CN107144626B - Ion selectivity photodissociation device, method and instrument - Google Patents
Ion selectivity photodissociation device, method and instrument Download PDFInfo
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Abstract
The invention discloses a kind of ion selectivity photodissociation device, method and instruments, wherein the device includes: electrode group, including first electrode, second electrode, third electrode and the 4th electrode, first electrode, second electrode, third electrode and the 4th electrode successively parallel arranged, wherein circular hole is equipped among each electrode, and in each electrode circular hole central coaxial, aperture plate is set on circular hole, and aperture plate for ion for passing through；Wherein first electrode, second electrode form quality gate, and quality gate is used to select the ion of extra fine quality number；Second electrode, third electrode form dissociation, for the ion selected by quality gate under the irradiation of dissociation laser to that dissociation occur to generate fragment ion；Second electrode, third electrode and the 4th electrode form two-stage accelerating field, for accelerating fragment ion, so that fragment ion reaches ion detector microchannel plate.The arrangement achieves the ions generated to ion source to carry out high-resolution selection and analysis.
Description
Technical field
The present invention relates to mass spectrum and field of spectral analysis technology more particularly to a kind of ion selectivity photodissociation device, lead to
Cross the device carry out ion selectivity photodissociation method and a kind of instrument with the device.
Background technique
Currently, prominent the representing as analysis test scientific instrument, mass spectrograph has sensitivity highest, and applicability is strongest
Advantage, all has irreplaceable important function in scientific research and production practices, and application spreads national economy and safety
The every field of information.In mass spectral analysis, test substance molecule is after ionizing according to different mass-to-charge ratioes (the ratio between quality and charge)
Spatially position and time order and function are distinguish and quantitative analysis under electromagnetic field control.Although mass spectrum is with powerful quality point
Function is analysed, but the technology has significant limitation in terms of structure determination, can not directly give tested species in most cases
Structural information significantly limit mass spectrum skill to identical mass number but the different isomer of structure cannot be distinguished
Art food safety, in terms of deep application.
Infrared spectroscopy is one of the most effectual way for studying the structure of matter, and every kind of molecule is made from it to be determined with structure
Characteristic infrared spectrum, structural analysis, species identification and quantitative measurment can be carried out to molecule accordingly.Therefore it is infrared to develop collection
Spectral composition measurement and mass spectrum quality analysis in one infrared-mass spectrometry instrument by with powerful analysis test function,
And have wide practical use.However since traditional infrared absorption spectrum method sensitivity is low, it is unsuitable for and mass-spectrometric technique string
Connection is used in structure of matter analysis.It is the high-sensitivity vibration spectrographic technique developed in recent years that infrared laser, which dissociates spectrum,.Since
The infrared laser solution of Nobel chemistry Prize winner Li Yuanzhe in 1985 et al. goes against accepted conventions experiment till now, infrared laser dissociation
Spectrum has become the important means of research gas phase small molecule and cluster chemistry.Infrared laser solution goes against accepted conventions (Infrared
Photodissociation Spectroscopy:IRPD) experiment be by detect parent ion fragment intensity with radiate it is red
The relationship of outer optical maser wavelength variation.For parent ion AB+, when it absorbs several infrared photons, intramolecule energy is increased
Dissociation more than certain weak bonds limits, it may occur that dissociation generates neutral or electrification fragment.It can biggish cluster body for combining
System can then compose its vibration frequency of detection by infrared predissociation (Infrared Predissociation Spectroscopy)
Rate information.Infrared predissociation spectrum make first research system AB+ weakly stable n inert atom of information or molecule (such as Ar, He,
H2 etc.), then system and infrared laser are acted on, the successively solution defection of information Ar atom reduces the interior energy of parent molecule, to obtain
Secure satisfactory grades the vibrational spectra distinguished.
The great advantage that mass spectrograph and Photodissociation spectroscopy instrument are used in combination with is, first, it can analyze
Select the molecular structure of ion.Its principle and experimentation are, first according to mass-spectrometry principle, the ion of specific mass-to-charge ratio to be selected
It selects out, then irradiates the ion selected with light source (usually laser) again, obtain the spectral information of such ion.Second,
Due to mass spectrum be work in high vacuum conditions, it can analyze some free radicals unstable at normal temperatures and pressures, ion with
And the various metastable state molecules combined by noncovalent interaction, such as molecular cluster.Some transmission spectra methods without
The metastable state molecule of method research can the method associated with mass spectrum-Photodissociation spectra conduct a research.
