CN1321714C - Filling material used for molecule brand solid phase extraction and preparation method thereof - Google Patents
Filling material used for molecule brand solid phase extraction and preparation method thereof Download PDFInfo
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- CN1321714C CN1321714C CNB2004100091399A CN200410009139A CN1321714C CN 1321714 C CN1321714 C CN 1321714C CN B2004100091399 A CNB2004100091399 A CN B2004100091399A CN 200410009139 A CN200410009139 A CN 200410009139A CN 1321714 C CN1321714 C CN 1321714C
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Abstract
The present invention relates to filling material for molecular imprinting solid-phase extraction and a preparation method thereof. A carrier for the filling material of the present invention is a micro glass bead with surface modification. The filling material has the advantages of high structural strength, good ball closing performance and no swelling performance. When different kinds of solvent are used, the unity and the uniformity of the cylinder can be maintained, and the pressure resistance performance is good. The filling material has the preparation method that a molecular imprinting polymer film layer is formed on the surface of the carrier by a liquid-film method. The polymers can be uniformly, compactly and completely distributed on the surface of the carrier by the method, can be firmly bonded on the surface of the carrier, and are difficult to shed off during use. The average pore size of the prepared polymers is large, and thus, the diffusion speed is increased; the extraction efficiency is enhanced.
Description
Technical field
The present invention relates to a kind of filler that is used for the molecular brand SPE, be specifically related to the carrier that a kind of novel molecular brand solid phase extraction filler is used, and with the molecular brand polymer filler of this preparing carriers.The invention still further relates to the preparation method of above-mentioned filler.
Background technology
Molecular imprinting technique is a kind of advanced means of carrying out separating substances, often separates the material that is difficult to separate with conventional means with the combination of SPE method, as separate specific active ingredient in the plant crude extract of complicated component.1972, Wullf etc. were used for molecular imprinting technique the chiral separation (G.Wulff, A.Sarhan, Angew.Chem., Int.Ed.Engl., 341,1972,11) of glucose analog derivative at first.
The most key when adopting molecular imprinting technique to carry out SPE is to prepare molecular brand polymer.The purposes of molecular brand polymer is that molecular shape, size and the functional group according to material to be separated carries out molecular recognition, be similar in the living things system enzyme to substrate, antibody to antigen or acceptor to the effect of inhibitor, have certain selectivity.
The preparation process of molecular brand polymer is generally: with molecule to be separated as template molecule, join in the pore-foaming agent (also simultaneously as solvent), the function monomer of template molecule and adding organic acid, alkali, the amides compound of thiazolinyl (as contain) is by chemical recognition reaction, form certain compound with form covalently or non-covalently, add crosslinking agent (being generally the polyene-based compound) again, the compound of formation is solidified by cross-linking polymerization.Template molecule is closed in the polymer by volume and shape recognition, and remove template molecule by acid-alkali washing in the duct that utilizes pore-foaming agent to form at last.Like this, just produced the hole of some sizes, shape and functional group arrangement and template molecule complementation in the polymer.These holes can be referred to as the branding of the template molecule formation of original adding.
The most frequently used method of prior art for preparing molecular brand polymer is mass polymerization (Jianchun Xie, Lili Zhu, Hongpeng Luo, et al., J.Chromatogr.A, 934,2001,1-11), promptly directly allow aforementioned polymerization liquid polymerization become a bulk of molecular brand polymer, again by grinding, sieve and the sedimentation sorting being used as filler with the molecular brand polymer particle that obtains being suitable for.
When using bulk polymerization to prepare polymer beads, raw material consumptions such as template molecule are very big, and because the influence of diffusion velocity only has the thin one deck of particle surface to work in real process, whole utilization rate is not high.In addition, the polymer beads that the method obtains is the particle diameter wider distribution often, also needs before the use to carry out particle size sorting, makes productive rate lower; And, limited the raising of flow velocity (directly related) with production efficiency because out-of-shape causes the post pressure in the use very big.Therefore this method cost is very high, and efficient is low, is not suitable for fairly large application.
