CN108760637A - A kind of device of research molecule photoisomerization - Google Patents

A kind of device of research molecule photoisomerization Download PDF

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Publication number
CN108760637A
CN108760637A CN201810832101.3A CN201810832101A CN108760637A CN 108760637 A CN108760637 A CN 108760637A CN 201810832101 A CN201810832101 A CN 201810832101A CN 108760637 A CN108760637 A CN 108760637A
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electrode group
ion
deviating
laser
linear
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CN108760637B (en
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傅晶晶
张向平
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Jinhua Polytechnic
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Jinhua Polytechnic
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited

Abstract

The present invention relates to spectrochemistry fields, a kind of device of research molecule photoisomerization, including electrospray device, ion bunch device, ion gate, laser, deviating electrode group, linear electrode group, octupole ion guide, quadrupole mass filter, detector, vacuum chamber, drift chamber, gas feed and outlet, the deviating electrode group has 19 annular electrodes, angle is five degree between adjacent annular electrode, linear electrode group has 20 annular electrodes, the annular electrode of deviating electrode group II has through-hole, the laser of laser III transmittings can enter drift region by the through-hole along z negative directions;The laser beam of laser I transmittings can enter drift region by deviating electrode group I, and the laser beam of laser II transmittings can enter drift region by linear electrode group II;Electrospray device is made of outer tube, inner tube, baffle, air inlet and liquid inlet, and outer tube and inner tube are cylindrical and are coaxial nested configuration, are fluid passage between outer tube and inner tube.

Description

A kind of device of research molecule photoisomerization
Technical field
The present invention relates to spectrochemistry field, a kind of especially a kind of research molecule light with a variety of smooth excitation modes is different The device of structure.
Background technology
Photoisomerization effect refers to the structure change that molecule occurs between isomerism under light excitation, can pass through analysis Certain spectrum lines judge light isomerization reaction to the influence of each group or even each atom chemistry displacement in molecule, usually It is studied using mass spectrum or ion mobility spectrometry, sample molecule is typically injected to drift region in the form of ion, and pass through electricity The electric field that pole generates makes its movement carry out subsequent measurement.Prior art defect one:The prior art can not be in the same apparatus Realize that laser is Chong Die with ion beam to interact from transverse direction and longitudinal direction;Prior art defect two:Generally use method of electrospraying Sample molecule is injected into drift region, the mass flow of the electron spray of the prior art exports a kind of relatively low, research molecule light The device of isomerization can solve the problems, such as.
Invention content
To solve the above-mentioned problems, a kind of device of research molecule photoisomerization of the present invention can be carried out before the mass spectrum stage Isomer selects and differentiates to the isomer in product, has a variety of smooth excitation modes;It can be used in studying The photodegradation of molecular ion can differentiate its charged products in terms of migration rate and quality two simultaneously;Injector head of the present invention With cricoid fluid passage, liquid is applied in upper high voltage with the shape of thin layer, so as to eject more uniform mist Change drop, improves the quality into the ion packet of drift region.
The technical solution adopted in the present invention is:
It is described it is a kind of research molecule photoisomerization device mainly include electrospray device, ion bunch device I, ion gate I, Laser I, deviating electrode group I, linear electrode group I, ion gate II, laser II, linear electrode group II, deviating electrode group II, Ion bunch device II, laser III, octupole ion guide, quadrupole mass filter, detector, vacuum chamber, drift chamber, gas Body import and gas vent, xyz are three-dimensional system of coordinate, the ion bunch device I, ion gate I, deviating electrode group I, linear electrode Group I, ion gate II, linear electrode group II, deviating electrode group II and ion bunch device II are sequentially connected, the ion bunch device I, Ion gate I, deviating electrode group I, linear electrode group I, ion gate II, linear electrode group II, deviating electrode group II and ion bunch Device II is respectively positioned on inside the drift chamber, the deviating electrode group I, linear electrode group I, linear electrode group II and deviating electrode group II is that 40 millimeters of annular electrode forms by internal diameter, the deviating electrode group I, linear electrode group I, linear electrode group II and The space that the annular electrode of deviating electrode group II is centrally formed is drift region, and the drift chamber has initiating terminal and end, institute It states initiating terminal and end all has an aperture for by ion beam current, the gas feed to be located at the side of drift chamber end Wall, the gas vent are located at the side wall of drift chamber initiating terminal, the gas feed be connected in turn mass flow controller and Air accumulator is equipped with buffer gas in air accumulator, and buffer gas is nitrogen or helium, and drift can be controlled by mass flow controller The buffer