Since main function of the mass spectrum in mass spectrograph and photodissociation spectrometer are used in combination is that separation selects specific point
Daughter ion, therefore, mass spectrometric mass resolving power will determine the performance of this research method and instrument, such as, for matter lotus
Than very similar two ions, can by they it is completely isolated be to determine whether result of study has unique guarantor of reliability
Card.
Therefore, how to ion source generate ion carry out it is high-resolution selection and analysis have become it is urgently to be resolved
Problem.
Summary of the invention
The purpose of the present invention is intended to solve above-mentioned one of technical problem at least to a certain extent.
For this purpose, the first purpose of this invention is to propose a kind of ion selectivity photodissociation device.The device passes through one
Group can be realized by the electrode group that four plate electrodes form to be carried out High Resolntion Mass-Spectrometry selection to the ion that ion source generates and realizes high
Resolved light dissociating product quality analysis obtains the molecular photodissociation of high quality from spectrum.
Second object of the present invention is to propose a kind of by ion selectivity photodissociation device progress ion selectivity
The method of photodissociation.
Third object of the present invention is to propose a kind of instrument.
In order to achieve the above object, the ion selectivity photodissociation device of first aspect present invention embodiment, comprising: electrode group,
The electrode group is set to the mass spectrographic field-free flight area of ion flight time, the electrode group include first electrode, second electrode,
Third electrode and the 4th electrode, the first electrode, second electrode, third electrode and the 4th electrode successively parallel arranged,
Wherein, circular hole is equipped among each electrode, and in each electrode circular hole central coaxial, grid are set on the circular hole
Net, the aperture plate for ion for passing through；Wherein, the first electrode, second electrode form quality gate, and the quality gate is used for
Select the ion of extra fine quality number；The second electrode, third electrode form dissociation, and the dissociation will be for that will pass through
Dissociation occurs under the irradiation of dissociation laser for the ion of the quality gate selection to generate fragment ion；The second electrode,
Three electrodes and the 4th electrode form two-stage accelerating field, and the two-stage accelerating field is for being added the fragment ion
Speed, so that the fragment ion reaches ion detector microchannel plate.
Ion selectivity photodissociation device according to an embodiment of the present invention is made of 4 plate electrodes of successively parallel arranged
Electrode group is constituted, wherein circular hole is equipped among each electrode, and in each electrode circular hole central coaxial, be arranged on circular hole
Aperture plate passes through for ion, and the quality gate being made up of first electrode, second electrode is led to selecting the ion of extra fine quality number
Cross second electrode, the dissociation of third electrode composition is issued with the irradiation by the ion selected by quality gate in dissociation laser
Raw dissociation is to generate fragment ion, and the composition two-stage accelerating field for passing through second electrode, third electrode and the 4th electrode
To accelerate fragment ion, so that fragment ion is finally reached ion detector microchannel plate.Realize by one group by
The electrode group of four plate electrodes composition, which can be realized, to be carried out High Resolntion Mass-Spectrometry selection to the ion that ion source generates and realizes high-resolution
The analysis of photodissociation product quality, obtains the molecular photodissociation of high quality from spectrum.
In order to achieve the above object, second aspect of the present invention embodiment carries out ion choosing by ion selectivity photodissociation device
The method of selecting property photodissociation, the ion selectivity photodissociation device are device described in first aspect present invention embodiment, institute
The method of stating includes:, when sample ions are cation, to apply in the second electrode negative during sample selects and dissociates
Pulse voltage controls the timing of pulse, and in the period for declining voltage, object ion passes through the first electrode and described the
Two electrodes, second electrode described in other time are in high positive potential, stop ion and pass through, wherein lead in the ion selected
Cross the second electrode in a flash, voltage is positive high pressure in the second electrode；When the ion that passes through of selection passes through described the
When two electrodes, controlling and select the ion passed through described in the dissociation laser bombardment, the ion for passing through the selection generates dissociation,
Wherein, the dissociation laser is pulsed, according to by the difference of selection ion, controls the timing of the dissociation laser so that described
It is synchronous by the process of the second electrode with ion to dissociate laser；It controls and applies DC voltage on the third electrode, so that
The second electrode and the 4th electrode collectively constitute the two-stage accelerating field, so that the ion after being dissociated adds again
Speed.
