CN204441247U - A kind of atmospheric pressure ion source apparatus of original position mass spectral analysis - Google Patents
A kind of atmospheric pressure ion source apparatus of original position mass spectral analysis Download PDFInfo
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- CN204441247U CN204441247U CN201520119228.2U CN201520119228U CN204441247U CN 204441247 U CN204441247 U CN 204441247U CN 201520119228 U CN201520119228 U CN 201520119228U CN 204441247 U CN204441247 U CN 204441247U
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- 238000010183 spectrum analysis Methods 0.000 title claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000001154 acute effect Effects 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 16
- 238000003384 imaging method Methods 0.000 abstract description 15
- 238000001819 mass spectrum Methods 0.000 abstract description 14
- 239000000523 sample Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 14
- 238000001514 detection method Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 150000002632 lipids Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 210000004556 brain Anatomy 0.000 description 4
- 238000000132 electrospray ionisation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000000375 direct analysis in real time Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 208000036632 Brain mass Diseases 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000000688 desorption electrospray ionisation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
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- 102000004196 processed proteins & peptides Human genes 0.000 description 1
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Abstract
The utility model relates to a kind of atmospheric pressure ion source apparatus of original position mass spectral analysis, it is characterized in that: it comprises a base plate, base plate left end two stands slides and fixes a baffle plate, wears a metal two and lead in the circular hole in the middle part of baffle plate; The logical outside pole connecting high voltage source of metal two, metal two leads to two ends twists joint connection feed pipe and feed flow capillary by hand; Base plate right-hand member two stands slides and fixes another baffle plate, in the circular hole in the middle part of another baffle plate, wear a threeway; A spray capillary is worn in threeway, one end of spray capillary is from the Single port being fixed on threeway after bracing frame passes, the end of spray capillary forms liquid bridge through after bracing frame with feed flow capillary, arranges the three axle travelling carriages being placed with sample below liquid bridge; Be fixed on the another port of threeway after the sheathed sheath tracheae of the spray capillary other end, the outlet of spray capillary is just to mass spectrometric entrance; 3rd port of threeway is fixedly connected with nitrogen tube.The utility model can be widely used in in-situ study and mass spectrum imaging application.
Description
Technical field
The utility model relates to mass spectrum original position ionization field, particularly about a kind of atmospheric pressure ion source apparatus of original position mass spectral analysis.
Background technology
Nowadays mass spectrometer is widely used in multiple fields as the strong analysis means of one, its cardinal principle utilizes ion source device by each component ionization of tested sample, then by the motor behavior that the ion measuring different mass-to-charge ratio is different in an electrical or magnetic field, thus the detection of material is realized.Ion source device is as one of mass spectrometric critical piece, and its core is ionization techniques.Electron spray ionisation (ESI) technology and substance assistant laser desorpted ionized (MALDI) technology is mainly contained at present at the wider ionization techniques of biomedical sector application.These two kinds of ionization techniques can be good at preserving the integrality of biomolecule, can be used for analysing protein, polypeptide, lipid, the different kinds of molecules such as small molecule metabolites and medicine.
In recent years, the normal pressure original position ionization technique come by ESI technical development obtains the concern of people gradually.The advantage of this technology is that tested sample is prepared without the need to complexity, under the prerequisite of not knowing sample information, and the different kinds of molecules on detection tested sample surface that can be real-time fast.Atmospheric pressure ion source apparatus, in conjunction with corresponding control software design, just can realize the in situ imaging of molecule on tested sample surface further.The development of mass spectrum imaging technology is also for the distribution of the biological sample surface different kinds of molecules of research provides new technological means.
Resolve electro-spray ionization (DESI) as the most widely used normal pressure original position ionization technique, proposed by people such as Cooks, R.G. first in 2004.Resolving electro-spray ionization technology is the measured object desorb directly utilizing charged liquid and gas to make tested sample surface, and reflection subsequently enters mass spectrometer analysis.This technology has filled up the blank that mass spectrum real-time in-situ is analyzed, and is widely used in multiple fields.Wherein, the atmospheric pressure ionization technology based on ESI has important effect when analyzing polar substances, and based on plasma as Direct Analysis in Real Time technology (DART) has greater advantage in analysis apolar substance.But these technology all use the charged liquid of injection or gas to tested sample surface analysis, and system is comparatively disperseed, and is difficult to have higher spatial resolution when carrying out in situ detection or mass spectrum imaging.