gas flow in chamber is moved, drift chamber is discharged from gas vent in buffer gas, and buffer gas flow representative value is 0.3SLM, SLM is every liter/min of calibrating gas, can form a back flow of gas by ion bunch device I, and can prevent neutral point Solvent molecule in son especially electron spray solution enters drift region, and drift chamber has vent valve, by adjusting buffer gas flow The frequency of the Push And Release of flow and the vent valve, can control the air pressure in drift region, and the air pressure representative value is 1000 Pascal, the electrospray device are located at the outer side of initiating terminal of drift chamber, and the vacuum chamber is located at one outside the end of drift chamber Side, the octupole ion guide, quadrupole mass filter and detector are located to linear array vacuum chamber successively, described There are one apertures to be used for through ion beam current for the initiating terminal tool of vacuum chamber, and vacuum chamber is connected with vacuum pump group, the vacuum pump group The vacuum chamber can be vacuumized, vacuum degree is better than 10-5Mbar, after electrospray device generates the ion of testing molecule, from Son passes through the ion bunch device I, ion gate I, deviating electrode group I, linear electrode group I, ion gate II, linear electrode group successively II, deviating electrode group II, ion bunch device II, octupole ion guide and quadrupole mass filter reach detector, to shape At ion beam current path.The deviating electrode group I and deviating electrode group II all have 19 annular electrodes, annular electrode respectively Perpendicular to yz planes, the angle between adjacent annular electrode is five degree, and in the deviating electrode group I, ion beam current first passes through The centers of ten annular electrodes be located in yz planes and on 1/8 circumference that radius is 50 millimeters, and with side clockwise To equally spacedly arranging, ion beam current followed by the centers of nine annular electrodes be located in yz planes and be located at radius It on 50 millimeters of 1/8 circumference, and equally spacedly arranges in a counterclockwise direction, in the deviating electrode group II, ion beam current is first By the centers of ten annular electrodes be located in yz planes and on 1/8 circumference that radius is 50 millimeters, and with up time Needle direction equally spacedly arranges, ion beam current followed by the centers of nine annular electrodes be located in yz planes and be located at On 1/8 circumference of 50 millimeters of radius, and equally spacedly arrange in a counterclockwise direction;The deviating electrode group I and deviating electrode One megohm of resistance is in series between adjacent annular electrode to divide, the deviating electrode group I and deviating electrode in group II Group II provide voltage by two high voltage power supplies respectively;Linear electrode group I and linear electrode group II all have 20 respectively Annular electrode, annular electrode have through-hole perpendicular to yz planes, the annular electrode of deviating electrode group II, laser III transmittings Laser can enter drift region by the through-hole along z negative directions;The laser beam of laser I transmittings can pass through the deviation Electrode group I enters drift region, and the laser beam of laser II transmittings can enter drift region by the linear electrode group II; Ion bunch device I is made of the metal ring electrode that 50 pieces of thickness are one millimeter, including the ring that ten internal diameters are 40 millimeters Shape electrode and be from 40 millimeters of linear 40 annular electrodes for being decreased to two millimeters, adjacent metal ring along z positive direction internal diameters Shape electrode is separated with the insulating trip of a millimeters thick;The ion bunch device II of drift region end connection is by 40 along z positive directions Internal diameter is to be formed from 40 millimeters of linear reduce to two millimeters of annular electrode;The electrospray device is by outer tube, inner tube, gear Plate, air inlet and liquid inlet composition, the baffle can be by the side port sealing of said inner tube, and the outer tube and inner tube are equal Internal diameter for cylinder, outer tube is 3000 microns, and the outer diameter of inner tube is 2700 microns, and the outer tube is coaxial nested structure with inner tube Type, is fluid passage between the outer tube and inner tube, air inlet and liquid inlet be separately connected outer tube outer wall and with the liquid Channel be connected to, outer tube wall have dispersion the groove along outer tube axial direction, the groove enable to liquid be partially formed it is prominent Go out shape to increase local electric field.The quantity of the groove of the outer tube wall is four to ten two, and grooved section shape is semicircle Or square or triangle.
When experiment, electron spray generate ion gathered in ion bunch device I, ion gate I periodically turn on so that Drift region leading portion where ion beam mutation deviating electrode group I, ion are acted on by drift field, to drift chamber end movement, And in drift region filled with nitrogen or helium mutually collide;Ion is received after leaving drift region by ion bunch device II Collection, passes sequentially through the aperture of drift chamber end, the aperture of vacuum chamber initiating terminal, octupole ion guide, quadrupole quality mistake later After filter, detector is eventually entered into.After ion is by ion bunch device I, or pass through the drift after ion bunch device II When region, ion can laterally be irradiated by laser, can axially be irradiated by laser when ion is among drift region, i.e., different Excitation mode.