The method of ion selectivity photodissociation according to an embodiment of the present invention, i.e. by the electrode group that is made of four plate electrodes
The ion for generating ion source can be achieved to carry out High Resolntion Mass-Spectrometry selection and realize the analysis of high-resolution photodissociation product quality, obtain
The molecular photodissociation of high quality is from spectrum.
In order to achieve the above object, the instrument of third aspect present invention embodiment, comprising: laser light source, for emitting laser, with
Sample is set to be ionized into ion under the laser action；Ionic modulation electrode, for taper hole will to be passed through in the case where applying pulse voltage
The ion that perpendicular quadrature accelerates into ionic modulation area enters accelerating field；Deflecting electrode, for will be through the accelerating field
Ion is deflected so that the ion enters field-free flight area；Ion selectivity light described in first aspect present invention embodiment
Device for dissociation, the ion selectivity photodissociation device are placed in the mass spectrographic field-free flight area of ion flight time；Detector is used for
The ion for carrying out photodissociation by the ion selectivity photodissociation device is handled, to obtain the sample ions selected
Mass spectrogram after photodissociation.
Instrument according to an embodiment of the present invention passes through the electrode being made of in ion selectivity photodissociation device four plate electrodes
Group, which can be realized, to be carried out High Resolntion Mass-Spectrometry selection to the ion that ion source generates and realizes that high-resolution photodissociation product quality is analyzed,
Obtain the molecular photodissociation of high quality from spectrum, so as to which mass spectral analysis and photodissociation analysis to be used in combination with, so both
The information of molecular composition, and the information of available molecular structure can be obtained.
The additional aspect of the present invention and advantage will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the structural schematic diagram of ion selectivity photodissociation device according to an embodiment of the invention.
Fig. 2 is the flow chart of the method for ion selectivity photodissociation according to an embodiment of the invention；
Fig. 3 is the exemplary diagram of the pulse train of second electrode 120 in Fig. 1；And
Fig. 4 is the structural schematic diagram of instrument according to an embodiment of the invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
Below with reference to the accompanying drawings it describes the ion selectivity photodissociation device of the embodiment of the present invention, ion is carried out by the device
The method that selective light dissociates and the instrument with the device.
Fig. 1 is the structural schematic diagram of ion selectivity photodissociation device according to an embodiment of the invention.It needs to illustrate
, the ion selectivity photodissociation device of the embodiment of the present invention can be applied in mass spectrum and field of spectral analysis technology, can lead to
The ion selectivity photodissociation device for crossing the embodiment of the present invention realizes that the quality of ion selects the height with fragment ion after photodissociation
Resolution mass analysis.
As shown in Figure 1, the ion selectivity photodissociation device may include: electrode group 100, which can be set
It is placed in the mass spectrographic field-free flight area of ion flight time.It should be noted that working as the ion selectivity photodissociation of the embodiment of the present invention
When being applied in mass spectrum and spectrometric instrument from device, the electrode in the device is determined by the difference of flight time mass spectrum
The positional relationship of group 100 and the other component in mass spectrum and spectrometric instrument.For example, for reflection time-of-flight mass and
Speech, electrode group 100 can be located at after acceleration and deflecting electrode, before reflected field；For linear flight time mass spectrum,
Electrode group 100 is located at after acceleration and deflecting electrode, before detector.
Wherein, as shown in Figure 1, electrode group 100 may include first electrode 110, second electrode 120, third electrode 130 and
4th electrode 140, first electrode 110, second electrode 120, third electrode 130 and the 4th electrode 140 successively parallel arranged,
In, circular hole E is equipped among each electrode, and in each electrode circular hole E central coaxial, aperture plate is set on circular hole E, and aperture plate is used
Pass through in for ion.In addition, in an embodiment of the present invention, the size of the circular hole E in each electrode is not specifically limited, example
Such as, the size of the circular hole E in each electrode may be the same or different, and the selection depending on specific sample ions is conciliate
From situation.The size present invention of aperture plate on circular hole E is also not specifically limited, for example, the size of aperture plate is slightly larger than circular hole E
Size, for another example, the size of aperture plate is identical as the size of circular hole E.
