- Example 1 Direct analysis of finger deposits by IMS
- a finger was pressed onto the chrome-coated glass slide.
- platinum nanoparticles having an average particle diameter of 3 nm were thinly deposited with a thickness of 20 nm by a magnetron sputtering apparatus (device name “E-1030” manufactured by Hitachi).
- E-1030 magnetron sputtering apparatus
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 60% ⁇ Measurement interval: 100 ⁇ m
- the peak of the mass-to-charge ratio (m / z) 210.9 derived from the glass substrate was not detected in the fingerprint region.
- the fingerprint region pressed against the glass could be mass analyzed with high accuracy by depositing platinum. This method is expected to be effective for scientific investigations such as criminal investigations.
- Example 2 Direct analysis and degradation evaluation of printed matter by IMS
- strip-shaped color printing magenta color
- UV irradiation was performed for 30 minutes on a part of the printed portion. It was observed that the printed matter was deteriorated by UV irradiation, and the color was changed (white color was lost) (see FIG. 5A).
- platinum nanoparticles having an average particle diameter of 3 nm were thinly deposited with a thickness of 20 nm by a magnetron sputtering device (device name “E-1030” manufactured by Hitachi) (see FIG. 5B).
- the sample was subjected to IMS measurement and analysis using a MALDI imaging mass spectrometer (device name “AutoFlex III” manufactured by Bruker). On the other hand, what did not vapor-deposit platinum nanoparticles was used as a control sample.
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 70% ⁇ Measurement interval: 200 ⁇ m
- a peak of m / z 602.8, which is a magenta pigment component, is observed from a portion not irradiated with UV (printing region) (see FIG. 6), and the distribution thereof is a band-shaped print pattern and They coincided (see FIG. 7).
- pigment and paper components could not be detected from a sample in which platinum nanoparticles were not deposited.
- platinum nanoparticles By depositing platinum nanoparticles, distribution of magenta pigment component, paper component, and distribution and analysis of substances caused by photo-degradation were achieved. This method is expected to be effective for component distribution and deterioration analysis such as printing parts and paints.
- Example 3 Direct analysis of TLC isolate by IMS 1
- a mixed solution of three kinds of dyes (rhodamine B: green, rhodamine 123: red, crystal violet: purple) was spotted on a plate for thin-layer chromatography (TLC) and developed on TLC.
- TLC thin-layer chromatography
- two of the three dyes (Rhodamine 123: Red and Crystal Violet: Purple) were confirmed, but the remaining one dye (Rhodamine B: Green) was It could not be confirmed (see FIG. 11 (a)).
- platinum nanoparticles having an average particle diameter of 3 nm were thinly deposited at a thickness of 20 nm by a magnetron sputtering apparatus (device name “E-1030” manufactured by Hitachi) (see FIG. 11B). On the other hand, what did not vapor-deposit platinum nanoparticles was used as a control sample.
- the sample was subjected to IMS measurement and analysis using a MALDI imaging mass spectrometer (device name “AutoFlex III” manufactured by Bruker).
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 40% ⁇ Measurement interval: 200 ⁇ m
- Rhodamine B which was a dye that could not be visually discerned, partially overlapped with other dye spots (see FIG. 13). For this reason, it became clear that Rhodamine B could not be confirmed visually.
- Example 4 (Direct analysis of TLC isolate by IMS 2) A mixed solution of three kinds of sugars (glucose, maltose, maltotriose) was spotted on a plate for thin-layer chromatography (TLC) and developed on TLC. The spot of sugar that migrated on the TLC plate was not visible (see FIG. 14 (a)). On top of that, platinum nanoparticles with an average particle diameter of 3 nm were thinly deposited at a thickness of 20 nm by a magnetron sputtering device (device name “E-1030” manufactured by Hitachi), and a MALDI imaging mass spectrometer (device name “AutoFlex III” manufactured by Bruker) The sample was subjected to IMS measurement and analysis.
- a magnetron sputtering device device name “E-1030” manufactured by Hitachi
- MALDI imaging mass spectrometer device name “AutoFlex III” manufactured by Bruker
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 50% ⁇ Measurement interval: 300 ⁇ m
- spots A, B, and C are confirmed on the TLC by imaging analysis using IMS (see FIG. 14B). From the mass spectra at the respective locations, spots A, B, and C are glucose, maltose, It was found to be maltotriose (see FIGS. 14 (c), (d), (e), and FIG. 15).