The principle of the invention is that apparatus of the present invention are mainly based upon ion mobility spectrometry measurement method, have in drift region curved Tune enables to laser beam Chong Die in axially or transversally generation with the ion of drift and interacts to change same point of ion Isomeric form causes the drift velocity of ion to change.
The operation principle of ion mobility spectrometry:The ion packet formed is excited to float under the action of electric field by electrojet or light Move region in move, and with the buffer gas collisions in drift region, molecular isomer more compact in configuration movement Speed, therefore can be distinguished from space and by its molecular isomer larger with configuration on the time.In addition, of the invention In the peculiar two sections of bending sections of drift region, bending section is made of a series of annular electrodes and has and special arrangement, It can achieve the effect that ion is made to converge again in drift region, principle is as follows:On the downside of first bending section, bending section The distance between annular electrode is short, therefore electric field strength is big and the motion path of ion is short, therefore close to curved in an ion packet The drift distance of the upper ion of ion ratio on the downside of tune is short, therefore moves to front, and in second bending section, bending The distance between annular electrode of section downside is long, therefore electric field strength is small and the motion path of ion is long, therefore under bending section Long therefore upper in ion packet and on the lower the ion of drift distance of the upper ion of ion ratio of side converges again It is poly-.The advantages of designing in this way is its rear end without larger ion bunch device is deflected to deflected ion beam direction, to keep away Exempt from ion and lost during by ion bunch device excessive, avoids the resolution ratio of spectrum for influencing to collect.Energy of the present invention Enough photoisomerization action spectrums for measuring the isomer by mobility selection, what device detected is the change of ion drift velocity Change, and the signal by measuring photoisomer obtains photoisomerization action spectrum with for the relationship of light activated optical maser wavelength.It is logical The function for measuring photoisomer yield as optical maser wavelength is crossed, can obtain reflecting molecule absorption spectrum and depends on light wavelength lambda Isomerization yield φ (λ) action spectrum, if yield φ (λ), independently of optical wavelength, photoisomerization action spectrum is inhaled with light Receipts spectrum is similar, and the photoisomerization action spectrum of this form compensates for the deficiency of the existing spectral technology for molecular detection ion.
It is using a kind of method and step studied of device of research molecule photoisomerization:
High pure nitrogen is passed through by one, from the air inlet of electrospray device, and flow representative value is 1.0SLM, and SLM is Standard Gases Every liter/min of body, while the solution comprising testing molecule being passed through from the liquid inlet of electrospray device, flow representative value is 2.0 ml/min;
Two, apply voltage, voltage range 1000V to 5000V so that solution between the outer tube and inner tube of electrospray device In part testing molecule become ionic species, and solution exports the drop to form atomization in electrospray device, adjusts voltage The shape of liquid spray can be adjusted, a part of drop enters drift chamber by the aperture of drift chamber initiating terminal;
Three, enter the ion of drift chamber when by ion bunch device I, first annular electrode of ion bunch device I and Only apply DC potential on the last one annular electrode, applies direct current and exchange potential on other annular electrodes, DC potential Range 150V to 300V, exchanges range 30V to the 50V of potential, and the phase phase of the exchange potential applied on adjacent annular electrode Instead, the driving frequency for exchanging potential is 300kHz, and the DC potential on each annular electrode is added to along z pros by divider To successively decreasing so that ion beam achievees the effect that convergence;
The direction of motion of the four, ion beams when drift region where deviating electrode group I is returned to after first deviateing the directions z The directions z, next successively after linear electrode group I, ion gate II, linear electrode group II, next in deviating electrode group II The direction of motion is returned to the directions z after first deviateing the directions z in the drift region at place;
Five, laser irradiations excite it to the ion packet in drift region, and laser beam cross-section is more than 5 millis Rice × 5 millimeters can be selected there are three types of light excitation mode so that entire ion packet is all irradiated to:
Pattern one:Ion 30 millimeters of positions after by ion gate I are shone by the laser pulse emitted by laser I It penetrates, parent ion and the photoisomer generated by light excitation, light fragment ion are can be in time and sky after drift region Between on be separated come, advantage is that entire ion packet can be before diffusion by relatively stronger laser irradiation;
Pattern two:In drift region intermediate ion packet after the selection of the mobility of ion gate II, emitted by laser II Laser irradiation.After ion gate I is opened and passes through some from subpacket transmission, ion gate II opens 100 microseconds, in ion gate The positions 15mm after II, the laser pulse emitted by laser II overlap with selected ion, and advantage is can be to drift tube In the photoisomer detached over time and space excited, generate by mobility selection isomers ion packet, As a result, photoisomer signal can be observed under conditions of zero back end;
Pattern three:The through-hole on annular electrode for pass through deviating electrode group II by the laser that laser III emits, along the side z To being radiated on ion, advantage is to be suitable for being energized into excitation state from ground state and relax towards the molecular ion of ground state rapidly, at this Under the conditions of kind, laser excitation can be used in establishing the CD-ROM drive dynamic balancing between ground state and excitation state;
Six, ion beams enter ion bunch device II, first annular electrode of ion bunch device II and the last one annular Only apply DC potential on electrode, applies direct current on other annular electrodes and exchange potential, the range 150V of DC potential are arrived 300V, exchanges range 30V to the 50V of potential, and the opposite in phase of the exchange potential applied on adjacent annular electrode, driving frequency For 500kHz, the DC potential linear decrease being added to by divider on each annular electrode so that ion beam further converges It is poly-;
The aperture for the aperture and vacuum chamber initiating terminal that seven, ion beams pass sequentially through drift chamber end enters vacuum chamber, ion Beam reduces after the ion guide of octupole in the section of xz planes;
Eight, ion beams pass through quadrupole mass filter, the voltage value on quadrupole rod by adjusting quadrupole mass filter, Voltage range 50V to 200V can carry out quality selection according to the charge-mass ratio difference of ion to ion;
Ions of nine, by quality selection enters detector, obtains corresponding signal;
Ten, analyze data, obtain power and the delay time for the ion signal that detector detects under different lasing conditions, Obtain Isomers ion packet reach detector time distribution, obtain Isomers ion packet reach detector time with The relationship of its charge-mass ratio obtains the pass that Isomers ion packet reaches the time and the optical maser wavelength of light excitation use of detector System, judge generate ion type and its from the relationship of different optical maser wavelengths, obtain photoisomerization action spectrum;
11, further analyze data, determine the relationship of the ionic mobility and molecular structure that measure.
The beneficial effects of the invention are as follows:
The present invention is used to study the photoisomerization of the molecular ion of gas phase, its advantage is that can be carried out before the mass spectrum stage same Divide isomeric compound to select and the isomer in product is differentiated, there are a variety of smooth excitation modes;The present invention can also use In the photodegradation of research molecular ion, it can differentiate its charged products in terms of migration rate and quality two simultaneously;In addition, this Invention injector head has cricoid fluid passage, and liquid is applied in upper high voltage with the shape of thin layer, so as to eject compared with For uniform atomized drop, the quality into the ion packet of drift region is improved.
Description of the drawings
It is further illustrated with reference to the figure of the present invention:
Fig. 1 is schematic diagram of the present invention;
Fig. 2 is the vertical view of electrospray device;
Fig. 3 is the side view of electrospray device.
In figure, 1. electrospray devices, 1-1. outer tubes, 1-2. inner tubes, 1-3. baffles, 1-4. air inlets, the liquid inlets 1-5., 2. ion bunch device I, 3. ion gate I, 4. laser I, 5. deviating electrode group I, 6. linear electrode group I, 7. ion gate II, 8. swash Light device II, 9. linear electrode group II, 10. deviating electrode group II, 11. ion bunch device II, 12. laser III, 13. octupoles from Sub- guiding device, 14. quadrupole mass filters, 15. detectors, 16. vacuum chambers, 17. drift chambers, 18. gas feeds, 19. gases Outlet.
