CN103226127A - Multi-channel micro-fluidic chip and mass spectrum combined device - Google Patents

Multi-channel micro-fluidic chip and mass spectrum combined device Download PDF

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CN103226127A
CN103226127A CN2013101020332A CN201310102033A CN103226127A CN 103226127 A CN103226127 A CN 103226127A CN 2013101020332 A CN2013101020332 A CN 2013101020332A CN 201310102033 A CN201310102033 A CN 201310102033A CN 103226127 A CN103226127 A CN 103226127A
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fluidic chip
main channel
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sample
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CN103226127B (en
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林金明
王聂君
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Tsinghua University
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Abstract

The invention discloses a multi-channel micro-fluidic chip and mass spectrum combined device. The multi-channel micro-fluidic chip and mass spectrum combined device comprises a micro-fluidic chip and an electric spraying mass spectrometer. The micro-fluidic chip is provided with a plurality of micro channels which are connected in parallel, and the outlet of each micro channel is communicated with a chamber. Each chamber is communicated with a main channel, and the other end of each main channel is a waste liquid outlet. One end of each main channel is close to a chamber and is communicated with a side channel, and the free end of the side channel is an extraction agent inlet. Height difference exists between the side channel and the main channel, and the upper rim of the side channel is arranged on the lower portion of the upper rim of the main channel. Sample outlets are communicated with sample outlet pipes respectively, wherein the outlets of the sample outlet pipes are arranged above the electric spraying device, and liquid drops generated by the electric spraying device is detected by the electric spraying mass spectrometer. A plurality groups of experiments can be simultaneously conducted by the multi-channel micro-fluidic chip and mass spectrum combined device, and real-time mass spectrum detection can be conducted after on-line sample pretreatment is conducted in the micro-fluidic chip.

Description

A kind of multichannel micro-fluidic chip-mass spectrometry device
Technical field
The present invention relates to a kind of multichannel micro-fluidic chip-mass spectrometry device.
Background technology
The micro-fluidic chip technology is because characteristics such as its low consumption, high flux, integrated level height have received increasing concern.By different designs, micro-fluidic chip can be realized diversified function, as fluid operated, sample preparation, biochemical reaction etc., these functions make micro-fluidic chip have very application prospects, and particularly it is significant in the application of biology and medical domain.The size of microfluidic chip structure can approach biological tissue, and can with different structure by different level, coherent integrating, make micro-fluidic chip having very big advantage aspect imitated biological tissue or the organ, as document Goral V.N.; Hsieh Y.-C.; Petzold O.N.; Clark J.S.; Yuen P.K.; Faris R.A.Lab Chip, 2010,10,3380-3386 in micro-fluidic chip to former generation human liver cell carry out dynamic 3 D and cultivate, successfully part has been recovered cell membrane polarity and has been produced the structure of similar bile microtubule.These advantages of micro-fluidic chip technology make it at biology and medical research field huge application potential be arranged.
At present, carry out cell capture, cultivation, stimulation etc. and all obtained certain achievement in micro-fluidic chip, some simple biochemical reactions also can carry out in the micro-fluidic chip system.As document Skelley A.M.; Kirak O.; Suh H.; Jaenisch R.; Voldman J.Nat.Methods, 6,147-152 utilizes the U-shaped fence structure to realize catching of cell and Fusion of Cells in micro-fluidic chip; Document Randall C.L.; Kalinin Y.V.; Jamal M.; Manohar T.; Gracias D.H.Lab Chip, 2011,11,127-131 has designed three-dimensional micro-pit array in micro-fluidic chip, and has realized the dimensional culture of cell therein; Document Liu T.; Lin B.; Qin J.Lab chip, 2010,10,1671-1677 has carried out three-dimensional cultivation altogether to cancer associated fibroblast cell and cancer cell in micro-fluidic, and has studied the interaction of two kinds of cells.The micro-fluidic chip technology has many advantages in these biology and medical research; played very positive effect; but, biochemical reaction in the micro-fluidic chip and bioprocess are monitored and analyzed with regard to needing more perfect detection method for simulation in the micro-fluidic chip system complicated more biochemical reaction or the complicated more bioprocess of simulation.
