CN100371710C - Portable liquid-phase chromatograph - Google Patents
Portable liquid-phase chromatograph Download PDFInfo
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- CN100371710C CN100371710C CNB2006100551090A CN200610055109A CN100371710C CN 100371710 C CN100371710 C CN 100371710C CN B2006100551090 A CNB2006100551090 A CN B2006100551090A CN 200610055109 A CN200610055109 A CN 200610055109A CN 100371710 C CN100371710 C CN 100371710C
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Abstract
The present invention relates to a liquid phase chromatograph, particularly to a portable liquid phase chromatograph. The present invention has the advantages of small volume, light weight, low power consumption, high integration density of each part, one object with multiple functions and compact structure. The present invention is provided with an injection pump, a sampling valve, an optical type ultraviolet-visible absorption / fluorescence dual-purpose flow cell, an optical fiber assembly, an integral capillary pipe column, a grating spectrograph, a photodiode light source, a computer, a waste liquid bottle and a power supply, wherein an outlet of the injection pump is connected with an inlet of the sampling valve; an outlet of the sampling valve is connected with an inlet of the integral capillary pipe column; an outlet of the integral capillary pipe column is connected with the flow cell; the light source is lead into the flow cell and the grating spectrograph; transmitted light or fluorescence of the flow cell is lead into the grating spectrograph by optical fibers; the absorbance or fluorescence intensity switching signal output end of the grating spectrograph is connected with the computer to obtain spectral information and a corresponding spectrogram of an object which is to be measured; an outlet pipeline of a flow path of the flow cell is connected with the waste liquid bottle; the control end of the injection pump is connected with a serial communication interface of the computer.
Description
Technical field
The present invention relates to a kind of liquid chromatograph, especially relate to a kind of portable liquid-phase chromatograph.
Background technology
High performance liquid chromatography (being called for short HPLC) is a technology that is widely used in compartment analysis, and it has advantages such as separation efficiency height, selectivity is good, detection sensitivity is high, analysis speed is fast.Widespread use in environmental analysis and life analysis more makes high performance liquid chromatography become one of core technology of modern analysis science, and the liquid chromatography instrument occupy analytical instrument demand first place always in recent years.
Existing high performance liquid chromatograph generally partly is made up of transfusion system 01, sampling system 02, chromatographic column 03, detection system 04, data recordin and procesin system 05 and temperature control equipment 06 etc., and detecting device, pump and chromatographic column are the three big critical components of HPLC.Sample is entered in the chromatographic column by injector, transfusion system driving liquid flow carries sample material mutually and flows through chromatographic column, different component in the sample is successively entered detecting device because of the difference of its character is separated from each other, be converted to the electric signal of easy measurement by its physicochemical characteristics, note or import computing machine 07 by data acquisition processing system and carry out display process.The basic structure signal of its instrument as shown in Figure 1.
Transfusion system mainly comprises device for storing liquid, degasser, infusion pump, gradient elution device and pipeline etc.The container of device for storing liquid is made with stainless steel, glass or polytetrafluoroethylplastic plastic etc. usually, places the imbibition conduit of liquid storage container that the filtrator of stainless steel sintering generally is housed; Moving phase by heat, vacuumize, nitrogen blowing or ultrasonic method pack into after outgasing in the liquid storage container, the instrument that has is equipped with online degasser; The resistance that is subjected to when flow communication is crossed performance liquid chromatographic column is bigger, need to use high pressure pump drive, high pressure pump commonly used is a reciprocating plunger pump, pressure up to 40～50MPa can be provided, but because of its structures shape, defectives such as there be existing of being difficult to avoid in reciprocating plunger pump, and the output pressure pulsation is big, the output flow velocity is limited in scope, precision is limited under ultralow flow, and volume weight is big, cost is higher; The method of separating effect is called gradient elution in the hope of obtaining preferably in the short as far as possible time can to change the moving phase composition in detachment process, the HPLC instrument all disposes gradient elution device usually, the mode of mixing in mixer with several moving phase components of a plurality of high pressure pump drive is called geopressure gradient, makes each component under low pressure mix the mode that enters a high-pressure pump again with electromagnetic proportional valve and is called low pressure gradient; Liquid line among the HPLC uses stainless steel or high polymer material to make usually, and internal diameter is generally 0.1～0.8mm; Transfusion system also comprises some utility appliance such as ripple damper, device for pressure measurement and flow rate measuring device etc.
The sampling device of highly effective liquid phase chromatographic system requires good airproof performance, dead volume is little and have good repeatability, and sampling device commonly used is the high pressure six-way valve on the HPLC instrument at present, has advantages such as quantitatively accurate, that compressive resistance is good.Shortcoming be it to sample quantitatively be quantity tube by certain volume, the sampling volume minimum value is limited, is not suitable as the sampling valve of microfluidic chromatography.
The separating column of HPLC mainly is made up of column jecket and filler.Column jecket is made up of tube wall and two ends splice kit and column cap sieve plate, is generally made the inside pipe wall high polish by stainless-steel tube or superpolymer.Internal diameter is generally between 1～4.6mm, and internal diameter is greater than the preparation type that the is commonly referred to as post of 4.6mm, and internal diameter is called microfluidic chromatography post or microtrabeculae less than 1mm's.Stainless steel column jecket intensity height, resistance to pressure are good, but corrosion resistivity is relatively poor; Polymeric material such as polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE) etc. have splendid corrosion resistance, but crushing resistance slightly is inferior to stainless steel, and cost is higher.The filler of chromatographic column is the key that sample realize to separate, and can be divided into packed column and integral post by the filling mode of filler.Packed column is that the diameter number micron spherical stationary-phase particle size to hundreds of microns closely is filled in the column jecket, and particle diameter is more little, and separation efficiency is high more, but permeability is poor more, and working pressure is big more; The stationary phase of integral post directly gathers to become in column jecket, and advantage is that permeability is good, simple in structure, but integral post is used seldom at present.
The detecting device of high performance liquid chromatography is divided into common detector and specific detectors.Common detector such as differential refraction detector, electric conductivity detector etc. are applied widely, but response are arranged and be not suitable for gradient elution for moving phase, and sensitivity is also lower, uses not extensive on instrument.Specific detectors has detected components and the moving phase component does not have that certain character produces response, and sensitivity is higher, and phase change is insensitive to flowing, and can carry out the detection of gradient elution.Using is ultraviolet-visible absorption detector and fluorescence detector very widely.
Ultraviolet absorption detector is based on Lambert-Beer's law, and by its concentration of absorbance measurement of measuring samples, it only has response to the material that has ultraviolet-visible to absorb.The ultraviolet-visible absorption detector generally comprises light source 08, flow cell 09, light path system 010 and 011 and electrooptical device 012.The light source that the ultraviolet-visible absorption detector is commonly used is low pressure mercury lamp, deuterium lamp, halogen tungsten lamp etc., and wavelength coverage is 190～800nm.Light path system generally is made up of prism, lens, grating etc., is used for the conduction and the beam split of light signal.The structure of flow cell has Z type, H type and pyramid type etc. usually.The flow cell volume is more little, and the detecting device dead volume is more little, and the influence of coupled columns separating effect is more little; The flow cell light path is long more, and sensitivity is high more.The electrooptical device of ultraviolet-visible absorption detector generally has photomultiplier, photodiode array (PDA) etc.The ultraviolet-visible absorption detector is easy to use, has wide range of applications.Present commercial apparatus volume weight is all bigger, and the flow cell volume of common product is that 8～10 μ l, light path are 5～10mm, is not suitable for the microfluidic chromatography system, and the product that has has been equipped with the flow cell of small volume, but its cost is higher.The ultimate principle of UV-detector such as Fig. 2.