Liquid micro-extraction surface-probe (LMJ-SSP) technology uses coaxial capillary charged liquid to be gathered, and extraction solution pumps into tested sample surface by outer capillary tube, is conveyed into mass spectrum detects after extraction by inner side capillary.The method is fast and convenient, and the extraction mode of probe-type allows it to be used to multiple place.But the coaxial capillary (650 μm) that diameter is larger limits the spatial resolution of its in situ detection.NanoDESI technology uses two angled capillary composition liquid bridges to tested sample surface extractions, and the liquid after extraction sends into mass spectrum by the capillary with nozzle needle, utilizes Nanospray ionization method to make measured object band carry out in-situ study.NanoDESI carries out the spatial resolution higher (10 μm) of original position parsing and mass spectrum imaging, but its nozzle needle is superfine, is easy to be blocked by the particle of irregular sample surface, and analysis is repeated and stability is limited.
Venturi effect was found before twoth century by Italian physicist Venturi, G.B. first, when this effect proposition high-speed gas flows through narrow conduit, air pressure can be made to reduce and occur spontaneous imbibition phenomena.The people such as Santos, V.G. utilize Venturi effect to propose venturi simple and easy normal pressure supersonic speed ionization (V-EASI) method in conjunction with supersonic speed electrospray ionisation (SSI), utilize the direct rapid analysis liquid of its spontaneous imbibition phenomena and solid sample.The people such as Han, J. add high pressure on V-EASI basis, find the sensitivity that the electron spray phenomenon produced by high pressure effectively can improve catalytic luminescence transducer and detects carbohydrate.
Summary of the invention
For the problems referred to above, the purpose of this utility model is to provide the atmospheric pressure ion source apparatus of a kind of simple structure, good stability, original position mass spectral analysis that Ionization Efficiency is high.
For achieving the above object, the utility model takes following technical scheme: a kind of atmospheric pressure ion source apparatus of original position mass spectral analysis, it is characterized in that: it comprises a base plate, the left and right two ends of described base plate arrange two stands in interval respectively, and mid-stent described in each all arranges an elongated hole; Slide in the described elongated hole of support described in described base plate left end two and fix a baffle plate, wear a metal two in the circular hole that in the middle part of described baffle plate, side is arranged and lead to; The outside that described metal two is logical connects a pole of high voltage source, and the two ends that described metal two leads to connect one end of feed pipe and feed flow capillary respectively by first-hand stubborn joint; Slide in the elongated hole of support described in described base plate right-hand member two and fix another baffle plate, in the circular hole arranged in the middle part of another baffle plate described, wear a threeway; The spray capillary of a band camber is worn in two parallel ports of described threeway, after one end of described spray capillary is passed from the side of one " L " type bracing frame, twisting joint by second-hand is fixed on a port of described threeway, and the end of described spray capillary forms liquid bridge through after the aperture of described " L " type bracing frame opposite side with other one end of described feed flow capillary, one or three axle travelling carriages are set below described liquid bridge, and sample placed by described three axle travelling carriages; A sheathed sheath tracheae on described spray capillary other end outer wall, and described sheath tracheae is twisted joint by the 3rd hand and is fixed on the another port of described threeway, the outlet of described spray capillary is just to mass spectrometric entrance; 3rd port of described threeway is twisted joint by the 4th hand and is fixedly connected with a nitrogen tube.
Described feed flow capillary and spray capillary adopt quartz capillary.
The camber of described spray capillary is acute angle, and angular range is 40 ~ 70 °.
The liquid bridge distance that described sample on described three axle travelling carriages and described feed flow capillary and spray capillary are formed is 5 ~ 10 μm.
The distance of described spray capillary and described mass spectrometer inlet is 5 ~ 10mm.
Described sheath tracheae employing internal diameter is the peek pipe of 360 μm.
The utility model is owing to taking above technical scheme, and it has the following advantages: 1, the utility model carries out situ extracting owing to adopting angled feed pipe and injection spray pipe composition liquid bridge to sample, effectively improves the spatial resolution of in situ detection.2, the utility model is owing to being combined liquid bridge extracting system with Venturi effect, utilizes venturi self-priming effect that extract is sucked mass spectrometer, avoids the blocking of meticulous nozzle needle, improve repeatability of the present utility model and stability.3, the utility model is owing to adding high pressure in liquid bridge one end, improves the sensitivity of Mass Spectrometer Method.The utility model has with low cost, simple structure, and Ionization Efficiency is high and not easily the advantages such as ion fragmentation reaction occur, and thus the utility model can be widely used in biology, medical science, pharmacy and the analysis of chemical field situ and mass spectrum imaging application.