Specific implementation mode
If Fig. 1 is schematic diagram of the present invention, mainly include electrospray device (1), ion bunch device I (2), ion gate I (3), Laser I (4), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), laser II (8), linear electrode group II (9), deviating electrode group II (10), ion bunch device II (11), laser III (12), octupole ion guide (13), quadrupole matter Measure filter (14), detector (15), vacuum chamber (16), drift chamber (17), gas feed (18) and gas vent (19), xyz For three-dimensional system of coordinate, the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion Door II (7), linear electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) are sequentially connected, and the ion is poly- Beam device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), linear electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) is respectively positioned on the drift chamber (17) inside, the deviating electrode group The annular that I (5), linear electrode group I (6), linear electrode group II (9) and deviating electrode group II (10) are 40 millimeters by internal diameter Electrode forms, the deviating electrode group I (5), linear electrode group I (6), linear electrode group II (9) and deviating electrode group II (10) The space that is centrally formed of annular electrode be drift region, the drift chamber (17) has initiating terminal and end, the initiating terminal An aperture is all had for by ion beam current, the gas feed (18) to be located at the side of drift chamber (17) end with end Wall, the gas vent (19) are located at the side wall of drift chamber (17) initiating terminal, and the gas feed (18) is connected with quality in turn Flow controller and air accumulator are equipped with buffer gas in air accumulator, and buffer gas is nitrogen or helium, is controlled by mass flow Device can control the buffer gas flow in drift chamber (17), and buffer gas delays from gas vent (19) discharge drift chamber (17) It is 0.3SLM to rush gas flow representative value, and SLM is every liter/min of calibrating gas, can form one by ion bunch device I (2) back flow of gas, and the solvent molecule in neutral molecule especially electron spray solution can be prevented to enter drift region, it drifts about Chamber (17) has vent valve, and the frequency of the Push And Release by adjusting buffer gas flow flow and the vent valve can control drift Air pressure in region, the air pressure representative value are 1000 Pascals, and the electrospray device (1) is located at the starting of drift chamber (17) The outer side in end, the vacuum chamber (16) are located at side outside the end of drift chamber (17), the octupole ion guide (13), quadrupole Mass filter (14) and detector (15) are located to linear array vacuum chamber (16) inside successively, and the vacuum chamber (16) is risen There are one apertures to be used for through ion beam current for beginning tool, and vacuum chamber (16) is connected with vacuum pump group, and the vacuum pump group can be right The vacuum chamber (16) vacuumizes, and vacuum degree is better than 10-5Mbar, after electrospray device (1) generates the ion of testing molecule, from Son passes through the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate successively II (7), linear electrode group II (9), deviating electrode group II (10), ion bunch device II (11), octupole ion guide (13) and Quadrupole mass filter (14) reaches detector (15), to form ion beam current path.The deviating electrode group I (5) and partially All have 19 annular electrodes respectively to electrode group II (10), annular electrode perpendicular to yz planes, adjacent annular electrode it Between angle be five degree, in the deviating electrode group I (5), the center for ten annular electrodes that ion beam current first passes through is located at yz It in plane and on 1/8 circumference that radius is 50 millimeters, and equally spacedly arranges in a clockwise direction, ion beam current connects Get off by the centers of nine annular electrodes be located in yz planes and on 1/8 circumference of 50 millimeters of radius, and with inverse Clockwise equally spacedly arranges, in the deviating electrode group II (10), in ten annular electrodes that ion beam current first passes through The heart is located in yz planes and on 1/8 circumference that radius is 50 millimeters, and equally spacedly arranges in a clockwise direction, from Beamlet stream followed by the centers of nine annular electrodes be located in yz planes and positioned at 1/8 circumference of 50 millimeters of radius On, and equally spacedly arrange in a counterclockwise direction;Adjacent ring in the deviating electrode group I (5) and deviating electrode group II (10) One megohm of resistance is in series between shape electrode to divide, the deviating electrode group I (5) and deviating electrode group II (10) are respectively Voltage is provided by two high voltage power supplies;Linear electrode group I (6) and linear electrode group II (9) all have 20 rings respectively Shape electrode, annular electrode have through-hole, laser III (12) perpendicular to yz planes, the annular electrode of deviating electrode group II (10) The laser of transmitting can enter drift region by the through-hole along z negative directions;The laser beam of laser I (4) transmittings can lead to It crosses the deviating electrode group I (5) and enters drift region, the laser beam of laser II (8) transmittings can pass through the linear electrode Group II (9) enters drift region;Ion bunch device I (2) is made of the metal ring electrode that 50 pieces of thickness are one millimeter, including The annular electrode and be linearly be decreased to two millimeters from 40 millimeters 40 along z positive direction internal diameters that ten internal diameters are 40 millimeters A annular electrode, adjacent metal annular electrode are separated with the insulating trip of a millimeters thick;The ion bunch of drift region end connection Device II (11) is to be formed from 40 millimeters of linear reduce to two millimeters of annular electrode along z positive direction internal diameters by 40;It is described The quantity of the groove of outer tube (1-1) inner wall is four to ten two, and grooved section shape is semicircle or square or triangle.
If Fig. 2 is the vertical view of electrospray device, if Fig. 3 is the side view of electrospray device, the electrospray device (1) It is made of outer tube (1-1), inner tube (1-2), baffle (1-3), air inlet (1-4) and liquid inlet (1-5), the baffle (1-3) Can be by the side port sealing of said inner tube (1-2), the outer tube (1-1) and inner tube (1-2) they are cylinder, outer tube (1- 1) internal diameter is 3000 microns, and the outer diameter of inner tube (1-2) is 2700 microns, and the outer tube (1-1) and inner tube (1-2) are coaxial embedding Configuration is covered, is fluid passage between the outer tube (1-1) and inner tube (1-2), air inlet (1-4) and liquid inlet (1-5) are respectively Connection outer tube (1-1) outer wall simultaneously be connected to the fluid passage, outer tube (1-1) inner wall have dispersion along outer tube axial direction it is recessed Slot, the groove enable to liquid being partially formed standing shape to increase local electric field.
