CN1885026A - Coated column for capillary electrophoresis - Google Patents
Coated column for capillary electrophoresis Download PDFInfo
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- CN1885026A CN1885026A CN 200610044550 CN200610044550A CN1885026A CN 1885026 A CN1885026 A CN 1885026A CN 200610044550 CN200610044550 CN 200610044550 CN 200610044550 A CN200610044550 A CN 200610044550A CN 1885026 A CN1885026 A CN 1885026A
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Abstract
The invention relates to a capillary electrophoresis column, with new polymer coat, wherein the invention is used in the electrophoresis separation of alkali protein, organic alkali small molecule, and inorganic cation, wherein said capillary electrophoresis coat column is made by physical adsorption and chemical bond on the tree branched macromolecule; said macromolecule is ultra branched polymer or tree macromolecule. The invention has the advantages that: it has better coat property, and better separation effect on alkali protein, organic alkali small molecule, and inorganic cation, to restrain the adsorption on alkali group and its derivantion.
Description
(1) technical field under
The present invention relates to a kind of capillary electrophoresis column, particularly a kind of Capillary Electrophoresis coating column that adopts the new polymers coating.
(2) background technology
The kapillary inside surface is because the ionization of Si-OH forms Si-O
-, there is absorption to alkaline matter, absorption causes the spectrogram hangover easily, and separating column is imitated and is descended defectives such as disengaging time growth.Therefore control electroosmotic flow, reducing absorption is very effective means that improve the alkaline matter separating effect.The method of utilizing voltage to reduce can reduce electroosmotic flow, but has also reduced the speed of electrophoresis, and the mobility between the alkaline matter reduces, and has increased disengaging time.Limit of utilization pH value can be slowed down absorption, control electroosmotic flow, but biomolecule such as picture alkaline protein, nucleosides, too high, cross and under the low pH value hydrolysis take place easily all, sex change makes separation lose meaning.By contrast, the surface charge that the capillary coating technology is used to change capillary tube inner wall is the control electroosmotic flow, the effective way that reduces to adsorb.
Traditional coating material adopts traditional polymer more, and traditional polymer is generally linear polymer, the viscosity of linear polymer often increases along with the increase of concentration, when kapillary is applied, coating concentration increases, can cause viscosity sharply to increase, be easy to cause coating uneven, even stop up kapillary.And concentration is too little, is easy to cause coating too thin again, can not fully the Si-OH on the capillary wall be covered; So the coating concentration of linear polymer generally about 5%, can not well cover the silicon hydroxyl, suppress the absorption of alkaline matter.
The big molecule of branching has regular tree crown structure, and space structure presents sphere (as appendix one).Avoided the interchain of traditional polymer crosslinked to a great extent, it is less to present viscosity on the macroscopic view, and the very little characteristics of increase viscosity variation along with concentration relatively are fit to the coating kapillary; Because partly there is a large amount of functional groups in the big molecule tree crown of branching, than the Si-OH combination that is easier to capillary wall, coating is simple, and coating is firm.
(3) summary of the invention
In order to overcome the deficiency of above technology, utilization of the present invention provides a kind of Capillary Electrophoresis coating column that adopts the new polymers coating, having overcome traditional coating material---linear polymer coating concentration is too low, and coating thickness is not enough, the shortcoming of ionization that can not fine inhibition silicon hydroxyl.
The present invention realizes by following measure:
Capillary Electrophoresis coating column of the present invention is to make the Capillary Electrophoresis coating column by the big molecule of branching through the mode of physisorption and chemical bonding, and the big molecule of described branching is dissaving polymer or dendritic macromole.
Capillary Electrophoresis coating column of the present invention, described dissaving polymer are hyperbranched poly (amine-ester) or hyper-branched polyester.Described physical adsorption way is for directly being coated in capillary tube inner wall with hyperbranched poly (amine-ester), hyper-branched polyester; Described chemical bonding mode is to utilize silanization coupling agent γ-diglycidyl oxygen propyl trimethoxy silicane that synthetic hyperbranched poly (amine-ester) or hyper-branched polyester are applied to capillary tube inner wall.
