CN104637774A - Electrospray ion leading-in device - Google Patents
Electrospray ion leading-in device Download PDFInfo
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- CN104637774A CN104637774A CN201310558287.5A CN201310558287A CN104637774A CN 104637774 A CN104637774 A CN 104637774A CN 201310558287 A CN201310558287 A CN 201310558287A CN 104637774 A CN104637774 A CN 104637774A
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- introducing device
- vacuum system
- electron spray
- millimeter
- metal thin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
- H01J49/0445—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for introducing as a spray, a jet or an aerosol
Abstract
The invention discloses an electrospray ion leading-in device. The electrospray ion leading-in device comprises a micro-injection pump, a connecting tube, a metal thin tube, a high-voltage power supply, a conductive metal wire, a quartz capillary tube and a vacuum system sampling nozzle. Continuous and stable sample solution with controlled flow is provided by the device through the micro-injection pump; voltage is provided by the combination of the high-voltage power supply, the metal thin tube and the conductive metal wire; and the ion source leading-in efficiency is improved by the sunken type vacuum system sampling nozzle. By the electrospray ion leading-in device, continuous and stable sample injection can be realized, an excellent desolvation effect is achieved, and the electrospray ion source strength can be improved obviously.
Description
Technical field
The present invention relates to a kind of electron spray ion introducing device, under the condition of continuous sample introduction, significantly can strengthen electric spray ion source intensity, belong to analytical chemistry mass spectral analysis field.
Background technology
Mass spectral analysis is a kind of analytical method with high sensitivity and high selectivity, is widely used in the fields such as isotope analysis, Analysis of Organic Substances and elementary analysis.Mass spectrometer forms primarily of ion introducing device, mass analyzer, detector and vacuum system.
Technology of ion source is the important support of mass-spectrometric technique, and Main Function makes analyzed sample be transformed into ion, by these ion focusing bunchys, and gives certain energy, make it fly to mass analyzer.Conventional ion source has electron impact ion source, chemical ionization source, matrix assisted laser desorption ionization ion source and electric spray ion source etc.
Electric spray ion source is the ionization techniques under a kind of normal pressure, and its special feature is to make analyte ions while the high polarity non-volatile compounds solution of introducing, belongs to Soft ionization techniques.From 1984, since Fenn etc. develop the first electron spray ion introducing device truly, electron spray ion introducing device was widely used in non-covalent interaction and solvated ion architectural study, and large biological molecule is analyzed and the field such as Pharmaceutical Analysis.
The general principle of electron spray ion introducing device is: when positive ion mode (needle point adds positive voltage), the anion in sample solution can be assembled to fog-spray nozzle, and cation moves formation taylor cone to opposite vacuum system sampling mouth.At taylor cone top, because charge density height is not enough to be maintained liquid to surface tension, charged drop will penetrate from fog-spray nozzle, moves under electric field action to vacuum system sampling mouth direction.In drop moving process, solvent can evaporate, and when its charge density and radius reach Rayleigh stability line, can divide because of coulomb repulsion effect.Repeatedly after division, the drop that radius is enough little directly can become gaseous ion and enter mass analyzer by vacuum system sampling mouth.
Existing electron spray ion introducing device mainly contains two types: the first uses the stainless steel capillary of the electric current that adds high pressure as fog-spray nozzle, and use micro-injection pump sampling solution.The advantage of this device to realize continous-stable sample introduction, but because the restriction of Stainless Steel Capillary pipe processing technique, fog-spray nozzle internal diameter is difficult to reach less than 250 microns.Therefore, the droplet size that this device fog-spray nozzle produces is comparatively large, and desolvation effect is undesirable.The second is using quartz capillary as fog-spray nozzle, and quartz capillary working properties is excellent, is easy to realize less than 100 microns internal diameters, and tool ductility makes spray outlet bore reduce further, and the droplet size that such fog-spray nozzle produces is little, is beneficial to desolvation.But because quartz capillary itself is non-conductive, needs to add wire wherein to provide high-tension current, because quartz capillary internal volume is less, so sample introduction can only continue 10 to 25 minutes usually, be difficult to the experiment demand meeting long-time continuous sample introduction.