- Example 5 and Comparative Example 1 Comparison between platinum vapor deposition and gold vapor deposition
- the letter “I” was drawn on the substrate with black ink used in an inkjet printer.
- Two types were prepared: a sample obtained by physical vapor deposition of platinum on the substrate (Example 5) and a sample obtained by physical vapor deposition of gold (Comparative Example 1). Imaging mass spectrometry of these substrates was performed. Imaging mass spectrometry was performed using a MALDI imaging mass spectrometer (device name “AXIMA-CFR Plus” manufactured by Shimadzu Corporation).
- IMS IMS-Irradiation laser: Nitrogen laser (337 nm) ⁇ Acceleration voltage: 20 kv ⁇ Linear mode measurement (positive ion mode) ⁇ Laser radius: about 100 ⁇ m ⁇ Laser intensity: 60 (reading of the device) ⁇ Measurement interval: 100 ⁇ m
- Example 6 (Concentration dependence of platinum deposition) Methylene blue (concentration: 1 mM, 0.5 mM, 0.25 mM, 0.1 mM, 0.01 mM) was dropped on the TLC plate, and physical vapor deposition of platinum was further performed (see FIG. 18). Subsequently, imaging mass spectrometry was performed. Imaging mass spectrometry was performed using a MALDI imaging mass spectrometer (device name “AXIMA-CFR Plus” manufactured by Shimadzu Corporation).
- IMS IMS-Irradiation laser: Nitrogen laser (337 nm) ⁇ Acceleration voltage: 20 kv ⁇ Linear mode measurement (positive ion mode) ⁇ Laser radius: about 100 ⁇ m ⁇ Laser intensity: 60 (reading of the device) ⁇ Measurement interval: 100 ⁇ m
- the peak intensity and the density of the imaging image change in a stepwise manner according to the concentration of the target substance.
- Example 7 (difference between platinum deposition and platinum nanoparticle dispersion) A spherical ink spot was drawn on the paper using black ink. Two types were prepared: a sample in which a methanol dispersion of platinum nanoparticles was applied onto an ink spot, and a sample in which platinum was physically vapor-deposited. Imaging mass spectrometry was performed using a MALDI imaging mass spectrometer (device name “AXIMA-CFR Plus” manufactured by Shimadzu Corporation).
- IMS IMS-Irradiation laser: Nitrogen laser (337 nm) ⁇ Acceleration voltage: 20 kv ⁇ Linear mode measurement (positive ion mode) ⁇ Laser radius: about 100 ⁇ m ⁇ Laser intensity: 60 (reading of the device) ⁇ Measurement interval: 100 ⁇ m
- the black spot-derived imaging image was displayed in the platinum-deposited ink spot (see FIG. 21B). Since the ink was dissolved in methanol, the shape of the ink spot could not be obtained (see FIG. 21A). This is considered to be based on the fact that platinum deposition exhibits higher detection sensitivity than the application of the platinum nanoparticle dispersion.
- Examples 8 to 10 and Comparative Examples 2 to 4 comparativative Examples 2 to 4 (difference between platinum deposition and existing organic matrix)
- Example 8 acephate, platinum deposition
- An aqueous solution of acephate (agrochemical) was dropped on the viola leaf and dried, and then a sample was prepared by depositing platinum nanoparticles with a thickness of 10 nm using a magnetron sputtering apparatus (E-3010: manufactured by Hitachi, Ltd.).
- Example 9 Acetamiprid, platinum deposition
- An aqueous solution of acetamiprid (agrochemical) was dropped onto the viola leaf and dried, and then a sample was prepared by depositing platinum nanoparticles with a thickness of 10 nm using a magnetron sputtering apparatus (E-3010: manufactured by Hitachi, Ltd.).
- Example 10 Polyethylene glycol, platinum deposition
- An aqueous solution of polyethylene glycol (synthetic polymer) was dropped onto a viola leaf and dried, and then a sample was prepared by depositing platinum nanoparticles with a thickness of 10 nm using a magnetron sputtering apparatus (E-3010: manufactured by Hitachi, Ltd.).
