CN105675593B - A kind of the gas-phase ion chemistry illuminated message detection device and method of liquid phase sample - Google Patents
A kind of the gas-phase ion chemistry illuminated message detection device and method of liquid phase sample Download PDFInfo
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- CN105675593B CN105675593B CN201610190494.3A CN201610190494A CN105675593B CN 105675593 B CN105675593 B CN 105675593B CN 201610190494 A CN201610190494 A CN 201610190494A CN 105675593 B CN105675593 B CN 105675593B
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Abstract
The present invention provides a kind of the gas-phase ion chemistry illuminated message detection device and method of liquid phase sample, described includes detection module, manual adjustment module, esi ion source, electric translation module and the cavity module for fixing above-mentioned each component, the main body of cavity module is the chamber structure equipped with multiple through-holes, and detection module is fixed on the through hole of the side of cavity module；Manual adjustment module is movably set in the upper through-hole of cavity module, and multiple esi ion sources are mounted on the top of manual adjustment module and the upper through-hole of transit chamber module stretches into chamber；Electric translation module is fixed on the one side of cavity module, and is connected with manual adjustment module.Compact in design of the present invention, of low cost, configuration is flexible, easy to use, and stability is high, can be used for detecting the chemiluminescence information for the gaseous ion that liquid phase sample is generated by normal pressure ESI technologies, can also be achieved sample ions from the continuous detection that liquid phase is gas phase process.
Description
Technical field
The invention belongs to analysis technical fields, are related to the gas-phase ion chemistry illuminated message detection technique of liquid phase sample, tool
Body is related to a kind of the gas-phase ion chemistry illuminated message detection device and method of liquid phase sample.
Background technology
For in the detection of liquid phase substance chemiluminescence information, easily by solvent microenvironment such as temperature, polarity, acidity, viscosity
Etc. factors influence, therefore the substance optical information obtained in the chemiluminescence infomation detection of liquid phase substance usually with the sheet of substance
There are certain deviations for matter optical property.Although scientific worker recognizes this, suitable method inspection is not found always
Survey the liquid phase substance chemiluminescence information of desolvation.
Nearly ten years, the optical information detection for developing into desolvation liquid phase substance of gas phase ion spectrometry technology provides
May, thus the detection of gas phase optical information is paid close attention to by more and more scientific workers.Wherein, electron spray ionisation
(ElectroSpray Ionization, ESI) technology is most common gaseous ion generation technique, certain from ESI taylor cones
In the space of distance, most of ion that ESI is generated becomes the gaseous ion that no solvent surrounds.Therefore, in this item
Under part, the radiative property of analyte is not influenced by solvent, closer to actual value.Currently, Konstantin
The gaseous ion that Chingin, Huanwen Chen, Gerardo Gamez et al. generate super-pressure, high vacuum ESI technologies
Optical information has carried out detection research [Konstantin Chingin, Huanwen Chen, Gerardo Gamez, et
al.Exploring Fluorescence and Fragmentation of Ions Produced by Electrospray
Ionization in Ultrahigh Vacuum[J].Am Soc Mass Spectrom,2009,20:1731~1738], institute
Device is complicated, expensive and limited by super-pressure, high vacuum, and the gas phase prepared due to extra-high voltage ESI technologies from
Son is captured in high vacuum ion trap, excites and detects, the factors such as temperature, capture energy, exciting light energy in ion trap
Different degrees of influence is generated to the optical information of gaseous ion.
Different from super-pressure ESI, normal pressure ESI technologies generate gaseous ion in atmospheric environment, and exciting light energy is in air
It is cooled rapidly in environment, the optical information of gaseous ion is influenced smaller, and the relatively low temperature of atmospheric environment is also beneficial to
The stabilization of gaseous ion, therefore normal pressure ESI technologies are more suitable for detecting the optical information of gaseous ion.
Gaseous ion is in flow regime after generating, how to capture optical information while gaseous ion generates is gas phase
The Major Difficulties of ion-optical infomation detection, Konstantin etc. grind the gaseous ion in atmospheric pressure environment
Study carefully, but the device, by manually building, there are poor air-tightness, stability is poor, configures the deficiencies of dumb, and the device
The fluorescence of gaseous ion can only be detected, and chemiluminescence information can not be detected simultaneously, use scope is narrow, currently used for normal
Press ESI technologies generate gaseous ion chemiluminescence infomation detection device it is also rarely found, this to a certain degree on limit gas
Detection, research and the application of the chemiluminescence information of phase ion.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of compact in design, of low cost, and configuration is flexible, easy to use, surely
The gas-phase ion chemistry illuminated message detection device of qualitative high liquid phase sample can be used for detecting liquid phase sample and pass through normal pressure
The chemiluminescence information for the gaseous ion that ESI technologies generate can also be achieved sample ions from the company that liquid phase is gas phase process
Continuous detection.
The above-mentioned purpose of the present invention is realized by following technical scheme：
A kind of gas-phase ion chemistry illuminated message detection device of liquid phase sample, including detection module, esi ion source with
And the cavity module for fixing above-mentioned each component, wherein：
The main body of cavity module is the chamber structure equipped with multiple through-holes, and multiple esi ion sources are mounted on cavity module
Upper end is simultaneously stretched by upper through-hole in chamber；
Detection module is fixed on the through hole of the side of cavity module.
The gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample further includes manual adjustment module；It is described manual
Adjustment module includes height adjustment mechanism and angle adjusting mechanism, wherein height adjustment mechanism is movably set in cavity mould
In the upper through-hole of block, angle adjusting mechanism is fixed on the upper end of height adjustment mechanism, and the two is respectively equipped with and cavity mould
The slot hole that the chamber of block is connected, esi ion source pass through the slot hole of height adjustment mechanism, angle adjusting mechanism to stretch into cavity mould
In the chamber of block.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, the height adjustment mechanism includes height
Adjust ion source(-)holder, height adjust ion source(-)holder be top be equipped with end cap cylinder, cylinder be set in cavity module it is described on
In portion's through-hole, the size of end cap is more than the diameter of cylinder, and the slot hole is offered in the middle part of end cap；Angle adjusting mechanism includes angle
Degree adjusts ion source(-)holder, and being fixed on height by pilot hole is adjusted on the end cap of ion source(-)holder, and middle part is equipped with to be adjusted with height
The slot hole that the positions and dimensions of ion source(-)holder match, the two sides on the plate body length direction are integrally extended with upwards
Two arc-shaped guide rails, the upper limb of the guide rail, which is respectively provided with, to be outward extended flange.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, before the angle adjusting mechanism further includes
Sliding block, ion source fixed frame, rear slider, slider locking screw head and ion source lock screw head：
Ion source fixed frame bottom surface is in the arc to match with the rail shapes, and middle part is equipped with to be connected with the slot hole
Mounting hole, be inserted into esi ion source in mounting hole；
Front-slider and rear slider are symmetrically installed on the flange of two arc-shaped guide rails respectively, and ion source fixed frame passes through assembly
Hole is fixed between front-slider and rear slider, and on two arc-shaped guide rail；
The rear slider is fixed on the arc-shaped guide rail to lock ion source fixed frame by slider locking screw head；Ion
Esi ion source is fixed in the mounting hole to lock esi ion source by source locking screw head.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, the top of the cavity module is additionally provided with
Clamp system is equipped in the middle part of the plate body and to be connected with the upper through-hole of the cavity module and chamber for the double-deck plate body
Through-hole, a top plate part and lower plywood integrally connected, another part are separated with lower plywood, and in a certain position of partitioning portion
It sets and is broken as the first clamping part and the second clamping part, the first clamping part and the second clamping part are equipped with adjusting bolt, by adjusting spiral shell
Bolt makes the first clamping part and elastic deformation, the manual adjustment module installed in locking or release through-hole occur for the second clamping part.
The gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample further includes electric translation module；It is described electronic
Translation module is mounted on the side of cavity module, and is connected with manual adjustment module, and manual adjustment module and spray can be driven
Mist ion source moves up and down together；The electric translation module include linking arm, electric platforms seat, screw support bearings, screw rod,
Feed slide unit, brake type stepper motor and two polished rods；Wherein：
Linking arm is used to electric translation module being connected to manual adjustment module；
Electric platforms seat is strip plate body, is fixed on the side of cavity module, and upper side is equipped with three separated
A side wall is respectively provided with circular hole on the side wall, and screw rod one end is mounted in the screw support bearings in the side wall circular hole of one end,
The other end is installed on across another two side wall on the output shaft of brake type stepper motor；
Two polished rods are located at the both sides of screw rod, and are fixed between both walls, and feeding slide unit is set on screw rod and polished rod,
And it is fixedly connected with linking arm.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, what the detection module was received at it
Detection lens mount, filter, planoconvex spotlight, optical fiber set and optical fiber screw head are equipped in light path successively, wherein filter, planoconvex spotlight peace
Loaded in a lens sleeve；Lens sleeve is installed in detection lens mount, and detection lens mount one end is installed on the one of cavity module
On side, the other end covers airtight connection with the optical fiber equipped with optical fiber screw head.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, the detection module further includes having lens
Compression spring, the lens compression spring are installed on lens sleeve successively in the inner cylinder of the detection lens mount；The detection lens mount with
Optical fiber set is connected with adjustable thread, and the depth realization that optical fiber set is screwed by control is finely adjusted detection module light path.
In the gas-phase ion chemistry illuminated message detection device of above-mentioned liquid phase sample, the bottom of the cavity module is equipped with bottom
Seat, the quadrangle of pedestal have been respectively fixedly connected with support leg, and support leg lower end is connected with the support leg for being used to support cavity module；Institute
The bottom surface of support leg is stated in cone, upper end is equipped with screw head, and screw head is connected with the threaded hole of support leg lower end, adjusts support leg
Screw head is screwed into depth with the levelness of adjusting cavity module.
The present invention also provides a kind of gas-phase ion chemistry illuminated message detection method of liquid phase sample, this method uses this hair
The gas-phase ion chemistry illuminated message detection device of bright liquid phase sample is detected, and is realized using following technical scheme：
A kind of gas-phase ion chemistry illuminated message detection method of liquid phase sample, using the gaseous ion of above-mentioned liquid phase sample
Chemiluminescence information detector is detected, and is included the following steps：
(1) detection module, manual adjustment module, at least two esi ion sources and electric translation module are assembled to cavity
In module, the support leg of adjusting cavity module makes the device be horizontal；
(2) optical fiber for being connected with optical signal detecting equipment is connected in the optical fiber screw head of detection module；
(3) injector is connected at the sample channel of two esi ion sources respectively, is led to from injector to sample channel
Enter sample solution, gas is passed through in gas passage；The stainless steel needle tubing that injector front end is equipped with is accessed into high voltage wire end and is connect
Logical high pressure；
(4) optical signal detecting equipment is opened to be detected；
(5) the distance between manual adjustable spraying ion source, angle, and pass through electric translation module adjustable spraying ion source
Relative to the height of detection fiber, detection sample ions are from liquid phase to the chemiluminescence information in gas phase change procedure, to obtain
The relationship of height parameter, angle parameter and testing result.