The Mass Spectrometer Method method is a kind of high-resolution, highly sensitive detection method, not only most of molecules is all had response, can also provide the structural information of target molecule by the mode of tandem mass spectrum.The coupling of Mass Spectrometer Method and some traditional separation methods has also developed very ripely, as gas chromatography-mass spectrography and liquid chromatograph mass spectrography etc.The coupling of mass spectrum and these classic methods not only provides reliable reference for the coupling of mass spectrum and other technologies, has also accumulated the mass spectrum information of various molecules and has set up the mass spectrometric data storehouse, makes that the Mass Spectrometer Method method is reliable more, applicability is wider.
Except micromolecular compound, mass spectrum also has response preferably to some biological samples, is suitable for the analyzing and testing of complex biological sample.At present, the also existing report of the research that the Mass Spectrometer Method method is combined with microflow control technique: document Zhu Y.; Fang Q.Anal.Chem., 2010,82,8361-8366 has designed the micro-fluidic chip that a kind of drop produces, and is used for the Mass Spectrometer Method of little reaction; Document Gao D.; Wei H.; Guo G.-S.; Lin J.-M.Anal.Chem., 2010,82,5679-568 has cultivated people's pulmonary epithelial cells A549 in micro-fluidic chip, and utilizes Solid-Phase Extraction and mass spectrum that the vitamin E metabolic process of A549 is detected and analyzes.These studies have shown that mass spectrum detection and micro-fluidic chip technology have adaptability preferably, can be applied in the micro-fluidic chip system as a kind of effective detection means.Yet, present stage mass spectrum detection can not satisfy the micro-fluidic chip technology requirement far away with combining also of micro-fluidic chip technology.Present stage mass spectrum with the micro-fluidic chip technology be connected great majority just at a micro-fluidic chip passage, for micro-fluidic chip system with hyperchannel parallel laboratory test or many group experiments, mass spectrum does not have the advantages of simplicity and high efficiency mode and combines with it, thereby makes the application of mass spectrum in high flux micro-fluidic chip system be subjected to certain limitation.
Summary of the invention
The purpose of this invention is to provide a kind of multichannel micro-fluidic chip-mass spectrometry device, can be used for the monitorings of organizing biochemical reactions or bioprocess in the high flux micro-fluidic chip more.Method when using combined apparatus provided by the invention to detect is simple, Mass Spectrometer Method more effectively can be combined with the micro-fluidic chip technology, makes full use of same mass spectrum many groups of experiments are monitored and analyzed.
A kind of multichannel micro-fluidic chip provided by the present invention-mass spectrometry device, it comprises micro-fluidic chip and electrospray mass spectrometer;
Described micro-fluidic chip is located on the moving stage; Described micro-fluidic chip is provided with several microchannels in parallel, and the outlet of described microchannel is connected with a chamber by connecting pipe respectively; Described chamber is connected with a main channel, and the other end of described main channel is a waste liquid outlet;
Near an end of described waste liquid outlet, described main channel is connected with a collection channel, and the free-end of described collection channel is a sample export;
Near an end of described chamber, described main channel is connected with a wing passage, and the free-end of described wing passage is the extractant inlet; Have difference in height between described wing passage and the described main channel, and the upper limb of described wing passage is located at the bottom of the upper limb of described main channel;
Described sample export is connected with the sample delivery line, and the top of electrospray device is located in the outlet of described sample delivery line, and the drop that described electrospray device produces is detected by described electrospray mass spectrometer.
In the above-mentioned combined apparatus, described moving stage is located on the stage carrier, described moving stage is connected with described stage carrier by the chute of being located on the described stage carrier, described stage carrier can be fixed on definite position in the moment of determining with described micro-fluidic chip by Electric Machine Control or software control.
In the above-mentioned combined apparatus, described electrospray device comprises the described metal clip and the lead that is connected with described metal clip with the scraps of paper at acute angle tip of the scraps of paper, clamping with acute angle tip;
The tip of the described scraps of paper with acute angle tip is towards the detection mouth of described electrospray mass spectrometer; Drop will be coupled with voltage when dropping onto the described scraps of paper with acute angle tip, produce electron spray, at last by Mass Spectrometer Method and analysis.
In the above-mentioned combined apparatus, described electrospray device comprises that spraying is with most advanced and sophisticated, the described spraying of the clamping metal clip and the lead that is connected with described metal clip with the tip, drop will be coupled with voltage when dropping onto described spraying with the tip, produce electron spray, at last by Mass Spectrometer Method and analysis.
In the above-mentioned combined apparatus, described main channel can be linear path or serpentine channel, described serpentine channel the distance that can increase fluid motion is set.