- Example 2 Acephate, existing organic matrix
- Example 8 except that instead of platinum deposition, an organic matrix layer of 2,5-Dihydroxybenzoic acid (DHB) was formed using a matrix spray apparatus (TM-sprayer: manufactured by HTX Imaging) for MALDI imaging mass spectrometry. Samples were prepared in the same manner.
- Example 3 Acetamiprid, existing organic matrix
- Example 9 except that instead of platinum deposition, an organic matrix layer of 2,5-Dihydroxybenzoic acid (DHB) was formed using a matrix spray apparatus for MALDI imaging mass spectrometry (TM-sprayer: manufactured by HTX Imaging). Samples were prepared in the same manner.
- Example 10 Comparative Example 4: Polyethylene glycol, existing organic matrix
- Example 10 except that instead of platinum deposition, an organic matrix layer of 2,5-Dihydroxybenzoic acid (DHB) was formed using a matrix spray apparatus for MALDI imaging mass spectrometry (TM-sprayer: manufactured by HTX Imaging). Samples were prepared in the same manner.
- TM-sprayer manufactured by HTX Imaging
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 50% ⁇ Measurement interval: 300 ⁇ m
- Examples 8 to 10 and Comparative Examples 2 to 4 are shown in FIG. In Examples 8 to 10 on which platinum deposition was performed, a sensitivity enhancement effect 3 to 100 times higher than that in Comparative Examples 2 to 4 in which an organic matrix layer was formed was confirmed.
- Example 8 As a result of analyzing the distribution of acephate in Example 8 and Comparative Example 2, in Example 8, an acephate peak was strongly observed in the dropped region, whereas in Comparative Example 2, the observed acephate peak was observed. Was weak (FIG. 26). Furthermore, in Comparative Example 2, an acephate peak was also observed from a region where no dripping occurred due to the migration effect of the solvent used for forming the organic matrix layer. The surface of the leaf is uneven in shape and has a wax layer, so it is easier to repel the solvent compared to the section sample and the migration effect tends to occur, but in the platinum deposition used in the example, the dripped region Only the peak was confirmed, and it was found that the migration effect was suppressed.
- Example 11 and Comparative Example 5 (difference between platinum deposition and existing organic matrix) (Example 11: DOP and DNP, platinum deposition)
- DOP and DNP platinum deposition
- a sample was prepared by depositing platinum nanoparticles with a thickness of 10 nm on a polyvinyl chloride (PVC) wallpaper using a magnetron sputtering apparatus (E-3010: manufactured by Hitachi, Ltd.).
- the PVC contains dioctyl phthalate (DOP) and dinonyl phthalate (DNP) as additives (plasticizer).
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 70% ⁇ Measurement interval: 300 ⁇ m
- Example 28 shows the peak intensities of Example 11 and Comparative Example 5.
- the sensitivity enhancement effect was confirmed to be 3 to 4 times that in Comparative Example 5 in which the organic matrix layer was formed.
- Example 12 (Acetamiprid, platinum deposition) In Example 9, the IMS measurement conditions were changed as follows. That is, the laser diameter was narrowed down and the measurement was performed in the high spatial resolution mode.
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: approx. 50 ⁇ m (MINIMUM mode) ⁇ Laser intensity: 50% ⁇ Measurement interval: 50 ⁇ m
- Example 13 (horticultural spray type insecticide / bactericide pesticide, platinum deposition) Spray spray-type insecticidal / bactericidal pesticides for gardening are sprayed on the leaves of Ivy, dried, and then deposited with a magnetron sputtering device (E-3010: manufactured by Hitachi, Ltd.) to deposit platinum nanoparticles to a thickness of 10 nm. Prepared. The used pesticide contains acetamiprid and thiophanate methyl as active ingredients.
- the sample was subjected to IMS measurement and analysis using a MALDI imaging mass spectrometer (device name “AutoFlex III” manufactured by Bruker).
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 100% ⁇ Measurement interval: 150 ⁇ m
- Example 14 (Growth Type Pesticide Pesticide, Platinum Deposition) Sprinkle pesticide pesticides for horticultural use on the soil where Ivy is planted, and after 4, 8, 11 and 14 days, the leaves of about 30 mm are collected from the soil, and the platinum nanoparticles are deposited with a magnetron sputtering device. Each sample was prepared by vapor deposition with a thickness of 10 nm. The agrochemical used as a granule contains acephate as an active ingredient.