The present invention is using above technical scheme, it can be achieved that following technique effect：(1) present invention has a wide range of application, Ke Yiyong
It, can also be by adjusting the distance between each esi ion source, angle in the chemiluminescence information of the gaseous ion of detection liquid phase sample
Degree and electrospray ionization source height realize the adjusting of a certain range internal spraying ion source space position parameter, and then realize sample
Ion is from liquid phase to the continuous detection of the chemiluminescence information in gas phase change procedure；(2) electrospray ionization may be implemented in the present invention
The manual adjusting of distance, angle between source can also control Driving Stepping Motor realization electrospray ionization source height oneself by program
It is dynamic to adjust, it is easy to use；(3) present invention uses modularized design, and convenient for block combiner and extension, flexibility is strong；(4) of the invention
The LED light source of light source module the laser of high-energy density may be used, common low-power consumption LED light source can also be used, can
Suitable for different application scenarios；(5) compact in design of the present invention, each main member is simple for process, and related accessory is to be easy buying
Standard component, thus cost is relatively low.
Description of the drawings
Fig. 1 is the three-dimensional structure diagram of apparatus of the present invention embodiment；
Fig. 2 is the exploded view of each component in Fig. 1；
Fig. 3 is the exploded view of cavity module；
Fig. 4 is the exploded view of detection module；
Fig. 5 is the exploded view of manual adjustment module；
Fig. 6 is the stereogram of normal pressure spray ion source；
Fig. 7 is the stereogram of electric translation module and its axial cut away view；
Fig. 8 is the stereogram and its partial cross sectional views of the clamp system of cavity module；
Fig. 9 is the stereogram of the main body different angle of cavity module；
Figure 10 is the stereogram of the pedestal of cavity module；
Figure 11 is the stereogram of the support leg of cavity module；
Figure 12 is the perspective cut away view of the detection lens mount of detection module；
Figure 13 is the perspective cut away view of the optical fiber set of detection module；
Figure 14 is the stereogram of the optical fiber screw head of detection module；
Figure 15 is that the height of manual adjustment module adjusts the stereogram of ion source(-)holder；
Figure 16 is the stereogram of the angular adjustment ion source(-)holder different angle of manual adjustment module；
Figure 17 is the stereogram of the front-slider of manual adjustment module；
Figure 18 is the stereogram of the ion source fixed frame different angle of manual adjustment module；
Figure 19 is the stereogram of the rear slider different angle of manual adjustment module；
Figure 20 is the stereogram of the electric platforms seat different angle of electric translation module；
Figure 21 is the stereogram of the screw rod of electric translation module；
Figure 22 is the stereogram and its cut away view of the feeding slide unit of electric translation module；
Figure 23 is the stereogram of the nut of electric translation module；
Figure 24 is the stereogram of the bearing (ball) cover of electric translation module.
Reference numeral is expressed as in figure：
1：Cavity module；10：Clamp system, 100：Screw hole, 101：First clamping part, 102：Second clamping part, 103：It is heavy
Head bore, 104：Threaded hole；11：Chamber body, 112,115：Threaded hole, 113：Through-hole, 114,118：Screw hole；12：Pedestal, 120,
123：Counter sink；13：Support leg；14：Support leg, 140：Screw head, 141：Bottom surface；
4：Detection module；40：Detection lens mount, 400：Periphery, 401：Counter sink, 402：Inner headed face, 403：Screw hole；
41：Lens compression spring；42：Interior bung flange；43：Dottle pin；44：Filter；45：Planoconvex spotlight；46：Lens sleeve；47：Optical fiber set, 470：
Screw head, 471：Screw hole；48：Optical fiber screw head, 480,482：Screw head, 481：Nut；
5：Manual adjustment module；50：Height adjusting ion source(-)holder, 500：Cylinder, 501：Round end cap, 502：Counter sink,
503：Pin hole, 504：Screw hole, 505：Altitude scale；51：Angular adjustment ion source(-)holder, 510：Screw hole, 511：Pin hole, 512：Arc
Guide rail, 513：Angle index；52：Front-slider, 520,541：Upper cambered surface, 522：Angle index index line, 523：Cone head hole；53：
Ion source fixed frame, 530：Through-hole, 531,533：Screw hole, 532：Side screw hole；54：Rear slider, 521,540：Lower camber side, 542：
Cone head hole, 543：Screw hole；55：Slider locking screw head；56：Ion source locks screw head；
6：Esi ion source, 60：Gas passage, 61：Sample channel, 62：Matrix；
7：Electric translation module；70：Linking arm；71：Fastening nut；72：Electric platforms seat, 720,723：Circular hole, 721：
Side opening, 722：Screw hole, 724：Threaded hole, 725：Counter sink；73：Screw support bearings；74：Screw rod；75：Feeding slide unit, 750：
Side opening, 753：Through-hole, 754：Screw hole, 755：Threaded hole；76：Nut, 760：Cylinder, 761：Counter sink；77：Bearing (ball) cover,
770：Screw hole, 771：Threaded hole；78：Elastic shaft joint；79：Brake type stepper motor；710：Polished rod.
Specific implementation mode
Below in conjunction with the drawings and specific embodiments, the gas-phase ion chemistry illuminated message of the liquid phase sample of the present invention is detected
Device and method is described in detail, wherein the device of identical structure and function is with identical reference numeral mark in attached drawing
Go out, attached drawing is only intended to help explain the present invention, does not represent limitation of the scope of the invention.
