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CN103972019B - Contactless DC induction electrospray ionization device and ioning method - Google Patents

Contactless DC induction electrospray ionization device and ioning method Download PDF

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CN103972019B
CN103972019B CN201410198671.3A CN201410198671A CN103972019B CN 103972019 B CN103972019 B CN 103972019B CN 201410198671 A CN201410198671 A CN 201410198671A CN 103972019 B CN103972019 B CN 103972019B
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shower nozzle
nanoliter electrospray
nanoliter
electrospray
cantilever
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CN103972019A (en
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张新荣
魏振威
张四纯
郭成安
李艳艳
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Tsinghua University
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Tsinghua University
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Abstract

The invention discloses a kind of contactless DC induction electrospray ionization device and ioning method.It comprises electrode, high-voltage DC power supply and Nanoliter electrospray shower nozzle.On the same line, shower nozzle is between electrode and mass spectrum injection port for the axis of Nanoliter electrospray shower nozzle and long straight conductor electrode.Eletrode tip excites the electric field line of lower generation to converge through after conical liquid dielectric at high voltage, is exaggerated the most advanced and sophisticated electric field strength of shower nozzle greatly, makes testing liquid generation electro-spray ionization.The present invention can solve current Nanoliter electrospray for several problem receiving upgrading very product direct ion, cannot can be used in Nanoliter electrospray array analysis simultaneously.Structure of the present invention is simple, convenient manufacture, only need to carry out simple and mechanical improvement on traditional Nanoliter electrospray ion source basis just can realize, convenient and existing commercialization mass spectrometer coupling uses, practical, and solve in many traditional Nanoliter electrosprays and have problems, have a wide range of applications and economic worth.

Description

Contactless DC induction electrospray ionization device and ioning method
Technical field
The present invention relates to a kind of electrospray ionization mass spectrum ionization apparatus and ioning method, be specifically related to a kind of contactless DC induction electrospray ionization device and ioning method.
Background technology
Organic Mass Spectrometry be a kind of in life science field widely used can realize qualitative, quantitatively and the analytical method of structural analysis.Electro-spray ionization (ESI) and laser assisted desorption ionisation (MALDI) are two kinds of development of organic mass spectrometers typical case and widely used Ionization mode the most.Classical ESI ionization process is as described below.Sample solution enters via one section, capillary, and the acting in conjunction being subject to strong electric field and sheath gas from other a section forms charged aerosol.Aerosol raises gradually through solvent evaporates process charge density and coulomb blast occurs, and finally makes determinand molecule generation ionization in solution.Nanoliter electrospray ionization (NSI) method developed subsequently, owing to further reducing the internal diameter of capillary spout, ionization can be realized with not using on the basis of sheath gas in lower spray voltage, and remolding sensitivity traditional E SI is higher, become now widely used ioning method in biological test analysis.
When carrying out NSI and analyzing, because sample solution is all inner at quartz ampoule, so need an electrode to be deep into quartz ampoule inside, comes in contact with solution to be measured, the generation of electron spray can be ensured.But the electric Contacts existed in NSI, but limit the use of electrospray techniques: 1, electrode contacts with spray solution and electrochemical reaction occurs, and has an impact for mensuration; When 2, measuring the small volumes of liquids received and rise even skin upgrading, electrical contact is very difficult; 3, NSI is utilized to carry out array analysis very difficult; 4, the flux of NSI analysis is lower.Therefore, for new analysis demand, the simple and practical contactless Nanoliter electrospray ion source of urgently exploitation one at present, and conveniently direct and commercialization mass spectrum coupling uses.
Summary of the invention
The object of this invention is to provide a kind of contactless DC induction electrospray ionization device and ioning method, the invention provides ionization apparatus, and ioning method operating aspect, be easy to and existing commercial organic mass spectrometry coupling.
