CN102315074A

CN102315074A - Rotary electric spraying free device, mass spectrometer and mass spectrometric analysis method

Info

Publication number: CN102315074A
Application number: CN2010102182735A
Authority: CN
Inventors: 谢建台
Original assignee: 谢建台
Current assignee: National Sun Yat-sen University
Priority date: 2010-06-29
Filing date: 2010-06-29
Publication date: 2012-01-11
Anticipated expiration: 2030-06-29
Also published as: CN102315074B

Abstract

The invention relates to a rotary electric spraying free device, which comprises a rotating mechanism and at least one spray nozzle, wherein the rotating mechanism can rotate around a center axis, the spray nozzles are arranged on the rotating mechanism in a way of being separated from the center axis, the spray nozzles can rotate around a rotating center for forming a sealed moving trace so that the spray nozzles can simultaneously spray electric spraying liquid drips when rotating along the moving trace. The invention also provides a mass spectrometer and a mass spectrometric analysis method. The spray nozzles spray the electric spraying liquid drips in a way of rotating along the moving trace so that each electrically sprayed charged particle (liquid drip) is uniformly distributed in the spray space, the mutually repelled space charge effect of the charged particles is overcome, the number and the proportion of most mini charged particle streams formed by electric spraying entering a mass analyzer inlet in the mass spectrometer are increased, the ion signal stability and the intensity can be improved, and the sensitivity of the spectrometric analysis can also be effectively improved.

Description

Rotary electric sprays free device, mass spectrometer, and mass spectrometric analysis method

Technical field

The present invention relates to a kind of EFI and spill free (electrospray ionization; ESI) device; Particularly relate to rotary electric sprinkling free (rotating electrospray ionization, RESI) device that a kind of EFI pivotably spills drop to be analyzed (aerosol droplets).The present invention also includes the mass spectrometer (mass spectrometer) that this rotary electric sprays free device relevant for one, and a mass spectrometric analysis method.

Background technology

By analytical technique of mass spectrum; People can be known the molecular weight of determinand in the sample (analytes); Then cooperated further contrast and confirmed the true status of this determinand, therefore since development early in the twentieth century, in order to implement the mass spectrometer of this analytical technique of mass spectrum; Because have easy and simple to handle and can obtain to detect result's advantage fast, become the Identification Tools used of each field widely already.

General mass spectrometer mainly comprises free device, mass analyzer (mass analyzer), and detector three big parts such as (detector).Each determinand in the sample is that freeization by free device obtains electric charge; And can be directed in this mass analyzer also according to its m/z value (just " charge-mass ratio " separately; Wherein m is a quality; Z is a chemical valence) and separated to come by the classification district, mass analyzer will discharge corresponding signal according to this and supply this detector acquisition simultaneously, at last comprehensive each signal of this detector; And present a series of statisticses with the collection of illustrative plates mode, can also further cooperate the software running and calculate the molecular weight of these determinands.

Spill free method and spill free device via an EFI with the EFI that produces gas molecule in space ion (molecular ions), suitable molecular substance is extensive, is the technology that a utmost point has development potentiality.It is earlier the determinand in the sample to be extracted and obtain a solution to be measured that EFI spills free method, as shown in Figure 1ly comprises the mass spectrometer 1 that an EFI spills free device 11 and carries out mass spectral analysis by one.Correlation technique can be consulted following paper: Yamashita, M.and Fenn, J.B.J.Phys.Chem.1984; 88,4451, Fenn, J.B.et al.Science 1989; 246,64., Fenn, J.B.et al.Mass Spectrom.Rev.1990; 9,37.

Traditional EFI spills free device 11 and includes an openend 111 and spill entry needle (electrospray needle) 112 towards the EFI of the inlet 121 of this mass analyzer 12; And generally be to set up an electric field when using, for example form the voltage difference of 2～5kV between the two at this at this entry needle openend 111 and 121 of this mass analyzer inlets.Then; Solution to be measured is flowed towards this openend 111 in this entry needle 112, can be at the solution of this openend 111 because of the traction and the capillary effect of liquid level of electric field, and form one be abound with electric charge taylor cone (Taylor cone) T; When electric field action power can overcome the surface tension of liquid; The drop that has the multivalence electric charge and include the determinand molecule will be formed, and sprays towards this mass analyzer 12, gets into these mass analyzers 12 to analyze by this inlet 121 then.

The liquid of these charged drops partly can evaporate along with running into the air-flow (for example N2) that adds in-flight, and this moment, the multivalence electric charge can be passed on the determinand molecule, and became the measured ion of treating with low m/z value.This method not only can let like the big molecule of protein free by expeditiously, and because of can the low m/z value of tool more not receiving the restriction of these mass analyzer 12 detecting limits, so even can record molecular weight and reach 100,000 protein molecule.

Spill at EFI aspect the improvement and research and development of free device: as shown in Figure 2; Be one to be disclosed in U.S. Patent number US6 by people such as Hindsgaul, 350,617 and US6; 621; In 075, the EFI that includes a rotating disk 113 spills free device 11, is a plurality of EFIs to be spilt entry needle 112 be arranged on this rotating disk 113; When each entry needle 112 being brought to an ad-hoc location in order by this rotating disk 113; The drop that is sprayed out just can get into corresponding to the mass analyzer of this ad-hoc location inlet 121, and each entry needle 112 is according to the rotary speed of rotating disk 113, and carrying out the time (dwelltime) that EFI spills at this ad-hoc location in turn is 0.5～10 second (sec); And each entry needle 112 is linked to the chromatography pipe (chromatography column) 114 that a sample solution injects respectively, so ability continous way ground spills free device 11 via this EFI and this mass analyzer 12 carries out the analysis of different sample solutions; As shown in Figure 3; U.S. Patent number US6; 066,848 a disclosed EFI spills free device 11 and includes an EFI and spill entry needle array (electrospray needle array), the drop that each entry needle 112 is sprayed out; Be arranged at the movable masking device (blocking device) 13 that this EFI spills 12 of free device 11 and mass analyzers via one; When the penetration hole (aperture) 131 on this masking device 13 moves to position corresponding with it in turn, just can get into this mass analyzer inlet 121, also can carry out to continous way the analysis of different sample solutions through this hole 131.

Yet all at present EFIs spill free device, comprise two above-mentioned background technologies; It all is to be fixed on the position or to treat to move in regular turn individually on the specified point and spill to carry out EFI that its single or a plurality of EFI spills entry needle; Spill the EFI that entry needle produces by EFI and spill ion, can be because of electrical identical relation, and mutually exclusive; So that cluster ion can produce the phenomenon toward outdiffusion, this just so-called space charge (space charge) effect.Owing to the position of mass analyzer inlet is fixed, the interior EFI of magnitude range that therefore has only part to be distributed in this mass analyzer inlet spills ion and could get in it, and is detected by mass analyzer, thereby has reduced the intensity and stability of detection signal.

Can know that by above-mentioned explanation above-mentioned existing EFI spills the product structure that is free in device and uses, and obviously still has inconvenience and defective, and demands urgently further improving.Spill the influence of free program if can further overcome space charge effect in EFI, will help to promote the development of industry in level and the field of the present invention of analysis of molecules technology.Therefore how to found a kind of new rotary electric and spray free device, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.

Summary of the invention

Main purpose of the present invention is; Overcome existing EFI and spill the defective that free device exists; And provide a kind of new mass spectrometric rotary electric that is used for to spray free device; Nozzle of the present invention is to follow a motion track pivotably to spray EFI and spill drop, makes each charged particle in spraying the space, evenly distribute and can overcome the space charge effect that charged particle repels each other, and the most small charged particle that makes EFI spill formation flows into the number and ratio increase of the mass analyzer inlet in the mass spectrometer; And cooperate with this detector and to carry out mass spectral analysis, be very suitable for practicality.