Fig. 1 is the three-dimensional structure diagram of apparatus of the present invention embodiment, and Fig. 2 shows the exploded views of each component in Fig. 1.Such as Fig. 1
Shown in Fig. 2, the gas-phase ion chemistry illuminated message detection device of liquid phase sample of the invention is the sealing structure with chamber,
Including detection module 4, manual adjustment module 5, esi ion source 6, electric translation module 7 and for fixing above-mentioned each component simultaneously
And the cavity module 1 of chamber is provided, the main body 11 of cavity module 1 is the chamber structure equipped with through-hole, and detection module 4 is installed on chamber
The through hole of 11 side of main body of module 1；Electric translation module 7 is mounted on the side adjacent with detection module 4 of cavity module 1
On face, manual adjustment module 5 is mounted at the upper through-hole of cavity module 1, and one or more esi ion sources 6 are inserted in manually
It is extend into the chamber of cavity module 1 in adjustment module 5 and by above-mentioned upper through-hole, and electric translation module 7 and hand
The height adjusting member of dynamic adjustment module 5 is connected so that when electric translation module 7 work, can drive manual adjustment module 5 and
Esi ion source 6 moves up and down together.
Cavity module
Fig. 3 shows that the decomposition texture of cavity module 1, Fig. 8 to Figure 11 respectively illustrate each building block of cavity module 1
Structure.As indicated at 3, cavity module 1 includes clamp system 10, chamber body 11, pedestal 12, support leg 13 and support leg 14,
Wherein：
The main body 11 of cavity module 1 is the chamber structure equipped with through-hole, and the upper end through hole is fixed with intermediate equipped with center
The clamp system 10 in hole, for the double-deck plate body structure, a top plate part and lower plywood integrally connected, another part and lower plywood
It separates, and the first clamping part 101 and the second clamping part 102 is broken as in a certain position of partitioning portion, in the second clamping part
102 are equipped with counter sink 103, are equipped with threaded hole 104, the first clamping part 101 and the second clamping part on the first clamping part 101
102 are equipped with adjusting bolt, when the adjusting bolt is screwed into counter sink 103 and threaded hole 104, the first clamping part 101 and second
Elastic deformation occurs for clamping part 102, to lock part (the height tune of manual adjustment module 5 in 10 centre bore of clamp system
Save ion source(-)holder 50 (referring to Fig. 5)), when unclamping dormant bolt, discharge the part in 10 centre bore of clamp system；Clamp system
10 quadrangle is fixedly connected by the screw hole 114 of its screw hole 100 and chamber body 11 with main body 11.
As shown in figure 9, in the side of the main body 11 of cavity module 1, the middle part of one of side is equipped with through-hole 113, leads to
Hole 113 is surrounded by threaded hole 112, for installing detection module 4；The side adjacent with 113 place side of through-hole is equipped with spiral shell
Hole 118, for installing electric translation module 7.
As shown in Figure 10 and Figure 11, pedestal 12 is the plate body to match with the bottom edge of the main body 11 of cavity module 1, pedestal 12
Upper position corresponding with the threaded hole 115 on 11 bottom edge of main body is equipped with counter sink 120, is connected by screw 120 He of counter sink
Pedestal 12 is fixedly connected by threaded hole 115 with the main body 11 of cavity module 1；The quadrangle of pedestal 12 is respectively provided with counter sink 123, passes through
Screw connects the threaded hole of counter sink 123 and 13 upper end of support leg, and pedestal 12 is fixedly connected with four support legs 13 respectively；Tool
There is the screw head 140 of the support leg 14 of conical bottom surface 141 to be screwed into the threaded hole of 13 lower end of support leg, bottom surface 141 is placed in work
On face, by the levelness for being screwed into depth and entire cavity module 1 being adjusted for adjusting four support legs 14.
Detection module
Fig. 4 shows that the decomposition texture of detection module 4, Figure 12, Figure 13 and Figure 14 respectively illustrate each group of detection module 4
At the structure of component.As shown in figure 4, detection module 4 include detection lens mount 40, lens compression spring 41, interior bung flange 42, dottle pin 43,
Filter 44, planoconvex spotlight 45, lens sleeve 46, optical fiber set 47 and optical fiber screw head 48, wherein：
As shown in figure 12, the detection lens mount 40 of detection module 4 is circular sleeve structure, and one end inside contracts to form annular inner circle
Face 402, the cartridge exterior close to annular inner headed face form prominent anchor ring around sleeve, separate on the protrusion anchor ring and are equipped with multiple sink
Head bore 401 forms periphery 400 close to the end of the protrusion anchor ring, and the other end is screw hole 403.
As shown in Figure 13 and Figure 14, optical fiber set 47 is the two-stage circular sleeve of one end open, and open end is equipped with screw head 470,
Another side Middle face is equipped with screw hole 471；Optical fiber screw head 48 is hollow structure, and both ends are respectively equipped with screw head 480 and 482, intermediate
Equipped with nut 481, screw head 480 is screwed into the screw hole 471 of optical fiber set 47, optical fiber screw head 48 is connect with optical fiber set 47, screw head 482
It can be used for connecting subsequent optical information detection device.
As shown in figure 4, lens sleeve 46 is the cylinder of horizontal opening, side is equipped with annular inboard face, and the other side is equipped with spiral shell
Hole；There are two dottle pin 43 is set, dottle pin 43, filter 44, planoconvex spotlight 45, dottle pin 43 are placed in the endoporus of lens sleeve 46 successively
In, then interior bung flange 42 is screwed into the screw hole of lens sleeve 46, so that above-mentioned component is held out against the medial surface of lens sleeve 46.
