CN101464427A - Open type atomizing field desorption ionization method and apparatus thereof - Google Patents
Open type atomizing field desorption ionization method and apparatus thereof Download PDFInfo
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- CN101464427A CN101464427A CNA2007103036490A CN200710303649A CN101464427A CN 101464427 A CN101464427 A CN 101464427A CN A2007103036490 A CNA2007103036490 A CN A2007103036490A CN 200710303649 A CN200710303649 A CN 200710303649A CN 101464427 A CN101464427 A CN 101464427A
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Abstract
The invention provides an open type spray field desorption and ionization method and an ionization device. The process of ionization comprises the following steps: a sample-containing assistant solution forms sample-containing spray drops in an open environment without the action of an electric field, or a sample is attached to an object carrier, and spray drops free of the sample absorb the sample on the object carrier and form a sample-containing spray; the two sample-containing spray drops enter an extra ionized electric field; and the sample is ionized under the action of the electric field. Due to the unique electrode design, the distribution of the ionized electric field has the function of ion focusing. By adopting the sample introduction method of attaching the sample to the object carrier, the sample can be analyzed in the original environment, and the analysis only requires a small amount of the sample. By adopting an independent electrode structure, the ionization device can ensure that the influence of a spray nozzle and a collection cone on the ionized electric field is reduced, so that an ion source is capable of working independently and is compatible with a common mass spectrometer.
Description
Technical field
The ionization that the present invention relates to (ionization) method and ionization apparatus (ion gun) are applied to the mass spectrophotometry field, belong to the correlation technique of the mass spectrometer that uses under the open environment.This ioning method also can promote the use of other ionization analysis field.
Background technology
Traditional ioning method may be summarized to be electron impact ionization method (EI), chemi-ionization ioning method (CI), field desorption ioning method (FD/FI), fast atom bombardment ionization method (FAB) etc.Traditional ionization techniques requires sample is introduced high vacuum system, device and complicated operation, causes problems such as ion gun and analyzer pollution easily.In addition, these ioning methods are because the energy transfer process fierceness, in ionization process, have destroy the biomacromolecule structure may and be not suitable for research field such as life science.
Last century late nineteen eighties, the Tanaka of fragrant grace (J.B.Fenn) of the J.B. of the U.S. and Japan ploughs electron spray ionisation method (ESI) and the substance assistant laser desorpted ioning method (MALDI) that first-class people develops respectively, makes that protein and other is carried out mass spectrophotometry becomes possibility.
At present, atmospheric pressure ionization method (API) comprises that Atmosphere Pressure Chemical Ionization (APCI) method (APCI), electron spray ionisation method (ESI) and substance assistant laser desorpted ioning method (MALDI) are the most widely used ioning methods in mass spectrophotometry field.Wherein, atmospheric pressure ionization methods such as ESI can under atmospheric pressure realize ionization, but because ionization process needs factors such as corona discharge, high pressure, ion gun still needs the structural design of sealing.
Electron spray ionisation method (ESI) makes between nozzle and the mass spectrometer vacuum interface and forms electrostatic field applying voltage on the nozzle, sample solution forms spraying from the nozzle ejection, the general way of auxiliary gas that adopts realizes spraying, also has the nanoscale of use kapillary directly to form spraying (nano-ESI).Typical electric field intensity is 3 * 10 during electric spray ion source work
4About V/m, correspondingly the voltage that applies on the nozzle is also higher, is generally 3～5kV.In addition, improve ionization effect (desolventizing process), be generally operational under the hot conditions in order to slough solvent molecule.
Substance assistant laser desorpted ioning method (MALDI) is to shine by the potpourri (crystal or solid solution) of high power laser to sample and matrix under vacuum condition, separates the ionization method of sucking-off sample ions.This ioning method needs vacuum condition and powerful laser, also needs to select suitable matrix, and sample molecule dissolved in is prepared into relatively more complicated pre-treatment such as uniform solid solution in the matrix, these condition restriction the application of this method.