Capillary Electrophoresis coating column of the present invention, described dendritic macromole are the organosilicon dendritic macromole.Described physical adsorption way is for directly being coated to the Capillary Electrophoresis column wall with the organosilicon dendritic macromole; Described chemical bonding mode is applied to capillary tube inner wall for utilizing silanization coupling agent γ-An Jibingjisanyiyangjiguiwan (KH-550), two [γ-(triethoxy is silica-based) propyl group] amine (KH-402) with the organosilicon dendritic macromole of synthetic silicon chlorine key end-blocking.Or with vinyltriethoxysilane (Vinyl tirethoxysilane A-151) is applied to capillary tube inner wall for the organosilicon dendritic macromole with two key end-blockings that coupling agent will synthesize.
1. the principle basis of coating column of the present invention
Characteristics the most outstanding of the big molecule of branching are exactly under equal condition, and its viscosity than traditional polymkeric substance is low.If therefore with the big molecule of branching as the capillary column coating material, must be accompanied by full-bodied problem with regard to having solved the traditional polymer high concentration.Because its viscosity is lower, thereby be coated on the capillary column inwall easily, form stable thin layer, and what is more important, the big molecule molecule of branching is with outward in a large number can supply the active end group of modification, thereby is easier to be bonded to the capillary column inside surface, improves the stability of polymer coating, just for can better suppressing electroosmotic flow and the minimizing absorption to alkaline matters such as protein, bases, the analysis separating effect that improves alkaline matter provides structural guarantee for this.
The big molecule of branching compares as table 1 with traditional linear polymer.
Table 1
| Content | The big molecule of branching | Traditional polymer |
| Version | Stereo structure, it is crosslinked to need not the outside, and this is regular as stereo structure | Wire or plane behind the adding crosslinking chemical, might become stereo structure, but irregular |
| Macromolecular chain | Relatively independent, chain does not take place twine good fluidity | Chain twines serious, does not have rule |
| The macromolecule cavity | Contain a large amount of cavitys, the space between the cavity is regular, can artificially control the element of branching arm and form length size etc. | Almost do not have cavity, chain twines irregular the following of cavity that forms |
| Molecular weight and viscosity | Molecular weight is big, but viscosity is low, good fluidity, and molecular weight can artificially be controlled | Molecular weight is big, and viscosity increases simultaneously, and mobile variation need be diluted to low concentration and just can flow, molecular weight control difficulty |
| Reactive group position and number | Reactive group is positioned at outermost tree crown position, and is big with extraneous touch opportunity, easily bonding | Reactive group is positioned at the side of strand, because factors such as chain winding, buried by chain, be not easy to contact, be not easy the modification bonding with extraneous |
| Effect as the coating material performance | On capillary tube inner wall, bring into play three-dimensional effect, can cover the silicon hydroxyl of quartz capillary inwall, and can provide enough sterically hindered, hinder the absorption of alkaline matter. | Only cover on the capillary tube inner wall as thin film, no cavity structure plays a role |
Therefore the big molecule of branching demonstrates and the distinct character of linear molecule owing to have highly branched 3 D stereo chondritic and a large amount of surface functional groups, twines and fine solubility as low viscosity, no chain.The big molecular coatings capillary electrophoresis column of branching of the present invention has important application prospects in national economy fields such as industry, agricultural, national defence, medical science, life science, environmental protection, will produce certain influence to the progress of human society.
2. the preparation of Capillary Electrophoresis coating of the present invention:
2.1 physisorption electrocapillary phoresis coating column
2.1.1 the physisorption Capillary Electrophoresis coating column of Si-Cl blocking silicone dendritic macromole
In each generation that has made, be dissolved in respectively in the methylene chloride that purifies that dewaters with Si-Cl blocking silicone dendritic macromole, be configured to 15% solution, nitrogen pressure with 1～2Mpa is pressed into solution in the capillary column, flow down at the nitrogen of 0.5MPa and slowly to blow out, make to be coated with stain liquid and on capillary tube inner wall, to form the layer of even liquid film being coated with stain liquid.