Accompanying drawing explanation
Fig. 1 is structural representation of the present utility model
Fig. 2 is cutaway view of the present utility model
Fig. 3 is the mass spectrogram adopting the utility model the ink on printing paper surface and blank to be carried out to in-situ study
Fig. 4 adopts the utility model to carry out the result of mass spectrum imaging to printing paper surface different in width ink
Fig. 5 adopts the utility model to the mass spectrogram of phosphatide standard items and mouse brain antinion district in-situ study
Fig. 6 adopts the utility model to the result of mouse brain mass spectrum imaging
Embodiment
Below in conjunction with drawings and Examples, the utility model is described in detail.
As shown in Figure 1 and Figure 2, the utility model comprises a base plate 1, and the left and right two ends of base plate 1 are arranged at intervals with two stands 2 respectively, is provided with an elongated hole 3 in the middle part of each support 2.Slide in the elongated hole 3 of base plate 1 left end two stands 2 and fix a baffle plate 4, in the middle part of baffle plate 4, side is provided with a circular hole, is equipped with a metal two logical 5 in circular hole.The outside of metal two logical 5 connects a pole of a high voltage source 6, and the two ends of metal two logical 5 connect one end of feed pipe 8 and feed flow capillary 9 respectively by the stubborn joint 7 of proficiency.Slide in the elongated hole 3 of base plate 1 right-hand member two stands 2 and fix another baffle plate 10, the middle part of baffle plate 10 is provided with a circular hole, is equipped with a threeway 11 in circular hole.The spray capillary 12 of a band camber is equipped with in two parallel ports of threeway 11, after one end of spray capillary 12 is passed from the side of one " L " type bracing frame 13, be fixed on a port of threeway 11 by twisting joint 14 on the other hand, and the end of spray capillary 12 forms liquid bridge through after the aperture on bracing frame 13 opposite side with other one end of feed flow capillary 9, be provided with three axle travelling carriages 15 below liquid bridge, and three axle travelling carriages 15 are placed with sample.The other end outer wall of spray capillary 12 is arranged with a sheath tracheae 16, and sheath tracheae 16 is twisted joint 17 by hand and is fixed on the another port of threeway 11, makes the outlet of spray capillary 12 just to the entrance of mass spectrometer 18.3rd port of threeway 11 is fixedly connected with a nitrogen tube 20 by twisting joint 19 on the other hand.
In above-described embodiment, feed flow capillary 9 and spray capillary 12 adopt internal diameter to be 50 μm, and external diameter is the quartz capillary of 150 μm, and the preferred length of feed flow capillary 9 is 40 ~ 60mm, and the preferred length of spray capillary 12 is 60 ~ 80mm.
In above-described embodiment, the camber of spray capillary 12 is acute angle, and scope is 40 ~ 70 °.
In above-described embodiment, the liquid bridge that feed flow capillary 9 and spray capillary 12 form has certain angle, preferably 60 ° of angles.
In above-described embodiment, three axle travelling carriages 15 can move up and down, and the liquid bridge that feed flow capillary 9 and spray capillary 12 form is 5 ~ 10 μm apart from the distance of sample on three axle travelling carriages 15.
In above-described embodiment, the port of spray capillary 12 and the entrance distance of mass spectrometer 18 are 5 ~ 10mm.
In above-described embodiment, sheath tracheae 16 adopt internal diameter be 360 μm peek pipe.
Operating process of the present utility model is:
1) cut the quartz capillary of appropriate length respectively as feed flow capillary 9 and spray capillary 12, and respectively feed flow capillary 9 and spray capillary 12 are connected by shown in Fig. 1.The feed flow capillary 9 intercepted in the present embodiment and the length of spray capillary 12 are respectively 50mm and 70mm.
2) adjust height and the angle of base plate 1 left end two stands 2 overhead gage 4, adjust the height of base plate 1 right-hand member two stands 2 overhead gage 10, making feed flow capillary 9 and spray capillary 12 form suitable angle, is such as 60 ° of angles simultaneously.
