KR20190083598A - Sample plate with adjustable ionization efficiency, method of fabricating the same and mass spectrometer analysis by using the same - Google Patents

Abstract

Embodiments of the present invention relate to a sample plate for mass analysis of a sample to be analyzed, a manufacturing method thereof, and mass spectrometry using the sample plate. According to one embodiment of the present invention, the sample plate for laser detachment/ionization mass spectrometry comprises: a substrate; and a photoactive catalyst layer containing a metallic oxide formed on the substrate. A sample to be analyzed is disposed on the photoactive catalyst layer.

Description

[0001] The present invention relates to a sample plate capable of adjusting the ionization efficiency, a method of manufacturing the same, and a mass spectrometry method using the same,

More particularly, the present invention relates to a sample plate for mass spectrometry, a method for producing the sample plate, and a mass spectrometry method using the sample plate.

Generally, a mass spectrometer is an analytical instrument for measuring the mass of a compound to be analyzed. The compound to be analyzed is charged and ionized, and mass-to-charge (m / z) is measured to determine the molecular weight of the compound . As methods for ionizing the analyte, there are known an electron ionization method using an electron beam, a method of impinging atoms at high speed, a method using a laser, or a method of injecting a sample in an electric field.

As a representative mass spectrometer, a MALDI-TOF MS Apparatus (Matrix-Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy) mixes an organic matrix for assisting ionization of a sample to be analyzed with the sample, And then irradiating the laser to the sample to be analyzed, the mass analysis is performed using the property that the sample to be analyzed is easily ionized with the help of the organic matrix. The maltodext mass spectrometry method has a high sensitivity, and thus it is possible to analyze a sample to be analyzed at the level of peptomol, and it is possible to greatly reduce the phenomenon of fragmentation of a compound to be analyzed at the time of ionization. Maldistal mass spectrometry using laser is effective for mass spectrometric analysis of large molecular biochemicals such as proteins and nucleic acids.

Generally, in the case of Maldastal mass spectrometry, when the sample to be analyzed is ionized, the valence number of the ion of the sample to be analyzed is +1 or +2, which is an easy method for measuring the molecular weight of the sample molecule before ionization. However, since the malduthth mass spectrometry method ionizes the sample to be analyzed using an organic matrix, different organic matrix materials must be determined according to the type of the sample to be analyzed. In addition, a commonly used organic matrix material has a molecular weight of several hundred Da. When the molecular weight of the sample to be analyzed is similar to or smaller than the molecular weight of the organic matrix material, the organic matrix degradation product is reflected in the mass peak of the mass spectrometry spectrum , There are limitations that are difficult to use in mass spectrometry for samples of analytes of several hundred Da levels.

In addition, the mass peaks corresponding to several hundreds of m / z, which are generated when the organic matrix is decomposed by the laser, may be made different from each other in measurement. Inorganic matrices have been studied to replace existing organic matrices in order to obtain reproducible measurement results for the purpose of measuring low molecular weight samples having molecular weights of several hundred Da.

It is known that the molecular ratio of the organic matrix to the sample molecule is suitably in the range of 10,000 to 1 to 20,000 to 1 for the ionization of the sample molecules after laser irradiation in the Maldistop mass spectrometry. In contrast, the inorganic matrix has nanostructures such as nanoparticles, nanowires, and nanotubes, which are larger in size than conventional organic matrices of several angstroms in size. Therefore, when an inorganic matrix of a nanostructure is used to substitute an organic matrix in the maldistop mass analysis, there is a limit to increase the ratio of inorganic matrix molecules to sample molecules. For this reason, when an inorganic matrix is used, the ionization efficiency is lower than that of the organic matrix, and the mass peak is small in the analysis of the same sample.

SUMMARY OF THE INVENTION The present invention provides a sample plate applicable to mass spectrometry and capable of performing reliable mass spectrometric analysis on a sample having a low molecular weight.

Another object of the present invention is to provide a method of manufacturing a sample plate which can easily produce a sample plate having the above advantages.

It is another object of the present invention to provide a mass spectrometry method using the sample plate having the above advantages.

Another object of the present invention is to provide a method for analyzing an amino acid sequence capable of identifying or quantifying a pap target compound using the sample plate.

According to an embodiment of the present invention, there is provided a sample plate for laser desorption / ionization mass spectrometry, comprising: a substrate having a polished surface to have a controlled surface roughness; And a photocatalytic catalyst layer comprising a metal oxide formed on the polished surface of the substrate, wherein a sample to be analyzed is disposed on the photocatalytic catalyst layer. The photoreaction catalyst layer may include a surface corrosion layer of the substrate. The metal oxide may comprise an oxide layer on the surface of the substrate. The metal oxide may be at least one of titanium (Ti), tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium (Ru), iridium (Ir) And may include an oxide of any one of the metals. The metal oxide may have a porous structure and may have a nanoscale structure having a fibrous, wire-like, needle-shaped, film-shaped, columnar or a combination thereof. The sample to be analyzed forms fragments by photolysis reaction by ultraviolet irradiation incident on the photoreaction catalyst layer, and mass analysis of the fragments can be performed.

According to another embodiment of the present invention, there is provided a method of manufacturing a sample plate for laser desorption / ionization mass spectrometry, comprising: providing a substrate comprising metal atoms constituting a photoreaction catalyst layer; Polishing the surface of the substrate so that the surface of the substrate has a cross stripe pattern formed by intersecting at least two or more stripe patterns extending in one direction or in different directions so as to control the surface roughness of the substrate ; And a step of exposing the surface of the metal-containing substrate to an oxidizing solvent to oxidize the metal while corroding the surface of the substrate to form a photoreaction catalyst layer containing an oxide of the metal .

The metal atom may include tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium (Ru), iridium (Ir) . By etching the surface of the substrate, the photoreaction catalyst layer can have a porous nanoscale structure. Wherein the step of forming the photoreaction catalyst layer comprises: immersing the substrate in the oxidizing solvent to form an oxide of the metal on the surface of the substrate; And cleaning the substrate on which the oxide of the metal is formed. The oxidizing solvent may include a substance that corrodes metal such as KOH, NaOH, and the like.

According to another embodiment of the present invention, there is provided a method of manufacturing a light-emitting device, comprising the steps of: providing a sample plate including the above-described photoreactive catalyst layer; Loading the sample to be analyzed on the photoreactive catalyst layer; Irradiating the sample to be analyzed with ultraviolet rays to induce photodecomposition reaction of the sample to be analyzed; And performing mass spectrometry by laser desorption / ionization on the sample to be analyzed that has undergone the photolysis reaction. The sample to be analyzed is dispersed in a dispersion solvent and provided on the photoreaction catalyst layer, and the ultraviolet ray is irradiated to the dispersion solution of the sample to be analyzed to induce the photolysis reaction. The sample to be analyzed includes an organic molecular compound, and the organic molecular compound can be fragmented by the photolysis reaction. The sample to be analyzed contains different types of organic molecular compounds, and the organic molecular compounds can be specifically fragmented by the photolysis reaction to identify the organic molecular compounds.