The object of the invention and solve its technical problem and adopt following technical scheme to realize.A kind of rotary electric that proposes according to the present invention sprays free device; Be used for a mass spectrometer, this mass spectrometer comprises a mass analyzer with an inlet, and a detector; This mass analyzer can receive charged particle stream, and cooperates with this detector and to carry out mass spectral analysis; This EFI spills free device and comprises: a rotating mechanism, and can be around a central axis rotation; And at least one nozzle; This nozzle is to be installed at intervals on this rotating mechanism with this central axis; And can be driven and round a pivot rotation by this rotating mechanism, and form the motion track of an enclosed shape, and make an EFI spill that fluid power is enough to be gone out from this nozzles spray; When this mass analyzer when analyzing; This nozzle is driven by this rotating mechanism and rotation synchronously; And follow this motion track and spray this electricity flushing liquor continuously; By between this nozzle and this mass analyzer, set up a potential difference, and make this electricity flushing liquor form most charged particle streams, and move towards the inlet of this mass analyzer along charge ion transfer path.

The object of the invention and solve its technical problem and also can adopt following technical measures further to realize.

Aforesaid rotary electric sprays free device; With a vertical plane perpendicular to described central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of described mass analyzer, overlap at least.

Aforesaid rotary electric sprays free device; Wherein said rotating mechanism have a power source, at least one by rotating shaft that this power source drove, at least one is installed on the pivoted arm in this rotating shaft; And one be installed in the turntable on this pivoted arm at intervals with this rotating shaft; And this turntable is around this central axis rotation, and this nozzle is to be installed at intervals on this turntable with this central axis.

Aforesaid rotary electric sprays free device; Wherein said rotating mechanism has two and is provided with separately and by rotating shaft that this power source drove; And two pivoted arms that are installed on respectively in this two rotating shaft, this turntable is to be installed on this two pivoted arm across ground, and forms the identical distance distance with this two rotating shaft; The power source of this rotating mechanism has a motor; And one driven and drive the acceleration group that this rotating shaft is rotated by this motor, and this acceleration group has one and driven the high gears that this two rotating shaft is rotated respectively by low-speed gear that this motor drove, two, and a tooth sector that is engaged between this two high gear; Forming the engagement order of this low-speed gear, one of them high gear, this tooth sector, another high gear, and the number of teeth of this low-speed gear is the number of teeth more than this two high gear.

Aforesaid rotary electric sprays free device; Wherein said turntable has one and is installed in the body on this two pivoted arm across ground; And t-joint that is installed on this body; This t-joint has first end that is connected in this nozzle, one and uses for this EFI and spill second end that flow is gone into; And one in order to setting up the 3rd end of this potential difference, and each pivoted arm of this rotating mechanism all has one and is installed on the rotating part in the corresponding rotating shaft of institute, the adjusting lever of this rotating part that stretched through, and reaches the sliding seat of an ability along this adjusting lever running fix; And the distance between this sliding seat and rotating shaft can be adjusted, the body of this turntable then is to be installed on the sliding seat of this two pivoted arm across ground.

Aforesaid rotary electric sprays free device; Wherein said rotary electric sprays free device and comprises most nozzles; Be first end that is communicated in this t-joint simultaneously, and each nozzle all is round the rotation of this pivot, and forms the motion track of enclosed shape; With a vertical plane perpendicular to this central axis; The motion track of each nozzle is along this central axis projection formed track region on this vertical plane, can with inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

The object of the invention and solve its technical problem and also adopt following technical scheme to realize.A kind of mass spectrometer according to the present invention's proposition; Comprise a mass analyzer; And a detector, this mass analyzer has an inlet, is used for receiving and analyzing charged particle stream; This detector is to be used to detect the signal that charged particle stream produced through this mass analyzer analysis, and produces a mass spectral analysis figure; Described mass spectrometer also comprises a rotary electric and sprays free device, and this rotary electric sprays free device and has the rotating mechanism of an ability around central axis rotation; And at least one nozzle; This nozzle is to be installed at intervals on this rotating mechanism with this central axis; And can be driven and round pivot rotation by this rotating mechanism, and form the motion track of an enclosed shape, and make an EFI spill that fluid power is enough to be gone out from this nozzles spray; When this mass analyzer when analyzing; This nozzle is to be rotated that mechanism drives and rotation synchronously; And follow this motion track and spray this electricity flushing liquor continuously; Set up a potential difference by between this nozzle and mass analyzer, and make this electricity flushing liquor form most charged particle streams, and spray electric charge transfer path along one and move towards the feeder connection of this mass analyzer.

Aforesaid mass spectrometer; With a vertical plane perpendicular to this central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

Aforesaid mass spectrometer; The rotating mechanism that described rotary electric sprays free device have a power source, at least one by rotating shaft that this power source drove, at least one is installed on the pivoted arm in this rotating shaft; And one be installed in the turntable on this pivoted arm at intervals with this rotating shaft; And this turntable is around this central axis rotation, and this nozzle is to be installed at intervals on this turntable with this central axis.

Aforesaid mass spectrometer; Described rotating mechanism has two and is provided with separately and by rotating shaft that this power source drove; And two pivoted arms that are installed on respectively in this two rotating shaft, this turntable is to be installed on this two pivoted arm across ground, and forms the identical distance distance with this two rotating shaft; The power source of this rotating mechanism has a motor; And one driven by this motor and drive the acceleration group that this rotating shaft is rotated, and this acceleration group has one and driven the high gears that this two rotating shaft is rotated and a tooth sector that is engaged between this two high gear respectively by low-speed gear that this motor drove, two; Forming the engagement order of this low-speed gear, one of them high gear, this tooth sector, another high gear, and the number of teeth of this low-speed gear is the number of teeth more than this two high gear.

Aforesaid mass spectrometer; Described turntable has one and is installed in the body on this two pivoted arm across ground; And t-joint that is installed on this body; This t-joint has first end that is connected in this nozzle, one and uses for this EFI and spill second end that flow is gone into; And one in order to setting up the 3rd end of this potential difference, and each pivoted arm of this rotating mechanism all has one and is installed on the rotating part in the corresponding rotating shaft of institute, the adjusting lever of this rotating part that stretched through, and reaches the sliding seat of an ability along this adjusting lever running fix; And the distance between this sliding seat and rotating shaft can be adjusted, the body of this turntable then is to be installed on the sliding seat of this two pivoted arm across ground.

Aforesaid mass spectrometer; Described rotary electric sprays free device and comprises most nozzles; Be first end that is communicated in this t-joint simultaneously, and each nozzle all is round the rotation of pivot, and forms the motion track of enclosed shape; With a vertical plane perpendicular to this central axis; The motion track of each nozzle is along this central axis projection formed track region on this vertical plane, can with inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

Aforesaid mass spectrometer, described mass spectrometer also comprise one and are connected to the tomographic system that this rotary electric sprays free device, so that after should the electricity flushing liquor carrying out chromatography, import this rotary electric again and spray in the free device.

Aforesaid mass spectrometer, described mass spectrometer also comprise one and are connected to the capillary electrophoresis system that this rotary electric sprays free device, so that after should the electricity flushing liquor carrying out capillary electrophoresis separation, import this rotary electric again and spray in the free device.

Aforesaid mass spectrometer, described mass spectrometer also comprise one between the nozzle of the free device of this rotary electric sprinkling and the extra electric field between this mass analyzer.

Aforesaid mass spectrometer, the inlet of described mass analyzer are the configurations that is an annular section.