As shown in Fig. 4, Figure 12, Figure 13 and Figure 14, lens compression spring 41 and the lens sleeve 46 being completed are placed in successively
In the screw hole 403 for detecting lens mount 40, the inner headed face 402 of the end thereof contacts detection lens mount 40 of lens compression spring 41 is equipped with light
Screw head 470 is screwed into the screw hole 403 of detection lens mount 40 by the optical fiber set 47 of fine screw head 48, and the lens sleeve 46 being completed exists
It under the action of lens compression spring 41 and optical fiber set 47, can move horizontally, can be realized by controlling the depth that optical fiber set 47 is screwed into
The fine tuning of 46 place light path of mirror sleeve cylinder, and achieve the purpose that compensation processing and rigging error, optimization infomation detection.It is completed
Detection module 4 coordinates positioning by that will detect the periphery 400 of lens mount 40 with the 11 side through-hole 113 of main body of cavity module 1,
The counter sink 401 for detecting lens mount 40 is connect with the threaded hole 112 on 11 side of main body of cavity module 1, by detection module 4
It is fixedly connected with cavity module 1.
Manual adjustment module
Fig. 5 shows that the decomposition texture of manual adjustment module 5, Figure 15 to Figure 19 show each group of manual adjustment module 5
At the structure of component.As shown in figure 5, manual adjustment module 5 includes height adjustment mechanism and angle adjusting mechanism, height adjusts machine
Structure includes that height adjusts ion source(-)holder 50, and angle adjusting mechanism includes that angular adjustment ion source(-)holder 51, front-slider 52, ion source are solid
Determine frame 53, rear slider 54, slider locking screw head 55 and ion source locking screw head 56, wherein：
As shown in figure 15, height adjusts the cylinder 500 that ion source(-)holder 50 is equipped with round end cap 501 for top, round end cap
501 diameter is more than the diameter of cylinder 500, and the middle part of round end cap 501 offers slot hole, and round end cap 501 is equipped with and is used for
It is fixedly connected with the counter sink 502, pin hole 503 and the screw hole for connecting electric translation module 7 of angular adjustment ion source(-)holder 51
504, the drum surface perpendicular to the slot hole length direction is equipped with altitude scale 505；Height adjusts ion source(-)holder 50 can be in electricity
It is moved up and down under the drive of dynamic translation module 7, altitude scale 505 is used to indicate its height, by chamber after the completion of height adjustment
It is screwed into adjusting bolt in the counter sink 103 of 102 parts on the clamp system 10 of module 1 and the threaded hole 104 of 101 parts,
Height is adjusted ion source(-)holder 50 to be locked.
As shown in figure 16, angular adjustment ion source(-)holder 51 is strip plate body, and middle part is equipped with adjusts ion source(-)holder with height
The corresponding slot hole of 50 positions and dimensions, be surrounded by and the height of the slot hole adjust the counter sink 502 of ion source(-)holder 50 relatively
The screw hole 510 and pin hole corresponding with pin hole 503 511 answered；Two sides on the plate body length direction are integrally extended with upwards
Two arc-shaped guide rails 512, the upper limb of the guide rail 512, which is respectively provided with, to be outward extended flange, and the outer surface of guide rail 512 is carved equipped with angle
Degree 513；The pin hole 503 of ion source(-)holder 50 is adjusted by height and the pin hole 511 of angular adjustment ion source(-)holder 51 is positioned, and is led to
Screw counter sink 502 connecting the two and screw hole 510 are crossed, height will be adjusted ion source(-)holder 50 and angular adjustment ion source(-)holder 51
It is fixedly connected.
As shown in Figure 17, Figure 18 and Figure 19, front-slider 52 and rear slider 54 are the identical sliding block of shape, are equipped in the middle part of sliding block
The arc groove to match with 512 shape of arc-shaped guide rail of angular adjustment ion source(-)holder 51, and the upper cambered surface of same arc groove
502/541 width is more than its lower camber side 521/541, and sliding block side surface upper part is equipped with cone head hole 523, for connecting ion source fixed frame
53,52 side lower of front-slider is equipped with an angle index index line, is used to indicate the angle of esi ion source；54 side of rear slider
Lower part is equipped with screw hole 543, and screw head 55 is locked for connection sliding block；Ion source fixed frame 53 is the arc-shaped plate body in bottom surface, plate body
Middle part is equipped with through-hole 530, and the diameter of the through-hole 530 is corresponding with the width of slot hole of angular adjustment ion source(-)holder 51, the plate body
It arcuately is respectively provided with screw hole 531 and 533 on the side in bottom surface direction, is respectively used to connection front-slider 52 and rear slider 54, outward
Side side be equipped with screw hole 532, for connect ion source lock screw head 56.