In order to reduce the consumption of template molecule, the someone adopts carrier to replace its kernel portion, promptly only at carrier surface molecular brand polymer is arranged, and method has following several:
A kind of method is to be carrier with the macro porous silica gel, after surface modification (introducing vinyl), adds in rare polymeric reaction solution, make it in solution, capture sedimentation polymer particles (Sean D., Plunkett, Frances H., J.Chromatogr.A, 708,1995,19-29), be about to the molecular brand polymer particulate attached on the silica gel surface, but this to adhere to be very unstable, particulate takes place in the use easily to come off, stop up splitter, and can't continue to separate.
Another kind method be the multistep polymerization method (Cacho C, Turiel E, Martin-Esteban A, et al.JCHROMATOGR B 802 (2): 347-353 APR 5 2004), the carrier of use is exactly the polymer beads of function monomer and crosslinking agent self.Promptly under the condition that does not add template molecule, allow earlier polymer fluid carry out sedimentation polymerization and sedimentation sorting repeatedly obtaining the particle of uniform particle diameter, and then add template molecule and carry out polymerization.But this preparation technology is too complicated, also is not suitable for fairly large application.
These two kinds are used the method for carrier to also have a common shortcoming: promptly when the splitter of packing into uses, all rely on the molecular brand material and itself bear pressure.And molecular brand polymer all is cellular structure from the surface to the kernel, the pressure that itself can bear is not too big, especially not strong to the tolerance that contacts pressure (reaction for partial high pressure) between the particle, in use broken easily, cause the loss and the post voltage rise height of recognition site.
The somebody prepares molecular brand film (Shoji R, Takeuchi T, Kubo I, ANAL CHEM75 (18): 4882-4886 SEP 15 2003), but because its surface area is too little, only can be used for trace detection at electrode surface in addition.
Summary of the invention
One of purpose of the present invention is to find a kind of carrier for preparing the molecular brand polymer filler, this carrier answers swellability very little, and resistance to pressure is good, avoids polymer layer broken in extruding, be applicable to the large-scale solid-phase extraction column of preparation, can keep the complete sum homogeneity of cylinder when using different solvents; This carrier also answers near spherical character good, make polymer be evenly distributed at carrier surface, fine and close and complete, in conjunction with firm, difficult drop-off in use.
Two of purpose of the present invention provides and a kind ofly forms the new method of molecular brand polymer at carrier surface, and prepares the molecular brand polymer filler with this method, uses this filler to extract to answer that diffusion velocity is fast, extraction efficiency is high, to realize quick separation; Also should be simple, be suitable for mass preparation.
For realizing above-mentioned first goal of the invention, the present invention selects for use through the glass microballoon of the surface modification carrier as the molecular brand solid phase extraction filler.
Described through surface modification, refer to use the silylating reagent that contains vinyl to carry out surface modification, with the binding ability between reinforcing glass microballon and the molecular brand polymer.All silylating reagents that contain vinyl all can use.
Above-mentioned glass microballoon can be with solid or hollow, particle diameter the 100-2500 order all can, but every batch answered particle size even when using.Therefore can before use glass microballoon be carried out sorting, make particle size distribution range narrow as far as possible.Method for separating can adopt in water sedimentation or other conventional method repeatedly.
Use glass microballoon to be as the advantage of carrier:
Structural strength height, near spherical character good, do not have swellability substantially, so when using different solvents, can keep the complete sum homogeneity of cylinder.
2. resistance to pressure is good, and the post pressure is little during use, thereby can use longer post core, improves separative efficiency.
3. compare with mass polymerization, owing to replaced the very low part of those utilization rates of filler center, thus significantly reduced the consumption of molecular brand material (especially template molecule);
For realizing above-mentioned second goal of the invention, the present invention uses based on capillary liquid-film method, and prepared filler is the particle that has the molecular brand polymer thin layer at carrier surface.
In order to the mode of operation effect is better down:
1. earlier with the carrier prepacked column of filler, build the main body framework of filler in the future, bear by carrier, prevent that polymer layer is broken in extruding with the structural pressure overwhelming majority that guarantees product;
2. polymerization liquid is injected above-mentioned prepacked column.