The burin-in process of coating column: will be coated with the capillary column that steeped with the organosilicon dendritic macromole and place in the gas chromatography stove in the nitrogen of 1Mpa and flow down from 50 ℃ of temperature programmes to 200 half an hour ℃, keep terminal temperature 3h, the cooling back rinses out unreacted dendritic macromole with anhydrous methylene chloride, absolute methanol flushing pillar half an hour then, react away remaining Si-Cl, promptly get the physisorption type capillary column having coated layer.Reaction equation is as follows:
2.1.2 the physisorption Capillary Electrophoresis coating column of the organosilicon dendritic macromole of two key end-blockings
With make the organosilicon dendritic macromole of De Gedai with two key end-blockings be configured to 20% dichloromethane solution, nitrogen pressure with 1～2Mpa is pressed into solution in the capillary column, flow down at the nitrogen of 0.5MPa and slowly to blow out, make to be coated with stain liquid and on capillary tube inner wall, to form the physisorption Capillary Electrophoresis coating column that the layer of even liquid film promptly gets the organosilicon dendritic macromole of pair key end-blockings being coated with stain liquid
2.1.3 the physisorption Capillary Electrophoresis coating column of hyperbranched poly (amine-ester)
Hyperbranched poly (amine-ester) is configured to 10% methanol solution and is used to apply capillary electrophoresis column,
The same 2.1.1 of detailed step
2.1.4 the physisorption capillary coating post of hyper-branched polyester
The same 2.1.3 of detailed step
2.2 chemical bonding Capillary Electrophoresis coating column
2.2.1 the chemical bonding capillary electrophoresis column coating column of Si-Cl blocking silicone dendritic macromole
The pre-service of capillary column: under certain nitrogen pressure, corrode the about 5min of capillary column inwall with hydrofluorite earlier, then sequentially clean with pretreated each 10min of capillary column of hydrofluorite, with nitrogen capillary column is dried up at last with redistilled water and methyl alcohol.
The silanization of capillary column is handled: coupling agent KH-550 is pressed in pretreated capillary column, and slowly blow out the remaining stain liquid that is coated with nitrogen, then capillary column is placed in the gas chromatography stove in certain nitrogen and flow down from 50 ℃ of temperature programmes to 150 half an hour ℃, keep terminal temperature 3h to carry out burin-in process, so that coating is solidified.This reaction is introduced the active end group amido on the capillary tube inner wall for ethoxy on the coupling agent γ-An Jibingjisanyiyangjiguiwan and the reaction of the Si-OH on the capillary wall, and concrete reaction equation is as follows:
The preparation of organosilicon dendritic macromole chemical bonding coating column: in each generation, be dissolved in respectively in the methylene chloride that purifies that dewaters with Si-Cl blocking silicone dendritic macromole, be configured to 15% solution, nitrogen pressure with 1～2Mpa is pressed into solution in the capillary column, flow down at the nitrogen of 0.5MPa and slowly to blow out being coated with stain liquid, make be coated with the stain liquid on capillary tube inner wall, form the layer of even liquid film, then capillary column having coated layer is placed in the gas chromatography stove in certain nitrogen and flow down from 50 ℃ of temperature programmes to 200 half an hour ℃, keep terminal temperature 3h to carry out burin-in process, so that the end Si-Cl on organosilicon organosilicon dendritic macromole surface and silanization were handled on the capillary wall-NH
2Reaction, thus organosilicon organosilicon dendritic macromole is bonded on the capillary tube inner wall.Reaction equation is as follows:
Utilize dichloromethane rinse to fall unreacted dendritic macromole at last, react away the not Si-Cl of bonding half an hour towards post, dry up with nitrogen and promptly be able to the heat cross-linking chemical bonding coating column that KH-550 is a coupling agent with methyl alcohol.
2.2.2 the same 2.2.1 of chemical bonding Capillary Electrophoresis coating column kapillary pre-service of the organosilicon dendritic macromole of two key end-blockings.
The preparation of the chemical bonding Capillary Electrophoresis coating column of the organosilicon dendritic macromole of two key end-blockings: after dendritic macromole, vinyltriethoxysilane and the azo-bis-isobutyl cyanide of each Dai Yishuan key end-blocking mixed with 10: 20: 1 ratio of mass ratio, be dissolved in the dichloromethane solvent, make dendritic macromole content and be 15% mixed solution.With mixed solution under 2MPa air pressure, mixed solution is charged in the capillary column, keep drying up with nitrogen after 5 minutes,, the polymerization and the bonding of vinyltriethoxysilane and the dendritic macromole of two key end-blockings are carried out simultaneously since 40 ℃ of temperature programmes to 120 half an hour ℃.Keep temperature 1h at terminal point, fall unreacted G3 and vinyltriethoxysilane, dry up the chemical bonding coating column of the organosilicon dendritic macromole that promptly gets two key end-blockings with nitrogen with dichloromethane rinse.