It should be noted that in an embodiment of the present invention, first electrode 110, second electrode 120, third electrode 130 with
And the 4th electrode 140 be plate electrode.In addition, first electrode 110, second electrode 120, third electrode 130 and the 4th
The shape of electrode 140 can be round, rectangle or square etc., it will be understood that according to actual needs, the shape of electrode can be with
It is other shapes.In addition, the thickness of each electrode, the size present invention are also not specifically limited, can come according to actual needs
It determines.
As shown in Figure 1, first electrode 110, second electrode 120 can form quality gate, quality gate can be used for selecting specific
The ion of mass number.Second electrode 120, third electrode 130 form dissociation, and dissociation by quality gate for that will be selected
Ion dissociation laser irradiation under occur dissociation to generate fragment ion.
As shown in Figure 1, second electrode 120, third electrode 130 and the 4th electrode 140 form two-stage accelerating field, two-stage
Accelerating field continues to fly, so that fragment ion is finally reached ion detector for being accelerated fragment ion again
Microchannel plate (Microchannel Plate, referred to as MCP).
It should be noted that in an embodiment of the present invention, the successively value range of the interelectrode distance of parallel arranged
It can be 5 millimeters~15 millimeters, wherein the distance between second electrode 120 and third electrode 130 are greater than first electrode 110 and the
The distance between two electrodes 120, and the distance between second electrode 120 and third electrode 130 are greater than third electrode 130 and the 4th
The distance between electrode 140.That is, interelectrode distance is between 5 millimeters~15 millimeters, wherein for photodissociation
Two interelectrode distances may be slightly larger than other interelectrode distances.
For example, as shown in Figure 1, ion source generate different mass-to-charge ratioes a series of samples ion packet, by mass-to-charge ratio
It is followed successively by A, B, C from big to small, by entering field-free flight area after accelerating electrode and deflecting electrode.Through after a period of time from
After flying, sample ions sequentially enter 110,120,130,140 4 electrodes of electrode according to the sequence of mass number from small to large
The electrode group 100 of composition.First electrode 110, second electrode 120 form quality gate, the selection of the ion for extra fine quality number.
Region between second electrode 120 and third electrode 130, the ion of the extra fine quality number selected is in the photograph for dissociating laser F
Penetrate it is lower dissociate, generate fragment ion G.Second electrode 120, third electrode 130, the 4th these three electrodes of electrode 140 composition
One two-stage accelerating field continues to fly, eventually arrives at ion detector microchannel for accelerating fragment ion again
Plate.Finally, after data collection system records and amplifies, then by the processing output of subsequent instrument, it is finally obtained selected
Mass spectrogram after the sample ions photodissociation selected.
It should be noted that in an embodiment of the present invention, in ion selectivity photodissociation through the embodiment of the present invention
During device carries out ion selectivity photodissociation, first electrode 110 and the 4th electrode 140 are grounding electrode, and second
Electrode 120 applies pulse voltage, and third electrode 130 applies DC voltage.Wherein, the pulse voltage that second electrode 120 applies
The present invention is not specifically limited for amplitude, direction, can according to the polarity of sample ions and the mass number of specific selected ion and
Specific setting.
To sum up, the ion selectivity photodissociation device of the embodiment of the present invention, during ion selectivity photodissociation, only
The voltage of different timing need to be applied on same plate electrode to achieve the purpose that quality selects, this structure design can save height
Finish electrode slice reduces manufacturing cost, while being also beneficial to the micromation of instrument.Moreover, reducing electrode slice, that is, reduce
Required aperture plate on electrode slice, so as to shorten the distance of ion transmission, so that ion transmission efficiency greatly improves.Example
Such as, by taking the electrode group of 5 plate electrodes composition is compared with the electrode group of four plate electrodes composition of the invention as an example, experiment shows four electricity
The quantity of pole still can guarantee 60% or more transmission rate, and the transmission rate of five plate electrodes only has 50% (wherein, monolithic aperture plate
Transmitance about 90%).