Aforesaid mass spectrometer; Described mass spectrometer also comprises a laser desorption device; And an article carrying platform, this article carrying platform has an end face, and is to supply one will and contain majority by mass spectral analysis and will be positioned on this end face by the sample of desorption and free determinand; This laser desorption device is to be used for this sample of laser light irradiation; When this this sample of laser light irradiation; At least one determinand in this sample can be by desorption; And transfer the flight path that intersects in path along one with this charge ion and fly, when this at least one determinand behind at least one charged particle, can be transferred because of electric charge and dissociated in the said charged particle stream of contact; And under the guiding of this potential difference, be received and analyze move and get into the inlet of this mass analyzer towards the inlet of this mass analyzer after.

Aforesaid mass spectrometer, described mass spectrometer also comprise an induced with laser sound wave desorption apparatus, a framework; And a base material that is fixed on this framework, this base material has one puts face and puts reverse one of face with this and hit face, and this face of putting be supply to place one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand; This induced with laser sound wave desorption apparatus is the face that hit that is used for this base material of laser light shooting; So that at least one determinand in this sample is because of accepting energy by desorption; And along a flight path flight of intersecting with this charge ion transfer path; When this at least one determinand in the said charged particle stream of contact behind at least one charged particle; Can because of electric charge transfer by free, and under this potential difference guiding, be received and analyze move and get into the inlet of this mass analyzer towards the inlet of this mass analyzer after.

The object of the invention and solve its technical problem and adopt following technical scheme to realize in addition again.A kind of mass spectrometric analysis method according to the present invention's proposition; Comprise following step: a preparation process; Provide one to have the mass analyzer of an inlet, a detector, and a rotary electric spray free device, the free device of this rotary electric sprinkling; Have the rotating mechanism of an ability, and at least one and this central axis are installed in the nozzle on this rotating mechanism at intervals around the rotation of central axis; A setting up procedure starts this rotating mechanism so that this nozzle is driven by this rotating mechanism and rotates round a pivot, and forms the motion track of an enclosed shape; An EFI spills step; The nozzle that makes this be rotated mechanism's drive and rotate synchronously follows this motion track and continuously an electric flushing liquor is sprayed; And make between this nozzle and this mass analyzer and set up a potential difference; And make this electricity flushing liquor form most charged particle streams, and move towards the inlet of this mass analyzer along charge ion transfer path; And an analytical procedure, make this mass analyzer receive and analyze getting into the charged particle stream that this mass analyzer enters the mouth, then by the signal that charged particle stream produced of this detector detecting, and produce a mass spectral analysis figure through this mass analyzer analysis.

Aforesaid mass spectrometric analysis method; With a vertical plane perpendicular to this central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

The motion track that aforesaid mass spectrometric analysis method, described EFI spill the nozzle in the step is to be a three-dimensional helical form in the space.

Aforesaid mass spectrometric analysis method; Also comprise one and be positioned at the preceding desorption of this analytical procedure; Borrowing the external energy that uses heating or vibrations; So that at least one determinand is by desorption and along flight path flight of intersecting with this charge ion transfer path in this sample, and make behind this determinand at least one charged particle in the said charged particle stream of contact, can because of the electric charge transfer by free; And under this potential difference guiding,, the inlet of this mass analyzer is received after moving and get into this inlet.

Aforesaid mass spectrometric analysis method also comprises: a sample preparation process is in the time of this preparation process, on the end face of an article carrying platform, place one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand; And laser desorption step; Be before this analytical procedure, use a laser beam to shine this sample, so that at least one determinand is by desorption and along a flight path flight of intersecting with this charge ion transfer path in this sample; And make this determinand behind contact at least one charged particle in the said charged particle stream; Can be free because of electric charge transfer quilt, and under this potential difference guiding, after the inlet of this mass analyzer moves and get into this inlet, be received.

Aforesaid mass spectrometric analysis method; Also comprise: a sample preparation process; Be in the time of this preparation process; an of base material put place on the face one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand, and this base material also has one and puts the reverse face that hit of face with this; And induced with laser sound wave desorption; Be before this analytical procedure; Use the face that hit of this base material of laser beam shooting; So that at least one determinand and makes behind this determinand at least one charged particle in the said charged particle stream of contact because of accepting energy by desorption and along flight path flight of intersecting with this charge ion transfer path in this sample, can because of the electric charge transfer by free; And under this potential difference guiding,, the inlet of this mass analyzer is received after moving and get into this inlet.

The present invention compared with prior art has tangible advantage and beneficial effect.Know by above; For achieving the above object; The invention provides a kind of mass spectrometric rotary electric that is used for and spray free device; This mass spectrometer comprise one have an inlet a mass analyzer and a detector, this mass analyzer can receive the charged particle stream that contains by free determinand, and cooperates with this detector and to carry out mass spectral analysis.

For achieving the above object, the present invention also provides a kind of new mass spectrometer, comprises: one has the mass analyzer of an inlet, is used to receive and analyze contain by the charged particle stream of free determinand; One detector is used to detect the signal that charged particle stream produced through this mass analyzer analysis, and produces a mass spectral analysis figure; And a described rotary electric sprays free device.

For achieving the above object, of the present invention a kind of mass spectrometric analysis method is provided again.

By technique scheme; Rotary electric of the present invention sprays free device and has advantage and beneficial effect at least: nozzle of the present invention is to follow a motion track pivotably to spray EFI and spill drop; And because the result of this nozzle rotation; The Ionization Efficiency that can increase drop is to produce multivalence electric charge drop; And can make each charged particle (drop) that EFI spills in spraying the space, evenly distribute, and overcoming the space charge effect that charged particle repels each other, the most small charged particle that makes EFI spill formation flows into the number and ratio increase of the mass analyzer inlet in the mass spectrometer of the present invention; Can only not improve the stable and intensity of ion signal, can effectively promote the sensitivity of mass spectral analysis yet.

In sum, a kind of rotary electric of the present invention sprays free device, is applicable to that one has the mass spectrometer of a mass analyzer and a detector, this EFI spill free device comprise one can be around the rotating mechanism of central axis rotation; And at least one and this central axis is installed in the nozzle on this rotating mechanism at intervals; This nozzle can rotate round a pivot; And form the motion track of an enclosed shape, so that this nozzle is when following the motion track rotation, side by side sprays EFI and spill drop.The present invention also provides a kind of mass spectrometer, and a kind of mass spectrometric analysis method.The present invention can overcome the space charge effect that charged particle repels each other, and obvious improvement is arranged technically, and has tangible good effect, really is the new design of a novelty, progress, practicality.

Above-mentioned explanation only is the general introduction of technical scheme of the present invention; Understand technological means of the present invention in order can more to know; And can implement according to the content of specification, and for let of the present invention above-mentioned with other purposes, feature and advantage can be more obviously understandable, below special act preferred embodiment; And conjunction with figs., specify as follows.