- IMS measurement of each sample was performed.
- IMS measurement was performed under the same conditions for the lower stem close to the root and the upper stem far from the root.
- IMS Irradiation laser: Nd: YAG laser (355 nm) ⁇ Acceleration voltage: 19 kv ⁇ Reflectron voltage: 21kv ⁇ Laser radius: about 100 ⁇ m (ULTRA mode) ⁇ Laser intensity: 100% ⁇ Measurement interval: 150 ⁇ m
- the mass spectrometry method of the present invention that performs platinum deposition can visually understand the behavior of the sprayed pesticides infiltrating and distributing in plants, and this method is effective in elucidating the mechanism of action of pesticides in plants. It shows that there is.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
1.イメージング質量分析に供する試料の表面に白金ナノ粒子を物理蒸着することによって調製されたサンプルを用いることを特徴とするイメージング質量分析方法。
2.前記白金ナノ粒子の平均粒子径は2~20nmである、上記項1に記載のイメージング質量分析方法。
3.前記物理蒸着により形成される白金ナノ粒子層の厚さは2~50nmである、上記項1又は2に記載のイメージング質量分析方法。
4.前記物理蒸着は、マグネトロンスパッタリングによる物理蒸着である、上記項1~3のいずれかに記載のイメージング質量分析方法。
5.マトリックス支援レーザー脱離イオン化(MALDI)イメージング質量分析装置を用いる、上記項1~4のいずれかに記載のイメージング質量分析方法。
6.イメージング質量分析に供する試料の表面に白金ナノ粒子を物理蒸着することを特徴とするイメージング質量分析用のサンプル調製方法。
7.前記白金ナノ粒子の平均粒子径は2~20nmである、上記項6に記載のイメージング質量分析用のサンプル調製方法。
8.前記物理蒸着により形成される白金ナノ粒子層の厚さは2~50nmである、上記項6又は7に記載のイメージング質量分析用のサンプル調製方法。
9.前記物理蒸着は、マグネトロンスパッタリングによる物理蒸着である、上記項6~8のいずれかに記載のイメージング質量分析用のサンプル調製方法。
クロムコートしたスライドガラスの上に指を押し付けた。その上にマグネトロンスパッタリング装置(装置名「E-1030」Hitachi製)によって平均粒子径3nmの白金ナノ粒子を厚さ20nmで薄く蒸着した。その結果、指紋が明確に浮かび上がった(図2参照)。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:60%
・測定間隔:100μm
インクジェット印刷により、紙の上に2mmの間隔で帯状のカラー印刷(マゼンダ色)を行った。次に、印刷物の劣化評価を行うために、印刷箇所のある一部分にUV照射を30分間行った。UV照射により、印刷物の劣化が生じて色が変色(白く色抜け)することが観察された(図5(a)参照)。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:70%
・測定間隔:200μm
薄層クロマトグラフィー(TLC:Thin-Layer Chromatography)用のプレート上に、染料3種類(ローダミンB:緑色、ローダミン123:赤色、クリスタルバイオレット:紫色)の混合溶液をスポットし、TLC上で展開させた。TLCプレート上で移動した染料スポットの目視観察では、3種類の染料のうち2種類(ローダミン123:赤色とクリスタルバイオレット:紫色)は確認できたが、残り1種類の染料(ローダミンB:緑色)は確認できなかった(図11(a)参照)。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:40%
・測定間隔:200μm
薄層クロマトグラフィー(TLC:Thin-Layer Chromatography)用のプレート上に、3種類の糖(グルコース、マルトース、マルトトリオース)の混合溶液をスポットし、TLC上で展開させた。TLCプレート上で移動した糖のスポットは、目視はできなかった(図14(a)参照)。その上にマグネトロンスパッタリング装置(装置名「E-1030」Hitachi製)によって平均粒子径3nmの白金ナノ粒子を厚さ20nmで薄く蒸着し、MALDIイメージング質量分析装置(装置名「AutoFlex III」Bruker社製)により、サンプルのIMS測定と解析を行った。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:50%
・測定間隔:300μm
インクジェットプリンターに使用される黒色インクで基板に“井”の字を描いた。その基板上に白金を物理蒸着したサンプル(実施例5)と金を物理蒸着したサンプル(比較例1)の二種類を用意した。これらの基板のイメージング質量分析を行った。イメージング質量分析は、MALDIイメージング質量分析装置(装置名「AXIMA-CFRプラス」島津製作所製)により行った。
・照射レーザー:窒素レーザー(337nm)
・加速電圧:20kv
・リニアーモード測定(正イオンモード)
・レーザー半径:約100μm
・レーザー強度:60(装置の読み)
・測定間隔:100μm
TLCプレート上に、メチレンブルー(濃度:1mM、0.5mM、0.25mM、0.1mM、0.01mMの5種類)を滴下し、更に白金の物理蒸着を行った(図18参照)。次いで、イメージング質量分析を行った。イメージング質量分析は、MALDIイメージング質量分析装置(装置名「AXIMA-CFRプラス」島津製作所製)により行った。