It is described it is a kind of research molecule photoisomerization device mainly include electrospray device (1), ion bunch device I (2), from It is cervical orifice of uterus I (3), laser I (4), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), laser II (8), straight Line electrode group II (9), deviating electrode group II (10), ion bunch device II (11), laser III (12), octupole ion guide (13), quadrupole mass filter (14), detector (15), vacuum chamber (16), drift chamber (17), gas feed (18) and gas go out Mouth (19), xyz is three-dimensional system of coordinate, the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode Group I (6), ion gate II (7), linear electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) connect successively It connects, it is the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), straight Line electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) are respectively positioned on the drift chamber (17) inside, described Deviating electrode group I (5), linear electrode group I (6), linear electrode group II (9) and deviating electrode group II (10) are 40 by internal diameter The annular electrode composition of millimeter, the deviating electrode group I (5), linear electrode group I (6), linear electrode group II (9) and deviation electricity The space that the annular electrode of pole group II (10) is centrally formed is drift region, and the drift chamber (17) has initiating terminal and end, The initiating terminal and end all have an aperture for by ion beam current, the gas feed (18) to be located at drift chamber (17) The side wall of end, the gas vent (19) are located at the side wall of drift chamber (17) initiating terminal, and the gas feed (18) connects successively It is connected to mass flow controller and air accumulator, buffer gas is housed in air accumulator, buffer gas is nitrogen or helium, passes through quality Flow controller can control the buffer gas flow in drift chamber (17), and drift chamber is discharged from gas vent (19) in buffer gas (17), buffer gas flow representative value is 0.3SLM, and SLM is every liter/min of calibrating gas, can form one and be gathered by ion The back flow of gas of beam device I (2), and the solvent molecule in neutral molecule especially electron spray solution can be prevented to enter drift region Domain, drift chamber (17) have vent valve, and the frequency of the Push And Release by adjusting buffer gas flow flow and the vent valve can be controlled Air pressure in drift region processed, the air pressure representative value are 1000 Pascals, and the electrospray device (1) is located at drift chamber (17) The outer side of initiating terminal, the vacuum chamber (16) is located at side outside the end of drift chamber (17), the octupole ion guide (13), quadrupole mass filter (14) and detector (15) are located to linear array vacuum chamber (16) inside, the vacuum successively There are one apertures to be used for through ion beam current for the initiating terminal tool of chamber (16), and vacuum chamber (16) is connected with vacuum pump group, the vacuum Pump group can vacuumize the vacuum chamber (16), and vacuum degree is better than 10-5Mbar, when electrospray device (1) generates testing molecule Ion after, ion successively pass through the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), linear electrode group II (9), deviating electrode group II (10), ion bunch device II (11), octupole ion draw It leads device (13) and quadrupole mass filter (14) reaches detector (15), to form ion beam current path.The deviating electrode Group I (5) and deviating electrode group II (10) all have 19 annular electrodes respectively, and annular electrode is adjacent perpendicular to yz planes Angle between annular electrode is five degree, in the deviating electrode group I (5), ten annular electrodes that ion beam current first passes through Center is located in yz planes and on 1/8 circumference that radius is 50 millimeters, and equally spacedly arranges in a clockwise direction, Ion beam current followed by the centers of nine annular electrodes be located in yz planes and positioned at 1/8 circle of 50 millimeters of radius Zhou Shang, and equally spacedly arranging in a counterclockwise direction, in the deviating electrode group II (10), ten rings that ion beam current first passes through The center of shape electrode is located in yz planes and on 1/8 circumference that radius is 50 millimeters, and in a clockwise direction equidistantly Ground arranges, ion beam current followed by the centers of nine annular electrodes be located in yz planes and positioned at 50 millimeters of radius 1/8 circumference on, and equally spacedly arrange in a counterclockwise direction;In the deviating electrode group I (5) and deviating electrode group II (10) One megohm of resistance is in series between adjacent annular electrode to divide, the deviating electrode group I (5) and deviating electrode group II (10) voltage is provided by two high voltage power supplies respectively;Linear electrode group I (6) and linear electrode group II (9) all have respectively 20 annular electrodes, annular electrode have through-hole, laser perpendicular to yz planes, the annular electrode of deviating electrode group II (10) The laser of III (12) transmittings can enter drift region by the through-hole along