Ion selectivity photodissociation device according to an embodiment of the present invention is made of 4 plate electrodes of successively parallel arranged
Electrode group is constituted, wherein circular hole is equipped among each electrode, and in each electrode circular hole central coaxial, be arranged on circular hole
Aperture plate passes through for ion, and the quality gate being made up of first electrode, second electrode is led to selecting the ion of extra fine quality number
Cross second electrode, the dissociation of third electrode composition is issued with the irradiation by the ion selected by quality gate in dissociation laser
Raw dissociation is to generate fragment ion, and the composition two-stage accelerating field for passing through second electrode, third electrode and the 4th electrode
To accelerate fragment ion, so that fragment ion is finally reached ion detector microchannel plate.Realize by one group by
The electrode group of four plate electrodes composition, which can be realized, to be carried out High Resolntion Mass-Spectrometry selection to the ion that ion source generates and realizes high-resolution
The analysis of photodissociation product quality, obtains the molecular photodissociation of high quality from spectrum.
In order to realize above-described embodiment, the invention also provides one kind to carry out ion by ion selectivity photodissociation device
The method of selective light dissociation, wherein the ion selectivity photodissociation device is device described in any of the above-described embodiment.
Fig. 2 is the flow chart of the method for ion selectivity photodissociation according to an embodiment of the invention.As shown in Fig. 2,
This method may include:
S210, when sample ions are cation, applies negative arteries and veins in second electrode during sample selects and dissociates
Voltage to be rushed, the timing of pulse is controlled, in the period for declining voltage, object ion passes through first electrode and second electrode,
Its time second electrode is in high positive potential, stops ion and passes through, wherein passes through the one of second electrode in the ion selected
Moment, voltage is positive high pressure in second electrode.
S220, when the ion that selection passes through passes through second electrode, control dissociation laser bombardment selects the ion passed through, makes
The ion passed through is selected to generate dissociation, wherein dissociation laser is pulsed, and according to by the difference of selection ion, control dissociation swashs
The timing of light is so that dissociation laser is synchronous by the process of second electrode with ion.
S230 is controlled and is applied DC voltage on third electrode, so that second electrode and the 4th electrode collectively constitute two-stage and add
Fast electric field, so that the ion after being dissociated is again speeded up.
In order to enable those skilled in the art can clearly understand the method for the present embodiment, below in conjunction with Fig. 1
And this method is described further in Fig. 3.
For example, firstly, as shown in Figure 1, first electrode and the 4th electrode 140 are grounding electrode, that is to say, that begin
It is zero potential eventually.During sample selects and dissociates, it is assumed that sample ions are cation, illustrate second electrode as example
120 and third electrode 130 on voltage's distribiuting situation.Wherein, apply pulse voltage, pulse voltage series in second electrode 120
Can be as shown in figure 3, ought be before B ion as shown in figure 1 reach first electrode 110, the voltage in second electrode 120 is V1, is kept
V1 voltage value is greater than the kinetic energy of ion, so that it may mass-to-charge ratio be stopped to be less than the ion of B, such as ion C.Assuming that at the T1 moment, from
Sub- B reaches first electrode 110, and the voltage in second electrode 120 drops to V2 from V1 at this time, and the voltage value of V2 is made to compare ion kinetic energy
Low certain numerical value, it can allow ion B by first electrode 110, and formed in first electrode 110 and second electrode 120
It realizes and slows down under electric field action, after ion B passes through second electrode 120, the voltage of second electrode 120 rapidly rises to V3,
Mass-to-charge ratio is stopped to be greater than the ion A of B.The ion B for being selected and being slowed down with infrared laser irradiation quality simultaneously, generates fragment ion,
The voltage of third electrode 130 can use DC voltage, and second electrode 120, third electrode 130 and the 4th electrode 140 are common
Two-stage accelerating field is formed, fragment ion and parent ion is made to obtain additional kinetic energy, and realizes separation.