According to another embodiment of the present invention, there is provided a method of manufacturing a light emitting device, comprising: providing a sample plate including a photoreactive catalyst layer including a porous metal oxide; Loading a peptide compound to be analyzed on the photoreaction catalyst layer; Irradiating the peptide compound with ultraviolet light to form peptide fragments by photodecomposition of the peptide compound; Desorbing and ionizing the peptide fragments from the photoreaction catalyst layer by irradiating a laser onto the photoreaction catalyst layer; And determining the amino acid sequence of the peptide compound by analyzing the molecular weight of the peptide compound and the molecular weight of the ionized peptide fragments before the ultraviolet irradiation. The sample to be analyzed may comprise a mixture of different peptide compounds. The photoreaction catalyst layer may be formed of at least one of titanium, tantalum, tungsten, zinc, vanadium, ruthenium, iridium, Or an oxide of at least one of the metals. The photoreactive catalyst layer may have a porous nanoscale structure.

According to one embodiment of the present invention, the sample matrix is a sample plate for laser desorption / ionization mass spectrometry, in which a photoreaction catalyst layer containing a metal oxide is formed, and the surface area of the plate causing the ionization reaction is adjusted to optimize the ionization degree of the sample A sample plate can be provided which can perform mass spectrometry with reliability and reproducibility unlike the conventional organic matrix even when the sample to be analyzed applied to the photoreaction catalyst layer is subjected to mass spectrometry by laser irradiation.

According to the embodiment of the present invention, a method of manufacturing a sample plate capable of easily forming a sample plate having the above-mentioned advantage by adjusting the surface area of the surface of the substrate including metal atoms can be provided.

In addition, according to the embodiment of the present invention, by irradiating ultraviolet rays to the sample to be analyzed to induce fragmentation of the sample to be analyzed, mass analysis effect on the fragment of the sample to be analyzed, which can be obtained using the conventional tandem mass A mass spectrometry method can be provided.

According to the embodiment of the present invention, when the sample to be analyzed is a peptide compound, the amino acid sequence of the peptide compound is determined by analyzing the molecular weight of the peptide compound before ultraviolet irradiation and the molecular weight of the peptide fragments formed by ultraviolet irradiation A method for analyzing the amino acid sequence that can be obtained can be provided. In addition, according to an embodiment of the present invention, the heteroduplex mass spectrometry is performed on heterologous peptides having the same molecular weight or the same ionic mass (m / z) using not only the amino acid sequence but also the identification and quantification of the heterologous peptides It is possible.

1A is a schematic view illustrating a method of manufacturing a sample plate including a photoreaction catalyst layer according to an embodiment of the present invention, FIG. 1B is a scanning electron microscope image showing a microstructure of a photoreaction catalyst layer, FIG. 1C Illustrate polishing processes for forming various types of stripe patterns to be performed on a substrate.
2 is a view showing a mass spectrometry method using a photoreaction catalyst layer according to an embodiment of the present invention.
FIG. 3A is a graph showing mass spectrometry results for a bare sample plate according to an embodiment of the present invention, and FIG. 3B is a graph showing mass spectrometry results of a cyan-4-hydroxycinnamic acid acid; CHCA). < tb >< TABLE >
4A to 4D are graphs showing mass spectrometry results of various organic molecular compounds using a sample plate including a TiO ₂ nanoscale structure photoreaction catalyst layer according to an embodiment of the present invention.
FIG. 5A shows primary sequence fragments according to the sequence of the R4K peptide, which is a sample to be analyzed for mass spectrometry. FIG. 5B and FIG. Are graphs showing mass spectrometry results before and after irradiation with ultraviolet rays.
FIG. 6A shows primary sequence fragments according to the sequence of the R4K peptide, which is a sample to be analyzed for mass spectrometry according to a comparative example, and FIGS. 6B and 6C show TiO ₂ particles according to comparative examples, Are graphs showing mass spectrometry results before and after irradiation with ultraviolet rays.
FIGS. 7A and 7B are graphs showing mass spectrometry results of GHP9 peptides using a sample plate according to an embodiment of the present invention before and after irradiation with ultraviolet light. FIG. 7C is a graph showing the results of mass spectrometry ≪ / RTI > amino acid sequence.
8A and 8B are graphs showing mass spectrometry results of a BPA peptide using a sample plate having a photoreaction catalyst layer according to an embodiment of the present invention before and after ultraviolet irradiation, The amino acid sequence obtained by the analysis is shown.
9A and 9B are graphs showing mass spectrometry results of a Biotin-PreS1 peptide using a sample plate having a photoreaction catalyst layer according to an embodiment of the present invention before and after UV irradiation, ≪ / RTI > shows the sequence of amino acids obtained by mass spectrometry.
FIGS. 10A to 10C are graphs showing mass spectrometry results of organic molecular compounds having the same ionic mass using a photoreactive catalyst layer according to an embodiment of the present invention. FIG.
11A and 11B show an atomic force microscope image of the substrate surface before and after forming the nanoscale structure after polishing the surface of the substrate in one direction and in both directions, respectively.
12A is an optical image showing the substrate surface before the substrate is exposed to corrode the surface of the substrate, and FIG. 12B is an optical image showing the surface of the substrate polished to form a bi- directional stripe pattern by diamond abrasive paper having roughnesses of 180, Scanning electron microscope image of the surface of the substrate.
13A shows a surface mount observed by an atomic force microscope on the surface of a polished and eroded substrate using diamond abrasive paper having a roughness of 180, 320 and 400 mesh according to an embodiment of the present invention, The surface roughness of a substrate formed with a nanoscale structure formed with a diamond sandpaper having roughnesses of 180, 320, 400, and 500 mesh was observed with an atomic force microscope.
14A shows mass spectrometry results of various organic molecular compounds measured using a sample plate having a photoreaction catalyst layer prepared according to an embodiment of the present invention, And mass spectrometry results using a polished substrate using a diamond sandpaper having roughnesses of 180, 320, and 400 mesh to form a pattern.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art, and the following embodiments may be modified in various other forms, The present invention is not limited to the following examples. Rather, these embodiments are provided so that this disclosure will be more faithful and complete, and will fully convey the scope of the invention to those skilled in the art.

