CN100565776C - Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer - Google Patents
Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer Download PDFInfo
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- CN100565776C CN100565776C CNB2007100099229A CN200710009922A CN100565776C CN 100565776 C CN100565776 C CN 100565776C CN B2007100099229 A CNB2007100099229 A CN B2007100099229A CN 200710009922 A CN200710009922 A CN 200710009922A CN 100565776 C CN100565776 C CN 100565776C
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Abstract
Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, relate to a kind of mass spectrometer.Substance assistant laser desorpted-laser-induced fluorescence (LIF) time-of-flight mass spectrometer that a kind of detection sensitivity height, resolution capability are strong, can realize single molecule analysis is provided.Be provided with cavity, sample introduction feeler lever, preposition aperture plate group, rearmounted aperture plate group, photomultiplier, microchannel plate electron multiplier, laser, laser focused lens, gas laser and gas laser condenser lens.Feeler lever, front and rear aperture plate group, multiplier tube and multiplier are located in the cavity; Laser and condenser lens, gas laser and condenser lens are located at outside the cavity, and the chamber wall of cavity is provided with laser and injects window, supplies valve, the vacuum pumping port of feeler lever turnover; The cavity axis is coaxial with the feeler lever axis; The forward and backward aperture plate group of putting is made of parallel interval and the aperture plate vertical with the cavity axis; Rearmounted aperture plate group axis is coaxial with the photomultiplier axis.
Description
Technical field
The present invention relates to a kind of mass spectrometer, especially relate to a kind of substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer.
Background technology
At present, technology commonly used comprises gel electrophoresis, flow cytometer and mass spectrum etc. in the large biological molecule analysis.Gel electrophoresis can separate preferably to the dna fragmentation of molecular weight up to thousands of bp, but for molecular weight greater than 20, the dna fragmentation that 000bp is above, PFGE (PFGE) is finished one-time detection needs long time (a few hours), and efficient is lower.And the sample size of this Technology Need is bigger, is generally μ g level, has increased the workload and the time of sample treatment greatly.In addition, the resolution capability of gel electrophoresis is relatively poor, for 1, and the dna fragmentation that 000bp is following, its resolution capability is about tens of bp, and to 10, the dna fragmentation that 000bp is above, its resolution capability is about hundreds of bp.The fluorescence flow cytometry is attached to fluorescent dye on the dna fragmentation, has very high detection sensitivity, only needs the sample of ng or pg level to detect.And the fluorescence fluidic cell detects only needs time a few minutes, and speed is very fast.But also there is the weakness of resolution capability difference in this technology, also only can reach hundreds of bp under the optimum condition.Light microscope and atomic force microscope are also attempted being used for DNA analysis, but are not sufficient to solve existing problem, and can't replace gel electrophoresis and the flow cytometry routine techniques as DNA analysis in present and foreseeable future.
Compare with said method, mass spectrum has high-resolution, high precision and highly sensitive characteristics.The appearance that ground substance assistant laser is resolved ion source (MALDI) makes mass spectrum obtain application more and more widely in the large biological molecule analysis.For daltonian large biological molecules up to a million, though the MALDI technology can be carried out ionization to it, its signal value very a little less than, be difficult to obtain detect.And,, the quality upper limit is arranged all as quadrupole rod, sector field and ion trap etc. for most mass analyzer, be generally several kilodaltons.Flight time mass spectrum is more special, and theoretically, it does not have the quality upper limit, and has the resolution capability up to 10ppm, exceeds 3 more than the order of magnitude than the resolution capability based on gel electrophoresis and flow cytometry.Yet, because the large biological molecule of super high molecular weight is slower at the flight time mass spectrum medium velocity, on microchannel plate electron multiplier detector, be difficult to obtain detect, thus the detection sensitivity of greatly reducing.Therefore, flight time mass spectrum is subject to analyzes 200,000～300, and the large biological molecule of 000Da comprises oligonucleotides and small protein etc.Fuerstenau, S.D. etc. attempted once that flight time mass spectrum was used for molecular weight and reached daltonian macromolecular detections up to a million, though this molecule can demonstrate very weak peak at mass spectrogram, still can't reach the analysis requirement, did not have practical value.Larson etc. have studied the signal difference of the microchannel plate electron multiplier of flight time mass spectrum to the different-energy ion, and the result shows that energy is ion (5kDa, 1.5 * 10 of 6kV
4M/s) it is ion (5kDa, 3 * 10 of 25kV that signal value has only energy
4M/s) half.The corresponding signal of this explanation microchannel plate electron solid multiplier is finally determined by the speed of ion.Therefore, be 1,000,000 daltonian big molecule for molecular weight, when its speed is 3 * 10
4During m/s, need apply about 5 * 10
6The accelerating voltage of V just might make it obtain detecting.Consider the restriction of factors such as vacuum degree, instrument, can not realize under the actual conditions up to 5 * 10
6The accelerating voltage of V.