Reaction equation is as follows:
2.2.3 the chemical bonding Capillary Electrophoresis coating column of hyperbranched poly (amine-ester)
The same 2.2.1 of kapillary pre-service.
The silanization of capillary column is handled: coupling agent γ-diglycidyl oxygen propyl trimethoxy silicane is sucked in pretreated capillary column, and slowly blow out the remaining stain liquid that is coated with nitrogen, capillary column is placed in the gas chromatography stove then and flow down temperature programme from 50 ℃ to 150 ℃ in certain nitrogen, keep terminal temperature 3h to carry out burin-in process, so that coating is solidified.This reaction is methoxyl on coupling agent γ-diglycidyl oxygen propyl trimethoxy silicane and the silicon hydroxyl reaction on the capillary wall, and the active end group epoxy radicals is introduced on the capillary tube inner wall, and concrete reaction equation is as follows:
The preparation of hyperbranched poly (amine-ester) chemical bonding coating column: what will synthesize is respectively the 5th generation of the hyperbranched poly (amine-ester) of nuclear with trimethylolpropane and pentaerythrite, the 6th generation, the product suction of the 7th generation is in the capillary column that silanization is handled, certain nitrogen flow down with remaining be coated with the stain liquid slowly blow out, then the chemical bonding capillary column having coated layer is placed in the gas chromatography stove and flow down temperature programme from 50 ℃ to 150 ℃ in certain nitrogen, keep terminal temperature 3h to carry out burin-in process, so that the terminal hydroxy group of hyperbranched poly (amine-ester) and the epoxy reaction on the capillary wall, thereby it is as follows that hyperbranched poly (amine-ester) is bonded on the capillary tube inner wall its concrete reaction:
2.2.4 the chemical bonding Capillary Electrophoresis coating column of hyper-branched polyester
Same 2.2.3
3. the performance test of Capillary Electrophoresis coating column of the present invention
The big molecular fur cons electrophoresis of prepared branching coating column, coating performance is good, when pH=5, the separating column of alkaline protein imitated generally reaches 10
6, effectively suppressed the absorption of the ionization of silicon hydroxyl to alkaline protein.Be suitable for the capillary electrophoresis separation prepared organic silicon dendritic macromole Capillary Electrophoresis coating column of biomacromolecule such as alkaline protein, coating performance is good, when pH=4.5, the separating column of base and derivant thereof imitated generally reaches 1.2 * 10
5, good separation has effectively suppressed the absorption of the ionization of silicon hydroxyl to base and derivant thereof.Be applicable to separating of organic basic micromolecule and inorganic cation.
The invention has the beneficial effects as follows that it is good to have a coating performance, the good separating effect to alkaline protein, organic basic micromolecule, inorganic cation etc. has effectively suppressed the absorption to base and derivant thereof.
(4) appendix explanation
Fig. 1. be two kinds of plane structure charts of branching macromolecule polyalcohol of the present invention
Fig. 2. be the separation spectrogram of Capillary Electrophoresis coating column of the present invention.
Among the figure, a, the phosphate buffered solution of the deposition condition of g: pH=5.0, separation voltage 15.8KV; Internal diameter 75 μ m electrophoretic columns, 51cm * 35.5cm; The guest reaches 1229 capillary electrophoresis apparatus, and UV-214 detects; 1. cromoci, 2. lysozyme, 3. α chymotrypsinogen A.
The phosphate buffered solution of the deposition condition of h: pH=5.0, separation voltage 16KV; Internal diameter 75 μ m electrophoretic columns, 55cm * 50cm; The guest reaches 1229 capillary electrophoresis apparatus, and UV-214 detects; 1. cromoci, 2. lysozyme, 3. α chymotrypsinogen A.