With high pressure nitrogen unnecessary polymerization liquid is blown out.Under capillary effect, the surplus very thin and uniform one deck polymerization liquid of carrier surface instrument with raw materials such as saving template molecules, and reaches the deoxygenation purpose simultaneously;
3. with after the pillar sealing two ends of handling well, put in the water-bath polymerisation about 24 hours, can obtain efficient molecular brand solid phase extraction filler.
The described carrier of this method can use the conventional various carrier materials that use of those skilled in the art, as silica gel (atresia), glass microballoon etc.
The beneficial effect that uses liquid-film method of the present invention to prepare the molecular brand solid phase extraction filler is:
1. it is even more, fine and close and complete that polymer is distributed at carrier surface, more firm in conjunction with getting, in use difficult drop-off;
2. because of surface tension effects, the polymer that obtains has bigger average pore size, thereby increases diffusion velocity, raising extraction efficiency, can realize the purpose of separating fast;
3. this method is simple, is suitable for mass preparation.
If as carrier material, and use liquid-film method of the present invention to prepare the molecular brand solid phase extraction filler the aforesaid glass microballoon of the present invention, better effects if then, bring out the best in each other:
1. owing in post, just add polymerization liquid behind the filling hollow glass micropearl earlier, therefore the structural pressure of whole filler itself is mainly born by glass microballoon, and glass microballoon itself can bear 1000 atmospheric pressure, so no matter be and mass polymerization, the multistep polymerization method is compared still with using macro porous silica gel and is compared as carrier that (they all rely on the molecular brand material and itself bear pressure, and molecular brand polymer is a cellular structure, the pressure that itself can bear is not too big), its withstand voltage properties of the solid phase extraction filler for preparing all much higher (being particularly useful for preparing large-scale solid-phase extraction column).
2. the high near spherical character of glass microballoon combines with capillary, can make the polymer surfaces for preparing smooth evenly, has better chromatographic performance (it is little at first to be exactly that its post is pressed, thereby can use longer post core and bigger flow velocity).
Description of drawings
Fig. 1 is a liquid film polymer adsorption rate experimental result;
Fig. 2 is a bulk polymer adsorption rate experimental result.
Among the above-mentioned figure, abscissa is represented the time, and ordinate is represented solution absorbance.
The specific embodiment
Following examples by showing preparation respectively molecular brand extraction stuffing bulk polymer and be the liquid film polymer of carrier with the hollow glass micropearl, to compare.
Molecular template in the present embodiment with archen as an example, but the present invention is not limited to this.In fact, as long as use material of the present invention and method, those skilled in the art can prepare various required molecular brand extraction stuffings.
Embodiment
1. experiment material
1.1 source
Archen is available from Huai safe biochemistry corporation,Ltd. of a specified duration, and purity is greater than 98%.
Acrylamide (AA), trihydroxy methyl propane trimethyl acrylate (TRIM), azodiisobutyronitrile (AIBN) are available from lark prestige chemical reagents corporation.TRIM handles with following method before use: TRIM with 10% aqueous sodium hydroxide washes after, use anhydrous magnesium sulfate drying, and then reduces pressure and distill again.AIBN uses recrystallizing methanol before using.
Oxolane (THF) is a chromatographically pure, and through the sodium drying, redistillation is handled before using.Methyl alcohol, acetonitrile are chromatographically pure, and acetic acid is pure for analyzing.
500 order hollow glass micropearls, triethoxy vinyl silanes, triethoxy aminoethyl silane are available from the big chemical reagents corporation in sea, Qingdao.
0.75mm internal diameter PEEK pipe and various PEEK joint (concave, convex) are available from Di Ma company.
1/16 inch of radius, aperture 10um stainless steel mesh is available from U.S. Valco Instruments Co.Inc..
500uL and 2.5mL sample introduction needle are available from U.S. HAMILTON Co..
500 order stainless steel sifts are customization.
4.6 the empty stainless steel chromatogram of * 50mm post is the processing of Beijing northization instrument reagent company.