Advantage such as that laser Induced Fluorescence Technology has is highly sensitive, be simple and easy to use is for obtained extensive use in the large biological molecule analysis.But, must before analysis, carry out fluorescence for the sample of no fluorophor and derive.Argon ion laser can provide the energy of 2W when 488nm, for dna fragmentation that combines the PicoGreen dyestuff and the protein molecule that combines the NanoOrange dyestuff excellent stimulation effect is arranged all.Studies show that, even have only the ion packet of 800 ions also can access the good detection signal.Because large biological molecule itself may be in conjunction with several or more dye molecule, and flight speed is slower, so laser Induced Fluorescence Technology can obtain better to detect effect for this quasi-molecule.
Chinese patent CN85104052 provides a kind of time-of-flight mass spectrometer, and it comprises the analyzer that is provided with many ring electrodes along same axle, and wherein, to used a voltage that is inversely proportional to distance by measured ion, this voltage produces electric field force.
Publication number provides a kind of series connection linear ion hydrazine and time-of-flight mass spectrometer for the application for a patent for invention of CN1926657, and wherein, ion trap has the straight line central shaft with mass spectrometric flight track quadrature.Ion trap comprises: one group of electrode (401,403,402,404), and at least one described electrode has the opening that is used for to the mass spectrometer emitting ions; One group of dc voltage power supply (+V ,-V, V1, V2), be used to provide discrete DC level, and the high-speed electronic switch of some (409), be used to make the DC power supply to be connected/to disconnect with at least two described electrodes; Neutral gas is filled ion trap; And digitial controller, be provided for the handoff procedure of ion trap, operation ion, cooling, and comprise state from ion trap to mass spectrometer that launch all ions from.
Summary of the invention
The object of the present invention is to provide substance assistant laser desorpted-laser-induced fluorescence (LIF) time-of-flight mass spectrometer that a kind of detection sensitivity height, resolution capability are strong, can realize single molecule analysis.
Purpose of the present invention is achieved through the following technical solutions: substance assistant laser desorpted-laser-induced fluorescence (LIF) time-of-flight mass spectrometer is provided with cavity, sample introduction feeler lever, preposition aperture plate group, rearmounted aperture plate group, photomultiplier, microchannel plate electron multiplier, laser, laser focused lens, gas laser and gas laser condenser lens.Sample introduction feeler lever, preposition aperture plate group, rearmounted aperture plate group, photomultiplier and microchannel plate electron multiplier are located in the cavity successively; The gas laser condenser lens of laser focused lens, gas laser and the corresponding gas laser of laser, corresponding laser is located at the cavity outside, the quartz window that the chamber wall of cavity is provided with quartz window that the laser for laser injects, injects for the valve of sample introduction feeler lever turnover, for the laser of vacuum pumping port that vacuumizes usefulness and supplied gas laser; The axis of the axis of cavity and sample introduction feeler lever is same axis; The aperture plate parallel interval of preposition aperture plate group is also vertical with the cavity axis; The aperture plate parallel interval of rearmounted aperture plate group is also vertical with the cavity axis, and the axis of rearmounted aperture plate group and the axis of photomultiplier are same axis.