Front-slider 52, ion source fixed frame 53,54 slider locking screw head 55 of rear slider and ion source locking screw head 56 coordinate
It uses, specific assembling process is as follows：The arc that front-slider 52 and rear slider 54 are symmetrically installed in angular adjustment ion source(-)holder 51 is led
On the flange of rail 512, the upper lower camber side and the flange of arc-shaped guide rail 512 of arc groove fit, and ion source fixed frame is fixed
Between front-slider 52 and rear slider 54, and on the arc-shaped guide rail 512, by the cone head hole 523 of front-slider 52 with from
The screw hole 532 of component fixed frame 53 connects, and front-slider 52 is fixedly connected with ion source fixed frame 53；Pass through the cone of rear slider 54
Head bore 542 is connect with the screw hole 533 of ion source fixed frame 53, and rear slider 54 is fixedly connected with ion source fixed frame 53；Upper arc
Face 520 and 541, lower camber side 521 and 540 and the flange of the arc-shaped guide rail 512 of angular adjustment ion source(-)holder 51 are slidably matched, advancing slip
Block 52, ion source fixed frame 53 and rear slider 54 slide on the arc-shaped guide rail 512 of angular adjustment ion source(-)holder 51 together, position
It can be indicated by the angle index 513 of 51 front of angular adjustment ion source(-)holder；Spraying is inserted into the through-hole 530 of ion source fixed frame 53
Ion source 6, the slot hole that esi ion source 6 adjusts ion source(-)holder 50 and angular adjustment ion source(-)holder 51 by height stretch into height tune
In the cylinder for saving ion source(-)holder 50；Ion source locking screw head 56 is screwed into the side screw hole 532 of ion source fixed frame 53 to lock
Tight esi ion source 6；Slider locking screw head 55 is screwed into behind rear slider 54 in screw hole 543 to fixed ion source fixed frame
53, the position of esi ion source 6 is fixed at this time.Front-slider 52, ion source fixed frame 53, rear slider 54, slider locking screw head
55,56 two groups of screw head of ion source locking is symmetrically arranged, separately adjustable, two esi ion sources 6 is installed respectively, for studying
The chemiluminescence of substance；Similarly, three even four esi ion sources 6 can be expanded to after slightly being changed in structure.
Electrospray ionization source module
As shown in fig. 6, esi ion source 6 is syringe-shaped structure, upper end cylinder base is equipped with gas passage 60 and sample channel
61, middle cylinder is equipped with scale, and the needle-shaped position in lower end is equipped with matrix 62.Sample channel 61 connects an injector, for introducing
Sample to be tested, the front end of the injector are equipped with stainless steel needle tubing, and high-voltage power supply is connected to the stainless steel needle tubing, when sample solution never
Pass through in rust draw point pipe, high pressure can be added on sample solution.Gas passage 60 introduces high pressure nitrogen (N2), electrification waits for test sample
Product form spraying under the action of high pressure nitrogen, on the head of matrix 62, and shape is in Taylor's taper, formed the gas phase of sample from
Son.
Electric translation module
Fig. 7 shows that the stereochemical structure of electric translation module 7, Figure 20 to Figure 24 show each of electric translation module 7
The structure of building block.As shown in fig. 7, electric translation module 7 includes linking arm 70, fastening nut 71, electric platforms seat 72, spiral shell
Bar spring bearing 73, screw rod 74, feeding slide unit 75, nut 76, bearing (ball) cover 77, yielding coupling 78, brake type stepper motor
79 and two polished rods 710, wherein：
As shown in figure 20, electric platforms seat 72 is rectangular plate body, and lateral separation is equipped with only there are three side wall thereon, outermost
The both walls of side are located at the both ends of plate body, and plate body top is equipped with multiple counter sinks 725,11 side of main body with cavity module 1
Screw hole 118 on face is connected, for fixing electric translation module 7；The circular hole 720 and 723 of coaxial line is provided on each side wall, circle
The both sides in hole 720 are respectively provided with side opening 721, and the side opening 721 of intermediate side wall is not through the side wall, and the side opening 721 of end side wall passes through
The side wall is worn, for two polished rods 710 to be fixedly mounted；Circular hole 723 is surrounded by multiple threaded holes 724, for connecting brake type
Stepper motor 79.
As shown in figure 22, feeding slide unit 75 is rectangular block, is located between the side wall and intermediate side wall at 721 place of through-hole,
Its upper side is equipped with threaded hole 755, the side plate of the inverted "L" shape linking arm 70 for connecting electric translation module 7, left side
The middle part in (left side of Figure 22) is equipped with kidney-shaped groove, offers through-hole 753 in the middle part of groove, in the groove floor around through-hole 753
Equipped with multiple screw holes 754, for being connected and fixed nut 76；The both sides of groove are equipped with side opening 750, the center and side of the gaging hole 750
The central coaxial in hole 721, for wearing two polished rods 710.
Two screw support bearings 73 are respectively placed in circular hole 720, and screw rod 74 is each passed through the screw rod branch on the side wall of end
Support the screw support bearings 73 on bearing 73, the through-hole 753 for feeding slide unit 75, nut 76 and intermediate side wall；As shown in figure 24, axis
Socket end lid 77 is annulus part, and middle part is with the circular hole 720 on intermediate side wall by connecting the threaded hole 771 of bearing (ball) cover 77 in
Between side wall screw hole, joint bearing end cap 77 is fixed on to the right side of intermediate side wall, and then by the screw support axis on intermediate side wall
73 fixations, screw rod left part and spring bearing 73 is held to be fixed with fastening nut 71；As shown in figure 23, nut 76 is hollow tubular
There is end cap, the end cap to be equipped with counter sink 761 for nut, one end, and cylinder 760 is inserted from the oval-shaped groove side of feeding slide unit 75
It being placed in the through-hole 753 of feeding slide unit 75, the counter sink 761 on the end cap of nut 76 is connect with the screw hole 754 of feeding slide unit 75,
Nut 76 is fixedly connected with feeding slide unit；The right end of screw rod 74 is defeated by yielding coupling 78 and brake type stepper motor 79
Go out axis connection, brake type stepper motor 79 is connected to the threaded hole 724 of right side side wall, and its output shaft passes through right side side wall
Circular hole 723 is connected with yielding coupling 78.