Fluorescence detector is based on and detects the tailored version detecting device that the fluorescence intensity of sending after some compound absorbing light radiation is measured material concentration, and fluorescence detector is applicable to that detection can fluoresce maybe can be by the fluorescence fluorescigenic material of deriving.Its sensitivity is the highest in the detecting device commonly used, therefore uses also very extensive.Fluorescence detector also is made up of parts such as light source 013, light path system 014 and 015, flow cell 016 and photoelectric commutators 017, with ultraviolet-visible absorption detector main difference part be detect light path and input path angled, be generally the right angle.The ultimate principle of fluorescence detector such as Fig. 3.
The data acquisition process of HPLC instrument and system control is at present all realized by microcomputer usually.The instrument of certain model also has attachment devices such as temperature control system and post switched system.
The portability of analytical instrument is the trend of present international environment monitoring instrument development of manufacturing.Develop " portable analytical instrument " and can reduce analytical test cost, technology on the one hand and be easy to grasp, use efficient and convenient, the more important thing is to be easy to carry, be suitable for the field condition monitoring, be easy to be accepted by environmental administration.And the infusion pump of liquid chromatography instrument commonly used, separating column, detecting device, controller etc. because structural limitations all be difficult to do small volume and less weight.Commercial portable liquid-phase chromatograph does not also appear at present.
Summary of the invention
The objective of the invention is at existing liquid chromatograph be difficult to do the deficiency of small volume and less weight, in order to realize the portability of liquid chromatography instrument, provide that a kind of volume is little, light weight, low in energy consumption, and each parts have high integration, one-object-many-purposes, the portable liquid-phase chromatograph of compact conformation.
Technical scheme of the present invention is; Drive moving phase with the precise injection pump, can carry out the eluent gradient wash-out; As preenrichment/separating column, the post end directly links to each other with the flow cell of detection system with capillary monolithic column; Detection system is a light source with the light emitting diode, is optical signal detector with the grating spectrograph, connects with optical fiber between light source, flow cell and the detecting device; The flow cell dual-use material of detection system both can be used as ultraviolet-visible absorption flow cell and also can be used as the use of fluorescence flow cell; Spectral characteristic per sample just can select ultraviolet-visible to absorb or two kinds of detecting patterns of fluoroscopic examination by the connected mode of changing optical fiber component.During the uneasiness packing, portable liquid-phase chromatograph also can be used as the flow injection type ultraviolet-visible spectrophotometer or fluorophotometer uses.
The present invention is provided with syringe pump, sampling valve, the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence and supporting optical fiber component, capillary monolithic column, grating spectrograph, photodiode light source, plate type computer, waste liquid bottle and power supply, and all parts are installed in the cabinet.The syringe outlet of syringe pump connects the import of sampling valve, the sample export of sampling valve connects the inlet of capillary monolithic column, the outlet of capillary monolithic column connects the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence, the photodiode light source imports dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence and grating spectrograph respectively by fork optical fiber, the transmitted light of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence or fluorescence are by in the optical fiber lead-in light grating spectrograph, the absorbance of grating spectrograph or fluorescence intensity switching signal are exported the termination plate type computer and are obtained the spectral information and the corresponding spectrogram of measured object, the flowing path outlet pipeline of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence connects waste liquid bottle, the control termination plate type computer serial communication interface of syringe pump.
Capillary monolithic column and the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence preferably are installed on the adjustable microtrabeculae erecting frame, adjustable microtrabeculae erecting frame is provided with fixed head, sliding block and top shoe, on fixed head, be provided with longitudinal groove, be used for fixing the cannelure and the fixed orifice of cylindrical threeway mixer, also be provided with at the fixed head back side and be used to limit front and back two transverse grooves that connect pump and threeway mixer pipeline; Sliding block is located at the fixed head upper surface, and by the longitudinal groove of bolt on fixed head, nut is embedded in the longitudinal groove, and sliding block is defined in the longitudinal groove and moves, and is provided with half slot at the upper surface of sliding block; Top shoe is located on the sliding block, and in the sliding block upper surface, nut is embedded in the deep gouge of fixed orifice of sliding block by bolt, is provided with half slot at the lower surface of top shoe.Described longitudinal groove is preferably two sections parallel longitudinal direction grooves.Sliding block is a rectangular cylinder, and half slot is located at the middle part of sliding block.Top shoe is a rectangular cylinder, and half slot is located at the middle part of top shoe, and the half slot on the top shoe docks with half slot on the sliding block.Used bolt is preferably hexagon socket head cap screw.The center of the hexa-prism two through-flow path connectors about being clamped in the middle of the slide block and the inlet of flow cell can not be subjected to the stress of cut point-blank when the capillary column two ends are separately fixed on two through-flow path connectors and the flow cell like this.Slide block adopts separated structures design be convenient to be fixedly clamped two through-flow path connectors of one six stupefied cylindricality in slide block up and down, simultaneously, is convenient to again free when changing the kapillary microtrabeculae.
The syringe of clamping is used to hold moving phase on two syringe pumps, and syringe outlet is respectively drawn a moving phase pipeline, and two pipelines converge on a threeway mixer, and this threeway mixer also is fixed on the adjustable microtrabeculae erecting frame.Be connected to the import of micro-sampling valve by the export pipeline of threeway mixer, be connected to hexa-prism two pass joints from the export pipeline of micro-sampling valve, this two pass joint is fastened on the adjustable microtrabeculae erecting frame.
One end of capillary monolithic column is connected on two pass joints by the cutting ferrule joint, and the other end inserts and is fixed in the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence of adjustable microtrabeculae erecting frame one end, connects by the cutting ferrule joint.Be fixed by bolts on the one flat plate on the adjustable microtrabeculae erecting frame, this flat board leans on support and screw retention in cabinet, and side space holds the power unit of instrument under it.Be connected to a waste liquid bottle from the flowing path outlet pipeline of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence, this waste liquid bottle is fixed in the cabinet one jiao, and other has a pipeline to be connected to waste liquid bottle from the removal waste fluid mouth of micro-sampling valve.
The dual-purpose flow cell of ultraviolet-visible absorption/fluorescence is provided with pond body, photoconduction quartz capillary, polyetheretherketone (PEEK) bushing pipe, GRIN Lens, packing washer, pad, optical fiber and liquid flow path pipeline.The photoconduction quartz capillary is installed in the polyether-ether-ketone liner tube and is seated in the tube chamber of pond body; GRIN Lens is arranged on the light entrance direction, with the pond body with packing washer sealing and fixing; Pad between GRIN Lens and polyether-ether-ketone liner tube, the notch alignment path direction of pad, its effect is a redundant space of filling up between the two row; Inlet optical fiber and outlet optical fiber and liquid in-out pipe are fixed on by joint and cutting ferrule respectively and constitute the sealing stream on the body of pond.The tube wall of photoconduction quartz capillary is three layers of concentric tubular structure, and skin is a polyimide coating, inwardly is doping quartz layer and pure quartz wall layer successively, and the interface between doping quartz layer and the pure quartz wall layer is the total reflection interface.