The present invention provide firstly a kind of contactless direct current induction Nanoliter electrospray ionization apparatus, it comprises a four-dimensional mobile platform, the chunk I that described four-dimensional mobile platform comprises a three-dimensional mobile platform I and is connected with the workbench of described three-dimensional mobile platform I, described chunk I is connected with chunk II, described chunk I connects a swing handle, and it is that axle center rotates with y-axis that described swing handle controls described chunk II; The upper surface of described chunk II connects a cantilever I, described cantilever I can rotate in xy plane;
One or two pass joint is fixed in the upper surface of described cantilever I; One end of wire is connected with electrode through after described two pass joints;
Nanoliter electrospray shower nozzle is fixed on one end of described two pass joints, and described electrode stretches to the inside of described Nanoliter electrospray shower nozzle, and and be provided with spacing between the point of described Nanoliter electrospray shower nozzle;
The internal diameter of the point of described Nanoliter electrospray shower nozzle is 1 ~ 2 μm.
Nanoliter electrospray ionization apparatus provided by the invention, in use, the solution to be measured that electrode and Nanoliter electrospray shower nozzle are introduced does not occur directly to contact, and can arrange the spacing of 0.3 ~ 1cm between the two.
In Nanoliter electrospray ionization apparatus provided by the invention, the xy plane of indication refers to the plane parallel with cantilever I, axis parallel with mass spectrometer when y-axis refers to sample introduction, axis vertical with mass spectrometer when x-axis refers to sample introduction.
In above-mentioned Nanoliter electrospray ionization apparatus, described Nanoliter electrospray shower nozzle can be drawn by quartz or borosilicate glass tube and obtain;
Described Nanoliter electrospray shower nozzle comprises columniform straight-tube portion and conical point.
Present invention also offers one utilizes above-mentioned contactless direct current induction Nanoliter electrospray ionization apparatus to carry out Ionized method, comprises the steps:
(1) solution to be measured is introduced in the point of Nanoliter electrospray shower nozzle described in described contactless direct current induction Nanoliter electrospray ionization apparatus;
(2) by described four-dimensional mobile platform, regulate and control the position of described cantilever I, make described Nanoliter electrospray shower nozzle and mass spectrometric injection port be positioned on straight line;
(3) apply high-voltage dc voltage by wire to described electrode, make described solution generation electron spray to be measured, namely realize the ionization to described solution to be measured.
In method provided by the invention, the solution to be measured introduced of Nanoliter electrospray shower nozzle with do not occur between electrode directly to contact, and the spacing of 0.3 ~ 1cm can be set between the two.
In above-mentioned method, by described Nanoliter electrospray shower nozzle is soaked in 10 ~ 15s in described solution to be measured, described solution to be measured can be introduced the point of described Nanoliter electrospray shower nozzle.
In above-mentioned method, the distance between the point controlling described electrode and described Nanoliter electrospray shower nozzle can be 0.3 ~ 1cm;
Distance between the point of described Nanoliter electrospray shower nozzle and described mass spectrometric injection port can be 0.3 ~ 1.5cm;
Described high-voltage dc voltage can be 1.0kV ~ 2.0kV.
Present invention also offers a kind of contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis, it comprises a four-dimensional mobile platform, the chunk I that described four-dimensional mobile platform comprises a three-dimensional mobile platform I and is connected with the workbench of described three-dimensional mobile platform I, described chunk I is connected with chunk II, described chunk I connects a swing handle, and it is that axle center rotates with y-axis that described swing handle controls described chunk II; The upper surface of described chunk II connects a cantilever I, described cantilever I can rotate in xy plane;
One or two pass joint is fixed in the upper surface of described cantilever I; One end of wire is connected with electrode through after described two pass joints;
Described electro-spray ionization device also comprises a three-dimensional mobile platform II, the workbench of described three-dimensional mobile platform II is connected with a cantilever II, described cantilever II is provided with the through hole of several array arrangements, be provided with a Nanoliter electrospray shower nozzle in each described through hole, and the point of described Nanoliter electrospray shower nozzle is located at outside described cantilever II;
The internal diameter of the point of described Nanoliter electrospray shower nozzle is 1 ~ 2 μm.