In the following drawings, thickness and size of each layer are exaggerated for convenience and clarity of description, and the same reference numerals denote the same elements in the drawings. As used herein, the term "and / or" includes any and all combinations of any of the listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

Although the terms first, second, etc. are used herein to describe various elements, components, regions, layers and / or portions, these members, components, regions, layers and / It is obvious that no. These terms are only used to distinguish one member, component, region, layer or section from another region, layer or section. Thus, a first member, component, region, layer or section described below may refer to a second member, component, region, layer or section without departing from the teachings of the present invention.

Herein, the analyte sample refers to any substance that can be effectively decomposed and fragmented by the photoreaction catalyst layer when ultraviolet rays are applied, placed, coated or combined on the photoreaction catalyst layer. The sample to be analyzed may be an organic molecular compound, protein or peptide as a representative example.

As used herein, the term " peptide compound " refers to a short protein having no more than 40 amino acids constituting it. Generally, the sequence of the amino acid, i.e., the sequence of the joined amino acids, refers to the amino acid binding sequence from the amine terminus (N-terminus) to the carboxyl terminus (C-terminus) of the peptide.

In the embodiments of the present invention, the sample to be analyzed is fragmented by the photoreaction catalyst layer of the sample plate, and the Tandem mass analysis can also be performed in the Malditi mass analysis. For example, in order to analyze the amino acid sequence of a peptide compound, mass fragment analysis of the fragmented peptide fragments using the above-described photoreaction catalyst layer yields peptide fragments in which amino acids are removed from the amine terminal end (N-terminal) Can be measured. For example, if a peptide compound composed of five amino acids is analyzed similarly to the Tandem mass method, the molecular weight of the whole peptide compound composed of the above five amino acids can be measured through mass spectrometry. Then, the photocatalytic catalytic layer is irradiated with ultraviolet rays to induce photodecomposition reaction of the peptide compound to form peptide fragments composed of four, three and / or two amino acids, and the molecular weight thereof is measured. When the peptide fragments are compared and analyzed, The sequence of the amino acid from the N-terminal to the C-terminal can be determined. The method of analyzing the amino acid sequence for the above-mentioned peptide substance is only illustrative and the present invention is not limited thereto.

FIG. 1A schematically illustrates a method of manufacturing a sample plate 100 including a photoreaction catalyst layer CL according to an embodiment of the present invention. FIG. 1B is a view for explaining the microstructure of a photoreaction catalyst layer CL 1C shows polishing processes for forming various types of stripe patterns to be performed on a substrate.

Referring to FIG. 1A, in order to manufacture a sample plate 100 having a photoreaction catalyst layer CL, a substrate SS on which a photoreaction catalyst layer is to be formed is first prepared. In one embodiment, the substrate SS may include metal atoms, some or all of which constitute a photoreaction catalyst layer. 1A, a substrate SS including metal atoms constituting a photoreaction catalyst layer is illustrated. In this case, a photoreaction catalyst layer can be formed by forming a reaction layer directly from the surface of the substrate SS. For example, when the light-responsive catalyst layer CL comprises a metal oxide, the surface or the entire surface of the substrate SS may contain the metal of the metal oxide, ) Can be formed.

The substrate SS is, for example, a titanium substrate provided by polishing a Ti plate. In another embodiment, the substrate SS may comprise at least one of tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium (Ru), iridium (Ir) Steel) or an alloy thereof.

In one embodiment, the roughness of the surface of the substrate SS can be adjusted to control the surface area of the substrate SS exposed to an oxidizing solvent (OS) for corroding the surface of the substrate SS, as described below. To this end, the surface of the substrate SS can be polished. A sand paper may be used for the polishing process, and the sand paper may be, for example, a diamond sandpaper having a roughness of 180, 320, 400 and 500 mesh. The polishing step may be performed by a polishing apparatus having a rotary plate on which the substrate is mounted and an abrasive pad on which the sand paper is mounted. A polishing process may be performed while each sandpaper is mounted on a polishing pad and the rotary plate is rotated at a speed of, for example, 100 rpm while pressing the substrate with a polishing pad. In another embodiment, the surface of the substrate may be polished by contacting and pressing a sandpaper rotating on the surface of the mounted substrate while rotating the sandpaper at a predetermined speed. The polishing process may be performed for several hours, for example, 5 minutes, or for example, 2 hours, and the present invention is not limited thereto.

In one embodiment, the polishing process may form a unidirectional stripe pattern, a bi-directional stripe pattern, or a combination pattern thereof on the polished surface of the substrate. The bidirectional stripe pattern may include an intersecting stripe pattern in which stripe patterns in two different directions intersect. The bi-directional stripe pattern may be formed by forming a plurality of stripe patterns overlappingly crossing the first stripe pattern at various angles, such as, but not limited to, 30 DEG, 45 DEG or 90 DEG, after forming the first stripe pattern Can be provided.

In one embodiment, the oxidized solvent (OS) can be exposed to the polished surface of the substrate (SS) to corrode the surface of the substrate (SS). For example, the substrate SS is immersed in an oxidizing solvent (OS) and kept at room temperature for about 24 hours to corrode the surface. The oxidizing solvent (OH) is, for example, an alkaline solution such as KOH or NaOH which causes corrosion of the metal. The concentration of the oxidizing solvent (OH) may be 10 M falling within the concentration range of 2 M to 20 M (see step 1 of FIG. 1A). The concentration of the oxidizing solvent is not limited thereto and may be variously selected depending on the kind and characteristics of the sample to be analyzed for mass analysis. The oxidation reaction proceeds on the surface of the substrate SS during the corrosion of the surface of the substrate SS by the oxidizing solvent OH to form the oxide layer OL.

Thereafter, the substrate SS is cleaned using a cleaning liquid CW such as alcohol or distilled water DW. For example, the substrate SS can be immersed in the cleaning liquid CW for, for example, about 48 hours to absorb the cleaning liquid CS into the surface layer of the corroded substrate SS, For example, three times (see step 2 of FIG. 1A). In this process, the oxidizing solvent remaining on the surface of the titanium substrate (SS) may be replaced with a cleaning liquid.

Since the surface of the substrate SS that has been corroded by the oxidizing solvent has porosity with pores of nanoscale, it is necessary to expose the corroded substrate SS for a sufficient time in the cleaning liquid CW . In one embodiment, the substrate SS may be immersed in a cleaning liquid CW for 48 hours at room temperature (RT) and subjected to three or more cleaning steps (see step 2 of FIG. 1A).

Thereafter, the cleaned substrate can be heat-treated (see step 3 in FIG. 1A). The heat treatment may be performed within a range of about 200 ° C to 1,200 ° C, but the present invention is not limited thereto, and the temperature of the heat treatment may be set such that the surface layer of the corroded substrate (SS) Can be adjusted to have a crystalline or microstructure suitable for inducing the reaction. In one embodiment, the substrate SS may be heat treated at about 600 占 폚 for a predetermined time (e.g., 2 hours) in an inert gas atmosphere, for example, an Ar gas atmosphere.