It is under vacuum condition that the field causes drop ioning method (FIDI), and in high-intensity electric field, the ionization under electric field action of single drop produces the method for ion.Its electric field intensity is 10
6The V/m magnitude, the particle diameter of drop is 10
2μ m magnitude.Because ioning method needs vacuum condition, so need the structural design of sealing.
Realize down that in open environment (Ambient Environment) Ionized mass-spectrometric technique has become the international forward position in mass-spectrometry field.This novel ionization techniques uses the ion source structure of open type, does not need the vacuum work condition, need not the complicated sample pre-treatment, analyzes under the primal environment of sample, helps using in the miniaturization of mass spectrometer and the lowered in field environment.This technology is with a wide range of applications at medicine, country and numerous areas such as public safety, court's medical science, commodity inspection and customs inspection.
U.S. R.G.Cooks professor research group in 2004 and NEC (U.S.) company in 2005 develop desorption electrospray technology (Desorption Electrospray Ionization respectively, DESI) and in real time directly analytical technology (Direct Analysis onReal Time, DART) ion gun.The ion gun of these two ionization techniques is the structural design of open type, has avoided complicated pre-treatment process.
Directly the key of analytical technology (DART) is to use metastable state gas and sample molecule effect to produce ion in real time, and the generation of metastable state gas needs a plurality of enclosed cavity structures and complicated electrode structure, needs helium or nitrogen during use.Adopt the DART ion gun to be more suitable for being used for low polar molecule, and sensitivity is not as good as the DESI ion gun.
Desorption electrospray ionization method (DESI) is distinguished and is that sample need not to be dissolved in the secondary solvent by electro-spray ionization method development, but places on the support board under the open environment.Make between nozzle and the mass spectrometer vacuum interface and form electrostatic field applying voltage on the nozzle, adopting the way of assisting gas at first to make solvent produce gaseous ion or form charged spray droplet under the electron spray effect sprays from nozzle, and spray to the sample that places on the support board, realize the ionization of sample molecule by drop seizure and charge exchanging process.Typical electric field intensity was 3 * 10 when but similar to ESI was the work of DESI method
4About V/m, the voltage that applies on nozzle reaches 3～5kV.
Desorption electrospray ionization device (DESI) has been realized the structural design of open type, but the subject matter that exists is: 1. Ionization Efficiency has much room for improvement, and properties of samples is bigger to the Ionization Efficiency influence.2. the ion transfer system haves much room for improvement, and does not possess the ion focus function.3. ionization apparatus has strict restriction to the size of support board, and the ionization effect is comparatively responsive to spray angle, and normal ionization need be strict with spray angle.
The ioning method that the present invention relates to be referred to as spray field desorption ionization method (Spray Field DesorptionIonization, SFDI).This ion gun is the structural design of open type, belongs in open environment (Ambient Environment) to realize Ionized ionization method down, can realize the analyzing and testing of dissimilar samples under condition of normal pressure.
Summary of the invention
The objective of the invention is to propose a kind of open type atomizing field desorption ioning method and ionization apparatus, this method improves the ion collecting efficiency, do not need the vacuum work condition, need not the complicated sample pre-treatment, can under condition of normal pressure, realize the analyzing and testing of dissimilar samples, satisfy the demand of using in the lowered in field environment; This ionization apparatus is realized miniaturization and is helped compatible existing mass analyzer.
Technical scheme of the present invention is as follows:
A kind of spray field desorption ionization method of open type is characterized in that this method carries out as follows:
1) contains the auxiliary liquid of sample, at open environment and do not have under the situation of electric field action, form the spray droplet that contains sample by spraying; Or sample invested on the object carrier, the auxiliary liquid of solvent that does not contain sample at open environment and do not have under the situation of electric field action, forms the spray droplet that does not contain sample by spraying, this spray droplet is adsorbed in the sample on the object carrier wherein, forms the spray droplet that contains sample;
2) under open environment, the spray droplet that contains sample enters in the ionized electric field; Under this effect of electric field, described spray droplet polarizes, and forms charged drop; This charged drop to gathering coning motion, forms sample ions under the effect of ionized electric field.