Cavity is preferably the cylindric stainless steel cavity of T shape, and 2 quartz windows and vacuum pumping port preferably are located at the bottom of cavity.The sample introduction feeler lever is preferably the stainless steel cylinder, and sample introduction feeler lever top is provided with at least 1 sample fixed part, can analyze a plurality of samples simultaneously.Laser is preferably selected wavelength 157～1100nm for use, average power＞1W, peak power＞100kW, pulsewidth 100fs～10ns, pulse energy 100 μ J～500mJ, pulse frequency 10Hz～10kHz, beam diameter 1～10mm.Gas laser preferably adopts helium neon laser or argon laser.Preposition aperture plate group preferably is made of 3 aperture plates.Rearmounted aperture plate group preferably is made of two aperture plates, and two aperture plate spacings are preferably 1mm, two aperture plate ground connection.The microchannel plate electron multiplier is preferably selected slab-thickness 0.5～1mm for use, distance 10～50 μ m between the passage, resistance 108～1010 Ω between the dull and stereotyped two sides, dull and stereotyped area＜30cm
2
The course of work of the present invention is as follows:
Whole mass spectrometer is in vacuum environment, adopts the substance assistant laser desorpted ionization that is used for sample molecule.Whole mass spectrometer is divided into 3 zones: be ionization and introducing district in sample introduction feeler lever and the preposition aperture plate group between last 1 aperture plate; Be the field-free flight district between the most preceding 1 aperture plate in last 1 aperture plate and the rearmounted aperture plate group in the preposition aperture plate group; Be the fluoroscopic examination district between rearmounted the most preceding 1 aperture plate of aperture plate group and last 1 aperture plate.Sample after fluorescence is derived is fixed on the sample introduction feeler lever, stretches into cavity by valve.After the laser beam line focus set of lenses that laser penetrates focused on, the quartz window by the ion source cavity was mapped to sample surfaces.Substrate molecule absorbs laser energy and gasifies rapidly, and involved sample molecule also is brought into gas phase.The substrate molecule of being excited simultaneously, produces ionization with proton translocation to sample molecule.Sample ions is introduced into the field-free flight district under the electric field action of preposition aperture plate group, separate according to its mass-to-charge ratio.The sample ions that process is separated is successively by the fluoroscopic examination district.Vertically inject by quartz window after the gas laser emitted laser line focus lens focus, thereby sample ions is subjected to laser excitation and produces fluorescence signal and detected by the photomultiplier record, and sample ions is got to the microchannel plate electron multiplier and also can be produced electronic signal about mass-to-charge ratio simultaneously.
Action principle of the present invention is as follows:
Flight time mass spectrum has very high resolution capability, and big molecule mixture can access better separation in the field-free flight district according to mass-to-charge ratio.Laser inductive fluorescence method has high detection sensitivity, detects even several molecule also can access.Sample ions is after the field-free flight district is through good the separation, thereby the irradiation that is subjected to vertical laser beam produces fluorescence signal and is detected by the photomultiplier record, and sample ions is got to the microchannel plate electron multiplier and also can be produced electronic signal about mass-to-charge ratio simultaneously.
The present invention has following outstanding advantage and effect mutually: 1) big molecule mixture can obtain high-resolution the separation in the field-free flight district.2) adopt laser Induced Fluorescence Technology to detect, can realize single molecule analysis.3) the microchannel plate electron multiplier can be collected the electronic signal about mass-to-charge ratio.
Description of drawings
Fig. 1 is the structural representation of the embodiment of the invention.
Embodiment
As shown in Figure 1, the present invention is provided with cavity 1, sample introduction feeler lever 2, preposition aperture plate group 3, rearmounted aperture plate group 4, photomultiplier 5, microchannel plate electron multiplier 6, laser 7, laser focused lens 8, gas laser 9 and gas laser condenser lens 10.Sample introduction feeler lever 2, preposition aperture plate group 3, rearmounted aperture plate group 4, photomultiplier 5 and microchannel plate electron multiplier 6 are located in the cavity 1 successively; The gas laser condenser lens 10 of the laser focused lens 8 of laser 7, corresponding laser 7, gas laser 9 and corresponding gas laser 9 is located at the cavity outside, the quartz window 14 that the chamber wall of cavity 1 is provided with quartz window 11 that the laser for laser 7 injects, injects for the valve 12 of sample introduction feeler lever 2 turnover, for the laser of vacuum pumping port 13 that vacuumizes usefulness and supplied gas laser 9; The axis of the axis of cavity 1 and sample introduction feeler lever 2 is same axis; Preposition aperture plate group 3 is made of 3 parallel interval and the aperture plate vertical with the cavity axis; Rearmounted aperture plate group 4 is made of 2 parallel interval and the aperture plate vertical with the cavity axis, and the axis of the axis of rearmounted aperture plate group 4 and photomultiplier 5 is same axis.
