CN114267573A - Matrix-assisted laser desorption ionization-time-of-flight mass spectrometer and sample detection method - Google Patents
Matrix-assisted laser desorption ionization-time-of-flight mass spectrometer and sample detection method Download PDFInfo
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- CN114267573A CN114267573A CN202111528477.3A CN202111528477A CN114267573A CN 114267573 A CN114267573 A CN 114267573A CN 202111528477 A CN202111528477 A CN 202111528477A CN 114267573 A CN114267573 A CN 114267573A
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- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 title claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 40
- 230000008025 crystallization Effects 0.000 claims abstract description 40
- 230000003287 optical effect Effects 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 238000005070 sampling Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 2
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 6
- 102000017011 Glycated Hemoglobin A Human genes 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 108010014663 Glycated Hemoglobin A Proteins 0.000 description 2
- 102100021519 Hemoglobin subunit beta Human genes 0.000 description 2
- 108091005904 Hemoglobin subunit beta Proteins 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 108091005995 glycated hemoglobin Proteins 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of detection, and particularly relates to a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer and a sample detection method. The matrix-assisted laser desorption ionization-time-of-flight mass spectrometer provided by the invention comprises a vacuum system and an optical system; the optical system comprises a laser, a lens group and a reflector group, the reflector group in the optical system is replaced by a vibrating mirror system, the light path of the laser is adjusted by utilizing the vibration of the vibrating mirror, so that the accurate bombardment on the sample is realized, the bombardment on the non-crystallization area is avoided, the ionization of the sample cannot be realized, and the detection efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer and a sample detection method.
Background
Matrix-assisted laser desorption ionization (MALDI) has been available for over 30 years and shows unique values in multiple disciplines and research fields, and laser indirectly carries out soft ionization on a sample through a Matrix, well reserves the structure of macromolecules, and is more and more widely applied to the research of biomacromolecules. The principle of matrix-assisted laser desorption ionization is that laser irradiates a cocrystal formed by a sample and a matrix, the matrix absorbs energy from the laser, and energy transfer occurs between the matrix and the sample, so that the sample is desorbed and ionized, and the ionized sample flies through a flying pipeline under the action of an electric field and reaches a detector to be detected.
With the wider and wider application of MALDI, the requirements of people on analysis efficiency and analysis time are higher and higher, but the traditional MALDI mass spectrometry technology cannot bypass the defect of matrix crystallization non-uniformity, namely the 'sweet spot' effect, and the improvement of MALDI efficiency is greatly limited. The "sweet spot" effect refers to the phenomenon that the co-crystallization formed by the sample and the matrix is not uniform on the surface of the sample target plate, some have crystallization points, some have no crystallization points, some have high crystallization points and some have low crystallization points. The inhomogeneous distribution of molecules makes the signal difference between the point of detection and the point very large, resulting in low detection efficiency of matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS).
At present, a laser introducing device of MALDI-TOF MS includes a laser, a reflector, and a lens assembly, where a laser beam emitted from the laser enters a vacuum cavity formed by a sealed housing through the reflector, and then enters the vacuum cavity formed by the sealed housing through a light path forming a certain angle with a bearing surface of a target plate, and then passes through the lens assembly arranged in the sealed housing and irradiates on a sample, where the light path of the laser is fixed, however, due to the influence of the "sweet spot" effect, the laser may hit a non-crystallized place with a certain probability, and in order to obtain a good signal, the laser spot needs to be continuously adjusted.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer and a sample detection method. The matrix-assisted laser desorption ionization-time of flight mass spectrometer provided by the invention improves the detection efficiency of MALDI-TOF MS.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer, which comprises a vacuum system and an optical system, wherein the vacuum system is connected with the optical system; the optical system comprises a laser, a lens group and a reflector group, and the reflector group in the optical system is replaced by a galvanometer system;
the galvanometer system comprises a first galvanometer, a second galvanometer and a control card;
the first galvanometer is used for reflecting a laser beam emitted by the laser; the initial position of the first galvanometer and the laser beam form an included angle of 45 degrees;
the second galvanometer is used for reflecting the laser beam reflected by the first galvanometer, and the initial position of the second galvanometer and the laser beam reflected by the first galvanometer form an included angle of 45 degrees;
and the control card regulates and controls the swing of the first galvanometer and the second galvanometer.