3) sample is placed on three axle travelling carriages 15, adjusts the position of three axle travelling carriages 15, the liquid bridge distance tested sample 5 ~ 10 μm that feed flow capillary 9 and spray capillary 12 are formed.
4) pole of high voltage source 6 is connected on metal two logical 5, and according to concrete requirement of experiment, the voltage of setting high voltage source 6, is such as set to 3 ~ 5kV.
5) in feed pipe 8, inject make-up solution, as methyl alcohol, acetonitrile, water or methyl alcohol/acetonitrile/water arbitrary proportion mixed liquor, and adjust its flow velocity and make flow velocity optimum, such as 75 ~ 150 μ L/h.
6) in nitrogen tube 20, pass into high flow rate nitrogen, and adjust nitrogen flow rate to optimum, such as 2 ~ 4L/min.
7) complete above-mentioned connection and after setting parameters, another of spray capillary 12 is rectified the entrance of confrontation spectrometer 18, and the distance adjusted between itself and mass spectrometer 18 entrance is 5-10mm, can carry out in situ detection.Mass spectrometer 18 can select Bruker 9.4 T Apex-ultraTM hybrid Qh-FTICR.Make-up solution to enter metal two logical 5 from feed pipe 8 and after high voltage source 6, enters in feed flow capillary 9.By liquid bridge, situ extracting is carried out to the sample on three axle travelling carriages 15.Simultaneously, the high flow rate nitrogen passed in nitrogen tube 20 passes through from the slype between threeway 11 right-hand member spray capillary 12 outer wall and sheath tracheae 16 inwall, and form self-priming effect at the left end of spray capillary 12, extract is entered by spray capillary 12 left end, and enters mass spectrometer 18 from right-hand member.
As shown in Figure 3, Figure 4, the utility model is adopted to carry out in situ detection to printing paper surface ink.First canonip2780 is adopted to load the blue bands that CL-816 ink prints different thicknesses on senior glossy paper, as tested sample.After the utility model being connected according to aforesaid operations process, be 5kV by the voltage sets of high voltage source 6, distance between liquid bridge and tested sample is adjusted to 5 μm, and selects acetonitrile/methanol/water (volume ratio is 5:4:1) solution as a supplement, is 150 μ L/min by its flow rate set.Nitrogen flow rate is 3.5L/min, and the horizontal movement velocity setting three axle travelling carriages 15 is 50 μm/s, and the picking rate of mass spectrometer 18 is 1 spectrogram/s.Start the utility model, detection is carried out to solution to be measured and analyzes.
As shown in Figure 3, the mass spectrogram for adopting the utility model to connect the rear in situ detection ink swath of mass spectrometer 18 and blank position.Can see, detect ink inside band signal to noise ratio better, moderate strength can carry out quantitative analysis, and in blank, signal is lower, illustrates that the utility model can truly reflect tested sample situation.As shown in Figure 4, for adopting the utility model to carry out mass spectrum imaging to different in width ink swath.Can see, the sign that mass spectrum imaging distributes for molecule m/z 645.5210 peculiar in ink is accurately clear, border is clearly demarcated and without disperse or conditions of streaking, the band that to the more important thing is for width be 50 μm still can blur-free imaging, illustrate that spatial discrimination performance of the present utility model is higher, the spatial resolution of in-situ study can reach 50 μm.
As shown in Figure 5, Figure 6, the utility model is adopted to carry out in situ detection to the biomolecule of tissue surface.First according to each parameter of aforesaid operations procedure regulation, the horizontal movement velocity setting three axle travelling carriages 15 is 200 μm/s, and the picking rate of mass spectrometer 18 is 1 spectrogram/s.Start the utility model, detection is carried out to solution to be measured and analyzes.
As shown in Figure 5, the utility model is adopted to carry out in situ detection to the cut into slices lipid metabolism thing at antinion position of standard lipids PC (34:2) and mouse brain respectively.Can see, ion fragmentation reaction does not occur during bioassay standard product substantially, illustrate that the utility model is applicable to analysing biomolecules and or can obtains complete molecular ion.During in-situ study mouse brain antinion district's lipid, find that the utility model can detect multiple lipid simultaneously, there is good signal to noise ratio, the detection that may be used for biological specimen is described.As shown in Figure 6, the utility model is adopted to carry out mass spectrum imaging to mouse brain.Can see, imaging space resolution for different lipid molecule is higher, organizational relationship is better, and imaging border is clear and definite, do not misplace shifting phenomena, illustrates that the utility model can carry out high accuracy to the different kinds of molecules of tissue surface, highly sensitive imaging analysis simultaneously, for mass-spectrometric technique is at biology, the application of medicine and chemical field provides new ionization techniques method.