・照射レーザー:窒素レーザー(337nm)
・加速電圧:20kv
・リニアーモード測定(正イオンモード)
・レーザー半径:約100μm
・レーザー強度:60(装置の読み)
・測定間隔:100μm
紙上に、黒色インクを用いて球状のインクスポットを描いた。インクスポット上に白金ナノ粒子のメタノール分散液を塗布したサンプルと白金を物理蒸着したサンプルの二種類を用意し、これらのイメージング質量分析を行った。イメージング質量分析は、MALDIイメージング質量分析装置(装置名「AXIMA-CFRプラス」島津製作所製)により行った。
・照射レーザー:窒素レーザー(337nm)
・加速電圧:20kv
・リニアーモード測定(正イオンモード)
・レーザー半径:約100μm
・レーザー強度:60(装置の読み)
・測定間隔:100μm
(実施例8:アセフェート、白金蒸着)
アセフェート(農薬)の水溶液をビオラの葉に滴下し、乾燥した後に、マグネトロンスパッタリング装置(E-3010:日立製作所製)で白金ナノ粒子を10nmの厚さで蒸着してサンプルを調製した。
(実施例9:アセタミプリド、白金蒸着)
アセタミプリド(農薬)の水溶液をビオラの葉に滴下し、乾燥した後に、マグネトロンスパッタリング装置(E-3010:日立製作所製)で白金ナノ粒子を10nmの厚さで蒸着してサンプルを調製した。
(実施例10:ポリエチレングリコール、白金蒸着)
ポリエチレングリコール(合成ポリマー)の水溶液をビオラの葉に滴下し、乾燥した後に、マグネトロンスパッタリング装置(E-3010:日立製作所製)で白金ナノ粒子を10nmの厚さで蒸着してサンプルを調製した。
(比較例2:アセフェート、既存の有機マトリックス)
白金蒸着の代わりに、MALDIイメージング質量分析用のマトリックス噴霧装置(TM-sprayer:HTX Imaging製)を用いて2,5-Dihydroxybenzoic acid(DHB)の有機マトリックス層を形成した以外は、実施例8と同様にしてサンプルを調整した。
(比較例3:アセタミプリド、既存の有機マトリックス)
白金蒸着の代わりに、MALDIイメージング質量分析用のマトリックス噴霧装置(TM-sprayer:HTX Imaging製)を用いて2,5-Dihydroxybenzoic acid(DHB)の有機マトリックス層を形成した以外は、実施例9と同様にしてサンプルを調整した。
(比較例4:ポリエチレングリコール、既存の有機マトリックス)
白金蒸着の代わりに、MALDIイメージング質量分析用のマトリックス噴霧装置(TM-sprayer:HTX Imaging製)を用いて2,5-Dihydroxybenzoic acid(DHB)の有機マトリックス層を形成した以外は、実施例10と同様にしてサンプルを調整した。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:50%
・測定間隔:300μm
実施例8及び比較例2の結果を図22に示す。実施例9及び比較例3の結果を図23に示す。また、実施例10及び比較例4の結果を図24に示す。
(実施例11:DOP及びDNP、白金蒸着)
ポリ塩化ビニル(PVC)製の壁紙に、マグネトロンスパッタリング装置(E-3010:日立製作所製)で白金ナノ粒子を10nmの厚さで蒸着してサンプルを調製した。ここで、PVCの中には、添加剤(可塑剤)としてフタル酸ジオクチル(DOP)及びフタル酸ジノニル(DNP)が含有されている。
(比較例5:DOP及びDNP、既存の有機マトリックス)
白金蒸着の代わりに、MALDIイメージング質量分析用のマトリックス噴霧装置(TM-sprayer:HTX Imaging製)を用いて1,8-dihydroxy-9(10H)-anthracenone (Dithranol)の有機マトリックス層を形成した以外は、実施例11と同様にしてサンプルを調製した。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:70%
・測定間隔:300μm
実施例11及び比較例5の結果を図27に示す。
実施例9において、IMS測定条件を下記の通りに変更した。即ち、レーザー径を絞り、高空間分解能モードで測定をおこなった。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約50μm(MINIMUMモード)
・レーザー強度:50%
・測定間隔:50μm
園芸用のスプレータイプの殺虫・殺菌剤農薬をアイビーの葉に散布し、乾燥した後に、マグネトロンスパッタリング装置(E-3010:日立製作所製)で白金ナノ粒子を10nmの厚さで蒸着してサンプルを調製した。使用した農薬中には、有効成分としてアセタミプリド及びチオファネートメチルが含有されている。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:100%
・測定間隔:150μm
園芸用の粒剤タイプの殺虫剤農薬をアイビーが植えてある土壌に散布し、4、8、11、14日後に土壌から約30mmの場所の葉を採取し、マグネトロンスパッタリング装置で白金ナノ粒子を10nmの厚さで蒸着して各サンプルを調製した。使用した粒剤の農薬中には、有効成分としてアセフェートが含有されている。
・照射レーザー:Nd:YAGレーザー(355nm)
・加速電圧:19kv
・リフレクトロン電圧:21kv
・レーザー半径:約100μm(ULTRAモード)
・レーザー強度:100%
・測定間隔:150μm
Claims (9)
- イメージング質量分析に供する試料の表面に白金ナノ粒子を物理蒸着することによって調製されたサンプルを用いることを特徴とするイメージング質量分析方法。
- 前記白金ナノ粒子の平均粒子径は2~20nmである、請求項1に記載のイメージング質量分析方法。
- 前記物理蒸着により形成される白金ナノ粒子層の厚さは2~50nmである、請求項1又は2に記載のイメージング質量分析方法。
- 前記物理蒸着は、マグネトロンスパッタリングによる物理蒸着である、請求項1~3のいずれかに記載のイメージング質量分析方法。
- マトリックス支援レーザー脱離イオン化(MALDI)イメージング質量分析装置を用いる、請求項1~4のいずれかに記載のイメージング質量分析方法。