The optical fiber component that is used for the portable liquid-phase chromatograph detection system comprises single strand optical fiber and two kinds of optical fiber components of bifilar fork optical fiber.Single strand optical fiber is provided with silica fibre and teflon sleeve, and silica fibre is located in the teflon sleeve, outwards is coated with silicon rubber protective seam and thermal contraction casing tube protective seam successively at teflon sleeve.Bifilar fork optical fiber is provided with two silica fibres that are arranged in parallel and teflon sleeve; two silica fibres that are arranged in parallel are located in the teflon sleeve, outwards are coated with silicon rubber protective seam and thermal contraction casing tube protective seam successively at teflon sleeve.Single strand optical fiber can be connected the light path endpiece of the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence during use, and the other end connects grating spectrograph when carrying out the UV, visible light absorption detecting, seal with sun-shading cap when carrying out fluoroscopic examination.The bifilar end of bifilar fork optical fiber is connected the light path entrance point of the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence, a sub-thread end connects light source, another root sub-thread end seals with sun-shading cap when carrying out the UV, visible light absorption detecting connect grating spectrograph when carrying out fluoroscopic examination.
Detector module is installed in the cabinet bottom of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence below, and by diode light-source, grating spectrograph, radiator fan and three fixed mounts are formed.Be connected by optical fiber component between detector module and the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence.Optical fiber component is divided into a single strand optical fiber and a bifilar fork optical fiber.One section light path endpiece that is connected dual-purpose flow cell of single strand optical fiber, the other end connects grating spectrograph when carrying out the UV, visible light absorption detecting, seal with sun-shading cap when carrying out fluoroscopic examination.The bifilar end of bifilar fork optical fiber is connected the light path entrance point of dual-purpose flow cell, and a sub-thread end connects light source, and another root sub-thread end connects grating spectrograph when carrying out fluoroscopic examination, seal with sun-shading cap when carrying out the UV, visible light absorption detecting.The plate type computer that is used for controlling with data acquisition is installed on box cover, and panel computer is by two syringe pumps of serial communication control, by USB line control grating spectrograph and image data.
Brief principle of the present invention and flow process are as follows: the syringe pump by plate type computer control drives moving phase, and sample injects stream from the micro-sampling valve, brings sample into capillary monolithic column and carries out preenrichment/separation; Each component is successively by the dual-purpose flow cell of optical fiber type ultraviolet-visible/fluorescence in the sample; The light that light source sends imports flow cell by optical fiber, and transmitted light or fluorescence are by in the optical fiber lead-in light grating spectrograph; By spectrometer the absorbance or the fluorescence intensity signals that collect are changed and be input in the plate type computer, through handling spectral information and the corresponding spectrogram that obtains measured object.
Because the post bed permeability of capillary monolithic column is good, can under lower pressure, work, and the sample size that needs is than conventional chromatogram post much less.Therefore make that volume is little, the syringe pump of light weight becomes possibility as the moving phase discharge pump.Along with the progress of contemporary optics technical device, the miniature of hand size and micro spectral detecting instrument appear on the market, for road has been paved in the appearance of integrated, microminiaturized chromatographic detector.
Description of drawings
Fig. 1 is existing high performance liquid chromatograph device basic structure synoptic diagram.
Fig. 2 is existing high performance liquid chromatograph UV-detector ultimate principle figure.
Fig. 3 is existing high performance liquid chromatograph fluorescence detector ultimate principle figure.
Fig. 4 is that the structure of the embodiment of the invention is formed synoptic diagram.
Fig. 5 is an embodiment of the invention overall appearance structural representation.The each several part title is as follows in Fig. 5: 51 loam cakes; 52 casings; 53 bunchs of cables; 54 top cover of faceplate; 55 plate type computer touch-screens; 56 keyboard interfaces; 57 mouse interfaces; 58 syringe pump power switches; 59 plate type computer power switches; 510 USB interface; 511 faceplate screws nail; 512 accessory lid plates; 513 removable covers; 514 silicon rubber keyboards; 515 detector module; 516 power supply cover plates; 517 micro-sampling valves.
Fig. 6 is an embodiment of the invention top cover of faceplate structural representation.The each several part title is as follows in Fig. 6: the 61 top cover of faceplate back sides; 62 plate type computer casings; 63 horizontal stiffeners; 64 screws; 65 stringers; 66 screws; 67 outlets; The 68USB port; 69 RS-232 serial ports; 610 mouse interfaces; 611 keyboard interfaces; 612 usb hubs; 613 two circumscribed USB ports; 614 plate type computer power switches; 615 syringe pump power switches; 616 mouse interfaces; 617 keyboard interfaces; 618 breach.
Fig. 7 removes inner structure vertical view behind accessory lid plate and the removable cover for the embodiment of the invention.The each several part title is as follows in Fig. 7: 71 install base plate; 72 terminal boxes; 73 fitting cases; 74,75 midfeathers; 76 diaphragm plates; 77 detector module; 78 spectrometer optical fiber interfaces; 79 luminous source optical fiber interfaces; 710 waste liquid bottle stationary platforms; 711 waste liquid bottles; 712 allen key putting holes; No. 713 syringe pumps; 714 No. two syringe pumps; No. 715 syringes; 716 No. two syringes; 717 syringe pump fixed screws; 718 syringe tube pipeline connectors; 719 moving phase pipelines; 720 threeway mixers; 721 capillary column erecting frames; 722 erecting frame fixed screws; 723 power supply cover plates; 724 moving phase pipelines; 725 micro-sampling valves; 726 injector discharging of waste liquid pipes; Pipeline before 727 posts; 728 sexangles, two pass joints; 729 capillary chromatographic columns; 730 flow cells; The outlet of 731 flow cell optical fiber; 732 flow cell optical fiber inlet; 733 flow cell discharging of waste liquid pipes; 734 workbins; 735 power supply heat sinking wind inlet of fan.
Fig. 8 removes inner structure vertical view behind syringe pump and the power supply cover plate for the embodiment of the invention.The each several part title is as follows in Fig. 8: 81 install base plate; 82 12V power transformer; 83 5V power transformer; 84 fan erecting frames; 85 sampling valve slots to make way; 86 syringe pump fixing screw holes; 87 grating spectrographs; 88 detector module radiator fans; 89 diode light-sources; 810 detector module fixed mounts; 811 light source pulse control lines; 812 power panel fixing screw holes.
Fig. 9 is an embodiment of the invention power circuit composition diagram.
Figure 10 is an embodiment of the invention signal flow graph.