Nanoliter electrospray ionization apparatus provided by the invention, in use, the solution to be measured that electrode and Nanoliter electrospray shower nozzle are introduced does not occur directly to contact, and can arrange the spacing of 0.3 ~ 1cm between the two.
In above-mentioned Nanoliter electrospray ionization apparatus, described Nanoliter electrospray shower nozzle is drawn by quartz or borosilicate glass tube and obtains;
Described Nanoliter electrospray shower nozzle comprises columniform straight-tube portion and conical point.
Invention further provides and utilize the above-mentioned contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis to carry out Ionized method, comprise the steps:
(1) the contactless direct current being used for array analysis described in solution introducing to be measured is responded in the point of Nanoliter electrospray shower nozzle described in Nanoliter electrospray ionization apparatus;
(2) described Nanoliter electrospray shower nozzle is inserted in the described through hole of array arrangement on described cantilever II, and make the point of described Nanoliter electrospray shower nozzle be positioned at outside described cantilever II, the other end of described Nanoliter electrospray shower nozzle and an end face of described cantilever II;
(3) by described four-dimensional mobile platform and described three-dimensional mobile platform II, regulate and control the position of described cantilever I and described cantilever II, make described electrode, described Nanoliter electrospray shower nozzle and mass spectrometric injection port be positioned on straight line;
(4) apply high-voltage dc voltage by wire to described electrode, make described solution generation electron spray to be measured, namely realize the ionization to the solution described to be measured in a described Nanoliter electrospray shower nozzle;
(5) by described three-dimensional mobile platform II, regulate and control the position of described cantilever II, make each described Nanoliter electrospray shower nozzle of described electrode, array arrangement and mass spectrometric injection port be positioned on straight line successively, thus realize the ionization of the solution described to be measured of pair array arrangement.
In method provided by the invention, the solution to be measured introduced of Nanoliter electrospray shower nozzle with do not occur between electrode directly to contact, and the spacing of 0.3 ~ 1cm can be set between the two.
In above-mentioned method, by the described Nanoliter electrospray shower nozzle being used for array analysis is soaked in 10 ~ 15s in described solution to be measured, described solution to be measured can be introduced the point of described Nanoliter electrospray shower nozzle; After described electrode inserts from shower nozzle afterbody, suitably can regulate the distance between eletrode tip and testing liquid, in order to ensure good electron spray effect, eletrode tip and testing liquid distance should be less than 1cm.
In above-mentioned method, the distance between the point controlling described electrode and described Nanoliter electrospray shower nozzle is 0.8 ~ 1cm;
Distance between the point of described Nanoliter electrospray shower nozzle and described mass spectrometric injection port is 0.3 ~ 1.5cm;
Described high-voltage dc voltage is 4.0kV ~ 7.0kV.
The present invention, owing to adopting above technical scheme, has the following advantages:
1, the geometric properties of testing liquid taper in Nanoliter electrospray shower nozzle, the DC electric field line focus excited by remote electrode, makes electric field strength greatly amplify, and is enough to make testing liquid generation electron spray under testing liquid and the discontiguous situation of electrode;
2, avoid the interference of electrode for electron spray, solving Nanoliter electrospray cannot for the problem of small samples direct ion.Combine with the method utilizing capillarity testing liquid to be introduced Nanoliter electrospray shower nozzle of original creation, can with not utilizing gel loading to adding too much liquid in shower nozzle, both facilitate the operation of Nanoliter electrospray, in turn save amount of samples, can for 1 ~ 2nL testing liquid direct ion;
3, not contacting the feature causing electron spray makes method of the present invention have great advantage in Nanoliter electrospray array analysis, substantially increases the detection flux that Nanoliter electrospray is analyzed.