The formal of mouth is sampled in vacuum system, the sampling mouth circular cone overall convex of conventional vacuum system sampling mouth samples front panel for vacuum system, and sampling mouth conical bottom plane is in vacuum system sampling front panel institute in the plane, although such design can reduce difficulty of processing, be unfavorable for that the raising of efficiency introduced by ion source.
Summary of the invention
The present invention is directed to the deficiency of existing electron spray ion introducing device, proposition one is reasonable in design, structure simple, can realize continous-stable sample introduction and the electron spray ion of tool excellent desolvation effect introducing technical scheme.
The object of this invention is to provide a kind of reasonable in design, structure simple, can realize continous-stable sample introduction and the electron spray ion introducing device of the excellent desolvation effect of tool.
The object of the invention is to adopt following technical scheme to realize: it is made up of syringe pump part, high voltage supply part, sprayhead portion, vacuum system sampling mouth and connecting line.Syringe pump part provides the sample solution of steady and continuous, flow controllable precise, and solution arrives sprayhead portion through high voltage supply part and deviates from, and enters mass analyzer after desolvation through vacuum system sampling mouth.
The present invention realizes particular by following technical scheme:
A kind of electron spray ion introducing device, it comprises micro-injection pump (Syringe Pump), tube connector, metal thin tube, conductive wire, quartz capillary, vacuum system sampling mouth (Skimmer).It is characterized in that:
Micro-injection pump discharge is connected with metal thin tube one end by pipeline, the metal thin tube other end is connected with quartz capillary one end by pipeline simultaneously, the quartz capillary other end and vacuum system sample mouth and are coaxially oppositely arranged, high voltage source is connected with metal thin tube by plain conductor, be connected with conductive wire at metal thin tube near one end inwall of quartz capillary, conductive wire stretches to quartz capillary inside;
In above-mentioned electron spray ion introducing device, high voltage source is connected with metal thin tube by plain conductor, conductive wire is connected with near one end inwall of quartz capillary at metal thin tube, high voltage source provides voltage for metal thin tube and conductive wire, and high voltage source, metal thin tube and conductive wire form high voltage supply part jointly;
In above-mentioned electron spray ion introducing device, described micro-injection pump refers to the flowing injection device with the controlled fluid supply capacity of continous-stable, flow;
In above-mentioned electron spray ion introducing device, the length of described metal thin tube can be 1 centimetre ~ 10 centimetres, and internal diameter can be 0.5 millimeter ~ 3 millimeters, and wall thickness can be 0.05 millimeter ~ 2 millimeters;
In above-mentioned electron spray ion introducing device, the length of described conductive wire can be 1 centimetre ~ 15 centimetres, and external diameter can be 0.1 millimeter ~ 0.5 millimeter;
In above-mentioned electron spray ion introducing device, the length of described quartz capillary can be 1 centimetre ~ 10 centimetres, and internal diameter can be 0.1 millimeter ~ 3 millimeters, and wall thickness can be 0.25 millimeter ~ 1 millimeter;
In above-mentioned electron spray ion introducing device, the power supply voltage range of high voltage source is-5000 volt ~+5000 volts;
In above-mentioned electron spray ion introducing device, within the conductive wire being connected to metal thin tube inwall extends into quartz capillary, the length entering quartz capillary interior section is 1 centimetre ~ 10 centimetres;
In above-mentioned electron spray ion introducing device, vacuum system sampling mouth is the conical structure of lower hollow, offer cone-shaped hole in cone tip along the axis of circular cone to circular cone bottom surface, make the female cone of formation through hole and form sample that the outer cone of mouth entity is coaxial, summit and bottom surface overlap; Sampling front panel in vacuum system is provided with groove, sampling mouth is placed in groove, and sampling mouth cone tip is in vacuum system sampling front panel institute in the plane, namely whole sampling mouth circular cone is sinking state on vacuum system sampling front panel, vacuum system sampling front panel thickness range is 2 millimeters ~ 5 millimeters, in sampling mouth cone, cone angle is 60 degree ~ 140 degree, and the bore scope of sampling mouth cone tip place manhole is 0.1 millimeter ~ 1 millimeter;
In above-mentioned electron spray ion introducing device, as preferably, metal thin tube can adopt stainless steel capillary, and conductive wire can adopt metal filamentary silver;
In above-mentioned electron spray ion introducing device, as preferably, stretch processing can be done in quartz capillary one end, to reduce nozzle bore further to can be 0.025 millimeter ~ 0.1 millimeter;
In above-mentioned electron spray ion introducing device, as preferably, vacuum system sampling mouth adopts stainless steel material;
Electron spray ion introducing device provided by the present invention can with existing mass spectrometer with the use of;
Electron spray ion introducing device provided by the present invention has following beneficial effect:
By adding the combination of metal thin tube and conductive wire, making high voltage supply part can provide a passage passed through for sample solution, and the connection with micro-injection pump can be realized thus, thus realize stablizing dynamic electron spray ion introducing effect;
By changing vacuum system sampling mouth shape, improve ion transmission efficiency, adding the intensity that ion source is introduced;
The present invention takes full advantage of the advantage of existing two kinds of electron spray ion introducing devices, overcomes corresponding shortcoming, provide a kind of reasonable in design, structure simple, can realize continous-stable sample introduction and the electron spray ion introducing device of the excellent desolvation effect of tool.