Description of drawings

Fig. 1 is that existing EFI spills free device and mass spectrometric sketch map;

Fig. 2 is US6,350,617 and US6, and 621,075 disclosed EFIs spill free device and mass spectrometer side-looking cutaway view;

Fig. 3 is US6, and 066,848 disclosed EFI spills free device and mass spectrometer side-looking cutaway view;

Fig. 4 is the vertical view that rotary electric of the present invention sprays first preferred embodiment of free device;

Fig. 5 is the end view of the configuration relation between the present invention's first preferred embodiment and mass spectrometer;

Fig. 6 is the pivoted arm of the present invention's first preferred embodiment when rotating to downward direction, and this nozzle is the front view that is positioned at the incision endpoint location of its circular motion track just;

Fig. 7 is the pivoted arm of the present invention's first preferred embodiment when rotating to the right direction, and this nozzle just can rotate to the front view of right cut end points along its circular motion track;

Fig. 8 is second preferred embodiment that rotary electric of the present invention sprays free device, and the end view of the configuration relation between mass spectrometer;

Fig. 9 is the 3rd preferred embodiment that rotary electric of the present invention sprays free device, and the end view of the configuration relation between mass spectrometer;

Figure 10 is that a plurality of nozzles of the 3rd preferred embodiment of the free device of rotary electric sprinkling of the present invention are a front view by the formed array nozzle system of a plurality of solid tubular structures;

Figure 11 is the end view that rotary electric of the present invention sprays the configuration relation between a free device and a tomographic system;

Figure 12 is the sketch map of the configuration relation between a mass spectrometer of the present invention and a capillary electrophoresis system;

Figure 13 is Figure 12 capillary electrophoresis system combines formed molten silicon structure capillaceous with nozzle a sketch map;

Figure 14 is that rotary electric of the present invention sprays the end view that adds the configuration mode of an electric field between free device and this mass analyzer;

Figure 15 is that the mass spectrometric mass analyzer inlet of the present invention is the configuration that is an annular section, to receive the profile of this charged particle stream;

Figure 16 is the end view that mass spectrometer of the present invention also comprises the aspect of a laser desorption device and an article carrying platform;

Figure 17 is that mass spectrometer of the present invention also comprises the end view that an induced with laser sound wave desorption apparatus, a framework and are fixed on the aspect of the base material on this framework.

Embodiment

For further setting forth technological means and the effect that the present invention takes for the predetermined goal of the invention of completion; Below in conjunction with accompanying drawing and preferred embodiment; The rotary electric that proposes according to the present invention is sprayed free device; Its embodiment, structure, method, step, characteristic and effect thereof, specify as after.

Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.

Fig. 4, shown in Figure 5 be first preferred embodiment that rotary electric of the present invention sprays free device 5; Be used for a mass spectrometer 2; This mass spectrometer 2 comprises one and has an inlet 31 a mass analyzer 3 and a detector 4; This mass analyzer 3 can receive and contain by the charged particle stream of free determinand; And cooperate with this detector 4 and to carry out mass spectral analysis, this rotary rotary electric spray free device 5 comprise one can be around the rotating mechanism 52 of central axis C rotation, and one is installed in the nozzle 57 on this rotating mechanism 52 at intervals with this central axis C.

Like Fig. 5, shown in Figure 6, this nozzle 57 is centered on the span rotation of a pivot RC by these rotating mechanism 52 drives, and forms the motion track A of an enclosed shape; In the present embodiment, the motion track A of this enclosed shape is to be example with the circle, at this moment; Its span is meant radius of turn R, can certainly be designed to the blunt cam profile of an ellipse or end point one end according to the enforcement demand; At this moment, its span on-fixed and then along with the different and in addition conversion in the position of this motion track A.

And in the present embodiment; The pivot RC of this motion track A forms separately with this central axis C; Can certainly directly move the position that is provided with of this nozzle 57; Make the pivot RC of its motion track A coincide, and its affiliated person skilled that is transformed to of this position can be understood easily, so do not give unnecessary details in detail at this with this central axis C.

Like Fig. 4, shown in Figure 5; This nozzle 57 is with a vertical plane P perpendicular to this central axis C with the preferable states of the relative position of inlet 31 settings of this mass analyzer 3 in the present embodiment; This nozzle 57 is gone up formed track region Z1 with the circular motion track A that its radius of turn R is constituted along this central axis C projection in this vertical plane P; Go up formed incidence zone Z2 with the inlet 31 surrounding edge projections of this mass analyzer 3 in this vertical plane P; At least overlap, Fig. 5 presents this track region Z1 to be contained overlapping by this incidence zone Z2 fully.Below introduce each mechanism more in detail:

This rotating mechanism 52 has that a power source 53, two are provided with separately and the rotating shaft that driven by this power source 53 54, two are installed on the pivoted arm 55 in this two rotating shaft 54 respectively; And one be installed in the turntable 56 on this two pivoted arm 55 across ground; And this turntable 56 is around this central axis C rotation; And this nozzle 57 is to be installed at intervals on this turntable 56 with this central axis C, and forms the identical distance distance with this two rotating shaft 54, what this will specify is; Though present embodiment discloses two rotating shafts 54 and two pivoted arms 55; But this is to dispose in order to make this turntable 56 its both sides when rotating can keep stable, can certainly cost to be set in order reducing, and a rotating shaft 54 and a pivoted arm 55 only to be installed; Can reach the purpose that this turntable 56 is rotated around this central axis C equally, so should not exceed with the explanation of present embodiment.

In addition; The power source 53 of this rotating mechanism 52 has a motor 531; And one driven and drive the acceleration group 532 that this two rotating shaft 54 is rotated by this motor 531; This acceleration group 532 has the low-speed gear that driven by this motor 531 533, two and drives the high gear 534 that this two rotating shaft 54 is rotated respectively; And a tooth sector 535 that is engaged in 534 of this two high gears, forming the engagement order of this low-speed gear 533, one of them high gear 534, this tooth sector 535, another high gear 534, and the number of teeth of this low-speed gear 533 is the numbers of teeth more than this two high gear 534.

56 of this turntables have one and are installed in the body 561 on this two pivoted arm 55 across ground; And t-joint 562 that is installed on this body 561; This t-joint 562 have one be connected in this nozzle 57 first end 563, a usefulness spill second end 564 that flow is gone into for this EFI, and one in order to set up the 3rd end 565 of this potential difference.

Optionally; This nozzle 57 is one to have capillary, a piezoelectric type (piezoelectric) nozzle or a thermal bubble type (bubble) nozzle of a nose end; This electricity flushing liquor is sprayed from this nose end capillaceous; The enforcement aspect of this piezoelectric type nozzle for example is a porous type dull and stereotyped (is generally 48 apertures are arranged in 1 square centimeter zone), is that the gasification that utilizes the piezoelectricity material to carry out electric flushing liquor is sprayed, and the enforcement aspect of this thermal bubble type nozzle then for example is to let this electricity flushing liquor through a thin nozzle; Under the effect of a heating resistor, with the sprinkling of gasifying of a part of electric flushing liquor in its pipe-line.

Each pivoted arm 55 of this rotating mechanism 52 all have one be installed on the stretched through adjusting lever 552 of this rotating part 551 of the rotating part 551, in the corresponding rotating shaft 54; Reaching one can be along the sliding seat 553 of these adjusting lever 552 running fixes; And the distance between this sliding seat 553 and this central axis C can be adjusted, 561 of the bodies of this turntable 56 are to be installed on the sliding seat 553 of this two pivoted arm 55 across ground.

Rotary electric of the present invention sprays free device 5, is by the distance of adjusting 54 of this sliding seat 553 and rotating shafts, accomplishes the change of radius of turn R; That is to say that like Fig. 5, shown in Figure 6, the central axis C of this rotating mechanism 52 is to be positioned on the same level with this two rotating shaft 54; And adjust the distance between this sliding seat 553 and this central axis C, will make that this sliding seat 553 is around this central axis C rotation, at this moment; Be arranged at the turntable 56 on this sliding seat 553, will and this central axis C between produce eccentric phenomena, when causing this turntable 56 to rotate; Can be that the center of circle produces rotation by a small margin with this central axis C, jointly, the nozzle 57 that is arranged on this turntable 56 just also can produce rotation by a small margin; Therefore, the sliding seat 553 of this two pivoted arm 55, this turntable 56, this nozzle 57 rotation that all can produce identical radius of turn R.