Figure 11 is that embodiment of the invention detection system detects Cd in the water with UV, visible light absorption mode PAR photometry
2+Signal graph.In Figure 11, horizontal ordinate is Time (sec), and ordinate is Absorbance.Cd in the sample
2+Concentration be 1 μ g mL
-1, PAR concentration is 5 * 10
-5MolL
-1
Figure 12 is the signal graph of embodiment of the invention detection system with fluorescein in the fluoroscopic examination mode detection water.In Figure 12, horizontal ordinate is Time (sec), and ordinate is Intenstity.Sample concentration is 20 μ g mL
-1
Figure 13 is the separate colors spectrogram of embodiment of the invention capillary monolithic column to six kinds of benzene series things.In Figure 13, horizontal ordinate is Time (min), and ordinate is Absorbance (mAU).Moving phase is 6: 4 acetonitrile/water solution, flow velocity 60 μ L min
-1, peak sequence is 1 thiocarbamide, 2 phenol, 3 benzene, 4 toluene, 5 ethylbenzene, 6 isopropyl benzenes.
Figure 14 is the adjustable microtrabeculae erecting frame Facad structure synoptic diagram of the embodiment of the invention.
Figure 15 is the adjustable microtrabeculae erecting frame structure synoptic diagram of the embodiment of the invention.
Figure 16 is that the dual-purpose flow cell structure of the ultraviolet-visible absorption/fluorescence of the embodiment of the invention is formed synoptic diagram.Each several part name label in Figure 16: pond body 31; Photoconduction quartz capillary 32; PEEK bushing pipe 33; C font pad 34; GRIN Lens 35; Packing washer 36; Pad 37; Light path import optical fiber and joint 38; Light path outlet optical fiber and joint 39; Stream inlet ductwork and joint 310; Stream inlet ductwork and joint 311.
Figure 17 is the single strand optical fiber structural representation in the optical fiber component of the embodiment of the invention.The each several part name label is in Figure 17: silica fibre 11; Teflon sleeve 12; Silicon rubber protective seam 13; Thermal contraction casing tube protective seam 14.
Figure 18 is the bifilar fork optical fiber structure synoptic diagram in the optical fiber component of the embodiment of the invention.The each several part name label is in Figure 18: silica fibre 21; Teflon sleeve 22; Silicon rubber protective seam 23; Thermal contraction casing tube protective seam 24.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Referring to Fig. 4, the present invention is provided with the dual-purpose flow cell 1 of optical fiber type ultraviolet-visible absorption/fluorescence and supporting optical fiber component, capillary monolithic column 2, miniature grating spectrograph 3, photodiode light source 4, syringe pump 5, sampling valve 6, plate type computer 7, waste liquid bottle 8 and power supply, and all parts are installed in the cabinet.The sample export of sampling valve 6 connects the inlet of capillary monolithic column 2, the outlet of capillary monolithic column 2 connects the dual-purpose flow cell 1 of optical fiber type ultraviolet-visible absorption/fluorescence, photodiode light source 4 imports dual-purpose flow cell 1 of optical fiber type ultraviolet-visible absorption/fluorescence and grating spectrograph 3 respectively by fork optical fiber 9, the transmitted light of the dual-purpose flow cell 1 of optical fiber type ultraviolet-visible absorption/fluorescence or fluorescence are by in the straight-through optical fiber 10 lead-in light grating spectrographs 3, and the absorbance of grating spectrograph 3 or fluorescence intensity switching signal are exported termination plate type computer 7 and obtained the spectral information and the corresponding spectrogram of measured object.This miniature grating spectrograph is of a size of 89.1mm * 63.3mm * 34.4mm, weighs 190 grams, and its size of grating spectrograph on ordinary meaning is obviously dwindled.Be connected to a waste liquid bottle 8 from the flowing path outlet pipeline of the dual-purpose flow cell 1 of optical fiber type ultraviolet-visible absorption/fluorescence, this waste liquid bottle 8 is fixed on one jiao (referring to Fig. 7) in the cabinet, and other has a pipeline to be connected to waste liquid bottle 8 from the removal waste fluid mouth of micro-sampling valve.
Referring to Fig. 5, embodiment of the invention overall appearance is designed to portable box-shaped, be divided into hinged loam cake 51 and casing 52, be of a size of 48cm * 38cm * 20cm, casing is made by high-strength engineering plastic, crushing resistance and anticorrosive property are good, and the hinge left end has bunch of cables 53, and two ends connect loam cake 51 and casing 52 respectively.In the loam cake 51 signal processing is housed, top cover of faceplate 54 is arranged in loam cake 51, be fixed on the loam cake 51 by 6 screws 511.On the top cover of faceplate 54 main portions be the band touch-screen plate type computer 55, by 4 screw fixings on top cover of faceplate.In the top cover of faceplate bottom, be distributed with some interfaces and switch, be respectively from left to right: keyboard interface 56, mouse interface 57, syringe pump power switch 58, plate type computer power switch 59, two circumscribed USB ports 510.Instrumented main each several part in the casing, casing left-hand component has accessory lid plate 511 and removable cover 512, places ultrathin silicon rubber keyboard 513 on the removable cover.The frivolous waterproof of this silicon rubber keyboard can be collected by convolution, is connected (not drawing among the figure) by data line with the keyboard interface 514 of loam cake.Under the removable cover two syringe pumps (not drawing among the figure) and adjustable kapillary erecting frame (not drawing among the figure).Casing right part surface uncovered plate, there are parts such as detector module 515, power supply cover plate 516 and micro-sampling valve 517 inside.Below each several part is described respectively.
Referring to Fig. 6, from at top cover of faceplate 61 back sides, plate type computer casing 62 is installed in the coffin of top cover of faceplate, article two, " ∏ " shape aluminium alloy structure stiffener 63 that laterally passes through total length lay respectively at plate type computer about, each is fixing with 2 screws 64, article two, short vertical " ∏ " shape aluminium alloy structure stiffener 65 lay respectively at plate type computer about, each is fixed together plate type computer panel, top cover of faceplate and vertical " ∏ " shape aluminium alloy structure stiffener with two screws 66.Plate type computer casing downside has various interface, is respectively outlet 67, USB port 68, RS-232 serial ports 69, mouse interface 610, keyboard interface 611 from left to right from the back side.The usb hub 612 that one four port is arranged on the left side, the top cover of faceplate back side, fixing with VELCRO (nylon adherent buckle of band adhesive sticker).There is an exclusive port that connects the top cover of faceplate lower end, and is respectively from left to right from the back side: two circumscribed USB ports 613, plate type computer power switch 614, syringe pump power switch 615, mouse interface 616, keyboard interface 617.There is a breach 618 in the lower right corner, the top cover of faceplate back side, is used to hold the bunch of cables that is connected to the main frame casing.