As can be seen that the combination of four plate electrodes realizes the high score of the quality selection and fragment ion after photodissociation of ion
Distinguish quality analysis.Due to must be loaded with aperture plate on each plate electrode with uniform electric field, although aperture plate has the efficiency of transmission of ion
It is certain to influence, and the quantity of four plate electrodes still can guarantee 60% or more transmission rate.Wherein, second electrode and third electrode
On application voltage need to be specifically arranged according to specific sample ions, voltage volt can be differed from 200 volts to 4000, and range is not
It is restricted.
According to the method for the embodiment of the present invention, it can be realized by the electrode group being made of four plate electrodes and ion source generated
Ion carry out High Resolntion Mass-Spectrometry selection and realize the analysis of high-resolution photodissociation product quality, obtain the molecular photodissociation of high quality from
Spectrum.
In order to realize above-described embodiment, the invention also provides a kind of instruments.
Fig. 4 is the structural schematic diagram of instrument according to an embodiment of the invention.As shown in figure 4, the instrument may include:
Laser light source 410, ionic modulation electrode 420, deflecting electrode 430, ion selectivity photodissociation device 440 and detector 450.
It should be noted that Fig. 4 provided is nothing that ion selectivity photodissociation device is located at a linear flight time mass spectrum
The example of movement area, and the example is merely to more preferable the understanding of the present invention and a kind of example for providing, and can not make
To be to specific restriction of the invention.
Wherein, laser light source 410 is for emitting laser, so that sample is ionized into ion under laser action.Ionic modulation
Electrode 420 is used in the case where applying pulse voltage, and the ion that ionic modulation area is accelerated by 411 perpendicular quadrature of taper hole is entered
Accelerating field 421.Deflecting electrode 430 be used for by the ion of accelerated electric field 421 deflect with when ion enter field-free flight
Area.It is placed in the ion selectivity photodissociation device 440 in the mass spectrographic field-free flight area of ion flight time, the ion selectivity photodissociation
Concrete function description from device 440 can refer to the function description of device described in any of the above-described a embodiment.Detector 450 is used
In by pass through ion selectivity photodissociation device 440 carry out photodissociation ion handle, with obtain the sample selected from
Mass spectrogram after sub-light dissociation.
For example, as shown in figure 4, sample L makees in laser light source 410 (or other ion sources such as high pressure pulse discharge)
Ion M is ionized under, after taper hole 411, orthogonal acceleration enters ionic modulation area, applies on ionic modulation electrode 420
Under the pulse voltage added, ion enters in accelerating field 421, by accelerating, after deflecting electrode 430, into field-free flight
Area.In the flight approach of ion, it is equipped with electrode group, the electrode group is by first electrode 110, second electrode 120, third electrode
130 and the 4th electrode 140 form, for selecting ion and carry out photodissociation, dissociation laser N enters the second electricity in the form of a pulse
Region between pole 120 and third electrode 130, with the specified ionization selected.Ion after dissociation leaves the 4th electricity
Behind pole 140, continues to fly in field-free region, ion detector microchannel plate (MCP) 450 is eventually arrived at, by data collection system
After record and amplification, then handled and exported by subsequent instrument, the mass spectrogram after finally obtained sample ions photodissociation, into
And the molecular photodissociation of high quality is obtained from spectrum.
The description of a specific embodiment is given below.In this embodiment, the knot of the electrode group of four plate electrodes composition
Structure is as follows: electrode group by 4 diameters is 90 millimeters, forms with a thickness of 0.5 millimeter of electrode wafer.Every plate electrode center is provided with directly
The spacing of the circular hole that diameter is 15 millimeters, second electrode 120 and third electrode 130 is 15 millimeters, and other electrode spacings are 5.5 millis
Rice.Aperture plate is stained on circular hole, grid dimensions are 0.32mm × 0.32mm.Electrode group is located at a linear flight time mass spectrum
Field-free flight area in, electrode group distance accelerate and 1.4 meters of deflecting electrode, 0.6 meter of distance detector.
First electrode 110, second electrode 120, third electrode 130 and the 4th electrode 140 it is combined voltage's distribiuting it is as follows, with
Sample ions keep zero potential, second electrode for for cation, first electrode 110 and the 4th electrode 140 are grounding electrode
Apply high voltage pulse on 120, for example, second electrode 120 is remained in most of time in the DC potential of 2500V,
Until need selection ion will by when, voltage is rapidly reduced to 1900V, the ion wait select pass through second electrode 120 after,
It is quickly raised to 2500V.