Preferably, the galvanometer system further comprises a galvanometer motor.
Preferably, the first galvanometer has a length, width and height of 10.9mm, 15mm and 0.5mm, respectively.
Preferably, the second galvanometer has a length, width and height of 10.9mm, 15mm and 0.5mm, respectively.
The invention also provides a sample detection method using the mass spectrometer, which comprises the following steps:
sampling a sample to be detected to obtain a matrix and a crystal image of the sample to be detected;
identifying the crystallization image to obtain a crystallization area;
converting the crystallization area into corresponding coordinate information, and after the computer obtains the corresponding coordinate information, indicating the control card to regulate and control the first vibrating mirror and the second vibrating mirror to swing according to the corresponding coordinate information, so as to regulate the light path of the laser beam and bombard the crystallization area to obtain effective ions;
and detecting the effective ions to obtain a detection result.
Preferably, the swing speeds of the first galvanometer and the second galvanometer are independently 0-2 kHz.
Preferably, the swing angles of the first galvanometer and the second galvanometer are independently preferably 0-0.15 degrees.
The invention provides a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer, which comprises a vacuum system and an optical system, wherein the vacuum system is connected with the optical system; the optical system comprises a laser, a lens group and a reflector group, and the reflector group in the optical system is replaced by a galvanometer system; the galvanometer system comprises a first galvanometer, a second galvanometer and a control card; the first galvanometer is used for reflecting a laser beam emitted by the laser; the initial position of the first galvanometer and the laser beam form an included angle of 45 degrees; the second galvanometer is used for reflecting the laser beam reflected by the first galvanometer, and the initial position of the second galvanometer and the laser beam reflected by the first galvanometer form an included angle of 45 degrees; and the control card regulates and controls the swing of the first galvanometer and the second galvanometer. According to the invention, the galvanometer system is introduced into the optical system of the matrix-assisted laser desorption ionization-time-of-flight mass spectrometer, and the light path of the laser is adjusted by utilizing the swinging of the first galvanometer and the second galvanometer in the galvanometer system, so that the accurate bombardment on the sample is realized, the bombardment on an amorphous area is avoided, the ionization of the sample cannot be realized, and the detection efficiency is improved.
The invention also provides a sample detection method using the mass spectrometer, which comprises the following steps: sampling a sample to be detected to obtain a matrix and a crystal image of the sample to be detected; identifying the crystallization image to obtain a crystallization area; converting the crystallization area into corresponding coordinate information, and after the computer obtains the corresponding coordinate information, indicating the control card to regulate and control the first vibrating mirror and the second vibrating mirror to swing according to the corresponding coordinate information, so as to regulate the light path of the laser beam and bombard the crystallization area to obtain effective ions; and detecting the effective ions to obtain a detection result. According to the invention, firstly, a sample to be detected is subjected to sample introduction to obtain a crystallization area, then, the change of a laser beam light path is realized by utilizing the swing of the vibrating mirror, so that the laser can be ensured to accurately act on the crystallization area (the crystallization area is an area containing the sample), and further, the ions desorbed each time are ensured to have analyte ions, thereby improving the detection efficiency. Meanwhile, because the crystallization area is predetermined, the laser can accurately bombard the target analyte through the galvanometer system, thereby overcoming the influence of the 'sweet spot' effect and greatly improving the time efficiency.
Drawings
FIG. 1 is a diagram of a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer provided by the present invention;
FIG. 2 is a flow chart of the operation of the present invention in which a laser strikes a crystalline region precisely;
FIG. 3 is a diagram of a region of crystallization of a glycoprotein obtained using a mass spectrometer of the present invention;
FIG. 4 is a mass spectrum of a Glycated hemoglobin component (Glycated β -Hb) standard substance having a standard value of 5.1;
FIG. 5 is a mass spectrum of a Glycated hemoglobin component (Glycated. beta. -Hb) standard substance having a standard value of 10.0.