6mL polyethylene solid phase extraction tube is that the C18 filler that the 6mL C18 solid phase extraction tube of J.T.Baker is emptied wherein obtains.
The quick specific area pore size determination of ASAP2010 instrument is chemistry institute of a Peking University middle rank instrument experiment chamber instrument.
1.2 the preliminary treatment of hollow glass micropearl
Get 200 grams, 500 order hollow glass micropearls, with clear water repeatedly sedimentation to remove the less particle of radius wherein and the black impurity of bottom.With the particle diameter that obtains after the sedimentation comparatively the hollow glass micropearl of homogeneous place the 500mL large beaker, add 2M HCl therein, heating (about 65 degree) reaction is 4 hours under electromagnetic agitation, removing the metal ion on glass microballoon surface, and the silicon hydroxyl on activation bead surface.Supernatant is removed in the activation hypsokinesis, with distilled water repeatedly rinsing to neutral, drop in being placed on baking oven in 110 ℃ of dryings 2 hours.
Hollow glass micropearl 50 grams that take by weighing after the activation place the 250mL round-bottomed flask, adding is through toluene 50mL, triethoxy vinyl silanes 5mL (binding ability between reinforcing glass microballon and the molecular brand polymer), the triethoxy aminoethyl silane 0.5mL (binding ability between reinforcing glass microballon and the masterplate molecule) of no water treatment, load onto reflux condensate device, back flow reaction is 72 hours under electromagnetic agitation.Supernatant is removed in the reaction hypsokinesis, with acetone repeatedly rinsing with remove unreacted solution, drain be placed in the vacuum desiccator dry.
2. experimental procedure and experimental result
2.1 prepare the molecular brand polymer of archen with mass polymerization
The 27mg archen is dissolved in the 700uL oxolane, adds 28.8mg acrylamide, 700uL TRIM, 6.5mg AIBN, step on the 1.5mL Chinese mugwort and mix back letting nitrogen in and deoxidizing, tube sealing polymerization (60 ℃ of water-bath 24h) in doffer's pipe.Polymerizate with acetone sedimentation repeatedly, obtains the comparatively about 350mg of product of homogeneous of particle after grinding is sieved.
2.2 is the archen molecular brand polymer of carrier with the liquid-film method preparation with the hollow glass micropearl
The hollow glass micropearl that surface modification is crossed is packed into (about 800mg packs into) in the empty stainless steel chromatogram of the 4.6 * 50mm post, after injecting 200uL polymerization liquid (forming same polymerisation in bulk) from an end with the 500uL sample introduction needle, letting nitrogen in and deoxidizing also makes the glass microballoon surface form one deck reactive polymeric liquid film.Seal the chromatographic column two ends with plug, polymerization 24h in 60 ℃ of water-baths.The about 850mg of the product that finally obtains.From preparation technology's angle, the method that the present invention is used even also simpler than mass polymerization.
2.3 the mensuration of archen concentration-absorbance calibration curve
The archen methanol solution of preparation 1.00ug/mL, 4.00ug/mL, 8.00ug/mL, 10.0ug/mL, 12.0ug/mL is a reference with methyl alcohol, measures their absorbance (1cm absorbance pond) respectively in 435nm wavelength place with 722 type spectrophotometers.
The absorbance (1cm absorbance pond) of archen methanol solution when the 435nm wavelength under table 1 variable concentrations
| Concentration (ug/mL) | 1.00 | 4.00 | 8.00 | 10.0 | 12.0 |
| Absorbance | 0.032 | 0.148 | 0.290 | 0.357 | 0.446 |
Be figure and get A=0.0365C (ug/mL), or C (ug/mL)=27.4A.
2.4 supersaturation SPE experiment
The filling of solid-phase extraction column: mass polymerization archen molecular brand solid-phase extraction column is that the product of 232.8mg after sedimentation is loaded on 6mL polyethylene solid phase extraction tube; Liquid film polymerization (is carrier with the bead) archen molecular brand solid-phase extraction column is 4.6 * 50mm stainless steel chromatogram post (being original preparation system).