Referring to Fig. 7, below provide each position component relation in the casing, bottom half has the installation base plate 71 with same size at the bottom of the case, and all parts all directly or indirectly are fixed on to be installed on the base plate.The base plate upper left corner is terminal box 72 among Fig. 7, and the power lead that connects loam cake and the interior each several part of casing is connected herein with signal wire, and instrument general supply line is also drawn thus.The silicon rubber keyboard that convolution gets up can be collected as the accessory box in the space that terminal box next door is separated out by midfeather 74,75 and diaphragm plate 76.Accessory lid plate and removable cover also are hinged on respectively on the diaphragm plate 76, can upwards start and open.Detector module 77 comprises grating spectrograph, LED source, radiator fan and 3 metal fixed mounts compositions, is being installed on the base plate by 3 screw fixings.Optical fiber interface 78 is wherein arranged on the grating spectrograph, optical fiber interface 79 is arranged on the light source.What the upper right corner and detector module were adjacent among the figure is waste liquid bottle fixed station 710, has a big hole to hold waste liquid bottle 711 on it, also has a small sircle hole 712 to be used to place the common tool allen key.Syringe pump 713,714 is fixed on the base plate by 4 long spiro nails 717, on it respectively clamping syringe 715,716 is arranged, be connected with tight joint 718 with lock at syringe outlet, be connected to two interfaces of threeway mixer 720 respectively by moving phase pipeline 719.The threeway mixer is embedded in the groove milling on the capillary column erecting frame 721, and the capillary column erecting frame is to be fixed on the power supply cover plate 723 by two erecting frame fixed screws 722.Between power supply cover plate and the installation base plate is the power transformer and the radiator fan (power supply and fan do not draw among the figure) thereof of instrument.The moving phase pipeline 724 of drawing from the central exit of threeway mixer 720 is connected to the import of micro-sampling valve 725, and an injector discharging of waste liquid pipe 726 is arranged between 711 from the sampling valve to the waste liquid bottle.Sampling valve is fixed on the power supply cover plate from the negative by two screws, and pipeline 727 is drawn from the sampling valve bottom before the post, passes the end that the power supply cover plate is connected to sexangle two pass joints 728.Sexangle two pass joints are fixed on the capillary column erecting frame 721, and the other end connects capillary chromatographic column 729.One protective sleeve (not drawing among the figure) is arranged on the capillary chromatographic column, and entrance point is connected on sexangle two pass joints 728, and endpiece directly is spun on the flow cell 730.Optical fiber outlet 731 and optical fiber import 732 are arranged on the flow cell, use optical fiber (not drawing among the figure) to be connected on spectrometer optical fiber interface 78 and the luminous source optical fiber interface 79 respectively.Opposite one side is drawn a discharging of waste liquid pipe 733 feeding waste liquid bottles 711 from flow cell in capillary chromatographic column.The shallow box of a bonding circle 734 is used for placing the finding of temporarily using in the experiment as workbin on the power supply cover plate 723.Also opened the power supply heat sinking wind inlet of fan of a circle on the power supply cover plate.
Referring to Fig. 8, below provide each position component of casing bottom relation, two power transformer are arranged installing on the base plate 81, be respectively 12V power transformer 82 and 5V power transformer 83, respectively with screw fixings on base plate.A shaped as frame power supply fan erecting frame 84 is arranged on the power transformer right side, a fan of blowing vertically downward is housed on it, with base plate one segment distance is arranged below the fan, owing to be subjected to the restriction of diaphragm plate and power supply cover plate, the space outflow that power transformer and syringe pump bottom are flowed through in the wind direction left side that fan blows out realizes the heat radiation to power transformer.On the fan erecting frame with the power supply cover plate on sample introduction valve position corresponding position have a slot to make way 85, be used to hold the structure of sampling valve bottom.In the top-right detector module of base plate, be respectively grating spectrograph 87, detector module radiator fan 88 and diode light-source 89 from top to bottom, be fixed on the base plate with screw by three fixed mounts 810.There is a light source pulse control line 811 to be connected to grating spectrograph from light source.At the diaphragm plate right-hand member and the fan erecting frame lower right corner power supply cover plate fixed screw holes 812 is arranged respectively.
Referring to Fig. 9, below provide the annexation of power circuit part, use AC 220V lighting circuit to power, obtain the direct supply of 12V and 5V respectively by 2 power transformer ( 12V 3A, 5V 10A).The 12V power supply by K switch 1 for two syringe pumps 91 and 92 and diode light-source 93 electric power is provided; The 5V power supply is respectively plate type computer 94, usb hub 95 and grating spectrograph 96 by K switch 2 electric power is provided.Each major metal parts all has good earth in the instrument.
Referring to Figure 10, below provide the simple introduction of control signal and data acquisition circuit, the USB of plate type computer 7 (USB (universal serial bus)) port is connected to usb hub 101; A USB cable of drawing from usb hub 101 is connected on the grating spectrograph 3, realizes data acquisition and to the control of spectrometer; A pulse signal cable connects grating spectrograph and diode light-source 102, and the led pulse that is used for spectrometer and light source is synchronous; Two USB external-connected port USB1 and USB2 are drawn out on the top cover of faceplate from usb hub respectively, to be provided to the connection of other external units: the upstream Interface of drawing rs 232 serial interface signal line to a syringe pump 105 from the RS-232 serial ports COM of plate type computer 7, have a signal line to be connected to the upstream Interface of second syringe pump from the downstream interface of first syringe pump 106, plate type computer can be controlled two syringe pumps by serially connected pump network.
Syringe pump can adopt the NE-501 type syringe pump of U.S. New Era company.Microfluidic chromatography system requirements liquid delivery pump must have higher precision and stability under extremely low flow velocity.Peristaltic pump, reciprocating type constant-flux pump commonly used all are difficult to satisfy these conditions, and syringe pump can satisfy above-mentioned requirements.NE-501 type syringe pump can be realized all functions with RS-232 serial ports and compunication by computer program control; Can move the nearly pump program of 41 steps.Can be on two syringe pumps the different syringe of two diameters of clamping realize the gradient elution of two kinds of moving phases, also can be by the different gradient elutions of realizing of the pushing speed of two syringe pumps of control.This pump also has stop detector in addition, can detect automatically because of superpressure or mechanical fault and warning;
Respectively have a moving phase pipeline to be connected to two imports of a threeway mixer on the syringe outlet of clamping on two syringe pumps, another root pipeline is connected to the moving phase import of micro-sampling valve from the outlet of threeway mixer.The threeway mixer is installed in the groove milling on kapillary microtrabeculae-flow cell erecting frame in the mode that embeds.
The 7520 type micro-sampling valves that the micro-sampling valve can adopt U.S. Rheodyne company to make, the sampling volume of this sampling valve is 0.2～1 μ l, is fit to the sample introduction requirement of microfluidic chromatography system.
The kapillary polyalcohol integral microtrabeculae that uses is with long 15～20cm, and internal diameter is 0.53mm, and the quartz capillary of outsourcing polyimide coating is an outer wall, and the octadecyl type methacrylate synthetic with bulk polymerization is stationary phase.This kapillary polyalcohol integral microtrabeculae is installed on adjustable kapillary microtrabeculae-flow cell erecting frame, and entrance point is linked to each other with sampling valve by a pipeline, and endpiece directly inserts in the flow cell of detection system.