As shown in Figure 6; When this two pivoted arm 55 rotates to downward direction; This nozzle 57 is the incision endpoint location that is positioned at its circular motion track A just, and when this two pivoted arm 55 rotated to direction to the right as shown in Figure 7, this nozzle 57 just can rotate to the right cut endpoint location along its circular motion track A; Therefore, can understand really that this nozzle 57 is driven by aforementioned rotating mechanism 52 and rotation synchronously.

Fig. 4, shown in Figure 5 for another example; Flowing into by this second end 564 should the electricity flushing liquor; The 3rd end 565 is switched on and is made this

nozzle

57 and 3 of mass analyzers set up a potential difference; And make this electricity flushing liquor form most small charged particle streams, and spray electric charge transfer path along one and move towards the inlet 31 of this mass analyzer 3, cooperate with this detector 4 for this mass analyzer 3 and carry out mass spectral analysis.

In sum; When carrying out mass spectrometric analysis method of the present invention; Be to comprise one to prepare step, a setting up procedure, an EFI and spill step, and an analytical procedure, this preparation process is to prepare the combination aspect that aforementioned mass analyzer 3, detector 4, rotary electric spray free device 5; Because preamble has been done and has been elaborated, so repeat no more; This setting up procedure then is to start this rotating mechanism 52 so that this nozzle 57 is driven by this rotating mechanism 52 and rotates with a radius of turn R; Then carry out this EFI and spill step; The nozzle 57 that makes this be rotated mechanism's 52 drives and rotate synchronously follows this circle motion track and should spray by the electricity flushing liquor continuously; And make this nozzle 57 and 3 of this mass analyzers set up a potential difference; And make this electricity flushing liquor form most small charged particle streams, and move towards the inlet 31 of this mass analyzer 3 along charge ion transfer path; Then carry out this analytical procedure at last, make this mass analyzer 3 receive and analyze the charged particle stream that gets into this inlet 31, the signal of then analyzing through this mass analyzer 3 that charged particle stream produced by these detector 4 detectings, and produce a mass spectral analysis figure.

Fig. 8 is second preferred embodiment that rotary electric of the present invention sprays free device 5; Roughly identical with this first preferred embodiment; Different places are: this nozzle 57 is not the aspect that is aligned with each other with the inlet 31 of this mass analyzer 3; But present the staggered aspect of certain angle; The extended line L1 that for example extends by this nozzle 57 with perpendicular to the ray L2 on these mass analyzer 3 inlets 31 planes perpendicular (just being the staggered of an angle of 90 degrees degree), though be not the alignment of 0 degree angle as shown in Figure 5, owing to the effect of potential difference; So still can be so that the charged particle stream that sprays of this nozzle 57 still can move towards the inlet 31 of this mass analyzer 3 certainly, just the relative position that is provided with of the inlet 31 of this nozzle 57 and this mass analyzer 3 is not limited to the enforcement aspect of embodiment 1.

Fig. 9 is the 3rd preferred embodiment that rotary electric of the present invention sprays free device 5; Roughly identical with this first preferred embodiment; Different places are: be installed on nozzle 57 on first end 563 of this t-joint 562 for a plurality of, and each nozzle 57 all is the motion track that is formed with its enclosed shape separately, each motion track is gone up formed track region Z1 along this central axis C projection in this vertical plane P; Can go up formed incidence zone Z2 in this vertical plane P with the inlet 31 surrounding edge projections of this mass analyzer 3; At least overlap, with present embodiment, the track region Z1 of outermost nozzle 57 can be greater than the incidence zone Z2 of the inlet 31 of this mass analyzer 3; The track region Z1 that is arranged at inboard nozzle 57 is then more and more little, less than this incidence zone Z2.

In addition; When the present invention is when being designed to the form of a plurality of nozzles 57 as shown in Figure 9, can also this EFI be spilt the drop amount of coming and improve, cooperate rotation constantly again; Make drop in the space, evenly distribute; And transfer path along this charge ion and move towards the inlet 31 of this mass analyzer 3, can significantly increase the charged particle flow amount that gets into mass analyzer inlet 31, also obviously improve mass analyzer 3 and carried out the sensitivity that ion is detected.

What specify is that it is to be positioned at outside the Z2 of incidence zone, therefore that present embodiment has portion nozzle 57; When carrying out EFI when spilling; Having portion nozzle 57 when rotated can be over against the inlet 31 of this mass analyzer 3, but because the effect of potential difference, so charged particle stream still can move towards the inlet 31 of this mass analyzer 3; Therefore, this 3rd preferred embodiment is not limited to this track region Z1 and is contained overlapping by this incidence zone Z2 fully.

Optionally; This nozzle 57 is except being aforementioned capillary; Printer ink-jetting style also capable of using such as piezoelectric type spray application or thermal bubble type spray technique spray; In addition, also can be shown in figure 10, a plurality of solid tubular structures 571 are tied together at grade; And form array nozzle system 572, and should the electricity flushing liquor be to import this array nozzle system 572 via pressing mode to spill to carry out EFI with a plurality of nozzles 57 by the space of 571 of each solid tubular structures.

Optionally, rotary electric of the present invention spray free device 5 employed electric flushing liquors contain an EFI spill medium (electrospray medium) and at least one will be by the determinand of mass spectral analysis.

This rotary electric sprays the EFI that free device 5 is suitable for and spills medium, as the EFI method of spilling can be and contain proton (H+), the isoionic solution of OH-, this for this reason in the field technical staff can understand easily, repeat no more at this.For ease of the deciphering of collection of illustrative plates, when carrying out spilling the relevant mass spectrometry of technology, generally be the positive ion mode that adopts the charged particle that includes H+ with EFI, therefore preferably, it is one to contain sour solution that this EFI spills medium.More preferably, it is to contain a volatile liquid that this EFI spills medium, and before being received and analyze by this mass analyzer, volatile liquid attached to it is able to first volatilization, and helps the simplification of collection of illustrative plates in order to this determinand.

Optionally, can spray

free device

5 and 3 increases of mass analyzer, one air-flow organization of supply in this rotary electric, it is the volatilization of assisting this volatile liquid by supply one non-reactive gas.Preferably, this non-reacted air-flow is to advance and have one between the temperature between room temperature to 325 ℃ towards this mass analyzer 3; More preferably, this non-reacted air-flow is to be selected from the following group that constitutes: nitrogen, helium, neon, argon gas, or the combination of said flow.

Optionally; This EFI spills fluid power and is directly imported in the free device 5 of this rotary electric sprinkling by a syringe pump (syringe pump); Analytic sample for complicated component; Also can utilize the LC (liquid chromatography) or the mode of Capillary Electrophoresis (capillary electrophoresis) to carry out the separation of sample earlier, be connected to this rotary electric again and spray free device 5 to carry out the sprinkling of sample free.The enforcement aspect of this LC be utilize shown in figure 11 one have a chromatography pipe (chromatogramphy column) 581 and one detector 582 tomographic system 58 carry out the chromatography of analytic sample after, import this rotary electric again and spray in the free device 5.Preferably, this tomographic system 58 be a high-effect LC appearance (high performance liquid chromatography, HPLC).And the enforcement aspect of this Capillary Electrophoresis be should the electricity flushing liquor via a capillary electrophoresis system; (10～30KV) effect of electric field are carried out capillary electrophoresis separation, and import in the free device 5 of this rotary electric sprinkling in a buffer solution (buffer) environment, to utilize high pressure.For example shown in the sketch map of Figure 12 and Figure 13; One capillary electrophoresis system 59 has at least one power supply unit 591, a buffer solution accumulator tank 592; And one spray the molten silicon capillary (fused-silica capillary) 593 that the nozzle 57 of free device 5 combines with this rotary electric; The tail end of this nozzle 57 has the metal (like gold or silver etc.) that one deck can conduct electricity, and with the conduction that provides Capillary Electrophoresis and follow-up EFI to spill, and is applied the electric flushing liquor of voltage in this electricity flushing liquor accumulator tank 592 of 30kV by this power supply unit 591; These nozzle 57 tail ends are then applied the voltage of 4.7kV by this power supply unit 591; Mixes with a buffer solution and carry out Capillary Electrophoresis in order to the electric flushing liquor that make to flow into this molten silicon capillary 593 with potential difference 25.3kV, with should electricity flushing liquor purifies and separates and import this rotary electric sprinkling and dissociate in the device 5, simultaneously with inlet 31 ground connection of this mass analyzer 3; Utilize the potential difference of 4.7V, just can successively carry out EFI and spill.