The removal of masterplate molecule: wash above-mentioned four kinds of archen molecular brand solid-phase extraction columns with 20mL methyl alcohol earlier, use 10mL acetonitrile balance again.
Last sample: 1.00mL 100ug/mL archen acetonitrile solution.
Clean:＞6mL acetonitrile (it is colourless substantially to be washed till outflow liquid).
Wash-out: 6mL methyl alcohol (it is colourless substantially to be washed till outflow liquid).
Measure: with methyl alcohol is reference, measure the absorbance (1cm absorbance pond) of meoh eluate respectively in 435nm wavelength place with 722 type spectrophotometers, on calibration curve, obtain archen concentration in the eluent, calculate the extraction quantity of above-mentioned two kinds of archen molecular brand solid-phase extraction columns again.
The archen molecular brand polymer SPE performance of two kinds of method preparations of table 2 relatively
| Filler weight (mg) | Elution volume (mL) | The eluent absorbance | Extraction quantity (ug) | Archen consumption (mg/g) | Loading capacity (ug/g) | |
| Bulk polymer | 232.8 | 5.0 | 0.015 | 2.0 | 36(77) * | 8.8 |
| The liquid film polymer | 850 | 6.0 | 0.401 | 65.9 | 2.1 | 77.6 |
* the numeral in the bracket is according to the result of the available product of reality (350mg) when converting.
Supersaturation SPE result of experiment has shown the actual available maximum column capacity of solid phase extraction filler.The liquid film polymer has the post appearance than bulk polymer much bigger (8.8 times) as can be seen from Table 2, and this only reduces the raw material consumption when just having broken through the multistep polymerization method and having used macro porous silica gel as carrier, but does not improve the restriction that post holds.This method has saved about 97% than mass polymerization on this external raw material consumption.
Liquid film polymerization (is carrier with the bead) archen molecular brand SPE column solid phase extraction determination of recovery rates
Applied sample amount is 20ug during measurement, but the sample concentration difference of using, condition is as follows:
Sample on the high concentration: 0.500mL 40.0ug/mL archen acetonitrile solution.
Sample on the middle concentration: 3.00mL 6.67ug/mL archen acetonitrile solution.
Sample on the low concentration: 10.0mL 2.00ug/mL archen acetonitrile solution.
All the other SPEs and detection step are the same.
Three kinds of rate of recovery that go up liquid-film method molecular brand polymer SPE under the sample concentration of table 3
| Filler | Last sample concentration (ug/mL) | Elution volume (mL) | Absorbance | Extraction quantity (ug) | The rate of recovery |
| The liquid film polymer | 40.0 | 4.0 | 0.172 | 18.9 | 94.4％ |
| 6.67 | 4.0 | 0.165 | 18.1 | 90.3％ | |
| 2.00 | 6.0 | 0.105 | 17.2 | 86％ |
Can see from table 3, be low to moderate 2ug/mL even go up sample concentration, when applied sample amount was 20ug, the filler of liquid-film method preparation still can reach 86% the rate of recovery.
2.5 the BET experiment of the archen molecular brand polymer of two kinds of method preparations
Respectively get the archen molecular brand polymer of polymerisation in bulk archen molecular brand polymer and liquid-film method preparation (all flush away masterplate molecule) a certain amount of in 120 ℃ of vacuum drying degassings.BET tests by chemistry institute of Peking University middle rank instrument experiment chamber on behalf of mensuration.Desorption and adsorption isotherm record have adopted 55 point pressure tables, pore-size distribution to use the BJH model to calculate.
The specific area and the average pore size of the archen molecular brand polymer of two kinds of method preparations of table 4
| Bulk polymer | The liquid film polymer | |
| Specific area (m 2/g) | 172.4 | 28.3 |
| Average pore size (nm) | 3.91 | 6.45 |
As can be seen from Table 4, its bigger post of filler of the present invention's preparation holds and does not come from the increase of specific area, but is the expansion of average pore size under the surface tension effects.This feature other nucleus replacement method just is unexistent, and this also is the key foundation of advantage of the present invention.