The right end of inverted "L" shape linking arm 70 is fixedly connected by screw hole on the threaded hole 755 of given slide unit 75, linking arm 70
Left end height be fixedly connected with by screw hole adjust on the screw hole 504 of ion source(-)holder 50, when brake type stepper motor 79 rotates,
Feeding slide unit 75 can be driven to move up and down, and then 50 upper and lower translation of ion source(-)holder is adjusted with dynamic height, realize automatic adjustment spraying
The purpose of 6 height of ion source.
It is the final assembly explanation of the present invention above, according to the characteristics of detection object and it detects target and is adjusted and makes
With.
The gas-phase ion chemistry illuminated message detection device configuration of the liquid phase sample of the present invention is flexible, easy to use, can use
In the chemiluminescence information for the gaseous ion that detection liquid phase sample is generated by normal pressure ESI technologies, sample ions are can also be achieved from liquid
Phase transition is the continuous detection of the process of gas phase.
When the chemiluminescence infomation detection for the gaseous ion that progress liquid phase sample is generated by normal pressure ESI technologies, need to examine
Survey module 4, manual adjustment module 5, esi ion source 6 and electric translation module 7 are assembled in cavity module 1, and after connecting
Continuous optical signal detecting equipment.
When carrying out the gas-phase ion chemistry illuminated message detection of liquid phase sample using the device of the invention, following operation is taken
Step：
(1) according to above-mentioned assembly relation, by detection module 4, manual adjustment module 5, at least two esi ion sources 6 and electricity
Dynamic translation module 7 is assembled in cavity module 1, and then the support leg 14 of adjusting cavity module 1, makes the device be horizontal
(can be adjusted by easy spirit bubble)；
(2) optical fiber for being connected with optical signal detecting equipment is connected in optical fiber screw head 48；
(3) injector is connected at the sample channel 61 of two esi ion sources 6 respectively, from injector to sample channel
61 are passed through sample solution, and gas (nitrogen of such as 1MPa) is passed through in gas passage 60；The stainless steel that will be equipped in injector front end
Needle tubing accesses high pressure (for example,+3KV) conductor wire end and connects high pressure；
(4) optical signal detecting equipment is opened to be detected；
(5) the distance between manual adjustable spraying ion source 6, angle, and pass through 7 adjustable spraying ion of electric translation module
Height of the source 6 relative to detection fiber, detection sample ions are from liquid phase to the chemiluminescence information in gas phase change procedure, to obtain
Obtain the height parameter of esi ion source 6, the relationship of angle parameter and testing result.
It will be appreciated by those skilled in the art that these embodiments are merely to illustrate model of the present invention without limiting the present invention
It encloses, the various equivalent variations and modification made to the present invention belong to the disclosure of invention.
Claims (9)
1. a kind of gas-phase ion chemistry illuminated message detection device of liquid phase sample, including detection module, esi ion source and
Cavity module for fixed test module and esi ion source, it is characterised in that：
The main body of cavity module is the chamber structure equipped with multiple through-holes, and multiple esi ion sources are mounted on the upper end of cavity module
And it is stretched into chamber by upper through-hole；
Detection module is fixed on the through hole of the side of cavity module；
It further include manual adjustment module；The manual adjustment module includes height adjustment mechanism and angle adjusting mechanism, wherein high
Degree regulating mechanism is movably set in the upper through-hole of cavity module, and angle adjusting mechanism is fixed on height adjusting machine
The upper end of structure, the two are respectively equipped with the slot hole being connected with the chamber of cavity module, esi ion source pass through height adjustment mechanism,
The slot hole of angle adjusting mechanism stretches into the chamber of cavity module.
2. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to claim 1, which is characterized in that institute
It includes that height adjusts ion source(-)holder to state height adjustment mechanism, and it is the cylinder that top is equipped with end cap, cylinder that height, which adjusts ion source(-)holder,
It is set in the upper through-hole of cavity module, the size of end cap is more than the diameter of cylinder, is offered in the middle part of end cap described
Slot hole；Angle adjusting mechanism includes angular adjustment ion source(-)holder, and angular adjustment ion source(-)holder is fixed on height by pilot hole to be adjusted
On the end cap for saving ion source(-)holder, middle part is equipped with and adjusts the slot hole that the positions and dimensions of ion source(-)holder match with height, institute
The two sides stated on angular adjustment ion source(-)holder length direction are integrally extended with two arc-shaped guide rails upwards, and the upper limb of the guide rail is respectively set
It outward extends flange.
3. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to claim 2, which is characterized in that institute
It further includes front-slider, ion source fixed frame, rear slider, slider locking screw head and ion source locking screw head to state angle adjusting mechanism：
Ion source fixed frame bottom surface is in the arc to match with the rail shapes, and middle part is equipped with the peace being connected with the slot hole
Hole is filled, esi ion source is inserted into mounting hole；
Front-slider and rear slider are symmetrically installed on the flange of two arc-shaped guide rails respectively, and ion source fixed frame is solid by pilot hole
Due between front-slider and rear slider, and on two arc-shaped guide rail；
The rear slider is fixed on the arc-shaped guide rail to lock ion source fixed frame by slider locking screw head；Ion source is locked
Esi ion source is fixed in the mounting hole to lock esi ion source by tight screw head.
4. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to any one of claims 1 to 3, special
Sign is that the top of the cavity module is additionally provided with clamp system, and for the double-deck plate body, the plate body middle part is equipped with and the chamber
The through-hole that the upper through-hole of module is connected with chamber, a top plate part and lower plywood integrally connected, another part is under
Laminate separates, and is broken as the first clamping part and the second clamping part, the first clamping part and in a certain position of partitioning portion
Two clamping parts are equipped with adjusting bolt, so that the first clamping part and the second clamping part is occurred elastic deformation by adjusting bolt, locking or
Discharge the manual adjustment module installed in through-hole.
5. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to claim 4, which is characterized in that also
Including electric translation module；The electric translation module is mounted on the side of cavity module, and is connected with manual adjustment module,
Manual adjustment module can be driven to be moved up and down together with esi ion source；The electric translation module includes linking arm, electronic
Platform base, screw support bearings, screw rod, feeding slide unit, brake type stepper motor and two polished rods；Wherein：
Linking arm is used to electric translation module being connected to manual adjustment module；
Electric platforms seat is strip plate body, is fixed on the side of cavity module, and upper side is equipped with three sides separated
Wall is respectively provided with circular hole on the side wall, and screw rod one end is mounted in the screw support bearings in the side wall circular hole of one end, another
End is on the output shaft that another two side wall is installed on brake type stepper motor；
Two polished rods are located at the both sides of screw rod, and are fixed between both walls, and feeding slide unit is set on screw rod and polished rod, and with
Linking arm is fixedly connected.
6. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to claim 5, which is characterized in that institute
It states detection module and is equipped with detection lens mount, filter, planoconvex spotlight, optical fiber set and optical fiber spiral shell successively in the light path that it is received
Head, wherein filter, planoconvex spotlight are installed in a lens sleeve；Lens sleeve is installed in detection lens mount, detects lens mount
One end is installed on the one side of cavity module, and the other end covers airtight connection with the optical fiber equipped with optical fiber screw head.
7. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to claim 6, which is characterized in that institute
It further includes having lens compression spring to state detection module, and the lens compression spring is installed on the interior of the detection lens mount with lens sleeve successively
In cylinder；The detection lens mount is connect with optical fiber set with adjustable thread, and the depth that optical fiber set is screwed by control is realized to detection
Module light path is finely adjusted.
8. the gas-phase ion chemistry illuminated message detection device of liquid phase sample according to any one of claims 1 to 3, special
Sign is that the bottom of the cavity module is equipped with pedestal, and the quadrangle of pedestal has been respectively fixedly connected with support leg, and support leg lower end connects
It is connected to the support leg for being used to support cavity module；In cone, upper end is equipped with screw head, screw head and support for the bottom surface of the support leg
The threaded hole of leg lower end is connected, and the screw head for adjusting support leg is screwed into depth with the levelness of adjusting cavity module.
9. the gas-phase ion chemistry illuminated message detection method of a kind of liquid phase sample, using claim 5 to 7 any one of them
The gas-phase ion chemistry illuminated message detection device of liquid phase sample is detected, and is included the following steps：
(1) detection module, manual adjustment module, at least two esi ion sources and electric translation module are assembled to cavity module
On, the support leg of adjusting cavity module makes the device be horizontal；
(2) optical fiber for being connected with optical signal detecting equipment is connected in the optical fiber screw head of detection module；
(3) injector is connected at the sample channel of two esi ion sources respectively, sample is passed through from injector to sample channel
Product solution is passed through gas in gas passage；The stainless steel needle tubing that injector front end is equipped with is accessed into high voltage wire end and connects height
Pressure；
(5) optical signal detecting equipment is opened to be detected；
(6) the distance between manual adjustable spraying ion source, angle, and it is opposite by electric translation module adjustable spraying ion source
In the height of detection fiber, detection sample ions are from liquid phase to the chemiluminescence information in gas phase change procedure, to obtain height
The relationship of parameter, angle parameter and testing result.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201993314U (en) * | 2010-11-19 | 2011-09-28 | 山东省科学院海洋仪器仪表研究所 | Chemiluminescent signal detection device |
| CN205581004U (en) * | 2016-03-30 | 2016-09-14 | 东华理工大学 | Liquid phase samples 's gas phase ions chemiluminescence information detection means |
-
2016
- 2016-03-30 CN CN201610190494.3A patent/CN105675593B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201993314U (en) * | 2010-11-19 | 2011-09-28 | 山东省科学院海洋仪器仪表研究所 | Chemiluminescent signal detection device |
| CN205581004U (en) * | 2016-03-30 | 2016-09-14 | 东华理工大学 | Liquid phase samples 's gas phase ions chemiluminescence information detection means |
Non-Patent Citations (5)
| Title |
|---|
| Approach for Selective Separation of Thiophenic and Sulfidic Sulfur Compounds from Petroleum by Methylation/Demethylation;Meng Wang et al;《Analytical Chemistry》;20141218;第87卷;第1083-1088页 * |
| Exploring Fluorescence and Fragmentation of Ions Produced by Electrospray Ionization in Ultrahigh Vacuum;Konstantin Chingin et al;《J Am Soc Mass Spectrom》;20091231;第20卷;第1731-1738页 * |
| Quality control of flavonoids in Ginkgo biloba leaves by high-performance liquid chromatography with diode array detection and on-line radical scavenging activity detection;Xiao-Ping Ding et al;《Journal of Chromatography A》;20080905;第1216卷;第2204-2210页 * |
| Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin;Meng Wang et al;《Energy & Fuels》;20150714;第29卷;第4842-4849页 * |
| 化学发光分析法、气相化学发光和电生化学发光;张帆等;《分析试验室》;19871231;第6卷(第9期);第53-59页 * |
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