Thereby, the sample plate 100 in which the light reaction catalyst layer CL is formed on the surface of the substrate SS can be provided. When the substrate SS is a titanium substrate, a TiO ₂ nanoarray layer may be formed as a light reaction catalyst layer CL.

In the above-described embodiment, the surface of the substrate SS is modified to form the photoreaction catalyst layer CL. In another embodiment, when the substrate SS does not include or is independent of the elements of the photoreaction catalyst layer CL, a metal layer containing a metal element of the photoreaction catalyst layer CL is formed on the surface of the substrate SS. And a photoreaction catalyst layer CL may be formed from the metal layer by performing the steps 1 to 3 shown in FIG. 1A.

In another example, the photoreaction catalyst layer CL may be formed by a dry vapor deposition process such as chemical vapor deposition, physical vapor deposition, or atomic layer deposition on a substrate SS on which a metal catalyst layer in the form of a dot array is formed for forming a nanoscale structure Or may be synthesized by a wet film forming method such as a sol-gel method. With respect to the precursor material for synthesis, well-known techniques may be taken into consideration and the present invention is not limited thereto. However, in the case of forming the light reaction catalyst layer CL by the wet etching method described with reference to FIG. 1A, it is preferable to obtain a porous surface layer by corrosion without forming the metal catalyst layer, (CL) may be easily formed.

The light reaction catalyst layer CL may be formed of a material that does not directly participate in the photolysis reaction of the organic molecular compound as an analyte but accelerates the photolysis of the organic molecular compound. In one embodiment, the photoreaction catalyst layer CL may be formed of a material selected from the group consisting of titanium (Ti), tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium Ir) and iron (Fe). The photoreaction catalyst layer CL is formed on or on the metal oxide with at least one of Au, Ag, Pt, Si, Ge, As shown in FIG. Such doping of the impurity may be effective in controlling the frequency of the light source for the photoreaction of the organic molecular compound.

Preferably, the photoreaction catalyst layer CL may include titanium oxide (TiO ₂ ) having an anatase crystal structure. The titanium oxide (TiO ₂ ) is relatively inexpensive as compared with other metal oxides, is smoothly supplied, is not photo-corrosive, and is photoactivated by short wavelength light irradiation including ultraviolet rays having a band gap of 3.2 eV and a UV of about 380 nm or less, There is an advantage of increasing the efficiency of the reaction.

The surface of the photoreactive catalyst layer CL may have a nanoscale structure according to the above corrosion method. The nanoscale structure has porosity and may have a shape such as a fibrous shape, a wire shape, a needle shape, a film shape, a column shape, or a combination thereof, and may be patterned by photolithography or a shadow masking method.

In FIG. 1A, the photoreaction catalyst layer CL is formed in an array on the substrate SS. The nanoscale structures of titanium oxide (TiO ₂ ) constituting the photoreaction catalyst layer CL shown in FIG. 1A can be patterned in the form of a spot having a diameter of 1 mm. For example, the size of the substrate SS is about 3 cm x 3 cm, and the spots of nanoscale structures of titanium oxide (TiO ₂ ) formed on the substrate SS may be plural.

The nanoscale structure of the photoreaction catalyst layer CL formed on the substrate SS forms the above-described porous structure. 1B shows a nanoscale structure having a nanowire structure of a photoreactive catalyst layer CL of TiO ₂ analyzed by a scanning electron microscope.

2 is a view showing a mass spectrometry method using the photoreaction catalyst layer CL according to an embodiment of the present invention.

Referring to FIG. 2, a sample to be analyzed (MS) is loaded on a sample plate 100 for analysis of the sample to be analyzed. The sample to be analyzed may be an organic molecular compound. The organic molecular compound may be dispersed in a suitable dispersion solvent and provided on the photoreaction catalyst layer (see CL in FIG. 1A). The dispersion solvent may be water, acetonitrile, methanol, ethanol, or the like, or may be a mixture thereof. A compound having a carboxyl group such as trifluoroacetic acid (a substance used as a source of H ⁺ when ionizing) Can be added. The dispersion solvent may be variously selected depending on the kind of the organic molecular compound to be analyzed, and the present invention is not limited to the exemplified solution.

When the photoreactive catalyst layer CL is formed in the form of a plurality of patterned spot arrays as described above, a dispersion solution MS in which organic molecular compounds are dispersed in each photoreaction catalyst layer (CL) spot may be provided. For example, one microliters of a dispersion solution of an organic molecular compound can be spotted on a nanoscale structure spot of the TiO ₂ light reaction catalyst layer (CL).

Then, ultraviolet rays (UV) are irradiated to the dispersed solution MS of the loaded organic molecular compound to induce the photolysis reaction of the organic molecular compound, for example, fragmentation reaction of organic molecules. When the organic molecular compound is a peptide substance, peptide fragments can be formed through a photolysis reaction by ultraviolet (UV).

For the photolytic reaction, for example, a UV exposure apparatus having a wavelength of 254 nm and an intensity of 23 mW / cm ² may be used. The sample plate 100 is positioned below a predetermined position from the UV exposer, and then a photolytic reaction, such as fragmentation, of the organic molecular compound (MS) can be induced by irradiating UV for 30 seconds. When the photolysis reaction of the organic molecular compound MS is completed, the sample plate 100 can be dried.

Laser desorption / ionization mass spectrometry can be performed on the organic molecular compound on which the photodegradation reaction has been completed on the dried sample plate 100, for example, using a mass spectrometer of a Microflex model of Bruker. The mass analyzer may be a mass spectrometer for horse-topology analysis. In one embodiment, the reflector of the mass spectrometer is set to a positive mode and the power of the laser is adjusted to a level of several to several tens of percent based on peak power, and the gain value of the detector can be adjusted appropriately.

In the malduthth mass spectrometry according to the embodiment of the present invention, when a laser beam is irradiated onto the surface of the sample plate 100, at least a part of the organic molecule fragments formed by the photolysis reaction are ionized, To pass through the flight tube of the Maldiste mass spectrometer. The ionized organic molecule fragments that have passed through the flight tube collide with the detector and the mass spectrometer calculates the mass of organic molecular debris by calculating the time it takes for the ionized sample to impact the detector from the surface of the sample plate 100 .