- イメージング質量分析に供する試料の表面に白金ナノ粒子を物理蒸着することを特徴とするイメージング質量分析用のサンプル調製方法。
- 前記白金ナノ粒子の平均粒子径は2~20nmである、請求項6に記載のイメージング質量分析用のサンプル調製方法。
- 前記物理蒸着により形成される白金ナノ粒子層の厚さは2~50nmである、請求項6又は7に記載のイメージング質量分析用のサンプル調製方法。
- 前記物理蒸着は、マグネトロンスパッタリングによる物理蒸着である、請求項6~8のいずれかに記載のイメージング質量分析用のサンプル調製方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/379,228 US9355826B2 (en) | 2012-02-17 | 2013-02-13 | Method for imaging mass analysis using physical vapor deposition of platinum nanoparticles |
KR1020147025014A KR102014160B1 (ko) | 2012-02-17 | 2013-02-15 | 백금 나노 입자의 물리적 증착을 이용한 이미징 질량 분석 방법 |
JP2013558757A JP6203056B2 (ja) | 2012-02-17 | 2013-02-15 | 白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-033258 | 2012-02-17 | ||
JP2012033258 | 2012-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013122225A1 true WO2013122225A1 (ja) | 2013-08-22 |
Family
ID=48984334
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/053743 WO2013122225A1 (ja) | 2012-02-17 | 2013-02-15 | 白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US9355826B2 (ja) |
JP (1) | JP6203056B2 (ja) |
KR (1) | KR102014160B1 (ja) |
WO (1) | WO2013122225A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2018185599A1 (ja) * | 2017-04-04 | 2020-03-19 | 株式会社半導体エネルギー研究所 | 有機半導体素子の分析方法 |
WO2022038843A1 (ja) * | 2020-08-19 | 2022-02-24 | 浜松ホトニクス株式会社 | 試料支持体 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102086716B1 (ko) * | 2017-07-10 | 2020-03-09 | 재단법인대구경북과학기술원 | 살아있는 생체 시료의 분석을 위한 고해상도 대기압 질량분석 이미징 시스템 및 이의 용도 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008204654A (ja) * | 2007-02-16 | 2008-09-04 | Univ Of Tokyo | Ldiプレート、レーザー脱離イオン化質量分析装置、レーザー脱離イオン化質量分析方法及びldiプレート製造方法 |
WO2009069816A1 (ja) * | 2007-11-30 | 2009-06-04 | University Of Yamanashi | イオン化方法ならびにイオン化方法を利用した質量分析方法および装置 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE491938T1 (de) * | 2004-10-29 | 2011-01-15 | Japan Science & Tech Agency | Substrat für maldi-tof-ms und massenspektrometrisches verfahren unter verwendung davon |
JP2007157353A (ja) | 2005-11-30 | 2007-06-21 | Osaka Univ | イメージング質量分析装置 |
US20070202304A1 (en) * | 2006-02-27 | 2007-08-30 | Cambridge University Technical Services Limited, | Nanoparticle colloid, method for its production and its use in the growth of carbon nanotubes |
JP4732951B2 (ja) | 2006-05-22 | 2011-07-27 | 株式会社島津製作所 | Maldi用サンプル調製方法及び質量分析方法 |
JP2008232842A (ja) | 2007-03-20 | 2008-10-02 | Mitsubishi Chemicals Corp | ポリマー被覆微粒子を用いる高解像度イメージング質量分析法 |
JP2009042206A (ja) | 2007-07-19 | 2009-02-26 | National Sun Yat-Sen Univ | 質量分析イメージング法及び質量分析システム |
JP2012007891A (ja) * | 2010-06-22 | 2012-01-12 | Kansai Univ | 質量分析用基板及びその製造方法 |
-
2013
- 2013-02-13 US US14/379,228 patent/US9355826B2/en active Active
- 2013-02-15 WO PCT/JP2013/053743 patent/WO2013122225A1/ja active Application Filing
- 2013-02-15 KR KR1020147025014A patent/KR102014160B1/ko active IP Right Grant