In the above-mentioned combined apparatus, be provided with Hydrophilized porous membrane in the described main channel, described Hydrophilized porous membrane is located between the junction and described waste liquid outlet of described collection channel and described main channel.
In the above-mentioned combined apparatus, described collection channel is provided with the absorbing agent inlet, before the extraction drop enters pick-up unit, and also can be according to the different requirements of pick-up unit, with corresponding buffer solution or solvent the extraction drop is absorbed, with the different detection architecture of compatibility.
In the above-mentioned combined apparatus, near an end of described sample export, be provided with a water conservancy diversion track in the described main channel, and the height of described water conservancy diversion track is greater than the height of described main channel, described water conservancy diversion track extends along the Width of described main channel;
One end of described water conservancy diversion track is connected with described main channel, and the other end is connected with described collection channel.
Among the present invention, difference in height between described water conservancy diversion track and the described main channel helps utilizing buoyancy and surface tension to the drop channeling conduct: the organic phase drop is because buoyancy can enter higher described water conservancy diversion track, drop deorbit in the described water conservancy diversion track need overcome buoyancy and change the surface tension that spherical state produced, and drop is more prone to along described water conservancy diversion orbital motion.
Chamber described in the present invention can carry out the simulation of biochemical reaction generation or bioprocess.
Micro-fluidic chip among the present invention can adopt standard soft lithographic method to make, make by channelled dimethyl silicone polymer piece and glass sheet bonding, have good light transmittance, gas penetration potential, and inanimate object toxicity, living things system there is excellent adaptability.
The invention provides a kind of multichannel micro-fluidic chip-mass spectrometry device that is applied to biology or medical research field, this combined apparatus can carry out many group experiments simultaneously, and in micro-fluidic chip, carry out monitoring in real time with mass spectrum simultaneously after the on-line sample pre-treatment.Use method of the present invention simple, not only can be applicable to various biological or medical system, still a kind of hyperchannel monitoring method with high sensitivity, pinpoint accuracy can greatly promote the micro-fluidic chip broad application.
Description of drawings
Fig. 1 is the structural representation of multichannel micro-fluidic chip of the present invention-mass spectrometry device.
Fig. 2 is the structural representation of micro-fluidic chip in multichannel micro-fluidic chip of the present invention-mass spectrometry device.
Fig. 3 is the structural representation of the single passage of micro-fluidic chip in multichannel micro-fluidic chip of the present invention-mass spectrometry device.
In this concrete example, cell is subjected to medicine irritation in cultivating chamber, and the metabolin of its generation is passed into the sample preparation structure and carries out the drop extraction, and the method that adopts Hydrophilized porous membrane to stop is at last carried out the collection of extractant drop.
Fig. 4 is the structural representation of micro-fluidic chip in multichannel micro-fluidic chip of the present invention-mass spectrometry device.
Fig. 5 is the microphotograph that micro-fluidic chip carries out droplet capture and recovery in multichannel micro-fluidic chip of the present invention-mass spectrometry device (a water conservancy diversion track way of recycling), followed the tracks of a certain drop among the figure in difference position constantly, the process of droplet capture and recovery has been described.
Fig. 6 is the structural representation of Mass Spectrometer Method device in multichannel micro-fluidic chip of the present invention-mass spectrometry device, and wherein Fig. 6 (a) and Fig. 6 (b) are respectively paper atomizing Mass Spectrometer Method device and most advanced and sophisticated atomizing Mass Spectrometer Method device.