z negative directions;The laser beam of laser I (4) transmittings Drift region can be entered by the deviating electrode group I (5), the laser beam of laser II (8) transmittings can be by described straight Line electrode group II (9) enters drift region;The metal ring electrode group that ion bunch device I (2) is one millimeter by 50 pieces of thickness At, including ten internal diameters be 40 millimeters annular electrode and be linear to be decreased to two millis from 40 millimeters along z positive direction internal diameters 40 annular electrodes of rice, adjacent metal annular electrode are separated with the insulating trip of a millimeters thick;The connection of drift region end Ion bunch device II (11) is linearly to be reduced to two millimeters of annular electrode group from 40 millimeters along z positive direction internal diameters by 40 At;The electrospray device (1) is by outer tube (1-1), inner tube (1-2), baffle (1-3), air inlet (1-4) and liquid inlet (1- 5) it forms, the baffle (1-3) can be by the side port sealing of said inner tube (1-2), the outer tube (1-1) and inner tube (1- 2) it is cylinder, the internal diameter of outer tube (1-1) is 3000 microns, and the outer diameter of inner tube (1-2) is 2700 microns, the outer tube (1- 1) and inner tube (1-2) is coaxial nested configuration, is fluid passage, air inlet (1- between the outer tube (1-1) and inner tube (1-2) 4) it is separately connected outer tube (1-1) outer wall with liquid inlet (1-5) and is connected to the fluid passage, outer tube (1-1) inner wall has The groove along outer tube axial direction of dispersion, the groove enable to liquid being partially formed standing shape to increase local electric field.Institute The quantity for stating the groove of outer tube (1-1) inner wall is four to ten two, and grooved section shape is semicircle or square or triangle.
When experiment, the ion that electron spray generates gathers in ion bunch device I (2), and ion gate I (3) is periodically turned on So that the drift region leading portion where ion beam mutation deviating electrode group I (5), ion are acted on by drift field, to drift chamber (17) end movement, and in drift region filled with nitrogen or helium mutually collide;Ion quilt after leaving drift region Ion bunch device II (11) collect, pass sequentially through later the aperture of drift chamber (17) end, the aperture of vacuum chamber (16) initiating terminal, After octupole ion guide (13), quadrupole mass filter (14), detector (15) is eventually entered into.When ion passes through ion bunch After device I (2), or when by drift region after ion bunch device II (11), ion can laterally be irradiated by laser, when from It can axially be irradiated by laser when son is among drift region, i.e., different excitation modes.
The present invention is used to study the photoisomerization of the molecular ion of gas phase, has a variety of smooth excitation modes, can be used in grinding Study carefully the photodegradation of molecular ion, can differentiate its charged products in terms of migration rate and quality two simultaneously;In addition, of the invention Injector head has cricoid fluid passage, can eject more uniform atomized drop, improves the ion into drift region The quality of packet increases the signal-to-noise ratio for the ion signal that detector obtains.

Claims (2)

1. a kind of device of research molecule photoisomerization, includes mainly electrospray device (1), ion bunch device I (2), ion gate I (3), laser I (4), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), laser II (8), linear electrode Group II (9), deviating electrode group II (10), ion bunch device II (11), laser III (12), octupole ion guide (13), four Pole mass filter (14), detector (15), vacuum chamber (16), drift chamber (17), gas feed (18) and gas vent (19), Xyz is three-dimensional system of coordinate, the ion bunch device I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), Ion gate II (7), linear electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) are sequentially connected, it is described from Sub- beam buncher I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), linear electrode group II (9), deviating electrode group II (10) and ion bunch device II (11) are respectively positioned on the drift chamber (17) inside, the deviating electrode The ring that group I (5), linear electrode group I (6), linear electrode group II (9) and deviating electrode group II (10) are 40 millimeters by internal diameter Shape electrode forms, the deviating electrode group I (5), linear electrode group I (6), linear electrode group II (9) and deviating electrode group II (10) space that annular electrode is centrally formed be drift region, the drift chamber (17) have initiating terminal and end, described Beginning and end all have an aperture for by ion beam current, the gas feed (18) to be located at drift chamber (17) end Side wall, the gas vent (19) are located at the side wall of drift chamber (17) initiating terminal, and the gas feed (18) is connected with matter in turn Flow controller and air accumulator are measured, buffer gas is housed in air accumulator, buffer gas is nitrogen or helium, passes through mass flow control Device processed can control the buffer gas flow in drift chamber (17), and drift chamber (17) is discharged from gas vent (19) in buffer gas, Buffer gas flow representative value is 0.3SLM, can form a back flow of gas by ion bunch device I (2), and can hinder Only the solvent molecule in neutral molecule especially electron spray solution enters drift region, and drift chamber (17) has vent valve, passes through The frequency for adjusting the Push And Release of buffer gas flow flow and the vent valve, can control the air pressure in drift region, the air pressure Representative value is 1000 Pascals, and the electrospray device (1) is located at the outer side of initiating terminal of drift chamber (17), the vacuum chamber (16) it is located at side outside the end of drift chamber (17), the octupole ion guide (13), quadrupole mass filter (14) and spy It surveys device (15) and is located to linear array vacuum chamber (16) inside successively, there are one apertures to use for the initiating terminal tool of the vacuum chamber (16) In by ion beam current, vacuum chamber (16) is connected with vacuum pump group, and the vacuum pump group can take out the vacuum chamber (16) true Sky, vacuum degree are better than 10-5Mbar, after electrospray device (1) generates the ion of testing molecule, ion passes through the ion successively Beam buncher I (2), ion gate I (3), deviating electrode group I (5), linear electrode group I (6), ion gate II (7), linear electrode group II (9), deviating electrode group II (10), ion bunch device II (11), octupole ion guide (13) and quadrupole mass filter (14) Detector (15) is reached, to form ion beam current path,
It is characterized in that:The deviating electrode group I (5) and deviating electrode group II (10) all have 19 annular electrodes, ring respectively Angle of the shape electrode between yz planes, adjacent annular electrode is five degree, in the deviating electrode group I (5), ion beam The center for ten annular electrodes that stream first passes through is located in yz planes and on 1/8 circumference that radius is 50 millimeters, and with Clockwise equally spacedly arrange, ion beam current followed by nine annular electrodes center be located in yz planes and On 1/8 circumference of 50 millimeters of radius, and equally spacedly arrange in a counterclockwise direction, the deviating electrode group II (10) In, the center for ten annular electrodes that ion beam current first passes through is located in yz planes and positioned at 1/8 circle that radius is 50 millimeters Zhou Shang, and equally spacedly arranging in a clockwise direction, ion beam current followed by the centers of nine annular electrodes be located at yz On 1/8 circumference in plane and positioned at 50 millimeters of radius, and equally spacedly arrange in a counterclockwise direction;The deviating electrode One megohm of resistance is in series between adjacent annular electrode in group I (5) and deviating electrode group II (10) to divide, it is described inclined To electrode group I (5) and deviating electrode group II (10) voltage is provided by two high voltage power supplies respectively;Linear electrode group I (6) and Linear electrode group II (9) all has 20 annular electrodes respectively, and annular electrode is perpendicular to yz planes, deviating electrode group II (10) Annular electrode have through-hole, laser III (12) transmitting laser can enter drift region along z negative directions by the through-hole Domain;The laser beam of laser I (4) transmittings can enter drift region, laser II (8) hairs by the deviating electrode group I (5) The laser beam penetrated can enter drift region by the linear electrode group II (9);Ion bunch device I (2) is by 50 pieces of thickness Formed for one millimeter of metal ring electrode, including ten internal diameters be 40 millimeters annular electrode and along z positive direction internal diameters be From 40 millimeters of linear 40 annular electrodes for being decreased to two millimeters, the insulating trip of one millimeters thick of adjacent metal annular electrode It separates;The ion bunch device II (11) of drift region end connection is linear from 40 millimeters along z positive direction internal diameters by 40 It reduces to two millimeters of annular electrode and forms;The electrospray device (1) by outer tube (1-1), inner tube (1-2), baffle (1-3), Air inlet (1-4) and liquid inlet (1-5) composition, the baffle (1-3) can be close by a side ports of said inner tube (1-2) Envelope, the outer tube (1-1) and inner tube (1-2) are cylinder, and the internal diameter of outer tube (1-1) is 3000 microns, outside inner tube (1-2) Diameter is 2700 microns, and the outer tube (1-1) and inner tube (1-2) are coaxial nested configuration, the outer tube (1-1) and inner tube (1-2) Between be fluid passage, air inlet (1-4) and liquid inlet (1-5) are separately connected outer tube (1-1) outer wall and lead to the liquid Road is connected to, and there is outer tube (1-1) inner wall the groove along outer tube axial direction of dispersion, the groove liquid to be enabled to be partially formed Standing shape is to increase local electric field.
2. a kind of device of research molecule photoisomerization according to claim 1, it is characterized in that:In the outer tube (1-1) The quantity of the groove of wall is four to ten two, and grooved section shape is semicircle or square or triangle.
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