2.6 the adsorption rate experiment of the archen molecular brand polymer of mass polymerization and liquid-film method preparation
The archen molecular brand polymer that takes by weighing 139mg polymerisation in bulk preparation places 1cm absorbance pond, wetting with the 340uL acetonitrile, after treating that the polymer sedimentation finishes, adding 1mL 6ug/mL archen acetonitrile solution along wall, is that reference is measured the absorbance when mixing different time with the acetonitrile.
The archen molecular brand polymer that takes by weighing the preparation of 139mg liquid-film method places 1cm absorbance pond, wetting with the 340uL acetonitrile, after treating that the polymer sedimentation finishes, adding 1mL 15ug/mL archen acetonitrile solution along wall, is that reference is measured the absorbance when mixing different time with the acetonitrile.
The adsorption rate result of experiment is seen accompanying drawing 1 and accompanying drawing 2.These two figure show that the polymer of this method preparation has very fast adsorption rate, and this also just average pore size increase the result who brings, be an advantage of the present invention.
Claims (5)
1. the carrier that the molecular brand solid phase extraction filler is used is the glass microballoon through surface modification, and described surface modification is with the silylating reagent that contains vinyl glass microballoon to be carried out surface treatment.
2. the carrier that molecular brand solid phase extraction filler according to claim 1 is used, described glass microballoon are solid or hollow.
3. the carrier that molecular brand solid phase extraction filler according to claim 1 is used, the particle diameter of described glass microballoon are the 100-2500 orders.
4. filler that is used for the molecular brand SPE is characterized in that: the glass microballoon that this filler is used with the described molecular brand solid phase extraction filler of arbitrary claim in the claim 1～3 is as carrier.
5. the filler that is used for the molecular brand SPE according to claim 4 is characterized in that: form the particle with molecular brand polymer thin layer with liquid-film method on the glass microballoon surface.
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| CN102350327A (en) * | 2011-08-12 | 2012-02-15 | 天津博纳艾杰尔科技有限公司 | Novel hydrophilic C18 filling material and its solid phase extraction column |
| CN113244791B (en) * | 2021-05-12 | 2022-06-17 | 佳木斯大学 | Preparation method of emodin-blended phenolphthalein polyethersulfone ultrafiltration membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440506A (en) * | 2000-06-23 | 2003-09-03 | 普罗米蒂克生物科学有限公司 | Particles and their use in molecular imprinting |
| US6660176B2 (en) * | 2001-01-24 | 2003-12-09 | Virginia Commonwealth University | Molecular imprinting of small particles, and production of small particles from solid state reactants |
| US20040072373A1 (en) * | 2002-10-15 | 2004-04-15 | Industrial Technology Research Institute | Biochemical labeling materials and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440506A (en) * | 2000-06-23 | 2003-09-03 | 普罗米蒂克生物科学有限公司 | Particles and their use in molecular imprinting |
| US6660176B2 (en) * | 2001-01-24 | 2003-12-09 | Virginia Commonwealth University | Molecular imprinting of small particles, and production of small particles from solid state reactants |
| US20040072373A1 (en) * | 2002-10-15 | 2004-04-15 | Industrial Technology Research Institute | Biochemical labeling materials and manufacturing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Molecularly imprinted composite polymers based ontrimethylopropane trimethacrylate(TRIM)particles for efficientenantiomeric separations Magnus Glad,Per Reinholdsson ,Klaus Mosbach,Reactive polymers,No.25 1995 * |
| Molecularly imprinted composite polymers based ontrimethylopropane trimethacrylate(TRIM)particles for efficientenantiomeric separations Magnus Glad,Per Reinholdsson ,Klaus Mosbach,Reactive polymers,No.25 1995;Moleculary imprinted polymers:useful materials for analyticalchemistry? Andrew G.Mayes,Klaus Mosbach,trends in analytical chemistry,Vol.16 No.6 1997 * |
| Moleculary imprinted polymers:useful materials for analyticalchemistry? Andrew G.Mayes,Klaus Mosbach,trends in analytical chemistry,Vol.16 No.6 1997 * |
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