Each mark is as follows among the figure: 1 stage carrier; 2 chutes; 3 moving stages; 4 metal holders; The 5 triangle scraps of paper; 6 mass spectrometer injection ports; 7 sample inlet tubes; 8 microchannels; 9 connecting pipes; 10 extractant inlet tubes; 11 absorbing agent inlet tubes; 12 waste liquid delivery lines; 13 sample delivery lines; 14 chambers; 15 water wettability barrier films; 16 main channels; 17 collection channels; 18 cells; 19 extractant drops; 20 water conservancy diversion tracks; 21 wing passages; 22 difference in height a; 23 difference in height b; 24 sample drop; 25 electron sprays; 26 sprayings are with most advanced and sophisticated.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing, but the present invention is not limited to following examples
Micro-fluidic chip among the present invention adopts the method for soft lithographic to make, and according to concrete needs, adopts multiexposure, multiple exposure.Concrete preparation method is as follows: silicon chip is immersed in heating in the mixed solution (ratio of sulfuric acid and hydrogen peroxide is 3:1) of sulfuric acid and hydrogen peroxide, little 40min that boils cleans silicon chip, dry then., can adjust the thickness of photoresist by the control rotating speed, thereby control the height of respective channel in the made micro-fluidic chip at silicon chip surface coating one deck SU-82050 photoresist with sol evenning machine.To being used to produce the chip channel structure of concentration gradient, cellular incubation in the concrete example as shown in Figure 1, channel height is controlled at 80~100 μ m.After the photoresist coating is finished, the silicon chip that scribbles photoresist is carried out preceding baking handle (65 ℃ of baking 1min, 95 ℃ of baking 2min), carrying out uv-exposure with exposure machine more afterwards can copy to the channel architecture on the photo etched mask on the silicon chip mould, channel architecture after (65 ℃ of baking 1min, 95 ℃ of baking 2min) are handled in baking later on the silicon chip mould will further be reinforced.Carry out multiexposure, multiple exposure if desired, can after preceding single exposure is finished, use similar operating process, continue on the silicon chip mould, to be coated with photoresist and to carry out uv-exposure.After required each time exposure is all finished, the silicon chip mould through developing and the silanization processing, is promptly obtained the mould of reusable making micro-fluidic chip.Pour in the above-mentioned micro-fluidic chip mould after dimethyl silicone polymer (PDMS) prepolymer and initiating agent mixed with the ratio of 10:1, handle to be placed on 75 ℃ of polymerization 2h, obtain the PDMS polymer blocks of micro-fluidic chip passage through the degassing.This PDMS polymer blocks is peeled off from mould, and entered the mouth and outlet with the solution of card punch punching as micro-fluidic chip.At last, this PDMS polymer blocks promptly obtains described micro-fluidic chip with the glass sheet bonding after oxygen plasma treatment.
As shown in Figure 1, multichannel micro-fluidic chip provided by the invention-mass spectrometry device comprises micro-fluidic chip and electrospray mass spectrometer; Wherein, this micro-fluidic chip is located on the moving stage 3, and this moving stage 3 is located on the stage carrier 1, and this moving stage 3 is connected with stage carrier 1 by the chute of being located on the stage carrier 12.This micro-fluidic chip is located on the moving stage 3, thereby when moving stage 3 moves, can drive the micro-fluidic chip associated movement that is fixed thereon, and this moving stage 3 can accurately be controlled by software.This micro-fluidic chip is provided with the microchannel in parallel 8 that a plurality of concentration gradients produce, and the outlet of this microchannel is connected with a chamber 14 by connecting pipe 9 respectively, can carry out cellular incubation and biochemical reaction in this chamber.Each chamber 14 is connected with a main channel 16, and the other end of this main channel 16 is waste liquid outlet (not marking among the figure), and this waste liquid outlet is connected with waste liquid delivery line 12.Near an end of waste liquid outlet, main channel 16 is connected with a collection channel 17, and the free-end of this collection channel 17 is that this sample export of sample export (not marking among the figure) is connected with sample delivery line 13; Near an end of chamber 14, main channel 16 is connected with a wing passage 21, and the free-end of this wing passage 21 is extractant inlet (not marking among the figure), and this extractant inlet is connected with extractant inlet tube 10; Have difference in height a22 between this wing passage 21 and the main channel 16, and wing passage 21 is located at the bottom of main channel 16; Sample export is connected with sample delivery line 13, and the top of electrospray device is located in the outlet of this sample delivery line 13, and the drop that electrospray device produces can be detected by electrospray mass spectrometer.Between the junction of collection channel 17 and main channel 16 and waste liquid outlet, be provided with Hydrophilized porous membrane 15, when set Hydrophilized porous membrane 15 can allow aqueous phase solution pass through smoothly, with the drop interception of organic phase and import in the collection channel 17.Simultaneously, absorbing agent inlet (not marking among the figure) also can be set on collection channel 17, this absorbing agent inlet is connected with absorbing agent inlet tube 11, thereby can be before the extraction drop enters pick-up unit, also can be according to the different requirements of pick-up unit, with corresponding buffer solution or solvent the extraction drop is absorbed, with the different detection architecture of compatibility.