In the case of the conventional maltodext mass analysis, it is necessary to mix the organic molecular compound and the organic matrix in order to desorb and ionize the organic molecular compound to be analyzed. In this case, since the mass peak due to the organic matrix is observed as a noise signal having no reproducibility, when the organic molecular compound is a low molecular weight organic molecular compound having m / z of 500 or less, It is difficult to separate the organic molecular compound and it is almost impossible to measure the signal of the low molecular weight organic molecular compound using the organic matrix. However, the sample plate according to an embodiment of the present invention induces photodegradation reaction such as fragmentation of an organic molecular compound by simply loading an organic molecular compound on a photoreaction catalyst layer without an organic matrix and irradiating ultraviolet rays, Desorption and ionization are induced by laser irradiation so that mass spectrometric signals of other substances having a low molecular weight such as the organic matrix are not generated in the mass spectrometric analysis.

As a result, according to the embodiment of the present invention, noise is not detected in a low molecular region having an m / z of 500 or less, unlike the conventional maltodext mass spectrometry using an organic matrix, Organic molecules such as peptides can be effectively detected.

FIG. 3A is a graph showing mass spectrometry results for a bare sample plate according to an embodiment of the present invention, and FIG. 3B is a graph showing mass spectrometry results of a cyan-4-hydroxycinnamic acid acid; CHCA). < tb > < TABLE >

Referring to FIG. 3A, a bare sample plate having a photocatalytic catalyst layer of TiO ₂ according to an embodiment of the present invention does not generate a mass peak when there is no sample to be analyzed. Particularly, it should be noted that there is no mass peak in the region of 500 m / z or less. 3B, in the case of the sample using the organic matrix of CHCA according to the comparative example, the mass peak due to the CHCA occurs in a region of 400 m / z or less, and these mass peaks are not reproducible It is difficult to be removed as a noise signal. Therefore, in the case of the comparative example, it is predicted that it is difficult to distinguish the mass peak of the organic molecular compound and the noise signal from each other in the region where m / z is 500 or less, unlike the embodiment of the present invention. Conversely, according to the embodiment of the present invention, reliable mass spectrometry results can be obtained even in a region where m / z is 500 or less.

4A to 4D are graphs showing mass spectrometry results of various organic molecular compounds using a sample plate including a photoreaction catalyst layer according to an embodiment of the present invention. The photoreaction catalyst layer has a TiO ₂ nanoscale structure.

Referring to FIG. 4A, the mass peak of a sample can be measured with [M + K] ⁺ and [M + 2K] ⁺ in the case of arginine (molecular weight 174.2 Da), which is a low molecular substance as an organic molecular compound. Since the sample plate according to the embodiment of the present invention is manufactured by corroding with KOH at a high concentration, a combination of the organic molecular compound and the K ⁺ ion is obtained by K ⁺ ions incorporated at this time.

Referring to FIG. 4B, it can be seen that laser desorption / ionization mass spectrometry can be performed without a noise signal using a sample plate according to an embodiment of the present invention even in the case of another low-molecular substance, lucine (molecular weight 131.17 Da).

Referring to FIG. 4C, laser desorption / ionization mass spectrometry can also be performed using bradykinin (molecular weight 756.85 Da), which is a peptide composed of amino acid bonds as an organic molecular compound having a molecular weight of 500 Da or more, using a sample plate according to an embodiment of the present invention. . Similarly, referring to FIG. 4D, laser desorption / ionization mass spectrometry can be performed using GHP9 (molecular weight 1007.18 Da) as an organic molecular compound having a molecular weight of 1,000 Da or more using a sample plate according to an embodiment of the present invention.

4D, a sample plate having a photoreactive catalyst layer according to an embodiment of the present invention, even in GHP9 (molecular weight 1007.18 Da), which is a peptide composed of amino acid bonds as an organic molecular compound having a molecular weight of 1,000 Da or more, Analysis is possible.

The Tandem mass analysis uses a method of generating and then analyzing the generated fragment when colliding with an electron beam or a molecular beam. In the case of peptide compounds, fragments are formed by electron beam or molecular beam and comparative analysis can analyze the amino acid sequence from the N-terminal to the C-terminal of the peptide compound. According to the embodiment of the present invention, instead of the electron beam or the molecular beam, the photodecomposition reaction of the sample to be analyzed on the photoreaction catalyst layer is induced only by irradiating ultraviolet rays to the photoreaction catalyst layer, Mass analysis based on Tandem mass analysis is possible. When the sample to be analyzed is a peptide, the sequence of the amino acid constituting the peptide can be determined by forming peptide fragments by the photolysis reaction and mass-analyzing the peptide fragments. Hereinafter, the tandem mass analysis using the sample plate according to the embodiment of the present invention will be described with reference to FIGS. 5A to 6C.

FIG. 5A shows primary sequence fragments according to the sequence of the R4K peptide, which is a sample to be analyzed for mass spectrometry. FIG. 5B and FIG. Are graphs showing mass spectrometry results before and after irradiation with ultraviolet rays. The photoreactive catalyst layer according to an embodiment of the present invention is a TiO ₂ layer having a porous nanoscale structure, and laser desorption / ionization mass spectrometry is performed on these organic molecular compounds using a Microflex model manufactured by Bruker. The gain is 10 x and the laser intensity is 90%.

FIG. 6A shows primary sequence fragments according to the sequence of the R4K peptide, which is a sample to be analyzed for mass spectrometry according to a comparative example, and FIGS. 6B and 6C show TiO ₂ particles according to comparative examples, Are graphs showing mass spectrometry results before and after irradiation with ultraviolet rays. The mass spectrometry according to the comparative example was carried out using a Microflex model of Bruker. The detector had a gain of 12.6 x and a laser intensity of 70%.

Referring to Figure 5a, the sample to be analyzed for mass spectrometry is a R4K peptide (1 mg / ml) with a molecular weight of 770.51 Da. The peptides may have three major fragments labeled as 1-3.

Referring to FIG. 5B, the mass peak of R4K is observed in the form of [M + K] ⁺ and [M + Na] ⁺ before UV irradiation for photodecomposition of the peptide. Such a mass spectrometric analysis results in that, when the photolysis reaction is not performed, fragmentation due to decomposition of the peptide does not occur only by laser irradiation for laser desorption / ionization mass spectrometry.

However, referring to FIG. 5C, it can be seen that after the ultraviolet (UV) irradiation, three pieces of peptide fragments whose sequences overlap each other are obtained. Thus, it can be seen that tandem mass analysis capable of determining the sequence of the amino acids constituting the whole peptide can be performed from the total molecular weight of the peptide against the peptide before the photolysis reaction and the molecular weight of the three peptide fragments obtained after the photolysis reaction.

Referring to FIG. 6A, the sample to be analyzed for mass spectrometry is a R4K peptide (1 mg / ml) having a molecular weight of 770.51 Da, similar to that described in FIG. 5a. Peptide fragments shown as 1 and 2 were detected through the above analysis.