Contactless direct current induction Nanoliter electrospray ionization apparatus provided by the invention, structure is simple, convenient manufacture, only needs to carry out simple and mechanical improvement on traditional Nanoliter electrospray ion source basis and just can obtain, convenient and existing commercialization mass spectrometer coupling uses, practical; And Problems existing in many traditional Nanoliter electrosprays can be solved, have a wide range of applications and economic worth.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the present invention's contactless direct current induction Nanoliter electrospray ionization apparatus.
Fig. 2 is the schematic diagram of the present invention for the contactless direct current induction Nanoliter electrospray ionization apparatus of array analysis.
Fig. 3 is the schematic diagram utilizing microscope to demarcate the liquid volume in capillarity inhalation spray head.
Fig. 4 utilizes apparatus of the present invention for the mass spectrogram of the several frequently seen analyte analyzation of 1.3nL.
Fig. 5 be utilize apparatus of the present invention for Angiotensin II 2 × 2 jet array analyze total ion current figure and mass spectrogram.
In Fig. 1 and Fig. 2, each mark is as follows:
1 three-dimensional mobile platform I, 2 chunk I, 3 chunk II, 4 swing handle, 5 cantilever, I, 6 liang of pass joints, 7 electrodes, 8 high voltage sourcies, 9 Nanoliter electrospray shower nozzles, 10 mass spectrum injection ports, 11 three-dimensional mobile platform II, 12 cantilevers II.
Embodiment
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, contactless direct current induction Nanoliter electrospray ionization apparatus
As shown in Figure 1, contactless direct current induction Nanoliter electrospray ionization apparatus provided by the invention, it comprises a four-dimensional mobile platform, the chunk I 2 that this four-dimensional mobile platform comprises a three-dimensional mobile platform I 1 and is connected with the workbench of this three-dimensional mobile platform I 1, chunk I 2 is connected with chunk II 3, and chunk I 2 connects a swing handle 4, it is that axle center rotates with y-axis that this swing handle 4 can control chunk II 3.The upper surface of chunk II 3 connects a cantilever I 5, and this cantilever I 5 can rotate in xy plane, and it is made up of polytetrafluoroethylene.Two pass joints 6 are fixed in the upper surface of cantilever I 5; One end of wire is connected with electrode 7 through after two pass joints 6, and wire is connected with high voltage source 8.Wherein, Nanoliter electrospray shower nozzle 9 is fixed on one end of two pass joints 6, and electrode 7 stretches to the inside of Nanoliter electrospray shower nozzle 9, and and is provided with spacing between the point of Nanoliter electrospray shower nozzle 9.In the present invention, Nanoliter electrospray shower nozzle 9 comprises columniform straight-tube portion and conical point, and as shown in Figure 3, the internal diameter of its conical point is 1 ~ 2 μm; And it can be obtained by quartz or borosilicate glass tube drawing.
Utilize contactless direct current induction Nanoliter electrospray ionization apparatus shown in Fig. 1, carry out the analysis of direct current induction Nanoliter electrospray for single small samples, process is as follows:
Four-dimensional mobile platform in this device is fixed on and is connected on an optical flat of mass spectrometer.During experiment, (external diameter of cylindrical straight tube portion is 1mm to get Nanoliter electrospray shower nozzle 9, the internal diameter of conical tip portion is 2 μm), Nanoliter electrospray shower nozzle 9 is immersed in solution example to be measured, and leave standstill 10s, 1.3nL testing liquid can be sucked in Nanoliter electrospray shower nozzle 9 (as shown in Figure 3, for the amount of liquid of inhalation spray head observed under the microscope, be similar to and think that shower nozzle tip is for conical, utilizing circular cone volume computing formula to calculate result for liquid volume in shower nozzle is 1.27nL).After solution stowage, (the cylindrical straight tube portion) of electrode 7 from Nanoliter electrospray shower nozzle 9 is inserted, regulate electrode 7 tip to be about 0.5cm with the distance of the conical tip of Nanoliter electrospray shower nozzle 9, Nanoliter electrospray shower nozzle 9 fixed by the joint screwing two pass joints 6.Regulate x, y, z, θ xyfour-dimensional mobile platform makes the tip of Nanoliter electrospray shower nozzle 9 and the distance of mass spectrum injection port 10 be 0.5cm, opens high-voltage DC power supply 8, regulation voltage 1.0kV ~ 2.0kV, can make testing liquid electro-spray ionization in Nanoliter electrospray shower nozzle 9.