Ionized electric field of the present invention adopts the electric field with ion focus effect, and this ionized electric field intensity is 10
4V/m～10
5Between the V/m.
The present invention also provides a kind of open type atomizing field desorption ionization apparatus of implementing said method, it is characterized in that: this device comprises nozzle and is arranged in the electrode structure of gathering awl the place ahead, and described electrode structure is by ionising electrode and be arranged in the auxiliary electrode of gathering between awl and the ionising electrode and form; Auxiliary electrode comprises one or more middle auxiliary electrodes and interface auxiliary electrode, described ionising electrode is made up of a plurality of parallel plate electrodes, one section circular arc is arranged on each plate electrode, and the plate electrode circular arc is towards the same side, and these circular arcs are approximate to be on the space sphere; Auxiliary electrode and interface auxiliary electrode are towards gathering the circular thin plate electrode that awl direction internal diameter reduces successively in the middle of described.
Technical characterictic of the present invention also is: described ionising electrode has a side of circular arc to gathering awl, and the centre of sphere of described space sphere is on the axis of gathering awl; Middle auxiliary electrode and interface auxiliary electrode vertically are installed on ionising electrode and gather between the awl, the plane at middle auxiliary electrode and interface auxiliary electrode place is parallel with the bottom surface of gathering awl, and the axis of collection awl and the intersection point on plane, interface auxiliary electrode place are positioned at the scope of interface auxiliary electrode circle.
The invention provides the method that a kind of formation has the ionized electric field of ion focus effect, it is characterized in that: the voltage that puts on ionising electrode, middle auxiliary electrode and the interface auxiliary electrode reduces successively, forms to have the ionized electric field of ion focus effect.Electric field intensity between ionising electrode and middle auxiliary electrode is at least 10
4V/m, and the electromotive force on the interface auxiliary electrode is higher than the electromotive force of gathering on the awl.
The present invention compares with existing ioning method and device thereof, has the following advantages and effect: 1. sample invests the method on the object carrier, can analyze it under the primal environment of sample, and amount of samples is few.2. take the mode of extra electric field, this ionized electric field by the Electric Field Distribution of uniqueness, can realize effect, the raising ionization effect of ion focus except having Ionized effect.3. the design of ion gun electrode structure has reduced nozzle and has gathered the influence of awl to ionized electric field, ion gun can be worked alone, compatible common mass analyzer.4. compare with desorption electrospray ion gun (DESI), the object carrier method that the present invention relates to is not strict with spray angle.This ionization apparatus requires lower to supply voltage, normal electrical is from only needing about 1kV.
Description of drawings
Fig. 1 is the synoptic diagram of open type atomizing field desorption ioning method.
Fig. 2 is to use the synoptic diagram of the open type atomizing field desorption ioning method of object carrier.
Fig. 3 is the structural representation of open type atomizing field desorption ionization apparatus.
Fig. 4 is to use the structural representation of the open type atomizing field desorption ionization apparatus of object carrier.
Fig. 5 is the structural drawing of ionising electrode 2.Figure a is ionising electrode 2 integrally-built front views, and figure b is ionising electrode 2 integrally-built side views, and figure c is the attached view of a plate electrode.
Fig. 6 is the circuit diagram that a kind of formation has the ionized electric field of ion focus effect.
Fig. 7 is the blend sample mass spectrogram that open type atomizing field desorption ionization apparatus obtains under the positive ion detecting pattern.
Fig. 8 is the blend sample mass spectrogram that open type atomizing field desorption ionization apparatus obtains under the negative ion detecting pattern.
Contained compound and content thereof in the table 1 blend sample solution.