So preferably, mass spectrometer of the present invention also comprises one and has the tomographic system 58 of an at least one chromatography pipe 581 and a detector 582, or a capillary electrophoresis system 59, after should electricity flushing liquor purifies and separates, imports this rotary electric and sprays in the free device 5.

Build on voltage extent and direction of an electric field that this rotary electric sprays 3 of nozzle 57 and this mass analyzers of free device 5; Be to be that principle is set should the electricity flushing liquor forming the small charged particle that is sprayed; This voltage difference can on the occasion of or be negative value, be to look electrically setting of charged particle that user institute desire forms.The nozzle 57 that for example spills device 5 at this EFI impose more than the 2kV voltage and with these mass analyzer 3 ground connection.

Optionally, can further set up an extra electric field in

nozzle

57 and 3 of this mass analyzers of the free device 5 of this rotary electric sprinkling.Shown in figure 14; For example add a columned cloche 8 at this

nozzle

57 and 3 of mass analyzers; This cloche 8 is electrically connected and imposes the voltage more than the 0.9kV near the ring-type electricity spray section G1 of this nozzle 57; And an acceptance division G2 of these cloche 8 nearly these mass analyzers 3 is electrically connected and imposes the voltage below one-0.5kV, utilize potential difference to change this charge ion transfer path to reach the effect that focuses on and guide electric charge with this electric field that adds.

When using free device 5 of rotary electric sprinkling of the present invention and mass spectrometric analysis method to carry out, the positive effect that can produce then is described below:

Prior art all is EFI to be spilt entry needle be fixed on the position or treat to move in regular turn individually on the specified point and spill to carry out EFI, and the drop that EFI spills is easy to generate the phenomenon toward outdiffusion, so that has reduced the sensitivity of ion detecting; Nozzle 57 of the present invention is to follow a motion track pivotably to spray EFI and spill drop; Make each charged particle in spraying the space, evenly distribute and also can overcome the space charge effect that charged particle repels each other; Number and ratio that the most small charged particle that makes EFI spill formation flows into the inlet 31 of the mass analyzer 3 in the mass spectrometer 2 of the present invention increase, and improve the stable and intensity of ion signal.

Preferably; This rotary electric sprays free device 5 can utilize the portable turntable 56 of an ability; Make this turntable 56 toward away from or move near the direction of this mass analyzer 3; And drive the nozzle 57 be installed on this turntable 56 except round pivot rotation rotation, also thereupon toward away from or move near the direction of this mass analyzer 3, the motion track that makes the EFI of mass spectrometric analysis method of the present invention spill the nozzle 57 in the step is to be a three-dimensional helical form in the space.

Optionally; Shown in figure 15; This mass analyzer inlet 31 is the configurations that are an annular section; Can cooperate via this nozzle 57 in the shape of a spiral the charged particle that sprays out of shape march to this mass analyzer through this charge ion transfer path and entered the mouth 31 o'clock, can be general become an annular form to distribute, therefore the entrance area with this ring-type receives this charged particle.

Except this rotary electric sprays free device 5; The present invention has also disclosed three kinds of mass spectrometers 2; First kind includes the combination aspect that mass analyzer 3, detector 4, rotary electric that Fig. 4, Fig. 5 disclose spray free device 5, and second kind and 2 in the third mass spectrometer can also combine the laser desorption function again.Shown in figure 16; Second kind of mass spectrometer 2 also comprises a laser desorption device 6 and an article carrying platform 61; This article carrying platform 61 has an end face 611; And be to supply one will and contain a plurality of will being positioned on its end face 611 by the sample S of desorption and free determinand by mass spectral analysis, this laser desorption (laser-induced desorption) device 6 then is to be used for this sample of laser beam L direct irradiation S, and makes that at least one determinand is gone out by desorption among this sample S.2 in the third mass spectrometer is shown in figure 17; This mass spectrometer 2 also comprises an induced with laser sound wave desorption (laser-inducedacoustic desorption; LIAD) device 7, one framework 71 and is fixed on the base material 72 on this framework 71; This base material 72 have the face of putting 721 with this put face 721 reverse one hit face 722; And this puts face 721 is to supply to place this sample S, and this induced with laser sound wave desorption apparatus 7 then is that formed seismic wave is delivered to this sample S when being used for this base material 72 of laser beam L irradiation, so that determinand is wherein gone out by desorption after absorbing energy indirectly.

What specify is; This laser desorption device 6 and this induced with laser sound wave desorption apparatus 7 are applied to characteristics and its enforcement aspect on the mass spectrometer 2, and be disclosed at this case inventor China Taiwan letters patent book number I271771 and Chinese Taiwan patent publication No. 200842359.

When this mass spectrometer 2 also comprises this laser desorption device 6 and this article carrying platform 61, second kind of mass spectrometer 2 just, its mass spectrometric analysis method also comprises:

One sample preparation process is in this preparation process, on the end face 611 of this article carrying platform 61, place one will by mass spectral analysis and contain a plurality of will be by the sample S of desorption and free determinand; And

One laser desorption step; Be before this analytical procedure, use a laser beam L to shine this sample S, so that at least one determinand flies with this crossing flight path in electric charge transfer path by desorption and along one among this sample S; And make this at least one determinand in contacting said charged particle stream behind at least one charged particle; Can be free because of electric charge transfer quilt, and under this potential difference guiding, after the inlet 31 of this mass analyzer 3 moves and get into this inlet 31, be received.

When this mass spectrometer 2 also comprises this induced with laser sound wave desorption apparatus 7, this framework 71 and this base material 72, the third mass spectrometer 2 just, its mass spectrometric analysis method also comprises:

One sample preparation process is in this preparation process, on the face of putting 721 of this base material 72, place one will by mass spectral analysis and contain a plurality of will be by the sample S of desorption and free determinand; And

One induced with laser sound wave desorption; Be before this analytical procedure; Use one of this base material 72 of laser beam L shooting to be hit face 722; So that at least one determinand flies with this crossing flight path in charge ion transfer path by desorption and along one because of accepting energy among this sample S, and feasible this at least one determinand behind at least one charged particle, can be transferred quilt because of electric charge and dissociate in the said charged particle stream of contact; And under this potential difference guiding,, the inlet 31 of this mass analyzer 3 is received after moving and get into this inlet 31.

Therefore; Mass spectrometric analysis method of the present invention is when using this to contain the mass spectrometer 2 of this laser desorption device 6 or this induced with laser sound wave desorption apparatus 7; The electric flushing liquor that this rotary electric sprays in the free device 5 then is that an EFI spills medium; And this laser desorption device 6 can be applicable to that one will and contain majority by mass spectral analysis and will and be positioned on the end face 611 of this article carrying platform 61 directly carrying out mass spectral analysis by the solid sample S of desorption and free determinand, and the sample S that this induced with laser sound wave desorption apparatus 7 can be suitable for then can be for solid-state or liquid and be positioned on the face of putting 711 of this base material 71 directly to carry out mass spectral analysis.