Multichannel micro-fluidic chip among the present invention is according to the biochemical reaction or the bioprocess difference of concrete research, and its specific design is difference to some extent.As shown in Figure 1, the multichannel micro-fluidic chip that provides is used for the research of stimulation of micro-fluidic chip cell drug and metabolism thereof.As shown in Figure 2, the specific design of this micro-fluidic chip is as follows: medicine is introduced the partly integrated structure that arborizations is arranged by sample inlet tube 7, be used for producing the drug concentration gradient fast, so that realize the research of the medicine irritation cell of variable concentrations in the downstream in the downstream of micro-fluidic chip; The end that concentration gradient produces structure is connected with the chamber of a plurality of cellular incubation respectively, and the cell 18 that is used for medicine irritation research is incubated at these chambers, will be to these cell generation effects from the medicine irritation solution that concentration gradient generation structural flow is come; Cell is subjected to after the medicine irritation, can produce corresponding response, and then changes at aspects such as metabolic activities, and the material that makes cell be discharged in the nutrient solution on every side also changes; The downstream of cellular incubation chamber links to each other with on-line sample pre-treatment structure, when the sample solution in the cellular incubation chamber is flowed through on-line sample pre-treatment structure, with the extractant solution extraction that is introduced into, extractant and sample solution is separated comes after extraction is finished, wherein extractant is absorbed by liquid absorption and derives micro-fluidic chip.
As shown in Figure 3, multichannel micro-fluidic chip uses the method for the drop extraction of single dispersant liquid drop as each passage sample pre-treatments in the present embodiment.Than laminar flow and embolic type drop, single dispersant liquid drop has improved the specific surface area of extractant, makes extractant more abundant with contacting of sample solution, and effect of extracting is better.Single dispersant liquid drop will be collected after in passage sample fully being extracted.The method that the collection employing Hydrophilized porous membrane of drop stops or the method for water conservancy diversion track drainage.The method that stops for Hydrophilized porous membrane that adopts as shown in Figure 3: extracting after channel end place is provided with hydrophilic perforated membrane, the sample solution of water can see through Hydrophilized porous membrane and enter waste fluid channel, and thereby the extractant drop of organic phase is stopped by hydrophilic perforated membrane and enters the collection channel that is communicated with the main channel, can in collection channel, feed absorption liquid or mass spectrum sample introduction damping fluid, to collect drop better and to be that Mass Spectrometer Method is carried out necessary solvent switch etc.As shown in Figure 4 and Figure 5, that adopts collects drop for the method for water conservancy diversion track drainage: an end of close sample export, in main channel 16, be provided with a water conservancy diversion track 20, and the height of water conservancy diversion track 20 is greater than the height of main channel 16, have difference in height b23 between the two, and water conservancy diversion track 20 16 Width extends along the main channel; One end of water conservancy diversion track 20 is connected with main channel 16, and the other end is connected with collection channel 17.Like this when extractant drop 19 process water conservancy diversion tracks 20, can enter water conservancy diversion track 20 owing to the reason of buoyancy, the drop that enters in the water conservancy diversion track 20 is restricted in the water conservancy diversion track 20 because of buoyancy and surface tension, thereby under the promotion of follow-up liquid stream, move, finally enter collection channel 17 along water conservancy diversion track 20.
In addition, as Fig. 3, Fig. 4 and shown in Figure 5, single dispersant liquid drop continues to produce at extraction feeder connection place, and after finishing, extraction constantly absorbed and derivation, make extractant be in the continual renovation, guaranteed that not only extraction process can continue to carry out in a long time, can also measure corresponding sample size in the different time sections, made this sample pre-treatments mode be suitable for long on-line monitoring more.