In order to verify the versatility of apparatus of the present invention, selecting the testing liquid that four kinds are representative, utilizing apparatus of the present invention to test, test sample specifying information is as follows:
Caffeine, molecular weight is 194.19, No. CAS is 58-08-2, and concentration of standard solution is 10ppm;
Angiotensin II, molecular weight is 1046.18, No. CAS is 4474-91-3, and solution concentration is 10ppm;
Synthetically grown chalone, molecular weight is 1637.88, No. CAS is 38916-34-6, and solution concentration is 10ppm;
Cromoci, molecular weight is about 12000, and No. CAS is 9007-43-6, and solution concentration is 100ppm.
Above four kinds of standard liquids comprise polarity organic micromolecule compound, peptide class and protein, are the samples that electron spray analysis is often analyzed, this example just with these four kinds of samples for the versatility of described technology is tested in representative.
Fig. 4 is the mass spectrogram utilizing direct current of the present invention to respond to Nanoliter electrospray analysis 1.3nL tetra-kinds of standard liquids, as can be seen from the figure, all analytes can both by ionization well, in mass spectrogram, demonstrate very strong signal, suffice to show that described technology has good versatility and analytical performance.
Embodiment 2, contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis
As shown in Figure 2, contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis provided by the invention, it comprises a four-dimensional mobile platform, the chunk I 2 that this four-dimensional mobile platform comprises three-dimensional mobile platform I 1 and is connected with the workbench of this three-dimensional mobile platform I 1, chunk I 2 is connected with chunk II 3, and chunk I 2 connects a swing handle 4, it is that axle center rotates with y-axis that this swing handle 4 can control chunk II 3.The upper surface of chunk II 3 connects a cantilever I 5, and this cantilever I 5 can rotate in xy plane, and it is made up of polytetrafluoroethylene.Two pass joints 6 are fixed in the upper surface of cantilever I 5; One end of wire is connected with electrode 7 through after two pass joints 6, and wire is connected with high voltage source 8.The present embodiment electro-spray ionization device also comprises a three-dimensional mobile platform II 11, the workbench of this three-dimensional mobile platform II 11 is connected with a cantilever II 12, this cantilever II 12 is provided with the through hole of multiple array arrangement, be provided with a Nanoliter electrospray shower nozzle 9 in each through hole, and the point of this Nanoliter electrospray shower nozzle 9 is located at outside cantilever II 12.In the present invention, Nanoliter electrospray shower nozzle 9 comprises columniform straight-tube portion and conical point, and as shown in Figure 3, the internal diameter of its conical point is 1 ~ 2 μm; And it can be obtained by quartz or borosilicate glass tube drawing.
Utilize the contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis shown in Fig. 2, analyze for Nanoliter electrospray jet array, process is as follows:
Four-dimensional mobile platform in this device and three-dimensional mobile platform II 11 are fixed on and are connected on an optical flat of mass spectrometer.When carrying out Nanoliter electrospray array analysis, first the cantilever II 12 of three-dimensional mobile platform II 11 is unloaded, the Nanoliter electrospray shower nozzle 11 having loaded liquid is inserted in the through hole that cantilever II 12 is accomplished fluently, during insertion, the afterbody (cylindrical straight tube portion) of Nanoliter electrospray shower nozzle 9 is inserted from the front end of cantilever II 12, the unnecessary afterbody utilizing ceramic cutter Nanoliter electrospray shower nozzle 9 to be stretched out cantilever II 12 after adjusting intubating length is clipped, then is fixed in three-dimensional mobile platform II 11 by cantilever II 12.Adjusting three-dimensional mobile platform II 11 afterwards makes cantilever II 12 be in the distance (the distance between two tips injection port 10 about 0.5cm of Nanoliter electrospray shower nozzle 9) suitable with mass spectrum injection port 10.Regulate three-dimensional mobile platform II 11 in x, z direction, the Nanoliter electrospray shower nozzle 9 needing preliminary sweep is alignd with mass spectrum injection port 10.Adjust four-dimensional mobile platform afterwards, make electrode 7 just to mass spectrum injection port 10.Mass spectrum record is opened after ready, open high voltage source 8, regulation voltage is 4.0kV ~ 6.0kV, three-dimensional mobile platform II 9 in the displacement of x direction, until sweep to last need measure shower nozzle after, regulate three-dimensional mobile platform II 11 in the displacement of z direction, second layer shower nozzle is between electrode 7 and mass spectrum injection port 10, then regulates three-dimensional mobile platform II 11 in x direction, complete the scanning of second layer jet array, by that analogy, until complete the scanning of all shower nozzles.