Compared to the laser desorption step of using this laser desorption device 6; The induced with laser sound wave desorption of using this induced with laser sound wave desorption apparatus 7 to be carried out is a kind of comparatively gentle desorption mode for this sample S, and the determinand that institute's desorption goes out also has higher probability to have complete structure.

But sample desorption mode of the present invention; Except using laser desorption device 6 or induced with laser sound wave desorption apparatus 7; Also can utilize the mode of simple heating or vibrations to accomplish; That is to say, before analytical procedure, carry out a desorption again, borrowing external energies such as using heating or vibrations to make at least one determinand among this sample S by desorption and along flight path flight of intersecting with this charge ion transfer path; And make this at least one determinand in contacting said charged particle stream behind at least one charged particle; Can be free because of electric charge transfer quilt, and under this potential difference guiding, after the inlet of this mass analyzer moves and get into this inlet, be received.

Preferably, this solid sample S can be a histotomy, a lozenge, or is that an aqueous analyte is formed after a dried.

When this solid sample is biological tissue section, optionally, be the histotomy that is selected from the animal organ in the following group that constitutes: brain, heart, liver, lungs, stomach, kidney, spleen, intestines, and uterus.When this sample is formed after dried by aqueous analyte, this aqueous analyte then can be various solution, for example body fluid, chemical solution, environmental sampling solution, or various LC parting liquid collect solution or the like.When this aqueous analyte is during by the secreted body fluid that goes out of biology, optionally, be to be selected from the following group that constitutes: blood, tear, sweat, intestinal juice, brains, spinal fluid, lymph liquid, fester, serum, saliva, snot, urine, and liquid manure.

Therefore; Can be with regard to one not via the biological tissue section of any pre-treatment; Directly carry out mass spectral analysis and know macromolecular molecular weight in the sample smoothly, follow-uply also can integrate each position on the same histotomy, to be informed in protein distribution state appearance under the various situation such as specific two dimension or three-dimensional; In its research and development and clinical practice, will be big sharp weapon for medical related industry in future.

In sum; It is pivotably to spray this electricity flushing liquor continuously that rotary electric of the present invention sprays free device 5; The Ionization Efficiency that can increase drop to be producing multivalence electric charge drop, and can overcome the space charge effect that charged particle repels each other, and the number that the most small charged particle that makes EFI spill formation gets into the inlet 31 of this mass analyzer 3 in the mass spectrometer 2 of the present invention increases; Can only not improve the stable and intensity of ion signal, can effectively promote the sensitivity of mass spectral analysis yet.

The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the method for above-mentioned announcement capable of using and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations; In every case be the content that does not break away from technical scheme of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.

Claims

1. a rotary electric sprays free device; Be used for a mass spectrometer; This mass spectrometer comprises a mass analyzer with an inlet, and a detector, and this mass analyzer can receive charged particle stream; And cooperate with this detector and to carry out mass spectral analysis, it is characterized in that: wherein said EFI spills free device and comprises:

A rotating mechanism can be around a central axis rotation; And

At least one nozzle; This nozzle is to be installed at intervals on this rotating mechanism with this central axis; And can be driven and round a pivot rotation by this rotating mechanism, and form the motion track of an enclosed shape, and make an EFI spill that fluid power is enough to be gone out from this nozzles spray;

When this mass analyzer when analyzing; This nozzle is driven by this rotating mechanism and rotation synchronously; And follow this motion track and spray this electricity flushing liquor continuously; By between this nozzle and this mass analyzer, set up a potential difference, and make this electricity flushing liquor form most charged particle streams, and move towards the inlet of this mass analyzer along charge ion transfer path.

2. rotary electric as claimed in claim 1 sprays free device; It is characterized in that: with a vertical plane perpendicular to described central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of described mass analyzer, overlap at least.

3. according to claim 1 or claim 2 rotary electric sprays free device; It is characterized in that: wherein said rotating mechanism have a power source, at least one by rotating shaft that this power source drove, at least one is installed on the pivoted arm in this rotating shaft; And one be installed in the turntable on this pivoted arm at intervals with this rotating shaft; And this turntable is around this central axis rotation, and this nozzle is to be installed at intervals on this turntable with this central axis.

4. rotary electric as claimed in claim 3 sprays free device; It is characterized in that: wherein said rotating mechanism has two and is provided with separately and by rotating shaft that this power source drove; And two pivoted arms that are installed on respectively in this two rotating shaft; This turntable is to be installed on this two pivoted arm across ground; And forming the identical distance distance with this two rotating shaft, the power source of this rotating mechanism has a motor, and one is driven and drives the acceleration group that this rotating shaft is rotated by this motor; This acceleration group has one by the low-speed gear that this motor drove, two high gears that drive this two rotating shafts rotation respectively; And a tooth sector that is engaged between this two high gear, forming the engagement order of this low-speed gear, one of them high gear, this tooth sector, another high gear, and the number of teeth of this low-speed gear is the number of teeth more than this two high gear.

5. rotary electric as claimed in claim 4 sprays free device; It is characterized in that: wherein said turntable has one and is installed in the body on this two pivoted arm across ground; And t-joint that is installed on this body; This t-joint has first end that is connected in this nozzle, one and uses for this EFI and spill second end that flow is gone into; And one in order to setting up the 3rd end of this potential difference, and each pivoted arm of this rotating mechanism all has one and is installed on the rotating part in the corresponding rotating shaft of institute, the adjusting lever of this rotating part that stretched through, and reaches the sliding seat of an ability along this adjusting lever running fix; And the distance between this sliding seat and rotating shaft can be adjusted, the body of this turntable then is to be installed on the sliding seat of this two pivoted arm across ground.

6. rotary electric as claimed in claim 5 sprays free device; It is characterized in that: wherein said rotary electric sprays free device and comprises most nozzles; Be first end that is communicated in this t-joint simultaneously, and each nozzle all is round the rotation of this pivot, and forms the motion track of enclosed shape; With a vertical plane perpendicular to this central axis; The motion track of each nozzle is along this central axis projection formed track region on this vertical plane, can with inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

7. a mass spectrometer comprises a mass analyzer, and a detector; This mass analyzer has an inlet; Be used for receiving and analyzing charged particle stream, this detector is to be used to detect the signal that charged particle stream produced through this mass analyzer analysis, and produces a mass spectral analysis figure; It is characterized in that: described mass spectrometer also comprises a rotary electric and sprays free device, and this rotary electric sprays free device and has the rotating mechanism of an ability around central axis rotation; And at least one nozzle; This nozzle is to be installed at intervals on this rotating mechanism with this central axis; And can be driven and round pivot rotation by this rotating mechanism, and form the motion track of an enclosed shape, and make an EFI spill that fluid power is enough to be gone out from this nozzles spray;

When this mass analyzer when analyzing; This nozzle is to be rotated that mechanism drives and rotation synchronously; And follow this motion track and spray this electricity flushing liquor continuously; Set up a potential difference by between this nozzle and mass analyzer, and make this electricity flushing liquor form most charged particle streams, and spray electric charge transfer path along one and move towards the feeder connection of this mass analyzer.

8. mass spectrometer as claimed in claim 7; It is characterized in that: with a vertical plane perpendicular to this central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

9. like claim 7 or 8 described mass spectrometers; It is characterized in that: the rotating mechanism that described rotary electric sprays free device have a power source, at least one by rotating shaft that this power source drove, at least one is installed on the pivoted arm in this rotating shaft; And one be installed in the turntable on this pivoted arm at intervals with this rotating shaft; And this turntable is around this central axis rotation, and this nozzle is to be installed at intervals on this turntable with this central axis.