Referring to FIG. 6B, the mass peak of R4K is observed in the form of [M + Na] ⁺ prior to ultraviolet (UV) irradiation for photodecomposition of the peptide. Such a mass spectrometric analysis results in that, when the photolysis reaction is not performed, fragmentation due to decomposition of the peptide does not occur only by laser irradiation for laser desorption / ionization mass spectrometry.

Referring to FIG. 6C, it can be seen that two peptide fragments are obtained after the ultraviolet (UV) irradiation. However, the information on the sequence is insufficient only by the total molecular weight of the peptide relative to the peptide before the photolysis reaction and the molecular weight of the two peptide fragments obtained after the photolysis reaction, so that the sequence analysis of the amino acids constituting the whole peptide is not easy.

According to the embodiments of the present invention, even if the same material and crystal structure are used, the result of the photolytic reaction can be varied due to the difference in the nanoscale structure, and the photocatalytic catalyst layer according to the embodiment of the present invention has a sequence It is necessary to analyze tandem mass for analysis.

7A and 7B are graphs showing mass spectrometry results of a GHP9 peptide using a sample plate having a photoreaction catalyst layer according to an embodiment of the present invention before and after UV irradiation, The amino acid sequence obtained by mass spectrometry is shown. The photoreactive catalyst layer according to an embodiment of the present invention is a TiO ₂ layer having a porous nanoscale structure, and laser desorption / ionization mass spectrometry is performed on these organic molecular compounds using a Microflex model manufactured by Bruker. The gain is 10 x and the laser intensity is 90%.

Referring to Figure 7a, the sample to be analyzed for mass spectrometry is a GHP5 peptide (1 mg / ml) with a molecular weight of 1007.18 Da. Prior to the photolysis reaction using ultraviolet irradiation, the mass peak of the organic chemical sample GHP9 was observed in the form of [M + K] ⁺ .

Referring to FIG. 7B, when the sample to be analyzed is fragmented through ultraviolet irradiation and subjected to mass analysis, mass peaks of ten peptide fragments whose sequences overlap with each other are detected. Using the total molecular weight of the peptide before the photolysis reaction and the molecular weight of the ten peptide fragments obtained after the photolysis reaction, it is possible to analyze the amino acid sequence of the GHP5 peptide as shown in FIG. 7C.

8A and 8B are graphs showing mass spectrometry results of a BPA peptide using a sample plate having a photoreaction catalyst layer according to an embodiment of the present invention before and after ultraviolet irradiation, The amino acid sequence obtained by the analysis is shown. The photoreactive catalyst layer is a TiO ₂ layer having a porous nanoscale structure. Using a Microflex model from Bruker, laser desorption / ionization mass spectrometry was performed on these organic molecular compounds, with a detector gain of 7 x and a laser intensity of 70%.

Referring to FIG. 8A, the sample to be analyzed for mass spectrometry is a BPA peptide (1 mg / ml) having a molecular weight of 1395.56 Da. Prior to photodecomposition by ultraviolet irradiation, the mass peak of BPA, an organic chemical sample, was observed in the form of [M + K] ⁺ .

Referring to FIG. 8B, when the sample to be analyzed is fragmented through ultraviolet irradiation and subjected to mass analysis, mass peaks of 14 peptide fragments whose sequences overlap with each other are detected. Using the total molecular weight of the peptide before the photolysis reaction and the molecular weight of the 14 peptide fragments obtained after the photolysis reaction, it is possible to analyze the amino acid sequence of the BPA peptide as shown in FIG. 8C.

9A and 9B are graphs showing mass spectrometry results of a Biotin-PreS1 peptide using a sample plate having a photoreaction catalyst layer according to an embodiment of the present invention before and after ultraviolet irradiation. ≪ / RTI > shows the sequence of amino acids obtained by mass spectrometry. The photoreactive catalyst layer is a TiO ₂ layer having a porous nanoscale structure. Using a Microflex model from Bruker, laser desorption / ionization mass spectrometry was performed on these organic molecular compounds with a detector gain of 8.6 x and a laser intensity of 70%.

Referring to FIG. 9A, the sample to be analyzed for mass spectrometry is a PreS1 peptide (1 mg / ml) having a molecular weight of 1934.01 Da. Prior to photodecomposition using ultraviolet irradiation, the mass peak of PreS1, an organic chemical sample, was observed in the form of [M + K] ⁺ .

Referring to FIG. 9B, the sample to be analyzed is fragmented through ultraviolet irradiation, and subjected to mass analysis to detect mass peaks of 14 peptide fragments whose sequences overlap with each other. Using the total molecular weight of the peptide compound before the photolysis reaction and the molecular weight of the 14 peptide fragments obtained after the photolysis reaction, it is possible to analyze the amino acid sequence of the Biotin-PreS1 peptide such as that shown in FIG. 9C.

In the case of general maldistopment mass spectrometry, when two or more kinds of ion samples having the same ionic mass (m / z) are mixed, they can be identified with the same mass peak, so that it is impossible to identify the mixed ion sample. When the sample is mixed, each ion forms a specific fragment. Therefore, it is possible to identify the mixed ions in the sample through analysis after formation of organic molecule fragments in the mixed sample.

According to an embodiment of the present invention, analysis of amino acid sequence is performed on peptides having 3 to 15 amino acid residues through fragmentation of organic molecules by ultraviolet rays using the photoreaction catalyst layer described with reference to Figs. 5A to 9C It is possible to apply the Tandem mass analysis method by inducing the photolysis reaction by ultraviolet irradiation without colliding with the conventional electron beam or molecular beam and thereby to show the same characteristics of the generated organic molecule fragments as possible through mass analysis, According to an embodiment of the present invention, identification of a mixed organic molecular compound is possible.

According to an embodiment of the present invention, fragments of an organic molecular compound are formed through photolysis reaction and analyzed to analyze an organic molecular compound or sequence of amino acids constituting a peptide. Further, even in the case of the sample having the same amount of ions in the photolysis reaction, organic molecule fragments reflecting the structural specificity of the organic molecular compound such as an amino acid sequence can be obtained. These and other advantages of the present invention will be further elucidated by the following disclosure.

FIGS. 10A to 10C are graphs showing mass spectrometry results of organic molecular compounds having the same ionic mass using a photoreactive catalyst layer according to an embodiment of the present invention. FIG. The organic molecular compounds shown in FIGS. 10A to 10C are all HPQ-1 peptides having a molecular weight of 884.46 Da and consisting of 7 amino acids and having a sequence of GYHPQRK, HPQ-2 peptide having a sequence of KRHPQYG and HPQ-3 having a sequence of RYHPQGK Lt; / RTI > The photoreactive catalyst layer is a TiO ₂ layer having a porous nanoscale structure. Using a Microflex model from Bruker, laser desorption / ionization mass spectrometry was performed on these organic molecular compounds, with a detector gain of 20 x and a laser intensity of 90%.