Apply DC voltage on third electrode 130, collectively constitutes two-stage with second electrode 120, the 4th electrode 140 and accelerate electricity
, so that fragment ion and parent ion is obtained additional kinetic energy, and realize separation.
Instrument according to an embodiment of the present invention passes through the electrode being made of in ion selectivity photodissociation device four plate electrodes
Group, which can be realized, to be carried out High Resolntion Mass-Spectrometry selection to the ion that ion source generates and realizes that high-resolution photodissociation product quality is analyzed,
Obtain the molecular photodissociation of high quality from spectrum, so as to which mass spectral analysis and photodissociation analysis to be used in combination with, so both
The information of molecular composition, and the information of available molecular structure can be obtained.
In the description of the present invention, it is to be understood that, term " center ", "left", "right", "vertical", "horizontal",
The orientation or positional relationship of the instructions such as "top", "bottom" "inner", "outside" be based on the orientation or positional relationship shown in the drawings, be only for
Convenient for the description present invention and simplify description, rather than the device or element of indication or suggestion meaning there must be specific side
Position is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Any process described otherwise above or method description are construed as in flow chart or herein, and expression includes
It is one or more for realizing specific logical function or process the step of executable instruction code module, segment or portion
Point, and the range of the preferred embodiment of the present invention includes other realization, wherein can not press shown or discussed suitable
Sequence, including according to related function by it is basic simultaneously in the way of or in the opposite order, Lai Zhihang function, this should be of the invention
Embodiment person of ordinary skill in the field understood.
Expression or logic and/or step described otherwise above herein in flow charts, for example, being considered use
In the order list for the executable instruction for realizing logic function, may be embodied in any computer-readable medium, for
Instruction execution system, device or equipment (such as computer based system, including the system of processor or other can be held from instruction
The instruction fetch of row system, device or equipment and the system executed instruction) it uses, or combine these instruction execution systems, device or set
It is standby and use.For the purpose of this specification, " computer-readable medium ", which can be, any may include, stores, communicates, propagates or pass
Defeated program is for instruction execution system, device or equipment or the dress used in conjunction with these instruction execution systems, device or equipment
It sets.The more specific example (non-exhaustive list) of computer-readable medium include the following: there is the electricity of one or more wirings
Interconnecting piece (electronic device), portable computer diskette box (magnetic device), random access memory (RAM), read-only memory
(ROM), erasable edit read-only storage (EPROM or flash memory), fiber device and portable optic disk is read-only deposits
Reservoir (CDROM).In addition, computer-readable medium can even is that the paper that can print described program on it or other are suitable
Medium, because can then be edited, be interpreted or when necessary with it for example by carrying out optical scanner to paper or other media
His suitable method is handled electronically to obtain described program, is then stored in computer storage.
It should be appreciated that each section of the invention can be realized with hardware, software, firmware or their combination.Above-mentioned
In embodiment, software that multiple steps or method can be executed in memory and by suitable instruction execution system with storage
Or firmware is realized.It, and in another embodiment, can be under well known in the art for example, if realized with hardware
Any one of column technology or their combination are realized: having a logic gates for realizing logic function to data-signal
Discrete logic, with suitable combinational logic gate circuit specific integrated circuit, programmable gate array (PGA), scene
Programmable gate array (FPGA) etc..
Those skilled in the art are understood that realize all or part of step that above-described embodiment method carries
It suddenly is that relevant hardware can be instructed to complete by program, the program can store in a kind of computer-readable storage medium
In matter, which when being executed, includes the steps that one or a combination set of embodiment of the method.
It, can also be in addition, each functional unit in each embodiment of the present invention can integrate in a processing module
It is that each unit physically exists alone, can also be integrated in two or more units in a module.Above-mentioned integrated mould
Block both can take the form of hardware realization, can also be realized in the form of software function module.The integrated module is such as
Fruit is realized and when sold or used as an independent product in the form of software function module, also can store in a computer
In read/write memory medium.