The 1-nozzle; The 2-ionising electrode; Auxiliary electrode in the middle of the 3-; 4-interface auxiliary electrode; 5-gathers awl; 6-does not contain the auxiliary liquid spray droplet of solvent of sample; 7-contains the auxiliary liquid spray droplet of sample; The 8-charged drop; The 9-sample; The 10-object carrier; The 11-ionized electric field.
Embodiment
Below in conjunction with accompanying drawing concrete structure of the present invention, principle and the course of work are further described:
Fig. 1 is the synoptic diagram of open type atomizing field desorption ioning method.
Ionization process is as follows:
1) contains the auxiliary liquid of sample, at open environment and do not have under the situation of electric field action, form the spray droplet 7 that contains sample, can realize spraying by auxiliary gas or other method by spraying;
2) under open environment, the spray droplet 7 that contains sample enters in the ionized electric field 11; Under this effect of electric field, described spray droplet polarizes, and forms charged drop 8, and this charged drop to gathering awl 5 motions, forms sample ions under the effect of ionized electric field.
Fig. 2 is to use the synoptic diagram of the open type atomizing field desorption ioning method of object carrier.
Ionization process is as follows:
1) sample 9 is invested object carrier 10, the auxiliary liquid of solvent that does not contain sample, at open environment and do not have under the situation of electric field action, form the spray droplet 6 that does not contain sample by auxiliary gas or other spray method, this spray droplet is adsorbed in the sample on the object carrier wherein, forms the spray droplet that contains sample;
2) under open environment, the spray droplet 7 that contains sample enters in the ionized electric field 11; Under this effect of electric field, described spray droplet polarizes, and forms charged drop 8; This charged drop to gathering awl 5 motions, forms sample ions under the effect of ionized electric field.
Fig. 3 is the structural representation of open type atomizing field desorption ionization apparatus, this device comprises nozzle 1 and is arranged in the electrode structure of gathering awl the place ahead, and described electrode structure is by ionising electrode 2 and be arranged in the auxiliary electrode of gathering between awl 5 and the ionising electrode 2 and form; Auxiliary electrode comprises one or more middle auxiliary electrodes 3 and interface auxiliary electrode 4, described ionising electrode 2 is made up of a plurality of parallel plate electrodes, one section circular arc is arranged on each plate electrode, and the plate electrode circular arc is towards the same side, and these circular arcs are approximate to be on the space sphere; Auxiliary electrode 3 and interface auxiliary electrode 4 are towards gathering the circular thin plate electrode that awl direction internal diameter reduces successively in the middle of described.
Fig. 4 is to use the structural representation of the open type atomizing field desorption ionization apparatus of object carrier.This device nozzle 1 is identical with Fig. 3 with electrode structure.Object carrier is arranged in the top of nozzle below, electrode structure.The object carrier that the present invention relates to can be latticed thin layer.Object carrier has certain viscosity, sample can be adsorbed on it, owing to be latticed, spraying can be passed through smoothly.
Fig. 5 is the structural drawing of ionising electrode 2.Figure a is ionising electrode 2 integrally-built front views, and figure b is ionising electrode 2 integrally-built side views, and figure c is the vertical view of a plate electrode.Ionising electrode 2 is made up of a plurality of plate electrodes, and the circular arc that has a segment length not wait on each plate electrode, plate electrode circular arc are towards a side, and after the parallel aggregate erection of spacing that equates, these circular arcs are approximate to be on the space sphere.
Fig. 6 is a kind of synoptic diagram of feasible ion gun circuit.By this circuit, the voltage that applies on ionising electrode 2 and auxiliary electrode reduces successively, forms to have the ionized electric field of ion focus effect, is at least 10 in the electric field intensity of 3 of ionising electrode 2 and middle auxiliary electrodes
4V/m, and the electromotive force on the interface auxiliary electrode 4 is higher than the electromotive force of gathering on the awl 5.