Accompanying drawing explanation
Fig. 1 is the structural representation of the electron spray ion introducing device of the embodiment of the present invention 1;
Fig. 2 is the structural representation of the vacuum system sampling mouth of the embodiment of the present invention 1;
Fig. 3 is the ion signal intensity time variation diagram that the electron spray ion introducing device of the embodiment of the present invention 1 produces;
Fig. 4 is that the vacuum system of the routine of the embodiment of the present invention 2 samples mouth and vacuum system used in the present invention samples the comparison diagram of mouth in ion signal intensity;
Fig. 5 is the result figure that the embodiment of the present invention 3 sulfuric acid carries out Mass Spectrometer Method;
In figure, each mark is as follows: 1 micro-injection pump, 2 polytetrafluoroethylene tube connectors, 3 stainless steel capillaries, 4 conduction filamentary silvers, 5 quartz capillaries, 6 nozzles, 7 plain conductors, 8 high voltage sourcies, 9 vacuum system sampling mouth, 10 picoammeters, 11 level Four bar mass spectrums.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described further, but the present invention is not limited to following examples.
Embodiment 1, electron spray ion introducing device
The electron spray ion introducing device that the present embodiment provides comprises micro-injection pump 1, stainless steel capillary 3, quartz capillary 5, vacuum system sampling mouth 9; Micro-injection pump 1 is connected with stainless steel capillary 3 one end by teflon tube, the other end of stainless steel capillary 3 is connected by teflon tube one end with quartz capillary 5 simultaneously, and the other end of quartz capillary 5 and vacuum system sample mouth 9 and be coaxially oppositely arranged; High voltage source 8 is connected to stainless steel capillary 3 medium position by plain conductor; The stainless steel capillary 3 used is circular straighttube, and length is 3.5 centimetres, and internal diameter is 0.7 millimeter, and external diameter is 0.4 millimeter; The length of conduction filamentary silver 4 is 7.5 centimetres, and external diameter is 0.2 millimeter; Conduction filamentary silver 4 is fixed in the inwall of stainless steel metal pipe 3 one end by the mode of welding and extends to inner 5 centimetres of quartz capillary 5; The quartz capillary 5 used is circular straighttube, and length is 7.5 centimetres, and internal diameter is 0.8 millimeter, and external diameter is 0.35 millimeter; One end of quartz capillary draws out nozzle 6, and it is trapezoidal along axle longitudinal cross-section, and bore is 0.025 millimeter; Vacuum system sampling front panel thickness is 3 millimeters, and in cone, angle of taper is 126 degree, and sampling mouth cone tip place manhole bore is 0.5 millimeter;
The sample introduction velocity interval of the micro-injection pump 1 that above-mentioned electron spray ion introducing device uses is 5 mul/min ~ 10 mul/min, the power supply voltage range of high voltage source 8 is+1100 volt ~+1300 volts, nozzle 6 and vacuum system sample mouth 9 and are oppositely arranged, between distance be 2 millimeters ~ 5 millimeters.
During analytic sample, first add to be increased by high voltage source 8 and be pressed on stainless steel capillary 3; After voltage stabilization, sample solution is flowed out by micro-injection pump 1 and arrives vacuum system after spraying and becoming ion sample mouth 9 through stainless steel capillary 3, quartz capillary 5 self-spray mouth 6, use picoammeter 10 to measure ion signal intensity at vacuum system sampling mouth 9 rear, ion finally enters the detection that mass spectrometer 11 realizes sample.