The various embodiments described above are only for illustration of the utility model; wherein the structure of each parts, connected mode and manufacture craft etc. all can change to some extent; every equivalents of carrying out on the basis of technical solutions of the utility model and improvement, all should not get rid of outside protection range of the present utility model.
Claims (10)
1. an atmospheric pressure ion source apparatus for original position mass spectral analysis, is characterized in that: it comprises a base plate, the left and right two ends of described base plate arrange two stands in interval respectively, and mid-stent described in each all arranges an elongated hole; Slide in the described elongated hole of support described in described base plate left end two and fix a baffle plate, wear a metal two in the circular hole that in the middle part of described baffle plate, side is arranged and lead to; The outside that described metal two is logical connects a pole of high voltage source, and the two ends that described metal two leads to connect one end of feed pipe and feed flow capillary respectively by first-hand stubborn joint; Slide in the elongated hole of support described in described base plate right-hand member two and fix another baffle plate, in the circular hole arranged in the middle part of another baffle plate described, wear a threeway; The spray capillary of a band camber is worn in two parallel ports of described threeway, after one end of described spray capillary is passed from the side of one " L " type bracing frame, twisting joint by second-hand is fixed on a port of described threeway, and the end of described spray capillary forms liquid bridge through after the aperture of described " L " type bracing frame opposite side with other one end of described feed flow capillary, one or three axle travelling carriages are set below described liquid bridge, and sample placed by described three axle travelling carriages; A sheathed sheath tracheae on described spray capillary other end outer wall, and described sheath tracheae is twisted joint by the 3rd hand and is fixed on the another port of described threeway, the outlet of described spray capillary is just to mass spectrometric entrance; 3rd port of described threeway is twisted joint by the 4th hand and is fixedly connected with a nitrogen tube.
2. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 1, is characterized in that: described feed flow capillary and spray capillary adopt quartz capillary.
3. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 1, is characterized in that: the camber of described spray capillary is acute angle, and angular range is 40 ~ 70 °.
4. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 2, is characterized in that: the camber of described spray capillary is acute angle, and angular range is 40 ~ 70 °.
5. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 1 or 2 or 3 or 4, is characterized in that: the liquid bridge distance that the described sample on described three axle travelling carriages and described feed flow capillary and spray capillary are formed is 5 ~ 10 μm.
6. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 1 or 2 or 3 or 4, is characterized in that: the distance of described spray capillary and described mass spectrometer inlet is 5 ~ 10mm.
7. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 5, is characterized in that: the distance of described spray capillary and described mass spectrometer inlet is 5 ~ 10mm.
8. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as described in claim 1 or 2 or 3 or 4 or 7, is characterized in that: described sheath tracheae employing internal diameter is the peek pipe of 360 μm.
9. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 5, is characterized in that: described sheath tracheae employing internal diameter is the peek pipe of 360 μm.
10. the atmospheric pressure ion source apparatus of a kind of original position mass spectral analysis as claimed in claim 6, is characterized in that: described sheath tracheae employing internal diameter is the peek pipe of 360 μm.
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| CN201520119228.2U CN204441247U (en) | 2015-02-28 | 2015-02-28 | A kind of atmospheric pressure ion source apparatus of original position mass spectral analysis |
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| CN201520119228.2U CN204441247U (en) | 2015-02-28 | 2015-02-28 | A kind of atmospheric pressure ion source apparatus of original position mass spectral analysis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389831A (en) * | 2017-09-26 | 2017-11-24 | 中国检验检疫科学研究院 | The quick determination method of banned substance oestrone in a kind of spraying cosmetics |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389831A (en) * | 2017-09-26 | 2017-11-24 | 中国检验检疫科学研究院 | The quick determination method of banned substance oestrone in a kind of spraying cosmetics |
| CN107389831B (en) * | 2017-09-26 | 2020-01-21 | 中国检验检疫科学研究院 | Method for rapidly detecting forbidden substance estrone in spray cosmetics |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150701 |