Referring to FIG. 10A, the mass peak of the sample peptide HPQ-1 was observed in the form of [M + K] ⁺ before the photolysis reaction using UV. The mass spectrometric peaks after UV irradiation for the photolysis reaction of the sample peptides are obtained from twelve peptide fragments with overlapping sequences. Analysis of the amino acid sequence constituting the entire peptide was possible by analyzing the total molecular weight of the peptide before photodegradation reaction and the molecular weight analysis of the twelve peptide fragments obtained after photodegradation reaction.

Referring to FIG. 10B, before the photodegradation reaction using UV, the mass peak of the sample peptide HPQ-2 was observed in the form of [M + K] ⁺ . Mass spectrometric peaks after UV irradiation for the photolysis reaction of the sample peptides are obtained from six peptide fragments whose sequence is different from HPQ-1. Analysis of the amino acid sequence constituting the entire peptide was possible by analyzing the total molecular weight of the peptide before the photolysis reaction and the molecular weight analysis of the six peptide fragments obtained after the photolysis reaction.

Referring to FIG. 10C, the mass peak of the sample peptide HPQ-3 was observed in the form of [M + K] ⁺ before the photolysis reaction using UV. In the case of mass spectrometric peaks after UV irradiation for the photolysis reaction of the sample peptides, 11 peptide fragments, which are unlike the previously analyzed peptides HPQ-1 and HPQ-2, are obtained. Analysis of the amino acid sequence constituting the entire peptide was possible by analyzing the total molecular weight of the peptide before the photolysis reaction and the molecular weight analysis of the eleven peptide fragments obtained after the photolysis reaction.

According to an embodiment of the present invention, when the peptide fragment produced by the light irradiation and the decomposition reaction are subjected to mass spectrometry using a laser desorption / ionization method, , Fragments of a peptide reflecting the structural specificity according to the amino acid sequence can be obtained, and the amino acid sequence constituting the peptide can be analyzed using the molecular weight of the peptide fragments. Although the above-described embodiments relate to peptides, embodiments of the present invention are not limited to these peptides, and may include organic peptides as well as organic analytical samples having distinct specific binding that may undergo different degradation reactions by light irradiation It should be understood that the present invention can also be applied to identification.

11A and 11B show an atomic force microscope image of the substrate surface before and after forming the nanoscale structure after polishing the surface of the substrate in one direction and in both directions, respectively. The substrate used was a Ti substrate, and a TiO ₂ layer was formed as a photoreaction catalyst layer. A diamond sandpaper having a surface roughness of about 500 mesh was used to polish the substrate.

11A and 11B, it can be seen that the polished surface of the substrate has different shapes in the unidirectional stripe pattern and the bidirectional stripe pattern when polished in one direction and polished in both directions.

A bare sample plate having a photocatalytic catalyst layer of TiO ₂ according to an embodiment of the present invention does not generate a mass peak without the sample to be analyzed. Particularly, it should be noted that there is no mass peak in the region of 500 m / z or less. Alternatively, in the case of a sample using an organic matrix of conventional-ciano-4-hydroxycinnamic acid (CHCA), the mass peak due to the CHCA occurs in a region of 400 m / z or less , These mass peaks occur without reproducibility and are therefore difficult to remove as noise signals. Therefore, in the case of the comparative example, it is predicted that it is difficult to distinguish the mass peak of the organic molecular compound and the noise signal from each other in the region where m / z is 500 or less, unlike the embodiment of the present invention. Conversely, according to the embodiment of the present invention, reliable mass spectrometry results can be obtained even in a region where m / z is 500 or less.

When analyzing the same concentration of arginine (molecular weight: 174.2 Da) using the conventional organic matrix, the mass of the sample is calculated by [M + K] ⁺ and [M + 2K] ⁺ without the noise occurring in the low m / It can be seen that the peak is measured. In addition, when the polishing of the substrate is performed in both directions of the stripe pattern and the cross pattern, the magnitude of the mass peak is significantly different. In the case of the bi-directional polishing substrate of the check pattern, It can be seen that the ionization of the sample occurs very effectively.

12A is an optical image showing the substrate surface before the substrate is exposed to corrode the surface of the substrate, and FIG. 12B is an optical image showing the surface of the substrate polished to form a bi- directional stripe pattern by diamond abrasive paper having roughnesses of 180, Scanning electron microscope image of the surface of the substrate.

Referring to FIG. 12A, the optical images have magnifications of about 10 times and 20 times. Referring to the optical images, a bi-directional stripe pattern is observed. Further, when a diamond sandpaper having a roughness of 180, 320, and 400 mesh is applied, the smaller the roughness of the sandpaper becomes, the closer the interval between adjacent stripe patterns becomes, and the depth of the stripe patterns becomes further reduced.

12B, surface grinding is performed in both directions so as to form a bi-directional stripe pattern by using diamond sand of roughness 180, 320, and 400 mesh, respectively, on the substrate SS, and then the surface of the substrate is polished using an electron microscope And magnification of 10,000 times. As can be seen from the electron micrographs, the bi-directional stripe pattern was generated by comparing the surface of the polished specimen with the surface of the polished specimen in both directions. The surface roughness of the substrate before polishing was observed to be similar to 320, but the surface structure was not observed according to the direction of polishing. When the sandpaper having roughnesses of 180, 320, and 400 mesh was used, the roughness of the sandpaper was small, so that a shape in which the spacing of the grooved grooves was observed as observed in an optical microscope was observed, and a shape in which the depth of the grooved grooves Respectively.

13A shows a surface mount observed by an atomic force microscope on the surface of a polished and eroded substrate using diamond abrasive paper having a roughness of 180, 320 and 400 mesh according to an embodiment of the present invention, The surface roughness of a substrate formed with a nanoscale structure formed with a diamond sandpaper having roughnesses of 180, 320, 400, and 500 mesh was observed with an atomic force microscope.

Referring to FIG. 13A, a bi-directional stripe pattern can be identified by comparing the surface of a bare substrate having a nanoscale structure with the surface of a polished substrate having a nanoscale structure, as shown in the atomic force microscope image. Further, in the case of using sand paper having roughnesses of 180, 320, and 400 mesh, the roughness of the sandpaper was reduced, and thus, a shape in which the spacing of the grooved grooves was observed as observed in an optical microscope and an electron microscope image was observed, And the depth of the groove to be formed becomes shallow.

Referring to FIG. 13B, a surface of a substrate on which nanoscale structures (i.e., nanowires) are formed on the surface of a polished substrate SS using a diamond sandpaper having roughnesses of 180, 320, 400, Roughness was observed with an atomic force microscope. The roughness can be quantified using the Rq value as shown in FIG. 13B.