Mass Spectrometer Method of the present invention adopts the ionization mode of paper spraying or most advanced and sophisticated spraying, and as shown in Figure 6, Fig. 6 (a) and Fig. 6 (b) are respectively paper atomizing Mass Spectrometer Method mode and most advanced and sophisticated atomizing Mass Spectrometer Method mode.Wherein, paper atomizing Mass Spectrometer Method mode adopts following electrospray device: it comprises the metal holder 4 and the lead that is connected with this metal holder (not marking among the figure) of the triangle scraps of paper 5, the clamping triangle scraps of paper 5, and the tip of the triangle scraps of paper 5 is towards mass spectrometer injection port 6; Most advanced and sophisticated atomizing Mass Spectrometer Method mode adopts following electrospray device: it comprise spraying with most advanced and sophisticated 26, clamping this spraying with the metal holder 4 at tip 26 and the lead that is connected with this metal holder (marking among the figure).Concrete testing process is as follows: the absorption liquid of each main channel is derived by sample delivery line 13 separately respectively in the micro-fluidic chip, and the end of each sample delivery line 13 is vertically sagging, so that allow absorption liquid formation sample drop 24 wherein drip.Punctual with 26 pairs at tip when the triangle scraps of paper 5 or spraying that a certain main channel 16 pairing sample delivery lines 13 and electron spray are used, the absorption liquid drop will drop onto on the scraps of paper or the tip, form electron spray and 25 by Mass Spectrometer Method.Method for utilizing the paper spraying it is advantageous that sample has chromatographic behavior when moving in the scraps of paper, can carry out further separation and purification to sample, and is residual but sample is easy in the scraps of paper, makes the paper spraying be unfavorable for long-time monitoring.And for the method for tip spraying, the Material Strength that it is advantageous that tip (as wooden tip) is better than the scraps of paper, more stable in long electron spray, and can greatly reduce the residual of sample through the tip of hydrophobic modification, thus help the long-time common monitoring of several samples.
When using multichannel micro-fluidic chip of the present invention-mass spectrometry device, drive by moving stage, the sample export of each main channel of micro-fluidic chip is aimed at the electrospray device of Mass Spectrometer Method successively, and the drop that respective channel is produced do short stay is detected by electrospray ionization mass spectrum.To-and-fro movement by mobile platform, constantly repeat above-mentioned testing process, just can obtain the mass signal of the sample of each passage in a period of time in different time points, at last these data are added up, integrated, can obtain each passage situation of change of sample composition during this period of time, realize the interior real-time monitoring of this time period to each passage mesophytization reaction or bioprocess, even can be according to this monitoring result, biochemical reaction or bioprocess are carried out real-time adjustment, and then realize monitoring in real time.

Claims (8)

1. multichannel micro-fluidic chip-mass spectrometry device, it is characterized in that: described combined apparatus comprises micro-fluidic chip and electrospray mass spectrometer;
Described micro-fluidic chip is located on the moving stage; Described micro-fluidic chip is provided with several microchannels in parallel, and the outlet of described microchannel is connected with a chamber by connecting pipe respectively; Described chamber is connected with a main channel, and the other end of described main channel is a waste liquid outlet;
Near an end of described waste liquid outlet, described main channel is connected with a collection channel, and the free-end of described collection channel is a sample export;
Near an end of described chamber, described main channel is connected with a wing passage, and the free-end of described wing passage is the extractant inlet; Have difference in height between described wing passage and the described main channel, and the upper limb of described wing passage is located at the bottom of the upper limb of described main channel;
Described sample export is connected with the sample delivery line, and the top of electrospray device is located in the outlet of described sample delivery line, and the drop that described electrospray device produces is detected by described electrospray mass spectrometer.
2. combined apparatus according to claim 1 is characterized in that: described moving stage is located on the stage carrier, and described moving stage is connected with described stage carrier by the chute of being located on the described stage carrier.
3. combined apparatus according to claim 1 and 2 is characterized in that: described electrospray device comprises the described metal clip and the lead that is connected with described metal clip with the scraps of paper at acute angle tip of the scraps of paper, clamping with acute angle tip;
The tip of the described scraps of paper with acute angle tip is towards the detection mouth of described electrospray mass spectrometer.
4. combined apparatus according to claim 1 and 2 is characterized in that: described electrospray device comprises that spraying is with most advanced and sophisticated, the described spraying of the clamping metal clip and the lead that is connected with described metal clip with the tip.
5. according to each described combined apparatus among the claim 1-4, it is characterized in that: described main channel is linear path or serpentine channel.
6. according to each described combined apparatus among the claim 1-5, it is characterized in that: be provided with Hydrophilized porous membrane in the described main channel, described Hydrophilized porous membrane is located between the junction and described waste liquid outlet of described collection channel and described main channel.
7. combined apparatus according to claim 6 is characterized in that: described collection channel is provided with the absorbing agent inlet.
8. according to each described combined apparatus among the claim 1-5, it is characterized in that: near an end of described sample export, be provided with a water conservancy diversion track in the described main channel, and the height of described water conservancy diversion track is greater than the height of described main channel, and described water conservancy diversion track extends along the Width of described main channel;
One end of described water conservancy diversion track is connected with described main channel, and the other end is connected with described collection channel.
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