Storage medium mentioned above can be read-only memory, disk or CD etc..Although having been shown and retouching above
The embodiment of the present invention is stated, it is to be understood that above-described embodiment is exemplary, and should not be understood as to limit of the invention
System, those skilled in the art can be changed above-described embodiment, modify, replace and become within the scope of the invention
Type.
Claims (7)
1. a kind of ion selectivity photodissociation device characterized by comprising
Electrode group, the electrode group are set to the mass spectrographic field-free flight area of ion flight time, and the electrode group includes the first electricity
Pole, second electrode, third electrode and the 4th electrode, the first electrode, second electrode, third electrode and the 4th electrode according to
Secondary parallel arranged, wherein circular hole is equipped among each electrode, and in each electrode circular hole central coaxial, the circle
Aperture plate is set on hole, and the aperture plate for ion for passing through；Wherein, the size of the aperture plate is not less than the ruler of the circular hole
Very little size；
Wherein, the first electrode, second electrode form quality gate, and the quality gate is used to select the ion of extra fine quality number；
The second electrode, third electrode form dissociation, what the dissociation was used to select by the quality gate
Dissociation occurs under the irradiation of dissociation laser for ion to generate fragment ion；
The second electrode, third electrode and the 4th electrode form two-stage accelerating field, and the two-stage accelerating field is used for will
The fragment ion is accelerated, so that the fragment ion reaches ion detector microchannel plate.
2. ion selectivity photodissociation device as described in claim 1, which is characterized in that passing through the ion selectivity light
During device for dissociation carries out ion selectivity photodissociation, the first electrode and the 4th electrode are ground connection electricity
Pole, the second electrode apply pulse voltage, and the third electrode applies DC voltage.
3. ion selectivity photodissociation device as described in claim 1, which is characterized in that the first electrode, second electrode,
Third electrode and the 4th electrode are plate electrode.
4. ion selectivity photodissociation device as described in claim 1, which is characterized in that the first electrode, second electrode,
The shape of third electrode and the 4th electrode is round or rectangle.
5. ion selectivity photodissociation device as described in claim 1, which is characterized in that the electrode of the successively parallel arranged
Between distance value range be 5 millimeters~15 millimeters, wherein the distance between the second electrode and the third electrode greatly
In the distance between the first electrode and the second electrode, and the distance between the second electrode and the third electrode
Greater than the distance between the third electrode and the 4th electrode.
6. a kind of ion selectivity photodissociation device by as described in any one of claims 1 to 5 carries out ion selectivity
The method of photodissociation, which comprises the following steps:
During sample selects and dissociates, when sample ions are cation, apply negative pulse electricity in the second electrode
Pressure, controls the timing of pulse, and in the period for declining voltage, object ion passes through the first electrode and second electricity
Pole, second electrode described in other time are in high positive potential, stop ion and pass through, wherein pass through institute in the ion selected
State second electrode in a flash, voltage is positive high pressure in the second electrode；
When the ion that passes through of selection is by the second electrode, control select to pass through described in the dissociation laser bombardment from
Son makes described the ion that passes through to be selected to generate dissociation, wherein the dissociation laser is pulsed, according to by selection ion not
Together, the timing of the dissociation laser is controlled so that the dissociation laser is synchronous by the process of the second electrode with ion；
Control and apply DC voltage on the third electrode so that the second electrode and the 4th electrode collectively constitute it is described
Two-stage accelerating field, so that the ion after being dissociated is again speeded up.
7. a kind of instrument characterized by comprising
Laser light source, for emitting laser, so that sample is ionized into ion under the laser action；
Ionic modulation electrode, for ionic modulation area will to be accelerated by taper hole perpendicular quadrature in the case where applying pulse voltage
Ion enters accelerating field；
Deflecting electrode, for being deflected the ion through the accelerating field so that the ion enters field-free flight area；
Ion selectivity photodissociation device as described in any one of claims 1 to 5, the ion selectivity photodissociation device
It is placed in the mass spectrographic field-free flight area of ion flight time；
Detector, for handling the ion for passing through the ion selectivity photodissociation device progress photodissociation, to obtain
Mass spectrogram after the sample ions photodissociation selected.
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