In order to said method is described, this example is chosen the simplest 2 × 2 jet array and is described.Selected standard liquid is the Angiotensin II solution of 10ppm, and its molecular weight is 1046.18, No. CAS is 4474-91-3.
As shown in Figure 5, move in x, z-plane with even speed moving three dimension mobile platform II 9, mass spectrum total ion current figure detects successively 4 spikes, respectively the corresponding ion being fixed on four shower nozzles on array.By average respectively for four peaks on mass spectrum total ion current figure, obtain the mass spectrogram of four different shower nozzles, can find out that the double charge peak of determinand Angiotensin II is that the base peak of mass spectrogram and intensity are very high, prove that the method can carry out ionization for Nanoliter electrospray jet array well.
Special declaration: the various embodiments described above are only for illustration of the present invention; wherein the structure, connected mode etc. of each parts all can change to some extent; every equivalents of carrying out on the basis of technical solution of the present invention and improvement, all should not get rid of outside protection scope of the present invention.

Claims (10)

1. a contactless direct current induction Nanoliter electrospray ionization apparatus, is characterized in that:
Described electro-spray ionization device comprises a four-dimensional mobile platform, the chunk I that described four-dimensional mobile platform comprises a three-dimensional mobile platform I and is connected with the workbench of described three-dimensional mobile platform I, described chunk I is connected with chunk II, described chunk I connects a swing handle, and it is that axle center rotates with y-axis that described swing handle controls described chunk II; The upper surface of described chunk II connects a cantilever I, described cantilever I can rotate in xy plane;
One or two pass joint is fixed in the upper surface of described cantilever I; One end of wire is connected with electrode through after described two pass joints;
Nanoliter electrospray shower nozzle is fixed on one end of described two pass joints, and described electrode stretches to the inside of described Nanoliter electrospray shower nozzle, and and be provided with spacing between the point of described Nanoliter electrospray shower nozzle, described spacing is 0.3 ~ 1cm;
The internal diameter of the point of described Nanoliter electrospray shower nozzle is 1 ~ 2 μm.
2. Nanoliter electrospray ionization apparatus according to claim 1, is characterized in that: described Nanoliter electrospray shower nozzle is drawn by quartz or borosilicate glass tube and obtains;
Described Nanoliter electrospray shower nozzle comprises columniform straight-tube portion and conical point.
3. the contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis, it is characterized in that: described electro-spray ionization device comprises a four-dimensional mobile platform, the chunk I that described four-dimensional mobile platform comprises a three-dimensional mobile platform I and is connected with the workbench of described three-dimensional mobile platform I, described chunk I is connected with chunk II, described chunk I connects a swing handle, and it is that axle center rotates with y-axis that described swing handle controls described chunk II; The upper surface of described chunk II connects a cantilever I, described cantilever I can rotate in xy plane;
One or two pass joint is fixed in the upper surface of described cantilever I; One end of wire is connected with electrode through after described two pass joints;
Described electro-spray ionization device also comprises a three-dimensional mobile platform II, the workbench of described three-dimensional mobile platform II is connected with a cantilever II, described cantilever II is provided with the through hole of several array arrangements, be provided with a Nanoliter electrospray shower nozzle in each described through hole, and the point of described Nanoliter electrospray shower nozzle is located at outside described cantilever II;
The internal diameter of the point of described Nanoliter electrospray shower nozzle is 1 ~ 2 μm;
Distance between the point of described electrode and described Nanoliter electrospray shower nozzle is 0.8 ~ 1cm.