The light source that uses in the detector module can adopt the LS-450 type LED source of U.S. Ocean Optics company.This light source can provide light source by changing light emitting diode in 380～680nm scope, little, the light weight of volume, can be connected with the USB2000 spectrometer and with pulsed illumination pattern work, the absorption spectrum and the fluorescence spectrum that are fit to visible light wave range detect with continuous light-emitting mode or by RS-232 interface.The small-sized deuterium lamp of DH-2000-CAL/halogen tungsten lamp light source made from U.S. Micropack company is as external additional light source in addition.The light emitting region of DH-200-CAL type deuterium/halogen tungsten lamp light source can be from 200～800nm, and luminous intensity is big, can be used as full wave absorption of ultraviolet-visible and fluorescence excitation light source.
Flow cell in the detector module is the dual-purpose flow cell of a kind of optical fiber type ultraviolet-visible/fluorescence, is fixed on an end of kapillary erecting frame.The stream import of flow cell directly connects the outlet of kapillary microtrabeculae, and flowing path outlet has a pipeline to be connected to waste liquid bottle.The light path import of flow cell is connected to one bifilar part trouble optical fiber, and the light path outlet is connected to a single strand optical fiber.By changing the different connection form of optical fiber and light detecting device, can realize the conversion of ultraviolet-visible absorption detecting pattern and fluoroscopic examination pattern.
The USB2000 type grating spectrograph that light detecting device in the detector module can adopt U.S. Ocean Optics company to make.This grating spectrograph is light-splitting device with the grating, and (CCD) is detection means with photoelectric coupled device, has the little (characteristics such as 89.1mm * 63.3mm * 34.4mm), light weight (190 gram), low in energy consumption, spectral detection wide ranges, spectral resolution height of volume.The USB2000 grating spectrograph is crossed USB interface with the computer expert and is connected, and uses supporting OOIBase32 software control and image data, has multiple mode of operations such as measured light intensity, absorbance, transmitance, time collection.
The evaluation of detector performance: detection system of the present invention is applied to the heavy metal element cadmium in 4 (2-pyridylazo) resorcinol (PAR) the spectrphotometric method for measuring water with ultraviolet-visible absorption detecting pattern, detects to be limited to 10ng mL
-1, the RSD that repeated test is 6 times is 2%.Repeated experiments figure is as a result seen Figure 11.Detection system of the present invention is applied to detect the fluorescent material fluorescein with the fluoroscopic examination pattern, detects to be limited to 1 μ g mLl
-1, the RSD that repeated test is 17 times is 3.8%.Repeated experiments figure is as a result seen Figure 12.
The PPC-121T/BEL type technical grade plate type computer that data acquisition of the present invention and control can adopt Shenzhen De Tekang Electronics Co., Ltd. to make.The Intel Celeron M that this plate type computer is equipped with 400MHz moves processor; The compactflash memory card of built-in 256 MB of memory and 1G; 12.1 inch touch LCD screen.This plate type computer is installed in the box cover of example model machine.
Capillary monolithic column of the present invention can adopt the octadecyl type capillary monolithic column, is used to separate the potpourri of thiocarbamide, phenol and four kinds of benzene homologues, the results are shown in Figure 13.
Shown in Figure 14 and 15, adjustable microtrabeculae erecting frame is provided with fixed head 41, sliding block 421 and top shoe 422, on fixed head 41, be provided with longitudinal groove 46, be used for fixing the cannelure 47 and the fixed orifice 43 of cylindrical threeway mixer, also be provided with at fixed head 41 back sides and be used to limit front and back two transverse grooves 48 that connect pump and threeway mixer pipeline; Sliding block 421 is located at fixed head 41 upper surfaces, be fixed in longitudinal groove 46 on the fixed head 41 by hexagon socket head cap screw 44, nut 45 is embedded in the longitudinal groove 46, and sliding block 421 is defined in the longitudinal groove 46 and moves, and is provided with half slot 4211 in the upper surface middle part of sliding block 421; Top shoe 422 is located on the sliding block 421, be fixed in sliding block 421 upper surfaces by hexagon socket head cap screw 44, nut 45 is embedded in the deep gouge of fixed orifice 49 of sliding block 421, be provided with half slot 4221 at the lower surface of top shoe 422 middle part, the half slot 4221 on the top shoe 422 docks with half slot 4211 on the sliding block 421.The end of capillary column is directly tapped in the flow cell that is fixed on the other end, determine the position of slide block by column length after, screwing up and down successively, the bolt of slide block gets final product.The center of the hexa-prism two through-flow path connectors about being clamped in the middle of the slide block and the inlet of flow cell are point-blank.
Below provide the preparation method of octadecyl type capillary monolithic column.1) capillary tube inner wall activation: clean the activation capillary tube inner wall with acetone, hydrochloric acid, secondary water, NaOH solution, secondary water successively, nitrogen dries up dry, makes capillary tube inner wall obtain abundant free type silicon hydroxyl; 2) prepolymerization of capillary tube inner wall: at the silylating reagent γ-methacrylic acid oxygen propyl trimethoxy silicane of capillary tube inner wall bonding one deck band thiazolinyl (γ-MAPS); 3) preparation methacrylic acid stearyl-ethylene glycol dimethacrylate integral post: reaction mixture comprises reaction monomers potpourri, initiating agent and pore-foaming agent, (down together) reaction monomers potpourri accounts for 40%～70% of entire reaction potpourri by mass percentage, the initiating agent azoisobutyronitrile is 0.5%～3% of a reaction monomers potpourri, and surplus is pore-foaming agent; Methacrylic acid stearyl (OMA) in the reaction monomers potpourri with the content ratio of ethylene glycol dimethacrylate (EDMA) is: OMA is 70%～40%, EDMA is 30%～60%, pore-foaming agent is by n-propanol and 1, the two-component mixture that 4 butylene glycols constitute, take by weighing OMA in proportion, EDMA and pore-foaming agent, mix nitrogen and blow the ultrasonic concussion degassing back injection kapillary of bonding in advance, one end closure, seal the other end after the ultrasonic concussion, react in the water-bath, continuous integral liquid chromatography micro-column with promptly obtaining porous structure after the flushing of high pressure pump drive acetonitrile can carry out chromatographic evaluation to it under μ-LC pattern.In step 1), described capillary tube inner wall cleans 15～30min, 1mol L with acetone successively
-1NaOH washes 0.5～3h, secondary water flushing 0.5h, 0.1molL
-1HCl washes 2h down at 50～70 ℃, and secondary water flushing 0.5h places the gas chromatography column oven then, 120～300 ℃, best 160 ℃ of slow nitrogen are blown over night, and sealing two ends and place exsiccator to preserve makes capillary tube inner wall obtain abundant free type silicon hydroxyl thereafter.In step 2) in, the prepolymerization of described capillary tube inner wall is organic acid γ-methacrylic acid oxygen propyl trimethoxy silicane (γ-MAPS) inject in the kapillary of overactivation drying of number percent usefulness adding 0.25%～0.5% by volume, sealing two ends, ambient temperature overnight, use nitrogen purging 30min then, repeat once, use nitrogen purging 0.5～3h at last.Organic acid is acetate or formic acid.In step 3), 1,4 butylene glycol that pore-foaming agent goes out 70% n-propanol and 30% constitutes.Mixed liquor injects the kapillary of bonding in advance, the time of the ultrasonic concussion degassing of one end closure is 15～30min, react in the water-bath, bath temperature is 50～70 ℃, the reaction time is 15～24h in the water-bath, be cut into suitable length then, with the continuous integral liquid chromatography micro-column that can obtain porous structure behind high pressure pump drive acetonitrile flushing 5～10h.