- 2013-02-15 JP JP2013558757A patent/JP6203056B2/ja active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008204654A (ja) * | 2007-02-16 | 2008-09-04 | Univ Of Tokyo | Ldiプレート、レーザー脱離イオン化質量分析装置、レーザー脱離イオン化質量分析方法及びldiプレート製造方法 |
WO2009069816A1 (ja) * | 2007-11-30 | 2009-06-04 | University Of Yamanashi | イオン化方法ならびにイオン化方法を利用した質量分析方法および装置 |
Non-Patent Citations (5)
Title |
---|
HIDEYA KAWASAKI ET AL.: "Platinum vapor deposition surface-assisted laser desorption/ ionization for imaging mass spectrometry of small molecules", RAPID COMMUNICATIONS IN MASS SPECTROMETRY, vol. 26, no. 16, 30 August 2012 (2012-08-30), pages 1849 - 1858 * |
HIDEYA KAWASAKI: "Platinum Nanoflowers for Surface-Assisted Laser Desorption/Ionization Mass Spectrometry of Biomolecules", THE JOURNAL OF PHYSICAL CHEMISTRY, vol. 111, no. 44, 8 November 2007 (2007-11-08), pages 16278 - 16283 * |
HO-WAI TANG ET AL.: "Gold Nanoparticles and Imaging Mass Spectrometry: Double Imaging of Latent Fingerprints", ANALYTICAL CHEMISTRY, vol. 82, no. 5, 1 March 2010 (2010-03-01), pages 1589 - 1593 * |
TETSU YONEZAWA ET AL.: "Detailed Investigation on the Possibility of Nanoparticles of Various Metal Elements for Surface-Assisted Laser Desorption/Ionization Mass Spectrometry", ANALYTICAL SCIENCES, vol. 25, no. 3, 10 March 2009 (2009-03-10), pages 339 - 346 * |
TOMOYUKI OZAWA ET AL.: "Pt Jochaku ni yoru SALDI/MS Imaging o Mochiita Yuki Zairyo no Bunpu Kaiseki", KOBUNSHI BUNSEKI KENKYU KONDANKAI, 25 October 2012 (2012-10-25), pages 119 - 120 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2018185599A1 (ja) * | 2017-04-04 | 2020-03-19 | 株式会社半導体エネルギー研究所 | 有機半導体素子の分析方法 |
JP7185620B2 (ja) | 2017-04-04 | 2022-12-07 | 株式会社半導体エネルギー研究所 | 有機半導体素子の分析方法 |
WO2022038843A1 (ja) * | 2020-08-19 | 2022-02-24 | 浜松ホトニクス株式会社 | 試料支持体 |
JP2022034747A (ja) * | 2020-08-19 | 2022-03-04 | 浜松ホトニクス株式会社 | 試料支持体 |
JP7471174B2 (ja) | 2020-08-19 | 2024-04-19 | 浜松ホトニクス株式会社 | 試料支持体 |
Also Published As
Publication number | Publication date |
---|---|
US9355826B2 (en) | 2016-05-31 |
KR102014160B1 (ko) | 2019-08-26 |
JP6203056B2 (ja) | 2017-09-27 |
JPWO2013122225A1 (ja) | 2015-05-18 |
US20150021470A1 (en) | 2015-01-22 |
KR20140133554A (ko) | 2014-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Müller et al. | Surface‐assisted laser desorption/ionization mass spectrometry imaging: A review | |
Spengler | Mass spectrometry imaging of biomolecular information | |
Bouschen et al. | Matrix vapor deposition/recrystallization and dedicated spray preparation for high‐resolution scanning microprobe matrix‐assisted laser desorption/ionization imaging mass spectrometry (SMALDI‐MS) of tissue and single cells | |
Chughtai et al. | Mass spectrometric imaging for biomedical tissue analysis | |