4. Nanoliter electrospray ionization apparatus according to claim 3, is characterized in that: described Nanoliter electrospray shower nozzle is drawn by quartz or borosilicate glass tube and obtains;
Described Nanoliter electrospray shower nozzle comprises columniform straight-tube portion and conical point.
5. utilize contactless direct current induction Nanoliter electrospray ionization apparatus described in claim 1 or 2 to carry out Ionized method, comprise the steps:
(1) solution to be measured is introduced in the point of Nanoliter electrospray shower nozzle described in described contactless direct current induction Nanoliter electrospray ionization apparatus;
(2) by described four-dimensional mobile platform, regulate and control the position of described cantilever I, make described Nanoliter electrospray shower nozzle and mass spectrometric injection port be positioned on straight line;
(3) apply high-voltage dc voltage by wire to described electrode, make described solution generation electron spray to be measured, namely realize the ionization to described solution to be measured.
6. method according to claim 5, is characterized in that: by described Nanoliter electrospray shower nozzle is soaked in 10 ~ 15s in described solution to be measured, described solution to be measured can be introduced the point of described Nanoliter electrospray shower nozzle.
7. the method according to claim 5 or 6, is characterized in that: the distance between the point controlling described electrode and described Nanoliter electrospray shower nozzle is 0.3 ~ 1cm;
Distance between the point of described Nanoliter electrospray shower nozzle and described mass spectrometric injection port is 0.3 ~ 1.5cm;
Described high-voltage dc voltage is 1.0kV ~ 2.0kV.
8. utilize the contactless direct current induction Nanoliter electrospray ionization apparatus for array analysis described in claim 3 or 4 to carry out Ionized method, comprise the steps:
(1) the contactless direct current being used for array analysis described in solution introducing to be measured is responded in the point of Nanoliter electrospray shower nozzle described in Nanoliter electrospray ionization apparatus;
(2) described Nanoliter electrospray shower nozzle is inserted in the described through hole of array arrangement on described cantilever II, and make the point of described Nanoliter electrospray shower nozzle be positioned at outside described cantilever II, the other end of described Nanoliter electrospray shower nozzle and an end face of described cantilever II;
(3) by described four-dimensional mobile platform and described three-dimensional mobile platform II, regulate and control the position of described cantilever I and described cantilever II, make described electrode, described Nanoliter electrospray shower nozzle and mass spectrometric injection port be positioned on straight line;
(4) apply high-voltage dc voltage by wire to described electrode, make described solution generation electron spray to be measured, namely realize the ionization to the solution described to be measured in a described Nanoliter electrospray shower nozzle;
(5) by described three-dimensional mobile platform II, regulate and control the position of described cantilever II, make each described Nanoliter electrospray shower nozzle of described electrode, array arrangement and mass spectrometric injection port be positioned on straight line successively, thus realize the ionization of the solution described to be measured of pair array arrangement.
9. method according to claim 8, is characterized in that: by the described Nanoliter electrospray shower nozzle being used for array analysis is soaked in 10 ~ 15s in described solution to be measured, described solution to be measured can be introduced the point of described Nanoliter electrospray shower nozzle.
10. method according to claim 8 or claim 9, is characterized in that: the distance between the point controlling described electrode and described Nanoliter electrospray shower nozzle is 0.8 ~ 1cm;
Distance between the point of described Nanoliter electrospray shower nozzle and described mass spectrometric injection port is 0.3 ~ 1.5cm;
Described high-voltage dc voltage is 4.0kV ~ 7.0kV.
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