This result shows that the surface area of the substrate can be adjusted when the substrate surface is polished by using diamond sand papers having different roughness as shown in Figs. 12A and 13B. In addition, the results of FIG. 13B show that the surface roughness when forming a nanoscale structure is similar regardless of the roughness of the diamond sandpaper used for polishing. Therefore, when the manufactured nanoscale structure is used as an inorganic matrix for mass spectrometry, the degree of ionization is determined according to the area of the nanowire to which the sample is contacted. Therefore, the area of the nanoscale structure according to the roughness of the sandpaper, It is determined by the pretreatment of the substrate that is performed before forming the scale structure.

14A shows mass spectrometry results of various organic molecular compounds measured using a sample plate having a photoreaction catalyst layer prepared according to an embodiment of the present invention, And mass spectrometry results using a polished substrate using a diamond sandpaper having roughnesses of 180, 320, and 400 mesh to form a pattern.

Referring to FIG. 14A, the photoreactive catalyst layer is a TiO ₂ nanoscale structure. The mass peak of a sample can be measured with [M + K] ⁺ and [M + 2K] ⁺ in the case of arginine (molecular weight 174.2 Da) as an organic molecular compound. Since the sample plate according to the embodiment of the present invention is manufactured by corroding with KOH at a high concentration, a combination of the organic molecular compound and the K ⁺ ion is obtained by K ⁺ ions incorporated at this time. Also, it can be seen that the laser desorption / ionization mass spectrometry can be performed without using a noise signal by using the sample plate according to the embodiment of the present invention.

Referring to FIG. 14B, after a unidirectional stripe pattern and a bidirectional stripe pattern are respectively formed by using diamond sand paper having roughnesses of 180, 320, and 400 mesh used for surface polishing, arginine Molecular weight 174.2 Da).

A mass spectrometric peak was also observed on a sample plate after forming a bi-directional stripe pattern using a diamond sand paper having a roughness of 180 meshes and forming a nanoscale structure thereafter. The substrate was polished in both directions with the same roughness diamond sand paper, In the case where a stripe pattern is formed and then a nanoscale structure is formed, a mass peak having a size much higher than that of the substrate having the unidirectional stripe pattern is shown. This phenomenon is attributed to an increase in the surface roughness of the substrate surface due to the bi-directional polishing, thereby increasing the substrate surface area for formation of the nanoscale structure, thereby improving the ionization efficiency per unit area of the sample plate, Respectively.

According to an embodiment of the present invention, sequence analysis is performed on peptides having 2 to 15 amino acid residues through mass spectrometry by fragmenting organic molecules by ultraviolet light using the photoreactive catalyst layer disclosed with reference to Figs. 5A to 14B .

Similarly, a tandem mass analysis is possible by inducing photolysis reaction by irradiation of ultraviolet rays without collision by conventional electron beam or molecular beam. According to an embodiment of the present invention, titration of a mixed organic molecular compound may also be possible.

According to an embodiment of the present invention, peptide fragments formed by light irradiation and decomposition reactions can be mass analyzed using a laser desorption / ionization method. Peptide fragments reflecting structural features according to amino acid sequence can be obtained and the amino acid sequences constituting the peptides can be determined by analyzing the molecular weight of the peptide fragments. Although the above-described embodiments relate to peptides, the present invention is not limited to the peptides, and the present invention can be applied not only to other peptides but also to organic compounds having specific binding that undergo different decomposition reactions by light irradiation It should be understood that the present invention can be applied to a specific application.

As described above, a sample plate according to various embodiments of the present invention, a method of manufacturing the same, and a mass spectrometry method using the sample plate have been described in detail. However, it will be understood by those skilled in the art that various modifications and variations can be made in the present invention within the scope of the present invention. Accordingly, the scope of the present invention is limited only by the following claims.

Claims (14)

As a sample plate for laser desorption / ionization mass spectrometry,
A substrate having a polished surface to have a controlled surface roughness; And
And a photocatalytic catalyst layer comprising a metal oxide formed on the polished surface of the substrate,
And a sample to be analyzed is disposed on the photoreactive catalyst layer. The method according to claim 1,
Wherein the photoreaction catalyst layer comprises a surface corrosion layer of the substrate. The method according to claim 1,
Wherein the metal oxide comprises an oxide layer on the surface of the substrate. The method according to claim 1,
The metal oxide may be at least one of titanium (Ti), tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium (Ru), iridium (Ir) A sample plate comprising an oxide of any one of the metals. The method according to claim 1,
Wherein the metal oxide has a porosity and has a nanoscale structure having a fibrous, wire-like, needle-like, film-like object, columnar shape, or a combination thereof. The method according to claim 1,
Wherein the sample to be analyzed forms fragments by photolysis reaction by ultraviolet irradiation incident on the photoreaction catalyst layer, and mass analysis of the fragments is performed. A method of producing a sample plate for laser desorption / ionization mass spectrometry,
Providing a substrate comprising metal atoms constituting a photoreactive catalyst layer;
Polishing the surface of the substrate so that the surface of the substrate has a cross stripe pattern formed by intersecting at least two or more stripe patterns extending in one direction or in different directions so as to control the surface roughness of the substrate ; And
And exposing the surface of the substrate having the polished surface to an oxidizing solvent to oxidize the metal while corroding the polished surface of the substrate to form a photoreaction catalyst layer comprising an oxide of the metal Gt; 8. The method of claim 7,
The metal atom may be at least one selected from the group consisting of tantalum (Ta), tin (Sn), tungsten (W), zinc (Zn), vanadium (V), ruthenium (Ru), iridium . 8. The method of claim 7,
Wherein the photocatalytic catalyst layer has a porous nanoscale structure by corroding the surface of the substrate. 8. The method of claim 7,
Wherein the step of forming the photoreaction catalyst layer comprises:
Immersing the substrate in the oxidizing solvent to form an oxide of metal on the surface of the substrate; And
And cleaning the substrate on which the oxide of the metal is formed. 8. The method of claim 7,
Wherein the oxidizing solvent comprises an alkaline solvent. Providing a sample plate comprising the photoreactive catalyst layer according to claim 1;
Loading the sample to be analyzed on the photoreactive catalyst layer;
Irradiating the sample to be analyzed with ultraviolet rays to induce photodecomposition reaction of the sample to be analyzed; And
And performing mass spectrometry by laser desorption / ionization on the sample to be analyzed that has undergone the photolysis reaction. 13. The method of claim 12,
Wherein the analyte sample contains an organic molecular compound and the organic molecular compound is fragmented by the photolysis reaction. 13. The method of claim 12,
Wherein the analyte sample contains different types of organic molecular compounds, and the organic molecular compounds are specifically fragmented by the photolysis reaction to identify the organic molecular compounds.

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