Zhang et al. | Colloidal graphite-assisted laser desorption/ionization MS and MS n of small molecules. 2. Direct profiling and MS imaging of small metabolites from fruits | |
Rubakhin et al. | Imaging mass spectrometry: fundamentals and applications to drug discovery | |
Todd et al. | Organic ion imaging of biological tissue with secondary ion mass spectrometry and matrix‐assisted laser desorption/ionization | |
Wu et al. | Nanoparticle-immersed paper imprinting mass spectrometry imaging reveals uptake and translocation mechanism of pesticides in plants | |
McDonnell et al. | Subcellular imaging mass spectrometry of brain tissue | |
Kawasaki et al. | Platinum nanoflowers for surface-assisted laser desorption/ionization mass spectrometry of biomolecules | |
Altelaar et al. | Direct molecular imaging of Lymnaea stagnalis nervous tissue at subcellular spatial resolution by mass spectrometry | |
Carado et al. | C60 secondary ion mass spectrometry with a hybrid-quadrupole orthogonal time-of-flight mass spectrometer | |
Altelaar et al. | Imaging mass spectrometry at cellular length scales | |
Lanni et al. | Biomolecular imaging with a C60-SIMS/MALDI dual ion source hybrid mass spectrometer: instrumentation, matrix enhancement, and single cell analysis | |
Yang et al. | Novel vacuum stable ketone‐based matrices for high spatial resolution MALDI imaging mass spectrometry | |
Trimpin et al. | Automated solvent-free matrix deposition for tissue imaging by mass spectrometry | |
US9625359B2 (en) | Tissue sample preparation, and MALDI MS imaging thereof | |
Judge et al. | Nonresonant femtosecond laser vaporization with electrospray postionization for ex vivo plant tissue typing using compressive linear classification | |
JP6203056B2 (ja) | 白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法 | |
Tsuyama et al. | Mass spectrometry for cellular and tissue analyses in a very small region | |
Ozawa et al. | Direct imaging mass spectrometry of plant leaves using surface-assisted laser desorption/ionization with sputterdeposited platinum film | |
US8080784B2 (en) | Ionization device | |
Shanta et al. | Plasmonic gold templates enhancing single cell lipidomic analysis of microorganisms | |
Muthu et al. | Nanopost array laser desorption ionization mass spectrometry (NAPA-LDI MS): Gathering moss? | |
Urban et al. | Microscale MALDI imaging of outer-layer lipids in intact egg chambers from Drosophila melanogaster |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13749115 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013558757 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14379228 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147025014 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13749115 Country of ref document: EP Kind code of ref document: A1 |