The structure that below provides the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence is formed embodiment and mode of operation and principle, referring to Figure 16, the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence is provided with parts such as pond body 31, photoconduction quartz capillary 32, polyetheretherketone (PEEK) bushing pipe 33, C font pad 34, GRIN Lens 35, packing washer 36 and 37, optical fiber 38 and 39, liquid flow path pipeline 310 and 311.Photoconduction quartz capillary 32 is installed in the PEEK bushing pipe 33 and is seated in the tube chamber of pond body 31; GRIN Lens 35 is arranged on the light entrance direction, with pond body 31 with packing washer 36 and 37 sealings and fixing; C font pad 34 between GRIN Lens 35 and PEEK bushing pipe 33, the notch alignment path direction of C font pad 34, its effect is a redundant space of filling up between the two row; Inlet optical fiber 38 and outlet optical fiber 39 and liquid in-out pipe 310,311 are fixed on by joint and cutting ferrule respectively and constitute the sealing stream on the body of pond.
UV, visible light absorbs and the principle of work of two kinds of mode of operations of fluoroscopic examination is: under ultraviolet-visible absorption detecting pattern, the light that sends from light source imports flow cell by one of bifilar fork optical fiber, absorb the back through sample solution and import miniature grating spectrograph, measure its absorbance by the outlet single strand optical fiber; Under the fluoroscopic examination pattern, the light that sends from light source imports flow cell by one of bifilar fork optical fiber, fluorescence activity material in the irradiation excited sample, the fluorescence that sends after the fluorescence activity material is stimulated another thigh along the direction opposite with incident light along bifilar fork optical fiber enters miniature grating spectrograph, measure its light intensity, obtain fluorescence intensity after the deduction parasitic light background.
The tube wall of the photoconduction quartz capillary in the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence is three layers of concentric tubular structure, skin is a polyimide coating, inwardly be doping quartz layer and pure quartz wall layer successively, the interface between doping quartz layer and the pure quartz wall layer is the total reflection interface.Connect difficult problem in order to solve the light path that causes because of photoconduction quartz capillary internal diameter is less, adopted light transmitting fiber to connect the flow cell light path, the intercapillary light path coupling of light transmitting fiber and photoconduction has used GRIN Lens as light collecting device.The light with certain angle of divergence that optical fiber is penetrated by GRIN Lens converges and enters the photoconduction quartz capillary, because photoconduction quartz capillary inwall can make light along pipe inner total reflection conduction, can do not absorbed by tube wall and lose, can on less light path cross section, keep higher optical density.Chi Tike is processed by polyimide material integral body, and the high size of length and width is respectively 47.2mm * 22.4mm * 20mm.The through hole that one internal diameter 1.6mm is arranged along body axis, pond, the internal diameter overstriking of two ends, hole also is processed with the internal thread that cooperates with fibre-optical splice.The bar duct of an internal diameter 1.6mm is respectively arranged on two sides of pond body, communicate with central duct, constitute a Z font stream, the outer end in these two ducts also is processed with internal thread, is used to connect the liquid flow path pipe joint.Body end face diagonal position is drilled with two through holes in the pond, passes bolt when being used for fixing flow cell.These two bolts hole not with the hole link of body inside, pond.Each parts of flow cell light path inflow point are described below: PEEK bushing pipe 33 internal diameter 0.38mm, external diameter 1.58mm, long 20mm; Photoconduction quartz capillary 32 internal diameter 0.25mm, external diameter 0.375mm, long 20mm; C font pad 34 is made for polytetrafluoroethylmaterial material, has the breach of a wide 0.6mm on it; GRIN Lens 35 is made for special optical glass, diameter 1.8mm, long 5.8mm; Packing washer 36 is made with rubber; Pad 37 is made for polytetrafluoroethylmaterial material, and light path import optical fiber and joint 38 comprise optical fiber bushing pipe, taper cutting ferrule and hand-tight joint, and concrete structure is described separately.
Each parts installation site relation of flow cell light path inflow point is described below: PEEK bushing pipe 33 is seated in the medium pore canal of pond body 31; Photoconduction quartz capillary 32 is seated in the PEEK bushing pipe 33.C font pad 34 is gripped by the two between PEEK bushing pipe 33 and GRIN Lens 35, its notch alignment stream pipeline; GRIN Lens 35 is inserted about half length of an end of pond body 31 medium pore canals; Flowing path outlet pipeline 310 inserts in the bodies of pond one and brings out mouth and just in time aim at the outlet of PEEK bushing pipe; 36 two of packing washers are on one group of cylinder that is enclosed within GRIN Lens; 37 two on pad is on one group of cylinder that is enclosed within GRIN Lens; In the threaded hole that is threaded into pond body medium pore canal one end in the tight coupling of ferrule armrest, the taper cutting ferrule inwardly compresses GRIN Lens and pad, and the distortion of pad compressing O-ring seal makes between GRIN Lens and the pond body and sealed.
Flow cell light path endpiece and entrance point are similar, but GRIN Lens and O-ring seal, pad are not installed, and are connected sealing with hand-tight joint with the pond body by the taper cutting ferrule on the fibre-optical splice.The stream pipeline of turnover flow cell is connected sealing with hand-tight joint with the pond body by the taper cutting ferrule.This flow cell optical path length is 20mm, greater than present common most of flow cells.The pond volume is about 1 μ L, can satisfy the request for utilization of kapillary microtrabeculae chromatogram.
Referring to Figure 17 and 18, in single strand optical fiber, core is the silica fibre 11 of an external diameter 0.46mm, is enclosed within the teflon sleeve 12 of an internal diameter 0.5mm, outwards is coated with silicon rubber protective seam 13 and thermal contraction casing tube protective seam 14 successively.In the bifilar fork optical fiber; core is the silica fibre 21 of two external diameter 0.46mm being arranged in parallel; be enclosed within the teflon sleeve 22 of an internal diameter 0.8mm; deformation can take place and hold two optical fiber in teflon sleeve 22, outwards also is coated with silicon rubber protective seam 23 and thermal contraction casing tube protective seam 24 successively.The three-layer protection layer makes optical fiber in use can carry out certain bending and non-frangibility.Prevent that simultaneously surround lighting from entering optical fiber.Single strand optical fiber is connected with the dual-purpose flow cell of ultraviolet-visible absorption/fluorescence respectively with bifilar fork optical fiber during use.The structure of optical fiber component and the dual-purpose flow cell link of ultraviolet-visible absorption/fluorescence joint is an example with the joint of single strand optical fiber, silica fibre 11 is enclosed within the teflon sleeve 12, taper cutting ferrule and hand-tight joint are enclosed within outside the teflon sleeve successively, and taper cutting ferrule and hand-tight joint can adopt the standard web member.When tightening hand-tight joint, the taper fit face between taper cutting ferrule and the hand-tight joint forces the most advanced and sophisticated contraction of taper cutting ferrule deformation, and inside banding teflon sleeve, teflon sleeve deformation banding silica fibre also take place realize sealing.Bifilar fork optical fiber is identical with the structure and the single strand optical fiber of flow cell link joint, but does not rely on taper cutting ferrule and hand-tight joint to realize sealing.