By using picoammeter 10 pairs of ion signal intensity to monitor continuously, obtain ion signal intensity time variations result as shown in Figure 3, can find out, the electric spray ion source of continous-stable can be obtained by embodiment 1.
Embodiment 2, conventional vacuum system sampling mouth and vacuum system used in the present invention sample mouth ion signal intensity contrast and test
The object of the present embodiment the vacuum system of routine sampling mouth and vacuum system used in the present invention is sampled mouth 9 carry out the experiment of ion signal intensity contrast, and the experimental provision used is as described in the embodiment of the present invention 1; Replace vacuum system used in the present invention sampling mouth 9 with the vacuum system sampling mouth of routine and carry out control experiment, and the unique difference not being both the present embodiment experimental example and reference examples of vacuum system sampling mouth.
The present embodiment has carried out two groups of contrast tests, conventional vacuum system sampling mouth experimental result be in A and B(A cone angle be 105 degree, in B cone angle be 114 degree), vacuum system sampling mouth experimental result used in the present invention be in C and D(C cone angle be 74 degree, in D cone angle be 126 degree)
Experimental result as shown in Figure 4, can be seen, vacuum system sampling mouth used in the present invention is 2 ~ 3 times that conventional vacuum system samples mouth ion signal intensity.
Embodiment 3, utilizes the electron spray ion introducing device of embodiment 1 to carry out Mass Spectrometer Method to sulfuric acid
The electron spray ion introducing device of embodiment 1 is utilized to be combined sulfuric acid to 0.0001 mol/L water and the acetonitrile of 1:4 (solvent to be volume ratio be) with level Four bar mass spectrometer, the sample introduction velocity interval of micro-injection pump 1 is 8 mul/min, voltage+1600 volt of high voltage source 8, nozzle 6 and vacuum system sample mouth 9 and are oppositely arranged, between distance for being 3 millimeters, the mass spectrogram of mensuration is as shown in Figure 5;
As seen from Figure 5, experiment obtains the mass spectrogram can seeing bisulfate ion hydrated ion and sulfate radical hydrated ion cluster mass signal peak clearly, illustrate that a kind of electron spray ion introducing device provided by the invention can realize continous-stable sample introduction, there is again excellent desolvation effect simultaneously, can significantly strengthen electric spray ion source intensity.
Claims (10)
1. an electron spray ion introducing device, is characterized in that: described ion introducing device comprises micro-injection pump (Syringe Pump), tube connector, metal thin tube, high voltage source, conductive wire, quartz capillary, vacuum system sampling mouth (Skimmer);
Micro-injection pump discharge is connected with metal thin tube one end by pipeline, the metal thin tube other end is connected with quartz capillary one end by pipeline simultaneously, the quartz capillary other end and vacuum system sample mouth and are coaxially oppositely arranged, high voltage source is connected with metal thin tube by plain conductor, be connected with conductive wire at metal thin tube near one end inwall of quartz capillary, conductive wire stretches to quartz capillary inside.
2. electron spray ion introducing device according to claim 1, is characterized in that: described micro-injection pump refers to the flowing injection device with the controlled fluid supply capacity of continous-stable, flow.
3. electron spray ion introducing device according to claim 1, is characterized in that: high voltage source provides voltage for metal thin tube and conductive wire, and high voltage source, metal thin tube and conductive wire form high voltage supply part jointly.
4., according to described electron spray ion introducing device arbitrary in claim 1 ~ 2, it is characterized in that: the length of described metal thin tube can be 1 centimetre ~ 10 centimetres, and internal diameter can be 0.5 millimeter ~ 3 millimeters, and wall thickness can be 0.05 millimeter ~ 2 millimeters.
5., according to described electron spray ion introducing device arbitrary in claim 1 ~ 2, it is characterized in that: the length of described conductive wire can be 1 centimetre ~ 15 centimetres, and external diameter can be 0.1 millimeter ~ 0.5 millimeter.
6., according to described electron spray ion introducing device arbitrary in claim 1 ~ 2, it is characterized in that: the length of described quartz capillary can be 1 centimetre ~ 10 centimetres, and internal diameter can be 0.1 millimeter ~ 3 millimeters, and wall thickness can be 0.25 millimeter ~ 1 millimeter.