B, c, d, e, the phosphate buffered solution of the deposition condition of f: pH=4.5, separation voltage 16KV; Internal diameter 75 μ m electrophoretic columns, 55cm * 50cm; The guest reaches 1229 capillary electrophoresis apparatus, and UV-254 detects; 1. adenine, 2. adenosine and 3.6-chaff adenine phosphate.
(5) embodiment
Example one
Blank post: separation spectrogram such as Fig. 2 a of pair cell pigment C, lysozyme, three kinds of alkaline proteins of α chymotrypsinogen A during pH=5, can't separate; To adenine, adenosine and three kinds of bases of 6-chaff adenine phosphate and derivant such as Fig. 2 b, separating effect is bad during pH=4.5, and post is imitated and is commonly 1.8 * 10
4, disengaging time is long, can separate fully in nearly 50 minutes.
Example two
With the tetrachloro silicane is the center nuclei originis, for increasing monomer, carries out the organosilicon dendritic macromole that Grignard reaction and hydrosilylation got for 3 generations with silicon chlorine key end-blocking three times with allyl bromination magnesium, methyl hydrogen dichlorosilane repeatedly.
In 3 generations, are with the organosilicon dendritic macromole physisorption coating column of silicon chlorine key end-blocking: make the coatings capillary pipe electrophoretic column as described in 2.1.1, test its column performance.Obtain spectrogram such as Fig. 2 c, separating column is imitated and is on average reached 9 * 10
4, adenine, three kinds of bases of adenosine and 6-chaff adenine phosphate and derivant thereof can be separated fully in 20 minutes.
Example three
With tetramethyl tetrem thiazolinyl cyclotetrasiloxane is the center nuclei originis, and with methyl hydrogen dichlorosilane, allyl bromination magnesium carries out the addition of silicon hydrogen repeatedly for increasing monomer, the organosilicon dendritic macromole that the Grignard reaction got for 3.5 generations with silicon chlorine key end-blocking 3.5 times
3.5 in generation, is with the organosilicon dendritic macromole chemical bonding coating column (KH-550 is a coupling agent) of silicon chlorine key end-blocking: make the coatings capillary pipe electrophoretic column as described in 2.2.1, test its column performance.Obtain spectrogram such as Fig. 2 d, separating column is imitated and is on average reached 12 * 10
4, can three kinds of separating substances are complete in 18 minutes.
Example four
Make the organosilicon dendritic macromole of 3.5 generations as example three with silicon chlorine key end-blocking.
3.5 in generation, is with the organosilicon dendritic macromole chemical bonding coating column (KH-402 is a coupling agent) of silicon chlorine key end-blocking: as being that coupling agent makes the coatings capillary pipe electrophoretic column as described in the 2.2.1 with KH-402.Reactional equation is as follows:
Obtain spectrogram such as Fig. 2 e, separating column is imitated and is on average reached 5 * 10
4, can three kinds of separating substances are complete in 23 minutes.
Example five
React the organosilicon dendritic macromole that got for 3 generations with two key end-blockings three times repeatedly as example three.
3 generations are with the organosilicon dendritic macromole chemical bonding coating column (A-151 is a coupling agent) of two key end-blockings: make the chemical bonding coating column as 2.2.2, measure its column performance and obtain spectrogram such as Fig. 2 f, separating column is imitated and is on average reached 10 * 10
4, can three kinds of separating substances are complete in 17 minutes.
Example 6
Wherein 1 is p-toluenesulfonic acid.
Single stage method synthesizing trimethylol propane 7 on behalf of nuclear hyperbranched poly (amine-ester): at 95.5g N, in N-dihydroxy ethyl-3-amido methyl propionate monomer, add 505.9mg p-toluenesulfonic acid and 723.0mg trimethylolpropane, being warming up to reflux temperature remains unchanged, reacted 4 hours, vacuumize again except that methyl alcohol that generates in the dereaction and unreacted micromolecular compound, promptly get hyperbranched poly (amine-ester) the 5th generation product (G5).Change the ratio of monomer, polymerization under similarity condition, obtain respectively hyperbranched poly (amine-ester) the 6th generation (G6) and the 7th generation (G7) product
With the immersion coating capillary electrophoresis column of hyperbranched poly (amine-ester) of trimethylolpropane 7: make the immersion coating capillary electrophoresis column with 2.2.3 on behalf of nuclear.