Optical fiber component and light source/when spectrometer link joint is connected; silica fibre 21 is enclosed within the teflon sleeve 22; mark 23 is silicon rubber protective seam (thermal contraction casing tube does not draw); be with the joint inner sleeve of one section external diameter 4mm on one section silica fibre that front end stretches out and the teflon sleeve; the silicon rubber protective seam is with the joint outer tube of one section silastic material outward and stretches out with the joint inner sleeve isometricly, is the tubular cavity between the joint internal and external casing.When on the fibre-optical splice that optical fiber is inserted in light source or spectrometer, the fibre-optical splice that the joint inner sleeve inserts light source or spectrometer is a fiber orientation, and the joint outer tube is enclosed within on the fibre-optical splice of light source or spectrometer and bears acting force.
Claims (8)
1. portable liquid-phase chromatograph, it is characterized in that being provided with syringe pump, the micro-sampling valve, dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence and supporting optical fiber component thereof, capillary monolithic column, grating spectrograph, the photodiode light source, plate type computer, waste liquid bottle and power supply, all parts are installed in the cabinet, the syringe outlet of syringe pump connects the import of sampling valve, the sample export of sampling valve connects the inlet of capillary monolithic column, the outlet of capillary monolithic column connects the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence, the photodiode light source imports dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence and grating spectrograph respectively by fork optical fiber, the transmitted light of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence or fluorescence are by in the optical fiber lead-in light grating spectrograph, the absorbance of grating spectrograph or fluorescence intensity switching signal are exported the termination plate type computer and are obtained the spectral information and the corresponding spectrogram of measured object, the flowing path outlet pipeline of the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence connects waste liquid bottle, the control termination plate type computer serial communication interface of syringe pump.
2. portable liquid-phase chromatograph as claimed in claim 1, it is characterized in that described capillary monolithic column and the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence are installed on the adjustable microtrabeculae erecting frame, adjustable microtrabeculae erecting frame is provided with fixed head, sliding block and top shoe, on fixed head, be provided with longitudinal groove, be used for fixing the cannelure and the fixed orifice of cylindrical threeway mixer, also be provided with at the fixed head back side and be used to limit front and back two transverse grooves that connect pump and threeway mixer pipeline; Sliding block is located at the fixed head upper surface, and by the longitudinal groove of bolt on fixed head, nut is embedded in the longitudinal groove, and sliding block is defined in the longitudinal groove and moves, and is provided with half slot at the upper surface of sliding block; Top shoe is located on the sliding block, and in the sliding block upper surface, nut is embedded in the deep gouge of fixed orifice of sliding block by bolt, is provided with half slot at the lower surface of top shoe.
3. portable liquid-phase chromatograph as claimed in claim 2, it is characterized in that described longitudinal groove is two sections parallel longitudinal direction grooves, sliding block is a rectangular cylinder, half slot is located at the middle part of sliding block, top shoe is a rectangular cylinder, half slot is located at the middle part of top shoe, and the half slot on the top shoe docks with half slot on the sliding block.
4. portable liquid-phase chromatograph as claimed in claim 1, it is characterized in that clamping has syringe on the described syringe pump, syringe is used to hold moving phase, syringe outlet is respectively drawn a moving phase pipeline, article two, pipeline converges on a threeway mixer, this threeway mixer also is fixed on the adjustable microtrabeculae erecting frame, be connected to the import of micro-sampling valve by the export pipeline of threeway mixer, be connected to hexa-prism two pass joints from the export pipeline of micro-sampling valve, this two pass joint is fastened on the adjustable microtrabeculae erecting frame.
5. portable liquid-phase chromatograph as claimed in claim 1 or 2, an end that it is characterized in that capillary monolithic column is connected on two pass joints by the cutting ferrule joint, the other end inserts and is fixed in the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence of adjustable microtrabeculae erecting frame one end, connect by the cutting ferrule joint, be fixed by bolts on the one flat plate on the adjustable microtrabeculae erecting frame, this flat board leans on support and screw retention in cabinet, and dull and stereotyped side space down holds the power unit of instrument.
6. portable liquid-phase chromatograph as claimed in claim 1, the flowing path outlet pipeline that it is characterized in that the dual-purpose flow cell of described optical fiber type ultraviolet-visible absorption/fluorescence is connected to a waste liquid bottle, waste liquid bottle is fixed in the cabinet one jiao, and other has a pipeline to be connected to waste liquid bottle from the removal waste fluid mouth of micro-sampling valve.
7. portable liquid-phase chromatograph as claimed in claim 1, it is characterized in that the dual-purpose flow cell of optical fiber type ultraviolet-visible absorption/fluorescence is provided with pond body, photoconduction quartz capillary, polyether-ether-ketone liner tube, GRIN Lens, packing washer, pad, optical fiber and liquid flow path pipeline, the photoconduction quartz capillary is installed in the polyether-ether-ketone liner tube and is seated in the tube chamber of pond body; GRIN Lens is arranged on the light entrance direction, with the pond body with packing washer sealing and fixing; Pad between GRIN Lens and polyether-ether-ketone liner tube, the notch alignment path direction of pad; Inlet optical fiber and outlet optical fiber and liquid in-out pipe are fixed on by joint and cutting ferrule respectively and constitute the sealing stream on the body of pond, the tube wall of photoconduction quartz capillary is three layers of concentric tubular structure, skin is a polyimide coating, inwardly be doping quartz layer and pure quartz wall layer successively, the interface between doping quartz layer and the pure quartz wall layer is the total reflection interface.
8. portable liquid-phase chromatograph as claimed in claim 1; it is characterized in that described optical fiber component comprises single strand optical fiber and two kinds of optical fiber components of bifilar fork optical fiber; single strand optical fiber is provided with silica fibre and teflon sleeve; silica fibre is located in the teflon sleeve; outwards be coated with silicon rubber protective seam and thermal contraction casing tube protective seam successively at teflon sleeve; bifilar fork optical fiber is provided with two silica fibres that are arranged in parallel and teflon sleeve; two silica fibres that are arranged in parallel are located in the teflon sleeve, outwards are coated with silicon rubber protective seam and thermal contraction casing tube protective seam successively at teflon sleeve.
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| US11054364B2 (en) | 2018-12-17 | 2021-07-06 | Thermo Finnigan Llc | Apparatus and methods for handling and spectrophotometry of small liquid samples |
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| CN101995387B (en) * | 2010-09-14 | 2012-05-23 | 杭州电子科技大学 | Multi-functional ultraviolet-visible spectrometer |
| CN102818869A (en) * | 2012-09-10 | 2012-12-12 | 山东汉方制药有限公司 | High performance liquid chromatograph |
| CN103105373A (en) * | 2013-01-14 | 2013-05-15 | 中国农业大学 | Dynamic spectrophotometry testing system and method for benzene in water |
| CN103207254B (en) * | 2013-03-13 | 2014-08-27 | 杭州纽蓝科技有限公司 | Reflecting ultraviolet-visible absorption and fluorescence integrated flow cell |
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