10. mass spectrometer as claimed in claim 9; It is characterized in that: described rotating mechanism has two and is provided with separately and by rotating shaft that this power source drove; And two pivoted arms that are installed on respectively in this two rotating shaft; This turntable is to be installed on this two pivoted arm across ground; And forming the identical distance distance with this two rotating shaft, the power source of this rotating mechanism has a motor, and one is driven by this motor and drives the acceleration group that this rotating shaft is rotated; This acceleration group has one by the low-speed gear that this motor drove, two high gears that drive this two rotating shafts rotation respectively; And a tooth sector that is engaged between this two high gear, forming the engagement order of this low-speed gear, one of them high gear, this tooth sector, another high gear, and the number of teeth of this low-speed gear is the number of teeth more than this two high gear.

11. mass spectrometer as claimed in claim 10; It is characterized in that: described turntable has one and is installed in the body on this two pivoted arm across ground; And t-joint that is installed on this body; This t-joint has first end that is connected in this nozzle, one and uses for this EFI and spill second end that flow is gone into; And one in order to setting up the 3rd end of this potential difference, and each pivoted arm of this rotating mechanism all has one and is installed on the rotating part in the corresponding rotating shaft of institute, the adjusting lever of this rotating part that stretched through, and reaches the sliding seat of an ability along this adjusting lever running fix; And the distance between this sliding seat and rotating shaft can be adjusted, the body of this turntable then is to be installed on the sliding seat of this two pivoted arm across ground.

12. mass spectrometer as claimed in claim 11; It is characterized in that: described rotary electric sprays free device and comprises most nozzles; Be first end that is communicated in this t-joint simultaneously, and each nozzle all is round the rotation of pivot, and forms the motion track of enclosed shape; With a vertical plane perpendicular to this central axis; The motion track of each nozzle is along this central axis projection formed track region on this vertical plane, can with inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

13. mass spectrometer as claimed in claim 7; It is characterized in that: described mass spectrometer also comprises one and is connected to the tomographic system that this rotary electric sprays free device; So that after should the electricity flushing liquor carrying out chromatography, import this rotary electric again and spray in the free device.

14. mass spectrometer as claimed in claim 7; It is characterized in that: described mass spectrometer also comprises one and is connected to the capillary electrophoresis system that this rotary electric sprays free device; So that after should the electricity flushing liquor carrying out capillary electrophoresis separation, import this rotary electric again and spray in the free device.

15. mass spectrometer as claimed in claim 7 is characterized in that: described mass spectrometer also comprises one between the nozzle of the free device of this rotary electric sprinkling and the extra electric field between this mass analyzer.

16. mass spectrometer as claimed in claim 7 is characterized in that: the inlet of described mass analyzer is the configuration that is an annular section.

17. mass spectrometer as claimed in claim 7; It is characterized in that: described mass spectrometer also comprises a laser desorption device; And article carrying platform; This article carrying platform has an end face, and is to supply one will and contain majority by mass spectral analysis and will be positioned on this end face by the sample of desorption and free determinand; This laser desorption device is to be used for this sample of laser light irradiation; When this this sample of laser light irradiation; At least one determinand in this sample can be by desorption; And transfer the flight path that intersects in path along one with this charge ion and fly, when this at least one determinand behind at least one charged particle, can be transferred because of electric charge and dissociated in the said charged particle stream of contact; And under the guiding of this potential difference, be received and analyze move and get into the inlet of this mass analyzer towards the inlet of this mass analyzer after.

18. mass spectrometer as claimed in claim 7 is characterized in that: described mass spectrometer also comprises an induced with laser sound wave desorption apparatus, a framework; And a base material that is fixed on this framework, this base material has one puts face and puts reverse one of face with this and hit face, and this face of putting be supply to place one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand; This induced with laser sound wave desorption apparatus is the face that hit that is used for this base material of laser light shooting; So that at least one determinand in this sample is because of accepting energy by desorption; And along a flight path flight of intersecting with this charge ion transfer path; When this at least one determinand in the said charged particle stream of contact behind at least one charged particle; Can because of electric charge transfer by free, and under this potential difference guiding, be received and analyze move and get into the inlet of this mass analyzer towards the inlet of this mass analyzer after.

19. a mass spectrometric analysis method is characterized in that: described mass spectrometric analysis method comprises following step:

A preparation process; Provide one to have the mass analyzer of an inlet, a detector; And a rotary electric sprays free device; This rotary electric sprays free device, has the rotating mechanism of an ability around a central axis rotation, and at least one and this central axis are installed in the nozzle on this rotating mechanism at intervals;

A setting up procedure starts this rotating mechanism so that this nozzle is driven by this rotating mechanism and rotates round a pivot, and forms the motion track of an enclosed shape;

An EFI spills step; The nozzle that makes this be rotated mechanism's drive and rotate synchronously follows this motion track and continuously an electric flushing liquor is sprayed; And make between this nozzle and this mass analyzer and set up a potential difference; And make this electricity flushing liquor form most charged particle streams, and move towards the inlet of this mass analyzer along charge ion transfer path; And

An analytical procedure makes this mass analyzer receive and analyzes getting into the charged particle stream that this mass analyzer enters the mouth, and then by the signal that charged particle stream produced of this detector detecting through this mass analyzer analysis, and produces a mass spectral analysis figure.

20. mass spectrometric analysis method as claimed in claim 19; It is characterized in that: with a vertical plane perpendicular to this central axis; The motion track of described nozzle is along this central axis projection formed track region on this vertical plane; With inlet surrounding edge projection formed incidence zone on this vertical plane of this mass analyzer, overlap at least.

21. mass spectrometric analysis method as claimed in claim 19 is characterized in that: the motion track that described EFI spills the nozzle in the step is to be a three-dimensional helical form in the space.

22. mass spectrometric analysis method as claimed in claim 19; It is characterized in that: described mass spectrometric analysis method also comprises one and is positioned at the preceding desorption of this analytical procedure; Borrowing the external energy that uses heating or vibrations; So that at least one determinand is by desorption and along flight path flight of intersecting with this charge ion transfer path in this sample, and make behind this determinand at least one charged particle in the said charged particle stream of contact, can because of the electric charge transfer by free; And under this potential difference guiding,, the inlet of this mass analyzer is received after moving and get into this inlet.

23. mass spectrometric analysis method as claimed in claim 19 is characterized in that: described mass spectrometric analysis method also comprises:

A sample preparation process is in the time of this preparation process, on the end face of an article carrying platform, place one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand; And

A laser desorption step; Be before this analytical procedure, use a laser beam to shine this sample, so that at least one determinand is by desorption and along a flight path flight of intersecting with this charge ion transfer path in this sample; And make this determinand behind contact at least one charged particle in the said charged particle stream; Can be free because of electric charge transfer quilt, and under this potential difference guiding, after the inlet of this mass analyzer moves and get into this inlet, be received.

24. mass spectrometric analysis method as claimed in claim 19 is characterized in that: described mass spectrometric analysis method also comprises:

A sample preparation process; Be in the time of this preparation process; an of base material put place on the face one will by mass spectral analysis and contain majority will be by the sample of desorption and free determinand, and this base material also has one and puts the reverse face that hit of face with this; And

An induced with laser sound wave desorption; Be before this analytical procedure; Use the face that hit of this base material of laser beam shooting; So that at least one determinand and makes behind this determinand at least one charged particle in the said charged particle stream of contact because of accepting energy by desorption and along flight path flight of intersecting with this charge ion transfer path in this sample, can because of the electric charge transfer by free; And under this potential difference guiding,, the inlet of this mass analyzer is received after moving and get into this inlet.