7., according to described electron spray ion introducing device arbitrary in claim 1 ~ 2, it is characterized in that: the power supply voltage range of high voltage source is-5000 volt ~+5000 volts.
8. according to described electron spray ion introducing device arbitrary in claim 1 ~ 2, it is characterized in that: within the conductive wire being connected to metal thin tube inwall extends into quartz capillary, the length entering quartz capillary interior section is 1 centimetre ~ 10 centimetres.
9. electron spray ion introducing device according to claim 1, it is characterized in that: vacuum system sampling mouth is the conical structure of lower hollow, offer cone-shaped hole in cone tip along the axis of circular cone to circular cone bottom surface, make the female cone of formation through hole and form sample that the outer cone of mouth entity is coaxial, summit and bottom surface overlap; Sampling front panel in vacuum system is provided with groove, and sampling mouth is placed in groove, and sampling mouth cone tip is in vacuum system sampling front panel institute in the plane, and namely whole sampling mouth circular cone samples on front panel in sinking state in vacuum system.
10. electron spray ion introducing device according to claim 9, it is characterized in that: vacuum system sampling front panel thickness range is 2 millimeters ~ 5 millimeters, in sampling mouth cone, cone angle is 60 degree ~ 140 degree, and the bore scope of sampling mouth cone tip place manhole is 0.1 millimeter ~ 1 millimeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310558287.5A CN104637774A (en) | 2013-11-08 | 2013-11-08 | Electrospray ion leading-in device |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310558287.5A CN104637774A (en) | 2013-11-08 | 2013-11-08 | Electrospray ion leading-in device |
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| CN104637774A true CN104637774A (en) | 2015-05-20 |
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| CN201310558287.5A Pending CN104637774A (en) | 2013-11-08 | 2013-11-08 | Electrospray ion leading-in device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106683973A (en) * | 2017-01-17 | 2017-05-17 | 中国科学技术大学 | Electrospray ionization source device and system for mass spectrometers |
| CN110085504A (en) * | 2019-05-09 | 2019-08-02 | 合肥工业大学 | A kind of ion source system and miniaturization mass spectrograph based on aperture in-situ sampling interface |
| CN110603440A (en) * | 2017-05-31 | 2019-12-20 | 株式会社岛津制作所 | Sample plate for PESI ion source and mass spectrometer using same |
| CN112106170A (en) * | 2018-05-16 | 2020-12-18 | 英国质谱公司 | Impact ionization spray ion source or electrospray ionization ion source |
| CN112595562A (en) * | 2020-12-11 | 2021-04-02 | 中国科学院工程热物理研究所 | Mass spectrum homothermal in-situ sampling interface capable of being flexibly arranged and mass spectrum homothermal in-situ sampling method |
-
2013
- 2013-11-08 CN CN201310558287.5A patent/CN104637774A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106683973A (en) * | 2017-01-17 | 2017-05-17 | 中国科学技术大学 | Electrospray ionization source device and system for mass spectrometers |
| CN110603440A (en) * | 2017-05-31 | 2019-12-20 | 株式会社岛津制作所 | Sample plate for PESI ion source and mass spectrometer using same |
| CN110603440B (en) * | 2017-05-31 | 2022-03-29 | 株式会社岛津制作所 | Sample plate for probe electrospray ionization ion source |
| CN112106170A (en) * | 2018-05-16 | 2020-12-18 | 英国质谱公司 | Impact ionization spray ion source or electrospray ionization ion source |
| CN110085504A (en) * | 2019-05-09 | 2019-08-02 | 合肥工业大学 | A kind of ion source system and miniaturization mass spectrograph based on aperture in-situ sampling interface |
| CN110085504B (en) * | 2019-05-09 | 2022-02-11 | 合肥工业大学 | Ion source system based on small-hole in-situ sampling interface and miniaturized mass spectrometer |
| CN112595562A (en) * | 2020-12-11 | 2021-04-02 | 中国科学院工程热物理研究所 | Mass spectrum homothermal in-situ sampling interface capable of being flexibly arranged and mass spectrum homothermal in-situ sampling method |
| CN112595562B (en) * | 2020-12-11 | 2022-12-06 | 中国科学院工程热物理研究所 | Mass spectrum homothermal in-situ sampling interface capable of being flexibly arranged and mass spectrum homothermal in-situ sampling method |
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Application publication date: 20150520 |