The composition and the content of blend sample are as shown in table 1, with sample dissolution in spraying secondary solvent methyl alcohol: in the system of water=80:20.The auxiliary flow velocity of spraying: 20 μ l/min; Gas flow rate: 2.0L/min.Under positive ion and negative ion detecting pattern, obtain the mass spectrum result of this blend sample respectively, as shown in Figure 7 and Figure 8.
Contained compound and content thereof in the table 1 blend sample solution
| Title | Molecular weight | Concentration (ng/ μ l) | Ionization mode |
| Quercetin | 302 | 15 | — |
| Kaempferol | 286 | 10 | — |
| Terramycin | 460 | 26 | + |
| Quadracycline | 444 | 15 | + |
| |
354 | 22 | |
| N-acetyl junket aa | 223 | 20 | +/— |
| Fangchinoline | 608 | 20 | + |
| Caffeic acid | 180 | 24 | — |
| Legalon | 482 | 22 | — |
| Baicalein | 270 | 11 | — |
| Cyanidenon | 286 | 18 | — |
Claims (6)
1. the spray field desorption ionization method of an open type is characterized in that this method carries out as follows:
1) contains the auxiliary liquid of sample, at open environment and do not have under the situation of electric field action, form the spray droplet (7) that contains sample by spraying; Or sample (9) invested on the object carrier (10), the auxiliary liquid of solvent that does not contain sample, at open environment and do not have under the situation of electric field action, form the spray droplet (6) that does not contain sample by spraying, this spray droplet is adsorbed in the sample on the object carrier wherein, forms the spray droplet (7) that contains sample;
2) under open environment, the spray droplet (7) that contains sample enters in the ionized electric field (11); Under this effect of electric field, described spray droplet polarizes, and forms charged drop (8); This charged drop to gathering awl (5) motion, forms sample ions under the effect of ionized electric field.
2. according to the described open type atomizing field desorption of claim 1 ioning method, it is characterized in that: described ionized electric field (11) adopts the electric field with ion focus effect, and this electric field intensity is 10
4V/m～10
5Between the V/m.
3. implement the open type atomizing field desorption ionization apparatus of method according to claim 1, it is characterized in that: this device comprises nozzle (1) and is arranged in the electrode structure of gathering awl the place ahead, and described electrode structure is by ionising electrode (2) and be arranged in the auxiliary electrode of gathering between awl (5) and the ionising electrode (2) and form; Auxiliary electrode comprises one or more middle auxiliary electrodes (3) and interface auxiliary electrode (4), described ionising electrode (2) is made up of a plurality of parallel plate electrodes, one section circular arc is arranged on each plate electrode, the plate electrode circular arc is towards the same side, and these circular arcs are approximate to be on the space sphere; Auxiliary electrode (3) and interface auxiliary electrode (4) are towards gathering the circular thin plate electrode that awl direction internal diameter reduces successively in the middle of described.
4. according to the described open type atomizing field desorption of claim 3 ionization apparatus, it is characterized in that: ionising electrode (2) has a side of circular arc to gathering awl, and the centre of sphere of described space sphere is on the axis of gathering awl; Middle auxiliary electrode (3) and interface auxiliary electrode (4) vertically are installed on ionising electrode (2) and gather between the awl (5), the plane at middle auxiliary electrode and interface auxiliary electrode place is parallel with the bottom surface of gathering awl, and the axis of collection awl and the intersection point on plane, interface auxiliary electrode place are positioned at the scope of interface auxiliary electrode circle.
5. adopt the method that forms ionized electric field as open type atomizing field desorption ionization apparatus as described in the claim 3 with ion focus effect, it is characterized in that: the voltage that puts on ionising electrode (2), middle auxiliary electrode (3) and the interface auxiliary electrode (4) reduces successively, forms to have the ionized electric field of ion focus effect.
6. it is characterized in that in accordance with the method for claim 5: the electric field intensity between ionising electrode (2) and middle auxiliary electrode (3) is at least 10
4V/m, and the electromotive force on the interface auxiliary electrode (4) is higher than the electromotive force of gathering on the awl (5).
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