Claims (7)
1. substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that being provided with cavity, sample introduction feeler lever, preposition aperture plate group, rearmounted aperture plate group, photomultiplier, microchannel plate electron multiplier, laser, laser focused lens, gas laser and gas laser condenser lens, sample introduction feeler lever, preposition aperture plate group, rearmounted aperture plate group, photomultiplier and microchannel plate electron multiplier are located in the cavity successively; The gas laser condenser lens of laser focused lens, gas laser and the corresponding gas laser of laser, corresponding laser is located at the cavity outside, the quartz window that the chamber wall of cavity is provided with quartz window that the laser for laser injects, injects for the valve of sample introduction feeler lever turnover, for the laser of vacuum pumping port that vacuumizes usefulness and supplied gas laser; The axis of the axis of cavity and sample introduction feeler lever is same axis; The aperture plate parallel interval of preposition aperture plate group is also vertical with the cavity axis; The aperture plate parallel interval of rearmounted aperture plate group is also vertical with the cavity axis, and the axis of rearmounted aperture plate group and the axis of photomultiplier are same axis;
Described laser is selected wavelength 157～1100nm for use, average power＞1W, peak power＞100kW, pulsewidth 100fs～10ns, pulse energy 100 μ J～500mJ, pulse frequency 10Hz～10kHz, the laser of beam diameter 1～10mm;
Described gas laser adopts helium neon laser or argon laser;
Described microchannel plate electron multiplier is selected slab-thickness 0.5～1mm for use, distance 10～50 μ m between the passage, resistance 108～1010 Ω between the dull and stereotyped two sides, dull and stereotyped area＜30cm
2The microchannel plate electron multiplier.
2. as claimed in claim 1 substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that cavity is the cylindric stainless steel cavity of T shape.
3. as claimed in claim 1 substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that 2 quartz windows and vacuum pumping port be located at the bottom of cavity.
4. as claimed in claim 1 substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that the sample introduction feeler lever is the stainless steel cylinder.
As claim 1 or 4 described substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that sample introduction feeler lever top is provided with at least 1 sample fixed part.
6. as claimed in claim 1 substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that preposition aperture plate group is made of 3 aperture plates.
7. as claimed in claim 1 substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer, it is characterized in that rearmounted aperture plate group is made of two aperture plates, two aperture plate spacings are 1mm, two aperture plate ground connection.
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| CNB2007100099229A CN100565776C (en) | 2007-12-03 | 2007-12-03 | Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer |
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| CNB2007100099229A CN100565776C (en) | 2007-12-03 | 2007-12-03 | Substance assistant laser desorpted-the laser-induced fluorescence (LIF) time-of-flight mass spectrometer |
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| CN101170044A CN101170044A (en) | 2008-04-30 |
| CN100565776C true CN100565776C (en) | 2009-12-02 |
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| CN102735658A (en) * | 2012-07-17 | 2012-10-17 | 中国科学技术大学 | Time resolution laser-induced breakdown spectroscopy measuring method |
| CN111830117A (en) * | 2020-07-20 | 2020-10-27 | 中山大学 | Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030042412A1 (en) * | 2001-06-13 | 2003-03-06 | Park Melvin A. | Means and method for a quadrupole surface induced dissociation quadrupole time-of-flight mass spectrometer |
| US20050116158A1 (en) * | 1998-01-23 | 2005-06-02 | University Of Manitoba | Spectrometer provided with pulsed ion source and transmission device to damp ion motion and method of use |
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2007
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050116158A1 (en) * | 1998-01-23 | 2005-06-02 | University Of Manitoba | Spectrometer provided with pulsed ion source and transmission device to damp ion motion and method of use |
| US20030042412A1 (en) * | 2001-06-13 | 2003-03-06 | Park Melvin A. | Means and method for a quadrupole surface induced dissociation quadrupole time-of-flight mass spectrometer |
Non-Patent Citations (4)
| Title |
|---|
| A fluorescence detection scheme for ultra large moleculesafter gas phase separation. JIAN HE et al.TALANTA,Vol.71 No.5. 2007 |
| A fluorescence detection scheme for ultra large moleculesafter gas phase separation. JIAN HE et al.TALANTA,Vol.71 No.5. 2007 * |
| 基体辅助激光解析电离飞行时间质谱仪的离子延时引出新技术研究. 查庆民等.质谱学报，第21卷第1期. 2000 |
| 基体辅助激光解析电离飞行时间质谱仪的离子延时引出新技术研究. 查庆民等.质谱学报，第21卷第1期. 2000 * |
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