Detailed Description
The invention provides a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer, which comprises a vacuum system and an optical system, wherein the vacuum system is connected with the optical system; the optical system comprises a laser, a lens group and a reflector group, and is characterized in that the reflector group in the optical system is replaced by a galvanometer system;
the galvanometer system comprises a first galvanometer, a second galvanometer and a control card;
the first galvanometer is used for reflecting a laser beam emitted by the laser; the initial position of the first galvanometer and the laser beam form an included angle of 45 degrees;
the second galvanometer is used for reflecting the laser beam reflected by the first galvanometer, and the initial position of the second galvanometer and the laser beam reflected by the first galvanometer form an included angle of 45 degrees;
and the control card regulates and controls the swing of the first galvanometer and the second galvanometer.
In the invention, the galvanometer system further comprises a galvanometer motor.
In the present invention, the length, width and height of the first galvanometer are preferably 10.9mm, 15mm and 0.5mm, respectively. In the present invention, the length, width and height of the second galvanometer are preferably 10.9mm, 15mm and 0.5mm, respectively.
Fig. 1 is a diagram of a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer provided by the invention, and the initial position of a galvanometer system of the invention can be seen from fig. 1: the first galvanometer is used for reflecting the laser beam emitted by the laser, and the initial position of the first galvanometer forms an included angle of 45 degrees with the laser beam. The second galvanometer is used for reflecting the laser beam reflected by the first galvanometer, and the initial position of the second galvanometer and the laser beam reflected by the first galvanometer form an included angle of 45 degrees.
The invention also provides a sample detection method using the mass spectrometer, which comprises the following steps:
sampling a sample to be detected to obtain a matrix and a crystal image of the sample to be detected;
identifying the crystallization image to obtain a crystallization area;
converting the crystallization area into corresponding coordinate information, and after the computer obtains the corresponding coordinate information, indicating the control card to regulate and control the first vibrating mirror and the second vibrating mirror to swing according to the corresponding coordinate information, so as to regulate the light path of the laser beam and bombard the crystallization area to obtain effective ions;
and detecting the effective ions to obtain a detection result.
The invention samples a sample to be detected to obtain a matrix and a crystal image of the sample to be detected.
In the invention, the acquisition of the crystallization images of the substrate and the sample to be detected is preferably acquired by using a camera of the instrument.
After obtaining the crystallization images of the matrix and the sample to be detected, identifying the crystallization images to obtain a crystallization area;
in the present invention, the identification preferably identifies the crystal region in the crystal image by using a computer image identification system to obtain the crystal region.
After the crystallization area is obtained, the crystallization area is converted into corresponding coordinate information, and after the computer obtains the corresponding coordinate information, the computer instructs the control card to regulate and control the first vibrating mirror and the second vibrating mirror to swing according to the corresponding coordinate information, so that the light path of the laser beam is regulated, the crystallization area is bombarded, and effective ions are obtained.
In the invention, the swing is preferably realized by controlling a rotor of a galvanometer motor to drive a first galvanometer and a second galvanometer to swing through a control card; the first vibrating mirror and the second vibrating mirror swing by a certain angle according to the conversion ratio of a certain voltage to the angle. In the invention, the first galvanometer controls the direction of the X axis of the laser beam; and the second galvanometer controls the trend of the laser beam in the Y-axis direction.
In the invention, the swing speeds of the first galvanometer and the second galvanometer are independently 0-2 kHz. In the invention, the swing angles of the first galvanometer and the second galvanometer are independently 0-0.15 degrees, and the swing angle is a range of swinging left and right by taking an initial angle as an axis.
After the effective ions are obtained, the invention detects the effective ions to obtain the detection result.
FIG. 2 is a flowchart illustrating the operation of the present invention in which a laser hits a crystallization area precisely, and as can be seen from FIG. 2, the present invention first samples a sample to obtain a crystallization image of a substrate and a sample to be measured; and then, the obtained crystal image is imported into an image recognition system to recognize the crystal image, so that a crystal region is obtained. And then, the trend of the laser beam is controlled by using a galvanometer to bombard a crystallization area, so that accurate dotting is realized.