The capillary electrophoresis column that makes is used for isolated cell pigment C, lysozyme, three kinds of alkaline proteins of α chymotrypsinogen A, obtains the spectrogram as Fig. 2 g, separating column is imitated and is reached 73 * 10
4Good separation has suppressed the absorption of alkaline protein fully.
Example 7
Accurate single stage method synthesis of super branched polyester: in four-necked bottle, add 2.0g trimethylolpropane, 30mg p-toluenesulfonic acid and 6.0g 2, the 2-dihydromethyl propionic acid, being warming up to 140 ℃ remains unchanged, reacted 2 hours, vacuum filtration promptly got the first generation product (G1) of hyper-branched polyester in 1 hour under this temperature; Add 12.0g 2 in this reaction system, 2-dihydromethyl propionic acid and 60mg p-toluenesulfonic acid react under same reaction conditions, promptly get the second generation product (G2) of hyper-branched polyester; Press different proportion successively and add 2,2-dihydromethyl propionic acid and p-toluenesulfonic acid, react under similarity condition, obtaining respectively with the trimethylolpropane is third generation product (G3), the 4th generation product (G4), the 5th generation product (G5) and the 6th generation product (G6) of hyper-branched polyester of nuclear.
Accurate single stage method synthetic with the immersion coating capillary electrophoresis column of trimethylolpropane 5 on behalf of the hyper-branched polyester of nuclear: according to making the physisorption coating column shown in the 2.1.4, be used for isolated cell pigment C, lysozyme, three kinds of alkaline proteins of α chymotrypsinogen A.Record its column performance, obtain the spectrogram as Fig. 2 .h, separating column is imitated average out to 3 * 10
4
Claims (6)
1. Capillary Electrophoresis coating column is characterized in that: be bonded in electrophoresis inwall capillaceous by the big molecule of branching through the mode of physisorption or chemical bonding and make, the big molecule of described branching is dissaving polymer or dendritic macromole.
2. Capillary Electrophoresis coating column according to claim 1 is characterized in that: described dissaving polymer is hyperbranched poly (amine-ester) or hyper-branched polyester.
3. Capillary Electrophoresis coating column according to claim 1 is characterized in that: described dendritic macromole is the organosilicon dendritic macromole.
4. Capillary Electrophoresis coating column according to claim 2 is characterized in that: the coupling agent of described chemical bonding mode is γ-diglycidyl oxygen propyl trimethoxy silicane.
5. Capillary Electrophoresis coating column according to claim 3, it is characterized in that: the coupling agent of described chemical bonding mode is γ-An Jibingjisanyiyangjiguiwan or two [γ-(triethoxy is silica-based) propyl group] amine, and described organosilicon dendritic macromole is the organosilicon dendritic macromole of silicon chlorine key end-blocking.
6. Capillary Electrophoresis coating column according to claim 3 is characterized in that: the coupling agent of described chemical bonding mode is a vinyltriethoxysilane, and described organosilicon dendritic macromole is the organosilicon dendritic macromole of two key end-blockings.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358946B (en) * | 2008-09-08 | 2012-06-06 | 天津大学 | Anionic polymer grafting coatings capillary pipe and analytical method for on-line enrichment for protein |
| CN103808786A (en) * | 2014-02-27 | 2014-05-21 | 福州大学 | Method for preparing capillary coating for inhibiting protein adsorption |
| CN107698768A (en) * | 2017-09-06 | 2018-02-16 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480727A (en) * | 2002-09-02 | 2004-03-10 | 中国科学院成都有机化学研究所 | Bonded stationary phase of bidentate amide chromatogram and its preparation method |
| CN1220055C (en) * | 2002-12-20 | 2005-09-21 | 中国科学院成都有机化学研究所 | Alkyl silica gel bonded chromatographic fixed phase and its prepn process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358946B (en) * | 2008-09-08 | 2012-06-06 | 天津大学 | Anionic polymer grafting coatings capillary pipe and analytical method for on-line enrichment for protein |
| CN103808786A (en) * | 2014-02-27 | 2014-05-21 | 福州大学 | Method for preparing capillary coating for inhibiting protein adsorption |
| CN107698768A (en) * | 2017-09-06 | 2018-02-16 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
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