Example 1
A glycosylated hemoglobin component (beta-globin) standard substance with a standard value of 5.1 is sampled, and a matrix assisted laser desorption ionization-time-of-flight mass spectrometer is utilized, so that a crystallization area graph is shown in figure 3, and a white crystallization area and a black non-crystallization area are shown in figure 3. The obtained mass spectrogram is shown in figure 4, the measurement results of 60 target points are shown in figure 4, and the good coincidence of the mass spectrogram can be seen from the figure, so that the repeatability of the test result of the mass spectrometer provided by the invention on the sample is proved to be good.
In addition, the invention also tests the glycosylated hemoglobin component (beta-globin) standard substance with the standard value of 10.0, the obtained mass spectrogram is shown in figure 5, the measurement results of 60 targets are also shown in figure 5, the graph coincidence is good as can be seen from the figure, and the test result repeatability of the mass spectrometer provided by the invention on the sample is proved to be good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A matrix-assisted laser desorption ionization-time-of-flight mass spectrometer comprises a vacuum system and an optical system; the optical system comprises a laser, a lens group and a reflector group, and is characterized in that the reflector group in the optical system is replaced by a galvanometer system;
the galvanometer system comprises a first galvanometer, a second galvanometer and a control card;
the first galvanometer is used for reflecting a laser beam emitted by the laser; the initial position of the first galvanometer and the laser beam form an included angle of 45 degrees;
the second galvanometer is used for reflecting the laser beam reflected by the first galvanometer, and the initial position of the second galvanometer and the laser beam reflected by the first galvanometer form an included angle of 45 degrees;
and the control card regulates and controls the swing of the first galvanometer and the second galvanometer.
2. The matrix assisted laser desorption ionization-time of flight mass spectrometer of claim 1 wherein the galvanometer system further comprises a galvanometer motor.
3. The matrix assisted laser desorption ionization-time of flight mass spectrometer of claim 1 wherein the first galvanometer has a length, width and height of 10.9mm, 15mm and 0.5mm, respectively.
4. The matrix assisted laser desorption ionization-time of flight mass spectrometer of claim 1 wherein the second galvanometer has a length, width and height of 10.9mm, 15mm and 0.5mm, respectively.
5. A sample detection method using the mass spectrometer as claimed in any one of claims 1 to 4, comprising the steps of:
sampling a sample to be detected to obtain a matrix and a crystal image of the sample to be detected;
identifying the crystallization image to obtain a crystallization area;
converting the crystallization area into corresponding coordinate information, and after the computer obtains the corresponding coordinate information, indicating the control card to regulate and control the first vibrating mirror and the second vibrating mirror to swing according to the corresponding coordinate information, so as to regulate the light path of the laser beam and bombard the crystallization area to obtain effective ions;
and detecting the effective ions to obtain a detection result.
6. The method according to claim 5, wherein the oscillating speeds of the first galvanometer and the second galvanometer are independently 0 to 2 kHz.
7. The method according to claim 5, wherein the first galvanometer and the second galvanometer are independently oscillated at an angle of 0 to 0.15 °.
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| US20040012676A1 (en) * | 2002-03-15 | 2004-01-22 | Affymetrix, Inc., A Corporation Organized Under The Laws Of Delaware | System, method, and product for scanning of biological materials |
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| CN109712862A (en) * | 2019-01-28 | 2019-05-03 | 安图实验仪器(郑州)有限公司 | Light path system suitable for Matrix-Assisted Laser Desorption Ionization Time of Flight instrument |
| CN110702614A (en) * | 2019-11-05 | 2020-01-17 | 北京环境特性研究所 | Ellipsometer device and detection method thereof |
| CN111351768A (en) * | 2018-12-20 | 2020-06-30 | 中国科学院合肥物质科学研究院 | Multi-component gas laser detection device and method using scanning galvanometer |
-
2021
- 2021-12-14 CN CN202111528477.3A patent/CN114267573A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040012676A1 (en) * | 2002-03-15 | 2004-01-22 | Affymetrix, Inc., A Corporation Organized Under The Laws Of Delaware | System, method, and product for scanning of biological materials |
| CN106444050A (en) * | 2016-11-02 | 2017-02-22 | 安图实验仪器(郑州)有限公司 | Laser-desorption ion source laser path |
| CN208537420U (en) * | 2018-07-18 | 2019-02-22 | 立穹(上海)光电科技有限公司 | A kind of Handheld Raman spectrum detection instrument of detectable explosive |
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